Chemistry of Electronic Materials

Collection Editor: Andrew R. Barron

Chemistry of Electronic Materials

Collection Editor: Andrew R. Barron Authors: Andrew R. Barron Pinn-Tsong Chiang Christopher E. Hamilton Jason Holden Christopher Kelty Inna Kurganskaya Andreas Luttge Avishek Saha Carissa Smith Elizabeth Whitsitt Bill Wilson

Online: < >

Rice University, Houston, Texas

This selection and arrangement of content as a collection is copyrighted by Andrew R. Barron. It is licensed under the Creative Commons Attribution 3.0 license ( Collection structure revised: February 10, 2010 PDF generated: June 29, 2010 For copyright and attribution information for the modules contained in this collection, see p. 308.

Table of Contents
Preface to the Chemistry of Electronic Materials 1 Background to Electronic Materials 1.1 1.2 1.3 1.4 1.5


sntrodu™tion to ƒemi™ondu™tors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F Q hoped ƒemi™ondu™tors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F W hi'usion F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IT gryst—l ƒtru™ture F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PH ƒtru™tures of ilement —nd gompound ƒemi™ondu™tors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F QV

2 Device Fundamentals 2.1 sntrodu™tion to fipol—r „r—nsistors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F SI 2.2 f—si™ wyƒ ƒtru™ture F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F SQ 2.3 sntrodu™tion to the wyƒ „r—nsistor —nd wyƒpi„s F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F F SV 2.4 vight imitting hiode F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F F TP 2.5 €olymer vight imitting hiodes F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F TT 2.6 v—ser F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F US 2.7 ƒol—r gells F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F UV 3 Bulk Materials 3.1 €roperties of q—llium ersenide F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F VS 3.2 ƒynthesis —nd €uri(™—tion of fulk ƒemi™ondu™tors F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F VW 3.3 ger—mi™ €ro™essing of elumin— F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IHI 3.4 €iezoele™tri™ w—teri—ls ƒynthesis F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IHR 4 Wafer Formation and Processing 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9

porm—tion of ƒili™on —nd q—llium ersenide ‡—fers F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IIQ hoping F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IPW eppli™—tions for ƒili™— „hin pilms F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IQH yxid—tion of ƒili™on F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IQR €hotolithogr—phy F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IQV ypti™—l sssues in €hotolithogr—phy F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IRQ gomposition —nd €hoto™hemi™—l we™h—nisms of €hotoresists F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IRU sntegr—ted gir™uit ‡ell —nd q—te gre—tion F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F ISQ epplying wet—lliz—tion ˜y ƒputtering F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F ITH

5 Thin Film Growth 5.1 wole™ul—r fe—m ipit—xy F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ITQ 5.2 etomi™ v—yer heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F ITW 5.3 ghemi™—l †—por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IUR 5.4 viquid €h—se heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F IVR 6 Chemical Vapor Deposition 6.1 6.2 6.3 6.4 6.5 6.6 6.7

ƒele™ting — wole™ul—r €re™ursor for ghemi™—l †—por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F IWI hetermin—tion of ƒu˜lim—tion inth—lpy —nd †—por €ressure for snorg—ni™ —nd wet—lEyrg—ni™ gompounds ˜y „hermogr—vimetri™ en—lysis F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F IWP IQEIS @sssE†A ƒemi™ondu™tor ghemi™—l †—por heposition F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F PHH yxide ghemi™—l †—por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PHV xitride ghemi™—l †—por heposition F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PPP wet—l yrg—ni™ ghemi™—l †—por heposition of g—l™ium pluoride F F F F F F F F F F F F F F F F F F F F F F F F F F F F PQH €re™ursors for ghemi™—l †—por heposition of gopper F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PQP

7 Materials Characterization

7.1 7.2

‚utherford f—™ks™—ttering of „hin pilms F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PQW „he eppli™—tion of †ƒs @†erti™—l ƒ™—nning snterferometryA to the ƒtudy of gryst—l ƒurf—™e €ro™esses F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PRU sntrodu™tion to x—nop—rti™le ƒynthesis F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PSW ƒemi™ondu™tor x—nop—rti™les F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PSW g—r˜on x—nom—teri—ls F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FF F F F F F F F F F F F PTI qr—phene F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PUP ‚olling wole™ules on ƒurf—™es …nder ƒ„w sm—ging F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F PUU w—nuf—™turing of ƒemin™ondu™tors F F F F F F F F F F F F F F F F F F F F F F PVU

8 Nanotechnology 8.1 8.2 8.3 8.4 8.5

9 Economic and Environmental Issues 9.1 „he invironment—l smp—™t of the

Index F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F QHH Attributions F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F FQHV

edu I .org/content/m25528/1.Preface to the Chemistry of Electronic Materials 1 „he intention of this text is not to provide — ™omprehensive referen™e to —ll —spe™ts of semi™ondu™tor devi™e f—˜ri™—tion or — review of rese—r™h results th—tD irrespe™tive of their promiseD h—ve not ˜een —dopted into m—instre—m produ™tionF snste—d it is —imed to provide — useful referen™e for those interested in the ™hemi™—l —spe™ts of the ele™troni™s industryF qiven the n—ture of gonnexionsD this ™ourse is )uid in stru™ture —nd ™ontentF sn —dditionD it ™ont—ins modules ˜y other —uthors where —ppropri—teF „he ™ontent will ˜e upd—ted —nd exp—nded with timeF sf —ny —uthors h—ve suit—˜le ™ontentD ple—se ™ont—™t me —nd s will ˜e gl—d to —ssist in tr—nsforming the ™ontent to — suit—˜le module stru™tureF endrew ‚F f—rron ‚i™e …niversityD roustonD „ˆ UUHHSF iEm—ilX —r˜dri™eFedu2 1 2 This content is available online at <http://cnx. arb@rice.1/>.

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Chapter 1 Background to Electronic Materials 1.1 Introduction to Semiconductors tors ˜y fill ‡ilsonF note: 1 „his module is —d—pted from the gonnexions module entitled Introduction to Semiconduc- sf we only h—d to worry —˜out simple ™ondu™torsD life would not ˜e very ™ompli™—tedD ˜ut on the other h—nd we wouldn9t ˜e —˜le to m—ke ™omputersD gh pl—yersD ™ell phonesD iE€ods —nd — lot of other things whi™h we h—ve found to ˜e usefulF ‡e will now move onD —nd t—lk —˜out —nother ™l—ss of ™ondu™tors ™—lled semi™ondu™torsF sn order to underst—nd semi™ondu™tors —nd in f—™t to get — more —™™ur—te pi™ture of how met—lsD or norm—l ™ondu™tors —™tu—lly workD we re—lly h—ve to resort to qu—ntum me™h—ni™sF ile™trons in — solid —re very tiny o˜je™tsD —nd it turns out th—t when things get sm—ll enoughD they no longer ex—™tly following the ™l—ssi™—l 4xewtoni—n4 l—ws of physi™s th—t we —re —ll f—mili—r with from everyd—y experien™eF st is not the purpose of this ™ourse to te—™h qu—ntum me™h—ni™sD so wh—t we —re going to do inste—d is des™ri˜e the results whi™h ™ome from looking —t the ˜eh—vior of ele™trons in — solid from — qu—ntum me™h—ni™—l point of viewF ƒolids @—t le—st the ones we will ˜e t—lking —˜outD —nd espe™i—lly semi™ondu™torsA —re ™ryst—lline m—teri—lsD whi™h me—ns th—t they h—ve their —toms —rr—nged in — ordered f—shionF ‡e ™—n t—ke sili™on @the most import—nt semi™ondu™torA —s —n ex—mpleF ƒili™on is — group IR@s†A elementD whi™h me—ns it h—s four ele™trons in its outer or v—len™e shellF ƒili™on ™ryst—llizes in — stru™ture ™—lled the di—mond ™ryst—l l—tti™eD shown in pigure IFIF i—™h sili™on —tom h—s four ™ov—lent ˜ondsD —rr—nged in — tetr—hedr—l form—tion —˜out the —tom ™enterF 1 This content is available online at <http://cnx. Q .3/>.org/content/m33647/1.

1: Crystal structure of silicon. sn two dimensionsD we ™—n s™hem—ti™—lly represent — pie™e of singleE™ryst—l sili™on —s shown in pigure IFPF i—™h sili™on —tom sh—res its four v—len™e ele™trons with v—len™e ele™trons from four ne—rest neigh˜orsD (lling the shell to V ele™tronsD —nd forming — st—˜leD periodi™ stru™tureF yn™e the —toms h—ve ˜een —rr—nged like thisD the outer v—len™e ele™trons —re no longer strongly ˜ound to the host —tomF „he outer shells of —ll of the —toms ˜lend together —nd form wh—t is ™—lled — ˜—ndF „he ele™trons —re now free to move —˜out within this ˜—ndD —nd this ™—n le—d to ele™tri™—l ™ondu™tivity —s we dis™ussed e—rlierF Figure 1.2: A 2-D representation of a silicon crystal.R CHAPTER 1. „his is not the ™omplete story howeverD for it turns out th—t due to qu—ntum me™h—ni™—l e'e™tsD there is not just one ˜—nd whi™h holds ele™tronsD ˜ut sever—l of themF ‡h—t will follow is — very qu—lit—tive pi™ture of how the ele™trons —re distri˜uted when they —re in — periodi™ solidD —nd there —re ne™ess—rily some det—ils whi™h we will ˜e for™ed to gloss overF yn the other h—nd this will give you — pretty good pi™ture of wh—t is going onD —nd m—y en—˜le you to h—ve some underst—nding of how — semi™ondu™tor re—lly worksF ile™trons —re not only distri˜uted throughout the solid ™ryst—l sp—ti—llyD ˜ut they —lso h—ve — distri˜ution in energy —s wellF „he potenti—l energy fun™tion within the solid is periodi™ in n—tureF „his potenti—l fun™tion ™omes from the positively ™h—rged —tomi™ nu™lei whi™h —re —rr—nged in the ™ryst—l in — regul—r —rr—yF e det—iled . BACKGROUND TO ELECTRONIC MATERIALS Figure 1.

S —n—lysis of how ele™tron w—ve fun™tionsD the m—them—ti™—l —˜str—™tion whi™h one must use to des™ri˜e how sm—ll qu—ntum me™h—ni™—l o˜je™ts ˜eh—ve when they —re in — periodi™ potenti—lD gives rise to —n energy distri˜ution somewh—t like th—t shown in pigure IFQF Figure 1.3: Schematic of the rst two bands in a periodic solid showing energy levels and bands. pirstlyD unlike the ™—se for free ele™tronsD in — periodi™ solidD ele™trons —re not free to t—ke on —ny energy v—lue they wishF „hey —re for™ed into spe™i(™ energy levels ™—lled —llowed st—tesD whi™h —re represented ˜y the ™ups in pigure IFQF „he —llowed st—tes —re not distri˜uted uniformly in energy eitherF „hey —re grouped into spe™i(™ ™on(gur—tions ™—lled energy ˜—ndsF „here —re no —llowed levels —t zero energy —nd for some dist—n™e —˜ove th—tF woving up from zero energyD we then en™ounter the (rst energy ˜—ndF et the ˜ottom of the ˜—nd there —re very few —llowed st—tesD ˜ut —s we move up in energyD the num˜er of —llowed st—tes (rst in™re—sesD —nd then f—lls o' —g—inF ‡e then ™ome to — region with no —llowed st—tesD ™—lled —n energy ˜—nd g—pF e˜ove the ˜—nd g—pD —nother ˜—nd of —llowed st—tes existsF „his goes on —nd onD with —ny given m—teri—l h—ving m—ny su™h ˜—nds —nd ˜—nd g—psF „his situ—tion is shown s™hem—ti™—lly in pigure IFQD where the sm—ll ™ups represent —llowed energy levelsD —nd the verti™—l —xis represents ele™tron energyF st turns out th—t e—™h ˜—nd h—s ex—™tly PN —llowed st—tes in itD where N is the tot—l num˜er of —toms in the p—rti™ul—r ™ryst—l s—mple we —re t—lking —˜outF @ƒin™e there —re IH ™ups in e—™h ˜—nd in the (gureD it must represent — ™ryst—l with just S —toms in itF xot — very ˜ig ™ryst—l —t —ll3A snto these ˜—nds we must now distri˜ute —ll of the v—len™e ele™trons —sso™i—ted with the —tomsD with the restri™tion th—t we ™—n only put one ele™tron into e—™h —llowed st—teF „his is the result of something ™—lled the €—uli ex™lusion prin™ipleF ƒin™e in the ™—se of sili™on there —re R v—len™e ele™trons per —tomD we would just (ll up the (rst two ˜—ndsD —nd the next would ˜e emptyF sf we m—ke the logi™—l —ssumption th—t the ele™trons will (ll in the levels with the lowest energy (rstD —nd only go into higher lying levels if the ones ˜elow —re —lre—dy (lledF „his situ—tion .

e met—l is —n element with —n odd num˜er of v—len™e ele™trons so th—t — met—l ends up with —n upper ˜—nd whi™h is just h—lf full of ele™tronsF „his is illustr—ted in pigure IFSF rere we see th—t one ˜—nd is fullD —nd the next is just h—lf fullF „his would ˜e the situ—tion for the qroup IQ@sssA element —luminum for .T CHAPTER 1. with rst two bands full and the next empty.4: Silicon. BACKGROUND TO ELECTRONIC MATERIALS is shown in pigure IFRD in whi™h we h—ve represented ele™trons —s sm—ll ˜l—™k ˜—lls with — 4E4 sign on themF sndeedD the (rst two ˜—nds —re ™ompletely fullD —nd the next is emptyF ‡h—t will h—ppen if we —pply —n ele™tri™ (eld to the s—mple of sili™onc ‚emem˜er the di—gr—m we h—ve —t h—nd right now is —n energy ˜—sed oneD we —re showing how the ele™trons —re distri˜uted in energyD not how they —re —rr—nged sp—ti—llyF yn this di—gr—m we ™—n not show how they will move —˜outD ˜ut only how they will ™h—nge their energy —s — result of the —pplied (eldF „he ele™tri™ (eld will exert — for™e on the ele™trons —nd —ttempt to —™™eler—te themF sf the ele™trons —re —™™eler—tedD then they must in™re—se their kineti™ energyF …nfortun—telyD there —re no empty —llowed st—tes in either of the (lled ˜—ndsF en ele™tron would h—ve to jump —ll the w—y up into the next @emptyA ˜—nd in order to t—ke on more energyF sn sili™onD the g—p ˜etween the top of the highest most o™™upied ˜—nd —nd the lowest uno™™upied ˜—nd is IFI e†F @yne e† is the potenti—l energy g—ined ˜y —n ele™tron moving —™ross —n ele™tri™—l potenti—l of one voltFA „he me—n free p—th or dist—n™e over whi™h —n ele™tron would norm—lly move ˜efore it su'ers — ™ollision is only — few hundred —ngstroms @caF QHH x IH-8 ™mA —nd so you would need — very l—rge ele™tri™ (eld @sever—l hundred thous—nd †G™mA in order for the ele™tron to pi™k up enough energy to 4jump the g—p4F „his m—kes it —ppe—r th—t sili™on would ˜e — very ˜—d ™ondu™tor of ele™tri™ityD —nd in f—™tD very pure sili™on is very poor ele™tri™—l ™ondu™torF Figure 1.

5: Electron distribution for a metal or good conductor. ƒoD ˜—™k to our sili™on s—mpleF sf there —re no pl—™es for ele™trons to 4move4 intoD then how does sili™on work —s — 4semi™ondu™tor4c ‡ellD in the (rst pl—™eD it turns out th—t not —ll of the ele™trons —re in the ˜ottom two ˜—ndsF sn sili™onD unlike s—y qu—rtz or di—mondD the ˜—nd g—p ˜etween the topEmost full ˜—ndD the next empty one is not so l—rgeF es we mentioned —˜ove it is only —˜out IFI e†F ƒo long —s the sili™on is not —t —˜solute zero temper—tureD some ele™trons ne—r the top of the full ˜—nd ™—n —™quire enough therm—l energy th—t they ™—n 4hop4 the g—pD —nd end up in the upper ˜—ndD ™—lled the ™ondu™tion ˜—ndF „his situ—tion is shown in pigure IFTF .U inst—n™eF sf we —pply —n ele™tri™ (eld to these ™—rriersD those ne—r the top of the distri˜ution ™—n indeed move into higher energy levels ˜y —™quiring some kineti™ energy of motionD —nd e—sily move from one pl—™e to the nextF sn re—lityD the whole situ—tion is — ˜it more ™omplex th—n we h—ve shown hereD ˜ut this is not too f—r from how it —™tu—lly worksF Figure 1.

sn sili™on —t room temper—tureD roughly IH10 ele™trons per ™u˜i™ ™entimeter —re therm—lly ex™ited —™ross the ˜—ndEg—p —t —ny one timeF st should ˜e noted th—t the ex™it—tion pro™ess is — ™ontinuous oneF ile™trons —re ˜eing ex™ited —™ross the ˜—ndD ˜ut then they f—ll ˜—™k down into empty spots in the lower ˜—ndF yn —ver—ge howeverD the IH10 in e—™h ™m3 of sili™on is wh—t you will (nd —t —ny given inst—ntF xow IH ˜illion ele™trons per ™u˜i™ ™entimeter seems like — lot of ele™tronsD ˜ut lets do — simple ™—l™ul—tionF „he mo˜ility of ele™trons in sili™on is —˜out IHHH ™m2 G†FsF ‚emem˜erD mo˜ility times ele™tri™ (eld yields the —ver—ge velo™ity of the ™—rriersF ile™tri™ (eld h—s units of †G™mD so with these units we get velo™ity in ™mGs —s we shouldF „he ™h—rge on —n ele™tron is IFT x IH-19 ™oulom˜sF „hus from @IFIAX @IFIA sf we h—ve — s—mple of sili™on I ™m long ˜y @I mm x ImmA squ—reD it would h—ve — resist—n™eD @IFPAD whi™h does not m—ke it mu™h of — 4™ondu™tor4F sn f—™tD if this were —ll there w—s to the sili™on storyD we ™ould p—™k up —nd move onD ˜e™—use —t —ny re—son—˜le temper—tureD sili™on would ™ondu™t ele™tri™ity very poorlyF @IFPA .V CHAPTER 1. BACKGROUND TO ELECTRONIC MATERIALS Figure 1.6: Thermal excitation of electrons across the band gap.

sf you sne—k — look —t the periodi™ t—˜leD you will see th—t phosphorus is — group † elementD —s ™omp—red with sili™on whi™h is — group IR@s†A elementF ‡h—t this me—ns is the phosphorus —tom h—s (ve outer or v—len™e ele™tronsD inste—d of the four whi™h sili™on h—sF sn — l—tti™e ™omposed m—inly of sili™onD the extr— ele™tron —sso™i—ted with the phosphorus —tom h—s no 4m—ting4 ele™tron with whi™h it ™—n ™omplete — shellD —nd so is left loosely d—ngling to the phosphorus —tomD with rel—tively low ˜inding energyF sn f—™tD with the —ddition of just — little therm—l energy @from the n—tur—l or l—tent he—t of the ™ryst—l l—tti™eA this ele™tron ™—n ˜re—k free —nd ˜e left to w—nder —round the sili™on —tom freelyF sn our 4energy ˜—nd4 pi™tureD we h—ve something like wh—t we see in pigure IFVF „he phosphorus —toms —re represented ˜y the —dded ™ups with €9s on themF „hey —re new —llowed energy levels whi™h —re formed within the 4˜—nd g—p4 ne—r the ˜ottom of the (rst empty ˜—ndF „hey —re lo™—ted ™lose enough to the empty @or 4™ondu™tion4A ˜—ndD so th—t the ele™trons whi™h they ™ont—in —re e—sily ex™ited up into the ™ondu™tion ˜—ndF „hereD they —re free to move —˜out —nd ™ontri˜ute to the ele™tri™—l ™ondu™tivity of the s—mpleF xote —lsoD howeverD th—t sin™e the ele™tron h—s left the vi™inity of the phosphorus —tomD there is now one more proton th—n there —re ele™trons —t the —tomD —nd hen™e it h—s — net positive ™h—rge of IqF ‡e h—ve represented this ˜y putting — little 4C4 sign in e—™h €E™upF xote th—t this positive ™h—rge is (xed —t the site of the phosphorous —tom ™—lled — donor sin™e it 4don—tes4 —n ele™tron up into the ™ondu™tion ˜—ndD —nd is not free to move —˜out in the ™ryst—lF 2 This content is available online at <http://cnx.7: A two dimensional representation of a silicon crystal lattice "doped" with phosphorus.W 1.2 Doped Semiconductors note: 2 „his module is —d—pted from the gonnexions module entitled Doped Semiconductors ˜y fill ‡ilsonF „o see how we ™—n m—ke sili™on — useful ele™troni™ m—teri—lD we will h—ve to go ˜—™k to its ™ryst—l stru™ture @pigure IFUAF ƒuppose somehow we ™ould su˜stitute — few —toms of phosphorus for some of the sili™on —tomsF Figure .2/>.

8: Silicon doped with phosphorus. BACKGROUND TO ELECTRONIC MATERIALS Figure 1. row m—ny phosphorus —toms do we need to signi(™—ntly ™h—nge the resist—n™e of our sili™onc ƒuppose we w—nted our I mm ˜y I mm squ—re s—mple to h—ve — resist—n™e of one ohm —s opposed to more th—n TH wΩF „urning the resist—n™e equ—tion —round we getD @IFQAF end hen™eD if we ™ontinue to —ssume —n ele™tron mo˜ility of IHHH ™m2 GvoltFse™D @IFRAF @IFQA @IFRA xow —dding more th—n T x IH17 phosphorus —toms per ™u˜i™ ™entimeter might seem like — lot of phosphorusD until you re—lize th—t there —re —lmost IH24 sili™on —toms in — ™u˜i™ ™entimeter —nd hen™e only one in every IFT million sili™on —toms h—s to ˜e ™h—nged into — phosphorus one to redu™e the resist—n™e of the s—mple from sever—l IHs of wΩ down to only one ΩF „his is the re—l power of semi™ondu™torsF ‰ou ™—n m—ke dr—m—ti™ ™h—nges in their ele™tri™—l properties ˜y the —ddition of only minute —mounts of impuritiesF „his pro™ess is ™—lled doping the semi™ondu™torF st is —lso one of the gre—t ™h—llenges of the semi™ondu™tor m—nuf—™turing industryD for it is ne™ess—ry to m—int—in f—nt—sti™ levels of ™ontrol of the impurities in the m—teri—l in order to predi™t —nd ™ontrol their ele™tri™—l propertiesF eg—inD if this were the end of the storyD we still would not h—ve —ny ™—l™ul—torsD ™ell phonesD or stereosD or —t le—st they would ˜e very ˜ig —nd ™um˜ersome —nd unreli—˜leD ˜e™—use they would h—ve to work using v—™uum tu˜esF ‡e now h—ve to fo™us on the few 4empty4 spots in the lowerD —lmost full ˜—nd @™—lled the valence bandFA ‡e will t—ke —nother view of this ˜—ndD from — somewh—t di'erent perspe™tiveF s must ™onfess —t this point th—t wh—t s —m giving you is even further from the w—y things re—lly workD then the 4™ups —t di'erent energies4 pi™ture we h—ve ˜een using so f—rF „he pro˜lem isD th—t in order to do things rightD we h—ve to get involved in momentum ph—seEsp—™eD — lot more qu—ntum me™h—ni™sD —nd gener—lly — ˜un™h .IH CHAPTER 1.

II of m—th —nd ™on™epts we don9t re—lly need in order to h—ve some ide— of how semi™ondu™tor devi™es workF ‡h—t follow ˜elow is re—lly intended —s — motiv—tionD so th—t you will h—ve some feeling th—t wh—t we st—te —s resultsD is —™tu—lly re—son—˜leF gonsider pigure IFWF rere we show —ll of the ele™trons in the v—len™eD or —lmost full ˜—ndD —nd for simpli™ity show one missing ele™tronF vet9s —pply —n ele™tri™ (eldD —s shown ˜y the —rrow in the (gureF „he (eld will try to move the @neg—tively ™h—rgedA ele™trons to the leftD ˜ut sin™e the ˜—nd is —lmost ™ompletely fullD the only one th—t ™—n move is the one right next to the empty spotD or hole —s it is ™—lledF Figure 1. with one missing. yne thing you m—y ˜e worrying —˜out is wh—t h—ppens to the ele™trons —t the ends of the s—mpleF „his is one of the pl—™es where we —re getting — somewh—t distorted view of thingsD ˜e™—use we should re—lly ˜e looking in momentumD or w—veEve™tor sp—™e r—ther th—n 4re—l4 sp—™eF sn th—t pi™tureD they m—gi™—lly drop o' one side —nd 4re—ppe—r4 on the otherF „his doesn9t h—ppen in re—l sp—™e of ™ourseD so there is no e—sy w—y we ™—n de—l with itF e short time —fter we —pply the ele™tri™ (eld we h—ve the situ—tion shown in pigure IFIHD —nd — little while —fter th—t we h—ve pigure IFIIF ‡e ™—n interpret this motion in two w—ysF yne is th—t we h—ve — net )ow of neg—tive ™h—rge to the leftD or if we ™onsider the e'e™t of the —ggreg—te of —ll the ele™trons in the ˜—nd we ™ould pi™ture wh—t is going on —s — single positive ™h—rgeD moving to the rightF „his is shown in pigure IFIPF xote th—t in either view we h—ve the s—me net e'e™t in the w—y the tot—l net ™h—rge is tr—nsported through the s—mpleF sn the mostly neg—tive ™h—rge pi™tureD we h—ve — net )ow of neg—tive ™h—rge to the leftF sn the single positive ™h—rge pi™tureD we h—ve — net )ow of positive ™h—rge to the rightF foth give the s—me sign for the ™urrent3 .9: Band full of electrons.

.IP CHAPTER 1. Figure 1. Figure 1.12: Motion of a "hole" due to an applied electric eld.10: Motion of the "missing" electron with an electric eld.11: Further motion of the "missing electron" spot. BACKGROUND TO ELECTRONIC MATERIALS Figure 1.

.IQ „husD it turns outD we ™—n ™onsider the ™onsequen™es of the empty sp—™es moving through the ™oEordin—ted motion of ele™trons in —n —lmost full ˜—nd —s ˜eing the motion of positive ™h—rgesD moving wherever these empty sp—™es h—ppen to ˜eF ‡e ™—ll these ™h—rge ™—rriers 4holes4 —nd they too ™—n —dd to the tot—l ™ondu™tion of ele™tri™ity in — semi™ondu™torF …sing ρ to represent the density @in ™m-3 of sp—™es in the v—len™e ˜—nd —nd µe —nd µh to represent the mo˜ility of ele™trons —nd holes respe™tively @they —re usu—lly not the s—meA we ™—n modify to give the ™ondu™tivity σ D when ˜oth ele™trons9 holes —re presentD @IFSAF @IFSA row ™—n we get — s—mple of semi™ondu™tor with — lot of holes in itc ‡h—t ifD inste—d of phosphorusD we dope our sili™on s—mple with — group sss elementD s—y ˜oronc „his is shown in pigure IFIQF xow we h—ve some missing or˜it—lsD or pl—™es where ele™trons ™ould go if they were —roundF „his modi(es our energy pi™ture —s follows in pigure IFIRF xow we see — set of new levels introdu™ed ˜y the ˜oron —tomsF „hey —re lo™—ted within the ˜—nd g—pD just — little w—y —˜ove the top of the —lmost fullD or v—len™e ˜—ndF ile™trons in the v—len™e ˜—nd ™—n ˜e therm—lly ex™ited up into these new —llowed levelsD ™re—ting empty st—tesD or holesD in the v—len™e ˜—ndF „he ex™ited ele™trons —re stu™k —t the ˜oron —tom sites ™—lled acceptorsD sin™e they 4—™™ept4 —n ele™tron from the v—len™e ˜—ndD —nd hen™e —™t —s (xed neg—tive ™h—rgesD lo™—lized thereF e semi™ondu™tor whi™h is doped predomin—ntly with —™™eptors is ™—lled p-typeD —nd most of the ele™tri™—l ™ondu™tion t—kes pl—™e through the motion of holesF e semi™ondu™tor whi™h is doped with donors is ™—lled n-typeD —nd ™ondu™tion t—kes pl—™e m—inly through the motion of ele™tronsF Figure 1.13: A two dimensional representation of a silicon crystal lattice doped with boron.

Na F sf there —re more —™™eptors th—n donors then the m—teri—l is pEtype —nd p ≈ Na . BACKGROUND TO ELECTRONIC MATERIALS Figure 1. due to boron acceptors.Nd F st should ˜e noted th—t in most ™ompens—ted m—teri—lD one type of impurity usu—lly h—s — mu™h gre—ter @sever—l order of m—gnitudeA ™on™entr—tion th—n the otherD —nd so the su˜tr—™tion pro™ess des™ri˜ed —˜ove usu—lly does not ™h—nge things very mu™hD eFgFD IH18 E IH16 ≈ IH18 F yne other f—™t whi™h you might (nd useful is th—tD —g—inD ˜e™—use of qu—ntum me™h—ni™sD it turns out th—t the produ™t of the ele™tron —nd hole ™on™entr—tion in — m—teri—l must rem—in — ™onst—ntF sn sili™on —t room temper—tureX @IFTA „husD if we h—ve —n nEtype s—mple of sili™on doped with IH17 donors per ™u˜i™ ™entimeterD then nD the ele™tron ™on™entr—tion is just p D the hole ™on™entr—tionD is IH20 GIH17 a IH3 ™m-3 F „he ™—rriers whi™h domin—te — m—teri—l —re ™—lled majority carriersD whi™h would ˜e the ele™trons in the —˜ove ex—mpleF „he other ™—rriers —re ™—lled minority carriers @the holes in the ex—mpleA —nd while IH3 might not seem like mu™h ™omp—red to IH17 the presen™e of minority ™—rriers is still quite import—nt —nd ™—n not ˜e ignoredF xote th—t if the m—teri—l is undopedD then it must ˜e th—t n a p —nd n a p a IH10 F „he pi™ture of 4™ups4 of di'erent —llowed energy levels is useful for g—ining — pi™tori—l underst—nding of wh—t is going on in — semi™ondu™torD ˜ut ˜e™omes somewh—t —wkw—rd when you w—nt to st—rt looking —t devi™es whi™h —re m—de up of ˜oth n —nd p type sili™onF „husD we will introdu™e one more w—y of des™ri˜ing wh—t is going on in our m—teri—lF „he pi™ture shown in pigure IFIS is ™—lled — ˜—nd di—gr—mF e band diagram is just — represent—tion of the energy —s — fun™tion of position with — semi™ondu™tor devi™eF sn — ˜—nd di—gr—mD positive energy for ele™trons is upw—rdD while for holesD positive energy is downw—rdsF „h—t . sn nEtype m—teri—lD we ™—n —ssume th—t —ll of the phosphorous —tomsD or donorsD —re fully ionized when they —re present in the sili™on stru™tureF ƒin™e the num˜er of donors is usu—lly mu™h gre—ter th—n the n—tiveD or intrinsi™ ele™tron ™on™entr—tionD @≈ IH10 ™m-3 AD if Nd is the density of donors in the m—teri—lD then nD the ele™tron ™on™entr—tionD ≈ Nd F sf —n ele™tron de(™ient m—teri—l su™h —s ˜oron is presentD then the m—teri—l is ™—lled p-type sili™onD —nd the hole ™on™entr—tion is just ≈ Na the ™on™entr—tion of acceptorsD sin™e these —toms 4—™™ept4 ele™trons from the v—len™e ˜—ndF sf ˜oth donors —nd —™™eptors —re in the m—teri—lD then whi™h ever one h—s the higher ™on™entr—tion wins outF „his is ™—lled ™ompens—tionF sf there —re more donors th—n —™™eptors then the m—teri—l is nEtype —nd n ≈ Nd .14: P-type silicon.IR CHAPTER 1.

„he dist—n™e @in energyA ˜etween the permi level —nd either Ec —nd Ev gives us inform—tion ™on™erning the density of ele™trons —nd holes in th—t region of the semi™ondu™tor m—teri—lF „he det—ilsD on™e —g—inD will h—ve to ˜e ˜egged o' on grounds of m—them—ti™—l ™omplexityF st turns out th—t you ™—n s—yX @IFUA @IFVA foth Nc —nd Nv —re ™onst—nts th—t depend on the m—teri—l you —re t—lking —˜outD ˜ut —re typi™—lly on the order of IH19 ™m-3 F „he expression in the denomin—tor of the exponenti—l is just foltzm—n9s ™onst—nt @VFTQ x IH-5 e†GuAD kD times the temper—ture T of the m—teri—l @in —˜solute temper—ture or uelvinAF et room temper—ture kT a 1 G40 of —n ele™tron voltF vook ™—refully —t the numer—tors in the exponenti—lF xote (rst th—t there is — minus sign in frontD whi™h me—ns the ˜igger the num˜er in the exponentD the fewer ™—rriers we h—veF „husD the top expression s—ys th—t if we h—ve nEtype m—teri—lD then Ef must not ˜e too f—r —w—y from the ™ondu™tion ˜—ndD while if we h—ve pEtype m—teri—lD then the permi levelDEf must ˜e down ™lose to the v—len™e ˜—ndF „he ™loser Ef gets to Ec the more ele™trons we h—veF „he ™loser Ef gets to Ev D the more holes we h—veF pigure IFIS therefore must ˜e for — s—mple of nEtype m—teri—lF xote —lso th—t if we know how he—vily — s—mple is doped @iFeFD we know wh—t Nd isA —nd from the f—™t th—t n ≈ Nd we ™—n use to (nd out how f—r —w—y the permi level is from the ™ondu™tion ˜—ndD @IFWAF @IFWA .IS isD if —n ele™tron moves upw—rdD its potenti—l energy in™re—ses just —s — with — norm—l m—ss in — gr—vit—tion—l (eldF elsoD just —s — m—ss will 4f—ll down4 if given — ™h—n™eD —n ele™tron will move down — slope shown in — ˜—nd di—gr—mF yn the other h—ndD holes g—in energy ˜y moving downw—rd —nd so they h—ve — tend—n™y to 4)o—t4 upw—rd if given the ™h—n™e E mu™h like — ˜u˜˜le in — liquidF „he line l—˜eled Ev in pigure IFIS shows the edge of the ™ondu™tion ˜—ndD or the ˜ottom of the lowest uno™™upied —llowed ˜—ndD while Ev is the top edge of the v—len™eD or highest o™™upied ˜—ndF „he ˜—nd g—pD Eg for the m—teri—l is o˜viously Ec E Ev F „he dotted line l—˜eled Ef is ™—lled the Fermi level —nd it tells us something —˜out the ™hemi™—l equili˜rium energy of the m—teri—lD —nd —lso something —˜out the type —nd num˜er of ™—rriers in the m—teri—lF wore on this l—terF xote th—t there is no zero energy level on — di—gr—m su™h —s thisF ‡e often use either the permi level or one or other of the ˜—nd edges —s — referen™e level on lieu of knowing ex—™tly where 4zero energy4 is lo™—tedF Figure 1.15: An electron band-diagram for a semiconductor.

1 Introduction vet us turn our —ttention to wh—t h—ppens to the ele™trons —nd holes on™e they h—ve ˜een inje™ted —™ross — forw—rdE˜i—sed jun™tionF ‡e will ™on™entr—te just on the ele™trons whi™h —re inje™ted into the pEside of the jun™tionD ˜ut keep in mind th—t simil—r things —re —lso h—ppening to the holes whi™h enter the nEsideF ‡hen ele™trons —re inje™ted —™ross — jun™tionD they move —w—y from the jun™tion region ˜y — di'usion pro™essD while —t the s—me timeD some of them —re dis—ppe—ring ˜e™—use they —re minority ™—rriers @ele™trons in ˜—si™—lly pEtype m—teri—lA —nd so there —re lots of holes —round for them to re™om˜ine withF „his is —ll shown s™hem—ti™—lly in pigure IFIUF 3 This content is available online at <http://cnx.3 Diusion note: 3 „his module is —d—pted from the gonnexions module entitled Diusion ˜y fill ‡ilsonF 1.16: Band diagram for an n-type semiconductor.IT CHAPTER 1. .2/>. BACKGROUND TO ELECTRONIC MATERIALS „o help further in our —˜ility to pi™ture wh—t is going onD we will often —dd to this ˜—nd di—gr—mD some sm—ll signed ™ir™les to indi™—te the presen™e of mo˜ile ele™trons —nd holes in the m—teri—lF xote th—t the ele™trons —re spre—d out in energyF prom our 4™ups4 pi™ture we know they like to st—y in the lower energy st—tes if possi˜leD ˜ut some will ˜e distri˜uted into the higher levels —s wellF ‡h—t is distorted here is the s™—leF „he ˜—ndEg—p for sili™on is IFI e†D while the —™tu—l spre—d of the ele™trons would pro˜—˜ly only ˜e — few tenths of —n e†D not ne—rly —s mu™h —s is shown in pigure IFITF vets look —t — s—mple of pEtype m—teri—lD just for ™omp—risonF xote th—t for holesD in™re—sing energy goes down not upD so their distri˜ution is inverted from th—t of the ele™tronsF ‰ou ™—n kind of think of holes —s ˜u˜˜les in — gl—ss of sod— or ˜eerD they w—nt to )o—t to the top if they ™—nF xote —lso for ˜oth n —nd pEtype m—teri—l there —re —lso — few 4minority4 ™—rriersD or ™—rriers of the opposite typeD whi™h —rise from therm—l gener—tion —™ross the ˜—ndEg—pF Figure 1.3.

IU Figure 1.17: Processes involved in electron transport across a p-n junction. xow let9s r—ise the num˜er of ele™trons to VD IP —nd IT respe™tively @pigure IFIWAF ‡e (nd th—t the net )ux —™ross e—™h ˜ound—ry is now P ele™trons per emptying timeD r—ther th—n oneF xote th—t the gr—dient @slopeA of the ™on™entr—tion in the ˜oxes h—s —lso dou˜led from one per ˜ox to two per ˜oxF „his le—ds us to — r—ther o˜vious st—tement th—t the )ux of ™—rriers is proportion—l to the gr—dient of their densityF „his is st—ted form—lly in wh—t is known —s pi™k9s pirst v—w of hi'usionD @IFIHAF ‡here De is simply — proportion—lity ™onst—nt ™—lled the di'usion ™oe0™ientF ƒin™e we —re t—lking —˜out the motion of ele™tronsD this di'usion )ux must give rise to — ™urrent density Jediff F ƒin™e —n ele™tron h—s — ™h—rge −q —sso™i—ted . 1.2 Diusion process quantied st is —™tu—lly f—irly e—sy to qu—ntify thisD —nd ™ome up with —n expression for the ele™tron distri˜ution within the pEregionF pirst we h—ve to look — little ˜it —t the di'usion pro™ess howeverF sm—gine th—t we h—ve — series of ˜insD e—™h with — di'erent num˜er of ele™trons in themF sn — given timeD we ™ould im—gine th—t —ll of the ele™trons would )ow out of their ˜ins into the neigh˜oring onesF ƒin™e there is no re—son to expe™t the ele™trons to f—vor one side over the otherD we will —ssume th—t ex—™tly h—lf le—ve ˜y e—™h sideF „his is —ll shown in pigure IFIVF ‡e will keep things simple —nd only look —t three ˜insF sm—gine there —re RD TD —nd V ele™trons respe™tively in e—™h of the ˜insF efter the required 4emptying timeD4 we will h—ve — net )ux of ex—™tly one ele™tron —™ross e—™h ˜ound—ry —s shownF Figure 1.3.18: A schematic representation of a diusion problem.

BACKGROUND TO ELECTRONIC MATERIALS Flux = (−De ) Jediff = qDe d n (x) dx @IFIHA @IFIIA d (n) dx Figure 1. xow we h—ve to invoke something ™—lled the ™ontinuity equ—tionF sm—gine we h—ve — volume @V A whi™h is (lled with some ™h—rge @Q AF st is f—irly o˜vious th—t if we —dd up —ll of the ™urrent density whi™h is )owing out of the volume th—t it must ˜e equ—l to the time r—te of de™re—se of the ™h—rge within th—t volumeF „his ide—s is expressed in the formul— ˜elow whi™h uses — ™losedEsurf—™e integr—lD —long with the —ll the other integr—ls to followX JdS = − S d (Q) dt @IFIPA ‡e ™—n write Q —sD @IFIQAD where we —re doing — volume integr—l of the ™h—rge density @ρ A over the volume @V AF xow we ™—n use q—uss9 theorem whi™h s—ys we ™—n repl—™e — surf—™e integr—l of — qu—ntity with — volume integr—l of its divergen™eD @IFIRAF Q= V ρ (v) dV @IFIQA @IFIRA JdS = S V divJdV ƒoD ™om˜ining @IFIPAD @IFIQA —nd @IFIRAD we h—veD @IFISAF   d (ρ) dV  dt @IFISA divJdV = −  V V pin—llyD we let the volume V shrink down to — pointD whi™h me—ns the qu—ntities inside the integr—l must ˜e equ—lD —nd we h—ve the di'erenti—l form of the ™ontinuity equ—tion @in one dimensionAD @IFITAF divJ = ∂ ∂x (J) d dt ρ (x) = − @IFITA .IV with itD @IFIIAF CHAPTER 1.19: A schematic representation of a diusion from bins.

t) − @IFPIA dt dx τr „his is — somewh—t spe™i—lized form of —n equ—tion ™—lled the —m˜ipol—r di'usion equ—tionF st seems kind of ™ompli™—ted ˜ut we ™—n get some ni™e results from it if we m—ke some simply ˜ound—ry ™ondition —ssumptionsF 1. t) τr @IFIUA ‡here τr ™—lled the minority ™—rrier re™om˜in—tion lifetimeF st is pretty e—sy to show th—t if we st—rt out with —n ex™ess minority ™—rrier ™on™entr—tion n0 ' —t t a HD then n' @xDtA will go —sD @IFIVAF futD the ele™tron ™on™entr—tion ™—n —lso ™h—nge ˜e™—use of ele™trons )owing into or out of the region xF „he ele™tron ™on™entr—tion n' @xDtA is just ρ(x.IW 1.3.3. t) = − dt n (x. t) = = 1 d q dt ρ (x. t) = De 2 n (x.3 What about the electrons? xow let9s go ˜—™k to the ele™trons in the diodeF „he ele™trons whi™h h—ve ˜een inje™ted —™ross the jun™tion —re ™—lled excess minority carriersD ˜e™—use they —re ele™trons in — pEregion @hen™e minorityA ˜ut their ™on™entr—tion is gre—ter th—n wh—t they would ˜e if they were in — s—mple of pEtype m—teri—l —t equili˜riumF ‡e will design—te them —s n'D —nd sin™e they ™ould ™h—nge with ˜oth time —nd position we sh—ll write them —s n' @xDtAF xow there —re two w—ys in whi™h n' @xDtA ™—n ™h—nge with timeF yne would ˜e if we were to stop inje™ting ele™trons in from the nEside of the jun™tionF e re—son—˜le w—y to —™™ount for the de™—y whi™h would o™™ur if we were not supplying ele™trons would ˜e to writeX d n (x. t) 1 q div (J (x.t) F „husD due to ele™tron )ow we h—veD @IFIWAF q n (x.1 Using the ambipolar diusion equation por —nything we will ˜e interested inD we will only look —t ste—dy st—te solutionsF „his me—ns th—t the time deriv—tive on the vrƒ of @IFPIA is zeroD —nd so letting n (x. t) ˜e™ome simply n (x) sin™e we no longer h—ve —ny time v—ri—tion to worry —˜outD we h—veX d2 1 n (x) − n (x) = 0 2 dt De τr @IFPPA €i™king the not unre—son—˜le ˜ound—ry ™onditions th—t n (0) = n0 @the ™on™entr—tion of ex™ess ele™trons just —t the st—rt of the di'usion regionA —nd n (x) → 0 —s x → ∞ @the ex™ess ™—rriers go to zero when we get f—r from the jun™tionA thenX „he expression in the r—di™—l De τr is ™—lled the ele™tron di'usion lengthD Le D —nd gives us some ide— —s to how f—r —w—y from the jun™tion the ex™ess ele™trons will exist ˜efore they h—ve more or less —ll re™om˜inedF √ n (x) = n0 e − “ √ x De τr ” @IFPQA . t) = De 2 n (x. t) from @IFIIAF ‚edu™ing the divergen™e in @IFIWA to one dimension ∂ @we just h—ve — ∂x (J)A we (n—lly end up withD @IFPHAF d d2 n (x. t) = n 0 e τr d dt n −t @IFIVA @IFIWA (x. t)) futD we ™—n get —n expression for J (x. t) @IFPHA dt dx gom˜ining @IFPHA —nd @IFIUA @ele™trons willD —fter —llD su'er from ˜oth re™om˜in—tion —nd di'usionA —nd we end up withX d n (x.3. t) d2 n (x.

2 Crystallography 1.4.4 Crystal Structure 1.2.10/>.1 Introduction 4 sn —ny sort of dis™ussion of ™ryst—lline m—teri—lsD it is useful to ˜egin with — dis™ussion of ™ryst—llogr—phyX the study of the form—tionD stru™tureD —nd properties of ™ryst—lsF e ™ryst—l stru™ture is de(ned —s the p—rti™ul—r repe—ting —rr—ngement of —toms @mole™ules or ionsA throughout — ™ryst—lF ƒtru™ture refers to the intern—l —rr—ngement of p—rti™les —nd not the extern—l —ppe—r—n™e of the ™ryst—lF roweverD these —re not entirely independent sin™e the extern—l —ppe—r—n™e of — ™ryst—l is often rel—ted to the intern—l —rr—ngementF por ex—mpleD ™ryst—ls of ™u˜i™ ro™k s—lt @x—glA —re physi™—lly ™u˜i™ in —ppe—r—n™eF ynly — few of the possi˜le ™ryst—l stru™tures —re of ™on™ern with respe™t to simple inorg—ni™ s—lts —nd these will ˜e dis™ussed in det—ilD howeverD it is import—nt to underst—nd the nomen™l—ture of ™ryst—llogr—phyF 1.4.PH CHAPTER .1 Bravais lattice „he fr—v—is l—tti™e is the ˜—si™ ˜uilding ˜lo™k from whi™h —ll ™ryst—ls ™—n ˜e ™onstru™tedF „he ™on™ept origin—ted —s — topologi™—l pro˜lem of (nding the num˜er of di'erent w—ys to —rr—nge points in sp—™e where e—™h point would h—ve —n identi™—l —tmosphereF „h—t is e—™h point would ˜e surrounded ˜y —n identi™—l set of points —s —ny other pointD so th—t —ll points would ˜e indistinguish—˜le from e—™h otherF w—them—ti™i—n euguste fr—v—is dis™overed th—t there were IR di'erent ™olle™tions of the groups of pointsD whi™h —re known —s fr—v—is l—tti™esF „hese l—tti™es f—ll into seven di'erent 4™ryst—l systemsD —s di'erenti—ted ˜y the rel—tionship ˜etween the —ngles ˜etween sides of the unit ™ell —nd the dist—n™e ˜etween points in the unit ™ellF „he unit ™ell is the sm—llest group of —tomsD ions or mole™ules th—tD when repe—ted —t regul—r interv—ls in three dimensionsD will produ™e the l—tti™e of — ™ryst—l systemF „he l—tti™e p—r—meter is the length ˜etween two points on the ™orners of — unit ™ellF i—™h of the v—rious l—tti™e p—r—meters —re design—ted ˜y the letters aD bD —nd cF sf two sides —re equ—lD su™h —s in — tetr—gon—l l—tti™eD then the lengths of the two l—tti™e p—r—meters —re design—ted a —nd cD with b omittedF „he —ngles —re design—ted ˜y the qreek letters αD β D —nd γ D su™h th—t —n —ngle with — spe™i(™ qreek letter is not su˜tended ˜y the —xis with its ‚om—n equiv—lentF por ex—mpleD α is the in™luded —ngle ˜etween the b —nd c —xisF „—˜le IFI shows the v—rious ™ryst—l systemsD while pigure IFPH shows the IR fr—v—is l—tti™esF st is import—nt to distinguish the ™h—r—™teristi™s of e—™h of the individu—l systemsF en ex—mple of — m—teri—l th—t t—kes on e—™h of the fr—v—is l—tti™es is shown in „—˜le IFPF System Axial lengths and angles Unit cell geometry continued on next page 4 This content is available online at <http://cnx. BACKGROUND TO ELECTRONIC MATERIALS „his will ˜e import—nt for us when we move on to ˜ipol—r tr—nsistorsF e typi™—l v—lue for the di'usion ™oe0™ient for ele™trons in sili™on would ˜e De a PS ™m2 Gse™ —nd the minority ™—rrier lifetime is usu—lly —round — mi™rose™ondF es shown in @IFPRA this is not very f—r —t —llF Le = = = √ De τr 25 × 10−6 @IFPRA −3 5 × 10 cm 1.4.

PI ™u˜i™ — a ˜ a ™D α a β a γ a WH ◦ tetr—gon—l — a ˜ = ™D α a β a γ a WH ◦ orthorhom˜i™ — = ˜ = ™D α a β a γ a WH ◦ rhom˜ohedr—l — a ˜ a ™D α a β a γ = WH ◦ hex—gon—l — a ˜ = ™D α a β a WH ◦ D γ a IPH ◦ — = ˜ = ™D α a γ a WH ◦ D β = WH ◦ mono™lini™ tri™lini™ — = ˜ = ™D α = β = γ Table 1.1 X qeometri™—l ™h—r—™teristi™s of the seven ™ryst—l systemsF .

20: Bravais lattices. BACKGROUND TO ELECTRONIC MATERIALS Figure 1. .PP CHAPTER 1. Atom positions and crystal axes „he stru™ture of — ™ryst—l is de(ned with respe™t to — unit ™ellF es the entire ™ryst—l ™onsists of repe—ting unit ™ellsD this de(nition is su0™ient to represent the entire ™ryst—lF ‡ithin the unit ™ellD the —tomi™ —rr—ngement is expressed using ™oordin—tesF „here —re two systems of ™oordin—tes ™ommonly in useD whi™h ™—n ™—use some ™onfusionF foth use — ™orner of the unit ™ell —s their originF „he (rstD lessE™ommonly seen system is th—t of g—rtesi—n or orthogon—l ™oordin—tes @ˆD ‰D AF „hese usu—lly h—ve the units of engstroms —nd rel—te to the dist—n™e in e—™h dire™tion ˜etween the origin of the ™ell —nd the —tomF „hese ™oordin—tes m—y ˜e .2 u2 ƒ2 y8 es4 ƒ4 D uxy2 rgD ƒ˜ nD goD xies q—D pe3 g snD „iy2 euD ƒiD x—gl X ix—mples of elements —nd ™ompounds th—t —dopt e—™h of the ™ryst—l systemsF „he ™u˜i™ l—tti™e is the most symmetri™—l of the systemsF ell the —ngles —re equ—l to WH ◦ D —nd —ll the sides —re of the s—me length @a a b a c AF ynly the length of one of the sides @aA is required to des™ri˜e this system ™ompletelyF sn —ddition to simple ™u˜i™D the ™u˜i™ l—tti™e —lso in™ludes ˜odyE™entered ™u˜i™ —nd f—™eE™entered ™u˜i™ @pigure IFPHAF fodyE™entered ™u˜i™ results from the presen™e of —n —tom @or ionA in the ™enter of — ™u˜eD in —ddition to the —toms @ionsA positioned —t the verti™es of the ™u˜eF sn — simil—r m—nnerD — f—™eE™entered ™u˜i™ requiresD in —ddition to the —toms @ionsA positioned —t the verti™es of the ™u˜eD the presen™e of —toms @ionsA in the ™enter of e—™h of the ™u˜es f—™eF „he tetr—gon—l l—tti™e h—s —ll of its —ngles equ—l to WH ◦ D —nd h—s two out of the three sides of equ—l length @a a bAF „he system —lso in™ludes ˜odyE™entered tetr—gon—l @pigure IFPHAF sn —n orthorhom˜i™ l—tti™e —ll of the —ngles —re equ—l to WH ◦ D while —ll of its sides —re of unequ—l lengthF „he system needs only to ˜e des™ri˜ed ˜y three l—tti™e p—r—metersF „his system —lso in™ludes ˜odyE™entered orthorhom˜i™D ˜—seE™entered orthorhom˜i™D —nd f—™eE™entered orthorhom˜i™ @pigure IFPHAF e ˜—seE™entered l—tti™e h—sD in —ddition to the —toms @ionsA positioned —t the verti™es of the orthorhom˜i™ l—tti™eD —toms @ionsA positioned on just two opposing f—™esF „he rhom˜ohedr—l l—tti™e is —lso known —s trigon—lD —nd h—s no —ngles equ—l to WH ◦ D ˜ut —ll sides —re of equ—l length @a a b a c AD thus requiring only ˜y one l—tti™e p—r—meterD —nd —ll three —ngles —re equ—l @α a β a γ AF e hex—gon—l ™ryst—l stru™ture h—s two —ngles equ—l to WH ◦ D with the other —ngle @ γ A equ—l to IPH ◦ F por this to h—ppenD the two sides surrounding the IPH ◦ —ngle must ˜e equ—l @a a bAD while the third side @c A is —t WH ◦ to the other sides —nd ™—n ˜e of —ny lengthF „he mono™lini™ l—tti™e h—s no sides of equ—l lengthD ˜ut two of the —ngles —re equ—l to WH ◦ D with the other —ngle @usu—lly de(ned —s β A ˜eing something other th—n WH ◦ F st is — tilted p—r—llelogr—m prism with re™t—ngul—r ˜—sesF „his system —lso in™ludes ˜—seE™entered mono™lini™ @pigure IFPHAF sn the tri™lini™ l—tti™e none of the sides of the unit ™ell —re equ—lD —nd none of the —ngles within the unit ™ell —re equ—l to WH ◦ F „he tri™lini™ l—tti™e is ™hosen su™h th—t —ll the intern—l —ngles —re either —™ute or o˜tuseF „his ™ryst—l system h—s the lowest symmetry —nd must ˜e des™ri˜ed ˜y Q l—tti™e p—r—meters @aD bD —nd c A —nd the Q —ngles @αD β D —nd γ AF 1.2 Atom positions. crystal directions and Miller indices 1.PQ Crystal system Example tri™lini™ mono™lini™ rhom˜ohedr—l hex—gon—l orthorhom˜i™ tetr—gon—l ™u˜i™ Table 1.4.

1 G3.2.PR CHAPTER 1.5 A or HFTV of the c —xisF „he fr—™tion—l ™oordin—tes of this —tom —reD thereforeD @HFRQD HFTHD HFTVAF „he ™oordin—tes of the equiv—lent —tom in the next ™ell over in the a dire™tionD howeverD —re e—sily ™—l™ul—ted —s this —tom is simply I unit ™ell —w—y in aF „husD —ll one h—s to do is —dd I to the x ™oordin—teX @IFRQD HFTHD HFTVAF ƒu™h tr—nsform—tions ™—n ˜e performed reg—rdless of the sh—pe of the unit ™ellF pr—™tion—l ™oordin—tesD thereforeD —re used to ret—in —nd m—nipul—te ™ryst—l inform—tionF 1.2.4 G3.52 A or HFRQ of the —xis —w—y from the originF ƒimil—rlyD it is @2.2 Crystal directions „he design—tion of the individu—l ve™tors within —ny given ™ryst—l l—tti™e is —™™omplished ˜y the use of whole num˜er multipliers of the l—tti™e p—r—meter of the point —t whi™h the ve™tor exits the unit ™ellF „he ve™tor is indi™—ted ˜y the not—tion ‘hkl “D where hD kD —nd l —re re™ipro™—ls of the point —t whi™h the ve™tor exits the unit ™ellF „he origin—tion of —ll ve™tors is —ssumed de(ned —s ‘HHH“F por ex—mpleD the dire™tion —long the aE—xis —™™ording to this s™heme would ˜e ‘IHH“ ˜e™—use this h—s — ™omponent only in the aEdire™tion —nd no ™omponent —long either the b or c —xi—l dire™tionF e ve™tor di—gon—lly —long the f—™e de(ned ˜y the a —nd b —xis would ˜e ‘IIH“D while going from one ™orner of the unit ™ell to the opposite ™orner would ˜e in the ‘III“ dire™tionF pigure IFPI shows some ex—mples of the v—rious dire™tions in the unit ™ellF „he ™ryst—l dire™tion not—tion is m—de up of the lowest ™om˜in—tion of integers —nd represents unit dist—n™es r—ther th—n —™tu—l dist—n™esF e ‘PPP“ dire™tion is identi™—l to — ‘III“D so ‘III“ is usedF pr—™tions —re not usedF por ex—mpleD — ve™tor th—t inter™epts the ™enter of the top f—™e of the unit ™ell h—s the ™oordin—tes x a IGPD y a IGPD z a IF ell h—ve to ˜e inversed to ™onvert to the lowest ™om˜in—tion of integers @whole num˜ersAY iFeFD ‘PPI“ in pigure IFPIF pin—llyD —ll p—r—llel ve™tors h—ve the s—me ™ryst—l dire™tionD eFgFD the four verti™—l edges of the ™ell shown in pigure IFPI —ll h—ve the ™ryst—l dire™tion ‘hkl “ a ‘HHI“F . BACKGROUND TO ELECTRONIC MATERIALS m—nipul—ted in the s—me f—shion —re used with twoE or threeEdimension—l gr—phsF st is very simpleD thereforeD to ™—l™ul—te interE—tomi™ dist—n™es —nd —ngles given the g—rtesi—n ™oordin—tes of the —tomsF …nfortun—telyD the repe—ting n—ture of — ™ryst—l ™—nnot ˜e expressed e—sily using su™h ™oordin—tesF por ex—mpleD ™onsider — ™u˜i™ ™ell of dimension QFSP ÅF €retend th—t this ™ell ™ont—ins —n —tom th—t h—s the ™oordin—tes @IFSD PFID PFRAF „h—t isD the —tom is IFS Å —w—y from the origin in the x dire™tion @whi™h ™oin™ides with the a ™ell —xisAD PFI Å in the y @whi™h ™oin™ides with the b ™ell —xisA —nd PFR Å in the z @whi™h ™oin™ides with the c ™ell —xisAF „here will ˜e —n equiv—lent —tom in the next unit ™ell —long the xEdire™tionD whi™h will h—ve the ™oordin—tes @IFS C QFSPD PFID PFRA or @SFHPD PFID PFRAF „his w—s — r—ther simple ™—l™ul—tionD —s the ™ell h—s very high symmetry —nd so the ™ell —xesD aD b —nd cD ™oin™ide with the g—rtesi—n —xesD ˆD ‰ —nd F roweverD ™onsider lower symmetry ™ells su™h —s tri™lini™ or mono™lini™ in whi™h the ™ell —xes —re not mutu—lly orthogon—lF sn su™h ™—sesD expressing the repe—ting n—ture of the ™ryst—l is mu™h more di0™ult to —™™omplishF e™™ordinglyD —tomi™ ™oordin—tes —re usu—lly expressed in terms of fr—™tion—l ™oordin—tesD @xD yD zAF „his ™oordin—te system is ™oin™ident with the ™ell —xes @aD bD c A —nd rel—tes to the position of the —tom in terms of the fr—™tion —long e—™h —xisF gonsider the —tom in the ™u˜i™ ™ell dis™ussion —˜oveF „he —tom w—s IFS Å in the a dire™tion —w—y from the originF es the a —xis is QFSP Å longD the —tom is @1.4.52 A or HFTH of the b —xis —nd @2.5 G3.

2.4. gryst—l dire™tions m—y ˜e grouped in f—miliesF „o —void ™onfusion there exists — ™onvention in the ™hoi™e of ˜r—™kets surrounding the three num˜ers to di'erenti—te — ™ryst—l dire™tion from — f—mily of dire™tionF por — dire™tionD squ—re ˜r—™kets ‘hkl “ —re used to indi™—te —n individu—l dire™tionF engle ˜r—™kets <hkl > indi™—te — f—mily of dire™tionsF e f—mily of dire™tions in™ludes —ny dire™tions th—t —re equiv—lent in length —nd types of —toms en™ounteredF por ex—mpleD in — ™u˜i™ l—tti™eD the ‘IHH“D ‘HIH“D —nd ‘HHI“ dire™tions —ll ˜elong to the <IHH> f—mily of pl—nes ˜e™—use they —re equiv—lentF sf the ™u˜i™ l—tti™e were rot—ted WH ◦ D the aD bD —nd c dire™tions would rem—in indistinguish—˜leD —nd there would ˜e no w—y of telling on whi™h ™ryst—llogr—phi™ positions the —toms —re situ—tedD so the f—mily of dire™tions is the s—meF sn — hex—gon—l ™ryst—lD howeverD this is not the ™—seD so the ‘IHH“ —nd ‘HIH“ would ˜oth ˜e <IHH> dire™tionsD ˜ut the ‘HHI“ dire™tion would ˜e distin™tF pin—llyD neg—tive dire™tions —re identi(ed with — ˜—r over the neg—tive num˜er inste—d of — minus signF 1.3 Crystal planes €l—nes in — ™ryst—l ™—n ˜e spe™i(ed using — not—tion ™—lled willer indi™esF „he willer index is indi™—ted ˜y the not—tion ‘hkl “ where hD kD —nd l —re re™ipro™—ls of the pl—ne with the xD yD —nd z —xesF „o o˜t—in the willer indi™es of — given pl—ne requires the following stepsX ƒtep ƒtep ƒtep ƒtep IF PF QF RF „he pl—ne in question is pl—™ed on — unit ™ellF sts inter™epts with e—™h of the ™ryst—l —xes —re then foundF „he re™ipro™—l of the inter™epts —re t—kenF „hese —re multiplied ˜y — s™—l—r to insure th—t is in the simple r—tio of whole num˜ersF por ex—mpleD the f—™e of — l—tti™e th—t does not interse™t the y or z —xis would ˜e @IHHAD while — pl—ne —long the ˜ody di—gon—l would ˜e the @IIIA pl—neF en illustr—tion of this —long with the @IIIA —nd @IIHA pl—nes is given in pigure IFPPF .PS Figure 1.21: Some common directions in a cubic unit cell.2.



Figure 1.22:

Examples of Miller indices notation for crystal planes.

es with ™ryst—l dire™tionsD willer indi™es dire™tions m—y ˜e grouped in f—miliesF sndividu—l willer indi™es —re given in p—rentheses @hkl AD while ˜r—™es {hkl } —re pl—™ed —round the indi™es of — f—mily of pl—nesF por ex—mpleD @HHIAD @IHHAD —nd @HIHA —re —ll in the {IHH} f—mily of pl—nesD for — ™u˜i™ l—tti™eF

1.4.3 Description of crystal structures
gryst—l stru™tures m—y ˜e des™ri˜ed in — num˜er of w—ysF „he most ™ommon m—nner is to refer to the size —nd sh—pe of the unit ™ell —nd the positions of the —toms @or ionsA within the ™ellF roweverD this inform—tion is sometimes insu0™ient to —llow for —n underst—nding of the true stru™ture in three dimensionsF gonsider—tion of sever—l unit ™ellsD the —rr—ngement of the —toms with respe™t to e—™h otherD the num˜er of other —toms they in ™ont—™t withD —nd the dist—n™es to neigh˜oring —tomsD often will provide — ˜etter underst—ndingF e num˜er of methods —re —v—il—˜le to des™ri˜e extended solidEst—te stru™turesF „he most —ppli™—˜le with

PU reg—rd to element—l —nd ™ompound semi™ondu™torD met—ls —nd the m—jority of insul—tors is the ™lose p—™king —ppro—™hF Close packed structures: hexagonal close packing and cubic close packing

w—ny ™ryst—l stru™tures ™—n ˜e des™ri˜ed using the ™on™ept of ™lose p—™kingF „his ™on™ept requires th—t the —toms @ionsA —re —rr—nged so —s to h—ve the m—ximum densityF sn order to underst—nd ™lose p—™king in three dimensionsD the most e0™ient w—y for equ—l sized spheres to ˜e p—™ked in two dimensions must ˜e ™onsideredF „he most e0™ient w—y for equ—l sized spheres to ˜e p—™ked in two dimensions is shown in pigure IFPQD in whi™h it ™—n ˜e seen th—t e—™h sphere @the d—rk gr—y sh—ded sphereA is surrounded ˜yD —nd is in ™ont—™t withD six other spheres @the light gr—y spheres in pigure IFPQAF st should ˜e noted th—t ™ont—™t with six other spheres the m—ximum possi˜le is the spheres —re the s—me sizeD —lthough lower density p—™king is possi˜leF glose p—™ked l—yers —re formed ˜y repetition to —n in(nite sheetF ‡ithin these ™lose p—™ked l—yersD three ™lose p—™ked rows —re presentD shown ˜y the d—shed lines in pigure IFPQF

Figure 1.23: Schematic representation of a close packed layer of equal sized spheres. The close packed rows (directions) are shown by the dashed lines.

„he most e0™ient w—y for equ—l sized spheres to ˜e p—™ked in three dimensions is to st—™k ™lose p—™ked l—yers on top of e—™h other to give — ™lose p—™ked stru™tureF „here —re two simple w—ys in whi™h this ™—n ˜e doneD resulting in either — hex—gon—l or ™u˜i™ ™lose p—™ked stru™turesF Hexagonal close packed

sf two ™lose p—™ked l—yers e —nd f —re pl—™ed in ™ont—™t with e—™h other so —s to m—ximize the densityD then the spheres of l—yer f will rest in the hollow @v—™—n™yA ˜etween three of the spheres in l—yer eF „his is demonstr—ted in pigure IFPRF etoms in the se™ond l—yerD f @sh—ded light gr—yAD m—y o™™upy one of two possi˜le positions @pigure IFPR— or ˜A ˜ut not ˜oth together or — mixture of e—™hF sf — third l—yer is pl—™ed on top of l—yer f su™h th—t it ex—™tly ™overs l—yer eD su˜sequent pl—™ement of l—yers will result in the following sequen™e FFFefefefFFFF „his is known —s hex—gon—l ™lose p—™king or hcpF



Schematic representation of two close packed layers arranged in A (dark grey) and B (light grey) positions. The alternative stacking of the B layer is shown in (a) and (b).
Figure 1.24:

„he hex—gon—l ™lose p—™ked ™ell is — deriv—tive of the hex—gon—l fr—v—is l—tti™e system @pigure IFPHA with the —ddition of —n —tom inside the unit ™ell —t the ™oordin—tes @1 G3 D2 G3 D1 G2 AF „he ˜—s—l pl—ne of the unit ™ell ™oin™ides with the ™lose p—™ked l—yers @pigure IFPSAF sn other words the ™lose p—™ked l—yer m—kesEup the {HHI} f—mily of ™ryst—l pl—nesF

Figure 1.25:

A schematic projection of the basal plane of the hcp unit cell on the close packed layers.

„he p—™king fr—™tion in — hex—gon—l ™lose p—™ked ™ell is URFHS7Y th—t is URFHS7 of the tot—l volume is o™™upiedF „he p—™king fr—™tion or density is derived ˜y —ssuming th—t e—™h —tom is — h—rd sphere in ™ont—™t with its ne—rest neigh˜orsF hetermin—tion of the p—™king fr—™tion is —™™omplished ˜y ™—l™ul—ting the num˜er of whole spheres per unit ™ell @P in h™pAD the volume o™™upied ˜y these spheresD —nd — ™omp—rison with the tot—l volume of — unit ™ellF „he num˜er gives —n ide— of how open or (lled — stru™ture isF fy ™omp—risonD the p—™king fr—™tion for ˜odyE™entered ™u˜i™ @pigure IFPHA is TV7 —nd for di—mond ™u˜i™ @—n import—nt semi™ondu™tor stru™ture to ˜e des™ri˜ed l—terA is it QR7F Cubic close packed: face-centered cubic

sn — simil—r m—nner to the gener—tion of the hex—gon—l ™lose p—™ked stru™tureD two ™lose p—™ked l—yers —re st—™ked @pigure IFPQA howeverD the third l—yer @gA is pl—™ed su™h th—t it does not ex—™tly ™over l—yer eD

PW while sitting in — set of troughs in l—yer f @pigure IFPTAD then upon repetition the p—™king sequen™e will ˜e FFFefgefgefgFFFF „his is known —s ™u˜i™ ™lose p—™king or ccpF

Schematic representation of the three close packed layers in a cubic close packed arrangement: A (dark grey), B (medium grey), and C (light grey).
Figure 1.26:

„he unit ™ell of ™u˜i™ ™lose p—™ked stru™ture is —™tu—lly th—t of — f—™eE™entered ™u˜i™ @fcc A fr—v—is l—tti™eF sn the fcc l—tti™e the ™lose p—™ked l—yers ™onstitute the {III} pl—nesF es with the hcp l—tti™e p—™king fr—™tion in — ™u˜i™ ™lose p—™ked @fcc A ™ell is URFHS7F ƒin™e f—™e ™entered ™u˜i™ or fcc is more ™ommonly used in preferen™e to ™u˜i™ ™lose p—™ked @ccp A in des™ri˜ing the stru™turesD the former will ˜e used throughout this textF Coordination number

„he ™oordin—tion num˜er of —n —tom or ion within —n extended stru™ture is de(ned —s the num˜er of ne—rest neigh˜or —toms @ions of opposite ™h—rgeA th—t —re in ™ont—™t with itF e slightly di'erent de(nition is often used for —toms within individu—l mole™ulesX the num˜er of donor —toms —sso™i—ted with the ™entr—l —tom or ionF roweverD this distin™tion is r—ther —rti(™i—lD —nd ˜oth ™—n ˜e employedF „he ™oordin—tion num˜ers for met—l —toms in — mole™ule or ™omplex —re ™ommonly RD SD —nd TD ˜ut —ll v—lues from P to W —re known —nd — few ex—mples of higher ™oordin—tion num˜ers h—ve ˜een reportedF sn ™ontr—stD ™ommon ™oordin—tion num˜ers in the solid st—te —re QD RD TD VD —nd IPF por ex—mpleD the —tom in the ™enter of ˜odyE™entered ™u˜i™ l—tti™e h—s — ™oordin—tion num˜er of VD ˜e™—use it tou™hes the eight —toms —t the ™orners of the unit ™ellD while —n —tom in — simple ™u˜i™ stru™ture would h—ve — ™oordin—tion num˜er of TF sn ˜oth fcc —nd hcp l—tti™es e—™h of the —toms h—ve — ™oordin—tion num˜er of IPF Octahedral and tetrahedral vacancies

es w—s mentioned —˜oveD the p—™king fr—™tion in ˜oth fcc —nd hcp ™ells is URFHS7D le—ving PSFWS7 of the volume un(lledF „he un(lled l—tti™e sites @intersti™esA ˜etween the —toms in — ™ell —re ™—lled interstiti—l sites or v—™—n™iesF „he sh—pe —nd rel—tive size of these sites is import—nt in ™ontrolling the position of —ddition—l —tomsF sn ˜oth fcc —nd hcp ™ells most of the sp—™e within these —toms lies within two di'erent sites known —s o™t—hedr—l sites —nd tetr—hedr—l sitesF „he di'eren™e ˜etween the two lies in their ™oordin—tion num˜erD or the num˜er of —toms surrounding e—™h siteF „etr—hedr—l sites @v—™—n™iesA —re surrounded ˜y four —toms —rr—nged —t the ™orners of — tetr—hedronF ƒimil—rlyD o™t—hedr—l sites —re surrounded ˜y six —toms whi™h m—keEup the —pi™es of —n o™t—hedronF por — given ™lose p—™ked l—tti™e —n o™t—hedr—l v—™—n™y will ˜e l—rger th—n — tetr—hedr—l v—™—n™yF ‡ithin — f—™e ™entered ™u˜i™ l—tti™eD the eight tetr—hedr—l sites —re positioned within the ™ellD —t the gener—l fr—™tion—l ™oordin—te of @n G4 Dn G4 Dn G4 A where n a I or QD eFgFD @1 G4 D1 G4 D1 G4 AD @1 G4 D1 G4 D3 G4 AD et™F „he



o™t—hedr—l sites —re lo™—ted —t the ™enter of the unit ™ell @1 G2 D1 G2 D1 G2 AD —s well —s —t e—™h of the edges of the ™ellD eFgFD @1 G2 DHDHAF sn the hex—gon—l ™lose p—™ked systemD the tetr—hedr—l sites —re —t @HDHD3 G8 A —nd @1 G3 D2 G3 D7 G8 AD —nd the o™t—hedr—l sites —re —t @1 G3 D1 G3 D1 G4 A —nd —ll symmetry equiv—lent positionsF Important structure types

„he m—jority of ™ryst—lline m—teri—ls do not h—ve — stru™ture th—t (ts into the one —tom per site simple fr—v—is l—tti™eF e num˜er of other import—nt ™ryst—l stru™tures —re foundD howeverD only — few of these ™ryst—l stru™tures —re those of whi™h o™™ur for the element—l —nd ™ompound semi™ondu™tors —nd the m—jority of these —re derived from fcc or hcp l—tti™esF i—™h stru™tur—l type is gener—lly de(ned ˜y —n —r™hetypeD — m—teri—l @often — n—tur—lly o™™urring miner—lA whi™h h—s the stru™ture in question —nd to whi™h —ll the simil—r m—teri—ls —re rel—tedF ‡ith reg—rd to ™ommonly used element—l —nd ™ompound semi™ondu™tors the import—nt stru™tures —re di—mondD zin™ ˜lendeD ‡urtziteD —nd to — lesser extent ™h—l™opyriteF roweverD ro™k s—ltD β EtinD ™inn—˜—r —nd ™esium ™hloride —re o˜served —s high pressure or high temper—ture ph—ses —nd —re therefore —lso dis™ussedF „he following provides — summ—ry of these stru™turesF het—ils of the full r—nge of solidEst—te stru™tures —re given elsewhereF Diamond Cubic

„he di—mond ™u˜i™ stru™ture ™onsists of two interpenetr—ting f—™eE™entered ™u˜i™ l—tti™esD with one o'set 1 G4 of — ™u˜e —long the ™u˜e di—gon—lF st m—y —lso ˜e des™ri˜ed —s f—™e ™entered ™u˜i™ l—tti™e in whi™h h—lf of the tetr—hedr—l sites —re (lled while —ll the o™t—hedr—l sites rem—in v—™—ntF „he di—mond ™u˜i™ unit ™ell is shown in pigure IFPUF i—™h of the —toms @eFgFD gA is four ™oordin—teD —nd the shortest inter—tomi™ dist—n™e @gEgA m—y ˜e determined from the unit ™ell p—r—meter @aAF @IFPSA

Figure 1.27:

Unit cell structure of a diamond cubic lattice showing the two interpenetrating facecentered cubic lattices.

QI Zinc blende

„his is — ˜in—ry ph—se @wiA —nd is n—med —fter its —r™hetypeD — ™ommon miner—l form of zin™ sul(de @nƒAF es with the di—mond l—tti™eD zin™ ˜lende ™onsists of the two interpenetr—ting fcc l—tti™esF roweverD in zin™ ˜lende one l—tti™e ™onsists of one of the types of —toms @n in nƒAD —nd the other l—tti™e is of the se™ond type of —tom @ƒ in nƒAF st m—y —lso ˜e des™ri˜ed —s f—™e ™entered ™u˜i™ l—tti™e of ƒ —toms in whi™h h—lf of the tetr—hedr—l sites —re (lled with n —tomsF ell the —toms in — zin™ ˜lende stru™ture —re RE™oordin—teF „he zin™ ˜lende unit ™ell is shown in pigure IFPVF e num˜er of interE—tomi™ dist—n™es m—y ˜e ™—l™ul—ted for —ny m—teri—l with — zin™ ˜lende unit ™ell using the l—tti™e p—r—meter @aAF @IFPTA


Unit cell structure of a zinc blende (ZnS) lattice. Zinc atoms are shown in green (small), sulfur atoms shown in red (large), and the dashed lines show the unit cell.
Figure 1.28: Chalcopyrite

„he miner—l ™h—l™opyrite gupeƒ2 is the —r™hetype of this stru™tureF „he stru™ture is tetr—gon—l @a a b = cD α a β a γ a WH ◦ D —nd is essenti—lly — superl—tti™e on th—t of zin™ ˜lendeF „husD is e—siest to im—gine th—t the ™h—l™opyrite l—tti™e is m—deEup of — l—tti™e of sulfur —toms in whi™h the tetr—hedr—l sites —re (lled in l—yersD FFFpegugupeFFFD et™F @pigure IFPWAF sn su™h —n ide—lized stru™ture c a PaD howeverD this is not true of —ll m—teri—ls with ™h—l™opyrite stru™turesF

Figure 1. BACKGROUND TO ELECTRONIC MATERIALS Unit cell structure of a chalcopyrite lattice. The dashed lines show the unit cell.3.29: 1.4. iron atoms are shown in green and sulfur atoms are shown in yellow. Copper atoms are shown in blue.QP CHAPTER 1.4 Rock salt es its n—me implies the —r™hetyp—l ro™k s—lt stru™ture is x—gl @t—˜le s—ltAF sn ™ommon with the zin™ ˜lende stru™tureD ro™k s—lt ™onsists of two interpenetr—ting f—™eE™entered ™u˜i™ l—tti™esF roweverD the se™ond l—tti™e is o'set IGPa —long the unit ™ell —xisF st m—y —lso ˜e des™ri˜ed —s f—™e ™entered ™u˜i™ l—tti™e in whi™h —ll of the o™t—hedr—l sites —re (lledD while —ll the tetr—hedr—l sites rem—in v—™—ntD —nd thus e—™h of the —toms in the ro™k s—lt stru™ture —re TE™oordin—teF „he ro™k s—lt unit ™ell is shown in pigure IFQHF e num˜er of interE—tomi™ dist—n™es m—y ˜e ™—l™ul—ted for —ny m—teri—l with — ro™k s—lt stru™ture using the l—tti™e p—r—meter @aAF @IFPVA @IFPWA .4.

6 Wurtzite „his is — hex—gon—l form of the zin™ sul(deF st is identi™—l in the num˜er of —nd types of —tomsD ˜ut it is ˜uilt from two interpenetr—ting hcp l—tti™es —s opposed to the fcc l—tti™es in zin™ ˜lendeF es with zin™ ˜lende —ll the —toms in — wurtzite stru™ture —re RE™oordin—teF „he wurtzite unit ™ell is shown in pigure IFQIF e num˜er of inter —tomi™ dist—n™es m—y ˜e ™—l™ul—ted for —ny m—teri—l with — wurtzite ™ell using the l—tti™e p—r—meter @aAF @IFQHA @IFQIA roweverD it should ˜e noted th—t these formul—e do not ne™ess—rily —pply when the r—tio aGc is di'erent from the ide—l v—lue of IFTQPF . Unit cell structure of a rock salt lattice.5 Cinnabar ginn—˜—rD n—med —fter the —r™hetype mer™ury sul(deD rgƒD is — distorted ro™k s—lt stru™ture in whi™h the resulting ™ell is rhom˜ohedr—l @trigon—lA with e—™h —tom h—ving — ™oordin—tion num˜er of sixF 1. Sodium ions are shown in purple (small spheres) and chloride ions are shown in red (large spheres). Figure 1.30: 1.3.4.

4 Defects in crystalline solids …p to this point we h—ve only ˜een ™on™erned with ide—l stru™tures for ™ryst—lline solids in whi™h e—™h —tom o™™upies — design—ted point in the ™ryst—l l—tti™eF …nfortun—telyD defe™ts ordin—rily exist in equili˜rium ˜etween the ™ryst—l l—tti™e —nd its environmentF „hese defe™ts —re of two gener—l typesX point defe™ts —nd extended defe™tsF es their n—mes implyD point defe™ts —re —sso™i—ted with — single ™ryst—l l—tti™e siteD while extended defe™ts o™™ur over — gre—ter r—ngeF .8 β -Tin.7 Cesium Chloride „he ™esium ™hloride stru™ture is found in m—teri—ls with l—rge ™—tions —nd rel—tively sm—ll —nionsF st h—s — simple @primitiveA ™u˜i™ ™ell @pigure IFPHA with — ™hloride ion —t the ™orners of the ™u˜e —nd the ™esium ion —t the ˜ody ™enterF „he ™oordin—tion num˜ers of ˜oth gs+ —nd gl.4.31: Unit cell structure of a wurtzite lattice. „he room temper—ture —llotrope of tin is β Etin or white tinF st h—s — tetr—gon—l stru™tureD in whi™h e—™h tin —tom h—s four ne—rest neigh˜ors @ƒnEƒn a QFHIT ÅA —rr—nged in — very )—ttened tetr—hedronD —nd two next ne—rest neigh˜ors @ƒnEƒn a QFIUS ÅAF „he over—ll stru™ture of β Etin ™onsists of fused hex—gonsD e—™h ˜eing linked to its neigh˜or vi— — fourEmem˜ered ƒn4 ringF 1.3. BACKGROUND TO ELECTRONIC MATERIALS Figure 1. Zinc atoms are shown in green (small spheres).D with the inner —tomi™ dist—n™es determined from the ™ell l—tti™e ™onst—nt @aAF @IFQPA @IFQQA 1.3.4. and the dashed lines show the unit cell.4.4.4. sulfur atoms shown in red (large spheres).QR CHAPTER 1. 1.

1 Point defects: too many or too few or just plain wrong €oint defe™ts h—ve — signi(™—nt e'e™t on the properties of — semi™ondu™torD so it is import—nt to underst—nd the ™l—sses of point defe™ts —nd the ™h—r—™teristi™s of e—™h typeF pigure IFQP summ—rizes v—rious ™l—sses of n—tive point defe™tsD howeverD they m—y ˜e divided into two gener—l ™l—ssesY defe™ts with the wrong num˜er of —toms @de(™ien™y or surplusA —nd defe™ts where the identity of the —toms is in™orre™tF Figure 1.QS 1.4.32: Point defects in a crystal lattice.4.1 Interstitial Impurity en interstiti—l impurity o™™urs when —n extr— —tom is positioned in — l—tti™e site th—t should ˜e v—™—nt in —n ide—l stru™ture @pigure IFQP˜AF ƒin™e —ll the —dj—™ent l—tti™e sites —re (lled the —ddition—l —tom will h—ve to squeeze itself into the interstiti—l siteD resulting in distortion of the l—tti™e —nd —lter—tion in the lo™—l .4.4.1. 1.

BACKGROUND TO ELECTRONIC MATERIALS ele™troni™ ˜eh—vior of the stru™tureF ƒm—ll —tomsD su™h —s ™—r˜onD will prefer to o™™upy these interstiti—l sitesF snterstiti—l impurities re—dily di'use through the l—tti™e vi— interstiti—l di'usionD whi™h ™—n result in — ™h—nge of the properties of — m—teri—l —s — fun™tion of timeF yxygen impurities in sili™on gener—lly —re lo™—ted —s interstiti—lsF Vacancies „he ™onverse of —n interstiti—l impurity is when there —re not enough —toms in — p—rti™ul—r —re— of the l—tti™eF „hese —re ™—lled v—™—n™iesF †—™—n™ies exist in —ny m—teri—l —˜ove —˜solute zero —nd in™re—se in ™on™entr—tion with temper—tureF sn the ™—se of ™ompound semi™ondu™torsD v—™—n™ies ™—n ˜e either ™—tion v—™—n™ies @pigure IFQP™A or —nion v—™—n™ies @pigure IFQPdAD depending on wh—t type of —tom —re missingF 1.4 Antisite Defects entisite defe™ts —re — p—rti™ul—r form of su˜stitution defe™tD —nd —re unique to ™ompound semi™ondu™torsF en —ntisite defe™t o™™urs when — ™—tion is mispl—™ed on —n —nion l—tti™e site or vi™e vers— @pigure IFQPg —nd hAF hepend—nt on the —rr—ngement these —re design—ted —s either eB —ntisite defe™ts or fA —ntisite defe™tsF por ex—mpleD if —n —rseni™ —tom is on — g—llium l—tti™e site the defe™t would ˜e —n esGa defe™tF entisite defe™ts involve (tting into — l—tti™e site —toms of — di'erent size th—n the rest of the l—tti™eD —nd therefore this often results in — lo™—lized distortion of the l—tti™eF sn —dditionD ™—tions —nd —nions will h—ve — di'erent num˜er of ele™trons in their v—len™e shellsD so this su˜stitution will —lter the lo™—l ele™tron ™on™entr—tion —nd the ele™troni™ properties of this —re— of the semi™ondu™torF 1.2 Extended Defects: Dislocations in a Crystal Lattice ixtended defe™ts m—y ˜e ™re—ted either during ™ryst—l growth or —s — ™onsequen™e of stress in the ™ryst—l l—tti™eF „he pl—sti™ deform—tion of ™ryst—lline solids does not o™™ur su™h th—t —ll ˜onds —long — pl—ne —re ˜roken —nd reformed simult—neouslyF snste—dD the deform—tion o™™urs through — dislo™—tion in the ™ryst—l l—tti™eF pigure IFQQ shows — s™hem—ti™ represent—tion of — dislo™—tion in — ™ryst—l l—tti™eF „wo fe—tures of this type of dislo™—tion —re the presen™e of —n extr— ™ryst—l pl—neD —nd — l—rge void —t the dislo™—tion ™oreF smpurities tend to segreg—te to the dislo™—tion ™ore in order to relieve str—in from their presen™eF . Substitution ƒu˜stitution of v—rious —toms into the norm—l l—tti™e stru™ture is ™ommonD —nd used to ™h—nge the ele™troni™ properties of ˜oth ™ompound —nd element—l semi™ondu™torsF eny impurity element th—t is in™orpor—ted during ™ryst—l growth ™—n o™™upy — l—tti™e siteF hepending on the impurityD su˜stitution defe™ts ™—n gre—tly distort the l—tti™e —ndGor —lter the ele™troni™ stru™tureF sn gener—lD ™—tions will try to o™™upy ™—tion l—tti™e sites @pigure IFQPeAD —nd —nion will o™™upy the —nion site @pigure IFQPfAF por ex—mpleD — zin™ impurity in q—es will o™™upy — g—llium siteD if possi˜leD while — sulfurD selenium —nd tellurium —toms would —ll try to su˜stitute for —n —rseni™F ƒome impurities will o™™upy either site indis™rimin—telyD eFgFD ƒi —nd ƒn o™™upy ˜oth q— —nd es sites in q—esF 1.QT CHAPTER 1.

33: Dislocation in a crystal lattice.4.4. 1.5 Epitaxy ipit—xyD is — tr—nsliter—tion of two qreek words epiD me—ning 4upon4D —nd taxisD me—ning 4ordered4F ‡ith respe™t to ™ryst—l growth it —pplies to the pro™ess of growing thin ™ryst—lline l—yers on — ™ryst—l su˜str—teF sn epit—xi—l growthD there is — pre™ise ™ryst—l orient—tion of the (lm in rel—tion to the su˜str—teF „he growth of epit—xi—l (lms ™—n ˜e done ˜y — num˜er of methods in™luding mole™ul—r ˜e—m epit—xyD —tomi™ l—yer epit—xyD —nd ™hemi™—l v—por depositionD —ll of whi™h will ˜e des™ri˜ed l—terF ipit—xy of the s—me m—teri—lD su™h —s — g—llium —rsenide (lm on — g—llium —rsenide su˜str—teD is ™—lled homoepit—xyD while epit—xy where the (lm —nd su˜str—te m—teri—l —re di'erent is ™—lled heteroepit—xyF gle—rlyD in homoepit—xyD the su˜str—te —nd (lm will h—ve the identi™—l stru™tureD howeverD in heteroepit—xyD it is import—nt to employ where possi˜le — su˜str—te with the s—me stru™ture —nd simil—r l—tti™e p—r—metersF por ex—mpleD zin™ selenide @zin™ ˜lendeD a a SFTTV ÅA is re—dily grown on g—llium —rsenide @zin™ ˜lendeD a a SFTSQ ÅAF eltern—tivelyD epit—xi—l ™ryst—l growth ™—n o™™ur where there exists — simple rel—tionship ˜etween the stru™tures of the su˜str—te —nd ™ryst—l l—yerD su™h —s is o˜served ˜etween el2 y3 @IHHA on ƒi @IHHAF ‡hi™hever route is ™hosen — ™lose m—t™h in the l—tti™e p—r—meters is requiredD otherwiseD the str—ins indu™ed ˜y the l—tti™e mism—t™h results in distortion of the (lm —nd form—tion of dislo™—tionsF sf the mism—t™h is signi(™—nt epit—xi—l growth is not energeti™—lly f—vor—˜leD ™—using — textured (lm or poly™ryst—lline untextured (lm to ˜e grownF es — gener—l rule of thum˜D epit—xy ™—n ˜e —™hieved if the l—tti™e p—r—meters of the two m—teri—ls —re within —˜out S7 of e—™h otherF por good qu—lity epit—xyD this should ˜e less th—n I7F „he l—rger the mism—t™hD the l—rger the str—in in the (lmF es the (lm gets thi™ker —nd thi™kerD it will try to relieve the str—in in the (lmD whi™h ™ould in™lude the loss of epit—xy of the growth of dislo™—tionsF st is import—nt to note th—t the <IHH> dire™tions of — (lm must ˜e p—r—llel to the <IHH> dire™tion of the su˜str—teF sn some ™—sesD su™h —s pe on wgyD the ‘III“ dire™tion is p—r—llel to the su˜str—te ‘IHH“F „he epit—xi—l rel—tionship is spe™i(ed ˜y giving (rst the pl—ne in the (lm th—t is p—r—llel to the su˜str—te ‘IHH“F 1.QU Figure 1.6 Bibliography • International Tables for X-ray CrystallographyF †olF s†Y uyno™h €ressX firmingh—mD …u @IWURAF • fF pF qF tohnsonD in Comprehensive Inorganic ChemistryD €erg—mon €ressD †olF RD gh—pter SP @IWUQAF • eF ‚F ‡estD Solid State Chemistry and its ApplicationsD ‡ileyD xew ‰ork @IWVRAF .

org/content/m23905/1.1 Introduction e single ™ryst—l of either —n element—l @eFgFD sili™onA or ™ompound @eFgFD g—llium —rsenideA semi™ondu™tor forms the ˜—sis of —lmost —ll semi™ondu™tor devi™esF „he —˜ility to ™ontrol the ele™troni™ —nd optoEele™troni™ properties of these m—teri—ls is ˜—sed on —n underst—nding of their stru™tureF sn —dditionD the met—ls —nd m—ny of the insul—tors employed within — mi™roele™troni™ devi™e —re —lso ™ryst—llineF 1.5 Structures of Element and Compound Semiconductors 1.34: Unit cell structure of a diamond cubic lattice showing the two interpenetrating facecentered cubic lattices.3 QFSTTVQ@IA SFRQIHPHI@QA SFTSUWHT@IA TFRVWP@IA QFSISPS PFQIWHHP SFQPQR UFPVS X v—tti™e p—r—meters —nd densities @me—sured —t PWV uA for the di—mond ™u˜i™ forms of the group s† @IRA elementsF es would ˜e expe™ted the l—tti™e p—r—meter in™re—se in the order g < ƒi < qe < αEƒnF ƒili™on —nd germ—nium form — ™ontinuous series of solid solutions with gr—du—lly v—rying p—r—metersF st is worth noting the high degree of —™™ur—™y th—t the l—tti™e p—r—meters —re known for high purity ™ryst—ls of these elementsF sn —dditionD it is import—nt to note the temper—ture —t whi™h stru™tur—l me—surements —re m—deD sin™e the 5 This content is available online at <http://cnx.5.6/>. a (Å) Density (g/cm3 ) ™—r˜on @di—mondA sili™on germ—nium tin @αEƒnA Table 1.QV CHAPTER 1.5.2 Group IV (14) elements i—™h of the semi™ondu™ting ph—ses of the group s† @IRA elementsD g @di—mondAD ƒiD qeD —nd αEƒnD —dopt the di—mond ™u˜i™ stru™ture @pigure IFQRAF „heir l—tti™e ™onst—nts @aD ÅA —nd densities @ρD gG™m3 A —re given in „—˜le IFQF Figure 1. . Element Lattice parameter. BACKGROUND TO ELECTRONIC MATERIALS 5 1.

QW l—tti™e p—r—meters —re temper—ture dependent @pigure IFQSAF „he l—tti™e ™onst—nt @aAD in ÅD for high purity sili™on m—y ˜e ™—l™ul—ted for —ny temper—ture @„A over the temper—ture r—nge PWQ E IHUQ u ˜y the formul— shown ˜elowF aT a SFRQHR C IFVIQV ˆ IH-5 @„ E PWVFIS uA C IFSRP ˆ IH-9 @„ ! PWVFIS uA Figure 1. iven though the di—mond ™u˜i™ forms of ƒi —nd qe —re the only forms of dire™t interest to semi™ondu™tor devi™esD e—™h exists in numerous ™ryst—lline high pressure —nd met—Est—˜le formsF „hese —re des™ri˜ed —long with their inter™onversionsD in „—˜le IFRF .35: Temperature dependence of the lattice parameter for (a) Si and (b) Ge.

36: . and the dashed lines show the unit cell.4 X righ pressure —nd met—st—˜le ph—ses of sili™on —nd germ—niumF 1. Figure 1. sulfur atoms shown in red (large).3 Group III-V (13-15) compounds „he st—˜le ph—ses for the —rsenidesD phosphides —nd —ntimonides of —luminumD g—llium —nd indium —ll exhi˜it zin™ ˜lende stru™tures @pigure IFQTAF sn ™ontr—stD the nitrides —re found —s wurtzite stru™tures @eFgFD pigure IFQUAF „he stru™tureD l—tti™e p—r—metersD —nd densities of the sssE† ™ompounds —re given in „—˜le IFSF st is worth noting th—t ™ontr—ry to expe™t—tion the l—tti™e p—r—meter of the g—llium ™ompounds is sm—ller th—n their —luminum homologY for q—es a a SFTSQ ÅY eles a a SFTTH ÅF es with the group s† elements the l—tti™e p—r—meters —re highly temper—ture dependentY howeverD —ddition—l v—ri—tion —rises from —ny devi—tion from —˜solute stoi™hiometryF „hese e'e™ts —re shown in pigure IFQVF Unit cell structure of a zinc blende (ZnS) lattice. BACKGROUND TO ELECTRONIC MATERIALS Phase Structure Remarks ƒi s ƒi ss ƒi sss ƒi s† ƒi † ƒi †s qe s qe ss qe sss qe s† di—mond ™u˜i™ grey tin stru™ture ™u˜i™ hex—gon—l unidenti(ed hex—gon—l ™lose p—™ked di—mond ™u˜i™ st—˜le —t norm—l pressure formed from ƒi s or ƒi † —˜ove IR q€— met—st—˜leD formed from ƒi ss —˜ove IH q€— st—˜le —˜ove QR q€—D formed from ƒi ss —˜ove IT q€— st—˜le —˜ove RS q€— lowEpressure ph—se formed from qe s —˜ove IH q€— formed ˜y quen™hing qe ss —t low pressure formed ˜y quen™hing qe ss to I —tm —t PHH u β Etin stru™ture tetr—gon—l ˜ody ™entered ™u˜i™ Table 1. Zinc atoms are shown in green (small).5.RH CHAPTER 1.

5 wurtzite zin™ ˜lende zin™ ˜lende zin™ ˜lende wurtzite zin™ ˜lende zin™ ˜lende wurtzite zin™ ˜lende zin™ ˜lende zin™ ˜lende a a QFII@IAD ™ a RFWV@IA a a SFRTQS@RA a a SFTTH a a TFIQSS@IA a a QFIWHD ™ a SFIVU a a SFRSHS@PA a a SFTSQPS@PA a a QFSRRTD c a SFUHQR a a SFVTV@IA a a TFHSVQ a a TFRUWQU QFPSS PFRH@IA QFUTH RFPT RFIQV SFQIUT@QA TFVI RFVI SFTTU SFUURU@RA X v—tti™e p—r—meters —nd densities @me—sured —t PWV uA for the sssE† @IQEISA ™ompound semi™ondu™torsF istim—ted st—nd—rd devi—tions given in p—renthesesF . sulfur atoms shown in red (large). Zinc atoms are shown in green (small). Figure 1.RI Unit cell structure of a wurtzite lattice. and the dashed lines show the unit cell.37: Compound Structure Lattice parameter (Å) Density (g/cm3 ) elx el€ eles elƒ˜ q—x q—€ q—es snx sn€ snes snƒ˜ Table 1.

38: Temperature dependence of the lattice parameter for stoichiometric GaAs and crystals with either Ga or As excess.RP CHAPTER 1.4 Group II-VI (12-16) compounds „he stru™tures of the ssE†s ™ompound semi™ondu™tors —re less predi™t—˜le th—n those of the sssE† ™ompounds @—˜oveAD —nd while zin™ ˜lende stru™ture exists for —lmost —ll of the ™ompounds there is — stronger tenden™y tow—rds the hex—gon—l wurtzite formF sn sever—l ™—ses the zin™ ˜lende stru™ture is o˜served under —m˜ient ™onditionsD ˜ut m—y ˜e ™onverted to the wurtzite form upon he—tingF sn gener—l the wurtzite form predomE in—tes with the sm—ller —nions @eFgFD oxidesAD while the zin™ ˜lende ˜e™omes the more st—˜le ph—se for the l—rger —nions @eFgFD telluridesAF yne ex™eption is mer™ury sul(de @rgƒA th—t is the —r™hetype for the trigon—l ™inn—˜—r ph—seF „—˜le IFT lists the st—˜le ph—se of the ™h—l™ogenides of zin™D ™—dmium —nd mer™uryD —long with their high temper—ture ph—ses where —ppli™—˜leF ƒolid solutions of the ssE†s ™ompounds —re not —s e—sily formed —s for the sssE† ™ompoundsY howeverD two import—nt ex—mples —re nƒx ƒe1-x —nd gdx rg1-x „eF .5. „he homogeneity of stru™tures of —lloys for — wide r—nge of solid solutions to ˜e formed ˜etween sssE † ™ompounds in —lmost —ny ™om˜in—tionF „wo ™l—sses of tern—ry —lloys —re formedX sssx Esss1-x E† @eFgFD elx Eq—1-x EesA —nd sssE†1-x E†x @eFgFD q—Ees1-x E€x A F ‡hile qu—tern—ry —lloys of the type sssx Esss1-x E†y E†1-y —llow for the growth of m—teri—ls with simil—r l—tti™e p—r—metersD ˜ut — ˜ro—d r—nge of ˜—nd g—psF e very import—nt tern—ry —lloyD espe™i—lly in optoele™troni™ —ppli™—tionsD is elx Eq—1-x Ees —nd its l—tti™e p—r—meter @aA is dire™tly rel—ted to the ™omposition @xAF a a SFTSQQ C HFHHUV x xot —ll of the sssE† ™ompounds h—ve well ™h—r—™terized highEpressure ph—sesF howeverD in e—™h ™—se where — highEpressure ph—se is o˜served the ™oordin—tion num˜er of ˜oth the group sss —nd group † element in™re—ses from four to sixF „husD el€ undergoes — zin™ ˜lende to ro™k s—lt tr—nsform—tion —t high pressure —˜ove IUH k˜—rD while elƒ˜ —nd q—es form orthorhom˜i™ distorted ro™k s—lt stru™tures —˜ove UU —nd IUP k˜—rD respe™tivelyF en orthorhom˜i™ stru™ture is proposed for the highEpressure form of sn€ @>IQQ k˜—rAF sndium —rsenide @snesA undergoes twoEph—se tr—nsform—tionsF „he zin™ ˜lende stru™ture is ™onverted to — ro™k s—lt stru™ture —˜ove UU k˜—rD whi™h in turn forms — β Etin stru™ture —˜ove IUH k˜—rF 1. BACKGROUND TO ELECTRONIC MATERIALS Figure 1.

5.5 I-III-VI2 (11-13-16) compounds xe—rly —ll sEsssE†s2 ™ompounds —t room temper—ture —dopt the ™h—l™opyrite stru™ture @pigure IFRHAF „he ™ell ™onst—nts —nd densities —re given in „—˜le IFUF elthough there —re few reports of high temper—ture or .RQ Density (g/cm3 ) Compound Structure Lattice parameter (Å) nƒ nƒe n„e gdƒ gdƒe gd„e rgƒ rgƒe rg„e Table 1. 1.39: Unit cell structure of a rock salt lattice.6 zin™ ˜lende wurtzite in™ ˜lende in™ ˜lende wurtzite wurtzite in™ ˜lende ™inn—˜—r in™ ˜lende in™ ˜lende in™ ˜lende a a SFRIH a a QFVPPD c a a SFTTV a a TFIH a a RFIQTD c a a RFQHHD c a a TFRVP a a RFIRWD c a a SFVSI a a TFHVS a a TFRT RFHUS a TFPTH RFHVU SFPU SFTQT a TFUIR a UFHII a WFRWS UFUQ VFPS VFHU RFVP SFVI SFVU X v—tti™e p—r—meters —nd densities @me—sured —t PWV uA for the ssE†s @IPEITA ™ompound semi™ondu™torsF „he zin™ ™h—l™ogenides —ll tr—nsform to — ™esium ™hloride stru™ture under high pressuresD while the ™—dmium ™ompounds —ll form ro™k s—lt highEpressure ph—ses @pigure IFQWAF wer™ury selenide @rgƒeA —nd mer™ury telluride @rg„eA ™onvert to the mer™ury sul(de —r™hetype stru™tureD ™inn—˜—rD —t high pressureF Figure 1. Sodium ions are shown in purple and chloride ions are shown in red.

Figure 1. Copper atoms are shown in blue.RR CHAPTER 1. The dashed lines show the unit cell. BACKGROUND TO ELECTRONIC MATERIALS highEpressure ph—sesD egsnƒ2 h—s ˜een shown to exist —s — high temper—ture orthorhom˜i™ polymorph @a a TFWSRD b a VFPTRD —nd c a TFTVQ ÅAD —nd egsn„e2 forms — ™u˜i™ ph—se —t high pressuresF Unit cell structure of a chalcopyrite lattice.40: . iron atoms are shown in green and sulfur atoms are shown in yellow.

5.RS Density (g.5 „e0.cm3 ) Compound Lattice parameter a (Å) Lattice parameter c (Å) guelƒ2 guelƒe2 guel„e2 guq—ƒ2 guq—ƒe2 guq—„e2 gusnƒ2 gusnƒe2 gusn„e2 egelƒ2 egq—ƒ2 egq—ƒe2 egq—„e2 egsnƒ2 egsnƒe2 egsn„e2 Table 1.6 Orientation eects yn™e single ™ryst—ls of high purity sili™on or g—llium —rsenide —re produ™ed they —re ™ut into w—fers su™h th—t the exposed f—™e of these w—fers is either the ™ryst—llogr—phi™ {IHH} or {III} pl—nesF „he rel—tive stru™ture of these surf—™es —re import—nt with respe™t to oxid—tionD et™hing —nd thin (lm growthF „hese pro™esses —re orient—tionEsensitiveY th—t isD they depend on the dire™tion in whi™h the ™ryst—l sli™e is ™utF .7 SFQP SFTI SFWT SFQS SFTI TFHH SFSP SFUV TFIU TFQH SFUS SFWV TFPW SFVP TFHWS TFRQ IHFRQH IHFWP IIFUU IHFRT IIFHH IIFWQ IIFHV IIFSS IPFQR IIFVR IHFPW IHFVV IIFWS IIFIU IIFTW IPFSW QFRS RFTW SFRU RFQV SFSU SFWS RFUR SFUU TFIH TFIS RFUH SFUH TFHV RFWU SFVP TFWT X gh—l™opyrite l—tti™e p—r—meters —nd densities @me—sured —t PWV uA for the sEsssE†s ™ompound semi™ondu™torsF v—tti™e p—r—meters for tetr—gon—l ™ellF yf the sEsssE†s2 ™ompoundsD the ™opper indium ™h—l™ogenides @gusni2 A —re ™ert—inly the most studied for their —ppli™—tion in sol—r ™ellsF yne of the —dv—nt—ges of the ™opper indium ™h—l™ogenide ™ompounds is the form—tion of solid solutions @—lloysA of the formul— gusni2-x i9x D where the ™omposition v—ri—˜le @xA v—ries from H to PF „he gusnƒ2-x ƒex —nd gusnƒe2-x „ex systems h—ve —lso ˜een ex—minedD —s h—s the guq—y sn1-y ƒ2-x ƒex qu—tern—ry systemF es would ˜e expe™ted from — ™onsider—tion of the rel—tive ioni™ r—dii of the ™h—l™ogenides the l—tti™e p—r—meters of the gusnƒ2-x ƒex —lloy should in™re—se with in™re—sed selenium ™ontentF †erg—rd9s l—w requires the l—tti™e ™onst—nt for — line—r solution of two semi™ondu™tors to v—ry line—rly with ™omposition @eFgFD —s is o˜served for elx q—1-x esAD howeverD the v—ri—tion of the tetr—gon—l l—tti™e ™onst—nts @a —nd c A with ™omposition for gusnƒ2-x ƒx —re ˜est des™ri˜ed ˜y the p—r—˜oli™ rel—tionshipsF a a SFSQP C HFHVHI x C HFHPTH x2 c a IIFIST C HFIPHR x C HFHTII x2 e simil—r rel—tionship is o˜served for the gusnƒe2-x „ex —lloysF a a SFUVQ C HFISTH x C HFHPIP x2 c a IIFTPV C HFQQRH x C HFHPUU x2 „he l—rge di'eren™e in ioni™ r—dii ˜etween ƒ —nd „e @HFQU ÅA prevents form—tion of solid solutions in the gusnƒ2-x „ex systemD howeverD the single —lloy gusnƒ1.5 h—s ˜een reportedF 1.

RT CHAPTER 1.6.5. Figure 1.1 Atom density and dangling bonds „he prin™iple pl—nes in — ™ryst—l m—y ˜e di'erenti—ted in — num˜er of w—ysD howeverD the —tom —ndGor ˜ond density —re useful in predi™ting mu™h of the ™hemistry of semi™ondu™tor surf—™esF ƒin™e ˜oth sili™on —nd g—llium —rsenide —re fcc stru™tures —nd the {IHH} —nd {III} —re the only te™hnologi™—lly relev—nt surf—™esD dis™ussions will ˜e limited to fcc {IHH} —nd {III}F „he —tom density of — surf—™e m—y ˜e de(ned —s the num˜er of —toms per unit —re—F pigure IFRI shows — s™hem—ti™ view of the {III} —nd {IHH} pl—nes in — fcc l—tti™eF „he {III} pl—ne ™onsists of — hex—gon—l ™lose p—™ked —rr—y in whi™h the ™ryst—l dire™tions within the pl—ne —re oriented —t TH ◦ to e—™h otherF „he hex—gon—l p—™king —nd the orient—tion of the ™ryst—l dire™tions —re indi™—ted in pigure IFRI˜ —s —n overl—id hex—gonF qiven the intr—Epl—n—r interE—tomi™ dist—n™e m—y ˜e de(ned —s — fun™tion of the l—tti™e p—r—meterD the —re— of this hex—gon m—y ˜e re—dily ™—l™ul—tedF por ex—mple in the ™—se of sili™onD the hex—gon h—s —n —re— of QVFQH Å2 F „he num˜er of —toms within the hex—gon is threeX the —tom in the ™enter plus IGQ of e—™h of the six —toms —t the verti™es of the hex—gon @e—™h of the —toms —t the hex—gons verti™es is sh—red ˜y three other —dj—™ent hex—gonsAF „husD the —tom density of the {III} pl—ne is ™—l™ul—ted to ˜e HFHUVQ Å-2 F ƒimil—rlyD the —tom density of the {IHH} pl—ne m—y ˜e ™—l™ul—tedF „he {IHH} pl—ne ™onsists of — squ—re —rr—y in whi™h the ™ryst—l dire™tions within the pl—ne —re oriented —t WH ◦ to e—™h otherF ƒin™e the squ—re is ™oin™ident with one of the f—™es of the unit ™ell the —re— of the squ—re m—y ˜e re—dily ™—l™ul—tedF por ex—mple in the ™—se of sili™onD the squ—re h—s —n —re— of PWFRW Å2 F „he num˜er of —toms within the squ—re is PX the —tom in the ™enter plus IGR of e—™h of the four —toms —t the verti™es of the squ—re @e—™h of the —toms —t the ™orners of the squ—re —re sh—red ˜y four other —dj—™ent squ—resAF „husD the —tom density of the {IHH} pl—ne is ™—l™ul—ted to ˜e HFHTUV Å-2 F ‡hile these v—lues for the —tom density —re spe™i(™ for sili™onD their r—tio is ™onst—nt for —ll di—mond ™u˜i™ —nd zin™ ˜lende stru™turesX {IHH}X{III} a IXIFISSF sn gener—lD the fewer d—ngling ˜onds the more st—˜le — surf—™e stru™tureF Schematic representation of the (111) and (100) faces of a face centered cubic (fcc) lattice showing the relationship between the close packed rows.41: en —tom inside — ™ryst—l of —ny m—teri—l will h—ve — ™oordin—tion num˜er @nA determined ˜y the stru™ture of the m—teri—lF por ex—mpleD —ll —toms within the ˜ulk of — sili™on ™ryst—l will ˜e in — tetr—hedr—l fourE ™oordin—te environment @n a RAF roweverD —t the surf—™e of — ™ryst—l the —toms will not m—ke their full ™ompliment of ˜ondsF i—™h —tom will therefore h—ve less ne—rest neigh˜ors th—n —n —tom within the ˜ulk of the m—teri—lF „he missing ˜onds —re ™ommonly ™—lled d—ngling ˜ondsF ‡hile this des™ription is not p—rti™ul—rly —™™ur—te it isD howeverD widely employed —nd —s su™h will ˜e used hereinF „he num˜er of d—ngling ˜onds m—y ˜e de(ned —s the di'eren™e ˜etween the ide—l ™oordin—tion num˜er @determined ˜y the ˜ulk ™ryst—l stru™tureA —nd the —™tu—l ™oordin—tion num˜er —s o˜served —t the surf—™eF pigure IFRP shows — se™tion of the {III} surf—™es of — di—mond ™u˜i™ l—tti™e viewed perpendi™ul—r to the . BACKGROUND TO ELECTRONIC MATERIALS 1.

RU {III} pl—neF „he —toms within the ˜ulk h—ve — ™oordin—tion num˜er of fourF sn ™ontr—stD the —toms —t the surf—™e @eFgFD the —tom shown in ˜lue in pigure IFRPA —re e—™h ˜onded to just three other —toms @the —toms shown in red in pigure IFRPAD thus e—™h surf—™e —tom h—s one d—ngling ˜ondF es ™—n ˜e seen from pigure IFRQD whi™h shows the —toms —t the {IHH} surf—™e viewed perpendi™ul—r to the {IHH} pl—neD e—™h —tom —t the surf—™e @eFgFD the —tom shown in ˜lue in pigure IFRQA is only ™oordin—ted to two other —toms @the —toms shown in red in pigure IFRQAD le—ving two d—ngling ˜onds per —tomF st should ˜e noted th—t the s—me num˜er of d—ngling ˜onds —re found for the {III} —nd {IHH} pl—nes of — zin™ ˜lende l—tti™eF „he r—tio of d—ngling ˜onds for the {IHH} —nd {III} pl—nes of —ll di—mond ™u˜i™ —nd zin™ ˜lende stru™tures is {IHH}X{III} a PXIF purthermoreD sin™e the —tom densities of e—™h pl—ne —re known then the r—tio of the d—ngling ˜ond densities is determined to ˜eX {IHH}X{III} a IXHFSUUF Figure 1.42: {111} plane. A section of the {111} surfaces of a diamond cubic lattice viewed perpendicular to the .

A section of the {100} surface of a diamond cubic lattice viewed perpendicular to the 1.3 Gallium arsenide „he zin™ ˜lende l—tti™e o˜served for g—llium —rsenide results in —ddition—l ™onsider—tions over th—t of sili™onF elthough the {IHH} pl—ne of q—es is stru™tur—lly simil—r to th—t of sili™onD two possi˜ilities existX — f—™e ™onsisting of either —ll g—llium —toms or —ll —rseni™ —tomsF sn either ™—se the surf—™e —toms h—ve two d—ngling ˜ondsD —nd the properties of the f—™e —re independent of whether the f—™e is g—llium or —rseni™F „he {III} pl—ne —lso h—s the possi˜ility of ™onsisting of —ll g—llium or —ll —rseni™F roweverD unlike the {IHH} pl—nes there is — signi(™—nt di'eren™e ˜etween the two possi˜ilitiesF pigure IFQT shows the g—llium —rsenide stru™ture represented ˜y two interpenetr—ting fcc l—tti™esF „he ‘III“ —xis is verti™—l within the pl—ne of the p—geF elthough the stru™ture ™onsists of —ltern—te l—yers of g—llium —nd —rseni™ st—™ked —long the ‘III“ —xisD the dist—n™e ˜etween the su™™essive l—yers —ltern—tes ˜etween l—rge —nd sm—llF essigning —rseni™ —s the p—rent l—tti™e the order of the l—yers in the ‘III“ dire™tion is esEq—EesEq—EesEq—D while in the −−− III .5.2 Silicon por sili™onD the {III} pl—nes —re ™loser p—™ked th—n the {IHH} pl—nesF es — resultD growth of — sili™on ™ryst—l is therefore slowest in the <III> dire™tionD sin™e it requires l—ying down — ™lose p—™ked —tomi™ l—yer upon —nother l—yer in its ™losest p—™ked formF es — ™onsequen™e <III> ƒi is the e—siest to growD —nd therefore the le—st expensiveF „he dissolution or et™hing of — ™ryst—l is rel—ted to the num˜er of ˜roken ˜onds —lre—dy present —t the surf—™eX the fewer ˜onds to ˜e ˜roken in order to remove —n individu—l —tom from — ™ryst—lD the e—sier it will ˜e to dissolve the ™ryst—lF es — ™onsequen™e of h—ving only one d—ngling ˜ond @requiring three ˜onds to ˜e ˜rokenA et™hing sili™on is slowest in the <III> dire™tionF „he ele™troni™ properties of — sili™on w—fer —re —lso rel—ted to the num˜er of d—ngling ˜ondsF ƒili™on mi™ro™ir™uits —re gener—lly formed on — single ™ryst—l w—fer th—t is di™ed —fter f—˜ri™—tion ˜y either s—wing p—rt w—y through the w—fer thi™kness or s™oring @s™ri˜ingA the surf—™eD —nd then physi™—lly ˜re—kingF „he physi™—l ˜re—k—ge of the w—fer o™™urs —long the n—tur—l ™le—v—ge pl—nesD whi™h in the ™—se of sili™on —re the {III} pl—nesF 1.6. BACKGROUND TO ELECTRONIC MATERIALS Figure 1.43: {100} plane.RV CHAPTER 1.5.6.

Phys.44: „he @IIIA es is distin™t from th—t of @IIIA q— due to the di'eren™e in the num˜er of ele™trons —t the surf—™eF es — ™onsequen™eD the @IIIA es f—™e et™hes more r—pidly th—n the @IIIA q— f—™eF sn —dditionD surf—™e ev—por—tion ˜elow UUH ◦ g o™™urs more r—pidly —t the @IIIA es f—™eF 1. Rev. Figure 1.D IWVSD 20D WPWF ‰F uF †ohr—D ƒF „F ‡eirD —nd eF vF ‚uo'D Phys. Phys. Res. Appl. SolidsD IWUQD 34D IPHSF hF ƒridevi —nd uF †F ‚eddyD Mat. Chem. Phys.D IWUQD 45D IRSTF . Appl.D IWWSD 7D TWWF wF ‚o˜˜insD tF gF €hillipsD —nd †F qF v—m˜re™htD J. Mater.RW dire™tion the l—yers —re orderedD q—EesEq—EesEq—Ees @pigure IFRRAF sn sili™on these two dire™tions —re of ™ourse identi™—lF „he surf—™e of — ™ryst—l would ˜e either —rseni™D with three d—ngling ˜ondsD or g—lliumD with one d—ngling ˜ondF gle—rlyD the l—tter is energeti™—lly more f—vor—˜leF „husD the @IIIA pl—ne shown in pigure IFRR is ™—lled the @IIIA q— f—™eF gonverselyD the the −−− −−− III pl—ne would ˜e either g—lliumD with three d—ngling ˜ondsD or —rseni™D with one d—ngling ˜ondF eg—inD the l—tter is energeti™—lly more f—vor—˜le —nd III pl—ne is therefore ™—lled the @IIIA es f—™eF The (111) Ga face of GaAs showing a surface layer containing gallium atoms (green) with one dangling bond per gallium and three bonds to the arsenic atoms (red) in the lower layer.5. BD IWVSD 31D UQRRF ‡F wF ‰in —nd ‚F tF €—'D J.7 Bibliography • • • • • • • wF f—u˜litz —nd eF vF ‚uo'D J.D IWVPD 53D TIUWF tF gF t—miesonD ScienceD IWTQD 139D VRSF gF gF v—ndryD tF vo™kwoodD —nd eF ‚F f—rronD Chem. Bull.


org/content/m33798/1.2/>.1 Introduction to Bipolar Transistors sistors ˜y fill ‡ilsonF note: 1 „his module is —d—pted from the gonnexions module entitled Introduction to Bipolar Tran- vet9s le—ve the world of two termin—l devi™es @whi™h —re —ll ™—lled diodes ˜y the w—yY diode just me—ns twoEtermin—lsA —nd venture into the mu™h more interesting world of three termin—lsF „he (rst devi™e we will look —t is ™—lled the bipolar transistorF gonsider the stru™ture shown in pigure PFIX Figure 2. „he devi™e ™onsists of three l—yers of sili™onD — he—vily doped nEtype l—yer ™—lled the emitterD — moder—tely doped pEtype l—yer ™—lled the ˜—seD —nd thirdD more lightly doped l—yer ™—lled the ™olle™torF sn — ˜i—sing @—pplied hg potenti—lA ™on(gur—tion ™—lled forward active biasingD the emitterE˜—se jun™tion is forw—rd ˜i—sedD —nd the ˜—seE™olle™tor jun™tion is reverse ˜i—sedF pigure PFP shows the ˜i—sing ™onventions we will useF foth ˜i—s volt—ges —re referen™ed to the ˜—se termin—lF ƒin™e the ˜—seEemitter jun™tion is forw—rd ˜i—sedD —nd sin™e the ˜—se is m—de of pEtype m—teri—lD †EB must ˜e neg—tiveF yn the other h—ndD in order to reverse ˜i—s the ˜—seE™olle™tor jun™tion †CB will ˜e — positive volt—geF 1 This content is available online at <http://cnx.Chapter 2 Device Fundamentals 2.1: Structure of a npn bipolar transistor. SI .

sn pigure PFQD we h—ve two di'erent kinds of —rrowsF „he open —rrows whi™h —re —tt—™hed to the ™—rriersD show us whi™h w—y the ™—rrier is movingF „he solid —rrows whi™h —re l—˜eled with some kind of su˜s™ripted ID represent ™urrent )owF ‡e need to do this ˜e™—use for holesD motion —nd ™urrent )ow —re in the s—me dire™tionD while for ele™tronsD ™—rrier motion —nd ™urrent )ow —re in opposite dire™tionsF tust —s we s—w in the l—st ™h—pterD the ele™trons whi™h —re inje™ted into the ˜—se di'use —w—y from the emitterE˜—se jun™tion tow—rds the @reverse ˜i—sedA ˜—seE™olle™tor jun™tionF es they move through the ˜—seD some of the ele™trons en™ounter holes —nd re™om˜ine with themF „hose ele™trons whi™h do get to the ˜—seE . xowD let9s dr—w the ˜—ndEdi—gr—m for this devi™eF et (rst this might seem h—rd to doD ˜ut we know wh—t forw—rd —nd reverse ˜i—sed ˜—nd di—gr—ms look likeD so we9ll just sti™k one of e—™h togetherF ‡e show this in pigure PFQD whi™h is — very ˜usy (gureD ˜ut it is —lso very import—ntD ˜e™—use it shows —ll of the import—nt fe—tures in the oper—tion the tr—nsistorF ƒin™e the ˜—seEemitter jun™tion is forw—rd ˜i—sedD ele™trons will go from the @nEtypeA emitter into the ˜—seF vikewiseD some holes from the ˜—se will ˜e inje™ted into the emitterF Figure 2. DEVICE FUNDAMENTALS Figure 2.3: Band diagram and carrier uxes in a bipolar transistor.SP CHAPTER 2.2: Forward active biasing of a npn bipolar transistor.

2 Basic MOS Structure 2 note: „his module is —d—pted from the gonnexions module entitled Basic MOS Structure ˜y fill ‡ilsonF pigure PFR shows the ˜—si™ steps ne™ess—ry to m—ke the wyƒ stru™tureF st will help us in our underst—nding if we now rot—te our pi™ture so th—t it is pointing sidew—ys in our next few dr—wingsF pigure PFS shows the rot—ted stru™tureF xote th—t in the pEsili™on we h—ve positively ™h—rged mo˜ile holesD —nd neg—tively ™h—rgedD (xed —™™eptorsF fe™—use we will need it l—terD we h—ve —lso shown the ˜—nd di—gr—m for the semi™ondu™tor ˜elow the sket™h of the devi™eF xote th—t sin™e the su˜str—te is pEtypeD the permi level is lo™—ted down ™lose to the v—l—n™e ˜—ndF Figure 2.4: Formation of the metal-oxide-semiconductor (MOS)>. . 2 This content is available online at <http://cnx.SQ ™olle™tor jun™tion run into — l—rge ele™tri™ (eld whi™h sweeps them out of the ˜—se —nd into the ™olle™torF „hey 4f—ll4 down the l—rge potenti—l drop —t the jun™tionF „hese e'e™ts —re —ll seen in pigure PFQD with —rrows representing the v—rious ™urrents whi™h —re —sso™i—ted with e—™h of the ™—rriers )uxesF IEe represents the ™urrent —sso™i—ted with the ele™tron inje™tion into the ˜—seD iFeFD it points in the opposite dire™tion from the motion of the ele™tronsD sin™e ele™trons h—ve — neg—tive ™h—rgeF IEh represents the ™urrent —sso™i—ted with holes inje™tion into the emitter from the ˜—seF IBr represents re™om˜in—tion ™urrent in the ˜—seD while ICe represents the ele™tron ™urrent going into the ™olle™torF st should ˜e e—sy for you to see th—tX IE = IEe + IEh IB = IEh + IBr IC = ICe @PFIA @PFPA @PFQA sn — 4good4 tr—nsistorD —lmost —ll of the ™urrent —™ross the ˜—seEemitter jun™tion ™onsists of ele™trons ˜eing inje™ted into the ˜—seF „he tr—nsistor engineer works h—rd to design the devi™e so th—t very little emitter ™urrent is m—de up of holes ™oming from the ˜—se into the emitterF „he tr—nsistor is —lso designed so th—t —lmost —ll of those ele™trons whi™h —re inje™ted into the ˜—se m—ke it —™ross to the ˜—seE™olle™tor reverseE˜i—sed jun™tionF ƒome re™om˜in—tion is un—void—˜leD ˜ut things —re —rr—nged so —s to minimize this e'e™tF 2.

5: Basic metal-oxide-semiconductor (MOS) structure. DEVICE FUNDAMENTALS Figure 2. .SR CHAPTER 2.6: Applying a negative gate voltage to a basic metal-oxide-semiconductor (MOS) structure. vet us now pl—™e — potenti—l ˜etween the g—te —nd the sili™on su˜str—teF ƒuppose we m—ke the g—te neg—tive with respe™t to the su˜str—teF ƒin™e the su˜str—te is pEtypeD it h—s — lot of mo˜ileD positively ™h—rged holes in itF ƒome of them will ˜e —ttr—™ted to the neg—tive ™h—rge on the g—teD —nd move over to the surf—™e of the su˜str—teF „his is —lso re)e™ted in the ˜—nd di—gr—m shown in pigure PFTF ‚emem˜er th—t the density of holes is exponenti—lly proportion—l to how ™lose the permi level is to the v—len™e ˜—nd edgeF ‡e see th—t the ˜—nd di—gr—m h—s ˜een ˜ent up slightly ne—r the surf—™e to re)e™t the extr— holes whi™h h—ve —™™umul—ted thereF Figure 2.

SS en ele™tri™ (eld will develop ˜etween the positive holes —nd the neg—tive g—te ™h—rgeF xote th—t the g—te —nd the su˜str—te form — kind of p—r—llel pl—te ™—p—™itorD with the oxide —™ting —s the insul—ting l—yer inE˜etween themF „he oxide is quite thin ™omp—red to the —re— of the devi™eD —nd so it is quite —ppropri—te to —ssume th—t the ele™tri™ (eld inside the oxide is — uniform oneF @‡e will ignore fringing —t the edgesFA „he integr—l of the ele™tri™ (eld is just the —pplied g—te volt—ge Vg F sf the oxide h—s — thi™kness xox then sin™e Eox is uniformD it is given ˜yD @PFRAF Eox = Vg xox @PFRA sf we fo™us in on — sm—ll p—rt of the g—teD we ™—n m—ke — little 4pill4 ˜ox whi™h extends from somewhere in the oxideD —™ross the oxideGg—te interf—™e —nd ends up inside the g—te m—teri—l somepl—™eF „he pillE˜ox will h—ve —n —re— ∆sF xow we will invoke q—uss9 l—w whi™h we reviewed e—rlierF q—uss9 l—w simply s—ys th—t the surf—™e integr—l over — ™losed surf—™e of the displ—™ement ve™tor D @whi™h isD of ™ourseD ε x E A is equ—l to the tot—l ™h—rge en™losed ˜y th—t surf—™eF ‡e will —ssume th—t there is — surf—™e ™h—rge density -Qg goulom˜sG™m2 on the surf—™e of the g—te ele™trode @pigure PFUAF „he integr—l form of q—uss9 v—w is justX ox EdS = Qencl @PFSA Figure 2. xote th—t we h—ve used εox E in pl—™e of DF sn this p—rti™ul—r setEup the integr—l is e—sy to performD sin™e the ele™tri™ (eld is uniformD —nd only pointing in through one surf—™e E it termin—tes on the neg—tive surf—™e ™h—rge inside the pillE˜oxF „he ™h—rge en™losed in the pill ˜ox is just E@Qg ∆s AD —nd so we h—ve @keeping in mind th—t the surf—™e integr—l of — ve™tor pointing into the surf—™e is neg—tiveAD @PFTAD or @PFUAF ox EdS = = ox Eox −( ox Eox ∆s) − (Qg ∆s) = Qg @PFTA @PFUA xowD we ™—n use @PFRA to get @PFVA or @PFWAF ox Vg xox = Qg @PFVA .7: Finding the surface charge density.

8: Increasing the voltage extends the depletion region further into the device. „he ele™tri™ (eld now extends into the semi™ondu™torF ‡e know from our experien™e with the pEn jun™tion th—t when there is —n ele™tri™ (eldD there is — shift in potenti—lD whi™h is represented in the ˜—nd di—gr—m ˜y ˜ending the ˜—ndsF fending the ˜—nds down @—s we should moving tow—rds positive ™h—rgeA ™—uses the v—len™e ˜—nd to pull —w—y from the permi level ne—r the surf—™e of the semi™ondu™torF sf you remem˜er the expression we h—d for the density of holes in terms of Ev —nd Ef it is e—sy to see th—t indeedD @PFIIAD there . DEVICE FUNDAMENTALS Qg ox = ≡ cox Vg xox @PFWA „he qu—ntity c ox is ™—lled the oxide ™—p—™it—n™eF st h—s units of p—r—dsG™m2 D so it is re—lly — ™—p—™it—n™e per unit —re— of the oxideF „he diele™tri™ ™onst—nt of sili™on dioxideD εox D is —˜out QFQ x IH-13 pG™mF e typi™—l oxide thi™kness might ˜e PSH Å @or PFS x IH-6 ™mAF sn this ™—seD c ox would ˜e —˜out IFQH x IH-7 pG™m2 F „he units we —re using hereD while they might seem — little —r˜itr—ry —nd ™onfusingD —re the ones most ™ommonly used in the semi™ondu™tor ˜usinessF „he most useful form of @PFWA is when it is turned —roundD @PFIHAD —s it gives us — w—y to (nd the ™h—rge on the g—te in terms of the g—te potenti—lF ‡e will use this equ—tion l—ter in our development of how the wyƒ tr—nsistor re—lly worksF Qg = cox Vg @PFIHA st turns out we h—ve not done —nything very useful ˜y —pply — neg—tive volt—ge to the g—teF ‡e h—ve dr—wn more holes there in wh—t is ™—lled —n —™™umul—tion l—yerD ˜ut th—t is not helping us in our e'ort to ™re—te — l—yer of ele™trons in the wyƒpi„ whi™h ™ould ele™tri™—lly ™onne™t the two nEregions togetherF vet9s turn the ˜—ttery —round —nd —pply — positive volt—ge to the g—te @pigure PFVAF e™tu—llyD let9s t—ke the ˜—ttery out for nowD —nd just let Vg ˜e — positive v—lueD rel—tive to the su˜str—te whi™h will tie to groundF w—king Vg positive puts positive Qg on the g—teF „he positive ™h—rge pushes the holes —w—y from the region under the g—te —nd un™overs some of the neg—tivelyE™h—rged (xed —™™eptorsF xow the ele™tri™ (eld points the other w—yD —nd goes from the positive g—te ™h—rgeD termin—ting on the neg—tive —™™eptor ™h—rge within the sili™onF Figure 2.ST CHAPTER 2.

„he ele™tri™ (eld extends further into the semi™ondu™torD —s more neg—tive ™h—rge is un™overed —nd the ˜—nds ˜end further downF fut now we h—ve to re™—ll the ele™tron density equ—tionD whi™h tells us how m—ny ele™trons we h—veX n = Nc e “ E −E ” c f − kT @PFIPA e gl—n™e —t pigure PFW reve—ls th—t with this mu™h ˜—nd ˜endingD Ec the ™ondu™tion ˜—nd edgeD —nd Ef the permi level —re st—rting to get ™lose to one —nother @—t le—st ™omp—red to kT AD whi™h me—ns th—t nD the ele™tron ™on™entr—tionD should soon st—rt to ˜e™ome signi(™—ntF sn the situ—tion represented ˜y pigure PFWD we s—y we —re —t thresholdD —nd the g—te volt—ge —t this point is ™—lled the threshold voltageD VT F xowD let9s in™re—se Vg —˜ove VT F rere9s the sket™h in pigure PFIHF iven though we h—ve in™re—sed Vg ˜eyond the threshold volt—geD VT D —nd more positive ™h—rge —ppe—rs on the g—teD the depletion region no longer moves ˜—™k into the su˜str—teF snste—d ele™trons st—rt to —ppe—r under the g—te regionD —nd the —ddition—l ele™tri™ (eld lines termin—te on these new ele™tronsD inste—d of on —ddition—l —™™eptorsF ‡e h—ve ™re—ted —n inversion layer of ele™trons under the g—teD —nd it is this l—yer of ele™trons whi™h we ™—n use to ™onne™t the two nEtype regions in our initi—l devi™eF .SU is — depletion region @region with —lmost no holesA ne—r the region under the g—teF @yn™e Ef E Ev gets l—rge with respe™t to kTD the neg—tive exponent ™—uses p → 0FA p = Nv e “ E −E ” v f − kT @PFIIA Figure 2. Ef is getting close to Ec .9: Threshold.

10: Inversion .org/content/m33805/1.1/>. . DEVICE FUNDAMENTALS Figure 2. ‡here did these ele™trons ™ome fromc ‡e do not h—ve —ny donors in this m—teri—lD so they ™—n not ™ome from thereF „he only pl—™e from whi™h ele™trons ™ould ˜e found would ˜e through therm—l gener—tionF ‚emem˜erD in — semi™ondu™torD there —re —lw—ys — few ele™tron hole p—irs ˜eing gener—ted ˜y therm—l ex™it—tion —t —ny given timeF ile™trons th—t get ™re—ted in the depletion region —re ™—ught ˜y the ele™tri™ (eld —nd —re swept over to the edge ˜y the g—teF s h—ve tried to suggest this with the ele™tron gener—tion event shown in the ˜—nd di—gr—m in the (gureF sn — re—l wyƒ devi™eD we h—ve the two nEregionsD —nd it is e—sy for ele™trons from one or ˜oth to 4f—ll4 into the potenti—l well under the g—teD —nd ™re—te the inversion l—yer of ele™tronsF 2.SV CHAPTER 2.electrons form under the gate.3 Introduction to the MOS Transistor and MOSFETs note: 3 „his module is —d—pted from the gonnexions modules entitled Introduction to MOSFETs —nd MOS Transistor ˜y fill ‡ilsonF ‡e now move on to —nother three termin—l devi™e E —lso ™—lled — tr—nsistorF „his tr—nsistorD howeverD works on mu™h di'erent prin™iples th—n does the ˜ipol—r jun™tion tr—nsistor of the l—st ™h—pterF ‡e will now fo™us on — devi™e ™—lled the eld eect transistorD or metal-oxide-semiconductor eld eect transistor or simply wyƒpi„F sn pigure PFII we h—ve — ˜lo™k of sili™onD doped pEtypeF snto it we h—ve m—de two regions whi™h —re doped nEtypeF „o e—™h of those nEtype regions we —tt—™h — wireD —nd ™onne™t — ˜—ttery ˜etween themF sf we try to get some ™urrentD ID to )ow through this stru™tureD nothing will h—ppenD ˜e™—use the nEp jun™tion on the ‚rƒ is reverse ˜i—sedD iFeFD the positive le—d from the ˜—ttery going to the nEside of the pEn jun™tionF sf we —ttempt to remedy this ˜y turning the ˜—ttery —roundD we will now h—ve the vrƒ jun™tion reverse ˜i—sedD —nd —g—inD no ™urrent will )owF sfD for wh—tever re—sonD we w—nt ™urrent to )owD we will need to ™ome up 3 This content is available online at <http://cnx.

11: The start of a eld eect transistor.SW with some w—y of forming — l—yer of nEtype m—teri—l ˜etween one nEregion —nd the otherF „his will then ™onne™t them togetherD —nd we ™—n run ™urrent in one termin—l —nd out the otherF Figure 2. „o see how we will do thisD let9s do two thingsF pirst we will grow — l—yer of ƒiy2 @sili™on dioxide or sili™—D ˜ut —™tu—lly refered to —s 4oxide4A on top of the sili™onF „o do this the w—fer is pl—™ed in —n oven under —n oxygen —tmosphereD —nd he—ted to IIHH ◦ gF „he result is — ni™eD highEqu—lity insul—ting ƒiy2 l—yer on top of the sili™onAF yn top of the oxide l—yer we then deposit — ™ondu™torD whi™h we ™—ll the g—teF sn the 4old d—ys4 the g—te would h—ve ˜een — l—yer of —luminumY hen™e the 4met—lEoxideEsili™on4 or wyƒ n—meF „od—yD it is mu™h more likely th—t — he—vily doped l—yer of poly™ryst—lline sili™on @polysili™onD or more often just 4poly4A would ˜e deposited to form the g—te stru™tureF €olysili™on is m—de from the redu™tion of — g—sD su™h —s sil—ne @ƒir4 AD @PFIQAF @PFIQA „he sili™on is poly™ryst—lline @™omposed of lots of sm—ll sili™on ™ryst—llitesA ˜e™—use it is deposited on top of the oxideD whi™h is —morphousD —nd so it does not provide — single ™ryst—l 4m—trix4 whi™h would —llow the sili™on to org—nize itself into one single ™ryst—lF sf we h—d deposited the sili™on on top of — single ™ryst—l sili™on w—ferD we would h—ve formed — single ™ryst—l l—yer of sili™on ™—lled —n epit—xi—l l—yerF „his is sometimes done to m—ke stru™tures for p—rti™ul—r —ppli™—tionsF por inst—n™eD growing — nEtype epit—xi—l l—yer on top of — pEtype su˜str—te permits the f—˜ri™—tion of — very —˜rupt pEn jun™tionF note: ipit—xyD is — tr—nsliter—tion of two qreek words epiD me—ning 4upon4D —nd taxisF me—ning 4ordered4F „hus —n epit—xi—l l—yer is one th—t follows the order of the su˜str—te on whi™h it is grownF xow we ™—n go ˜—™k now to our initi—l stru™tureD shown in pigure PFIID only this time we will —dd —n oxide l—yerD — g—te stru™tureD —nd —nother ˜—ttery so th—t we ™—n invert the region under the g—te —nd ™onne™t the two nEregions togetherF ‡ell —lso identify some n—mes for p—rts of the stru™tureD so we will know wh—t we —re t—lking —˜outF por re—sons whi™h will ˜e ™le—r l—terD we ™—ll the nEregion ™onne™ted to the neg—tive side of the ˜—ttery the sour™eD —nd the other one the dr—inF ‡e will ground the sour™eD —nd —lso the pEtype su˜str—teF ‡e —dd two ˜—tteriesD Vgs ˜etween the g—te —nd the sour™eD —nd Vds ˜etween the dr—in —nd the sour™eF .

13: The inversion channel and its resistance.TH CHAPTER 2.12: Biasing a MOSFET transistor st will ˜e helpful if we —lso m—ke —nother sket™hD whi™h gives us — perspe™tive view of the devi™eF por this we strip o' the g—te —nd oxideD ˜ut we will im—gine th—t we h—ve —pplied — volt—ge gre—ter th—n VT to the g—teD so there is — nEtype regionD ™—lled the ™h—nnel whi™h ™onne™ts the twoF ‡e will —ssume th—t the ™h—nnel region is L long —nd W wideD —s shown in pigure PFIQF Figure 2. DEVICE FUNDAMENTALS Figure 2. xext we w—nt to t—ke — look —t — little se™tion of ™h—nnelD —nd (nd its resist—n™e dRD when the little se™tion is dx longD @PFIRAF dR = dx σs W @PFIRA ‡e h—ve introdu™ed — slightly di'erent form for our resist—n™e formul— hereF xorm—llyD we would h—ve — simple σ in the denomin—torD —nd —n —re— AD for the ™rossEse™tion—l —re— of the ™h—nnelF st turns out to ˜e very h—rd to (gure out wh—t th—t ™ross se™tion—l —re— of the ™h—nnel is howeverF „he ele™trons whi™h form the inversion l—yer ™rowd into — very thin sheet of surf—™e ™h—rge whi™h re—lly h—s little or no thi™knessD or penetr—tion into the su˜str—teF sfD on the other h—nd we ™onsider — surf—™e ™ondu™tivity @unitsX simply mhosAD σs D @PFISAD then we will h—ve —n expression whi™h we ™—n ev—lu—teF rereD µs is — surf—™e mo˜ilityD with units of ™m2 G†Fse™D th—t is the qu—ntity whi™h represented the proportion—lity ˜etween the —ver—ge ™—rrier velo™ity —nd the ele™tri™ (eldD .

TI @PFITA —nd @PFIUAF σs = µs Qchan v = µE µ= @PFISA @PFITA qτ @PFIUA m „he surf—™e mo˜ility is — qu—ntity whi™h h—s to ˜e me—sured for — given systemD —nd is usu—lly just — num˜er whi™h is given to youF ƒomething —round QHH ™m2 G†Fse™ is —˜out right for sili™onF Qchan is ™—lled the surf—™e ™h—rge density or ™h—nnel ™h—rge density —nd it h—s units of goulom˜sG™m2 F „his is like — sheet of ™h—rgeD whi™h is di'erent from the ˜ulk ™h—rge densityD whi™h h—s units of goulom˜sG™m2 F xote th—tX cm2 Coulombs Voltsec cm2 = = = Coul sec Volt I V @PFIVA mhos st turns out th—t it is pretty simple to get —n expression for Qchan D the surf—™e ™h—rge density in the ™h—nnelF por —ny given g—te volt—ge Vgs D we know th—t the ™h—rge density on the g—te is given simply —sX Qg = cox Vgs @PFIWA roweverD until the g—te volt—ge Vgs gets l—rger th—n VT we —re not ™re—ting —ny mo˜ile ele™trons under the g—teD we —re just ˜uilding up — depletion regionF ‡e9ll de(ne QT —s the ™h—rge on the g—te ne™ess—ry to get to thresholdF QT = cox VT F eny ™h—rge —dded to the g—te —˜ove QT is m—t™hed ˜y ™h—rge Qchan in the ™h—nnelF „husD it is e—sy to s—yX @PFPHA or @PFPIAF Qchannel = Qg − QT Qchan = cox (Vg − VT ) „husD putting @PFPHA —nd @PFISA into @PFIRAD we getX @PFPHA @PFPIA dR = dx µs cox (Vgs − VT ) W @PFPPA sf you look ˜—™k —t pigure PFIPD you will see th—t we h—ve de(ned — ™urrent Id )owing into the dr—inF „h—t ™urrent )ows through the ™h—nnelD —nd hen™e through our little in™rement—l resist—n™e dRD ™re—ting — volt—ge drop dVc —™ross itD where Vc is the ™h—nnel volt—geD @PFPQAF dVc (x) = Id dR = Id dx µs cox (Vgs −VT )W @PFPQA vet9s move the denomin—tor to the leftD —nd integr—teF ‡e w—nt to do our integr—l ™ompletely —long the ™h—nnelF „he volt—ge on the ™h—nnel Vc (x) goes from H on the left to Vds on the rightF et the s—me timeD x is going from H to LF „hus our limits of integr—tion will ˜e H —nd Vds for the volt—ge integr—l dVc (x) —nd from H to L for the x integr—l dxF Vds L µs cox (Vgs − VT ) W dVc = 0 0 Id dx @PFPRA .

TP CHAPTER 2.4 Light Emitting Diode 4 note: „his module is —d—pted from the gonnexions module entitled Light Emitting Diode ˜y fill ‡ilsonF vet9s t—lk —˜out the re™om˜ining ele™trons for — minuteF ‡hen the ele™tron f—lls down from the ™ondu™tion ˜—nd —nd (lls in — hole in the v—len™e ˜—ndD there is —n o˜vious loss of energyF „he question isY where does th—t energy goc sn sili™onD the —nswer is not very interestingF ƒili™on is wh—t is known —s —n indirect band-gap m—teri—lF ‡h—t this me—ns is th—t —s —n ele™tron goes from the ˜ottom of the ™ondu™tion ˜—nd to the top of the v—len™e ˜—ndD it must —lso undergo — signi(™—nt ™h—nge in momentumF „his —ll ™omes —˜out from the det—ils of the ˜—nd stru™ture for the m—teri—lD whi™h we will not ™on™ern ourselves with hereF es we —ll knowD whenever something ™h—nges st—teD we must still ™onserve not only energyD ˜ut —lso momentumF sn the ™—se of —n ele™tron going from the ™ondu™tion ˜—nd to the v—len™e ˜—nd in sili™onD ˜oth of these things ™—n only ˜e ™onserved if the tr—nsition —lso ™re—tes — qu—ntized set of l—tti™e vi˜r—tionsD ™—lled phononsD or 4he—t4F €honons posses ˜oth energy —nd momentumD —nd their ™re—tion upon the re™om˜in—tion of —n ele™tron —nd hole —llows for ™omplete ™onserv—tion of ˜oth energy —nd momentumF ell of the energy whi™h the ele™tron gives up in going from the ™ondu™tion ˜—nd to the v—len™e ˜—nd @IFI e†A ends up in phononsD whi™h is —nother w—y of s—ying th—t the ele™tron he—ts up the ™ryst—lF sn some other semi™ondu™torsD something else o™™ursF sn — ™l—ss of m—teri—ls ™—lled direct band-gap semi™ondu™torsD the tr—nsition from ™ondu™tion ˜—nd to v—len™e ˜—nd involves essenti—lly no ™h—nge in momentumF €hotonsD it turns outD possess — f—ir —mount of energy @sever—l e†Gphoton in some ™—sesA ˜ut they h—ve very little momentum —sso™i—ted with themF „husD for — dire™t ˜—nd g—p m—teri—lD the ex™ess energy of the ele™tronEhole re™om˜in—tion ™—n either ˜e t—ken —w—y —s he—tD or more likelyD —s — photon of lightF „his r—di—tive tr—nsition then ™onserves energy —nd momentum ˜y giving o' light whenever —n ele™tron —nd hole re™om˜ineF „his gives rise to the light emitting diode @vihAF imission of — photon in —n vih is shown s™hem—ti™—lly in pigure PFIRF 4 This content is available online at <http://cnx. DEVICE FUNDAMENTALS foth integr—ls —re pretty trivi—lF vet9s sw—p the equ—tion orderD sin™e we usu—lly w—nt Id —s — fun™tion of —pplied volt—gesF Id L = µs cox W (Vgs − VT ) Vds @PFPSA ‡e now simply divide ˜oth sides ˜y LD —nd we end up with —n expression for the dr—in ™urrent Id D in terms of the dr—inEsour™e volt—geD Vds D the g—te volt—ge Vgs —nd some physi™—l —ttri˜utes of the wyƒ tr—nsistorF Id = µs cox W (Vgs − VT ) Vds L @PFPTA .1/>.

st w—s €l—n™k who postul—ted th—t the energy of — photon w—s rel—ted to its frequen™y ˜y — ™onst—ntD whi™h w—s l—ter n—med —fter himF sf the frequen™y of os™ill—tion is given ˜y the qreek letter 4nu4 @ν AD then the energy of the photon is just given ˜yD @PFPUAD where h is €l—n™k9s ™onst—ntD whi™h h—s — v—lue of RFIR x IH-15 e†Fse™F E = hν @PFPUA ‡hen we t—lk —˜out light it is ™onvention—l to spe™ify its w—velengthD λD inste—d of its frequen™yF †isi˜le light h—s — w—velength on the order of n—nometersD eFgFD red is —˜out THH nmD green —˜out SHH nm —nd ˜lue is in the RSH nm regionF e h—ndy 4rule of thum˜4 ™—n ˜e derived from the f—™t th—t c a λν D where c is the speed of light @Q x IH3 mGse™ or Q x IH17 nmGse™D @PFPVAF λ (nm) = = hc E(eV) 1242 E(eV) @PFPVA „husD — semi™ondu™tor with — P e† ˜—ndEg—p should give o' light —t —˜out TPH nm @in the redAF e Q e† ˜—ndEg—p m—teri—l would emit —t RIR nmD in the violetF „he hum—n eyeD of ™ourseD is not equ—lly responsive to —ll ™olors @pigure PFISAF „he m—teri—ls whi™h —re used for import—nt light emitting diodes @vihsA for e—™h of the di'erent spe™tr—l regions —re —lso shown in pigure PFISF .14: Radiative recombination in a direct band-gap semiconductor.TQ Figure 2.

st is worth noting th—t — num˜er of the import—nt vihs —re ˜—sed on the q—es€ systemF q—es is — dire™t ˜—ndEg—p semi™ondu™tor with — ˜—nd g—p of IFRP e† @in the infr—redAF q—€ is —n indire™t ˜—ndEg—p m—teri—l with — ˜—nd g—p of PFPT e† @SSH nmD or greenAF foth es —nd € —re group † elementsF @ren™e the nomen™l—ture of the m—teri—ls —s sssE† @or IQEISA ™ompound semi™ondu™torsFA ‡e ™—n repl—™e some of the es with € in q—es —nd m—ke — mixed ™ompound semi™ondu™tor q—es1-x €x F ‡hen the mole fr—™tion of phosphorous is less th—n —˜out HFRS the ˜—nd g—p is dire™tD —nd so we ™—n 4engineer4 the desired ™olor of vih th—t we w—nt ˜y simply growing — ™ryst—l with the proper phosphorus ™on™entr—tion3 „he properties of the q—es€ system —re shown in pigure PFITF st turns out th—t for this systemD there —re —™tu—lly two di'erent ˜—nd g—psD —s shown in pigure PFITF yne is — dire™t g—p @no ™h—nge in momentumA —nd the other is indire™tF sn q—esD the dire™t g—p h—s lower energy th—n the indire™t one @like in the insetA —nd so the tr—nsition is — r—di—tive oneF es we st—rt —dding phosphorous to the systemD ˜oth the dire™t —nd indire™t ˜—nd g—ps in™re—se in energyF roweverD the dire™t g—p energy in™re—ses f—ster with phosphorous fr—™tion th—n does the indire™t oneF et — mole fr—™tion x of —˜out HFRSD the g—p energies ™ross over —nd the m—teri—l goes from ˜eing — dire™t g—p semi™ondu™tor to —n indire™t g—p semi™ondu™torF et x a HFQS the ˜—nd g—p is —˜out IFWU e† @TQH nmAD —nd so we would only expe™t to get light up to the red using the q—es€ system for m—king vih9sF portun—telyD people dis™overed th—t you ™ould —dd —n impurity @nitrogenA to the q—es€ systemD whi™h introdu™ed — new level in the systemF en ele™tron ™ould go from the indire™t ™ondu™tion ˜—nd @for — mixture with — mole fr—™tion gre—ter th—n HFRSA to the nitrogen siteD ™h—nging its momentumD ˜ut not its energyF st ™ould then m—ke — dire™t tr—nsition to the v—len™e ˜—ndD —nd light with ™olors —ll the w—y to the green ˜e™—me possi˜leF „he use of — nitrogen re™om˜in—tion ™enter is depi™ted in the pigure PFIUF . DEVICE FUNDAMENTALS Figure 2.15: Relative response of the human eye to various colors.TR CHAPTER 2.

16: Band gap for the GaAsP system Figure 2.TS Figure 2.17: Addition of a nitrogen recombination center to indirect GaAsP. sf we w—nt ™olors with w—velengths shorter th—n the greenD we must —˜—ndon the q—es€ system —nd look for more suit—˜le m—teri—lsF e ™ompound semi™ondu™tor m—de from the ssE†s elements n —nd ƒe m—ke up one promising systemD —nd sever—l rese—r™h groups h—ve su™™essfully m—de ˜lue —nd ˜lueEgreen vihs from nƒeF ƒig is —nother @we—kA ˜lue emitter whi™h is ™ommer™i—lly —v—il—˜le on the m—rketF ‚e™entlyD workers —t — tinyD unknown ™hemi™—l ™omp—ny stunned the 4displ—y world4 ˜y —nnoun™ing th—t they h—d su™™essfully f—˜ri™—ted — ˜lue vih using the ssE† m—teri—l q—xF e good ˜lue vih w—s the 4holy gr—il4 of the displ—y —nd .

5.5 Polymer Light Emitting Diodes 2.2 Device physics and materials science of polymer LEDs e s™hem—ti™ di—gr—m of — polymer vih is shown in pigure PFIVF e polymer vih ™—n ˜e divided into three di'erent ™omponentsX eF AnodeX the hole supplierD m—de of met—l of high working fun™tionF ix—mples of the ™ommon —node —re indium tin oxide @s„yAD gold et™F „he —node is usu—lly tr—nsp—rent so th—t light ™—n ˜e emitted throughF fF CathodeX the ele™tron supplierD m—de of met—l of low working fun™tionF ix—mples of the ™ommon ™—thode —re —luminum or ™—l™iumF gF PolymerX m—de of ™onjug—ted polymer (lm with thi™kness of IHH nmF 5 This content is available online at <http://cnx. .TT CHAPTER 2.1 Introduction 5 „his module w—s developed —s p—rt of — ‚i™e …niversity ™ourse griwRWTX Chemistry of Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of €ui ‰ee rungF sn IWWHD ele™trolumines™ent @ivA from ™onjug—ted polymers w—s (rst reported ˜y furroughes et —lF of g—m˜ridge …niversityF e l—yer of poly@paraEphenylenevinyleneA @€€†A w—s s—ndwi™hed ˜etween l—yers of indium tin oxide @s„yA —nd —luminumF ‡hen this devi™e is under — IR † d™ ˜i—sD the €€† emits — yellowishE green light with — qu—ntum e0™ien™y of HFHS7F „his report —ttr—™ted — lot of —ttentionD ˜e™—use the potenti—l th—t polymer light emitting diodes @vihsA ™ould ˜e inexpensively m—ss produ™ed into l—rge —re— displ—y —re—F „he pro™essing steps in m—king polymer vihs —re re—dily s™—le—˜leF „he industri—l ™o—ting te™hniques is well developed to m—ss produ™e polymer l—yers of IHH nm thi™knessD —nd the devi™e ™ould ˜e p—tterned onto l—rge surf—™e —re— ˜y pixell—tion of met—lF ƒin™e the initi—l dis™overyD —nd in™re—sing —mount of rese—r™hes h—s ˜een performedD —nd signi(™—nt progress h—s ˜een m—deF sn IWWH the polymer vih only emitted yellowish green ™olorD now the emission ™olor r—nged from deep ˜lue to ne—r infr— redF „he e0™ien™y of the multiEl—yer polymer vih even re—™hed — qu—ntum e0™ien™y of >R7 —nd the oper—ting volt—ge h—s ˜een redu™ed signi(™—ntlyF sn term of e0™ien™yD ™olor sele™tion —nd oper—ting volt—geD polymer vihs h—ve —tt—ined —dequ—te levels for ™ommer™i—liz—tionF fut there —re reli—˜ility pro˜lems th—t —re symptom—ti™ of —ny org—ni™ devi™esF>. DEVICE FUNDAMENTALS gh ‚yw rese—r™h ™ommunity for — num˜er of ye—rsF y˜viouslyD —dding ˜lue to the —lre—dy working green —nd red vih9s ™ompletes the set of Q prim—ry ™olors ne™ess—ry for — fullE™olor )—t p—nel displ—yF purthermoreD using — ˜lue vih or l—ser in — gh ‚yw would more th—n qu—druple its d—t— ™—p—™ityD —s ˜it di—meter s™—les —s λD —nd hen™e the —re— —s λ2 F 2.

19: . ‡hen — polymer vih is under — dire™t ™urrent @d™A ˜i—sD holes —re inje™ted from the —node @s„yA —nd ele™trons —re inje™ted from the ™—thode @—luminumAF …nder the in)uen™es of the ele™tri™—l (eldD the ele™trons —nd holes will migr—te tow—rd e—™h otherF ‡hen they re™om˜ine in the ™onjug—ted polymer l—yerD — ˜ound ex™ited st—tes @ex™itonsA will ˜e formedF ƒome of the ex™itons @singletsA then de™—ys in the ™onjug—ted polymer l—yer to emit light through the tr—nsp—rent su˜str—tes @gl—ssAF „he emission ™olor will ˜e depended on the energy g—p of the polymersF „here is energy g—p in — ™onjug—ted polymer ˜e™—use the π ele™tron —re not ™ompletely delo™—lized over the entire polymer ™h—inF snste—d there —re —ltern—te region in the polymer ™h—in th—t h—s — higher ele™tron density @pigure PFIW—AF „he ™h—in length of this region is —˜out ISEPH multiple ˜ondsF „he emission ™olor ™—n ˜e ™ontrolled ˜y tuning this energy ˜—nd g—p @pigure PFIW˜AF st shows th—t ˜ond —ltern—tion limits the extent of delo™—liz—tionF „—˜le PFI summ—rizes the stru™ture —nd emission ™olor of some ™ommon ™onjug—ted polymersF Alternation of bond lengths along a conjugated polymer chain (a) results in a material with properties of a large band gap semiconductor (b).18: Schematic set-up of polymer LED. and Eg is the band gap. where CB is the conductive band gap.TU Figure 2. and VB is the valence band. Figure 2.

5.1 X ix—mple of ™ommon ™onjug—ted polymersF 2. DEVICE FUNDAMENTALS π -π * energy gap (eV) IFS IFU Emission (nm) peak €e €he trans E poly—™etylene polydi—™etylene THH €€€ €€† poly@paraE phenyleneA €oly@paraE phenylenevinyleneA poly@PDSE di—lkoxyEpE phenlyenevinylenA QFH @redA PFS @greenA RTS STS ‚yE€€† PFP @˜lueA ∼SVH €„ €Qe„ polythiophene €oly@QE —lkythiopheneA €oly@PDSE thiophenevinyleneA €olypyrrole PFH @redA PFH @redA TWH €„† IFV €€y QFI €eni €oly—niline QFP Table 2.TV Polymer Chemical name Structure CHAPTER 2.3 Approaches to improve the eciency i0™ien™y for —ny vih is de(nedX next a nesc B nint where next is the extern—l qu—ntum e0™ien™yD nint is the intern—l e0™ien™y @represents the fr—™tion of inje™ted ™—rrierD usu—lly ele™tronD th—t is ™onverted to photonAD —nd nesc is the es™—pe e0™ien™y @represent fr—™tion of photons th—t ™—n re—™h to the outsideAF „he most ™ommon w—y to improve the intern—l e0™ien™y is to ˜—l—n™e the num˜er of ele™trons —nd holes whi™h —rrives —t the polymer l—yerF yrigin—llyD there —re more holes th—n ele™tron th—t —rrive of the polymer l—yer ˜e™—use ™onjug—ted polymers h—ve — higher ele™tron —0nityD —nd —s — ™onsequen™e will f—vor the tr—nsport of hole th—n ele™tronF „here —re two w—ys to m—int—ins the ˜—l—n™eX .

20: Structure of CN-PPV.1 Improvement in internal quantum eciency using low working function cathode gonjug—ted polymer is ele™tron ri™hD the mo˜ility for hole is higher th—n ele™tronD —nd more holes will —rrive in the polymer l—yer th—n ele™tronsF yne w—y to in™re—se the popul—tion of the ele™tron is to use — lower working fun™tion met—l —s ™—thodeF fr—un —nd reeger h—ve repl—™ed the —luminum ™—thode with ™—l™ium results in improved intern—l e0™ien™y ˜y — f—™tor of tenD to HFI7F „his —ppro—™h is dire™t —nd f—st ˜ut low working fun™tion ele™trode like ™—l™ium will ˜e oxidized e—sily —nd shorten the devi™es9 lifeF 2.5.TW IA w—t™h the work fun™tion of ele™trode with the ele™tron —0nity —nd ioniz—tion potenti—l of the polymerF PA „une the polymer9s ele™tron —0nity —nd ioniz—tion potenti—l to m—t™h the work fun™tion of the ele™E trodeF „he es™—pe e0™ien™y is —lso import—nt ˜e™—use — polymer vih is m—de up of l—yers of m—teri—ls th—t h—ve di'erent refr—™tive indexD —nd some of the photon gener—ted from the ex™ition m—y ˜e re)e™ted —t the ˜ound—ry —nd tr—pped inside the devi™eF 2. .5.3.2 Improvement in internal quantum eciency using multiple polymer layers e l—yer of poly‘PDSEdi@hexyloxyA™y—noterephth—lylidene“ @gxE€€†D pigure PFPHA is ™o—ted on top of €€† to improve the tr—nsport —nd re™om˜in—tion of ele™tron —nd holes @pigure PFPIAF Figure 2.3.

DEVICE FUNDAMENTALS Figure 2. „he nitrile group in the gxE€€† h—s two e'e™t on the polymerF IA st in™re—ses the ele™tron —0nity so ele™trons ™—n tr—vel more e0™ient from the —luminum to the polymer l—yerF end met—l of rel—tive high working fun™tion like —luminum —nd gold ™—n ˜e now ˜e used —s ™—thode inste—d of ™—l™iumF PA st in™re—ses the ˜inding energy of the o™™upied π —nd uno™™upied π B st—te ˜ut m—int—in — simil—r π Eπ B g—pF ƒo when the €€† —nd gxE€€† is pl—™ed togetherD holes —nd ele™tron will ˜e ™on(ned —t the heterojun™tionF „he resulting energy levels —re shown in pigure PFPPF .UH CHAPTER 2.21: Schematic representation of a CN-PPV and PPV multi-layer LED.

D. 365. Adapted from N. R. D. C. „he —˜solute energies of levels —re not known —™™ur—telyD ˜ut the di—gr—m show the rel—tive position of the rywy —nd v…wy levels in the polymersD —nd the permi levels of the v—rious possi˜le met—l ™ont—™tsD the di'eren™es in ele™tron —0nity @∆ieA —nd ioniz—tion potenti—l @∆s€A ˜etween €€† —nd gxE€€† —re —lso shown @pigure PFPPAF et the polymers interf—™e there is — siz—˜le o'set in the energies of rywy —nd v…wy of €€† —nd gxE €€†D the holes tr—nsported from the s„y —nd the ele™trons tr—nsport from the —luminum will ˜e ™on(ned in the heterojun™tionF „he lo™—l ™h—rge density will ˜e su0™iently high to ensure the holes —nd ele™trons will p—ss within — ™ollision ™—pture r—diusF „his setEup in™re—ses the ™h—n™e for —n ele™trons to ™om˜ine with holes to form —n ex™itionF sn —dditionD the emission will ˜e ™lose to the jun™tionD f—r —w—y from the ele™trode jun™tion whi™h will quen™h the singlet ex™itionsF „he result is th—t — multiEl—yers vih h—s —n intern—l qu—ntum e0™ien™y of IH7 —nd extern—l qu—ntum e0™ien™y @for light emitted in foreword dire™tionA of PS7F f—sed on this —ppro—™hD — ™ouple of polymers h—ve ˜een developed or modi(ed to produ™e the desir—˜le emission ™olor —nd pro™essing propertyF „he dr—w˜—™k of this method is th—t desir—˜le properties m—y not ˜e ™omment—ry to e—™h otherF por ex—mpleD in wirE€€† —n —lkoxy side group @‚yA is introdu™ed to €€† so th—t it ™—n ˜e dissolved in org—ni™ solventF fut the undesir—˜le e'e™t is th—t wirE€€† is less therm—lly st—˜leF woreover in multiple l—yers vihsD di'erent polymer l—yers h—ve di'erent refr—™tive indi™es —nd — fr—™tion of the photons will undergo tot—l intern—l re)e™tion —t the refr—™tive ˜ound—ries —nd ™—nnot es™—pe —s lightF „his pro˜lem ™—n ˜e over™ome ˜y pe˜ryE€ert mi™ro™—vity stru™tureF 2.1993. Nature. H. Bradley. C. and A. Holmes. Friend.UI Figure 2.5. B.22: Schematic energy-level diagram for a PPV and CN-PPV under foreword bias.3 Improvement in external quantum eciency using microcavity p—˜ryE€erot reson—nt stru™tures —re —lso used in inorg—ni™ vihD —nd —re is ˜—sed on permi9s golden ruleX ur ∼ | <w > | r(v) where w @the m—trix element of the pertur˜—tion ˜etween (n—l —nd initi—l st—tesA depends on the n—ture of the m—teri—lD —nd r(v) ™—n ˜e —ltered ˜y ™h—nging the density of v—rious density st—tesD eFgF using — lumines™ent thin (lms to sele™t ™ert—in v—lue of †F sn ˜uilding — mi™ro™—vity for — polymer vihD the polymer is pl—™ed ˜etween two mirrorsF @pigure PFPQAD in whi™h one of the mirrors is m—de up of —luminumD the other mirror @— fr—gg wirrorA is form ˜y epit—xi—l .3. 62. C. S. Maratti. Greenham.

3. DEVICE FUNDAMENTALS Figure 2.UP multil—yer st—™ks of ƒix xy —nd ƒiy2 F CHAPTER 2.5.23: Schematic set-up of micro-cavity.4 Polymer LEDs on a silicon substrate: an application advantage over inorganic LEDs sn the initi—l rese—r™h polymer vihs were in dire™t ™ompetition with the inorg—ni™ vihs —nd tried to —™hieve the existing vih st—nd—rdF „his is — di0™ult t—sk —s polymer vihs h—ve — lower long term st—˜ilityF roweverD there —re some —ppli™—tions in whi™h polymer vihs h—ve — ™le—r —dv—nt—ge over their more tr—dition—l inorg—ni™ —n—logsF yne of these is to in™orpor—te vihs with the sili™on integr—ted ™ir™uits for interE™hip ™ommuni™—tionF st is di0™ult to ˜uild inorg—ni™ vihs on — sili™on su˜str—teD ˜e™—use of the therm—l stress developing ˜etween the inorg—ni™ vih @usu—lly — sssE† ˜—sed devi™eA —nd the sili™on interf—™eF fut polymer vihs o'er — solutionD sin™e polymers ™—n ˜e e—sily spinE™o—ted on the sili™onF „he oper—ting volt—ge of polymer vih is less th—n R †D —nd the turn on volt—ge ™—n ˜e —s low —s P †F „ogether with — swit™hing time of less th—n SH nsD m—ke polymer vih — perfe™t ™—ndid—teF .2 IH R x IH -4 foreword SD reversed IP V x IH-3 X ‚esults of iodine doping of —n elGwirE€€†Gs„yE˜—sed vihF 2.4 Improvement in internal quantum eciency: doping of polymer hoping is — pro™ess th—t ™re—tes ™—rrier ˜y purposely introdu™ing impurities —nd is very popul—r method in the semi™ondu™tor industryF roweverD this te™hnique w—s not used in polymer vih until IWWSD when — ™oEpolymer polystyreneEpoly@QEhexylthipheneA @€ƒE€Qr„A w—s doped with pegl3.5. hoping of wirE€€† with iodine h—s improved the e0™ien™y ˜y PHH7 —nd the polymer vih ™—n ˜e oper—ted under ˜oth forw—rd —nd reverse ˜i—s @„—˜le PFPAF „he doping is —™™omplsihed ˜y mixing I wt7 wirE€€† with HFP wt7 s2 F „he mol—r r—tio of wirE€€† to s2 is SXIF „h—t is — huge doping  r—tio when you ™omp—re the doping ™on™entr—tion in the semi™ondu™torF Un-doped Doped „urn on volt—ge @†A ixtern—l e0™ien™y @7A Table 2. 2.

24: FTIR as a function of photo-oxidation of PPV.5 Reliability and degradation of polymer LEDs sn terms of the e0™ien™yD ™olor sele™tionD —nd driving volt—geD polymer vih h—ve —tt—ined —dequ—te level for ™ommer™i—liz—tionF roweverD the devi™e lifetime is still f—r from s—tisf—™toryF ‚ese—r™h into underst—nding the reli—˜ility —nd degred—tion me™h—nisms of polymer vihs h—s gener—lly ˜een divided into two —re—X IA €hotoEdegr—d—tion of polymerF PA snterf—™e degr—d—tionF 2. Rothberg.5. F. Lett. Papadimitrakopoulos. Adapted from M. Rev.1 Polymer photo degradation €hotolumines™e™e @€vA studies of the photoEoxid—tion of €€† h—ve ˜een undert—kenD sin™e it is ˜elieves th—t iv is ™losely rel—ted with €vF st w—s found th—t there is — r—pid de™—y in emission when €€† is exposed to oxygenF …sing time resolved p„s‚ spe™tros™opy —n in™re—se in the ™—r˜onyl sign—l —nd — de™re—se in gag sign—l with time @pigure PFPRAF st w—s suggested th—t the ™—r˜onyl group h—s — strong ele™tron —0nity level to ™h—rge tr—nsfer ˜etween mole™ules segment in the polymerD there˜y disso™i—ting the ex™ition —nd quen™hing the €vF Figure 2. J. Yan. 73. M.5.UQ 2.5. ƒimil—r rese—r™h w—s performed ˜y gumpston —nd tensen using fgreE€€† —nd €Qy„ @pigure PFPSA —nd exposing them to dry —ir in …† irr—di—tionF sn fgreE€€†D there is —n in™re—se in ™—r˜onyl sign—l with timeD while the €Qy„ rem—in int—™tF e me™h—nism proposed for the degr—d—tion of fgreE€€† involves the tr—nsfer of energy from the ex™ited triplet st—te of the €€† to oxygen to from singlet oxygen whi™h —tt—™k the vinyl dou˜le ˜ond in the €€† ˜—™k˜oneF end €Qy„ dose not h—s vinyl ˜ond so it ™—n resist the oxid—tion F . Miller.. 1994. Galvin and T. 744. E. M. Phys. L.



Figure 2.25:

Structure of (a) BCHA-PPV and (b) P3OT.

„he rese—r™h des™ri˜ed —˜ove w—s —ll performed on polymer thin (lms deposited on —n inert surf—™eF „he presen™e of ™—thode —nd —node m—y —lso —'e™t the oxid—tion me™h—nismF ƒ™ott et —lF h—ve t—ken s‚ spe™tr— from — wirE€€† vih in the —˜sen™e of oxygenF „hey o˜t—ined simil—r result —s in ‰—n et —lFD howeverD — de™re—se in s„y9s oxygen sign—l w—s noti™ed suggesting th—t the s„y —node —™ts like — oxygen reservoir —nd supplies the oxygen for the degr—d—tion pro™essF Polymer LED interface degradation

„here —re few interf—™e degred—tion studies in polymer vihsF yne of them ˜y ƒ™ott et —lF took ƒiw im—ge of the ™—thode from — f—iled polymer vihF „he polymer vih used s„y —s the —nodeD wirE€€† —s the polymer l—yerD —nd —n —luminum ™—l™ium —lloy —s ™—thodeF ƒiw im—ges showed ™r—ters formed in the ™—thodeF „he ™r—ters —re formed when the ™—thode met—l is melted —nd pull —w—y from the polymer l—yerF st w—s suggested th—t — high ™urrent density will gener—te he—t —nd result in lo™—l hot spotF „he temper—ture in the hot spot is high enough to melt the ™—thodeF end when it meltD it will pull —w—y from the polymerF „his pro™ess will de™re—se the e'e™tive ™—thode —re—D —nd redu™e the lumines™en™e gr—du—llyF

2.5.6 Bibliography
• hF ‚F f—igentD xF gF qreenh—mD tF qrunerD ‚F xF w—rksD ‚F rF priendsD ƒF gF wor—ttiD —nd eF fF rolmesD Synth.Met., IWWRD 67D QF • fF rF gumpston —nd uF pF tensenD Synth. Met., IWWSD 73D IWSF • tF rF furroughesD hF hF gF fr—dleyD eF ‚F frownD ‚F xF w—rksD uF w—™k—yD ‚F rF priendD €F vF furnsD —nd eF fF rolmesD NatureD IWWHD 347D SQWF • xF gF qreenh—mD ƒF gFw—r—ttiD hF hF gF fr—dleyD ‚F rF priendD —nd eF fF rolmesD NatureD IWWQD 365D TPVF • tF qrunerD pF g—™i—lliD sF hF ‡F ƒ—muelD ‚F rF priendD Synth. Met, IWWTD 76, IWUF • wF reroldD tF qmeinerD ‡F ‚iessD —nd wF ƒ™hwoererD Synth. Met.D IWWTD 76D IHWF • ‚F rF tord—nD eF hod—˜—l—purD vF tF ‚oth˜ergD —nd ‚F iF ƒlusherD Proceeding of SPIED IWWUD 3002D WPF


• sF hF €—rker —nd rF rF uimD Appl. Phys. Lett.D IWWRD 64D IUURF • tF gF ƒ™ottD tF u—ufm—nD €F tF fro™kD ‚F hi€ietroD tF ƒ—lemD —nd tF eF qoiti—D J. Appl. Phys.D IWWTD 79D PURSF • wF ƒF ‡e—verD hF qF vidz—eyD „F eF pisherD wF eF €—teD hF y9frienD eF fleyerD eF „—j˜—khshD hF hF gF fr—dleyD wF ƒF ƒkolni™kD —nd qF rillD Thin solid Films, IWWTD 273D QWF • wF ‰—nD vF tF‚oth˜ergD pF €—p—dimitr—kopoulosD wF iF q—lvinD —nd „F wF willerD Phys. Rev. Lett.D IWWRD 73D URRF

2.6 Laser


„his module is —d—pted from the gonnexions module entitled LASER ˜y fill ‡ilsonF

‡h—t is the di'eren™e ˜etween —n vih —nd — solid st—te l—serc „here —re some di'eren™esD ˜ut ˜oth devi™es oper—te on the s—me prin™iple of h—ving ex™ess ele™trons in the ™ondu™tion ˜—nd of — semi™ondu™torD —nd —rr—nging it so th—t the ele™trons re™om˜ine with holes in — r—di—tive f—shionD giving o' light in the pro™essF ‡h—t is di'erent —˜out — l—serc sn —n vihD the ele™trons re™om˜ine in — r—ndom —nd unorg—nized m—nnerF „hey give o' light ˜y wh—t is known —s spontaneous emissionD whi™h simply me—ns th—t the ex—™t time —nd pl—™e where — photon ™omes out of the devi™e is up to e—™h individu—l ele™tronD —nd things h—ppen in — r—ndom w—yF „here is —nother w—y in whi™h —n ex™ited ele™tron ™—n emit — photon howeverF sf — (eld of light @or — set of photonsA h—ppens to ˜e p—ssing ˜y —n ele™tron in — high energy st—teD th—t light (eld ™—n indu™e the ele™tron to emit —n —ddition—l photon through — pro™ess ™—lled stimul—ted emissionF „he photon (eld stimulates the ele™tron to emit its energy —s —n —ddition—l photonD whi™h ™omes out in phase with the stimulating eldF „his is the ˜ig di'eren™e ˜etween incoherent light @wh—t ™omes from —n vih or — )—shlightA —nd coherent light whi™h ™omes from — l—serF ‡ith ™oherent lightD —ll of the ele™tri™ (elds —sso™i—ted with e—™h phonon —re —ll ex—™tly in ph—seF „his ™oheren™e is wh—t en—˜les us to keep — l—ser ˜e—m in tight fo™usD —nd to —llow it to tr—vel — l—rge dist—n™e without mu™h divergen™e or spre—ding outF ƒo how do we restru™ture —n vih so th—t the light is gener—ted ˜y stimul—ted emission r—ther th—n spont—neous emissionc pirstlyD we ˜uild wh—t is ™—lled — heterostru™tureF ell this me—ns is th—t we ˜uild up — s—ndwi™h of somewh—t di'erent m—teri—lsD with di'erent ™h—r—™teristi™sF sn this ™—seD we put two wide ˜—ndEg—p regions —round — region with — n—rrower ˜—nd g—pF „he most import—nt system where this is done is the elq—esGq—es systemF e ˜—nd di—gr—m for su™h — set up is shown in pigure PFPTF elq—es @pronoun™ed 4elEq—s4A h—s — l—rger ˜—ndEg—p then does q—esF „he potenti—l 4well4 formed ˜y the q—es me—ns th—t the ele™trons —nd holes will ˜e ™on(ned thereD —nd —ll of the re™om˜in—tion will o™™ur in — very n—rrow stripF „his gre—tly in™re—ses the ™h—n™es th—t the ™—rriers ™—n inter—™tD ˜ut we still need some w—y for the photons to ˜eh—ve in the proper m—nnerF pigure PFPU is — di—gr—m of wh—t — typi™—l diode might look likeF ‡e h—ve the —™tive q—es l—yer s—ndwi™h inE˜etween the two heterostru™ture ™on(nement l—yersD with — ™ont—™t on top —nd ˜ottomF yn either end of the devi™eD the ™ryst—l h—s ˜een 4™le—ved4 or ˜roken —long — ™ryst—l l—tti™e pl—neF „his results in — shiny 4mirrorElike4 surf—™eD whi™h will re)e™t photonsF „he ˜—™k surf—™e @whi™h we ™—n not see hereA is —lso ™le—ved to m—ke — mirror surf—™eF „he other surf—™es —re purposely roughened so th—t they do not re)e™t lightF xow let us look —t the devi™e from the sideD —nd dr—w just the ˜—nd di—gr—m for the q—es region @pigure PFPVAF ‡e st—rt things o' with —n ele™tron —nd hole re™om˜ining spont—neouslyF „his emits — photon whi™h he—ds tow—rds one of the mirrorsF es the photon goes ˜y other ele™tronsD howeverD it m—y ™—use one of them to de™—y ˜y stimul—ted emissionF „he two @in ph—seA photons hit the mirror —nd —re re)e™ted —nd st—rt ˜—™k the other w—y F es they p—ss —ddition—l ele™tronsD they stimul—te them into — tr—nsition —s wellD —nd the opti™—l (eld within the l—ser st—rts to ˜uild upF efter — ˜itD the photons get down to the other end of the ™—vityF „he ™le—ved f—™etD while it —™ts like — mirrorD is not — perfe™t oneF ƒome light is not re)e™tedD ˜ut r—ther 4le—ks4Y thoughD —nd so ˜e™omes the output ˜e—m from the l—serF „he det—ils of (nding wh—t the r—tio of re)e™ted to tr—nsmitted light is will

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h—ve to w—it until l—ter in the ™ourse when we t—lk —˜out diele™tri™ interf—™esF „he rest of the photons —re re)e™ted ˜—™k into the ™—vity —nd ™ontinue to stimul—te emission from the ele™trons whi™h ™ontinue to enter the g—in region ˜e™—use of the forw—rd ˜i—s on the diodeF

Figure 2.26:

The band diagram for a double heterostructure GaAs/AlGaAs laser.

Figure 2.27:

A schematic diagram of a typical laser diode.


Figure 2.28:

Build up of a photon eld in a laser diode.

sn re—lityD the photons do not move ˜—™k —nd forth in — ˜ig 4™lump4 —s we h—ve des™ri˜ed hereD r—ther they —re distri˜uted uniformly —long the g—in region @pigure PFPWAF „he (eld within the ™—vity will ˜uild up to the point where the loss of energy ˜y light le—king out of the mirrors just equ—ls the r—te —t whi™h energy is repl—™ed ˜y the re™om˜ining ele™tronsF

Figure 2.29:

Output coupling in a diode laser.



2.7 Solar Cells

„his module is —d—pted from the gonnexions module entitled Solar Cells ˜y fill ‡ilsonF

xow let us look —t the opposite pro™ess of light gener—tion for — momentF gonsider the following situ—tion where we h—ve just — pl—in old norm—l pEn jun™tionD only nowD inste—d of —pplying —n extern—l volt—geD we im—gine th—t the jun™tion is ˜eing illumin—ted with light whose photon energy is gre—ter th—n the ˜—ndEg—p @pigure PFQH—AF sn this situ—tionD inste—d of re™om˜in—tionD we will get photoEgener—tion of ele™tron hole p—irsF „he photons simply ex™ite ele™trons from the full st—tes in the v—len™e ˜—ndD —nd 4ki™k4 them up into the ™ondu™tion ˜—ndD le—ving — hole ˜ehindF „his is simili—r to the therm—l ex™it—tion pro™essF es ™—n ˜e seen from pigure PFQH˜D this ™re—tes ex™ess ele™trons in the ™ondu™tion ˜—nd in the pEside of the diodeD —nd ex™ess holes in the v—len™e ˜—nd of the nEsideF „hese ™—rriers ™—n di'use over to the jun™tionD where they will ˜e swept —™ross ˜y the ˜uiltEin ele™tri™ (eld in the depletion regionF sf we were to ™onne™t the two sides of the diode together with — wireD — ™urrent would )ow through th—t wire —s — result of the ele™trons —nd holes whi™h move —™ross the jun™tionF

Figure 2.30:

A schematic representation of a p-n diode under illlumination.

‡hi™h w—y would the ™urrent )owc e qui™k look —t pigure PFQH™ shows th—t holes @positive ™h—rge ™—rriersA gener—ted on the nEside will )o—t up to the pEside —s they go —™ross the jun™tionF ren™e positive ™urrent must ˜e ™oming out of the —nodeD or pEside of the jun™tionF vikewiseD ele™trons gener—ted on the pEside will f—ll down the jun™tion potenti—lD —nd ™ome out the nEsideD ˜ut sin™e they h—ve neg—tive ™h—rgeD this )ow represents ™urrent going into the ™—thodeF ‡e h—ve ™onstru™ted — photovoltaic diodeD or solar cellF

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UW pigure PFQI is — pi™ture of wh—t this would look like s™hem—ti™—llyF ‡e might like to ™onsider the possi˜ility of using this devi™e —s — sour™e of energyD ˜ut the w—y we h—ve things set up nowD sin™e the volt—ge —™ross the diode is zeroD —nd sin™e power equ—ls ™urrent times volt—geD we see th—t we —re getting n—d— from the ™ellF ‡h—t we needD o˜viouslyD is — lo—d resistorD so let9s put one inF st should ˜e ™le—r from pigure PFQP th—t the photo ™urrent )owing through the lo—d resistor will develop — volt—ge whi™h it ˜i—ses the diode in the forw—rd dire™tionD whi™hD of ™ourse will ™—use ™urrent to )ow ˜—™k into the —nodeF „his ™ompli™—tes thingsD it seems we h—ve ™urrent ™oming out of the diode —nd ™urrent going into the diode —ll —t the s—me time3 row —re we going to (gure out wh—t is going onc

Figure 2.31:

Schematic representation of a photovoltaic cell.

Figure 2.32:

Photovoltaic cell with a load resistor.

„he —nswer is to m—ke — modelF „he ™urrent whi™h —rises due to the photon )ux ™—n ˜e ™onveniently represented —s — ™urrent sour™eF ‡e ™—n le—ve the diode —s — diodeD —nd we h—ve the ™ir™uit shown in pigure PFQQF iven though we show sout ™oming out of the devi™eD we know ˜y the usu—l pol—rity ™onvention th—t when we de(ne †out —s ˜eing positive —t the topD then we should show the ™urrent for the photovolt—i™D spv —s ™urrent going into the topD whi™h is wh—t w—s done in pigure PFQQF xote th—t spv a sdiode E sphoto D so —ll we need to do is to su˜tr—™t the two ™urrentsY we do this gr—phi™—lly in pigure PFQRF xote th—t we h—ve num˜ered the four qu—dr—nts in the sE† plot of the tot—l €† ™urrentF sn qu—dr—nt s —nd sssD the produ™t of I —nd V is — positive num˜erD me—ning th—t power is ˜eing dissip—ted in the ™ellF por qu—dr—nt ss —nd s†D the

VH CHAPTER 2. . DEVICE FUNDAMENTALS produ™t of I —nd V is neg—tiveD —nd so we —re getting power from the devi™eF gle—rly we w—nt to oper—te in qu—dr—nt s†F sn f—™tD without the —ddition of —n extern—l ˜—ttery or ™urrent sour™eD the ™ir™uitD will only run in the s†9th qu—dr—ntF gonsider —djusting ‚L D the lo—d resistor from H @— shortA to ∞ @—n openAF ‡ith ‚L D we would ˜e —t point e on pigure PFQRF es ‚L st—rts to in™re—se from zeroD the volt—ge —™ross ˜oth the diode —nd the resistor will st—rt to in™re—se —lsoD —nd we will move to point fD s—yF es ‚L gets ˜igger —nd ˜iggerD we keep moving —long the ™urve untilD —t point gD where ‚L is —n open —nd we h—ve the m—ximum volt—ge —™ross the devi™eD ˜utD of ™ourseD no ™urrent ™oming out3 Figure 2.33: A model of a PV cell.

€ower is V I so —t f for inst—n™eD the power ™oming out would ˜e represented ˜y the —re— en™losed ˜y the two dotted lines —nd the ™oordin—te —xesF ƒomepl—™e —˜out where s h—ve point f would ˜e where we would ˜e getting the most power out of out sol—r ™ellF pigure PFQS shows you wh—t — re—l sol—r ™ell would look likeF „hey —re usu—lly m—de from — ™omplete w—fer of sili™onD to m—ximize the us—˜le —re—F e sh—llow @HFPS µmA jun™tion is m—de on the topD —nd top ™ont—™ts —re —pplied —s stripes of met—l ™ondu™tor —s shownF en —ntiEre)e™tion @e‚A ™o—ting is —pplied on top of th—tD whi™h —™™ounts for the ˜luish ™olor whi™h — typi™—l sol—r ™ell h—s @pigure PFQTAF .34: Combining the diode and the current source.VI Figure 2.

36: A solar cell showing the blue tint due to the AR coating. „he sol—r power )ux on the e—rth9s surf—™e is @™onvenientlyA —˜out I k‡Gm2 or IHH m‡G™m2 F ƒo if we m—de — sol—r ™ell from — R in™h di—meter w—fer @typi™—lA it would h—ve —n —re— of —˜out 81cm2 —nd so would ˜e re™eiving — )ux of —˜out VFI ‡—ttsF „ypi™—l ™ell e0™ien™ies run from —˜out IH7 to m—y˜e IS7 unless spe™i—l @—nd ™ostlyA tri™ks —re m—deF „his me—ns th—t we will get —˜out IFP ‡—tts out from — single w—ferF vooking —t f on PFSW we ™ould guess th—t Vout will ˜e —˜out HFS to HFT voltsD thus we ™ould expe™t to get m—y˜e —round PFS —mps from — R in™h w—fer —t HFS volts with IS7 e0™ien™y under the illumin—tion of one .VP CHAPTER 2. Figure 2.35: A schematic diagram of a real solar cell. DEVICE FUNDAMENTALS Figure 2.

VQ sunF .


M Observed properties of gallium (discovered 1875) 1 etomi™ weight hensityD gF™m-3 welting point †—por pressure †—len™e yxide hensity of oxide @gG™m3 A ™—F TV SFW vow xonEvol—tile Q w2 y3 SFS TWFUP SFWHR PWFUV IH-3 mmrgD IHHH ◦ g Q q—2 y3 SFVV continued on next page 1 This content is available online at <http://cnx.7/>. VS .1 Properties of Gallium Arsenide 3.Chapter 3 Bulk Materials Gallium: the element „he element g—llium w—s predi™tedD —s ek—E—luminumD ˜y wendeleev in IVUHD —nd su˜sequently dis™overed ˜y ve™oq de fois˜—udr—n in IVUSY in f—™t de fois˜—udr—n h—d ˜een se—r™hing for the missing element for some ye—rsD ˜—sed on his own independent theoryF „he (rst experiment—l indi™—tion of g—llium ™—me with the o˜serv—tion of two new violet lines in the sp—rk spe™trum of — s—mple deposited on zin™F ‡ithin — month of these initi—l results de fois˜—udr—n h—d isol—ted I g of the met—l st—rting from sever—l hundred kilogr—ms of ™rude zin™ ˜lende oreF „he new element w—s n—med in honor of pr—n™e @v—tin GalliaAD —nd the striking simil—rity of its physi™—l —nd ™hemi™—l properties to those predi™ted ˜y wendeleev @„—˜le QFIA did mu™h to est—˜lish the gener—l —™™ept—n™e of the periodi™ v—wY indeedD when de fois˜—udr—n (rst st—ted th—t the density of q— w—s RFU gG™m3 r—ther th—n the predi™ted SFW gG™m3 D wendeleev wrote to him suggesting th—t he redetermine the v—lue @the ™orre™t v—lue is SFWHR gG™m3 AF Property Mendeleev's prediction (1871) for eka-aluminum.

VT €roperties of met—l €roperties of hydroxide €roperties of s—lts w should dissolve slowly in —™ids —nd —lk—lis —nd ˜e st—˜le in —ir w@yrA3 should dissolve in ˜oth —™ids —nd —lk—lis w s—lts will tend to form ˜—E si™ s—ltsY the sulf—te should form —lumsY w2 ƒ3 should ˜e pre™ipE it—ted ˜y r2 ƒ or @xr4 A2 ƒY —nE hydrous wgl3 should ˜e more vol—tile th—n ngl2

q— met—l dissolves slowly in —™ids —nd —lk—lis —nd is st—˜le in —ir q—@yrA3 dissolves in ˜oth —™ids —nd —lk—lis q— s—lts re—dily hydrolyze —nd form ˜—si™ s—ltsY —lums —re knownY q—2 ƒ3 ™—n ˜e pre™ipE it—ted under spe™i—l ™onditions ˜y r2 ƒ or @xr4 A2 ƒD —nhydrous q—gl3 is more vol—tile th—n ngl2 F

Table 3.1

X gomp—rison of predi™ted —nd o˜served properties of g—lliumF

q—llium h—s — ˜e—utiful silvery ˜lue —ppe—r—n™eY it wets gl—ssD por™el—inD —nd most other surf—™es @ex™ept qu—rtzD gr—phiteD —nd „e)on A —nd forms — ˜rilli—nt mirror when p—inted on to gl—ssF „he —tomi™ r—dius —nd (rst ioniz—tion potenti—l of g—llium —re —lmost identi™—l with those of —luminum —nd the two elements frequently resem˜le e—™h other in ™hemi™—l propertiesF foth —re —mphoteri™D ˜ut g—llium is less ele™tropositive —s indi™—ted ˜y its lower ele™trode potenti—lF hi'eren™es in the ™hemistry of the two elements ™—n ˜e rel—ted to the presen™e of — (lled set of Qd or˜it—ls in g—lliumF q—llium is very mu™h less —˜und—nt th—n —luminum —nd tends to o™™ur —t low ™on™entr—tions in sul(de miner—ls r—ther th—n —s oxidesD —lthough g—llium is —lso found —sso™i—ted with —luminum in ˜—uxiteF „he m—in sour™e of g—llium is —s — ˜yEprodu™t of —luminum re(ningF et IW ppm of the e—rth9s ™rustD g—llium is —˜out —s —˜und—nt —s nitrogenD lithium —nd le—dY it is twi™e —s —˜und—nt —s ˜oron @W ppmAD ˜ut is more di0™ult to extr—™t due to the l—™k of —ny m—jor g—lliumE™ont—ining oreF q—llium —lw—ys o™™urs in —sso™i—tion either with zin™ or germ—niumD its neigh˜ors in the periodi™ t—˜leD or with —luminum in the s—me groupF „husD the highest ™on™entr—tions @HFI E I7A —re in the r—re miner—l germ—nite @— ™omplex sul(de of nD guD qeD —nd esAY ™on™entr—tions in sph—lerite @nƒAD ˜—uxiteD or ™o—lD —re — hundredEfold lessF


3.1.2 Gallium pnictides
q—llium9s m—in use is in semi™ondu™tor te™hnologyF por ex—mpleD q—es —nd rel—ted ™ompounds ™—n ™onvert ele™tri™ity dire™tly into ™oherent light @l—ser diodesA —nd is employed in ele™trolumines™ent lightEemitting diodes @vih9sAY it is —lso used for doping other semi™ondu™tors —nd in solidEst—te devi™es su™h —s heteroE jun™tion ˜ipol—r tr—nsistors @rf„sA —nd high power high speed met—l semi™ondu™tor (eld e'e™t tr—nsistors @wiƒpi„sAF „he ™ompound wgq—2 y4 is used in ultr—violetE—™tiv—ted powders —s — ˜rilli—nt green phosphor used in ˆerox ™opying m—™hinesF winor uses —re —s highEtemper—ture liquid se—lsD m—nometri™ )uids —nd he—tEtr—nsfer medi—D —nd for lowEtemper—ture soldersF …ndou˜tedly the ˜in—ry ™ompounds of g—llium with the most industri—l interest —re those of the qroup IS @†A elementsD q—i @i a xD €D esD ƒ˜AF „he ™ompounds whi™h g—llium forms with nitrogenD phosphorusD —rseni™D —nd —ntimony —re isoele™troni™ with the qroup IR elementsF „here h—s ˜een ™onsider—˜le interestD p—rti™ul—rly in the physi™—l properties of these ™ompoundsD sin™e IWSP when ‡elker (rst showed th—t they h—d semi™ondu™ting properties —n—logous to those of sili™on —nd germ—niumF q—llium phosphideD —rsenideD —nd —ntimonide ™—n —ll ˜e prep—red ˜y dire™t re—™tion of the elementsY this is norm—lly done in se—led sili™— tu˜es or in — gr—phite ™ru™i˜le under hydrogenF €h—se di—gr—m d—t— is h—rd to o˜t—in in the g—lliumEphosphorus system ˜e™—use of loss of phosphorus from the ˜ulk m—teri—l —t elev—ted temper—turesF „husD q—€ h—s — v—por pressure of more th—n IQFS —tm —t its melting pointY —s ™omp—red to HFVW —tm for q—esF „he physi™—l properties of these three ™ompounds —re ™omp—red with those of the nitride in „—˜le QFPF ell three —dopt the zin™ ˜lende ™ryst—l stru™ture —nd —re more highly ™ondu™ting th—n g—llium nitrideF







welting point @ ◦ gA hensity @gG™m A gryst—l stru™ture gell dimenF @ÅA k @ohm-1 ™m-1 A f—nd g—p @e†A
Table 3.2

> IPSH @de™A
™—F TFI ‡urtzite ¨

IQSH RFIQV zin™ ˜lende

IPRH SFQIUT zin™ ˜lende

UIP SFTIQU zin™ ˜lende


a b





‚efr—™tive index

X €hysi™—l properties of IQEIS ™ompound semi™ondu™torsF a †—lues given for QHH uF b hependent on photon energyY v—lues given for IFS e† in™ident photonsF c hependent on temper—tureY v—lues given for QHH uF

3.1.3 Gallium arsenide versus silicon
q—llium —rsenide is — ™ompound semi™ondu™tor with — ™om˜in—tion of physi™—l properties th—t h—s m—de it —n —ttr—™tive ™—ndid—te for m—ny ele™troni™ —ppli™—tionsF prom — ™omp—rison of v—rious physi™—l —nd ele™troni™ properties of q—es with those of ƒi @„—˜le QFQA the —dv—nt—ges of q—es over ƒi ™—n ˜e re—dily —s™ert—inedF …nfortun—telyD the m—ny desir—˜le properties of g—llium —rsenide —re o'set to — gre—t extent ˜y — num˜er of undesir—˜le propertiesD whi™h h—ve limited the —ppli™—tions of q—es ˜—sed devi™es to d—teF
Properties GaAs Si

pormul— weight gryst—l stru™ture v—tti™e ™onst—nt welting point @ gA



hensity @gG™m A „herm—l ™ondu™tivity @‡G™mFuA f—nd g—p @e†A —t QHH u sntrinsi™ ™—rrier ™on™F @™m-3 A sntrinsi™ resistivity @ohmF™mA fre—kdown (eld @†G™mA winority ™—rrier lifetime @sA wo˜ility @™m2 G†FsA
Table 3.3


X gomp—rison of physi™—l —nd semi™ondu™tor properties of q—es —nd ƒiF Band gap

„he ˜—nd g—p of q—es is IFRP e†Y resulting in photon emission in the infr—Ered r—ngeF elloying q—es with el to give elx q—1-x es ™—n extend the ˜—nd g—p into the visi˜le red r—ngeF …nlike ƒiD the ˜—nd g—p of q—es



is dire™tD iFeFD the tr—nsition ˜etween the v—len™e ˜—nd m—ximum —nd ™ondu™tion ˜—nd minimum involves no momentum ™h—nge —nd hen™e does not require — ™oll—˜or—tive p—rti™le inter—™tion to o™™urF €hoton gener—tion ˜y interE˜—nd r—di—tive re™om˜in—tion is therefore possi˜le in q—esF ‡here—s in ƒiD with —n indire™t ˜—ndEg—pD this pro™ess is too ine0™ient to ˜e of useF „he —˜ility to ™onvert ele™tri™—l energy into light forms the ˜—sis of the use of q—esD —nd its —lloysD in optoele™troni™sY for ex—mple in light emitting diodes @vihsAD solid st—te l—sers @light —mpli(™—tion ˜y the stimul—ted emission of r—di—tionAF e signi(™—nt dr—w˜—™k of sm—ll ˜—nd g—p semi™ondu™torsD su™h —s ƒiD is th—t ele™trons m—y ˜e therm—lly promoted from the v—len™e ˜—nd to the ™ondu™tion ˜—ndF „husD with in™re—sing temper—ture the therm—l gener—tion of ™—rriers eventu—lly ˜e™omes domin—nt over the intention—lly doped level of ™—rriersF „he wider ˜—nd g—p of q—es gives it the —˜ility to rem—in 9intention—lly9 semi™ondu™ting —t higher temper—turesY q—es devi™es —re gener—lly more st—˜le to high temper—tures th—n — simil—r ƒi devi™esF Carrier density

„he low intrinsi™ ™—rrier density of q—es in — pure @undopedA form indi™—tes th—t q—es is intrinsi™—lly — very poor ™ondu™tor —nd is ™ommonly referred to —s ˜eing semiEinsul—tingF „his property is usu—lly —ltered ˜y —dding dop—nts of either the pE @positiveA or nE @neg—tiveA typeF „his semiEinsul—ting property —llows m—ny —™tive devi™es to ˜e grown on — single su˜str—teD where the semiEinsul—ting q—es provides the ele™tri™—l isol—tion of e—™h devi™eY —n import—nt fe—ture in the mini—turiz—tion of ele™troni™ ™ir™uitryD iFeFD †vƒs @veryE l—rgeEs™—leEintegr—tionA involving over IHHDHHH ™omponents per ™hip @one ™hip is typi™—lly ˜etween I —nd IH mm squ—reAF Electron mobility

„he higher ele™tron mo˜ility in q—es th—n in ƒi potenti—lly me—ns th—t in devi™es where ele™tron tr—nsit time is the ™riti™—l perform—n™e p—r—meterD q—es devi™es will oper—te with higher response times th—n equiv—lent ƒi devi™esF roweverD the f—™t th—t hole mo˜ility is simil—r for ˜oth q—es —nd ƒi me—ns th—t devi™es relying on ™ooper—tive ele™tron —nd hole movementD or hole movement —loneD show no improvement in response time when q—es ˜—sedF Crystal growth

„he ˜ulk ™ryst—l growth of q—es presents — pro˜lem of stoi™hiometri™ ™ontrol due the lossD ˜y ev—por—tionD of —rseni™ ˜oth in the melt —nd the growing ™ryst—l @> ca. THH ◦ gAF welt growth te™hniques —reD thereforeD designed to en—˜le —n overpressure of —rseni™ —˜ove the melt to ˜e m—int—inedD thus preventing ev—por—tive lossesF „he loss of —rseni™ —lso neg—tes di'usion te™hniques ™ommonly used for w—fer doping in ƒi te™hnologyY sin™e the di'usion temper—tures required ex™eed th—t of —rseni™ lossF Crystal Stress

„he therm—l gr—dient —ndD hen™eD stress gener—ted in melt grown ™ryst—ls h—ve limited the m—ximum di—meter of q—es w—fers @™urrently T4 di—meter ™omp—red to over IP4 for ƒiAD ˜e™—use with in™re—sed w—fer di—meters the therm—l stress gener—ted dislo™—tion @™ryst—l imperfe™tionsA densities eventu—lly ˜e™omes un—™™ept—˜le for devi™e —ppli™—tionsF Physical strength

q—llium —rsenide single ™ryst—ls —re very ˜rittleD requiring th—t ™onsider—˜ly thi™ker su˜str—tes th—n those employed for ƒi devi™esF

VW Native oxide

q—llium —rsenide9s n—tive oxide is found to ˜e — mixture of nonEstoi™hiometri™ g—llium —nd —rseni™ oxides —nd element—l —rseni™F „husD the ele™troni™ ˜—nd stru™ture is found to ˜e severely disrupted ™—using — ˜re—kdown in 9norm—l9 semi™ondu™tor ˜eh—vior on the q—es surf—™eF es — ™onsequen™eD the q—es wsƒpi„ @met—lEinsul—torEsemi™ondu™torE(eldEe'e™tEtr—nsistorA equiv—lent to the te™hnologi™—lly import—nt ƒi ˜—sed wyƒpi„ @met—lEoxideEsemi™ondu™torE(eldEe'e™tEtr—nsistorA isD thereforeD presently un—v—il—˜leF „he p—ssiv—tion of the surf—™e of q—es is therefore — key issue when ende—voring to utilize the pi„ te™hnology using q—esF €—ssiv—tion in this dis™ussion me—ns the redu™tion in midEg—p ˜—nd st—tes whi™h destroy the semi™ondu™ting properties of the m—teri—lF eddition—llyD this —lso me—ns the produ™tion of — ™hemi™—lly inert ™o—ting whi™h prevents the form—tion of —ddition—l re—™tive st—tesD whi™h ™—n e'e™t the properties of the devi™eF

3.1.4 Bibliography
• ƒF uF qh—ndhiD VLSI Fabrication Principles: Silicon and Gallium Arsenide. ‡ileyEsnters™ien™eD xew ‰orkD @IWWRAF • Properties of Gallium Arsenide. idF wF ‚F frozel —nd qF iF ƒtillm—nF Qrd idF snstitution of ile™tri™—l ingineersD vondon @IWWTAF

3.2 Synthesis and Purication of Bulk Semiconductors
3.2.1 Introduction


„he synthesis —nd puri(™—tion of ˜ulk poly™ryst—lline semi™ondu™tor m—teri—l represents the (rst step tow—rds the ™ommer™i—l f—˜ri™—tion of —n ele™troni™ devi™eF „his poly™ryst—lline m—teri—l is then used —s the r—w m—teri—l for the form—tion of single ™ryst—l m—teri—l th—t is pro™essed to semi™ondu™tor w—fersF „he strong in)uen™e on the ele™tri™ ™h—r—™teristi™s of — semi™ondu™tors exhi˜ited ˜y sm—ll —mounts of some impurities requires th—t the ˜ulk r—w m—teri—l ˜e of very high purity @> WWFWWWW7AF elthough some level of puri(™—tion is possi˜le during the ™ryst—lliz—tion pro™ess it is import—nt to use —s high — purity st—rting m—teri—l —s possi˜leF ‡hile — wide r—nge of su˜str—te m—teri—ls —re —v—il—˜le from ™ommer™i—l vendorsD sili™on —nd q—es represent the only l—rgeEs™—le ™ommer™i—l semi™ondu™tor su˜str—tesD —nd thus the dis™ussion will ˜e limited to the synthesis —nd puri(™—tion of these m—teri—lsF

3.2.2 Silicon
pollowing oxygen @RT7AD sili™on @vF sili™is )intA is the most —˜und—nt element in the e—rth9s ™rust @PV7AF roweverD sili™on does not o™™ur in its element—l formD ˜ut —s its oxide @ƒiy2 A or —s sili™—tesF ƒ—ndD qu—rtzD —methystD —g—teD )intD —nd op—l —re some of the forms in whi™h the oxide —ppe—rsF qr—niteD horn˜lendeD —s˜estosD feldsp—rD ™l—y —nd mi™—D et™F —re — few of the numerous sili™—te miner—lsF ‡ith su™h ˜oundless supplies of the r—w m—teri—lD the ™osts —sso™i—ted with the produ™tion of ˜ulk sili™on is not one of —˜str—™tion —nd ™onversion of the oxide@sAD ˜ut of puri(™—tion of the ™rude element—l sili™onF ‡hile WV7 element—l sili™onD known —s met—llurgi™—lEgr—de sili™on @wqƒAD is re—dily produ™ed on — l—rge s™—leD the requirements of extreme purity for ele™troni™ devi™e f—˜ri™—tion require —ddition—l puri(™—tion steps in order to produ™e ele™troni™Egr—de sili™on @iqƒAF ile™troni™Egr—de sili™on is —lso known —s semi™ondu™torEgr—de sili™on @ƒqƒAF sn order for the purity levels to ˜e —™™ept—˜le for su˜sequent ™ryst—l growth —nd devi™e f—˜ri™—tionD iqƒ must h—ve ™—r˜on —nd oxygen impurity levels less th—n — few p—rts per million @ppmAD —nd met—l impurities —t the p—rts per ˜illion @pp˜A r—nge or lowerF „—˜le QFR —nd „—˜le QFS give typi™—l impurity ™on™entr—tions in wqƒ —nd iqƒD respe™tivelyF fesides the purityD the produ™tion ™ost —nd the spe™i(™—tions must meet the industry desiresF

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Element Concentration (ppm) Element Concentration (ppm)

—luminum ˜oron ™—l™ium ™hromium ™opper iron m—gnesium
Table 3.4


m—ng—nese moly˜denum ni™kel phosphorus tit—nium v—n—dium zir™onium


< PH

X „ypi™—l impurity ™on™entr—tions found in met—llurgi™—lEgr—de sili™on @wqƒAF
Concentration (ppb) Element Concentration (ppb)


—rseni™ —ntimony ˜oron ™—r˜on ™hromium ™o˜—lt ™opper
Table 3.5


gold iron ni™kel oxygen phosphorus silver zin™





X „ypi™—l impurity ™on™entr—tions found in ele™troni™Egr—de sili™on @iqƒAF Metallurgical-grade silicon (MGS)

„he typi™—l sour™e m—teri—l for ™ommer™i—l produ™tion of element—l sili™on is qu—rtzite gr—velY — rel—tively pure form of s—nd @ƒiy2 AF „he (rst step in the synthesis of sili™on is the melting —nd redu™tion of the sili™— in — su˜mergedEele™trode —r™ furn—™eF en ex—mple of whi™h is shown s™hem—ti™—lly in pigure QFID —long with the —ppropri—te ™hemi™—l re—™tionsF e mixture of qu—rtzite gr—vel —nd ™—r˜on —re he—ted to high temper—tures @™—F IVHH ◦ gA in the furn—™eF „he ™—r˜on ˜ed ™onsists of — mixture of ™o—lD ™okeD —nd wood ™hipsF „he l—tter providing the ne™ess—ry porosity su™h th—t the g—ses ™re—ted during the re—™tion @ƒiy —nd gyA —re —˜le to )ow through the ˜edF


Schematic of submerged-electrode arc furnace for the production of metallurgical-grade silicon (MGS).
Figure 3.1:

„he over—ll redu™tion re—™tion of ƒiy2 is expressed in @QFIAD howeverD the re—™tion sequen™e is more ™omplex th—n this over—ll re—™tion impliesD —nd involves the form—tion of ƒig —nd ƒiy intermedi—tesF „he initi—l re—™tion ˜etween molten ƒiy2 —nd g @@QFPAA t—kes pl—™e in the —r™ ˜etween —dj—™ent ele™trodesD where the lo™—l temper—ture ™—n ex™eed PHHH ◦ gF „he ƒiy —nd gy thus gener—ted )ow to ™ooler zones in the furn—™e where ƒig is formed @@QFQAAD or higher in the ˜ed where they reform ƒiy2 —nd g @@QFPAAF „he ƒig re—™ts with molten ƒiy2 @@QFRAA produ™ing the desired sili™on —long with ƒiy —nd gyF „he molten sili™on formed is dr—wnEo' from the furn—™e —nd solidi(edF @QFIA



@QFRA „he —sEprodu™ed wqƒ is —pproxim—tely WVEWW7 pureD with the m—jor impurities ˜eing —luminum —nd iron @„—˜le QFRAD howeverD o˜t—ining low levels of ˜oron impurities is of p—rti™ul—r import—n™eD ˜e™—use it is di0™ult to remove —nd serves —s — dop—nt for sili™onF „he dr—w˜—™ks of the —˜ove pro™ess —re th—t it is energy —nd r—w m—teri—l intensiveF st is estim—ted th—t the produ™tion of one metri™ ton @IDHHH kgA of wqƒ requires PSHHEPUHH kg qu—rtziteD THH kg ™h—r™o—lD THHEUHH kg ™o—l or ™okeD QHHESHH kg wood ™hipsD —nd SHHDHHH k‡h

2. BULK MATERIALS of ele™tri™ powerF gurrentlyD —pproxim—tely SHHDHHH metri™ tons of wqƒ —re produ™ed per ye—rD worldwideF wost of the produ™tion @™—F UH7A is used for met—llurgi™—l —ppli™—tions @eFgFD —luminumEsili™on —lloys —re ™ommonly used for —utomotive engine ˜lo™ksA from when™e its n—me is derivedF eppli™—tions in — v—riety of ™hemi™—l produ™ts su™h —s sili™one resins —™™ount for —˜out QH7D —nd only I7 or less of the tot—l produ™tion of wqƒ is used in the m—nuf—™turing of highEpurity iqƒ for the ele™troni™s industryF „he ™urrent worldwide ™onsumption of iqƒ is —pproxim—tely S x IH6 kg per ye—rF 3.2 Electronic-grade silicon (EGS) ile™troni™Egr—de sili™on @iqƒA is — poly™ryst—lline m—teri—l of ex™eption—lly high purity —nd is the r—w m—teE ri—l for the growth of singleE™ryst—l sili™onF iqƒ is one of the purest m—teri—ls ™ommonly —v—il—˜leD see „—˜le QFSF „he form—tion of iqƒ from wqƒ is —™™omplished through ™hemi™—l puri(™—tion pro™essesF „he ˜—si™ ™on™ept of whi™h involves the ™onversion of wqƒ to — vol—tile sili™on ™ompoundD whi™h is puri(ed ˜y distilE l—tionD —nd su˜sequently de™omposed to reEform element—l sili™on of higher purity @iFeFD iqƒAF srrespe™tive of the puri(™—tion route employedD the (rst step is physi™—l pulveriz—tion of wqƒ followed ˜y its ™onversion to the vol—tile sili™on ™ompoundsF e num˜er of ™ompoundsD su™h —s monosil—ne @ƒir4 AD di™hlorosil—ne @ƒir2 gl2 AD tri™hlorosil—ne @ƒirgl3 AD —nd sili™on tetr—™hloride @ƒigl4 AD h—ve ˜een ™onsidered —s ™hemi™—l intermedi—tesF emong theseD ƒirgl3 h—s ˜een used predomin—ntly —s the intermedi—te ™ompound for su˜sequent iqƒ form—tionD —lthough ƒir4 is used to — lesser extentF ƒili™on tetr—™hloride —nd its lower ™hlorin—ted deriv—tives —re used for the ™hemi™—l v—por deposition @g†hA growth of ƒi —nd ƒiy2 F „he ˜oiling points of sil—ne —nd its ™hlorin—ted produ™ts @„—˜le QFTA —re su™h th—t they —re ™onveniently sep—r—ted from e—™h other ˜y fr—™tion—l distill—tionF Compound Boiling point ( ◦ C) ƒir4 ƒir3 gl ƒir2 gl2 ƒirgl3 ƒigl4 Table 3.6 EIIPFQ EQHFR VFQ QIFS SUFT X foiling points of sil—ne —nd ™hlorosil—nes —t UTH mmrg @I —tmosphereAF „he re—sons for the predomin—nt use of ƒirgl3 in the synthesis of iqƒ —re —s followsX IF ƒirgl3 ™—n ˜e e—sily formed ˜y the re—™tion of —nhydrous hydrogen ™hloride with wqƒ —t re—son—˜ly low temper—tures @PHH E RHH ◦ gAY PF it is liquid —t room temper—ture so th—t puri(™—tion ™—n ˜e —™™omplished using st—nd—rd distill—tion te™hniquesY QF it is e—sily h—ndled —nd if dry ™—n ˜e stored in ™—r˜on steel t—nksY RF its liquid is e—sily v—porized —ndD when mixed with hydrogen it ™—n ˜e tr—nsported in steel lines without ™orrosionY SF it ™—n ˜e redu™ed —t —tmospheri™ pressure in the presen™e of hydrogenY TF its deposition ™—n t—ke pl—™e on he—ted sili™onD thus elimin—ting ™ont—™t with —ny foreign surf—™es th—t m—y ™ont—min—te the resulting sili™onY —nd UF it re—™ts —t lower temper—tures @IHHH E IPHH ◦ gA —nd —t f—ster r—tes th—n does ƒigl4 F .WP CHAPTER 3.2.

„he shift in the equili˜rium from forming ƒirgl3 from ƒi —t low temper—tureD to forming ƒi from ƒirgl3 —t high temper—ture is —s — ™onsequen™e of the temper—ture dependen™e @@QFTAA of the equili˜rium ™onst—nt @@QFUAD where ρ a p—rti—l pressureA for @QFSAF ƒin™e the form—tion of ƒirgl3 is exothermi™D iFeFD ∆r < HD —n in™re—se in the temper—ture ™—uses the p—rti—l pressure of ƒirgl3 to de™re—seF „husD the ƒiemens pro™ess is typi™—lly run —t ™—F IIHH ◦ gD while the reverse )uidized ˜ed pro™ess is ™—rried out —t QHH ◦ gF @QFTA .2.WQ 3.2.1 Chlorosilane (Seimens) process „ri™hlorosil—ne is synthesized ˜y he—ting powdered wqƒ with —nhydrous hydrogen ™hloride @rglA —t —round QHH ◦ g in — )uidizedE˜ed re—™torD @QFSAF @QFSA ƒin™e the re—™tion is —™tu—lly —n equili˜rium —nd the form—tion of ƒirgl3 highly exothermi™D e0™ient remov—l of gener—ted he—t is essenti—l to —ssure — m—ximum yield of ƒirgl3 F ‡hile the stoi™hiometri™ re—™tion is th—t shown in iqF SD — mixture of ™hlorin—ted sil—nes is —™tu—lly prep—red whi™h must ˜e sep—r—ted ˜y fr—™tion—l distill—tionD —long with the ™hlorides of —ny impuritiesF sn p—rti™ul—r ironD —luminumD —nd ˜oron —re removed —s pegl3 @˜FpF a QIT ◦ gAD elgl3 @mFpF a IWH ◦ g su˜lFAD —nd fgl3 @˜FpF a IPFTS ◦ gAD respe™tivelyF pr—™tion—l distill—tion of ƒirgl3 from these impurity h—lides result in gre—tly in™re—sed purity with — ™on™entr—tion of ele™tri™—lly —™tive impurities of less th—n I pp˜F iqƒ is prep—red from puri(ed ƒirgl3 in — ™hemi™—l v—por deposition @g†hA pro™ess simil—r to the epiE t—xi—l growth of ƒiF „he highEpurity ƒirgl3 is v—porizedD diluted with highEpurity hydrogenD —nd introdu™ed into the ƒeimens deposition re—™torD shown s™hem—ti™—lly in pigure QFPF ‡ithin the re—™torD thin sili™on rods ™—lled slim rods @™—F R mm di—meterA —re supported ˜y gr—phite ele™trodesF ‚esist—n™e he—ting of the slim rods ™—uses the de™omposition of the ƒirgl3 to yield sili™onD —s des™ri˜ed ˜y the reverse re—™tion shown in iqF SF Figure 3.2: Schematic representation of a Seimens deposition reactor.2.

Figure 3.3: .WR CHAPTER 3. BULK MATERIALS @QFUA „he slim rods —™t —s — nu™le—tion point for the deposition of sili™onD —nd the resulting poly™ryst—lline rod ™onsists of ™olumn—r gr—ins of sili™on @polysili™onA grown perpendi™ul—r to the rod —xisF qrowth o™™urs —t less th—n I mm per hourD —nd —fter deposition for PHH to QHH hours highEpurity @iqƒA polysili™on rods of ISHEPHH mm in di—meter —re produ™edF por su˜sequent )o—tEzone re(ning the polysili™on iqƒ rods —re ™ut into long ™ylindri™—l rodsF eltern—tivelyD the —sEformed polysili™on rods —re ˜roken into ™hunks for single ™ryst—l growth pro™essesD for ex—mple gzo™hr—lski melt growthF sn —ddition to the form—tion of sili™onD the rgl ™oprodu™t re—™ts with the ƒirgl3 re—™t—nt to form sili™on tetr—™hloride @ƒigl4 A —nd hydrogen —s m—jor ˜yprodu™ts of the pro™essD @QFVAF „his re—™tion represents — m—jor dis—dv—nt—ge with the ƒeimens pro™essX poor e0™ien™y of sili™on —nd ™hlorine ™onsumptionF „ypi™—llyD only QH7 of the sili™on introdu™ed into g†h re—™tor is ™onverted into highEpurity polysili™onF @QFVA sn order to improve e0™ien™y the rglD ƒigl4 D r2 D —nd unre—™ted ƒirgl3 —re sep—r—ted —nd re™overed for re™y™lingF pigure QFQ illustr—tes the entire ™hlorosil—ne pro™ess st—rting with wqƒ —nd in™luding the re™y™ling of the re—™tion ˜yprodu™ts to —™hieve high over—ll pro™ess e0™ien™yF es — ™onsequen™eD the produ™tion ™ost of highEpurity iqƒ depends on the ™ommer™i—l usefulness of the ˜yprodu™tD ƒigl4 F eddition—l dis—dv—nt—ges of the ƒeimens pro™ess —re derived from its rel—tively sm—ll ˜—t™h sizeD slow growth r—teD —nd high power ™onsumptionF „hese issues h—ve le—d to the investig—tion of —ltern—tive ™ost e0™ient routes to iqƒF Schematic representation of the reaction pathways for the formation of EGS using the chlorosilane process.

WS Silane process en —ltern—tive pro™ess for the produ™tion of iqƒ th—t h—s ˜egun to re™eive ™ommer™i—l —ttention is the pyrolysis of sil—ne @ƒir4 AF „he —dv—nt—ges of produ™ing iqƒ from ƒir4 inste—d of ƒirgl3 —re potenti—lly lower ™osts —sso™i—ted with lower re—™tion temper—turesD —nd less h—rmful ˜yprodu™tsF ƒil—ne de™omposes < WHH ◦ g to give sili™on —nd hydrogenD @QFWAF @QFWA ƒil—ne m—y ˜e prep—red ˜y — num˜er of routesD e—™h h—ving —dv—nt—ges with respe™t to purity —nd produ™tion ™ostF „he simplest pro™ess involves the dire™t re—™tion of wqƒ powders with m—gnesium —t SHH ◦ g in — hydrogen —tmosphereD to form m—gnesium sili™ide @wg2 ƒiAF „he m—gnesium sili™ide is then re—™ted with —mmonium ™hloride in liquid —mmoni— ˜elow H ◦ gD @QFIHAF @QFIHA „his pro™ess is ide—lly suited to the remov—l of ˜oron impurities @— pEtype dop—nt in ƒiAD ˜e™—use the di˜or—ne @f2 r6 A produ™ed during the re—™tion forms the vewis —™idE˜—se ™omplexD r3 f@xr3 AD whose vol—tility is su0™iently lower th—n ƒir4 D —llowing for the puri(™—tion of the l—tterF st is possi˜le to prep—re iqƒ with — ˜oron ™ontent of ≤ PH ppt using ƒir4 synthesized in this m—nnerF roweverD phosphorus @—nother dop—ntA in the form of €r3 m—y ˜e present —s — ™ont—min—nt requiring su˜sequent puri(™—tion of the ƒir4 F eltern—tive routes to ƒir4 involve the ™hemi™—l redu™tion of ƒigl4 ˜y either lithium hydride @@QFIIAAD lithium —luminum hydride @@QFIPAAD or vi— hydrogen—tion in the presen™e of element—l sili™on @@QFIQA E @QFITAAF „he hydride redu™tion re—™tions m—y ˜e ™—rriedEout on rel—tively l—rge s™—les @™—F SH kgAD ˜ut only ˜—t™h pro™essesF sn ™ontr—stD …nion g—r˜ide h—s —d—pted the hydrogen—tion to — ™ontinuous pro™essD involving disproportion—tion re—™tions of ™hlorosil—nes @@QFIRA E @QFITAA —nd the fr—™tion—l distill—tion of sil—ne @„—˜le QFTAF @QFIIA @QFIPA @QFIQA @QFIRA @QFISA @QFITA €yrolysis of sil—ne on resistively he—ted polysili™on (l—ments —t UHHEVHH g yields poly™ryst—lline iqƒF es noted —˜oveD the iqƒ formed h—s rem—rk—˜ly low ˜oron impurities ™omp—red with m—teri—l prep—red from tri™hlorosil—neF woreoverD the resulting iqƒ is less ™ont—min—ted with tr—nsition met—ls from the re—™tor ™ont—iner ˜e™—use ƒir4 de™omposition does not ™—use —s mu™h of — ™orrosion pro˜lem —s is o˜served with h—lide pre™ursor ™ompoundsF ◦ .2. 3.3 Granular polysilicon deposition CHAPTER 3.7 HFHHP HFV HFHU R x IH -6 iron oxygen phosphorus —ntimony V x IH-6 HFPS HFQS HFHPQ X ƒegreg—tion ™oe0™ients for ™ommon impurity —nd dop—nt elements in sili™onF .2.3 Zone rening „he te™hnique of zone re(ning is used to purify solid m—teri—ls —nd is ™ommonly employed in met—llurgi™—l re(ningF sn the ™—se of sili™on m—y ˜e used to o˜t—in the desired ultim—te purity of iqƒD whi™h h—s —lre—dy ˜een puri(ed ˜y ™hemi™—l pro™essesF one re(ning w—s invented ˜y €f—nnD —nd m—kes use of the f—™t th—t the equili˜rium solu˜ility of —ny impurity @eFgFD elA is di'erent in the solid —nd liquid ph—ses of — m—teri—l @eFgFD ƒiAF por the dilute solutionsD —s is o˜served in iqƒ sili™onD —n equili˜rium segreg—tion ™oe0™ient @k0 A is de(ned ˜y k0 a gs Ggl D where gs —nd gl —re the equili˜rium ™on™entr—tions of the impurity in the solid —nd liquid ne—r the interf—™eD respe™tivelyF sf k0 is less th—n I then the impurities —re left in the melt —s the molten zone is moved —long the m—teri—lF sn — pr—™ti™—l sense — molten zone is est—˜lished in — solid rodF „he zone is then moved —long the rod from left to rightF sf k < I then the frozen p—rt left on the tr—iling edge of the moving molten zone will ˜e purer th—n the m—teri—l th—t melts in on the rightEside le—ding edge of the moving molten zoneF gonsequently the solid to the left of the molten zone is purer th—n the solid on the rightF et the ™ompletion of the (rst p—ss the impurities ˜e™ome ™on™entr—ted to the right of the solid s—mpleF ‚epetition of the pro™ess —llows for puri(™—tion to ex™eption—lly high levelsF „—˜le QFUF lists the equili˜rium segreg—tion ™oe0™ients for ™ommon impurity —nd dop—nt elements in sili™onY it should ˜e noted th—t they —re —ll less th—n IF Element k0 Element k0 —luminum ˜oron ™—r˜on ™opper Table 3. BULK MATERIALS foth the ™hlorosil—ne @ƒeimensA —nd sil—ne pro™esses result in the form—tion of rods of iqƒF roweverD there h—s ˜een in™re—sed interest in the form—tion of gr—nul—r poly™ryst—lline iqƒF „his pro™ess w—s developed in IWVH9sD —nd relies on the de™omposition of ƒir4 in — )uidizedE˜ed deposition re—™tor to produ™e freeE)owing gr—nul—r polysili™onF „iny sili™on p—rti™les —re )uidized in — ƒir4 Gr2 )owD —nd —™t —s seed ™ryst—l onto whi™h polysili™on deposits to form freeE)owing spheri™—l p—rti™lesF „he size distri˜ution of the p—rti™les thus formed is over the r—nge from HFI to IFS mm in di—meter with —n —ver—ge p—rti™le size of HFU mmF „he )uidizedE˜ed seed p—rti™les —re origin—lly m—de ˜y grinding iqƒ in — ˜—ll @or h—mmerA mill —nd le—™hing the produ™t with —™idD hydrogen peroxideD —nd w—terF „his pro™ess is timeE™onsuming —nd ™ostlyD —nd tended to introdu™e undesir—˜le impurities from the met—l grindersF sn — new methodD l—rge iqƒ p—rti™les —re (red —t e—™h other ˜y — highEspeed stre—m of inert g—s —nd the ™ollision ˜re—ks them down into p—rti™les of suit—˜le size for — )uidized ˜edF „his pro™ess h—s the m—in —dv—nt—ge th—t it introdu™es no foreign m—teri—ls —nd requires no le—™hing or other post puri(™—tionF „he )uidizedE˜ed re—™tors —re mu™h more e0™ient th—n tr—dition—l rod re—™tors —s — ™onsequen™e of the gre—ter surf—™e —re— —v—il—˜le during g†h growth of sili™onF st h—s ˜een suggested th—t )uidizedE˜ed re—™tors require 1 G5 to 1 G10 the energyD —nd h—lf the ™—pit—l ™ost of the tr—dition—l pro™essF „he qu—lity of )uidizedE˜ed polysili™on h—s proven to ˜e equiv—lent to polysili™on produ™ed ˜y the ™onvention—l methodsF woreoverD gr—nul—r iqƒ in — freeE)owing formD —nd with high ˜ulk densityD en—˜les ™ryst—l growers to o˜t—in the highD reprodu™i˜le produ™tion yields out of e—™h ™ryst—l growth runF por ex—mpleD in the gzo™hr—lski ™ryst—l growth pro™essD ™ru™i˜les ™—n ˜e qui™kly —nd e—sily (lled to uniform lo—ding with gr—nul—r iqƒD whi™h typi™—lly ex™eed those of r—ndomly st—™ked polysili™on ™hunks produ™ed ˜y the ƒiemens sil—ne pro™essF 3.

2.1 Isolation and purication of gallium metal et IW ppm g—llium @vF GalliaD pr—n™eA is —˜out —s —˜und—nt —s nitrogenD lithium —nd le—dY it is twi™e —s —˜und—nt —s ˜oron @W ppmAD ˜ut is more di0™ult to extr—™t due to the l—™k of —ny m—jor g—lliumE™ont—ining oreF q—llium —lw—ys o™™urs in —sso™i—tion either with zin™ or germ—niumD its neigh˜ors in the periodi™ t—˜leD or with —luminum in the s—me groupF „husD the highest ™on™entr—tions @HFIEI7A —re in the r—re miner—l germ—nite @— ™omplex sul(de of nD guD qeD —nd esAD while ™on™entr—tions in sph—lerite @nƒAD di—spore ‘ely@yrA“D ˜—uxiteD or ™o—lD —re — hundredEfold lessF sndustri—llyD g—llium w—s origin—lly re™overed from the )ue dust emitted during sul(de ro—sting or ™o—l ˜urning @up to IFS7 q—AD howeverD it is now o˜t—ined —s side produ™t of v—st —luminum industry —nd in p—rti™ul—r from the f—yer pro™ess for o˜t—ining —lumin— from ˜—uxiteF „he f—yer pro™ess involves dissolution of ˜—uxiteD elyx yr3-2x D in —queous x—yrD sep—r—tion of insolu˜le impuritiesD p—rti—l pre™ipit—tion of the trihydr—teD el@yrA3 D —nd ™—l™in—tion —t IDPHH ◦ gF huring pro™essing the —lk—line solution is gr—du—lly enri™hed in g—llium from —n initi—l weight r—tio q—Gel of —˜out IGSHHH to —˜out IGQHHF ile™trolysis of these extr—™ts with — rg ™—thode results in further ™on™entr—tionD —nd the solution of sodium g—ll—te thus formed is then ele™trolyzed with — st—inless steel ™—thode to give q— met—lF ƒin™e ˜—uxite ™ont—ins HFHHQEHFHI7 g—lliumD ™omplete re™overy would yield some SHHEIHHH tons per —nnumD however present ™onsumption is only HFI7 of this —˜out IH tons per —nnumF e typi™—l —n—lysis of the WVEWW7 pure g—llium o˜t—ined —s — side produ™t from the f—yer pro™ess is shown in „—˜le QFVF „his m—teri—l is further puri(ed to WWFWW7 ˜y ™hemi™—l tre—tment with —™ids —nd y2 —t high temper—tures followed ˜y ™ryst—lliz—tionF „his ™hemi™—l pro™ess results in the redu™tion of the m—jority of met—l impurities —t the ppm levelD see „—˜le QFVF €uri(™—tion to seven nines WWFWWWW7 is possi˜le through zone re(ningD howeverD sin™e the equili˜rium distri˜ution ™oe0™ient of the residu—l impurities k0 ≈ ID multiple p—sses —re requiredD typi™—lly > SHHF „he low melting point of g—llium ensures th—t ™ont—min—tion from the ™ont—iner w—ll @whi™h is signi(™—nt in sili™on zone re(ningA is minimizedF sn order to f—™ilit—te the multiple zone re(ning in — suit—˜le timeD — simple modi(™—tion of zone re(ning is employed shown in pigure QFRF „he g—llium is ™ont—ined in — pl—sti™ tu˜e wr—pped —round — rot—ting ™ylinder th—t is h—lf immersed in — ™ooling ˜—thF e he—ter is positioned —˜ove the g—llium pl—sti™ ™oilF „husD est—˜lishing — series of molten zones th—t p—ss upon rot—tion of the drum ˜y one heli™—l segment per revolutionF sn this m—nnerD SHH p—sses m—y ˜e m—de in rel—tively short time periodsF „he typi™—l impurity levels of g—llium zone re(ned in this m—nner —re given in „—˜le QFVF Element Bayer process (ppm) After acid/base leaching (ppm) 500 zone (ppm) passes continued on next page .3.2.WU 3.3 Gallium arsenide sn ™ontr—st to ele™troni™ gr—de sili™on @iqƒAD whose use is — minor fr—™tion of the glo˜—l produ™tion of element—l sili™onD g—llium —rsenide @q—esA is produ™ed ex™lusively for use in the semi™ondu™tor industryF roweverD —rseni™ —nd its ™ompounds h—ve signi(™—nt ™ommer™i—l —ppli™—tionsF „he m—in use of element—l —rseni™ is in —lloys of €˜D —nd to — lesser extent guD while —rseni™ ™ompounds —re widely used in pesti™ides —nd wood preserv—tives —nd the produ™tion of ˜ottle gl—ssF „husD the ele™troni™s industry represents — minor user of —rseni™F sn ™ontr—stD —lthough g—llium h—s minor uses —s — highEtemper—ture liquid se—lD m—nometri™ )uids —nd he—t tr—nsfer medi—D —nd for low temper—ture soldersD its m—in use is in semi™ondu™tor te™hnologyF 3.

2.4: Schematic representation of a zone rening apparatus. BULK MATERIALS IHHEIDHHH IHEIHH IHHEIDHHH IHHEIDHHH U not dete™ted P U QH I not dete™ted not dete™ted <I not dete™ted <I <I not dete™ted not dete™ted not dete™ted not dete™ted not dete™ted not dete™ted < PHHH IHEIHH IHEIHH IHEIHH IHEIHH IHEIHH IHEIHH QHDHHH ≈I ≈I I <I not dete™ted ≈I X „ypi™—l —n—lysis of g—llium o˜t—ined —s — side produ™t from the f—yer pro™essF Figure 3. 3.2 Isolation and purication of elemental arsenic ilement—l —rseni™ @vF —rseni™umD yellow orpimentA exists in two formsX yellow @™u˜i™D es4 A —nd gr—y or met—lli™ @rhom˜ohedr—lAF et — n—tur—l —˜und—n™e of IFV ppm —rseni™ is rel—tively r—reD howeverD this is o'set ˜y its presen™e in — num˜er of ™ommon miner—ls —nd the rel—tive e—se of isol—tionF erseni™ ™ont—ining miner—ls —re grouped into three m—in ™l—ssesX the sul(des re—lg—r @es4 ƒ4 A —nd orpiment @es2 ƒ3 AD the oxide —rsenolite @es2 y3 AD —nd the —rsenides —nd sulf—resenides of the ironD ™o˜—ltD —nd ni™kelF winer—ls in this l—tter ™l—ss in™ludeX loellinginite @pees2 AD s—'orlite @goesAD ni™™olite @xiesAD r—mmels˜ergite @xies2 AD —nsenopyrite or mispi™kel @peesƒAD ™o˜—ltite @goesƒAD en—rgite @gu3 esƒ4 AD gerdsor(te @xiesƒAD —nd the qu—rturn—ry sul(de gl—u™odot ‘@goDpeAesƒ“F „—˜le QFW shows the typi™—l impurities in —rsenopyriteF .8 CHAPTER 3.WV —luminum ™—l™ium ™opper iron le—d m—gnesium mer™ury ni™kel sili™on tin tit—nium zin™ Table 3.3.

3. q—llium —rsenide ™—n ˜e prep—red ˜y the dire™t re—™tion of the elementsD @QFIVAF roweverD while ™on™eptu—lly simple the synthesis of q—es is ™ompli™—ted ˜y the di'erent v—por pressures of the re—gents —nd the highly exothermi™ n—ture of the re—™tionF purthermoreD sin™e the synthesis of q—es —t —tmospheri™ pressure is —™™omp—nied ˜y its simult—neous de™omposes due to the loss ˜y su˜lim—tionD of —rseni™D the synthesis must ˜e ™—rried out under —n overpressure of —rseni™ in order to m—int—in — stoi™hiometri™ ™omposition of the synthesized q—esF @QFIVA sn order to over™ome the pro˜lems —sso™i—ted with —rseni™ lossD the re—™tion is usu—lly ™—rried out in — se—led re—™tion tu˜eF roweverD if — stoi™hiometri™ qu—ntity of —rseni™ is used in the re—™tion — ™onst—nt temper—ture of IPQV ◦ g must ˜e employed in order to m—int—in the desired —rseni™ overpressure of I —tmF €r—™ti™—llyD it is e—sier to use — l—rge ex™ess of —rseni™ he—ted to — lower temper—tureF sn this situ—tion the pressure in the tu˜e is —pproxim—tely equ—l to the equili˜rium v—por pressure of the vol—tile ™omponent @—rseni™A —t the lower temper—tureF „husD —n over pressure of I —tm —rseni™ m—y ˜e m—int—ined if within — se—led tu˜e element—l —rseni™ is he—ted to THHETPH ◦ g while the q—es is m—int—ined —t IPRHEIPSH ◦ gF pigure QFS shows the se—led tu˜e ™on(gur—tion th—t is typi™—lly used for the synthesis of q—esF „he tu˜e is he—ted within — twoEzone furn—™eF „he ˜o—ts holding the re—™t—nts —re usu—lly m—de of qu—rtzD howeverD gr—phite is —lso used sin™e the l—tter h—s — ™loser therm—l exp—nsion m—t™h to the q—es produ™tF sf higher purity is required then pyrolyti™ ˜oron nitride @€fxA is usedF yne of the ˜o—ts is lo—ded with pure g—llium the other with —rseni™F e plug of qu—rtz wool m—y ˜e pl—™ed ˜etween the ˜o—ts to —™t —s — di'userF „he tu˜e is then ev—™u—ted —nd se—ledF yn™e ˜rought to the ™orre™t re—™tion temper—tures @pigure QFSAD the —rseni™ v—por is tr—nsported to the g—lliumD —nd they re—™t to form q—es in — ™ontrolled m—nnerF „—˜le QFIH gives the typi™—l impurity ™on™entr—tions found in poly™ryst—lline q—esF .2.WW Element Concentration (ppm) Element Concentration (ppm) silver gold ™o˜—lt ™opper germ—nium m—ng—nese moly˜denum WH V QHDHHH PHH QH QDHHH TH Table 3.9 ni™kel le—d pl—tinum rhenium selenium v—n—dium zin™ < QDHHH SH HFR SH SH QHH RHH X „ypi™—l impurities in —rsenopyriteF erseni™ is o˜t—ined ™ommer™i—lly ˜y smelting either pees2 or peesƒ —t TSHEUHH ◦ g in the —˜sen™e of —ir —nd ™ondensing the su˜limed element @„sub a TIQ ◦ gAD @QFIUAF @QFIUA „he —rseni™ thus o˜t—ined is ™om˜ined with le—d —nd then su˜limed @„sub a TIR gA whi™h ˜inds —ny sulfur impurities more strongly th—n —rseni™F eny residu—l —rseni™ th—t rem—ins tr—pped in the iron sul(de is sep—r—ted ˜y forming the oxide @es2 y3 A ˜y ro—sting the sul(de in —irF „he oxide is su˜limed into the )ue system during ro—sting from where it is ™olle™ted —nd redu™ed with ™h—r™o—l —t UHHEVHH ◦ g to give element—l —rseni™F ƒemi™ondu™tor gr—de —rseni™ @> WWFWWWW7A is formed ˜y zone re(ningF ◦ 3.3 Synthesis and purication of gallium arsenide.

D IWVPD 129D ISQIF • tF ur—uskopfD tF hF weyerD fF ‡iedem—nnD wF ‡—lds™hmidtD uF fethgeD qF ‡olfD —nd ‡F ƒ™hultzeD ¨ Sth gonferen™e on ƒemiEinsul—ting sssE† w—teri—lsD w—lmoD ƒwedenD IWVVD idsF qF qrossm—n —nd vF vede˜oD ed—mErilgerD xew ‰ork @IWVVAF • tF ‚F w™gormi™D gonfF ‚e™F IRth siii €hotovoltF ƒpe™i—lists gonfFD ƒ—n hiegoD ge @IWVHAF • tF ‚F w™gormi™D in Semiconductor Silicon 1981D idF rF ‚F ru'D ile™tro™hemi™—l ƒo™ietyD €rin™etonD xew tersey @IWVIAF • ‡F gF y9w—r—D idF Handbook of Semiconductor Silicon TechnologyD xoyes €u˜FD xew tersey @IWWHAF .D „he i™onomi™ qeology €u˜lishing gomp—nyD v—n™—sterD €e @IWSSAF • qF rsuD xF ‚oh—tgiD —nd tF rousem—nD AIChE J.10 X smpurity ™on™entr—tions found in poly™ryst—lline q—esF €oly™ryst—lline q—esD formed in from the dire™t re—™tion of the elements is often used —s the st—rting m—teri—l for single ™ryst—l growth via fridgem—n or gzo™hr—lski ™ryst—l growthF st is —lso possi˜le to prep—re single ™ryst—ls of q—es dire™tly from the elements using inEsituD or dire™tD ™ompounding within — highEpressure liquid en™—psul—ted gzo™hr—lski @r€vigA te™hniqueF 3. Soc.2.5: Schematic representation of a sealed tube synthesis of GaAs. Vol. Electrochem. Element Concentration (ppm) Element Concentration (ppm) ˜oron ™—r˜on nitrogen oxygen )uorine m—gnesium —luminum HFI HFU HFI HFS HFP HFHP HFHP sili™on phosphorus sulfur ™hlorine ni™kel ™opper zin™ HFHP HFI HFHI HFHV HFHR HFHI HFHS Table 3.IHH CHAPTER 3. BULK MATERIALS Figure 3. 50th Aniv.4 Bibliography • uF qF f—r—™loughD uF qFD in The Chemistry of the Semiconductor IndustryD idsF ƒF tF woss —nd eF vedwithD fl—™kie —nd ƒonsD ql—sgowD ƒ™otl—nd @IWVUAF • vF hF grossm—n —nd tF eF f—kerD Semiconductor Silicon 1977D ile™tro™hemF ƒo™FD €rin™etonD xew tersey @IWUUAF • wF pleisherD in Economic Geology.D IWVUD 33D UVRF • ƒF uF sy—D ‚F xF pl—gell—D —nd pF ƒF hip—oloD J.

IHI • ‡F qF €f—nnD Zone MeltingD tohn ‡iley 8 ƒonsD xew ‰orkD @IWTTAF • pF ƒhimur—D Semiconductor Silicon Crystal TechnologyD e™—demi™ €ress @IWVWAF 3.1 Introduction 3 ‡hile —luminum is the most —˜und—nt met—l in the e—rth9s ™rust @ca.3 Ceramic Processing of Alumina 3.1 Ternary and mixed-metal oxides e further ™onsequen™e of the st—˜ility of —lumin— is th—t most if not —ll of the n—tur—lly o™™urring —luminum ™ompounds —re oxidesF sndeedD m—ny pre™ious gemstones —re —™tu—lly ™orundum doped with impuritiesF ‚epl—™ement of —luminum ions with tr—™e —mounts of tr—nsitionEmet—l ions tr—nsforms the formerly ™olorless miner—l into ru˜y @redD gr3+ AD s—pphire @˜lueD pe2+/3+ D „i4+ AD or top—z @yellowD pe3+ AF „he —ddition of stoi™hiometri™ —mounts of met—l ions ™—uses — shift from the αEel2 y3 h™p stru™ture to the other ™ommon oxide stru™tures found in n—tureF ix—mples in™lude the perovskite stru™ture for efy3 type miner—ls @eFgFD ge„iy7 or v—ely3 A —nd the spinel stru™ture for ef2 y4 miner—ls @eFgFD ˜erylD feel2 y4 AF eluminum oxide —lso forms tern—ry —nd mixedEmet—l oxide ph—sesF „ern—ry systems su™h —s mullite @el6 ƒi2 y13 AD yttrium —luminum g—rnet @‰eqD ‰3 el5 y12 AD the β -—lumin—s @eFgFD x—el11 y17 A —nd —lumin—tes su™h —s hi˜onite @g—el12 y19 A possessing β E—lumin— or m—gnetoplum˜iteEtype stru™tures ™—n o'er —dv—nt—ges over those of the ˜in—ry —luminum oxidesF 3 This content is available online at <http://cnx. V7A —nd —luminum ™ompounds su™h —s —lumD u‘el@ƒy4 A2 “FIP@r2 yAD were known throughout the world in —n™ient timesD it w—s not until the isol—tion of —luminum in the l—te eighteenth ™entury ˜y the h—nish s™ientist rF gF Öersted th—t rese—r™h into the ™hemistry of the qroup IQ elements ˜eg—n in e—rnestF sniti—llyD met—lli™ —luminum w—s isol—ted ˜y the redu™tion of —luminum tri™hloride with pot—ssium or sodiumY howeverD with the —dvent of inexpensive ele™tri™ power in the l—te IVHH9sD it ˜e™—me e™onomi™—lly fe—si˜le to extr—™t the met—l via the ele™trolyis of —lumin— @el2 y3 A dissolved in ™ryoliteD x—3 elp6 D @the r—llEreroult pro™essAF „od—yD —lumin— is prep—red ˜y the f—yer pro™essD in whi™h the miner—l ˜—uxite @n—med for ves f—uxD pr—n™eD where it w—s (rst dis™overedA is dissolved with —queous hydroxidesD —nd the solution is (ltered —nd tre—ted with gy2 to pre™ipit—te —lumin—F ‡ith —v—il—˜ility of ˜oth the miner—l —nd ™he—p ele™tri™ power ˜eing the m—jor ™onsider—tions in the e™onomi™—l produ™tion of —luminumD it is not surprising th—t the le—ding produ™ers of —luminum —re the …nited ƒt—tesD t—p—nD eustr—li—D g—n—d—D —nd the former ƒoviet …nionF 3.2. .org/content/m22376/1.5/>. Aluminum oxides and hydroxides „he m—ny forms of —luminum oxides —nd hydroxides —re linked ˜y ™omplex stru™tur—l rel—tionshipsF f—uxite h—s the formul— elx @yrA3-2x @H < x < IA —nd is thus — mixture of el2 y3 @αE—lumin—AD el@yrA3 @gi˜˜siteAD —nd ely@yrA @˜oehmiteAF „he l—tter is —n industri—lly import—nt ™ompound whi™h is used in the form of — gel —s — preE™er—mi™ in the produ™tion of (˜ers —nd ™o—tingsD —nd —s — (re ret—rding —gent in pl—sti™sF re—ting ˜oehmite —nd di—spore to RSH ◦ g ™—uses dehydr—tion to yield forms of —lumin— whi™h h—ve stru™tures rel—ted to their oxideEhydroxide pre™ursorsF „husD ˜oehmite produ™es the lowEtemper—ture form γ E—lumin—D while he—ting di—spore will give αE—lumin— @™orundumAF γ E—lumin— ™onverts to the h™p stru™ture —t IIHH ◦ gF e third form of el2 y3 forms on the surf—™e of the ™le—n —luminum met—lF „he thinD toughD tr—nsp—rent oxide l—yer is the re—son for mu™h of the usefulness of —luminumF „his oxide skin is r—pidly selfErep—iring ˜e™—use its he—t of form—tion is so l—rge @∆r a QQSI ktGmolAF @QFIWA 3.

IHP CHAPTER 3.3 Synthesis of aluminum oxide ceramics sn ™ommon with the m—jority of oxide ™er—mi™sD two prim—ry syntheti™ pro™esses —re employed for the produ™tion of —luminum oxide —nd mixed met—l oxide m—teri—lsX IF „he tr—dition—l ™er—mi™ powder pro™essF PF „he solutionEgel—tionD or 4solEgel4 pro™essF „he environment—l imp—™t of —lumin— —nd —lumin—E˜—sed ™er—mi™s is in gener—l negligi˜leY howeverD the s—me ™—nnot ˜e s—id for these methods of prep—r—tionF es pr—™ti™ed ™ommer™i—llyD ˜oth of the —˜ove pro™esses ™—n h—ve — signi(™—nt detriment—l environment—l imp—™tF 3. BULK MATERIALS eppli™—tions of these m—teri—ls —re found in —re—s su™h —s engineering ™omposite m—teri—lsD ™o—tingsD te™hni™—l —nd ele™troni™ ™er—mi™sD —nd ™—t—lystsF por ex—mpleD mullite h—s ex™eption—l high temper—ture sho™k resist—n™e —nd is widely used —s —n infr—redEtr—nsp—rent window for high temper—ture —ppli™—tionsD —s — su˜str—te in multil—yer ele™troni™ devi™e p—™k—gingD —nd in high temper—ture stru™tur—l —ppli™—tionsF ri˜onite —nd other hex—lumin—tes with simil—r stru™tures —re ˜eing ev—lu—ted —s interf—™i—l ™o—tings for ™er—mi™ m—trix ™omposites due to their high therm—l st—˜ility —nd unique ™ryst—llogr—phi™ stru™turesF purthermoreD —luminum oxides doped with —n —lk—liD —lk—line e—rthD r—re e—rthD or tr—nsition met—l —re of interest for their enh—n™ed ™hemi™—l —nd physi™—l properties in —ppli™—tions utilizing their unique optoele™troni™ propertiesF Traditional ceramic processing „r—dition—l ™er—mi™ pro™essing involves three ˜—si™ steps gener—lly referred to —s powderEpro™essingD sh—peE formingD —nd densi(™—tionD often with — (n—l me™h—ni™—l (nishing stepF elthough sever—l steps m—y ˜e energy intensiveD the most dire™t environment—l imp—™t —rises from the sh—peEforming pro™ess where v—rious ˜indersD solventsD —nd other potenti—lly toxi™ —gents —re —dded to form —nd st—˜ilize — solid @4green4A ˜ody @„—˜le QFIIAF Function Composition Volume (%) €owder ƒolvent he)o™™ul—nt finder €l—sti™izer —lumin— @el2 y3 A IDIDIEtri™hloroeth—neGeth—nol menh—den oil poly@vinyl ˜utyrolA poly@ethylene gly™olAGo™tyl phth—l—te PU SV IFV RFR VFV Table 3.11 X „ypi™—l ™omposition of —lumin— green ˜ody „he ™omponent ™hemi™—ls —re mixed to — slurryD ™—stD then dried —nd (redF sn —ddition to —ny inn—te he—lth risk —sso™i—ted with the ™hemi™—l pro™essing these —gents —re su˜sequently removed in g—seous form ˜y dire™t ev—por—tion or pyrolysisF „he repl—™ement of ™hlorin—ted solvents su™h —s IDIDIEtri™hloroethylene @„giA must ˜e reg—rded —s — high priority for limiting environment—l pollutionF „he …nited ƒt—tes invironment—l €rote™tion egen™y @i€eA in™luded „gi on its IWWI list of IU highEpriority toxi™ ™hemi™—ls t—rgeted for sour™e redu™tionF „he pl—sti™izersD ˜indersD —nd —l™ohols used in the pro™ess present — num˜er of potenti—l environment—l imp—™ts —sso™i—ted with the rele—se of ™om˜ustion produ™ts during (ring of the ™er—mi™sD —nd the need to re™y™le or dis™h—rge —l™ohols whi™hD in the ™—se of dis™h—rge to w—terw—ysD m—y exert high ˜iologi™—l oxygen dem—nds in the re™eiving ™ommunitiesF st would ˜e desir—˜leD thereforeD to ˜e —˜le to use —queous pro™essingY howeverD this h—s previously ˜een unsu™™essful due to pro˜lems —sso™i—ted with ˜—t™hingD millingD —nd formingF xeverthelessD with — suit—˜le ™hoi™e of ˜indersD et™FD —queous pro™essing is possi˜leF …nfortun—telyD in m—ny ™—stEp—rts formed ˜y green ˜ody pro™essing the liquid solvent —lone ™onsists of over SH 7 of the initi—l volumeD —nd while this is not dire™tly of —n environment—l ™on™ernD the result—nt shrink—ge m—kes ne—r net sh—pe pro™essing di0™ultF .3.

12 eƒf ‘—luminum sec E˜utoxideD el@yg4 r9 A3 “ rxy3 HFHU moleGmole eƒf gly™erol caF IH wtF7 X „ypi™—l ™omposition of —n —lumin— solEgel for slip™—st ™er—mi™sF „he prin™ip—l environment—l ™onsequen™es —rising from the solEgel pro™ess —re those —sso™i—ted with the use of strong —™idsD pl—sti™izersD ˜indersD solventsD —nd sec E˜ut—nol formed during the re—™tionF hepending on the (ring ™onditionsD v—ri—˜le —mounts of org—ni™ m—teri—ls su™h —s ˜inders —nd pl—sti™izers m—y ˜e rele—sed —s ™om˜ustion produ™tsF xyx 9s m—y —lso ˜e produ™ed in the o'Eg—s from residu—l nitri™ —™id or nitr—te s—ltsF woreoverD —™ids —nd solvents must ˜e re™y™led or disposed ofF inergy ™onsumption in the pro™ess ent—ils upstre—m environment—l emissions —sso™i—ted with the produ™tion of th—t energyF 3.3..3.IHQ 3.D IWPPD 44D PIUSF • eF ‚F f—rronD Comm.4 Bibliography • Advances in CeramicsD idsF tF eF w—ngels —nd qF vF wessingD emeri™—n ger—mi™ ƒo™ietyD ‡estvilleD yrD IWVRD †olF WF • edkinsD J. Eng. Sci.2 Sol-gel ‡here—s the tr—dition—l sintering pro™ess is used prim—rily for the m—nuf—™ture of dense p—rtsD the solutionE gel—tion @solEgelA pro™ess h—s ˜een —pplied industri—lly prim—rily for the produ™tion of porous m—teri—ls —nd ™o—tingsF ƒolEgel involves — four st—ge pro™essX dispersionD gel—tionD dryingD —nd (ringF e st—˜le liquid dispersion or sol of the ™olloid—l ™er—mi™ pre™ursor is initi—lly formed in — solvent with —ppropri—te —dditivesF fy ™h—nging the ™on™entr—tion @—gingA or prD the dispersion is 4polymerized4 to form — solid dispersion or gelF „he ex™ess liquid is removed from this gel ˜y drying —nd the (n—l ™er—mi™ is formed ˜y (ring the gel —t higher temper—turesF „he ™ommon solEgel route to —luminum oxides employs —luminum hydroxide or hydroxideE˜—sed m—teri—l —s the solid ™olloidD the se™ond ph—se ˜eing w—ter —ndGor —n org—ni™ solventD howeverD the strong inter—™tions of the freshly pre™ipit—ted —lumin— gels with ions from the pre™ursor solutions m—kes it di0™ult to prep—re these gels in pure formF „o —void this ™ompli™—tionD —lumin— gels —re —lso prep—red from the hydrolysis of —luminum —lkoxidesD el@y‚A3 F @QFPHA @QFPIA „he ex—™t ™omposition of the gel in ™ommer™i—l systems is ordin—rily propriet—ryD howeverD — typi™—l ™omE position will in™lude —n —luminum ™ompoundD — miner—l —™idD —nd — ™omplexing —gent to inhi˜it prem—ture pre™ipit—tion of the gelD eFgFD „—˜le QFIPF Function Composition foehmite pre™ursor ile™trolyte gomplexing —gent Table 3. Inorg. ProcFD IWWRD 15D UPIF • pF eF gotton —nd qF ‡ilkinsonD Advanced Inorganic ChemistryD Sth idFD tohn ‡iley —nd ƒonsD xew ‰ork @IWVVAF • xF xF qreenwood —nd eF i—rnsh—wD Chemistry of the ElementsD €erg—mon €ressD yxford @IWVRAF • €F rF rsu —nd „F pF f—tesD Mineral MagFD IWTRD 33D URWF . Am. Soc. Chem.3. ChemFD IWWQD 14D IPQF • wF uF gini˜ulkD Ceram.

4.4 Piezoelectric Materials Synthesis 3.2 Piezoelectric ceramics wost piezoele™tri™ tr—nsdu™ers —re m—de up of ™er—mi™ m—teri—ls for — ˜ro—d r—nge of ele™trome™h—ni™—l ™onversion t—sks —s tr—nsmittersD r—nging from ˜uzzers in —l—rm ™lo™ks to son—rsD —nd —s re™eiversD r—nging from ultr— high frequen™y @…rpA (lters to hydrophonesF wost of the piezoele™tri™ m—teri—ls in us—ge —re from the le—d zir™on—te tit—n—te @€„A f—milyD ˜e™—use of their ex™ellent piezoele™tri™ p—r—metersD therm—l st—˜ilityD —nd diele™tri™ propertiesF eddition—lly the properties of this f—mily ™—n ˜e modi(ed ˜y ™h—nging the zir™onium to tit—nium r—tio or ˜y —ddition of ˜oth met—lli™ —nd nonEmet—lli™ elementsF €„ @€˜r1-x „iX y3 A ™er—mi™s —nd their solid solutions with sever—l ™omplex perovskite oxides h—ve ˜een studiedY —mong the v—rious ™omplex oxide m—teri—lsD nio˜—tes h—ve —ttr—™ted spe™i—l —ttentionF „ern—ry ™er—mi™ m—teri—lsD le—d met—nio˜—teD —s well —sD ˜—rium —nd modi(ed le—d tit—n—tes ™omplete the list of piezo™er—mi™ m—teri—lsF 4 This content is available online at <http://cnx. BULK MATERIALS • ‡F hF uingeryD rF uF fowenD —nd hF ‚F …hlm—nnD Introduction to CeramicsD Pnd idF ‡ileyD xew ‰ork @IWUTAF • rF ƒ™hneiderD uF yk—d—D —nd tF €—skD Mullite and Mullite CeramicsD ‡iley @IWWRAF • ‚F †F „hom—sD Systems Analysis and Water Quality ManagementD w™qr—wErillD xew ‰ork @IWUPAF • tF gF ‡illi—msD in Treatise on Materials Science and TechnologyD idF pF pF ‰F ‡—ngD e™—demi™ €ressD xew ‰ork @IWUTAF 3.4.1 Introduction 4 „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of slse ‰F quzm—nEtimenezF €iezoele™tri™ity is the gener—tion of —n ele™tri™ moment ˜y — ™h—nge of stress —pplied to — solidF „he word piezoele™tri™ity liter—lly me—ns pressure ele™tri™ityY the pre(x piezo is derived from the qreek word piezeinD to pressF „he piezoele™tri™ e'e™t w—s dis™overed in IVVH ˜y the ˜rothers t—™ques —nd €ierre gurieF xot only did they demonstr—te the phenomenonD ˜ut they —lso est—˜lished the ™riteri— for its existen™e in — given ™ryst—lF yf the thirtyEtwo ™ryst—l ™l—ssesD twentyEone —re nonE™entrosymmetri™ @not h—ving — ™entre of symmetryAD —nd of theseD twenty exhi˜it dire™t piezoele™tri™ityF „he (rst pr—™ti™—l —ppli™—tion of the piezoele™tri™ e'e™t w—s developed when ground qu—rtz ™ryst—ls were pl—™ed ˜etween the pl—tes of — tuning ™—p—™itor in order to st—˜ilize os™ill—ting ™ir™uits in r—dio tr—nsmitters —nd re™eiversY howeverD the phenomenon of piezoele™tri™ity w—s not well exploited until ‡orld ‡—r sD when v—ngevin used piezoele™tri™—lly ex™ited qu—rtz pl—tes to gener—te sounds w—ves in w—ter for use in su˜m—rine dete™tionF €iezoele™tri™ity ™—n —lso o™™ur in poly™ryst—lline or —morphous su˜st—n™es whi™h h—ve ˜e™ome —nisotropi™ ˜y extern—l —gentsF ƒyntheti™ piezoele™tri™ m—teri—ls ˜e™—me —v—il—˜le ne—r the end of ‡orld ‡—r ssD with the —™™ident—l dis™overy of the f—™t th—t m—teri—ls like ˜—rium tit—n—te —nd r—re e—rth oxides ˜e™ome piezoele™tri™ when they —re pol—rized ele™tri™—llyF huring the postw—r ye—rsD when germ—nium —nd sili™on were revoluE tionizing the ele™troni™s industryD piezo™er—mi™s —ppe—red for — while to ˜e joining the revolutionD ˜ut the limited —v—il—˜ility of m—teri—ls —nd ™omponentsD m—de the piezoele™tri™ phenomenon f—iled to le—d m—ture —ppli™—tions during the IWSHsF st is only now th—t — v—riety of piezoele™tri™ m—teri—ls —re ˜eing synthesized —nd optimizedF es — ™onsequen™e piezoele™tri™E˜—sed devi™es —re undergoing — revolution—ry developmentD spe™i—lly for medi™ine —nd —erosp—™e —ppli™—tionsF 3.IHR CHAPTER 3. .org/content/m25441/1.2/>.

IHS ƒele™tive p—r—meters for piezo™er—mi™ m—teri—ls —re given in „—˜le QFIQD where m is the me™h—ni™—l qu—lity f—™torD „c is the gurie pointD d31 is the the tr—nsverse ™h—rge ™oe0™ientD —nd kp D kt —nd k31 —re the ele™trome™h—ni™—l ™oupling f—™tors for pl—n—rD thi™knessD —nd tr—nsvers—l mode respe™tivelyF Material property PZT modied Lead metaniobate PSZNT 31/40/29 PZT. x = 0. The viscous-suspension-spinning process (VSSP) for the production of continuous piezoce- ƒynthesis of re—™tive €„ pre™ursor powder ˜y the ox—l—te ™opre™ipit—tion te™hnique h—s —lso ˜een develE opedF „he pre™ursor tr—nsforms to ph—se pure €„ —t or —˜ove VSH ◦ g the €„ o˜t—ined ˜y this te™hnique showed — gurie temper—ture of QSS ◦ gF „he —dv—nt—ges of the ™opre™ipit—tion te™hnique —re the l—™k of moisture sensitive —nd spe™i—l h—ndling pre™ursorsF .48 m „c @ ◦ gA d31 @xIH gGxA kp kt k31 -12 QSH PWH RH RTP PPP UR QTW RI ISP EUW VVU QSS SH RTFS HFS HFQP HFPI Table 3.5 PSNPLT TsTS-421 50/50 PZT.6: ramic ber. x = 0.13 TH HFRPV HFRQV HFPTQ QHFU E IUFW X ƒele™tive p—r—meters for illustr—tive piezo™er—mi™ m—teri—lsF ‚e™entlyD solEgel pro™essing h—s ˜een used to prep—re ™er—mi™sD m—king possi˜le the prep—r—tion of m—teE ri—ls th—t —re di0™ult to o˜t—in ˜y ™onvention—l methodsF fothD inorg—ni™ —nd org—ni™ pre™ursor h—ve ˜een reportedF eddition—llyD new te™hniques for the produ™tion of ™er—mi™ (˜ers h—ve ˜een developedF fetter pro™essing —nd geometri™—l —nd mi™roestru™tur—l ™ontrol —re the m—in go—ls in the produ™tion of (˜ersF „he l—test development in piezo™er—mi™ (˜ers is the modi(™—tion of the vis™ousEsuspensionEspinning pro™ess @†ƒƒ€A for the produ™tion of ™ontinuos piezoele™tri™ ™er—mi™ (˜ers for sm—rt m—teri—ls —nd —™tive ™ontrol devi™esD su™h —s tr—nsdu™ersD sensorG—™tu—tors —nd stru™tur—lE™ontrol devi™esF „he †ƒƒ€ utilizes ™onvention—l synthesized ™er—mi™ powders —nd ™elluloseD —s the fugitive ™—rrierD to produ™e green ™er—mi™ (˜er —t — re—son—˜le ™ostF pigure QFT shows the s™hem—ti™ represent—tion of the †ƒƒ€F Figure 3.

5 q—5.IHT CHAPTER 3.4.5 y14 single ™ryst—ls h—ve ˜een grown ˜y using this methodF roweverD the g te™hnique ™—n ˜e —pplied only to m—teri—ls th—t ™—n ˜e synthesized ˜y ordin—ry solidEst—te re—™tion —nd ™—n undergo the pulling methodF f—fe2 ƒi2 y7 @˜—ryliteA h—s ˜een known —s m—teri—l with — strong piezoele™tri™ityD howeverD it ™—n not ˜e o˜t—ined ˜y solidEst—te re—™tion —nd g te™hnique therefore is not —ppli™—˜leF es —n —ltern—tive for piezoele™tri™ ™ryst—ls growth hydrotherm—l synthesis h—s ˜een developedF pigure QFU shows the experiment—l —pp—r—tus for the growth of ˜—ryliteF iventhoughD ™ryst—ls ™—n ˜e o˜t—ined using this te™hniqueD high pressure @SHH E IHHH ˜—rA —nd — solvent for the r—w m—teri—ls —re requiredF .5 y14 —nd v—3 „—0. „he re™ent progress of the ele™troni™ te™hnology requires new piezoele™tri™ ™ryst—ls with — high therm—l st—˜ility —nd l—rge ele™trome™h—ni™—l ™oupling f—™torsF ƒingleE™ryst—l m—teri—ls h—ve ˜een ™onsidered —s repl—™ements for poly™ryst—lline ™er—mi™sF sde—lly singleE™ryst—ls of le—d zir™on—te tit—n—te @€„A itself would ˜e the m—in ™hoi™e —s it is the most prev—iling piezoele™tri™ m—teri—lD ˜ut it is di0™ult to grow l—rge single ™ryst—lsF yn the other h—ndD the f—™t th—t singleE™ryst—ls o'er m—ny —dv—nt—ges over poly™ryst—lline systems h—s ˜een re™ognizedF w—teri—ls su™h —s lithium nio˜—te present essenti—lly no —gingD no me™h—ni™—l ™reep —nd ex™ellent perform—n™e in high temper—ture ™onditionsF xew piezoele™tri™ single ™ryst—ls grown ˜y ™onvention—l ‚pEhe—ting gzo™hr—lski @gA te™hnique h—ve ˜een synthesizedF righ purity st—rting m—teri—lsD m—inly oxides powdersD —nd er —tmosphere —re reE quiredF v—3 q—5 ƒiy14 D v—3 x˜0.3 Piezoelectric single crystals.5 q—5. BULK MATERIALS elthough new m—teri—ls h—ve ˜een investig—ted with the purpose of ™re—te repl—™ements for ™er—mi™sD there h—s ˜een — gre—t improvement in their properties —ndD ™urrent rese—r™h is fo™used in the development of new te™hniques for ˜oth synthesis —nd pro™essingF 3.

30. G = growth capsule. H.. Jpn. H = heater. ‡hile the piezo™er—mi™s domin—te the single ™ryst—l m—teri—ls in us—geD single ™ryst—ls piezoele™tri™s ™ontinue to m—ke import—nt ™ontri˜utions ˜oth in pri™eE™ons™ious ™onsumer m—rket —nd in perform—n™eE driven defense —ppli™—tionsF ere—s su™h —s frequen™y st—˜ilized os™ill—torsD surf—™e —™ousti™ w—ve devi™es —nd (lters with — wide p—ss ˜—ndD —re still domin—ted ˜y single ™ryst—lsF 3.4 Piezoelectric thin lms ‚e™entlyD there h—s ˜een gre—t interest in the deposition of piezoele™tri™ thin (lmsD m—inly for mi™roele™E troni™—l systems @wiwƒA —ppli™—tionsY where the go—l is to integr—te sensors —nd —™tu—tors ˜—sed on €„ (lms with ƒi semi™ondu™torE˜—sed sign—l pro™essingY —nd for surf—™e —™ousti™ w—ve @ƒe‡A devi™esY where the go—l is to —™hieve higher ele™trome™h—ni™—l ™oupling ™oe0™ient —nd temper—ture st—˜ilityF €iezoele™tri™—l mi™ro™—ntileversD mi™ro—™tu—torsD reson—tors —nd ƒe‡ devi™es using thin (lms h—ve ˜een reportedF ƒever—l methods h—ve ˜een investig—ted for €„ thin (lmsF sn the met—lloEorg—ni™ thin (lm depositionD —lkoxides —re stirred during long periods of time @up to IV hoursAF efter pyrolisisD €„ —morphous (lms —re formed —nd then ™—l™in—tion ˜etween RHH ! THH ◦ g for VH hours le—ds to €„ ™ryst—lliz—tion @perovskit— ph—seA ˜y — ™onse™utive ph—se tr—nsform—tion pro™essD whi™h involves — tr—nsition—l pyro™hlore ph—seF e hy˜rid met—llorg—ni™ de™omposition @wyhA route h—s —lso ˜een developed to prep—re €„ thin (lmsF ve—d —nd tit—nium —™et—tes —ndD zir™onium —™etyl—™eton—te —re usedF „he ferroele™tri™ piezoele™tri™ —nd . 2240. Uehara.4. F = furnace. and T = thermocouples. J. 1991. Ikeda. Sato and T. Phys. P = pressure gauge. Maeda. Appl. T. Adapted from M.7: Experimental apparatus for the hydrothermal synthesis of barylite. S = specimen vessel.IHU Figure 3.

BULK MATERIALS diele™tri™ properties indi™—te th—t the wyh route provides €„ (lms of good qu—lity —nd ™omp—r—˜le to liter—ture v—luesF sn —ddition to ˜eing simpleD wyh h—s sever—l —dv—nt—ges whi™h in™ludeX homogeneity —t mole™ul—r level —nd e—se ™omposition ™ontrolF wet—lorg—ni™ ™hemi™—l v—por deposition @wyg†hA h—s ˜een —pplied to €„ thin (lms deposition —lsoF st h—s ˜een proved th—t ex™ellent qu—lity €„ (lms ™—n ˜e grown ˜y using wyg†hD ˜ut just re™ently the ™ontrol of mi™rostru™ture the deposition ˜y v—rying the temper—tureD r to „i r—tio —nd pre™ursors )ow h—s ˜een studiedF ‚e™ent progress in €„ (lms deposition h—s led to lower temper—ture growth —nd it is expe™ted th—t ˜y lowering the deposition temper—ture ˜etter ele™tri™—l properties ™—n ˜e —™hievedF eddition—llyD novel te™hniques su™h —s urp ex™imer l—ser —˜l—tion —ndD ion —nd photoE—ssisted depositionsD h—ve —lso ˜een used for €„ (lms synthesisF yn the other h—ndD — single pro™ess to deposit €„ thin (lm ˜y — hydrotherm—l method h—s ˜een reported re™entlyF ƒin™e the solEgel methodD sputtering —nd ™hemi™—l v—por deposition te™hniques —re useful only for m—king )—t m—teri—lsD the hydrotherm—l method o'ers the —dv—nt—ge of m—king ™urved sh—ped m—teri—lsF „he hydrotherm—l method utilizes the ™hemi™—l re—™tion ˜etween tit—nium —nd ions melted in solutionF e €„ thin (lm h—s ˜een su™™essfully deposited dire™tly on — tit—nium su˜str—te —nd the optimum ion r—tio in the solution is ˜eing investig—ted to improve the piezoele™tri™ e'e™tF emong the ™urrent reported piezoele™tri™ m—teri—lsD the €˜@xi1/3 x˜2/3 A0.5 Piezoelectric polymers „he dis™overy of piezoele™tri™ity in polymeri™ m—teri—ls su™h —s polyvinylidene di)uoride @€†pAD w—s ™onE sidered —s —n indi™—tion of — ren—iss—n™e in piezoele™tri™ityF sntensive rese—r™h w—s fo™used in the synthesis —nd fun™tion—liz—tion of polymersF e potenti—l piezoele™tri™ polymer h—s to ™ont—in — high ™on™entr—tion of dipoles —nd —lso ˜e me™h—ni™—lly strong —nd (lmEformingF „he degree of ™ryst—llinity —nd the morphology of the ™ryst—lline m—teri—l h—ve profound e'e™ts on the me™h—ni™—l ˜eh—vior of polymersF eddition—llyD in order to indu™e — piezoele™tri™ response in —morphous systems the polymer is poled ˜y —ppli™—tion of — strong ele™tri™ (eld —t elev—ted temper—ture su0™ient to —llow mo˜ility of the mole™ul—r dipoles in the polymerF ‚e™ent —ppro—™hes h—ve ˜een fo™used in the development of ™y—noE™ont—ining polymersD due to the f—™t th—t ™y—no polymers ™ould h—ve m—ny dipoles whi™h ™—n ˜e —ligned in the s—me dire™tionF €h—se tr—nsfer ™—t—lyzed re—™tion h—s ˜een used for piezoele™tri™ polymer prep—r—tion from m—lonitrileD however this method le—ds to low mole™ul—r weightD —nd low yield of impure vinylidene ™y—nide units ™onE t—ining m—teri—lF „he use of solid u2 gy3 —nd —™etonitrile without —dded ph—se tr—nsfer ™—t—lyst shows ex™ellent yields for polyester possessing ˜—™k˜one gemEdinitriles —nd for poly—mide synthesisF „he polyester .4 y3 @€xx„D PGRGRA ferroele™tri™ ™er—mi™ h—s piezoele™tri™ properties th—t —re —˜out TH —nd Q times l—rger th—n the reported v—lues for ny —nd €„F e solEgel te™hnique h—s ˜een developed for the deposition of — novel piezoele™tri™ €xx„ thin (lmF e PEmethoxyeth—nol ˜—sed pro™ess is usedF sn this pro™ess pre™ursors —re he—ted —t lower temper—ture th—n the ˜oiling point of the solventD to distill o' w—terF „hen prior high temper—ture —nne—lingD —ddition of ex™ess €˜ pre™ursor in the pre™ursor solution is required to ™ompens—te the le—d lossF „he pure perovskite ph—se is then o˜t—ined —t THH o gD —fter —nne—lingF „hin (lms of zin™ oxide @nyAD — piezoele™tri™ m—teri—l —nd nEtype wideE˜—ndg—p semi™ondu™torD h—ve ˜een depositedF ny (lms —re ™urrently used in ƒe‡ devi™es —nd in ele™troEopti™ modul—torsF ny thin (lms h—ve ˜een grown ˜y ™hemi™—l v—por deposition —nd ˜oth dF™F —nd rFfF sputtering te™hniquesF ‚e™entlyD optimiz—tion of ny (lms ˜y rFfF m—gnetron sputtering h—s ˜een developedF roweverD homogeneity is one of the m—in pro˜lems when using this te™hniqueD sin™e (lms grown ˜y this optimized methodD showed two regions with di'erent piezoele™tri™ propertiesF hg m—gnetron sputtering is other te™hnique for piezoele™tri™ thin (lm growthD re™ently —luminum nitrideD — promising m—teri—l for use in thinE(lm ˜ulk —™ousti™ w—ve reson—tors for —ppli™—tions in ‚p ˜—ndp—ss (ltersD h—s ˜een grown ˜y this methodF „he ˜est qu—lity (lms —re o˜t—ined on ƒi su˜str—tesF sn order to —™hieve the highest reson—tor ™ouplingD the elx must ˜e grown dire™tly on the ele™trodesF „he m—in pro˜lem in the elx growth is the oxygen ™ont—min—tionD whi™h le—ds to the form—tion of n—tive oxide on the el surf—™eD preventing ™ryst—lline growth of elxF 3.4 „i0.IHV CHAPTER 3.4.2 r0.

8: Scheme of a ordered piezoelectric networks via a liquid-crystalline monomer strategy. Gin and B. Baxter.IHW —nd poly—mide o˜t—ined ™ont—ined — dinitrile group net dipole whi™h ™—n ˜e —lign in the s—me dire™tion —s the ™—r˜onyl groupsF „he pursuit for ˜etter piezoele™tri™ polymers h—s led to mole™ul—r modeling whi™h indi™—tes th—t one ™y—no su˜stituent should ˜e —lmost —s e'e™tive —s two gemin—l ™y—no su˜stituentsD opening — new —re— of potenti—l m—teri—ls h—ving —n —™rylonitrile group —s the ˜—si™ ˜uilding ˜lo™kF roweverD poly—™rilonitrile itself is not suit—˜le ˜e™—use it forms — helixF „hus —™rylonitrile ™opolymers h—ve ˜een investig—tedF wost of the piezoele™tri™ polymers —v—il—˜le —re still synthesized ˜y ™onvention—l methods su™h —s polyE ™ondens—tion —nd r—di™—l polymeriz—tionF „herefore piezoele™tri™ polymer synthesis h—s the s—me pro˜lems —s the ™ommer™i—l polymer prep—r—tionD su™h —s ™ontrolling the degree of polymeriz—tion —nd ™ryst—llinityF e novel te™hnique of v—por deposition polymeriz—tion h—s ˜een reported —s —n —ltern—tive method to ™opolymeri™ thin (lmsF eliph—ti™ polyure— W w—s synthesized ˜y ev—por—ting monomers of IDWEdi—minonon—no —nd IDWEdiiso™y—n—tonon—no onto gl—ss su˜str—te in v—™uumF heposition r—tes were improved —t temper—E tures ˜elow H o gF efter poling tre—tment (lms showed f—irly l—rge piezoele™tri™ —™tivitiesF eddition—llyD — ™ompletely novel —ppro—™h to piezoele™tri™ polymers h—s ˜een presentedF „his —ppro—™hD ™onsists in the synE thesis of ordered piezoele™tri™ polymer networks vi— ™rosslinking of liquidE™ryst—lline monomersF „he m—in go—l in this —ppro—™h is to —™hieve — polymer network whi™h ™om˜ines the long term st—˜ility of piezoele™tri™ singleE™ryst—ls with the e—se of pro™ess—˜ility —nd f—˜ri™—tion of ™onvention—l polymersF pigure QFV shows the s™hem—ti™ represent—tion of this —ppro—™hF Figure 3. Polymer Preprints. 38. C. L. €iezoele™tri™ polymers —re ˜e™oming in™re—singly import—nt ™ommer™i—lly ˜e™—use of their e—sier pro™essE —˜ilityD lower ™ostD —nd higher imp—™t resist—n™e th—n ™er—mi™sD ˜ut the l—™k of high temper—ture st—˜ility —nd the —˜sen™e of — solid underst—nding of the mole™ul—r level ˜—sis for the ele™tri™—l properties —re limit—tionsF „he requirements for strong piezoele™tri™ity in — polymer —reX the polymer ™h—in h—s — l—rger result—nt dipole moment norm—l to the ™h—in —xisY polymer ™ryst—llizes into — pol—r ™ryst—l with the pol—r —xis perpendi™ul—r to the ™h—in —xisD h—s — high ™ryst—llinity —nd (n—lly the polymer pol—r —xis —ligns e—sily in the thi™kness dire™tion during polingF 3.4. Adapted from D. 1996. 211.6 Piezoelectric composites €iezo™omposites h—ve ˜een o˜t—ined ˜y the ™om˜in—tion of piezoele™tri™ ™er—mi™s —nd polymersD the resulting m—teri—l posses ˜oth the high piezoele™tri™ properties of ™er—mi™s —nd the pro™ess—˜ility of polymersF IEQ type piezo™omposites h—ve found wide —ppli™—tions —s medi™—l —nd industri—l ultr—soni™ tr—nsdu™ersF „he ™urrent method for piezo™omposite produ™tion is the di™eE—ndE(ll te™hniqueD whi™h ™onsists in ™utting two sets of grooves in — ˜lo™k of piezo™er—mi™ —t right —ngles e—™h otherD then — polymer is ™—st into these grooves —nd the solid ™er—mi™ ˜—se is ground o'F €olishing —nd poling —re the following steps in order to —™hieve the (n—l thi™kness —nd propertiesF „his method is expensiveD time ™onsuming —nd size limitedF .

7 Piezoelectric coatings. BULK MATERIALS es —n —ltern—tive for the di™eE—ndE(ll te™hniqueD ™ontinuos green (˜ers o˜t—ined ˜y the modi(ed vis™ousE suspensionEspinning pro™essD ™—n ˜e ˜undled into — ™otton˜—llElike sh—peD then ˜urned —nd sinteredF „he sintered ˜undle impregn—ted with epoxy resin ™—n ˜e sli™ed into dis™s —nd then pol—rizedF ‚e™ent results h—ve yielded IEQ type ™omposites with ex™ellent piezoele™tri™ propertiesF yn the other h—ndD —n innov—tive pro™ess h—s ˜een developed for ƒr2 @x˜0.IIH CHAPTER 3.4.5 „—0. w—ny potenti—l —ppli™—tions exist whi™h require (lm thi™kness of I to QH µmF ƒome ex—mples of these m—™roE s™opi™ devi™es in™lude ultr—soni™ high frequen™y tr—nsdu™ersD (˜er opti™ modul—tors —nd for self ™ontrolled vi˜r—tion—l d—mping systemsF ny —nd €„ h—ve ˜een used for piezoele™tri™ (˜er opti™ ph—se modul—tors f—˜ri™—tionF „he piezoele™tri™ m—teri—ls h—ve ˜een sputter deposited using d™ m—gnetron sour™e —nd multim—gnetron sputtering systemsF go—tings of T µm thi™k of ny —nd HFS µm of €„ —re possi˜le to —™hieve using these systemsF roweverD thi™kness v—ri—tion of —pproxim—tely IS7 o™™urs ˜etween the ™enter —nd the end of ny ™o—tingsD results on —'e™ted modul—tion perform—n™eF elthough €„ ™o—tings —™hieved ˜y sputtering posses uniformity —nd do not exhi˜it ™r—™kingD the €„ is only p—rti—lly ™ryst—llized —nd it is —™tu—lly — ™omposite stru™ture ™onsisting of ™ryst—lline —nd —morphous m—teri—lD diminishing the piezoele™tri™ propertiesF ƒolEgel te™hnique for thi™k €„ (lms h—ve ˜een developedF st is now possi˜le to f—˜ri™—te €„ solEgel (lms of up to TH µmF „he ele™tri™—l —nd piezoele™tri™—l properties of the thi™k (lms reported —re ™omp—r—˜le with ™er—mi™ €„F €iezoele™tri™ polymer ™o—tings for highEfrequen™y (˜erEopti™ modul—tors h—ve ˜een —lso investig—tedF gommer™i—l vinylidene )uoride —nd tetr—)uoroethylene ™opolymer h—s ˜een usedF „he —dv—nt—ge of using .14 3 SFS E V X €—r—meter r—nges for piezoele™tri™ ™er—mi™sD polymers —nd ™ompositesF 3.5 A2 y7 G€†hp ™ompositesD in this new f—˜ri™—tion methodD —ppropri—te —mounts of oxides —re mixedD pressed —nd sinteredF „he porous resulting m—teri—l is su˜sequently in(ltr—ted with €†hp solution —nd then poledF „his new method for ™omposites prep—r—tion is simple —nd o'ers — le—dEfree —ltern—tive sm—rt m—teri—lF enother kind of piezo™omposites ™—n ˜e —™hieved ˜y spinning (lms of piezo™er—mi™ onto met—l —lloysD su™h —s „ixiF „he resulting m—teri—ls is — hy˜rid ™omposite th—t ™—n utilize the di'erent —™tive —nd —d—ptive properties of the individu—l ˜ulk m—teri—lsF hue to the sh—pe memory n—ture of „ixiD — possi˜le —ppli™—tion for this new heterostru™tures ™ould ˜e sm—rt —™tive d—mping of me™h—ni™—l vi˜r—tionsF hg sputtering —nd spin ™o—ting —re the te™hniques ne™ess—ry for the sm—rt thin (lm „ixiGpiezoele™tri™ heterostru™tures f—˜ri™—tionF roweverD eventhough the (lms h—d — (ne gr—in stru™ture —nd high me™h—ni™—l qu—litiesD the ferroele™tri™ properties were poor ™omp—red to liter—ture v—luesF sn the futureD the properties of piezo™omposites will ˜e t—iloredD ˜y v—rying the ™er—mi™D the polymer —nd their rel—tive proportionsF edjustments in the m—teri—l properties will le—d to ful(llment of the requireE ments for — p—rti™ul—r devi™eF „—˜le QFIR shows — ™omp—rison —mong piezoele™tri™ ™er—mi™sD polymers —nd ™omposites p—r—meters where  is the imped—n™eD εt 33 is the diele™tri™—l ™onst—ntD —nd ρ is the densityF Material parameter Piezoceramics Piezopolymers Piezocomposites kt @7A  @IH ‚—ylsA 6 RS E SS PH E QH PHH E SHHH PH E QH IFS E R TH E US R E PH SH E PSHH ε t 33 Gε0 ∼IH IFS E S S E IH IEP t—n γ @7A m <I IH E IHHH 3 <I P E SH PES ρ @IH kgGm A Table 3.

Phys. Appl.D IWWUD 33D TQVF vF hel ylmo —nd wF vF g—lz—d—D J. Res.D IWWUD 36D IIRIF sF ekimov —nd qF uF ƒ—v™hukD Inorg. Symp. Soc. SolidsD IWWHD 121D RPRF „F xishiD uF sg—r—shiD „F ƒhimizuD uF uoumotoD —nd rF ‰—n—gid—D J.III polymer ™o—tings is th—t the polymer j—™ket @™o—tingA ™—n ˜e e—sily o˜t—ined ˜y melt extrusion on — singleE mode (˜erF „husD uniformity is e—sily —™hieved —nd surf—™e roughness is not presentF purthermoreD if —nne—ling of the polymer is m—de prior polingD — high degree of ™ryst—llinity is enh—n™edD le—ding to ˜etter piezoele™tri™ propertiesF 3. Proc. Lett. Lett. GrowthD IWWTD 163D QVVF rF „—ked—D uF ƒhim—mur—D „F uohnoD —nd „F pukud—D J. J. Phys. GrowthD IWWTD 169D SHQF veeD „F stoh —nd „F ƒug—D Thin Solid FilmsD IWWUD 299D VVF vF tF w—thi—sD hF eF €—rrishD —nd ƒF ƒte—dm—nD PolymerD IWWRD 35D TSWF qF ‚F poxD xF ƒetterD —nd rFqF vim˜ergerD J. Mater.D IWWTD 28D RTQF uF ƒhim—mur—D rF „—ked—D „F uohnoD —nd „F pukud—D J.D IWWTD 406D PPIF „F ‰—m—motoD Jpn. Res.D IWVWD 8D VHSF uF ‚F wF ‚—oD eF †F €F ‚—oD —nd ƒF uom—rneniD Mater.8 Bibliography • • • • • • • • • • • • • ‚F xF uleim—nD Mat. Appl. Mater. J. Cryst. Sci. Non-Cryst. Cryst.4.D IWWTD 35D SIHRF ‰F ‰—m—shit—D ‰F rosonoD —nd xF s™hinoseD Jpn.D IWWTD 11D PHSIF vF qin —nd fF gF f—xterD Polymer PreprintsD IWWTD 38D PIIF . Mater.


3/>. IIQ .org/content/m16627/1.1.1 Formation of Silicon and Gallium Arsenide Wafers 4.1.1 Introduction sntegr—ted ™ir™uits @sgsA —nd dis™rete solid st—te devi™es —re m—nuf—™tured on semi™ondu™tor w—fersF ƒili™on ˜—sed devi™es —re m—de on sili™on w—fersD while sssE† @IQEISA semi™ondu™tor devi™es —re gener—lly f—˜ri™—ted on q—es w—fersD howeverD for ™ert—in optoele™troni™ —ppli™—tions sn€ w—fers —re —lso usedF „he ele™tri™—l —nd ™hemi™—l properties of the w—fer surf—™e must ˜e well ™ontrolled —nd therefore the prep—r—tion of st—rting w—fers is — ™ru™i—l portion of sg —nd devi™e m—nuf—™turingF sn order to o˜t—in high f—˜ri™—tion yields —nd good devi™e perform—n™eD it is very import—nt th—t the st—rting w—fers ˜e of reprodu™i˜ly high qu—lityF por ex—mpleD the front surf—™e must ˜e smooth —nd )—t on ˜oth — m—™roE —nd mi™ros™—leD ˜e™—use highEresolution p—tterns @lithogr—phyA —re opti™—lly formed on the w—ferF sn prin™ipleD ™utting — ™ryst—l into thin sli™es —nd polishing one side until —ll s—w m—rks —re removed —nd the surf—™e —ppe—rs smooth —nd glossy ™ould produ™e — suit—˜le w—ferF roweverD due in p—rt to the ˜rittleness of ƒi —nd q—es ™ryst—lsD —s well —s the in™re—sing requirements of w—fer ™le—nliness —nd surf—™e defe™t redu™tion with ever de™re—sing devi™e geometriesD — very ™omplex series of pro™essing steps —re required to produ™e —n—lyti™—lly ™le—nD )—t —nd d—m—geEfree w—fer surf—™esF „he following fo™uses on the gener—l prin™iples —nd methods with reg—rd to w—fer form—tionF het—iled forE mul—sD re™ipesD —nd spe™i(™ pro™ess p—r—meters —re not given —s they v—ry ™onsider—˜ly —mong di'erent w—fer produ™ersF roweverD in gener—lD te™hniques for f—˜ri™—tion of ƒi w—fers h—ve gener—lly ˜e™ome st—nd—rdized within the semi™ondu™tor industryF sn ™ontr—stD q—es w—fer te™hnology is less st—nd—rdizedD possi˜ly due to either @—A the simil—rity to sili™on pr—™ti™es or @˜A the lower produ™tion volume of q—es w—fersF „here —re two gener—l ™l—sses of pro™esses in the methodology of m—king w—fersX me™h—ni™—l —nd ™hemi™—lF es ˜oth ƒi —nd q—es —re ˜rittle m—teri—lsD the me™h—ni™—l pro™esses for their w—fer f—˜ri™—tion —re simil—rF roweverD the di'erent ™hemistry of ƒi —nd q—es require th—t the ™hemi™—l pro™esses ˜e de—lt with sep—r—telyF 1 4.2 Wafer formation procedures i—™h of the pro™essing steps in the ™onversion of — semi™ondu™tor ingot @formed ˜y gzo™hr—lski or fridgem—n growthA into — polished w—fer re—dy for devi™e f—˜ri™—tionD results in the remov—l of m—teri—l from the origin—l ingotY ˜etween 1 G3 —nd 1 G2 of the origin—l ingot is s—™ri(™ed during pro™essingF wethods for the remov—l of m—teri—l from — ™ryst—l ingot —re ™l—ssi(ed depending on the size of the p—rti™les ˜eing removed during the pro™essF sf the removed p—rti™les —re mu™h l—rger th—n —tomi™ or mole™ul—r dimensions the pro™ess is des™ri˜ed —s ˜eing m—™roEs™—leF gonverselyD if the m—teri—l is removed —tomE˜yE—tom or mole™uleE˜yEmole™ule then the pro™ess is termed mi™roEs™—leF e further distin™tion ˜etween v—rious types of pro™esses is whether 1 This content is available online at <http://cnx.Chapter 4 Wafer Formation and Processing 4.

(b) grind to required diameter.1. and (d) slice sample for measurements.IIR CHAPTER 4. (c) grind at. WAFER FORMATION AND PROCESSING the remov—l o™™urs —s — result of me™h—ni™—l or ™hemi™—l pro™essesF „he form—tion of — (nished w—fer from — semi™ondu™tor ingot norm—lly requires six m—™hining @me™h—ni™—lA oper—tionsD two ™hemi™—l oper—tionsD —nd —t le—st one polishing @™hemi™—lEme™h—ni™—lA oper—tionF eddition—llyD multiple inspe™tion —nd ev—lu—tion steps —re in™luded in the over—ll pro™essF e summ—ry of the individu—l stepsD —nd their fun™tionsD involved in w—fer produ™tion is shown in „—˜le RFIF Process Type Function ™ropping grinding orient—tion )—tting et™hing w—fering he—t tre—tment edge ™ontouring l—pping et™hing polishing ™le—ning Table 4. Figure 4.1: .3 Crystal shaping elthough —n —sEgrown ™ryst—l ingot is of high purity @WWFWWWW7A —nd ™ryst—llinityD it does not h—ve the su0™iently pre™ise sh—pe required for re—dy w—fer form—tionF „husD prior to sli™ing —n ingot into individu—l w—fersD sever—l steps —re neededF „hese oper—tions required to prep—re the ™ryst—l for sli™ing —re referred to —s ™ryst—l sh—pingD —nd —re shown in pigure RFIF Schematic representation of crystal shaping operations: (a) remove crown and taper.1 me™h—ni™—l me™h—ni™—l me™h—ni™—l ™hemi™—l me™h—ni™—l therm—l me™h—ni™—l me™h—ni™—l ™hemi™—l me™h—noE™hemi™—l ™hemi™—l remov—l of ™oni™—l sh—ped ends —nd impure portions o˜t—in pre™ise di—meter identi(™—tion of ™ryst—l orient—tion —nd dop—nt type remov—l of surf—™e d—m—ge form—tion of individu—l w—fers ˜y ™utting —nnihil—tion of undesir—˜le ele™troni™ donors provide r—dius on the edge of the w—fer provides requisite )—tness of the w—fer remov—l of surf—™e d—m—ge provides — smooth @spe™ul—rA surf—™e remov—l of org—ni™sD he—vy met—lsD —nd p—rti™ul—tes X ƒumm—ry of the pro™ess steps involved in semi™ondu™tor w—fer produ™tionF 4. Shaded area represents material removed.

3. genterless grinding elimin—tes the pro˜lems —sso™i—ted with lo™—ting the ™ryst—l ™enterF „he ™enterless method is superior for long ™ryst—lsY howeverD — ™enterless grinder is mu™h l—rger th—n — ™enter grinder of the .1.1.2 Grinding „he prim—ry purpose of ™ryst—l grinding is to o˜t—in w—fers of pre™ise di—meter ˜e™—use the —utom—ti™ di—meter ™ontrol systems on ™ryst—l growth equipment —re not ™—p—˜le of meeting the tight w—fer di—meter spe™i(™—tionsF sn —dditionD ™ryst—ls —re seldom grown perfe™tly round in ™ross se™tionF „husD ingots —re usu—lly grown with — I E P mm —llow—n™e —nd redu™ed to the proper di—meter ˜y grinding pigure RFI˜F gryst—l grinding is — str—ightforw—rd pro™ess using —n —˜r—sive grinding wheelD howeverD it must ˜e well ™ontrolled in order to —void pro˜lems in su˜sequent oper—tionsF ixit ™hipping in w—fering —nd l—tti™e slip in therm—l pro™essing —re pro˜lems often resulting from improper ™ryst—l grindingF „wo methods —re used for ™ryst—l grindingX @—A grinding on ™enter —nd @˜A ™enterless grindingF pigure RFP shows — s™hem—ti™ of the gener—l setEup for grinding — ™ryst—l ingot on ™enterF „he ™ryst—l is supported —t e—™h end in — l—theElike m—™hineF „he rot—ting ™utting toolD employing — w—terE˜—sed ™ool—ntD m—kes multiple p—sses down the rot—ting ingot until the requisite di—meter is o˜t—inedF „he ™enter grinder ™—n —lso ˜e used for grinding the identi(™—tion )—ts —s well —s providing — uniform ingot di—meterF roweverD grinding the ™ryst—l on ™enters requires th—t the oper—tor lo™—te the ™ryst—l —xis in order to o˜t—in the ˜est yieldF Figure 4.1 Cropping „he —sEgrown ingots h—ve ™oni™—l sh—ped seed @topA —nd t—ng @˜ottomA ends th—t —re removed using — ™ir™ul—r di—mond s—w for e—se of further m—nipul—tion of the ingot @pigure RFI—AF „he ™uttings —re su0™iently pure th—t they —re ™le—ned —nd the re™y™led in the ™ryst—l growth oper—tionF €ortions of the ingot th—t f—il to meet spe™i(™—tions of resistivity —re —lso removedF sn the ™—se of sili™on ingots these se™tions m—y ˜e sold —s met—llurgi™—lEgr—de sili™on @wqƒAF gonverselyD portions of the ™ryst—l th—t meet desired resistivity spe™i(™—tions m—y ˜e preferenti—lly sele™tedF e s—mple sli™e is —lso ™ut to en—˜le oxygen —nd ™—r˜on ™ontent to ˜e determinedY usu—lly this is —™™omplished ˜y pourier tr—nsform infr—red spe™tros™opi™ me—surements @p„Es‚AF pin—llyD ™ropping is used to ™ut ™ryst—ls to — suit—˜le length to (t the s—w ™—p—™ityF 4.2: Schematic representation of grinding on center.3.IIS 4.

3. 4.3 Orientation/identication ats pollowing grinding of the ingot to the desired di—meterD one or two )—ts —re ground —long the length of the ingotF „he identi(™—tion )—ts @one or twoA —re ground lengthwise —long the ™ryst—l —™™ording to the orient—tion —nd the dop—nt typeF efter grinding the ™ryst—l on ™enters the ™ryst—l is rot—ted to the proper orient—tionD then the wheel is positioned with its —xis of rot—tion perpendi™ul—r to the ™ryst—l —xis —nd moved —long the ™ryst—l from end to end until the —ppropri—te )—t size is o˜t—inedF en opti™—l or ˆEr—y orient—tion (xture m—y ˜e used in ™onjun™tion with the ™ryst—l mounting to f—™ilit—te the proper orient—tion of the ™ryst—l on the grinderF „he l—rgest )—t is ™—lled the prim—ry )—t @pigure RFI™A —nd is p—r—llel to one of the ™ryst—l pl—nesD —s determined ˜y ˆEr—y di'r—™tionF „he prim—ry )—t is used for —utom—ted positioning of the w—fer during su˜E sequent pro™essing stepsD eFgFD lithogr—phi™ p—tterning —nd di™ingF yther sm—ller )—ts —re ™—lled 4se™ond—ry )—ts4 —nd —re used to identify the ™ryst—l orient—tion @<III> versus <IHH>A —nd the m—teri—l @nEtype versus pEtypeAF ƒe™ond—ry )—ts provide — qui™k —nd e—sy m—nner ˜y whi™h unknown w—fers ™—n ˜e sortedF „he )—ts shown s™hem—ti™—lly in pigure RFR —re lo™—ted —™™ording to — ƒemi™ondu™tor iquipment —nd w—teri—ls snstitute @ƒiws A st—nd—rd —nd —re ground to spe™i(™ widthsD depending upon ™ryst—ls di—meterF xot™hes —re —lso used in pl—™e of the se™ond—ry )—tY howeverD the rel—tive orient—tions of the not™h —nd prim—ry )—t with reg—rd to ™ryst—l orient—tion —nd dop—nt —re m—int—inedF ® . WAFER FORMATION AND PROCESSING s—me di—meter ™—p—™ityF sn ™enterless grinding the ingot is supported ˜etween two wheelsD — grinding wheel —nd — drive wheelF e s™hem—ti™ of the ™enterless grinder is shown in pigure RFQF „he —xis of the drive wheel is ™—nted with respe™t to th—t of the ™ryst—l ingot —nd the grinding wheel pushing the ™ryst—l ingot p—st the st—tion—ry @˜ut rot—tingA grinding wheelD see pigure RFQ˜F Figure 4.IIT CHAPTER 4.1.3: Schematic representation of centerless grinding viewed (a) along and (b) perpendicular to the crystal axis.

3.4 Wafering „he purpose of w—fering is to s—w the ™ryst—l into thin sli™es with pre™ise geometri™ dimensionsF fy f—rD the most ™ommon method of w—fering semi™ondu™tor ™ryst—ls is the use of —n —nnul—rD or inner di—meter @shAD di—mond s—w ˜l—deF e s™hem—ti™ di—gr—m of sh sli™ing te™hnology is shown in pigure RFSF .IIU Figure 4.1.1. 4.4: SEMI locations for orientation/identication ats.4 Etching „he ™ropping —nd grinding pro™esses —re performed with rel—tively ™o—rse —˜r—sive —nd ™onsequently — gre—t de—l of su˜surf—™e d—m—ge resultsF €itsD ™hipsD —nd ™r—™ks —ll ™ontri˜ute to stress in the ™ut w—fer —nd provide nu™lei for ™r—™k prop—g—tion —t the edges of the (nished w—ferF sf regions of stress —re removed then ™r—™ks will no longer prop—g—teD redu™ing exit ™hipping —nd w—fer ˜re—k—ge during su˜sequent f—˜ri™—tion stepsF „he gener—l method for removing surf—™e d—m—ge is to et™h the ™ryst—l in — hot solutionF „he most ™ommon et™h—nts for ƒi —re ˜—sed on the rxy3 Erp systemD in whi™h et™h—nt modi(ers su™h —s —™eti™ —™id —lso ™ommonly usedF sn the ™—se of q—es rglErxy3 is the —ppropri—te systemF „hese et™h—nts sele™tively —tt—™k the ™ryst—l —t the d—m—ged regionsF efter et™hingD the ™ryst—l is tr—nsferred to the sli™ing prep—r—tion —re—F 4.

WAFER FORMATION AND PROCESSING Figure 4. „he ™ryst—lD when it —rrives —t the s—wing —re—D h—s ˜een ground to di—meterD )—ttedD —nd et™hedF sn order to sli™e itD the ™ryst—l must ˜e (rmly mounted in su™h — w—y th—t it ™—n ˜e ™ompletely ™onverted to w—fers with minimum w—steF „he ™ryst—l is —tt—™hed with w—x or epoxy to — mounting ˜lo™kD whi™h is usu—lly ™ylindri™—l in sh—pe —nd of the s—me di—meter —s the ingotF elsoD — mounting ˜e—m @or stripA is —tt—™hed —long the length of the ™ryst—l —t the ˜re—kout point of the s—w ˜l—deF „his redu™es exit ™hipping @˜re—k—ge th—t o™™urs —s the ˜l—de exits the ™ryst—l —t the end of — ™utA —nd —lso provides support for the s—wn w—fer until it is retrievedF qr—phite or phenoli™ resins —re ™ommon m—teri—ls for the mounting ˜lo™k —nd ˜e—msD —lthough some su™™ess h—s ˜een o˜t—ined in mounting ingots using hydr—uli™ pressureF „he s—w ˜l—de is — thin sheet of st—inless steel @QPS µmAD with di—mond ˜onded to its inner edgeF „his ˜l—de is mounted on — drum th—t rot—tes —t caF PHHH rpmF ƒ—w ˜l—des SV ™m @≈PQ in™hesA in di—meter with — PH ™m @V in™hesA opening —re ™ommonD howeverD —s w—fer sizes in™re—se l—rger ˜l—des —re employedX QH ™m @IP in™hesA w—fers —re now ™ommon for ƒiF „he ˜l—de moves rel—tive to the st—tion—ry ™ryst—l —t — speed of HFHS ™mGsD —nd the ™utting pro™ess is w—terE™ooledF „husD ™onsidering th—t w—fers —re sli™ed sequenti—lly @one —t — timeAD the over—ll pro™ess is very slowF e further pro˜lem is th—t the kerf loss @loss due to the width of the ˜l—deA results in —pproxim—tely IGQ of the m—teri—l ˜eing lost —s s—w dustF pin—llyD the depth of the drum onto whi™h the ˜l—de is —tt—™hed limits the length of the ingot se™tion th—t is —™™essi˜leF sn order to over™ome this pro˜lemD —nother style of sh ˜l—de s—w w—s developed in whi™h the ˜l—de is mounted on —n —ir ˜e—ring —nd is rot—ted ˜y — ˜elt driveF „his —llows the entire length of the ™ryst—l ingot to ˜e sli™edF foth sili™on —nd q—es ™ryst—ls —re grown with either the ™ryst—llogr—phi™ <IHH> or <III> dire™tion p—r—llel to the ™ylindri™—l —xis of the ™ryst—lF ‡—fers m—y ˜e ™ut either ex—™tly perpendi™ul—r to the ™rysE t—llogr—phi™ —xis or deli˜er—tely o'E—xis ˜y sever—l degreesF sn order to o˜t—in the proper w—fer orient—tionD the ™ryst—l must ˜e properly oriented on the s—wF ell produ™tion sli™ing m—™hines h—ve —djustments for orient—tion of the ™ryst—lY howeverD it is usu—lly ne™ess—ry to ™he™k the orient—tion of the (rst sli™e in order to —ssure th—t —ll su˜sequent sli™es will ˜e properly orientedF y˜vious v—ri—˜les introdu™ed during the w—fering pro™ess in™ludeX ™utting r—teD wheel speedD —nd ™ool—nt )ow r—teF roweverD the ™ondition of the m—™hinesD su™h —s —lignment —nd vi˜r—tionD is the most import—nt v—ri—˜le followed ˜y the ™ondition of the ˜l—deF e devi—ted ˜l—de rim m—y ™—use t—perD ˜owD or w—rpF „—˜le RFP summ—rizes the types of deform—tions th—t ™—n o™™ur during w—feringD their physi™—l —ppe—r—n™e —nd their ™h—r—™teristi™sF .IIV CHAPTER 4.5: Schematic diagrams of ID slicing process.

6 Lapping or grinding „he —sE™ut w—fers v—ry su0™iently in thi™kness to require —n —ddition—l oper—tionD the sli™ing oper—tion does not ™onsistently produ™e the required )—tness —nd p—r—llelism required for m—ny w—fer spe™i(™—tionsD see „—˜le RFPF ƒin™e ™onvention—l polishing does not ™orre™t v—ri—tions in )—tness or thi™knessD — me™h—ni™—l twoEsided l—pping oper—tion is performedF v—pping is ™—p—˜le of —™hieving very pre™ise thi™kness uniformityD )—tness —nd p—r—llelismF v—pping —lso prep—res the surf—™e for polishing ˜y removing the su˜Esurf—™e s—wing d—m—geD repl—™ing it with — more uniform —nd sm—ller l—pping d—m—geF „he pro™ess used for l—pping semi™ondu™tor w—fers evolved from the opti™—l lens m—nuf—™turing industry using prin™iples developed over sever—l hundred ye—rsF roweverD —s the lens h—s — ™urved surf—™e —nd the w—fers —re )—tD the equipment for l—pping w—fers is me™h—ni™—lly simpler th—n lens pro™essing m—™hinesF „he simplest dou˜leEside l—pping m—™hine ™onsists of two very )—t ™ounterErot—ting pl—tesD ™—rriers to hold —nd move the w—fers ˜etween the pl—tesD —nd — devi™e to feed —˜r—sive slurry ste—dily ˜etween the pl—tesF „he —˜r—sive is typi™—lly — W µm el2 y3 gritF gommer™i—l —˜r—sives —re suspended in w—ter or gly™erin with propriet—ry —dditives to —ssist in suspension —nd dispersion of the p—rti™lesD to improve the )ow properties .IIW Type warp of bow and Surface appearance Lattice curvature Comments )—t ™urved ™urved )—t ™urved )—t )—t ™urved ™urved )—t ide—l slips Table Heat treatment esEprodu™ed gzo™hr—lski grown ™ryst—ls often h—ve — level of oxygen impurity th—t m—y ex™eed the ™on™enE tr—tion of dop—nt in the semi™ondu™tor m—teri—l @iFeFD ƒi or q—esAF „his oxygen impurity h—s — deleterious e'e™t on the semi™ondu™tor propertiesD espe™i—lly upon su˜sequent therm—l pro™essingD eFgFD therm—l oxide growth or epit—xi—l (lm growth ˜y met—l org—ni™ ™hemi™—l v—por deposition @wyg†hAF por ex—mpleD when sili™on ™ryst—ls —re he—ted to —˜out RSH ◦ g the oxygen undergoes — tr—nsform—tion th—t ™—uses it to ˜eh—ve —s —n ele™tron donorD mu™h like —n nEtype dop—ntF „hese oxygen donorsD or 4therm—l donors4D m—sk the true resistivity of the semi™ondu™tor ˜e™—use they either —dd —ddition—l ™—rrier ele™trons to — nEtype ™ryst—l or ™ompens—te for the positive holes in — pEtype ™ryst—lF portun—telyD these therm—l donors ™—n ˜e 4—nnihil—ted4 ˜y he—t tre—ting the m—teri—ls ˜rie)y in the r—nge of SHH E VHH ◦ g —nd then ™ooling qui™kly through the RSH ◦ g region ˜efore donors ™—n reformF sn prin™iple therm—l donor —nnihil—tion ™—n ˜e performed on w—fers —t —ny time during their f—˜ri™—tionY howeverD it is usu—lly ˜est to perform the he—t tre—tment immedi—tely —fter w—fering sin™e su˜Est—nd—rd w—fers m—y ˜e reje™ted ˜efore —ddition—l pro™essing steps —re undert—ken —nd thus limiting —ddition—l ™ostF honor —nnihil—tion is — ˜ulk e'e™tD —nd therefore the therm—l tre—tment ™—n ˜e performed in —irD sin™e —ny surf—™e oxide th—t m—y form will ˜e removed in su˜sequent l—pping —nd polishing stepsF 4.2 X heformed w—fers —nd their ™h—r—™teristi™sF 4.

4. WAFER FORMATION AND PROCESSING of the slurryD —nd to prevent ™orrosion of the l—pping m—™hineF rydr—uli™s or —n —ir ™ylinder —pplies l—pping pressure with low st—rting pressure for P to S minutesD whi™h is then in™re—sed through most of the pro™essF „he ™ompletion of l—pping m—y ˜e determined ˜y el—psed time or ˜y —n extern—l thi™kness sensing devi™eF „he (nished pro™ess gives — w—fer with — surf—™e uniform to within P µmF epproxim—tely PH µm per side is removed during the l—pping pro™essF elthough l—pping would —ppe—r to ˜e simple in ™on™eptD the su™™essful implement—tion of — produ™tion l—pping oper—tion requires the development of — te™hnique —nd experien™e to —™hieve —™™ept—˜le qu—lity with good yieldsF ƒm—ll —djustments to the rot—tion r—tes of the pl—tes —nd ™—rriers will ™—use the pl—tes to we—r ™on™—veD ™onvex or )—tF es l—pping is — messy pro™essD v—rious e'orts h—ve ˜een m—de to —void it or to su˜stitute —n —ltern—tive pro™essF „he most likely —ppro—™h —t present is grindingD in whi™h the w—fer is held on — v—™uum ™hu™k —nd — series of progressively (ner di—mond wheels is moved over the w—fer while it is rot—ted on — turn t—˜leF qrinding gives — ™le—rer surf—™e th—n l—ppingD howeverD only one side m—y ˜e ground —t — time —nd the resulting )—tness is not —s good —s th—t o˜t—ined ˜y l—ppingF 4.IPH CHAPTER 4.1.8 Etching „he me™h—ni™—l pro™esses des™ri˜ed —˜ove to sh—pe the w—fer le—ve the surf—™e —nd edges d—m—ged —nd ™ont—min—tedF „he depth of the work d—m—ge depends on the spe™i(™ pro™essD howeverD IH µm is typi™—lF .1.7 Edge contouring „he rounding of the edge of the w—fer to — spe™i(™ ™ontour is — f—irly re™ent development in the te™hnology of w—fer prep—r—tionF st w—s known ˜y the e—rly seventies th—t — signi(™—nt num˜er of devi™e yield pro˜lems ™ould ˜e tr—™ed to the physi™—l ™ondition of the w—fer edgeF en —™ute edge —'e™ts the strength of the w—fer due toX stress ™on™entr—tionD —nd — lowering of its resist—n™e to therm—l stressD —s well —s ˜eing the sour™e of p—rti™le ™hipD ˜re—k—geD —nd l—tti™e d—m—geF sn —dditionD the p—rti™les origin—ting from the ™hipped edges ™—nD if present on the w—fer surf—™eD —dd to the defe™t density @h0 A of the sg pro™ess redu™ing f—˜ri™—tion yieldF purther pro˜lems —sso™i—ted with — squ—re edge in™lude the ˜uildEup of photoresist —t the w—fer edgeF „he solution to these pro™ess pro˜lems is to provide — ™ontoured edge with — de(ned r—dius @rAF ghemi™—l et™hing of w—fers results in — degree of edge roundingD ˜ut it is di0™ult to ™ontrolF „husD me™h—ni™—l edge ™ontouring h—s ˜een developed —nd the result h—s ˜een — dr—m—ti™ improvement in yields in downstre—m w—fer pro™essingF vosses due to w—fer ˜re—k—ge —re —lso redu™edF „he edge ™ontouring pro™ess is usu—lly performed in ™—ssetteEfed high speed equipmentD in whi™h e—™h w—fer is rot—ted r—pidly —g—inst — sh—ped ™utting tool @pigure RFTAF Figure 4.6: Schematic illustration of edge contouring.

Rate limiting step Etching rate Results Comments hi'usion of re—gent to the surf—™e ‚e—™tion —t semi™onE du™tor surf—™e hi'usion produ™ts surf—™e of re—™tion from the slow f—st slow et™hing@—nisotropi™A polishing@isotropi™A polishing@isotropi™A enh—n™ed surf—™e roughE ness ide—l re—™tion produ™t m—ins on surf—™e reE Table 4.7: Schematic representation of the three steps involved in wet chemical etching: (i) diusion of the chemical etch reagents through the boundary layer.IPI ƒu™h d—m—ge is re—dily removed ˜y ™hemi™—l et™hingF it™hing is used —t multiple points during the f—˜ri™—tion of — semi™ondu™tor devi™eF „he dis™ussion ˜elow is limited to et™hes suit—˜le for w—fer f—˜ri™—tionD iFeFD nonE sele™tive et™hing of the entire w—fer surf—™eF 4.3 X i'e™ts of r—te limiting step in semi™ondu™tor et™hingF en et™h—nt th—t is limited ˜y the r—te of re—™tion —t the surf—™e will tend to enh—n™e —ny surf—™e fe—tures —nd promote surf—™e roughness due to preferenti—l et™hing —t defe™ts @—nisotropi™AF sn ™ontr—stD if the et™h r—te is limited ˜y the di'usion of the et™h—nt re—gent through — st—gn—nt @de—dA ˜ound—ry l—yer ne—r the surf—™eD then the et™h will result in uniform polishing —nd the surf—™e will ˜e™ome smooth @isotropi™AF sf remov—l of the re—™tion produ™ts is r—te limiting then the et™h r—te will ˜e slow ˜e™—use the et™h equili˜rium will ˜e shifted tow—rds the re—™t—ntsF sn the ™—se of —n individu—l et™h—nt re—™tionD the r—te determining step m—y ˜e ™h—nged ˜y r—pid stirring to —id remov—l of re—™tion produ™tsD or ˜y in™re—sing the temper—ture of the et™h solutionD see pigure RFVF „he ex—™t et™hing ™onditions —re ™hosen depending on the —ppli™—tionF por ex—mpleD dilute high temper—ture et™hes —re often employed where the et™h d—m—ge must ˜e minimizedD while ™ooled et™hes ™—n ˜e used where pre™ise et™h ™ontrol is requiredF .8. and (iii) diusion of the reaction products into the etch solution through the boundary layer. (ii) chemical reaction at the surface.1 Wet chemical etching „he wet ™hemi™—l et™hing of —ny m—teri—l ™—n ˜e ™onsidered to involve three stepsX @—A tr—nsport—tion of the re—™t—nts to the surf—™eD @˜A re—™tion —t the surf—™eD —nd @™A movement of the re—™tion produ™ts into the et™h—nt solution @pigure RFUAF i—™h of these m—y ˜e the r—te limiting step —nd thus ™ontrol the et™h r—te —nd uniformityF „his e'e™t is summ—rized in „—˜le RFQF Figure 4.1.

8.4 QU WV UW WW PW rp r3 €y4 rgly4 r2 y2 RW VS UH QH X ‡eight per™ent ™on™entr—tion of ™ommonly used ™on™entr—ted —queous re—gentsF „he equipment used for — typi™—l et™h—nt pro™ess in™ludes —n —™id @or —lk—lineA resist—nt t—nkD whi™h ™ont—ins the et™h—nt solution —nd one or more positions for rinsing the w—fers with deionized w—terF „he pro™ess is ˜—t™h in n—ture involving tens of w—fers —nd the ˜est equipment provides — me—ns of rot—ting the w—fers during the et™h step to m—int—in uniformityF sn order to —ssure the remov—l of —ll surf—™e d—m—geD su˜st—nti—l overEet™hing is performedF „husD the remov—l of PH µm from e—™h side of the w—fer is typi™—lF it™h times —re usu—lly sever—l minutes per ˜—t™hF 4.1. (45%) and (35%). WAFER FORMATION AND PROCESSING Figure 4.8: Typical etch rate versus temperature plot for a mixture of HF (20%). „r—dition—lly mixtures of hydro)uori™ —™id @rpAD nitri™ —™id @rxy3 A —nd —™eti™ —™id @wegy2 rA h—ve ˜een used for sili™onD ˜ut —lk—line et™hes using pot—ssium hydroxide @uyrA or sodium hydroxide @x—yrA solutions —re in™re—singly ™ommonF ƒimil—rlyD g—llium —rsenide et™hes m—y ˜e either —™idi™ or ˜—si™D howeverD in ˜oth ™—ses the et™hes —re oxid—tive due to the use of hydrogen peroxideF e wide r—nge of ™hemi™—l re—gents —re ™ommer™i—lly —v—il—˜le in 4tr—nsistor gr—de4 purity —nd these —re employed to minimize ™ont—min—tion of the semi™ondu™torF heionized w—ter is ™ommonly used —s — diluent for e—™h of these re—gents —nd the ™on™entr—tion of ™ommonly used —queous re—gents is given in „—˜le RFRF Reagent Weight % Reagent Weight % rgl r2 ƒy4 rxy3 wegy2 r xr4 yr Table 4.2 Etching silicon „he most ™ommonly used et™h—nts for sili™on —re mixtures of hydro)uori™ —™id @rpA —nd nitri™ —™id @rxy3 A in w—ter or —™eti™ —™id @wegy2 rAF „he et™hing involves — redu™tionEoxid—tion @redoxA re—™tionD followed ˜y .IPP CHAPTER 4.

1.IPQ dissolution of the re—™tion produ™tsF sn the rpErxy3 system the rxy3 oxidizes the sili™on —nd the rp removes the re—™tion produ™ts from the surf—™eF „he over—ll re—™tion isX @RFIA „he oxid—tion re—™tion involves the oxid—tion of ƒi0 to ƒi4+ D —nd it is —utoE™—t—lyti™ in th—t the re—™tion produ™t promotes the re—™tion itselfF „he initi—l step involves tr—™e impurities of rxy2 in the rxy3 solution @@RFPAAD whi™h re—™t to li˜er—te nitrogen dioxide @xy2 AD @RFQAF @RFPA @RFQA „he nitrogen dioxide oxidizes the sili™on surf—™e in the presen™e of w—terD resulting in the form—tion of ƒi@yrA2 —nd the reform—tion of rxy2 @@RFRAAF „he ƒi@yrA2 de™omposes to give ƒiy2 @@RFSAAF ƒin™e the re—™tion ˜etween rxy2 —nd rxy3 @@RFPAA is r—te limitingD —n indu™tion period is o˜servedF roweverD this is over™ome ˜y the —ddition of xy2 .ions in the form of ‘xr4 “‘xy2 “F @RFRA @RFSA „he (n—l step of the et™h pro™ess is the dissolution of the ƒiy2 ˜y rp @@RFTAAF ƒtirring serves to remove the solu˜le produ™ts from the re—™tion surf—™eF „he role of the rp is to —™t —s — ™omplexing re—gentD —nd thus the re—™tion shown in @RFTA is known —s — ™omplexing re—™tionF „he form—tion of w—ter —s — re—™tion produ™t requires th—t —™eti™ —™id ˜e used —s — diluent @solventA to ensure ˜etter ™ontrolF @RFTA „he et™hing re—™tion is highly dependent on the rel—tive r—tios of the et™h—nt re—gentsF „husD if —n rpEri™h solution is usedD the re—™tion is limited ˜y the oxid—tion step @@RFRAA —nd the et™hing is —nisotropi™D sin™e the oxid—tion re—™tion is sensitive to dopingD ™ryst—l orient—tionD —nd defe™tsF sn ™ontr—stD the use of — rxy3 Eri™h solution produ™es isotropi™ et™hing sin™e the dissolution pro™ess is r—te limiting @„—˜le RFQAF „he re—™tion of rxy3 Eri™h solutions h—s ˜een found to ˜e di'usionE™ontrolled over the temper—ture r—nge PH E SH ◦ g @pigure RFVAD —nd is therefore ™ommonly employed for removing work d—m—ge produ™ed during w—fer f—˜ri™—tionF „he ˜ound—ry l—yer thi™kness @pigure RFUA —nd therefore the dimension—l ™ontrol over the w—fer is ™ontrolled ˜y the rot—tion r—te of the w—fersF e ™ommon et™h formul—tion is — RXIXQ mixture of rxy3 @UW7AD rp @RW7AD —nd wegy2 r @WW7AF „here —re some et™h—nt formul—tions th—t —re ˜—sed on —ltern—tive @or —ddition—lA oxidizing —gentsD su™h —sX fr2 D s2 D —nd uwny4 F elk—line et™hing @uyrGr2 y or x—yrGr2 yA is ˜y n—ture —nisotropi™ —nd the et™h r—te depends on the num˜er of d—ngling ˜onds whi™h in turn —re dependent on the surf—™e orient—tionF ƒin™e et™hing is re—™tion r—te limited no rot—tion of the w—fers is ne™ess—ry —nd ex™ellent uniformity over l—rge w—fers is o˜t—inedF elk—line et™h—nts —re used with l—rge w—fers where dimension—l uniformity is not m—int—ined during l—ppingF e typi™—l formul—tion uses uyr in — RS7 weight solution in r2 y —t WH ◦ gF 4.3 Etching gallium arsenide elthough — wide r—nge of et™hes h—ve ˜een investig—ted for q—esD few —re truly isotropi™F „his is ˜e™—use the surf—™e —™tivity of the @IIIA q— —nd @IIIA es f—™es —re very di'erentF „he es ri™h f—™e is ™onsider—˜ly .8.

5 X „he ™omposition —nd —ppli™—tion of sele™ted et™h systems for q—esF . WAFER FORMATION AND PROCESSING more re—™tive th—n the q— ri™h f—™eD thus under identi™—l ™onditions it will et™h f—sterF es — result most et™hes give — polished surf—™e on the es f—™eD ˜ut the q— f—™e tends to —ppe—r ™loudy or frosted due to the highlighting of surf—™e fe—tures —nd ™ryst—llogr—phi™ defe™tsF es with sili™on the et™h systems involve oxid—tion —nd ™omplex—tionF roweverD in the ™—se of q—es the g—llium is —lre—dy fully oxidized @form—lly q—3+ AD thusD it is the —rseni™ @form—lly the —rsenide ionD es3.IPR CHAPTER—t is oxidized ˜y — suit—˜le oxidizing —gent @eFgFD r2 y2 A to the solu˜le oxideD es2 y3 @@RFUAAF „he g—llium ions form the oxide q—2 y3 vi— the hydroxide @@RFVAAF foth oxides —re solu˜le in —™id solutionsD resulting in their remov—l from the surf—™eF @RFUA @RFVA „he peroxide ˜—sed oxid—tive et™hes for q—es —re divided into —™idi™ —nd ˜—si™ et™hesF „he ™omposition —nd —ppli™—tion of some of these systems —re summ—rized in „—˜le RFSF „he most widely used of these is r2 ƒy4 Gr2 y2 Gr2 y —nd is referred to —s g—ro9s —™idF „he high vis™osity of r2 ƒy4 results in di'usionE limited et™hing with high —™id ™on™entr—tionsF it™hes with low —™id ™on™entr—tions tend to ˜e —nisotropi™F €hosphori™ —™id @r3 €y4 A or ™itri™ —™id @pigure RFWA m—y ˜e ex™h—nged for sulfuri™ —™id @r2 ƒy4 AF ‚epl—™ement of the —™id ™omponent with ˜—ses su™h —s xr4 yr or x—yr ™—n result in ne—r to truly isotropi™ et™h—ntsD —lthough ™ert—in ™om˜in—tions ™—n result in strong —nisotropyF Formulation Volume ratio (100) etch rate (µm/min) (110) etch rate (µm/min) (111)As etch rate (µm/min) (111)Ga etch rate (µm/min) r2 ƒy4 G r2 y2 G r2 y r2 ƒy4 G r2 y2 G r2 y r2 ƒy4 G r2 y2 G r2 y ™itri™ —™idG r2 y2 G r2 y xr4 yrG r2 y2 G r2 y x—yrG r2 y2 G r2 y VXIXI IXVXI QXIXSH IXIXI IXUHH IXHFUT IFS VFH HFV HFT HFQ HFP IFS VFH HFV HFT HFQ HFP IFS IPFH HFV HFT HFQ HFP HFV QFH HFR HFR HFQ HFP Table 4.

IPS Figure 4. yne of the e—rliest et™hing systems for q—es is ˜—sed on the use of — dilute @™—F HFHS volF7A solution of ˜romine @fr2 A in eth—nolF „he fr2 —™ts —s the oxid—ntD resulting in the form—tion of solu˜le ˜romidesF „he et™h r—te of this system is di'erent for di'erent ™ryst—llogr—phi™ pl—nesD iFeFD the et™h r—tes for the @IIIA esD @IHHAD —nd @IIIA q— f—™es —re in the r—tio TXSXID —lthough more uniform et™h r—tes —re o˜served with high fr2 ™on™entr—tions @™—F IH volF7AF „hese higher ™on™entr—tion solutions —re used for the remov—l of d—m—ge due to ™utting with the s—wF 4.9: Structure of citric acid.9.1 Dierences between polishing and lapping sf the surf—™e of — w—fer th—t h—s undergone l—pping @or grindingA is ex—mined with —n ele™tron mi™ros™opeD ™r—™ksD ridges —nd v—lleys —re o˜servedF „he top 4relief l—yer4 ™onsists of pe—ks —nd v—lleysF felow this l—yer is — d—m—ged l—yer ™h—r—™terized ˜y mi™ro™r—™ksD dislo™—tionsD slip —nd stressF pigure RFIH shows — s™hem—ti™ represent—tion of the —˜r—ded surf—™eF foth of these l—yers must ˜e removed ™ompletely prior to further f—˜ri™—tionF he™re—sing the p—rti™le size of the —˜r—sive during l—pping only de™re—ses the s™—le of the d—m—geD ˜ut does not elimin—te it entirelyF sn f—™t this surf—™e d—m—ge is — ™h—r—™teristi™ of the ˜rittle fr—™ture of single ™ryst—l ƒi —nd q—esD —nd o™™urs ˜e™—use during l—pping the —˜r—sive gr—ins —re moved —™ross the surf—™e under — pressure ˜eyond th—t of the fr—™ture strength of the w—fer m—teri—ls @ƒi or q—esAF sn ™ontr—st to the me™h—ni™—l —˜r—sion employed in l—ppingD polishing is — me™h—noE™hemi™—l pro™ess during whi™h ˜rittle fr—™ture does not o™™urF e polished w—fer does not displ—y —ny eviden™e of — relief surf—™e su™h —s th—t produ™ed ˜y l—ppingD even —t highest resolution ele™tron mi™ros™opeF .1.1.9 Polishing „he purpose of polishing is to produ™e — smoothD spe™ul—r surf—™e on whi™h devi™e fe—tures ™—n ˜e de(ned ˜y lithogr—phyF sn order to —llow for very l—rge s™—le integr—tion @†vƒsA or ultr— l—rge s™—le integr—tion @…vƒsA f—˜ri™—tion the w—fer must h—ve — surf—™e with — high degree of )—tnessF †—ri—tions less th—n S to IH µm —™ross the w—fer di—meter —re typi™—l )—tness spe™i(™—tionsF sn —dditionD given the pre™eding stepsD w—fer polishing must not le—ve residu—l ™ont—min—tion or surf—™e d—m—geF „he te™hniques of w—fer polishing —re derived from the gl—ss lens industryD with some import—nt modi(™—tions th—t h—ve ˜een developed to meet the spe™i—l requirements of the mi™roele™troni™s industryF 4.

1.IPT CHAPTER 4. sn order to —™hieve — re—son—˜le r—te of remov—l of the relief —nd d—m—ged l—yers —nd still o˜t—in the highest qu—lity surf—™eD the polishing is done in two stepsD sto™k remov—l —nd h—ze remov—lF „he former is .11: Schematic representation of the wafer polishing process. WAFER FORMATION AND PROCESSING Figure 4. Schematic representation of a cross sectional view of an abraded wafer surface prior to 4.2 Process of Polishing idIQQTPSQH shows — s™hem—ti™ of the polishing pro™essF €olishing m—y ˜e ™ondu™ted on single w—fers or —s — ˜—t™h pro™ess depending on the equipment employedF ƒingle w—fer polishing is preferred for l—rger w—fers —nd —llows for ˜etter surf—™e )—tnessF sn ˜oth pro™essesD w—fers —re mounted onto — (xtureD ˜y either w—x or — ™omposite pelxEwount—D —nd pressed —g—inst the polishing p—dF „he polishing p—d is usu—lly m—de from —n —rti(™i—l f—˜ri™ su™h —s polyester feltEpolyureth—ne l—min—teF €olishing is —™™omplished ˜y — me™h—noE ™hemi™—l pro™ess in whi™h —queous polishing slurry is dripped onto the polishing p—dD see idIQQTPSQHF „he polishing slurry performs ˜oth — ™hemi™—l —nd me™h—ni™—l pro™essD —nd ™onsists of (ne sili™— @ƒiy2 A p—rti™les @IHH Å di—meterA —nd —n oxidizing —gentF equeous sodium hydroxide @x—yrA is used for ƒiD while —queous sodium ™hlor—te @x—yglA is preferred for q—esF ƒuspending —gents —re usu—lly —dded to prevent settling of the sili™— p—rti™lesF …nder the he—t ™—used ˜y the fri™tion of the w—fer on the polishing p—d the w—fer surf—™e is oxidizedD whi™h is the ™hemi™—l stepD while in the me™h—ni™—l step the sili™— p—rti™les in the slurry —˜r—de the oxidized surf—™e —w—yF Figure 4.9.10: polishing.

1.10 Cleaning huring the pro™esses des™ri˜ed —˜oveD semi™ondu™tor w—fers —re su˜je™ted to physi™—l h—ndling th—t le—ds to signi(™—nt ™ont—min—tionF €ossi˜le sour™es of physi™—l ™ont—min—tion in™ludeX —F —ir˜orne ˜—™teri—D ˜F gre—se —nd w—x from ™utting oils —nd physi™—l h—ndlingD ™F —˜r—sive p—rti™ul—tes @usu—llyD sili™—D sili™on ™—r˜ideD —lumin—D or di—mond dustA from l—ppingD grinding or s—wing oper—tionsD dF pl—sti™izers whi™h —re derived from ™ont—iners —nd wr—pping in whi™h the w—fers —re h—ndled —nd shippedF ghemi™—l ™ont—min—tion m—y —lso o™™ur —s — result of improper ™le—ning —fter et™h stepsF vightEmet—l @espeE ™i—lly sodium —nd pot—ssiumA spe™ies m—y ˜e tr—™ed to impurities in et™h—nt solutions —nd —re ™hemisor˜ed on to the surf—™e where they —re p—rti™ul—rly pro˜lem—ti™—l for met—l oxide semi™ondu™tor @wyƒA ˜—sed devi™esD —lthough higher levels of su™h impurities —re toler—˜le for ˜ipol—r devi™esF re—vy met—l impurities @eFgFD guD euD peD —nd egA —re usu—lly ™—used ˜y ele™trodeposition from et™h—nt solutions during f—˜ri™—tionF ‡hile w—fers —re ™le—ned prior to shippingD ™ont—min—tion —™™umul—ted during shipping —nd stor—ge ne™essit—tes th—t —ll w—fers ˜e su˜je™ted to s™rupulous ™le—ning prior to f—˜ri™—tionF purthermoreD ™le—ning is required —t e—™h step during the f—˜ri™—tion pro™essF elthough w—fer ™le—ning is — vit—l p—rt of e—™h f—˜ri™—tion stepD it is ™onvenient to dis™uss ™le—ning within the gener—l topi™ of w—fer f—˜ri™—tionF 4.10.IPU ™—rried out with — higher ™on™entr—tion slurry —nd m—y pro™eed for —˜out QH minutes —t — remov—l r—te of I µmGminF r—ze remov—l is performed with — very dilute slurryD — softer p—d with — re—™tion time of —˜out S to IH minutesD during whi™h the tot—l —mount of m—teri—l removed is only —˜out I µmF hue to the —™tive ™hemi™—l re—™tion ˜etween the w—fer —nd the polishing —gentD the w—fers must ˜e rinsed in deionized w—ter immedi—tely —fter polishing to prevent h—ze or st—ins from reformingF „here —re m—ny v—ri—˜les th—t will in)uen™e the r—te —nd qu—lity of polishingF righ pressure results in — higher polishing r—teD ˜ut ex™essive pressure m—y ™—use nonEuniform polishingD ex™essive he—t gener—tion —nd f—st p—d we—rF „he r—te of polishing is in™re—sed with higher temper—tures ˜ut this m—y —lso le—d to h—ze form—tionF righ wheel speeds —™™eler—te the polishing r—te ˜ut ™—n r—ise the temper—ture —nd —lso results in pro˜lems in m—int—ining — uniform )ow of slurry —™ross the p—dF hense slurry ™on™entr—tions in™re—se the polishing r—te ˜ut —re more ™ostlyF „he pr of the slurry solution ™—n —lso —'e™t the polishing r—teD for ex—mple the polishing r—te of ƒi gr—du—lly in™re—ses with in™re—sed pr @higher ˜—si™ityA until — pr of —˜out IP where — dr—m—ti™ de™re—se is o˜servedF sn gener—lD the optimum polishing pro™ess for — given f—™ility depends l—rgely upon the interpl—y of produ™t spe™i(™—tionD yieldsD ™ostD —nd qu—lity ™onsider—tions —nd must ˜e developed uniquelyF „he w—fer polishing pro™ess does not improve the w—fer )—tness —ndD —t ˜estD polishing will not degr—de the w—fer )—tness —™hieved in the l—pping oper—tionF 4.1 Cleaning silicon „he (rst step in ™le—ning — ƒi w—fer is remov—l of —ll physi™—l ™ont—min—ntsF „hese ™ont—min—tes —re removed ˜y rinsing the w—fer in hot org—ni™ solvents su™h —s IDIDIEtri™hloroeth—ne @gl3 gr3 A or xylene @g6 r4 we2 AD —™™omp—nied ˜y me™h—ni™—l s™ru˜˜ingD ultr—soni™ —git—tionD or ™ompressed g—s jetsF ‚emov—l of the m—E jority of light met—l ™ont—min—nts is —™™omplished ˜y rinsing in hot deionized w—terD howeverD ™omplete remov—l requires — further more —ggressive ™le—ning pro™essF „he most widely used ™le—ning method in the ƒi semi™ondu™tor industry is ˜—sed on — two stepD two solution sequen™e known —s the ‚ge gle—ning wethodF „he (rst solution ™onsists of r2 yEr2 y2 Exr4 yr in — volume r—tio of SXIXI to UXPXID whi™h is used to remove org—ni™ ™ont—min—nts —nd he—vy met—lsF „he oxid—tion of the rem—ining org—ni™ ™ont—min—nts ˜y the hydrogen peroxide @r2 y2 A produ™es w—ter solu˜le produ™tsF ƒimil—rlyD met—l ™ont—min—nts su™h —s ™—dmiumD ™o˜—ltD ™opperD mer™uryD ni™kelD —nd silver —re solu˜ilized ˜y the xr4 yr through the form—tion .1.

WAFER FORMATION AND PROCESSING @RFWA „he se™ond solution ™onsists of r2 yEr2 y2 Ergl in — TXIXI to VXPXI volume r—tio —nd removes the qroup s@IAD ss@PA —nd sss@IQA met—lsF sn —dditionD the se™ond solution prevents reEdeposition of the met—l ™ont—min—ntsF i—™h of the w—shing steps is ™—rried out for IH E PH minF —t US E VS ◦ g with r—pid —git—tionF pin—llyD the w—fers —re ˜lown dry under — stre—m of nitrogen g—sF 4.11 Measurements.D IWWHD 137D IVVUF • ‰F wori —nd xF ‡—t—n—˜eD J.2 Cleaning GaAs sn prin™iple q—es w—fers m—y ˜e ™le—ned in — simil—r m—nner to sili™on w—fersF „he (rst step involves su™™essive ™le—ning with hot org—ni™ solvents su™h —s IDIDIEtri™hloroeth—neD —™etoneD —nd meth—nolD e—™h for SEIH minutesF q—es w—fers ™le—ned in this m—nner m—y ˜e stored under meth—nol for short periods of timeF wost ™le—ning solutions for q—es —re —™tu—lly et™hesF e typi™—l solution is simil—r to the se™ond ‚ge solution —nd ™onsists of —n VHXIHXI r—tio of r2 yEr2 y2 ErglF „his solution is gener—lly used —t elev—ted temper—tures @UH ◦ gA with short dip times sin™e it h—s — very f—st et™h r—te @RFH µmGminAF 4.10. Soc.1. Soc.1.D IWUVD 125D ISIHF . ActaD IWTVD 13D IQPWF • €F hF qreenD Solid State Electron.D IWUID 118D IQRTF • rF qeris™her —nd ‡F windtD Electrochem. Electrochem. inspections and packaging u—lity ™ontrol me—surements of the semi™ondu™tor ™ryst—l —nd su˜sequent w—fer —re performed throughout the pro™ess —s —n essenti—l p—rt of the f—˜ri™—tion of w—fersF prom ™ryst—l —nd w—fer sh—ping through the (n—l w—fer (nishing stepsD qu—lity ™ontrol me—surements —re used to ensure th—t the m—teri—ls meets ™ustomer spe™i(™—tionsD —nd th—t pro˜lems ™—n ˜e ™orre™ted ˜efore they ™re—te s™r—p m—teri—l —nd thus —void further pro™essing of reje™t m—teri—lF u—lity ™ontrol me—surements ™—n ˜e ˜ro—dly ™l—ssi(ed into me™h—ni™—lD ele™tri™—lD stru™tur—lD —nd ™hemi™—lF we™h—ni™—l me—surements —re ™on™erned with the physi™—l dimensions of the w—ferD in™ludingX thi™knessD )—tnessD ˜owD t—per —nd edge ™ontourF ile™tri™—l me—surements usu—lly in™ludeX resistivity —nd l—ter—l resistivity gr—dientD ™—rrier type —nd lifetimeF we—surements giving inform—tion on the perfe™tion of the semi™ondu™tor ™ryst—l l—tti™e —re ™l—ssi(ed in the stru™tur—l ™—tegory —nd in™ludeX testing for st—™king f—ultsD —nd dislo™—tionsF ‚outine ™hemi™—l me—surements —re limited to the me—surement of dissolved oxygen —nd ™—r˜on ˜y pourier tr—nsform infr—red spe™tros™opy @p„Es‚AF pinished w—fers —re individu—lly m—rked for the purpose of identi(™—tion —nd tr—™e—˜ilityF €—™k—ging helps prote™t the (nished w—fers from ™ont—min—tion during shipping —nd stor—geF sndustry st—nd—rds de(ning in det—il how qu—lity ™ontrol me—surements —re to ˜e m—de —nd determining the —™™ept—˜le r—nges for me—sured v—lues h—ve ˜een developed ˜y the emeri™—n ƒo™iety of „esting w—teri—ls @eƒ„wA —nd the ƒemi™ondu™tor iquipment —nd w—teri—ls snstitute @ƒiwsAF 4. Etching.12 Bibliography • eF gF fonor—D Silicon Wafer Process Technology: Slicing.D IWUID 118D UTVF • ‡F uernD J.IPV of solu˜le —mino ™omplexesD eFgFD @RFWAF CHAPTER 4. Electrochem.D IWUTD 19D VISF • gF eF r—rper —nd ‚F wF ƒompsonD Electronic Materials & Processing HandbookD w™qr—w rillD xew ‰orkD Pnd iditionF • ƒF sid— —nd uF stoD J. Soc. PolishingD ƒemi™ondu™tor ƒili™on IWUUD ile™tro™hemF ƒo™FD €enningtonD xt @IWUUAF • vF hF hyerD in Proceeding of the low-cost solar array wafering workshop 1981D hoiEt€vEPIHIPETTD tet €ropulsion v—˜FD €—s—den— ge @IWVPAF • tF gF hyment —nd qF eF ‚ozgonyiD J.1. Electrochem. Soc. Electrochem.

"CMOS Logic".org/content/m11359/latest/#g46> 4 "Silicon Growth". Electrochem.D IWTTD 113D WSVF pF ƒnimur—D Semiconductor Silicon Crystal TechnologyD e™—demi™ €ressD xew ‰ork @IWVWAF hF ‚F „urnerD> 2 3 . Figure 1 <http://cnx.12: Implant distribution with acceleration energy This content is available online at <http://cnx. Soc. Electrochem. Electrochem.2/>.D IWTHD 107D VIHF 4.IPW • • • • hF vF €—rtinD eF qF wilnesD —nd vF pF †—ss—milletD J. Soc. Soc.2 Doping 2 ƒt—rting with — prep—redD polished w—fer then how do we get —n integr—ted ™ir™uitc ‡e will fo™us on the gwyƒ pro™essD des™ri˜ed in the l—st ™h—pterF vet9s —ssume we h—ve w—fer whi™h w—s doped during growth so th—t it h—s — ˜—™kground ™on™entr—tion of —™™eptors in it @iFeF it is pEtypeAF ‚eferring ˜—™k to gwyƒ vogi™3 D you ™—n see th—t the (rst thing we need to ˜uild is — nEt—nk or mo—tF sn order to do thisD we need some w—y in whi™h to introdu™e —ddition—l impurities into the semi™ondu™torF „here —re sever—l w—ys to do thisD ˜ut ™urrent te™hnology relies —lmost ex™lusively on — te™hnique ™—lled ion implantationF e di—gr—m of —n ionEimpl—nter is shown in the (gure in the previous se™tion4 F en ion impl—nter uses — dop—nt sour™e g—sD ionizes itD —nd drives the ions into the w—ferF „he dop—nt g—s is ionized —nd the result—nt ™h—rged ions —re —™™eler—ted through — m—gneti™ (eldD where they —re m—ssE—n—lyzedF „he verti™—l m—gneti™ (eld ™—uses the ˜e—m of ions to spre—d outD —™™ording to their m—ssF e thin —perture sele™ts the ions of interestD —nd lets them p—ssD ˜lo™king —ll the othersF „his m—kes sure we —re only impl—nting the ion we w—ntD —nd in f—™tD even sele™ts for the proper isotope3 „he ionized —toms —re then —™™eler—ted through sever—l tens to hundreds of k†D —nd then de)e™ted ˜y —n ele™tri™ (eldD mu™h like in —n os™illos™ope g‚„F sn f—™tD most of the time the ion ˜e—m is 4r—stered4 —™ross the surf—™e of the sili™on w—ferF „he ions strike the sili™on w—fer —nd p—ss into its interiorF e me—surement of the ™urrent )ow in the system —nd its integr—lD is — me—sure of how mu™h dop—nt w—s deposited into the w—ferF „his is usu—lly given in terms of the num˜er of dop—nt atoms to whi™h cm2 the w—fer h—s ˜een exposedF efter the —toms enter the sili™onD they inter—™t with the l—tti™eD ™re—ting defe™tsD —nd slowing down until (n—lly they stopF „ypi™—l —tomi™ distri˜utionsD —s — fun™tion of impl—nt volt—ge —re show in pigure RFIP for impl—nt—tion into —morphous sili™onF ‡hen impl—nt—tion is done on single ™ryst—l m—teri—lD ™h—nnelingD the improved mo˜ility of —n ion down the 4h—llw—y4 of — given l—tti™e dire™tionD ™—n skew the impurity distri˜ution signi(™—ntlyF tust slight ™h—nges of less th—n — degree ™—n m—ke ˜ig di'eren™es in how the impurity —toms —re (n—lly distri˜uted in the w—ferF …su—llyD the oper—tor of the impl—nt m—™hine purposely tilts the w—fer — few degrees o' norm—l to the ˜e—m in order to —rrive —t more reprodu™i˜le resultsF Figure 4.D IWUWD 126D ISVIF hF ‡F ƒh—wD J. Figure 3 <

IQH CHAPTER 4.5/>. WAFER FORMATION AND PROCESSING es you might expe™tD shooting IHH k† ions —t — sili™on w—fer pro˜—˜ly does quite — ˜it of d—m—ge to the ™ryst—l stru™tureF xot only th—tD ˜ut just h—vingD s—y ˜oronD in your w—fer does not me—n you —re going to h—ve holesF por the ˜oron to ˜e™ome 4ele™tri™—lly —™tive4 E th—t is to —™t —s —n —™™eptor E it h—s to reside on — sili™on l—tti™e siteF iven if the ˜oron —tom doesD somehowD end up on —n —™tu—l l—tti™e site when it stops ™r—shing —round in the w—ferD the m—ny defe™ts whi™h h—ve ˜een ™re—ted will —™t —s deep tr—psF „husD the hole whi™h is formed will pro˜—˜ly ˜e ™—ught —t — tr—p site —nd will not ˜e —˜le to ™ontri˜ute to ele™tri™—l ™ondu™tivity in the w—fer —nyw—yF row ™—n we (x this situ—tionc sf we ™—refully he—t up the w—ferD we ™—n ™—use the —toms in the ™ryst—l to sh—ke —roundD —nd if we do it rightD they —ll get ˜—™k where they ˜elongF xot only th—tD ˜ut the newly —dded impurities end up on l—tti™e sites —s well3 „his step is ™—lled annealing —nd it does just wh—t it is supposed toF „ypi™—l temper—tures —nd times for su™h —n —nne—l —re SHH to IHHH ◦ g for IH to QH minutesF ƒomething else o™™urs during the —nne—l step howeverF ‡e h—ve just —ddedD ˜y our impl—nt—tion stepD impurities with — f—irly tight distri˜ution —s shown in pigure RFIPF „here is —n o˜vious gr—dient in impurity distri˜utionD —nd if there is — gr—dientD th—n things m—y st—rt moving —round ˜y di'usionD espe™i—lly —t elev—ted temper—turesF 4.3 Applications for Silica Thin Films 4. .org/content/m24883/1.3.1 Introduction 5 ‡hile the physi™—l properties of sili™— m—ke it suit—˜le for use in prote™tive —nd opti™—l ™o—ting —ppli™—tionsD the ˜iggest —ppli™—tion of insul—ting ƒiy2 thin (lms is undou˜tedly in semi™ondu™tor devi™esD in whi™h the insul—tor performs — num˜er of spe™i(™ t—sksD in™ludingX surf—™e p—ssiv—tionD (eld e'e™t tr—nsistor @pi„A g—te l—yerD isol—tion l—yersD pl—n—riz—tion —nd p—™k—gingF „he term insul—tor gener—lly refers to — m—teri—l th—t exhi˜its low therm—l or ele™tri™—l ™ondu™tivityY ele™tri™—lly insul—ting m—teri—ls —re —lso ™—lled diele™tri™sF st is in reg—rd to the high resist—n™e to the )ow of —n ele™tri™ ™urrent th—t ƒiy2 thin (lms —re of the gre—test ™ommer™i—l import—n™eF „he diele™tri™ ™onst—nt @εA is — me—sure of — diele™tri™ m—teri—ls —˜ility to store ™h—rgeD —nd is ™h—r—™terized ˜y the ele™trost—ti™ energy stored per unit volume —™ross — unit potenti—l gr—dientF „he m—gnitude of ε is —n indi™—tion of the degree of pol—riz—tion or ™h—rge displ—™ement within — m—teri—lF „he diele™tri™ ™onst—nt for —ir is ID —nd for ioni™ solids is gener—lly in the r—nge of S E IHF hiele™tri™ ™onst—nts —re de(ned —s the r—tio of the m—teri—l9s ™—p—™it—n™e to th—t of —irD iFeFD @RFIHAF „he diele™tri™ ™onst—nt for sili™on dioxide r—nges from QFW to RFWD for therm—lly —nd pl—sm— g†h grown (lmsD respe™tivelyF @RFIHA en insul—ting l—yer is — (lm or deposited l—yer of diele™tri™ m—teri—l sep—r—ting or ™overing ™ondu™tive l—yersF sde—llyD in these —ppli™—tion —n insul—ting m—teri—l should h—ve — surf—™e resistivity of gre—ter th—n IH13 ΩG™m2 or — volume resistivity of gre—ter th—n IH11 ΩF™mF roweverD for some —ppli™—tionsD lower v—lues —re —™™ept—˜leY —n ele™tri™—l insul—tor is gener—lly —™™epted to h—ve — resistivity gre—ter th—n IH5 ΩF™mF g†h ƒiy2 thin (lms h—ve — resistivity of IH6 E IH16 ΩF™mD depending on the (lm growth methodF es — ™onsequen™e of its diele™tri™ properties ƒiy2 D —nd rel—ted sili™—sD —re used for isol—ting ™ondu™ting l—yersD to f—™ilit—te the di'usion of dop—nts from doped oxidesD —s di'usion —nd ion impl—nt—tion m—sksD ™—pping doped (lms to prevent loss of dop—ntD for gettering impuritiesD for prote™tion —g—inst moisture —nd oxid—tionD —nd for ele™troni™ p—ssiv—tionF yf the m—ny methods used for the deposition of thin (lmsD ™hemi™—l v—por deposition @g†hA is most often used for semi™ondu™tor pro™essingF sn order to —ppre™i—te the unique pro˜lems —sso™i—ted with the g†h of insul—ting ƒiy2 thin (lms it is worth (rst reviewing some of their —ppli™—tionsF ƒumm—rized ˜elow —re three —re—s of gre—test import—n™e to the f—˜ri™—tion of ™ontempor—ry semi™ondu™tor devi™esX isol—tion —nd g—te insul—tionD p—ssiv—tionD —nd pl—n—riz—tionF 5 This content is available online at <http://cnx.

13: Schematic diagrams of a Si-MOSFET (metal-oxide-semiconductor eld eect transistor).3 Passivation €—ssiv—tion is often de(ned —s — pro™ess where˜y — (lm is grown on the surf—™e of — semi™ondu™tor to either @—A ™hemi™—lly prote™t it from the environmentD or @˜A provide ele™troni™ st—˜iliz—tion of the surf—™eF .IQI 4.3.2 Device isolation and gate insulation e mi™ro™ir™uit m—y ˜e des™ri˜ed —s — ™olle™tion of devi™es e—™h ™onsisting of 4—n —ssem˜ly of —™tive —nd p—ssive ™omponentsD inter™onne™ted within — monolithi™ ˜lo™k of semi™ondu™ting m—teri—l4F i—™h devi™e is required to ˜e isol—ted from —dj—™ent devi™es in order to —llow for m—ximum e0™ien™y of the over—ll ™ir™uitF purthermore within — devi™eD ™ont—™ts must —lso ˜e ele™tri™—lly isol—tedF ‡hile there —re — num˜er of methods for isol—ting individu—l devi™es within — ™ir™uit @reverseE˜i—sed jun™tionsD mes— isol—tionD use of semiEinsul—ting su˜str—tesD —nd oxide isol—tionAD the isol—tion of the —™tive ™omponents in — single devi™e is —lmost ex™lusively —™™omplished ˜y the deposition of —n insul—torF sn pigure RFIQ is shown — s™hem—ti™ represent—tion of — sili™on wyƒpi„ @met—lEoxideEsemi™ondu™tor (eld e'e™t tr—nsistorAF „he wyƒpi„ is the ˜—si™ ™omponent of sili™onEgwyƒ @™ompliment—ry met—lEoxideE semi™ondu™torA ™ir™uits whi™hD in turnD form the ˜—sis for logi™ ™ir™uitsD su™h —s those used in the g€… @™entr—l pro™essing unitA of — modern person—l ™omputerF st ™—n ˜e seen th—t the wyƒpi„ is isol—ted from —dj—™ent devi™es ˜y — reverseE˜i—sed jun™tion @p+ E™h—nnel stopA —nd — thi™k oxide l—yerF „he g—teD sour™e —nd dr—in ™ont—™t —re ele™tri™—lly isol—ted from e—™h other ˜y — thin insul—ting oxideF e simil—r s™heme is used for the isol—tion of the ™olle™tor from ˜oth the ˜—se —nd the emitter in ˜ipol—r tr—nsistor devi™esF Figure 4. es — tr—nsistorD — wyƒpi„ h—s m—ny —dv—nt—ges over —ltern—te designsF „he key —dv—nt—ge is low power dissip—tion resulting from the high imped—n™e of the devi™eF „his is — result of the thin insul—tion l—yer ˜etween the ™h—nnel @region ˜etween sour™e —nd dr—inA —nd the g—te ™ont—™tD see pigure RFIQF „he presen™e of —n insul—ting g—te is ™h—r—™teristi™ of — gener—l ™l—ss of devi™es ™—lled wsƒpi„s @met—lEinsul—torE semi™ondu™tor (eld e'e™t tr—nsistorAF wyƒpi„s —re — su˜set of wsƒpi„s where the insul—tor is spe™i(™—lly —n oxideD eFgFD in the ™—se of — sili™on wsƒpi„ devi™e the insul—tor is ƒiy2 D hen™e wyƒpi„F st is the f—˜ri™—tion of wyƒpi„ ™ir™uits th—t h—s —llowed sili™on te™hnology to domin—te digit—l ele™troni™s @logi™ ™ir™uitsAF roweverD in™re—ses in ™omputing power —nd speed require — ™onst—nt redu™tion in devi™e size —nd in™re—sed ™omplexity in devi™e —r™hite™tureF 4.3.

3.IQP CHAPTER 4. WAFER FORMATION AND PROCESSING prom the e—rliest d—ys of solid st—te ele™troni™s it h—s ˜een re™ognized th—t the presen™e or —˜sen™e of surf—™e st—tes pl—ys — de™isive role in the usefulness of —ny semi™ondu™ting m—teri—lF yn the surf—™e of —ny solid st—te m—teri—l there —re sites in whi™h the ™oordin—tion environment of the —toms is in™ompleteF „hese sitesD ™ommonly termed 4d—ngling ˜onds4D —re the ™—use of the ele™troni™—lly —™tive st—tes whi™h —llow for the re™om˜in—tion of holes —nd ele™tronsF „his re™om˜in—tion o™™urs —t energies ˜elow the ˜ulk v—lueD —nd interferes with the inherent properties of the semi™ondu™torF sn order to optimize the properties of — semi™ondu™tor devi™e it is desir—˜le to ™ov—lently s—tisfy —ll these surf—™e ˜ondsD there˜y shifting the surf—™e st—tes out of the ˜—nd g—p —nd into the v—len™e or ™ondu™tion ˜—ndsF ile™troni™ p—ssiv—tion m—y therefore ˜e des™ri˜ed —s — pro™ess whi™h redu™es the density of —v—il—˜le ele™troni™ st—tes present —t the surf—™e of — semi™ondu™torD there˜y limiting hole —nd ele™tron re™om˜in—tion possi˜ilitiesF sn the ™—se of sili™on ˜oth the n—tive oxide —nd other oxides —dmir—˜ly ful(ll these requirementsF ghemi™—l p—ssiv—tion requires — m—teri—l th—t inhi˜its the di'usion of oxygenD w—terD or other spe™ies to the surf—™e of the underlying semi™ondu™torF sn —dditionD the m—teri—l is ide—lly h—rd —nd resist—nt to ™hemi™—l —tt—™kF e perfe™t p—ssiv—tion m—teri—l would s—tisfy ˜oth ele™troni™ —nd ™hemi™—l p—ssiv—tion requirementsF 4.4 Planarization por the v—st m—jority of ele™troni™ devi™esD the st—rting point is — su˜str—te ™onsisting of — )—t single ™ryst—l w—fer of semi™ondu™ting m—teri—lF huring pro™essingD whi™h in™ludes the growth of ˜oth insul—ting —nd ™ondu™ting (lmsD the surf—™e ˜e™omes in™re—singly nonEpl—n—rF por ex—mpleD — g—te oxide in — typi™—l wyƒpi„ @see pigure RFIQA m—y ˜e typi™—lly IHH E PSH Å thi™kD while the isol—tion or (eld oxide m—y ˜e IHDHHH ÅF sn order for the su™™essful su˜sequent deposition of ™ondu™ting l—yers @met—lliz—tionA to o™™ur without ˜re—king met—l lines @often due to the di0™ulty in m—int—ining step ™over—geAD the surf—™e must ˜e )—t —nd smoothF „his pro™ess is ™—lled pl—n—riz—tionD —nd ™—n ˜e ™—rried out ˜y — te™hnique known —s s—™ri(™i—l et™h˜—™kF „he steps for this pro™ess —re outlined in pigure RFIRF en —˜rupt step @pigure RFIR—A is ™o—ted with — ™onform—l l—yer of — low melting diele™tri™D eFgFD ˜orophosphorosili™—te gl—ssD f€ƒq @pigure RFIR˜AD —nd su˜sequently — s—™ri(™i—l org—ni™ resin @pigure RFIR™AF „he s—mple is then pl—sm— et™hed su™h th—t the resin —nd diele™tri™ —re removed —t the s—me r—teF ƒin™e the pl—sm— et™h follows the ™ontour of the org—ni™ resinD — smooth surf—™e is left ˜ehind @pigure RFIRdAF „he pl—n—riz—tion pro™ess thus redu™es step height di'erenti—ls signi(™—ntlyF sn —ddition regions or v—lleys ˜etween individu—l met—lliz—tion elements @vi—sA ™—n ˜e ™ompletely (lled —llowing for — route to produ™ing uniformly )—t surf—™esD eFgFD the f€ƒq (lm shown in pigure RFIQF .

Electrochem. and subsequently coated with an organic resin (c). Soc.14: „he pro™esses of pl—n—riz—tion is vit—l for the development of multilevel stru™tures in †vƒs ™ir™uitsF „o minimize inter™onne™tion resist—n™e —nd ™onserve ™hip —re—D multilevel met—lliz—tion s™hemes —re ˜eing developed in whi™h the inter™onne™ts run in QEdimensionsF 4. TodayD IWVHD 33D PTF • ƒF uF qh—ndhiD VLSI Fabrication Principles.3.5 Bibliography • tF vF †ossen —nd ‡F uernD Phys. Silicon and Gallium ArsenideD ‡ileyD ghi™hesterD Pnd idF @IWWRAF • ƒF wF ƒzeD Physics of Semiconductor DevicesD Pnd iditionD tohn ‡iley 8 ƒonsD xew ‰ork @IWVIAF • ‡F iF fe—dleD tF gF gF „s—iD ‚F hF €lummerD Quick Reference Manual for Silicon Integrated Cuircuit TechnologyD ‡ileyD ghi™hester @IWVSAF • eF gF ed—ms —nd gF hF g—pioD J.D IWVID 128D PTQHF . A metallization feature (a) is CVD covered with silicate glass (b). Figure 4.IQQ Schematic representation of the planarization process. After etching the resist a smooth silicate surface is produced (d).

3/>.org/content/m24908/1.2 Oxidation of silicon ƒili™on9s surf—™e h—s — high —0nity for oxygen —nd thus —n oxide l—yer r—pidly forms upon exposure to the —tmosphereF „he ™hemi™—l re—™tions whi™h des™ri˜e this form—tion —reX @RFIIA @RFIPA sn the (rst re—™tion — dry pro™ess is utilized involving oxygen g—s —s the oxygen sour™e —nd the se™ond re—™tion des™ri˜es — wet pro™ess whi™h uses ste—mF „he dry pro™ess provides — 4good4 sili™on dioxide ˜ut is slow —nd mostly used —t the ˜eginning of pro™essingF „he wet pro™edure is pro˜lem—ti™ in th—t the purity of the w—ter used ™—nnot ˜e gu—r—nteed to — suit—˜le degreeF „his pro˜lem ™—n ˜e e—sily solved using — pyrogeni™ te™hnique whi™h ™om˜ines hydrogen —nd oxygen g—ses to form w—ter v—por of very high purityF w—int—ining re—gents of high qu—lity is essenti—l to the m—nuf—™turing of integr—ted ™ir™uitsD —nd is — ™on™ern whi™h pl—gues e—™h step of this pro™essF „he form—tion of the oxide l—yer involves sh—red v—len™e ele™trons ˜etween sili™on —nd oxygenD whi™h —llows the sili™on surf—™e to rid itself of 4d—ngling4 ˜ondsD su™h —s lone p—irs —nd v—™—nt or˜it—lsD pigure RFISF „hese v—™—n™ies ™re—te midEg—p st—tes ˜etween the v—len™e —nd ™ondu™tion ˜—ndsD whi™h prevents the desired ˜—nd g—p of the semi™ondu™torF „he ƒiEy ˜ond strength is ™ov—lent @strongAD —nd so ™—n ˜e used to —™hieve the loss of midEg—p st—tes —nd p—ssiv—te the surf—™e of the sili™onF 6 This content is available online at <http://cnx. . WAFER FORMATION AND PROCESSING 6 4.IQR CHAPTER 4.4.1 Introduction sn the f—˜ri™—tion of integr—ted ™ir™uits @sgsAD the oxid—tion of sili™on is essenti—lD —nd the produ™tion of superior sgs requires —n underst—nding of the oxid—tion pro™ess —nd the —˜ility to form oxides of high qu—lityF ƒili™on dioxide h—s sever—l usesX IF PF QF RF SF ƒerves —s — m—sk —g—inst impl—nt or di'usion of dop—nt into sili™onF €rovides surf—™e p—ssiv—tionF ssol—tes one devi™e from —nother @diele™tri™ isol—tionAF e™ts —s — ™omponent in wyƒ stru™turesF €rovides ele™tri™—l isol—tion of multiElevel met—lliz—tion systemsF wethods for forming oxide l—yers on sili™on h—ve ˜een developedD in™luding therm—l oxid—tionD wet —nodiz—E tionD ™hemi™—l v—por deposition @g†hAD —nd pl—sm— —nodiz—tion or oxid—tionF qener—llyD g†h is used when putting the oxide l—yer on top of — met—l surf—™eD —nd therm—l oxid—tion is used when — lowE™h—rge density level is required for the interf—™e ˜etween the oxide —nd the sili™on surf—™eF 4.4 Oxidation of Silicon note: Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of endre— ueysF „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of 4.4.

1 Pre-oxidation cleaning „he (rst step in oxidizing — surf—™e of sili™on is the remov—l of the n—tive oxide whi™h forms due to exposure to open —irF „his m—y seem redund—nt to remove —n oxide only to put on —notherD ˜ut this is ne™ess—ry sin™e un™ert—inty exists —s to the purity of the oxide whi™h is presentF „he ™ont—min—tion of the n—tive oxide ˜y ˜oth org—ni™ —nd inorg—ni™ m—teri—ls @—rising from previous pro™essing steps —nd h—ndlingA must ˜e removed to prevent the degr—d—tion of the essenti—l ele™tri™—l ™h—r—™teristi™s of the devi™eF e ™ommon pro™edure uses — r2 yEr2 y2 Exr4 yr mixture whi™h removes the org—ni™s presentD —s well —s some group s —nd ss met—lsF ‚emov—l of he—vy met—ls ™—n ˜e —™hieved using — r2 yEr2 y2 Ergl mixtureD whi™h ™omplexes with the ions whi™h —re formedF efter remov—l of the n—tive oxideD the desired oxide ™—n ˜e grownF „his growth is useful ˜e™—use it providesX ™hemi™—l prote™tionD ™onditions suit—˜le for lithogr—phyD —nd p—ssiv—tionF „he prote™tion prevents unw—nted re—™tions from o™™urring —nd the p—ssiv—tion (lls v—™—n™ies of ˜onds on the surf—™e not present within the interior of the ™ryst—lF „hus the oxid—tion of the surf—™e of sili™on ful(lls sever—l fun™tions in one stepF 4.2 Thermal oxidation „he growth of oxides on — sili™on surf—™e ™—n ˜e — p—rti™ul—rly tedious pro™essD sin™e the growth must ˜e uniform —nd pureF „he thi™kness w—nted usu—lly f—lls in the r—nge SH E SHH ÅD whi™h ™—n t—ke — long time —nd must ˜e done on — l—rge s™—leF „his is done ˜y st—™king the sili™on w—fers in — horizont—l qu—rtz tu˜e while the oxygen sour™e )ows over the w—fersD whi™h —re situ—ted verti™—lly in — slotted p—ddle @˜o—tAD see pigure RFITF „his pro™edure is performed —t I —tm pressureD —nd the temper—ture r—nges from UHH to IPHH ◦ gD ˜eing held to within ±I ◦ g to ensure uniformityF „he ™hoi™e of oxid—tion te™hnique depends on the thi™kness —nd oxide properties requiredF yxides th—t —re rel—tively thin —nd those th—t require low ™h—rge —t the interf—™e —re typi™—lly grown in dry oxygenF ‡hen thi™k oxides —re required @> HFS mmA —re desiredD ste—m is the sour™e of ™hoi™eF ƒte—m ™—n ˜e used —t wide r—nge of pressures @I —tm to PS —tmAD —nd the higher pressures —llow thi™k oxide growth to ˜e —™hieved —t moder—te temper—tures in re—son—˜le —mounts of timeF .2.15: Removal of dangling bonds by oxidation of surface.2.4. „he oxid—tion of sili™on o™™urs —t the sili™onEoxide interf—™e —nd ™onsists of four stepsX ƒtep IF hi'usive tr—nsport of oxygen —™ross the di'usion l—yer in the v—por ph—se —dj—™ent to the sili™on oxideEv—por interf—™eF ƒtep PF sn™orpor—tion of oxygen —t the outer surf—™e into the sili™on oxide (lmF ƒtep QF hi'usive tr—nsport —™ross the sili™on oxide (lm to its interf—™e with the sili™on l—tti™eF ƒtep RF ‚e—™tion of oxygen with sili™on —t this inner interf—™eF es the ƒiEƒiy2 interf—™e moves into the sili™on its volume exp—ndsD —nd ˜—sed upon the densities —nd mole™ul—r weights of ƒi —nd ƒiy2 D HFRR Å ƒi is used to o˜t—in IFH Å ƒiy2 F 4.IQS Figure 4.4.

16: Horizontal diusion tube showing the oxidation of silicon wafers at 1 atm pressure.IQT CHAPTER 4. „he thi™kness of ƒiy2 l—yers on — ƒi su˜str—te is re—dily determined ˜y the ™olor of the (lmF „—˜le RFT provides — guidline for therm—l grown oxidesF Film thickness (µm) Color Film thickness (µm) Color HFHS HFHU HFIH HFIP HFIS HFIU HFPH HFPP HFPS HFPU HFQH HFQI HFQP t—n ˜rown d—rk violet to redEviolet roy—l ˜lue light ˜lue to met—lli™ ˜lue met—lli™ to light yellowE green light gold gold or—nge to melon redEviolet ˜lue to violet ˜lue ˜lue ˜lue to ˜lueEgreen HFTQ HFTV HFUP HFUU HFVH HFVP HFVS HFVT HFVU HFVW HFWP HFWS HFWU violetEred 4˜luish4 ˜lueEgreen to gree 4yellowish4 or—nge s—lmon light redEviolet violet ˜lue violet ˜lue ˜lueEgreen yellowEgreen yellow continued on next page . WAFER FORMATION AND PROCESSING Figure 4.

4 Plasma oxidation €l—sm— oxid—tion —nd —nodiz—tion of sili™on is re—dily —™™omplished ˜y the use of —™tiv—ted oxygen —s the oxidizing spe™iesF „he highly re—™tive oxygen is formed within —n ele™tri™—l dis™h—rge or pl—sm—F „he oxid—tion is ™—rried out in — low pressure @HFHS E HFS „orrA ™h—m˜erD —nd the the pl—sm— is produ™ed either ˜y — hg ele™tron sour™e or — highEfrequen™y dis™h—rgeF sn simple pl—sm— oxid—tion the s—mple @iFeFD the sili™on w—ferA is held —t ground potenti—lF sn ™ontr—stD —niodiz—tion systems usu—lly h—ve — hg ˜i—s ˜etween the s—mple —nd —n ele™trode with the s—mple ˜i—sed positively with respe™t to the ™—thodeF €l—tinum ele™trodes —re ™ommonly used —s the ™—thodesF .2.2.IQU HFQR HFQS HFQT HFQU HFQW HFRI HFRP HFRR HFRT HFRU HFRV HFRW HFSH HFSP HFSR HFST HFSU HFSV HFTH Table 4.4.3 High pressure oxidation righ pressure oxid—tion is —nother method of oxidizing the sili™on surf—™e whi™h ™ontrols the r—te of oxid—tionF „his is possi˜le ˜e™—use the r—te is proportion—l to the ™on™entr—tion of the oxideD whi™h in turn is proportion—l to the p—rti—l pressure of the oxidizing spe™iesD —™™ording to renry9s l—wD @RFIQAD where g is the equili˜rium ™on™entr—tion of the oxideD r is renry9s l—w ™onst—ntD —nd pO is the p—rti—l pressure of the oxidizing spe™iesF @RFIQA „his —ppro—™h is f—stD with — r—te of oxid—tion r—nging from IHH to IHHH mmGhD —nd —lso o™™urs —t — rel—tively low temper—tureF st is — useful pro™essD preventing dop—nts from ˜eing displ—™ed —nd —lso forms — low num˜er of defe™tsD whi™h is most useful —t the end of pro™essingF 4.6 light green green to yellowEgreen yellowEgreen greenEyellow yellow light or—nge ™—rn—tion pink violetEred redEviolet violet ˜lueEviolet ˜lue ˜lue green green yellowEgreen greenEyellow 4yellowish4 light or—nge to pink ™—rn—tion pink HFWW IFHH IFHP IFHS IFHT IFHU IFIH IFII IFIP IFIV IFIW IFPI IFPR IFPS IFPV IFQP IFRH IFRT IFSH or—nge ™—rn—tion pink violet red redEviolet violet ˜lueEviolet green yellowEgreen green violet redEviolet violetEred ™—rn—tion s—lmon or—nge 4yellowish4 sky ˜lue to greenE˜lue or—nge ˜lueEviolet ˜lue pink to X golor ™h—rt for therm—lly grown ƒiy2 (lms o˜served under d—ylight )uores™ent lightingF 4.4.

Sci.D IWUVD 21D IIWWF • ‡F iF ƒpi™erD €F ‡F ghyeD €F ‚F ƒke—thD —nd gF ‰F ƒuD sF vind—uD Photolithography note: 7 7 „his module is ˜—sed upon the gonnexions module entitled Photolithography ˜y fill ‡ilsonF This content is available online at <http://cnx.—nd y2+ F foth ˜eing produ™ed in ne—r equ—l qu—ntitiesD —lthough only the former is relev—nt to pl—sm— —niodiz—tionF ‡hile these spe™ies m—y ˜e —™tive with respe™t to surf—™e oxid—tionD it is more likely th—t —n ele™tron tr—nsfer o™™urs from the semi™ondu™tor surf—™e yields —™tiv—ted oxygen spe™iesD whi™h —re the —™tu—l re—™t—nts in the oxid—tion of the sili™onF „he signi(™—nt —dv—t—ge of pl—sm— pro™esses is th—t while the ele™tron temper—ture of the ionized oxygen g—s is in ex™ess of IHDHHH uD the therm—l temper—tures required —re signi(™—ntly lower th—n required for the high pressure methodD iFeFD < THH ◦ gF „he —dv—nt—ges of the lower re—™tion temper—tures in™ludeX the minimiz—tion of dop—nt di'usion —nd the impediment of the gener—tion of defe™tsF hespite these —dv—nt—ges there —re two prim—ry dis—dv—nt—ges of —ny pl—sm— ˜—sed pro™essF pirstD the high ele™tri™ (elds present during the pro™esses ™—use d—m—ge to the result—nt oxideD in p—rti™ul—rD — high density of interf—™e tr—ps often resultF roweverD post —nne—ling m—y improve (lm qu—lityF ƒe™ondD the growth r—tes of pl—sm— oxid—tion —re lowD typi™—lly IHHH ÅGhF „his growth r—te is in™re—sed ˜y —˜out — f—™tor of IH for pl—sm— —niodiz—tionD —nd further improvements —re o˜served if I E Q7 ™hlorine is —dded to the oxygen sour™eF 4. Electron DevicesD IWVHD ED-27D IRQTF • tF ‚F roll—nh—n —nd eF „F fellsD Techniques and Applications of Plasma ChemistryD ‡ileyD xew ‰ork @IWURAF • ‚F €F rF gh—ng —nd eF uF ƒinh—D Appl.IQV CHAPTER 4. LettFD IWUTD 29D STF 4. Technol. Phys.4.4.D IWUWD 16D IRPPF • †F F ro —nd „F ƒug—noD IEEE Trans. WAFER FORMATION AND PROCESSING „here h—ve ˜een —t le—st QR di'erent re—™tions reported to o™™ur in —n oxygen pl—sm—D howeverD the v—st m—jority of these —re in™onsequenti—l with respe™t to the form—tion of —™tive spe™iesF purthermoreD m—ny of the potenti—lly —™tive spe™ies —re su0™iently short lived th—t it is unlikely th—t they m—ke — signi(™—nt ™ontri˜utionF „he prim—ry —™tive spe™ies within the oxygen pl—sm— —re undou˜tedly y. Vac. Silicon and Gallium ArsenideD ‡ileyD ghi™hesterD Pnd idF @IWWRAF • ƒF wF ƒzeD Physics of Semiconductor Devices D Pnd iditionD tohn ‡iley 8 ƒonsD xew ‰ork @IWVIAF • hF vF vileD Solid State Electron.5 Masking e sele™tive m—sk —g—inst the di'usion of dop—nt —toms —t high temper—tures ™—n ˜e found in — sili™on dioxide l—yerD whi™h ™—n prove to ˜e very useful in integr—ted ™ir™uit pro™essingF e predeposition of dop—nt ˜y ion impl—nt—tionD ™hemi™—l di'usionD or spinEon te™hniques typi™—lly results in — dop—nt sour™e —t or ne—r the surf—™e of the oxideF huring the initi—l highEtemper—ture stepD di'usion in the oxide must ˜e slow enough with respe™t to di'usion in the sili™on th—t the dop—nts do not di'use through the oxide in the m—sked region —nd re—™h the sili™on surf—™eF „he required thi™kness m—y ˜e determined ˜y experiment—lly me—suringD —t — p—rti™ul—r temper—ture —nd timeD the oxide thi™kness ne™ess—ry to prevent the inversion of — lightly doped sili™on su˜str—te of opposite ™ondu™tivityF „o this is then —dded — s—fety f—™torD with typi™—l tot—l v—lues r—nging from HFS to HFU mmF „he impurity m—sking properties result when the oxide is p—rti—lly ™onverted into — sili™— impurity oxide 4gl—ss4 ph—seD —nd prevents the impurities from re—™hing the ƒiy2 Eƒi interf—™eF 4.3 Bibliography • wF wF et—ll—D in Properties of Elemental and Compound SemiconductorsD idF rF q—tosD snters™ien™eX xew ‰ork @IWTHAF • ƒF uF qh—ndhiD VLSI Fabrication Principles. .2.1/>.

IQW e™tu—llyD impl—nts @espe™i—lly for mo—tsA —re usu—lly done —t — su0™iently high energy so th—t the dop—nt @phosphorusA is —lre—dy pretty f—r into the su˜str—te @often sever—l mi™rons or soAD even ˜efore the di'usion st—rtsF „he —nne—lGdi'usion moves the impurities into the w—fer — ˜it moreD —nd —s we sh—ll see —lso m—kes the nEregion grow l—rgerF 4„he nEregion43 ‡e h—ve not s—id — thing —˜out how we m—ke our mo—t in only ™ert—in —re—s of the w—ferF prom the des™ription we h—ve so f—rD is seems we h—ve simply ˜uilt —n nEtype l—yer over the whole surf—™e of the w—ferF „his would ˜e ˜—d3 ‡e need to ™ome up with some kind of 4window4 to only permit the impl—nting impurities to enter the sili™on w—fer where we w—nt them —nd not elsewhereF ‡e will do this ˜y ™onstru™ting —n impl—nt—tion 4˜—rrier4F „o do thisD the (rst thing we do is grow — l—yer of sili™on dioxide over the entire surf—™e of the w—ferF ‡e t—lked —˜out oxide growth when we were dis™ussing wyƒpi„s ˜ut let9s go into — little more det—ilF ‰ou ™—n grow oxide in either — dry oxygen —tmosphereD or in — —n —tmosphere whi™h ™ont—ins w—ter v—porD or ste—mF sn pigure RFIUD we show oxide thi™kness —s — fun™tion of time for growth with ste—mF hry y2 does not ˜eh—ve too mu™h di'erentlyD the r—te is just somewh—t slowerF Figure 4. yn top of the oxideD we —re now going to deposit yet —nother m—teri—lF „his is sili™on nitrideD ƒi3 x4 or just pl—in 4nitride4 —s it is usu—lly ™—lledF ƒili™on nitride is deposited through — method ™—lled ™hemi™—l v—por deposition or 4g†h4F „he usu—l te™hnique is to re—™t di™hlorosil—ne —nd —mmoni— in — hot w—lled low pressure ™hemi™—l v—por deposition system @v€g†hAF „he re—™tion isX @RFIRA ƒili™on nitride is — good ˜—rrier for impuritiesD oxygen —nd other things whi™h do not w—nt to get into the w—ferF „—ke — look —t pigure RFIV —nd see wh—t we h—ve so f—rF e word —˜out s™—le —nd dimensionsF „he sili™on w—fer is —˜out PSH µm thi™k @—˜out HFHI4A sin™e it h—s to ˜e strong enough not to ˜re—k —s it is ˜eing h—ndledF „he two deposited l—yers —re e—™h —˜out I µm thi™kD so they should —™tu—lly ˜e dr—wn —s lines thinner th—n the other lines in the (gureF „his would o˜viously m—ke the whole ide— of — sket™h ridi™ulousD so we will le—ve things distorted —s they —reD keeping in mind th—t the deposited —nd di'used l—yers —re —™tu—lly mu™h thinner th—n the rest of w—ferD whi™h re—lly does not do —nything ex™ept support the —™tive ™ir™uits up on topF .17: A plot of oxide thickness as a function of time.

18: Initial wafer conguration. WAFER FORMATION AND PROCESSING Figure 4.IRH CHAPTER 4. „he n—me 4photoresist4 gives some ™lue —s to wh—t this stu' isF f—si™—llyD photoresist is — polymer mixed with some kind of light sensitizing ™ompoundF sn positive photoresistD wherever light strikes itD the polymer is we—kenedD —nd it ™—n ˜e more e—sily removed with — solvent during the development pro™essF gonverselyD neg—tive photoresist is strengthened when it is illumin—ted with lightD —nd is more resist—nt to the solvent th—n is the unillumin—ted photoresistF €ositive resist is soE™—lled ˜e™—use the im—ge of the developed photoresist on the w—fer looks just like the m—sk th—t w—s used to ™re—te itF xeg—tive photoresist m—kes —n im—ge whi™h is the opposite of wh—t the m—sk looks likeF ‡e h—ve to ™ome up with some w—y of sele™tively illumin—ting ™ert—in portions of the photoresistF enyone who h—s ever seen — proje™tor know how we ™—n do thisF futD sin™e we w—nt to m—ke sm—ll thingsD not ˜ig onesD we will ™h—nge —round our proje™tor so th—t it m—kes — sm—ller im—geD inste—d of — ˜igger oneF „he instrument th—t proje™ts the light onto the photoresist on the w—fer is ™—lled — proje™tion printer or stepper pigure RFPHF .19: After the photoresist is spun on. xow wh—t we w—nt to do is remove p—rt of the nitrideD so we ™—n m—ke our nEwellD ˜ut not put in phosE phorous where do not w—nt itF ‡e do this with — pro™esses ™—lled photolithography —nd etching respe™tivelyF pirst thing we do is ™o—t the w—fer with yet —nother l—yer of m—teri—lF „his is — liquid ™—lled photoresist —nd it is —pplied through — pro™ess ™—lled spinE™o—tingF „he w—fer is put on — v—™uum ™hu™kD —nd — l—yer of liquid photoresist is spr—yed un™—p of the w—ferF „he ™hu™k is then spun r—pidlyD getting to sever—l thous—nd ‚€w in — sm—ll fr—™tion of — se™ondF gentrifug—l for™e ™—uses the resist to spre—d out uniformly —™ross the w—fer surf—™eF „he solvent for the photoresist is quite vol—tile —nd so the l—yer of photoresist dries while the w—fer is still spinningD resulting in — thinD uniform ™o—ting —™ross the w—fer pigure RFIWF Figure 4.

es shown in pigure RFPHD the stepper ™onsists of sever—l p—rtsF „here is — light sour™e @usu—lly — mer™ury v—por l—mpD —lthough ultr—Eviolet ex™imer l—sers —re —lso st—rting to ™ome into useAD — ™ondenser lens to im—ge the light sour™e on the m—sk or reti™leF „he m—sk ™ont—ins —n im—ge of the p—ttern we —re trying the pl—™e on the w—ferF „he proje™tion lens then m—kes — redu™ed @usu—lly SxA im—ge of the m—sk on the w—ferF fe™—use it would ˜e f—r too ™ostlyD if not just pl—in impossi˜leD to proje™t onto the whole w—fer —ll —t on™eD only — sm—ll sele™ted —re— is printed —t one timeF „hen the w—fer is s™—nned or stepped into — new positionD —nd the im—ge is printed —g—inF sf previous p—tterns h—ve —lre—dy ˜een formed on the w—ferD „† ™—mer—sD with —rti(™i—l intelligen™e —lgorithms —re used to —lign the ™urrent im—ge with the previously formed fe—turesF „he stepper moves the whole surf—™e of the w—fer under the lensD until the w—fer is ™ompletely ™overed with the desired p—tternF e stepper is one of the most import—nt pie™es of equipment in the whole sg f—˜ howeverD sin™e it determines wh—t the minimum fe—ture size on the ™ir™uit will ˜eF efter exposureD the photoresist is pl—™ed in — suit—˜le solventD —nd 4developed4F ƒuppose for our ex—mple the stru™ture shown in pigure RFPI is wh—t results from the photolithogr—phi™ stepF .20: A schematic of a stepper conguration.IRI Figure 4.

21: After photoresist exposure and development.IRP CHAPTER 4.23: Implanting phospohrus. ‡e now t—ke our w—ferD put it in the ion impl—nter —nd su˜je™t it to — 4˜l—st4 of phosphorus ions pigure RFPQF Figure 4. „he p—ttern th—t w—s used in the photolithogr—phi™ @€vA step exposed h—lf of our —re— to lightD —nd so the photoresist @€‚A in th—t region w—s removed upon developmentF „he w—fer is now immersed in — hydro)uori™ —™id @rpA solutionF rp —™id et™hes sili™on nitride quite r—pidlyD ˜ut does not et™h sili™on dioxide ne—rly —s f—stD so —fter the et™h we h—ve wh—t we see in pigure RFPPF Figure 4.22: After the nitride etch step. . WAFER FORMATION AND PROCESSING Figure 4.

.IRQ „he ions go right through the oxide l—yer on the ‚rƒD ˜ut sti™k in the resistGnitride l—yer on the vrƒ of our stru™tureF 4.4/>.org/content/m25448/1.6 Optical Issues in Photolithography note: 8 Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of —ne f—llF „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of 4.1 Introduction €hotolithogr—phy is one of the most import—nt te™hnology in the produ™tion of —dv—n™ed integr—ted ™ir™uitsF st is through photolithogr—phy th—t semi™ondu™tor surf—™es —re p—tterned —nd the ™ir™uits formedF sn order to m—ke extremely sm—ll fe—turesD on the order of the w—velength of the lightD —dv—n™ed opti™—l te™hniques —re used to tr—nsfer — p—ttern from — m—sk onto the surf—™eF e polymeri™ (lm or resistD is modi(ed ˜y the light —nd re™ords the inform—tion in — pro™ess not dissimil—r to ordin—ry photogr—phyF en illustr—tion of the photolithogr—phi™ pro™ess is shown in pigure RFPRF „he pro™ess follows the following ˜—si™ stepsX ƒtep IF „he w—fer is spin ™o—ted with resist to form — uniform ∼I µm thin (lm of resist on the surf—™eF ƒtep PF „he w—fer is exposed with ultr—violet light through — m—sk whi™h ™ont—ins the desired p—tternF sn the simplest pro™esses the m—sk is simply pl—™ed over the w—ferD ˜ut —dv—n™ed su˜Emi™ron te™hnologies require the p—ttern to im—ged through — ™omplex opti™—l systemF ƒtep QF „he photoresist is developed —nd the irr—di—ted —re— is w—shed —w—y @positive resistA or the unirr—di—ted —re— is w—shed —w—y @neg—tive resistAF ƒtep RF €ro™essing @et™hingD deposition et™FA ƒtep SF ‚em—ining resist is strippedF 8 This content is available online at <http://cnx.6.

IRR CHAPTER 4.2 Optical issues in photolithography 4. WAFER FORMATION AND PROCESSING Figure 4.24: Steps in optical printing using photolithography.6. sn —ddition to ˜eing possi˜ly the most import—nt semi™ondu™tor pro™ess stepD photolithogr—phy is —lso the most expensive te™hnology in semi™ondu™tor m—nuf—™turingF „his expense is the result of two ™onsider—tionsX IF „he opti™s in photolithogr—phy tools —re expensive where — single lens ™—n ™ost — 6I million or more PF i—™h ™hip @often referred to —s — 4dye4A must ˜e exposed individu—lly unlike other semi™ondu™tor pro™esses su™h —s g†h where —n entire w—fer ™—n ˜e pro™essed —t — time or oxid—tion pro™esses where m—ny w—fers ™—n ˜e pro™essed simult—neouslyF „his me—ns th—t not only —re photolithogr—phy m—™hines the most expensive of semi™ondu™tor pro™essing equipmentD ˜ut more of them —re needed in order to m—int—in throughputF 4.2.1 The critical dimension and depth of focus e semi™ondu™tor pro™ess te™hnology is often des™ri˜ed ˜y — ™h—r—™teristi™ length known —s the ™riti™—l dimensionF „he ™riti™—l dimension @ghA is the sm—llest fe—ture th—t needs to ˜e p—tterned on the surf—™eF „he ex—™t de(nition v—ries from pro™ess to pro™ess ˜ut is often the ™h—nnel length of the sm—llest tr—nsistor @typi™—l of — memory ™hipA or the width of the sm—llest met—l inter™onne™tion line @logi™ ™hipsAF „his ™riti™—l dimension is de(ned ˜y the photolithogr—phi™ pro™ess —nd is perh—ps the most import—nt (gure of merit in the m—nuf—™ture of integr—ted ™ir™uitsF w—king the ™riti™—l dimension sm—ller is the prim—ry fo™us of improving semi™ondu™tor te™hnology for the following re—sonsX IF w—king the gh sm—ller dr—m—ti™—lly in™re—ses the num˜er of devi™es per unit —re— —nd this in™re—se goes with the squ—re of the gh @iFeFD — redu™tion in gh ˜y — f—™tor of P gener—tes R times the num˜er of devi™esAF .6.

IRS PF w—king the gh sm—ller of — devi™e —lre—dy in produ™tion will m—ke — sm—ller ™hipF „his me—ns th—t the num˜er of ™hips per w—fer in™re—ses dr—m—ti™—llyD —nd sin™e ™osts gener—lly s™—le with the num˜er of w—fers —nd not the num˜er of ™hips to — w—ferD ™osts —re dr—m—ti™—lly redu™edF QF ƒm—ller devi™es —re f—sterF „hereforeD improvements in lithogr—phy te™hnology tr—nsl—te dire™tly into ˜etterD f—sterD more ™omplex ™irE ™uits —t lower ™ostF r—ving est—˜lished the import—n™e of the ™riti™—l dimension it is import—nt to underst—nd wh—t fe—tures of — photolithogr—phy system imp—™tF „he theory ˜ehind proje™tion lithogr—phy is very well knownD d—ting from the origin—l —n—lysis of the mi™ros™ope ˜y e˜˜eF st isD in f—™tD the e˜˜e sine ™ondition th—t di™t—tes the ™riti™—l dimensionX @RFISA where the two expressions refer to the limit of — purely ™oherent illumin—ting sour™e —nd purely in™oherent sour™e respe™tivelyD —nd λ is the v—™uum w—velength of the illumin—ting light sour™eD n the index of refr—™tion of the o˜je™tive lensD —nd Θ refers to the —ngle ˜etween the —xis of the lens —nd the line from the ˜—™k fo™—l point to the —perture of the entr—n™e of the lensF „he qu—ntity in the denomin—torD nsin@ΘA is referred to —s the numeri™—l —perture or xeF es the degree of ™oheren™e ™—n ˜e —djusted in — lithogr—phy systemD the ™riti™—l dimension is usu—lly written more gener—lly —sX @RFITA prom this equ—tionD we ˜egin to see wh—t ™—n ˜e done to redu™e the ™riti™—l dimension of — lithogr—phy systemX IF gh—nge the w—velength of the sour™eF PF sn™re—se the numeri™—l —perture @xeAF QF ‚edu™e k 1 F fefore we dis™uss how this is —™™omplishedD we must ™onsider one other key qu—ntityD the depth of fo™us or hypF „he depth of fo™us is the length —long the —xis in whi™h — sh—rp im—ge existsF x—tur—lly — l—rge hyp is desir—˜le for e—se of —lignmentD sin™e the entire dye must with lie within this regionF sn re—lityD howeverD the more me—ningful ™onstr—int is th—t the hyp must ˜e thi™ker th—n the resist l—yer so th—t the entire volume of resist is exposed —nd ™—n ˜e developedF elsoD if the surf—™e morphology of the devi™e di™t—tes th—t the resist to ˜e exposed is not pl—n—rD then the hyp must ˜e l—rge enough so th—t —ll fe—tures —re properly illumin—tedF gurrent resists must ˜e I µm in thi™kness in order to h—ve the ne™ess—ry et™h resist—n™eD so this ™—n ˜e ™onsidered — minimum v—lue for —n —™™ept—˜le hypF „he depth of fo™us ™—n —lso ˜e expressed —s — fun™tion of numeri™—l —perture —nd w—velengthX @RFIUA sf we desire to minimize the ™riti™—l dimension simply ˜y m—king opti™s of l—rge numeri™—l —perture th—t we will simult—neously redu™e the depth of fo™us —nd —t — mu™h f—ster r—te owing to the dependen™e on the squ—re of the numeri™—l —pertureF „hese two qu—ntitiesD hyp —nd ghD provide the dire™tion in lithogr—phy —nd semi™ondu™tor pro™essing —s — wholeF por ex—mpleD — design with —n improved surf—™e pl—n—rity or — new resist th—t is e'e™tive —t sm—ller thi™knesses would —llow for — sm—ller depth of fo™us whi™h would in turn —llow for — l—rger numeri™—l —perture implying — sm—ller ™riti™—l dimensionF „he resistD the sour™e w—velengthD —nd the opti™—l delivery system .

2.2. WAFER FORMATION AND PROCESSING —ll —'e™t the ™riti™—l dimension —nd th—t further re(nements require — multif—™eted —ppro—™h to improving lithogr—phy systemsF ‡h—t —lso must ˜e re—lized is th—tD —s f—r —s the opti™—l system is ™on™ernedD virtu—lly —ll th—t ™—n ˜e done with ™onvention—l opti™s h—s ˜een done —nd th—t fund—ment—l restr—ints on k 1 h—ve ˜een re—™hedF 4.2 Wavefront engineering yne w—y to get —round the fund—ment—l limit—tions of —n im—ging system illustr—ted in @RFISA is through one of — v—riety of te™hniques often termed wavefront engineering.6.IRT CHAPTER 4.6.3 Interaction with resists „he ultim—te resolution of — photolithogr—phi™ pro™ess is not dependent on opti™s —loneD ˜ut —lso on the inter—™tion with the resistF yne of the key ™on™ernsD p—rti™ul—rly —s w—velengths of sour™es ˜e™ome shorterD is the —˜ility of the sour™e light to penetr—te the resist (lmF w—ny polymers —˜sor˜ strongly in the …† whi™h ™—n limit the inter—™tion to the surf—™eF sn su™h — ™—se only — thin l—yer of the polymer is exposed —nd the p—ttern m—y not ˜e fully un™overed during developingF yne import—nt property of resist is the presen™e of saturable absorptionFF ƒ—tur—˜le —˜sor˜ers —re those —˜sorption sites in the polymer th—t when ex™ited to — higher st—te rem—in there for rel—tively long periods of time —nd do not ™ontinue to —˜sor˜ into higher st—tesF sf only s—tur—˜le —˜sorption is present in — polymer (lmD then ™ontinued irr—di—tion eventu—lly le—ds to tr—nsp—ren™y —s —ll —˜sorption sites will ˜e s—tur—tedF „his —llows light penetr—tion through the resist (lm with full exposure to the su˜str—te surf—™eF pull penetr—tion of the (lm le—ds to — se™ond pro˜lemD multiple re)e™tion interferen™eF „his o™™urs when light whi™h h—s penetr—ted the (lm to the su˜str—te is then re)e™ted ˜—™k tow—rds the surf—™eF „he result is — st—nding w—ve interferen™e p—ttern whi™h ™—uses uneven exposure through the (lmF „he pro˜lem ˜e™omes more severe —s opti™—l limits —re —ppro—™hed where fe—ture size is —pproxim—tely equ—l to the w—velength of the light sour™e me—ning su™h st—nding w—ves —re the s—me size —s the irr—di—ted fe—turesF sn the most —dv—n™ed lithogr—phy te™hniques su™h —s PRV nm lithogr—phy with ex™imer l—sersD — spe™i—l —ntiEre)e™t—n™e ™o—ting must ˜e l—id down ˜efore the resist is depositedF hevelopment of —n e‚ ™o—ting th—t h—s no —dverse e'e™ts during the exposure —nd development pro™ess is di0™ultF yne ™ompletely new —ppro—™h to photolithogr—phy resists —re topEsurf—™eEim—ged resists or „ƒs resistsF „hese pro™esses do not require light penetr—tion through the whole volume of resistF sn — „ƒs resistD — silyl —mine is sele™tively inEdi'used from the g—s ph—se into — phenoli™ polymer in response to the l—ser irr—di—tionF „his di'usion pro™ess ™re—tes — silyl etherD —nd development t—kes pl—™e in the form of —n oxygen pl—sm— et™hD sometimes termed 9dry developing9F hepth of fo™us limit—tions —re thus —voided —s exposure is ne™ess—ry only —t the surf—™e of the resist l—yerD —nd the resolution of the et™hing pro™ess determines the (n—l resist pro(leF ƒu™h — te™hnique h—s tremendous —dv—nt—gesD p—rti™ul—rly —s sour™e w—velengths ˜e™ome shorter —nd tr—nsp—rent polymers more r—reF ƒu™h —s resist h—s — ™le—r opti™—l —dv—nt—ge —s well sin™e the im—ge need only ˜e formed —t the surf—™e of the resist l—yer redu™ing the hyp needed to IHH nm or lessD —llowing for l—rger numeri™—l —perture lithogr—phy systems with sm—ller ™riti™—l dimensionsF . rereD not only is the —mplitude m—pped from the o˜je™t pl—ne to the im—ge pl—neD ˜ut the ph—se stru™ture of the light going through the m—sk is m—nipul—ted to improve the ™ontr—st —nd —llow for e'e™tive v—lues of k 1 lower th—n the theoreti™—l minimum for uniform illumin—tionF „he most import—nt ex—mple of these te™hniques is the ph—se shift m—sk or €ƒwF rere the m—sk ™onsists of two types of —re—sD those th—t —llow light to p—ss through un—'e™ted —nd some regions where the —mplitude of the light is un—'e™ted ˜ut its ph—se is shiftedF „he resulting ele™tri™ (elds will then sum to zero in some pl—™es where use of —n ordin—ry m—sk would h—ve resulted in — positive intensityF „here —re m—ny pro˜lems with the pr—™ti™—l introdu™tion of v—rious ph—se shifting te™hniquesF gonstru™E tion of m—sks with ph—se shifting elements @usu—lly — thin l—yer of €wweA is di0™ult —nd expensiveF w—sk d—m—geD —lre—dy — key pro˜lem in ™onvention—l produ™tion te™hniquesD ˜e™omes —n even gre—ter issue —s tr—dition—l m—sk rep—ir te™hniques ™—n no longer ˜e usedF elso identifying errors in — m—sk is m—de more di0™ult ˜y the odd designF 4.

7.D IWWQD E76-CD PTF • wF ‚oths™hildD eF ‚F porteD wF ‡F rornD ‚F ‚F uunzD ƒF gF €—lm—teerD —nd tF rF gF ƒedl—™ekD IEEE J.6.1 Photolithography sn photolithogr—phyD — p—ttern m—y ˜e tr—nsferred onto — photoresist (lm ˜y exposing the photoresist to light through — m—sk of the p—tternF sn the semi™ondu™tor industryD the photolithogr—phi™ pro™edure in™ludes the following steps —s illustr—ted in pigure RFPSX ™o—ting — ˜—se m—teri—l with photoresistD exposing the resist through — m—sk to lightD developing the resistD et™hing the exposed —re—s of the ˜—seD —nd stripping the rem—ining resist o'F 9 This content is available online at <http://cnx.7 Composition and Photochemical Mechanisms of Photoresists 9 note: „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of engel— gindy ‡eiF 4.2/>.3 Bibliography • wF forn —nd iF ‡olfD Principles of Optics 6th EditionD €erg—mon €ressD xew ‰ork @IWVHAF • wF x—k—seD IEICE Trans.IRU 4.6. Selected Topics in Quantum ElectronicsD IWWSD 1D WITF 4. .4 Light sources gurrent photolithogr—phy te™hniques in produ™tion utilize ultr—violet l—mps —s the light sour™eF sn the most —dv—n™ed produ™tion f—™ilitiesD HFQS µm mer™ury iEline te™hnology is usedF por the next gener—tion of ™hips su™h —s TR w˜it h‚ewƒ ˜etter perform—n™e is ne™ess—ry —nd either iEline te™hnology ™om˜ined with €ƒw or — new light sour™e is requiredF gert—inly for the PST w˜it gener—tion using HFPS µm te™hnologyD the iEline sour™e is no longer —dequ—teF „he —pp—rent su™™essor is the PRV nm urp l—serD whi™h entered the most —dv—n™ed produ™tion f—™ilities in the l—te IWWHsF urp te™hnology is often referred to in the liter—ture —s heep …† or h…† lithogr—phyF por further shrink—ge to HFIV µm te™hnologyD the erp ex™imer l—ser —t IWQ nm will likely ˜e used with the tr—nsition likely to t—ke pl—™e in the (rst few ye—rs of the next de™—deF et ™riti™—l dimensions lower th—n HFIV E HFI µm —nd ˜elowD — whole host of te™hnologi™—l pro˜lems will need to ˜e over™ome in every st—ge of m—nuf—™turing in™luding photolithogr—phyF yne likely s™heme for future lithogr—phy is to use ˆEr—ys where the w—velength of the light is so mu™h sm—ller th—n the fe—ture size su™h th—t proximity printing ™—n ˜e usedF „his is where the m—sk is pl—™ed ™lose to the surf—™e —nd —n ˆEr—y sour™e is s™—nned —™ross using no opti™sF gommon ˆEr—y sour™es for su™h te™hniques in™lude syn™hrotron r—di—tion —nd l—ser produ™ed pl—sm—sF st h—s —lso ˜een widely suggested th—t the ™ost of implementing ˆEr—y or other postEopti™—l te™hniques together with the in™re—sed ™ost of every other m—nuf—™turing pro™ess step will m—ke improvements ˜eyond HFI µm ™ost prohi˜itive where ˜ene(ts in in™re—sed ™ir™uit speed —nd density will ˜e dw—rfed ˜y m—ssive m—nuf—™turing ™ostF st is noted however th—t su™h predi™tions h—ve ˜een m—de in the p—st with reg—rd to other te™hnologi™—l ˜—rriersF 4.

25: Steps in optical printing using photolithography.7.IRV CHAPTER 4.1 Photoresist composition ƒever—l fun™tion—l requirements must ˜e met for — photoresist to ˜e used in the semi™ondu™tor industryF €hotoresist polymers must ˜e solu˜le for e—sy deposition onto — su˜str—te ˜y spinE™o—tingF qood photoresistE su˜str—te —dhesion properties —re required to minimize under™uttingD to m—int—in edge —™uityD —nd to ™ontrol the fe—ture sizesF „he photoresist must ˜e ™hemi™—lly resist—nt to whi™hever et™h—nts —re to ˜e usedF ƒenE sitivity of the photoresist to — p—rti™ul—r light sour™e is essenti—l to the fun™tion—lity of — photoresistF „he speed —t whi™h ™hemi™—l ™h—nges o™™ur in — photoresist is its ™ontr—stF „he ™ontr—st of — resist is dependent . …pon exposure to lightD the photoresist m—y ˜e™ome more or less solu˜le depending on the ™hemi™—l properties of the p—rti™ul—r resist m—teri—lF „he photo™hemi™—l re—™tions in™lude ™h—in s™issionD ™rossElinkingD —nd the re—rr—ngement of mole™ulesF sf the exposed —re—s of the photoresist ˜e™ome more solu˜leD then it is — positive resistY ™onverselyD if the exposed resist ˜e™omes less solu˜leD then it is — neg—tive resistF sn developing the photoresistD the more solu˜le m—teri—l is removed le—ving — positive or — neg—tive im—ge of the m—sk p—tternF Photoresist €hotoresists were initi—lly developed for the printing industryF sn the IWPHsD the —ppli™—tion of photoresists spre—d to the printed ™ir™uit ˜o—rd industryF €hotoresists for semi™ondu™tor use were (rst developed in the IWSHsY uod—k developed ™ommer™i—l neg—tive photoresists —nd shortly —fterD ƒhipley developed — line of positive resistsF ƒever—l other ™omp—nies h—ve entered the m—rket sin™e th—t time in hopes of m—nuf—™turing resist produ™ts whi™h meet the in™re—sing dem—nds of the semi™ondu™tor industryX n—rrower line widthsD fewer defe™tsD —nd higher produ™tion r—tesF 4. WAFER FORMATION AND PROCESSING Figure 4.

2 Negative photoresist chemistry „he m—trix resin m—teri—l used in the formul—tion of these @neg—tiveA resists is — syntheti™ ru˜˜er o˜t—ined ˜y — ieglerEx—tt— polymeriz—tion of isoprene whi™h results in the form—tion of poly@™isEisopreneAF e™idE ™—t—lyz—tion of poly@™isEisopreneA produ™es — p—rti—lly ™y™lized polymer m—teri—lY the ™y™lized polymer h—s — higher gl—ss tr—nsition temper—tureD ˜etter stru™tur—l propertiesD —nd higher densityF yn the —ver—geD mi™roele™troni™ resist polyisoprenes ™ont—in IEQ rings per ™y™li™ unitD with SEPH7 unre—™ted isoprene units rem—ining9F „he result—nt m—teri—l is extremely solu˜le in nonEpol—rD org—ni™ solvents in™luding tolueneD xyleneD —nd h—logen—ted —liph—ti™ hydro™—r˜onsF „he ™ondens—tion of p—r—E—zido˜enz—ldehyde with — su˜stituted ™y™lohex—none produ™es ˜isE—ryl—zide sensitizersF „o m—ximize the —˜sorption of — p—rti™ul—r light sour™eD the —˜sor˜—n™e spe™trum of the phoE toresist m—y ˜e shifted ˜y m—king stru™tur—l modi(™—tions to the sensitizersY for ex—mpleD ˜y using su˜stiE tuted ˜enz—ldehydesD the —˜sorption pe—k m—y ˜e shifted to longer w—velengthsF e typi™—l ˜is—zideE™y™lized polyisoprene photoresist formul—tion m—y ™ont—in WU p—rts ™y™lized polyisoprene to Q p—rts ˜is—zide in — @IH wt7A xylene solventF ell neg—tive photoresists fun™tion ˜y ™rossElinking — ™hemi™—lly re—™tive polymer vi— — photosensitive —gent th—t initi—tes the ™hemi™—l ™rossElinking re—™tionF sn the ˜is—zideE™y™lized polyisoprene resistsD the —˜sorption of photons ˜y the photosensitive ˜is—zide in the photoresist results in —n insolu˜le ™rosslinked polymerF …pon exposure to lightD the ˜is—zide sensitizers de™ompose into nitrogen —nd highly re—™tive ™hemi™—l intermedi—tesD ™—lled nitrenes @RFIVAF „he nitrines re—™t to produ™e polymer link—ges —nd threeEdimension—l ™rossElinked .IRW on the mole™ul—r weight distri˜ution of the polymersX — ˜ro—d mole™ul—r weight distri˜ution results in — low ™ontr—st resistF righ ™ontr—st resists produ™e higher resolution im—gesF „he four ˜—si™ ™omponents of — photoresist —re the polymerD the solventD sensitizersD —nd other —dditivesF „he role of the polymer is to either polymerize or photosolu˜ilize when exposed to lightF ƒolvents —llow the photoresist to ˜e —pplied ˜y spinE™o—tingF „he sensitizers ™ontrol the photo™hemi™—l re—™tions —nd —dditives m—y ˜e used to f—™ilit—te pro™essing or to enh—n™e m—teri—l propertiesF €hoto™hemi™—l ™h—nges to polymers —re essenti—l to the fun™tion—lity of — photoresistF €olymers —re ™omposed prim—rily of ™—r˜onD hydrogenD —nd oxygenE˜—sed mole™ules —rr—nged in — repe—ted p—tternF xeg—tive photoresists —re ˜—sed on polyisopreme polymersY neg—tive resist polymers —re not ™hemi™—lly ˜onded to e—™h otherD ˜ut upon exposure to lightD the polymers ™rosslinkD or polymerizeF €ositive photoresists —re formul—ted from phenolEform—ldehyde novol—k resinsY the positive resist polymers —re rel—tively insolu˜leD ˜ut upon exposure to lightD the polymers undergo photosolu˜iliz—tionF ƒolvents —re required to m—ke the photoresist — liquidD whi™h —llows the resist to ˜e spun onto — su˜E str—teF „he solvents used in neg—tive photoresists —re nonEpol—r org—ni™ solvents su™h —s tolueneD xyleneD —nd h—logen—ted —liph—ti™ hydro™—r˜onsF sn positive resistsD — v—riety of org—ni™ solvents su™h —s ethyl ™ellosolve —™et—teD ethoxyethyl —™et—teD diglymeD or ™y™lohex—none m—y ˜e usedF €hotosensitizers —re used to ™ontrol or ™—use polymer re—™tions resulting in the photosolu˜iliz—tion or ™rosslinking of the polymerF „he sensitizers m—y —lso ˜e used to ˜ro—den or n—rrow the w—velength response of the photoresistF fis—zide sensitizers —re used in neg—tive photoresists while positive photoresists utilize di—zon—phthoquinonesF yne me—sure of photosensitizers is their qu—ntum e0™ien™iesD the fr—™tion of photons whi™h result in photo™hemi™—l re—™tionsY the qu—ntum e0™ien™y of positive di—zon—phthoquinone photoresist sensitizers h—s ˜een me—sured to ˜e HFP E HFQ —nd the qu—ntum e0™ien™y of neg—tive ˜isE—ryl—zide sensitizers is in the r—nge of HFS E IFHF edditives —re —lso introdu™ed into photoresists depending on the spe™i(™ needs of the —ppli™—tionF eddiE tives m—y ˜e used to in™re—se photon —˜sorption or to ™ontrol light within the resist (lmF edhesion promoters su™h —s hex—methyldisil—z—ne —nd —dditives to improve su˜str—te ™o—ting —re —lso ™ommonly usedF 4.2.7.

WAFER FORMATION AND PROCESSING stru™tures th—t —re less solu˜le in the developer solutionF @RFIVA 4.2.3 Positive photoresist chemistry €ositive photoresist m—teri—ls origin—lly developed for the printing industry h—ve found use in the semi™onE du™tor industryF „he ™ommonly used novol—™ resins @phenolEform—ldehyde ™opolymerA —nd @photosensitiveA di—zoquinone ˜oth were produ™ts of the printing industryF „he novol—k resin is — ™opolymer of — phenol —nd form—ldehyde @pigure RFPTAF xovol—k resins —re solu˜le in ™ommon org—ni™ solvents @in™luding ethyl ™ellosolve —™et—te —nd diglymeA —nd —queous ˜—se solutionsF gommer™i—l resists usu—lly ™ont—in met—E™resol resins formed ˜y the —™idE™—t—lyzed ™ondens—tion of met—E ™resol —nd form—ldehydeF Figure 4.7. „he positive photoresist sensitizers —re su˜stituted di—zon—phthoquinonesF „he ™hoi™e of su˜stituents —'e™ts the solu˜ility —nd the —˜sorption ™h—r—™teristi™s of the sensitizersF gommon su˜stituents —re —ryl sulfon—tesF „he di—zoquinones —re formed ˜y — re—™tion of di—zon—phthoquinone sulfonyl ™hloride with —n —l™ohol to form sulfon—te esterY the sensitizers —re then in™orpor—ted into the resist vi— — ™—rrier or ˜onded to the resinF „he sensitizer —™ts —s — dissolution inhi˜itor for the nov—l—™ resin —nd is ˜—seEinsolu˜leF „he positive photoresist is formul—ted from — novol—™ resinD — di—zon—phthoquinone sensitizerD —nd —dditives dissolved in — PH E RH wt7 org—ni™ solventF sn — typi™—l resistD up to RH wt7 of the resist m—y ˜e the sensitizerF „he photo™hemi™—l re—™tion of quinonedi—zide is illustr—ted in @RFIWAF …pon —˜sorption of — photonD the quinonedi—zide de™omposes through ‡ol' re—rr—ngementD spe™i(™—lly — ƒus re—™tionD —nd produ™es g—seous nitrogen —s — ˜yEprodu™tF sn the presen™e of w—terD the de™omposition produ™t forms —n indene ™—r˜oxyli™ —™idD whi™h is ˜—seEsolu˜leF roweverD the form—tion of —™id m—y not ˜e the re—son for in™re—sed solu˜ilityY the rele—se of nitrogen g—s produ™es — porous stru™ture through whi™h the developer m—y re—dily di'useD .26: Structure of a novolak resin.ISH CHAPTER 4.

3 Comparison of positive and negative photoresists snto the IWUHsD neg—tive photoresist pro™esses domin—tedF „he poor —dhesion —nd the high ™ost of positive photoresists prevented its widespre—d use —t the timeF es devi™e dimensions grew sm—llerD the —dv—nt—ges of positive photoresistsD ˜etter resolution —nd pinhole prote™tionD suited the ™h—nging dem—nds of the semi™onE du™tor industry —nd in the IWVHs the positive photoresists ™—me into prominen™eF e ™omp—rison of neg—tive —nd positive photoresists is given in pigure RFPUF .7.7.ISI resulting in in™re—sed solu˜ilityF @RFIWA 4.2.4 Image reversal fy introdu™ing —n —dditive to the novol—™ resins with di—zon—phth—quiones sensitizersD the result—nt photoreE sist m—y ˜e used to form — neg—tive im—geF e sm—ll —mount of — ˜—si™ —dditive su™h —s mon—zolineD imid—zoleD —nd triethyl—mine is mixed into — positive novol—™ resistF …pon exposure to lightD the di—zon—phth—quiones sensitizer forms —n indene ™—r˜oxyli™ —™idF huring the su˜sequent ˜—king pro™essD the ˜—se ™—t—lyzes — therE m—l de™—r˜oxyl—tionD resulting in — su˜stituted indene th—t is insolu˜le in —queous ˜—seF „henD the resist is )ood exposed destroying the dissolution inhi˜itors rem—ining in the previously unexposed regions of the resistF „he development of the photoresist in —queous ˜—se results in — neg—tive im—ge of the m—skF 4.

WAFER FORMATION AND PROCESSING Figure 4.4 Bibliography • ‡FwF elvinoD Plastics For ElectronicsD w™qr—wErillD sn™D xew ‰ork @IWWSAF • ‚F ‡F flevinsD ‚F gF h—lyD —nd ƒF ‚F „urnerD in Encyclopedia of Polymer Science and EngineeringD idF tF sF uro™ehwitzD ‡ileyD xew ‰ork @IWVSAF • wF tF fowdenD in Materials for Microlithography: Radiation-Sensitive PolymersD idF vF pF „hompE sonD gF qF ‡illsonD —nd tF wF tF pre™hetD emeri™—n ghemi™—l ƒo™iety ƒymposium ƒeries xoF PTTD ‡—shingtonD hFgF @IWVRAF • ƒF tF woss —nd eF vedwithD The Chemistry of the Semiconductor IndustryD fl—™kie 8 ƒon vimitedD ql—sgow @IWVUAF • iF ‚ei™hm—nisD pF wF roulih—nD yF x—l—m—suD —nd „F ˆF xeen—nD in Polymers for MicroelectronicsD idF vF pF „hompsonD gF qF ‡illsonD —nd ƒF „—g—w—D emeri™—n ghemi™—l ƒo™iety ƒymposium ƒeriesD xoF SQUD ‡—shingtonD hFgF @IWWRAF • €F v—n —ntD Microchip FabricationD Pnd edFD w™qr—wErill €u˜lishing gomp—nyD xew ‰ork @IWWHAF .27: A comparison of negative and positive photoresists.7.ISP CHAPTER 4. „he ˜etter resolution of positive resists over neg—tive resists m—y ˜e —ttri˜uted to the swelling —nd im—ge distortion of neg—tive resists during developmentY this prevents the form—tion of sh—rp verti™—l w—lls of neg—tive resistF his—dv—nt—ges of positive photoresists in™lude — higher ™ost —nd lower sensitivityF €ositive photoresists h—ve ˜e™ome the industry ™hoi™e over neg—tive photoresistsF xeg—tive photoresists h—ve mu™h poorer resolution —nd the positive photoresists exhi˜it ˜etter et™h resist—n™e —nd ˜etter therm—l st—˜ilityF es opti™—l m—sking pro™esses —re still preferred in the semi™ondu™tor industryD e'orts to improve the pro™esses —re ongoingF gurrentlyD rese—r™hers —re studying v—rious forms of ™hemi™—l —mpli(™—tion to in™re—se the photon —˜sorption of photoresistsF 4.

1/>.ISQ • gF qr—nt ‡illsonD in Introduction to MicrolithographyD Pnd edFD idF vF pF „hompsonD gF qF ‡illsonD wF tF fowdenD emeri™—n ghemi™—l ƒo™ietyD ‡—shingtonD hFgF @IWVQAF .28: After the anneal/drive-in.8 Integrated Circuit Well and Gate Creation note: 10 Gate Creation ˜y fill ‡ilsonF „his module is ˜—sed upon the gonnexions module entitled Integrated Circuit Well and ‡e then remove the rem—ining resistD —nd perform —n —™tiv—tionG—nne—lGdi'usion stepD —lso sometimes ™—lled the 4driveEin4F „he purpose of this step is two foldF ‡e w—nt to m—ke the nEt—nk deep enough so th—t we ™—n use it for our pE™h—nnel wyƒD —nd we w—nt to ˜uild up —n impl—nt ˜—rrier so th—t we ™—n impl—nt into the pEsu˜str—te region onlyF ‡e introdu™e oxygen into the re—™tor during the —™tiv—tionD so th—t we grow — thi™ker oxide over the region where we impl—nted the phosphorusF „he nitride l—yer over the pEsu˜str—te on the vrƒ prote™ts th—t —re— from —ny oxide growthF ‡e then end up with the stru™ture shown in pigure RFPVF Figure 4. xow we strip the rem—ining nitrideF ƒin™e the only w—y we ™—n ™onvert from p to n is to —dd — donor ™on™entr—tion whi™h is gre—ter th—n the ˜—™kground —™™eptor ™on™entr—tionD we h—d to keep the doping in the su˜str—te f—irly light in order to ˜e —˜le to m—ke the nEt—nkF „he lightly doped pEsu˜str—te would h—ve too low — threshold volt—ge for good nEwyƒ tr—nsistor oper—tionD so we will do — VT —djust impl—nt through the thin oxide on the vrƒD with the thi™k oxide on the ‚rƒ ˜lo™king the ˜oron from getting into the nEt—nkF „his is shown in pigure RFPWD where ˜oron is impl—nted into the pEtype su˜str—te on the vrƒD ˜ut is ˜lo™ked ˜y the thi™k oxide in the region over the nEwellF 10 This content is available online at <http://cnx.

ISR CHAPTER 4. „he nitride is p—tterned @™overed with photoresistD exposedD developedD et™hedD —nd remov—l of photoreE sistA to m—ke two —re—s whi™h —re ™—lled 4—™tive4 pigure RFQIF „he w—fer is then su˜je™ted to — highEpressure oxid—tion step whi™h grows — thi™k oxide wherever the nitride w—s removedF „he nitride is — good ˜—rrier for oxygenD so essenti—lly no oxide grows underne—th itF „he thi™k oxide is used to isol—te individu—l tr—nsistorsD —nd —lso to m—ke for —n insul—ting l—yer over whi™h ™ondu™ting p—tterns ™—n ˜e runF „he thi™k oxide is ™—lled (eld oxide @or pyˆ for shortA pigure RFQPF . WAFER FORMATION AND PROCESSING Figure 4.30: Strip of the oxide and grow a new nitride layer.29: VT adjust implant. xextD we strip o' —ll the oxideD grow — new thin l—yer of oxideD —nd then — l—yer of nitride pigure RFQHF „he oxide l—yer is grown only ˜e™—use it is ˜—d to grow ƒi3 x4 dire™tly on top of sili™onD —s the di'erent ™oe0™ients of therm—l exp—nsion ˜etween the two m—teri—ls ™—uses d—m—ge to the sili™on ™ryst—l stru™tureF elsoD it turns out to ˜e ne—rly impossi˜le to remove nitride if it is deposited dire™tly on to sili™onF Figure 4.

Figure 4. „henD the nitrideD —nd some of the oxide —re et™hed o'F „he oxide is et™hed enough so th—t —ll of the oxide under the nitride regions is removedD whi™h will t—ke — little o' the (eld oxide —s wellF „his is ˜e™—use we now w—nt to grow the g—te oxideD whi™h must ˜e very ™le—n —nd pure pigure RFQQF „he oxide under the nitride is sometimes ™—lled — sacricial oxideD ˜e™—use it is s—™ri(™ed in the n—me of ultr— perform—n™eF .31: Nitride remaining after etching.ISS Figure 4.32: After growth of the eld oxide (FOX).

„he polysili™on is then p—tterned to form the two regions whi™h will ˜e our g—tesF „he w—fer is ™overed on™e —g—in with photoresistF „he resist is removed over the region th—t will ˜e the nE™h—nnel devi™eD ˜ut is left ™overing the pE™h—nnel devi™eF e little —re— ne—r the edge of the nEt—nk is —lso un™overed pigure RFQSF „his will —llow us to —dd some —ddition—l phosphorus into the nEwellD so th—t we ™—n m—ke — ™ont—™t thereD so th—t the nEwell ™—n ˜e ™onne™ted to Vdd F . „hen the g—te oxide is grownD —nd immedi—tely there—fterD the whole w—fer is ™overed with polysili™on pigure RFQRF Figure 4.34: Polysilicon deposition over the gate oxide.33: Ready to grow gate oxide. WAFER FORMATION AND PROCESSING Figure 4.IST CHAPTER 4.

ISU Figure 4.35: Preparing for NMOS channel/drain implant.36: Phosphorus S/D implant. f—™k into the impl—nter we goD this time exposing the w—fer to phosphorusF „he poly g—teD the pyˆ —nd the photoresist —ll ˜lo™k phosphorus from getting into the w—ferD so we m—ke two nEtype regions in the pEtype su˜str—teD —nd we h—ve m—de our nE™h—nnel wyƒ sour™eGdr—in regionsF ‡e —lso —dd phosphorous to the Vdd ™ont—™t region in the nEwell so —s the m—ke sure we get good ™ont—™t perform—n™e there pigure RFQTF Figure 4. „he form—tion of the sour™e —nd dr—in were performed with — self-aligning technologyF „his me—ns th—t we used the g—te stru™ture itself to de(ne where the two inside edges of the sour™e —nd dr—in would ˜e for the wyƒpi„F sf we h—d m—de the sour™eGdr—in regions ˜efore we de(ned the g—teD —nd then tried to line the g—te up right over the sp—™e ˜etween themD we might h—ve gotten something th—t looks like wh—t is shown in pigure RFQUF ‡h—t9s going to ˜e the pro˜lem with this tr—nsistorc y˜viouslyD if the g—te does not extend —ll the w—y to ˜oth the sour™e —nd the dr—inD then the ™h—nnel will not eitherD —nd the tr—nsistor will never turn on3 ‡e ™ould try m—king the g—te widerD to ensure th—t it will overl—p ˜oth —™tive —re—sD even if it is slightly mis—lignedD ˜ut then you get — lot of extr—neous fringing ™—p—™it—n™e whi™h will signi(™—ntly slow down the speed of oper—tion of the tr—nsistor pigure RFQVF „his is ˜—d3 „he development of the selfE—ligned g—te te™hnique w—s one of the ˜ig ˜re—kthroughs whi™h h—s propelled us into the †vƒs —nd …vƒs er—F .

‡e pull the w—fer out of the impl—nterD —nd strip o' the photoresistF „his is sometimes di0™ultD ˜e™—use the —™t of ion impl—nt—tion ™—n 4˜—ke4 the photoresist into — very tough (lmF ƒometimes —n rf dis™h—rge in —n y2 —tmosphere is used to 4—sh4 the photoresistD —nd liter—lly ˜urn it o' the w—fer3 ‡e now —pply some more €‚D —nd this time p—ttern to h—ve the mo—t —re—D —nd — su˜str—te ™ont—™t exposedD for — ˜oron p+ impl—ntF „his is shown in pigure RFQWF . Figure 4.37: A representation of a misaligned gate.ISV CHAPTER 4.38: A representation of a wide gate. WAFER FORMATION AND PROCESSING Figure 4.

ISW Figure 4. .40: Final oxide growth. ‡e —re —lmost doneF „he next thing we do is remove —ll the photoresistD —nd grow one more l—yer of oxideD whi™h ™overs everythingD —s shown in pigure RFRHF ‡e put photoresist over the whole w—fer —g—inD —nd p—ttern for ™ont—™t holes to go through the oxideF ‡e will put ™ont—™ts for the two dr—insD —nd for e—™h of the sour™esD m—ke sure th—t the holes —re ˜ig enough to —lso —llow us to ™onne™t the sour™e ™ont—™t to either the pEsu˜str—te or the nEmo—t —s is —ppropri—te pigure RFRIF Figure 4.39: Boron p-channel S/D implant. CHAPTER 4.9 Applying Metallization by Sputtering note: 11 „his module is —d—pted from the gonnexions module entitled Applying Metal/Sputtering ˜y fill ‡ilsonF ‡e now put the w—fer in — sputter deposition systemF sn the sputter systemD we ™o—t the entire surf—™e of the w—fer with — ™ondu™torF en —luminumEsili™on —lloy is usu—lly usedD —lthough other met—ls —re employed —s wellF e sputtering system is shown s™hem—ti™—lly in pigure RFRPF e sputtering system is — v—™uum ™h—m˜erD whi™h —fter it is pumped outD is reE(lled with — lowEpressure —rgon g—sF e high volt—ge ionizes the g—sD —nd ™re—tes wh—t is known —s the grookes d—rk sp—™e ne—r the ™—thodeD whi™h in our ™—seD ™onsists of — met—l t—rget m—de out of the met—l we w—nt to depositF elmost —ll of the potenti—l of the highEvolt—ge supply —ppe—rs —™ross the d—rk sp—™eF „he glow dis™h—rge ™onsists of —rgon ions —nd ele™trons whi™h h—ve ˜een stripped o' of themF ƒin™e there —re —˜out equ—l num˜er of ions —nd ele™tronsD the net ™h—rge density is —˜out zeroD —nd hen™e ˜y q—uss9 l—wD so is the (eldF 11 This content is available online at <http://cnx. . WAFER FORMATION AND PROCESSING Figure 4.3/>.41: After the contact holes are etched.

„he ele™tri™ (eld —™™eler—tes the —rgon —toms whi™h sl—m into the —luminum t—rgetF „here is —n ex™h—nge of momentumD —nd —n —luminum —tom is eje™ted from the t—rget @pigure RFRQA —nd he—ds to the sili™on w—ferD where it sti™ksD —nd ˜uilds up — met—l (lm pigure RFRRF Figure 4.42: A schematic representation of a sputtering apparatus.ITI Figure 4. .43: The sputtering mechanism.

44: Wafer coated with metal.ITP CHAPTER 4. WAFER FORMATION AND PROCESSING Figure 4.45: After interconnect patterning. sf you look —t pigure RFRRD you will note th—t we h—ve seemingly done something pretty stupidF ‡e h—ve wired —ll of the elements of our gwyƒ inverter togetherY ˜ut —ll is not lostF ‡e ™—n do one more photolithogr—phi™ stepD —nd p—ttern —nd et™h the —luminumD so we only h—ve it where we need itF „his is shown in pigure RFRSF Figure 4. .

1 Introduction sn the pro™ess of epit—xyD — thin l—yer of m—teri—l is grown on — su˜str—teF ‡ith respe™t to ™ryst—l growth it —pplies to the pro™ess of growing thin ™ryst—lline l—yers on — ™ryst—l su˜str—teF sn epit—xi—l growthD there is — pre™ise ™ryst—l orient—tion of the (lm in rel—tion to the su˜str—teF por ele™troni™ devi™esD the su˜str—te is — single ™ryst—l @usu—lly ƒi or q—esA —nd therefore so is the epit—xi—l l—yer @epil—yerAF sn the most ˜—si™ form of mole™ul—r ˜e—m epit—xy @wfiAD the su˜str—te is pl—™ed in ultr— high v—™uum @…r†A —nd the sour™e m—teri—ls for the (lm —re ev—por—ted from element—l sour™esF „he ev—por—ted mole™ules or —toms )ow —s — ˜e—mD striking the su˜str—teD where they —re —dsor˜ed on the surf—™eF yn™e on the surf—™eD the —toms move ˜y surf—™e di'usion until they re—™h — thermodyn—mi™—lly f—vor—˜le lo™—tion to ˜ond to the su˜str—teF wole™ules will disso™i—te to —tomi™ form during di'usion or —t — f—vor—˜le siteF pigure SFI illustr—tes the pro™esses th—t ™—n o™™ur on the surf—™eF fe™—use the —toms require time for surf—™e di'usionD the qu—lity of the (lm will ˜e ˜etter with slower growthF „ypi™—lly growth r—tes of —˜out I monol—yer per se™ond provide su0™iently high qu—lityF 1 This content is available online at <http://cnx.2/>.1 Molecular Beam Epitaxy 1 note: „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of ƒ—r—h ‡est™ottF 5.1. ITQ .org/content/m25712/1.Chapter 5 Thin Film Growth 5.

THIN FILM GROWTH Figure 5. e typi™—l wfi ™h—m˜er is shown in pigure SFPF „he su˜str—te is ™hemi™—lly w—shed —nd then put into — lo—ding ™h—m˜er where it is further ™le—ned using —rgon ion ˜om˜—rdment followed ˜y —nne—lingF „his removes the top l—yers of the su˜str—teD whi™h is usu—lly —n undesired oxide whi™h grew in —ir —nd ™ont—ins impuritiesF „he —nne—ling he—ls —ny d—m—ge ™—used ˜y the ˜om˜—rdmentF „he su˜str—te then enters the growth ™h—m˜er vi— the s—mple ex™h—nge lo—d lo™kF st is se™ured on — moly˜denum holder either me™h—ni™—lly or with melted indium or g—llium whi™h hold the su˜str—te ˜y surf—™e tensionF Figure 5. Adsorption of atoms on the surface. i—™h e'usion ™ell @see pigure SFPA is — sour™e of one element in the (lmF „he e'usion ™ellD —lso ™—lled — . surface diusion of atoms.ITR CHAPTER 5. formation of crystalline lattice.1: Schematic illustration of processes on growing surface during MBE. desorption of particles from the surface.2: The MBE growth chamber.

1.2 Elemental and molecular sources „he e'usion ™ell is used for the m—jority of wfi growthF ell m—teri—ls used in the ™ell —re ™—refully ™hosen to ˜e noninter—™ting with the element ˜eing ev—por—tedF por ex—mpleD the ™ru™i˜le is pyroliti™ ˜oron nitrideF roweverD it h—s dis—dv—nt—gesD su™h —sX • „he ev—por—ted spe™ies m—y ˜e mole™ul—rD r—ther th—n monomeri™D whi™h will require further disso™—tion —t the surf—™eF • ‡hen the shutter is openedD the he—t loss from the ™ell results in — tr—nsient in the ˜e—m )ux whi™h l—st for sever—l minutes —nd ™—use v—ri—tions of up to SH7F • „he growth ™h—m˜er must ˜e opened up to repl—™e the solid sour™esF gr—™ker ™ells —re used to improve the r—tio of monomeri™ to mole™ul—r @or —t le—st dimeri™ to tetr—meri™A p—rti™les from the sour™eF „he ™r—™ker ™ellD pl—™ed so th—t the ˜e—m p—sses through it —fter the e'usion ™ellD is m—int—ined —t — high temper—ture @—nd sometimes high pressureA to en™our—ge disso™i—tionF „he disso™i—tion pro™ess gener—lly requires — ™—t—lyst —nd the ˜est ™—t—lysts for — given spe™ies h—ve ˜een studiedF ƒome elementsD su™h —s sili™onD h—ve low enough v—por pressure th—t more dire™t he—ting te™hniques su™h —s ele™tron ˜om˜—rdment or l—ser r—di—tion he—ting —re usedF „he ele™tron ˜e—m is ˜ent using ele™trom—gneti™ fo™using to prevent —ny impurities in the ele™tron sour™e from ™ont—min—ting the sili™on to ˜e used in wfiF fe™—use the he—t is ™on™entr—ted on the surf—™e to ˜e ev—por—tedD inter—™tions with —nd ™ont—min—tion from the ™ru™i˜le w—lls is redu™edF sn —dditionD this design does not require — shutterD so there is no pro˜lem with tr—nsientsF wodul—tion of the ˜e—m ™—n produ™e very sh—rp interf—™es on the su˜str—teF sn l—ser r—di—tion he—tingD the ele™tron ˜e—m is repl—™ed ˜y — l—ser ˜e—mF „he —dv—nt—ges of lo™—lized he—ting —nd r—pid modul—tion —re —lso m—int—ined without h—ving to worry —˜out ™ont—min—tion from the ele™tron sour™e or str—y ele™tronsF ƒome of the ssE†s @IPEITA ™ompounds h—ve su™h high v—por pressure th—t — unudson ™ell ™—nnot ˜e usedF por ex—mpleD the mer™ury sour™e must ˜e kept ™ooler th—n the su˜str—te to keep the v—por pressure low enough to ˜e fe—si˜leF „he rg sour™e must —lso ˜e se—led o' from the growth ™h—m˜er to —llow the ™h—m˜er to ˜e pumped downF „wo other methods of o˜t—ining the elements for use in epit—xy —re g—sEsour™e epit—xy —nd ™hemi™—l ˜e—m epit—xy @gfiAF foth of these methods use g—s sour™esD ˜ut they —re distinguished ˜y the use of element—l ˜e—ms in g—s sour™e epit—xyD while org—nomet—lli™ ˜e—ms —re used in gfiF por the ex—mple of sssE† @IQEISA semi™ondu™torsD in g—s epit—xyD the group sss m—teri—l m—y ™ome from —n e'usion ™ell while the group † m—teri—l is the hydrideD su™h —s esr3 or €r3 D whi™h is ™r—™ked ˜efore entering the growth ™h—m˜erF sn gfiD the group † m—teri—l is —n org—nomet—lli™D su™h —s triethylg—llium ‘q—@g2 r5 A3 “ or trimethyl—luminum ‘el@gr3 A3 “D whi™h —dsor˜s on the surf—™eD where it disso™i—tesF „he g—s sour™es h—ve sever—l —dv—nt—gesF q—s lines ™—n ˜e run into the ™h—m˜erD whi™h —llows the supply to ˜e replenished without opening the ™h—m˜erF ‡hen m—king —lloysD su™h —s elx q—1-x esD the g—ses ™—n ˜e premixed for the ™orre™t sto™hiometry or even h—ve their ™omposition gr—du—lly ™h—nged for m—king gr—ded stru™turesF por —˜rupt stru™turesD it is ne™ess—ry to ˜e —˜le to swit™h the g—s lines with speeds of I se™ond or lessF roweverD the g—s lines in™re—se the ™omplexity of the pro™ess —nd ™—n ˜e h—rd on the pumping systemF .ITS unudsen ™ellD ™ont—ins the element—l form in very high purity @gre—ter th—n WWFWWWWW7 for q— —nd esAF „he ™ell is he—ted to en™our—ge ev—por—tionF por q—es growthD the temper—ture is typi™—lly ™ontrolled for — v—por pressure of IH-2 to IH-3 „orr inside the e'usion ™ellD whi™h results in — tr—nsport of —˜out IH15 mole™ulesG™m2 to the su˜str—te when the shutter for th—t ™ell is openedF „he sh—pe —nd size of the opening in the ™ell is optimized for —n even distri˜ution of p—rti™les on the su˜str—teF hue to the rel—tively low ™on™entr—tion of mole™ulesD they typi™—lly do not inter—™t with other mole™ules in the ˜e—m during the S E QH ™m journey to the su˜str—teF „he su˜str—te is usu—lly rot—tedD —t — few rpmD to further even the distri˜utionF fe™—use wfi t—kes pl—™e in …r† —nd h—s rel—tively low pressure of residu—l g—s —t the surf—™eD —n—lysis te™hniques su™h —s re)e™tion high energy di'r—™tion —nd ellipsometry ™—n ˜e used during growthD ˜oth to study —nd ™ontrol the growth pro™essF „he …r† environment —lso —llows pre or post growth —n—lysis te™hniques su™h —s euger spe™tros™opyF 5.

1.3 Substrate choice and preparation w—teri—ls ™—n ˜e grown on su˜str—tes of di'erent stru™tureD orient—tionD —nd ™hemistryF sn de™iding whi™h m—teri—ls ™—n ˜e grown on — p—rti™ul—r su˜str—teD — prim—ry ™onsider—tion w—s expe™ted to ˜e l—tti™e misE m—t™hD iFeFD di'eren™es in sp—™ing ˜etween —tomsF roweverD while l—tti™e mism—t™h ™—n ™—use str—in in the grown l—yerD ™onsider—˜le —™™ommod—tion ˜etween m—teri—ls of di'erent sizes ™—n t—ke pl—™e during growthF e gre—ter sour™e of str—in ™—n ˜e di'eren™es in therm—l exp—nsion ™h—r—™teristi™s ˜e™—use the l—yer is grown —t high temper—tureF yn ™ooling to room temper—tureD dislo™—tion defe™ts ™—n ˜e formed —t the interf—™e or in severe ™—sesD the devi™e m—y ˜re—kF ghemi™—l ™onsider—tionsD su™h —s whether the l—yer9s elements will dissolve in the su˜str—te or form ™ompounds with the su˜str—teD must —lso ˜e ™onsideredF hi'erent orient—tions of the su˜str—te ™—n —lso —'e™t growthF gloseEp—™ked pl—nes h—ve the lowest surf—™e energyD whi™h —llows —toms to desor˜ from the surf—™eD resulting in slower growth r—tesF qrowth is f—vored where ˜onds ™—n ˜e m—de in sever—l dire™tions —t the s—me timeF „hereforeD the su˜str—te is often ™ut o'E—xis ˜y — P E R ◦ to provide — rougher growth surf—™eF por ™ompound semi™ondu™torsD some orient—tions result in the num˜er of loose ˜onds ™h—nging ˜etween l—yersF „his results in ™h—nges of surf—™e energy with e—™h l—yerD whi™h slows growth downF „he gre—test ™—use of defe™ts in the epit—xi—l l—yer is defe™ts on the su˜str—te9s surf—™eF sn gener—lD —ny dislo™—tions on the su˜str—te —re repli™—ted or even multiplied in the epit—xi—l growthD whi™h is wh—t m—kes the ™le—ning of the su˜str—te so import—ntF 5.4 Materials grown wfi is ™ommer™i—lly used prim—rily for q—es devi™esF „his is p—rtly ˜e™—use the high speed mi™row—ve devi™es m—de from q—es required the superior ele™tri™—l qu—lity of epit—xi—l l—yersF „—king pl—™e —t lower temper—ture —nd under ˜etter ™ontrolled ™onditionsD wfi gener—lly results in l—yers of ˜etter qu—lity th—n meltEgrownF prom solid q— —nd es sour™esD element—l q— —nd tetr—meri™ es4 —re ev—por—tedF por — q—es su˜str—teD the q— )ux h—s — sti™king ™oe0™ient very ™lose to I @—lmost ™ert—in to —dsor˜AF „he es is mu™h less likely to —dsor˜D so —n ex™ess is usu—lly suppliedF gr—™ker ™ells —re often used on the es4 in order to o˜t—in es2 inste—dD whi™h results in f—ster growth —nd more e0™ient utiliz—tion of the sour™e ˜e—mF por nomin—lly undoped q—es grown ˜y wfiD the residu—l impurities —re usu—lly ™—r˜onD from su˜str—te ™ont—min—tion —nd residu—l g—s —fter the growth ™h—m˜er is pumped downD —nd sulphurD from the es sour™eF „he most ™ommon surf—™e defe™ts —re 4ov—l4 defe™tsD whi™h seem to form when q— m—n—ges to form met—lli™ droplets during the growth pro™essD whi™h ™—n p—rti™ul—rly o™™ur if the su˜str—te w—s not ™le—ned properlyF „hese defe™ts ™—n —lso ˜e redu™ed ˜y ™—refully ™ontrolling the q— )uxF huring wfi growthD dop—nts ™—n ˜e introdu™ed ˜y h—ving — sep—r—te e'usion ™ell or g—s sour™e for e—™h dop—ntF „o —™hieve — desired dop—nt ™on™entr—tion in the (lmD not only must the r—te of dop—nts striking the su˜str—te ˜e ™ontrolledD ˜ut the ™h—r—™teristi™s of how the dop—nt ˜eh—ves on the surf—™e must ˜e knownF vowEv—por pressure dop—nts tend to desor˜ from the surf—™e —nd their ˜eh—vior is very temper—ture dependent —nd so —re —voided when possi˜leF ƒlow di'using dop—nts —dsor˜ to surf—™e sites —nd —re eventu—lly ™overed —s more q—es is grownF „heir in™orpor—tion depends line—rly on the p—rti—l pressure of the dop—nt present in the growth ™h—m˜erF „his is the ˜eh—vior exhi˜ited ˜y most nEtype dop—nts in q—es —nd most dop—nts of ˜oth types in ƒiF sf the dop—ntD like most pEtype q—es dop—ntsD is —˜le to di'use through the surf—™e of the su˜str—te into the ™ryst—l ˜elowD then there will ˜e higher in™orpor—tion e0™ien™yD whi™h will depend on the squ—re root of the dop—nt p—rti—l pressure for re—son—˜le ™on™entr—tionsF hue to in™re—sing l—tti™e str—inD —ll dop—nts will s—tur—te —t very high ™on™entr—tionsF „hey m—y —lso tend to form ™lustersF hop—nt ˜eh—vior depends on m—ny f—™tors —nd is —™tively studiedF „he growth of q—es epit—xi—l l—yers on sili™on su˜str—tes h—s —lso ˜een investig—tedF ƒili™on su˜str—tes —re grown in l—rger w—fersD h—ve ˜etter therm—l ™ondu™tivity —llowing more devi™esG™hip to ˜e grown on themD —nd —re ™he—perF roweverD ˜e™—use ƒi is nonpol—r —nd q—es is pol—rD the q—es tends to form isl—nds on the surf—™e with di'erent ph—se @wh—t should ˜e — q— site ˜—sed on — neigh˜oring dom—in9s p—ttern will —™tu—lly ˜e —n es siteAF „here is —lso — f—irly l—rge l—tti™e mism—t™hD le—ding to m—y dislo™—tionsF roweverD . THIN FILM GROWTH 5.ITT CHAPTER 5.1.

3: Schematic illustrating the formation of a RHEED pattern.5 Analysis techniques „he most popul—r inEsitu —n—lysis te™hnique for wfiEgrown l—yers is re)e™tion high energy di'r—™tion @‚riihAD see pigure SFQF ile™trons of energy S E RH ke† —re dire™ted tow—rds the s—mpleF „hey re)e™t from the surf—™e —t — very sm—ll —ngle @less th—n Q ◦ A —nd —re dire™ted onto — s™reenF „hese ele™trons inter—™t with only the top few —tomi™ l—yers —nd thus provide inform—tion —˜out the surf—™eF pigure SFR shows — typi™—l p—ttern on the s™reen for ele™trons re)e™ted from — smooth surf—™eD in whi™h ™onstru™tive interferen™e ˜etween some of the ele™trons re)e™ted from the l—tti™e stru™ture results in linesF sf the surf—™e is roughD spots will —ppe—r on the s™reenD —lsoF fy looking —t the tot—l intensity of the re)e™ted ele™tron p—tternD —n ide— of the num˜er of monol—yers deposited —nd how epil—yers grow ™—n ˜e o˜t—inedF „he isl—ndEtype growth shown in this (gure is —n —re— of intense interestF „hese os™ill—tions in intensity —re gr—du—lly d—mped —s more l—yers —re grownD ˜e™—use the over—ll roughness of the surf—™e in™re—sesF Figure 5.1.ITU pi„sD vihsD —nd l—sers h—ve —ll ˜een m—de in l—˜or—toriesF w—ny devi™es require —˜rupt jun™tions ˜etween l—yers of di'erent m—teri—lsF yne groupD studying how to m—ke high qu—lityD —˜rupt q—es —nd eles l—yersD found th—t r—pid movement of the q— or el on the surf—™e w—s requiredF „his migr—tion w—s enh—n™ed —t high temper—turesD ˜ut unfortun—telyD di'usion into the su˜str—te —lso in™re—sedF roweverD they —lso dis™overed th—t migr—tion of q— or el in™re—sed if the es supply w—s turned o'F fy —ltern—ting the q— —nd es suppliesD the q— w—s —˜le to re—™h the su˜str—te —nd migr—te to provide more even monol—yer ™over—ge ˜efore the es —toms —rrived to re—™tF fesides q—esD most other sssE† semi™ondu™tors h—ve —lso ˜een grown using wfiF ƒtru™tures involving very thin l—yers @only — few —tomi™ l—yers thi™kAD often ™—lled superl—tti™es or str—ined superl—tti™es if there is — l—rge l—tti™e mism—t™hD —re routinely grownF fe™—use di'erent m—teri—ls h—ve di'erent energy levels for ele™trons —nd holesD it is possi˜le to tr—p ™—rriers in one of these thin l—yersD forming — qu—ntum wellF „his type of ™on(nement stru™ture is p—rti™ul—rly popul—r for vihs or l—sersD in™luding ˜lue light l—sersF „he str—ined superl—tti™e stru™ture —™tu—lly shifts —nd splits the energy levels of the m—teri—ls in some ™—ses m—king devi™es possi˜le for su™h —ppli™—tions —s infr—red light dete™tionD whi™h requires very sm—ll ˜—nd g—psF „hin (lms of m—ny other m—teri—ls h—ve —lso ˜een grown using wfi methodsF ƒili™on te™hnology h—s ™he—per methods of growth —nd so ƒi l—yers —re not very popul—rF roweverD possi˜le devi™es m—de of ƒiEqe —lloys h—ve ˜een grownF „he ssE†s ™ompoundsD h—ve —lso ˜een grownF w—gneti™ m—teri—lsD su™h —s goE€t —nd peE€t —lloysD h—ve ˜een grown in the hopes of providing ˜etter m—gneti™ stor—geF 5. .

1. Appl. Phys. Figure 5.D IWVTD 25D vVTVF • tF rF w™peeD fF sF willerD —nd uF tF f—™hm—nnD J. Appl.4: €h—se lo™ked epit—xy t—kes —dv—nt—ge of the p—tterns of the os™ill—tions to grow very —˜rupt l—yersF fy sending the os™ill—tion inform—tion to — ™omputerD it ™—n de™ide when to open or ™lose the shutters of the e'usion ™ell ˜—sed on the lo™—tion in the os™ill—tion ™y™leF „his te™hnique selfE—djusts for )u™tu—tions in ˜e—m )ux when the shutters —re opened —nd ™—n grow very —˜rupt l—yersF enother —n—lysis te™hnique th—t ™—n ˜e used to study surf—™e smoothness during growth is ellipsometryF €ol—rized l—ser light is re)e™ted from the surf—™e —t — sm—ll —ngleF „he pol—riz—tion of the light ™h—ngesD depending on the roughness of the surf—™eF smproved growth ™h—r—™teristi™s —lso require th—t the —™tu—l )ux from the sour™es is me—suredF „his is typi™—lly done with —n ion g—uge )ux monitorD whi™h is either used to me—sure residu—l ˜e—m th—t misses the su˜str—te or is moved into the ˜e—m p—th for ™—li˜r—tion when — new sour™e is usedF fe™—use of the import—n™e of ™le—n su˜str—te surf—™es for lowEdefe™t growthD euger spe™tros™opy is used following ™le—ning ˜y sputteringF euger spe™tros™opy t—kes pl—™e ˜y ionizing —n inner shell ele™tron from —n —tomF ‡hen —n outer shell ele™tron then deex™ites to the inner shellD the energy rele—sed ™—n prompt the emission of —nother outer shell ele™tronF „he energy —t whi™h this o™™urs is ™h—r—™teristi™ of the —tom involved —nd the sign—l ™—n ˜e used to dete™t impurities —s sm—ll —s HFI7F 5. J.6 Bibliography • uF tF f—™hm—nnD The Materials Science of MicroelectronicsD †gr @IWWSAF • ƒF uF qh—ndhiD VLSI Fabrication Principles: Silicon and Gallium ArsenideD Pnd iditionD ‡ileyE snters™ien™eD x‰ @IWWRAF • wF eF rerm—n —nd rF ƒitterD Molecular Beam Epitaxy: Fundamentals and Current StatusD ƒpringerE †erl—g @IWVWAF • ‰F rorikoshiD wF u—w—shim—D —nd rF ‰—m—gu™hiD Jpn. J. Crystal GrowthD IWVUD 81D PTIF .D IWUUD 124D PSWF • „F ƒ—k—motoD rF pun—˜—shiD uF yht—D „F x—k—g—w—D xF tF u—w—iD —nd „F uojim—D Jpn.D IWVRD 23D vTSUF • ‡F „F „s—ngD J.ITV CHAPTER 5. Soc. THIN FILM GROWTH RHEED diraction pattern of a GaAs Adapted from images by the MBE Laboratory in the Institute of Physics of the ASCR (http://www.html). Phys. Electrochem.

2.1 Introduction 2 MaterialsF „his module w—s prep—red with the —ssist—n™e of tulie eF pr—n™isF „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of Electronic „he growth of thin (lms h—s h—d dr—m—ti™ imp—™t on te™hnologi™—l progressF fe™—use of the v—rious properties —nd fun™tions of these (lmsD their —ppli™—tions —re limitless espe™i—lly in mi™roele™troni™sF „hese l—yers ™—n —™t —s super™ondu™torsD semi™ondu™torsD ™ondu™torsD insul—torsD diele™tri™D or ferroele™tri™sF sn semi™ondu™tor devi™esD these l—yers ™—n —™t —s —™tive l—yers —nd diele™tri™D ™ondu™tingD or ion ˜—rrier l—yersF hepending on the type of (lm m—teri—l —nd its —ppli™—tionsD v—rious deposition te™hniques m—y ˜e employedF por g—sE ph—se depositionD these in™lude v—™uum ev—por—tionD re—™tive sputteringD ™hemi™—l v—por deposition @g†hAD espe™i—lly met—l org—ni™ g†h @wyg†hAD —nd mole™ul—r ˜e—m epit—xy @wfiAF etomi™ l—yer deposition @evhAD origin—lly ™—lled —tomi™ l—yer epit—xy @eviAD w—s (rst reported ˜y ƒuntol— et —lF in IWVH for the growth of zin™ sul(de thin (lms to f—˜ri™—te ele™trolumines™ent )—t p—nel displ—ysF evh refers to the method where˜y (lm growth o™™urs ˜y exposing the su˜str—te to its st—rting m—teri—ls —ltern—telyF st should ˜e noted th—t evi is —™tu—lly — su˜Eset of evhD in whi™h the grown (lm is epit—xi—l to the su˜str—teY howeverD the terms —re often used inter™h—nge—˜lyF elthough ˜oth evh —nd g†h use ™hemi™—l @mole™ul—rA pre™ursorsD the di'eren™e ˜etween the te™hniques is th—t the former uses self limiting ™hemi™—l re—™tions to ™ontrol in — very —™™ur—te w—y the thi™kness —nd ™omposition of the (lm depositedF sn this reg—rd evh ™—n ˜e ™onsidered —s t—king the ˜est of g†h @the use of mole™ul—r pre™ursors —nd —tmospheri™ or low pressureA —nd wfi @—tomE˜yE—tom growth —nd — high ™ontrol over (lm thi™knessA —nd ™om˜ining them in single methodF e sele™tion of m—teri—ls deposited ˜y evh is given in „—˜le SFIF Compound class Examples ss!†s ™ompounds nƒD nƒeD n„eD nƒ1−x ƒex D g—ƒD ƒrƒD f—ƒD ƒrƒ1−x ƒex D gdƒD gd„eD wn„eD rg„eD rg1−x gdx „eD gd1−x wnx „e nƒXw @w a wnD „˜D „mAD g—ƒXw @w a iuD geD „˜D €˜AD ƒrƒXw @w a geD „˜D €˜D wnD guA q—esD elesD el€D sn€D q—€D snesD elx q—1−x esD q—x sn1−x esD q—x sn1−x € elxD q—xD snxD ƒixx „ixD „—xD „—3 x5 D x˜xD wox el2 y3 D „iy2 D ry2 D rfy2 D „—2 y5 D x˜2 y5 D ‰2 y3 D wgyD gey2 D ƒiy2 D v—2 y3 D ƒr„iy3 D f—„iy3 sn2 y3 D sn2 y3 XƒnD ƒny2 Xƒ˜D nyD sn2 y3 XpD sn2 y3 XrD ƒny2 D ss!†s ˜—sed thinE(lm ele™trolumines™ent @„pivA phosphors sss!† ™ompounds ƒemi™ondu™torsGdiele™tri™ nitrides wet—lli™ nitrides hiele™tri™ oxides „r—nsp—rent ™ondu™tor oxides continued on next page 2 This content is available online at <http://cnx.2 Atomic Layer Deposition>.ITW 5. .

THIN FILM GROWTH nyXelD q—2 y3 D xiyD goyx ‰f—2 gu3 y7-x g—p2 D ƒrp2 D np2 Table 5. „he deposition m—y ˜e de(ned —s selfElimiting sin™e oneD —nd only oneD monol—yer of the re—™t—nt spe™ies rem—ins on the surf—™e —fter e—™h exposureF sn this ™—seD one ™omplete ™y™le results in the deposition of one monol—yer of the ™ompound on the su˜str—teF ‚epe—ting this ™y™le le—ds to — ™ontrolled l—yerE˜yEl—yer growthF „hus the (lm thi™kness is ™ontrolled ˜y the num˜er of pre™ursor ™y™les r—ther th—n the deposition timeD —s is the ™—se for — g†h pro™essesF „his selfElimiting ˜eh—vior is the fund—ment—l —spe™t of evh —nd underst—nding the underlying me™h—nism is ne™ess—ry for the future exploit—tion of evhF .2 How ALD works „he premise ˜ehind the evh pro™ess is — simple oneF „he su˜str—te @—morphous or ™ryst—llineA is exposed to the (rst g—seous pre™ursor mole™ule @element—l v—por or vol—tile ™ompound of the elementA in ex™ess —nd the temper—ture —nd g—s )ow is —djusted so th—t only one monol—yer of the re—™t—nt is ™hemisor˜ed onto the surf—™e @pigure SFS—AF „he ex™ess of the re—™t—ntD whi™h is in the g—s ph—se or physisor˜ed on the surf—™eD is then purged out of the ™h—m˜er with —n inert g—s pulse ˜efore exposing the su˜str—te to the other re—™t—nt @pigure SFS˜AF „he se™ond re—™t—nt then ™hemisor˜s —nd undergoes —n ex™h—nge re—™tion with the (rst re—™t—nt on the su˜str—te surf—™e @pigure SFS™AF „his results in the form—tion of — solid mole™ul—r (lm —nd — g—seous side produ™t th—t m—y then ˜e removed with —n inert g—s pulse @pigure SFSdAF Figure 5.IUH ƒemi™ondu™tor oxides ƒuper™ondu™tor oxides pluorides CHAPTER 5.2.1X ix—mples of thin (lm m—teri—ls deposited ˜y evh in™luding (lms deposited in epit—xi—lD poly™ryst—lline or —morphous formF ed—pted from wF ‚it—l— —nd wF veskelD NanotechnologyD IWWWD 10D IWF 5.5: Schematic representation of an ALD process.

IUI yne ˜—si™ ™ondition for — su™™essful evh pro™ess is th—t the ˜inding energy of — monol—yer ™hemisor˜ed on — surf—™e is higher th—n the ˜inding energy of su˜sequent l—yers on top of the formed l—yerY the temper—ture of the re—™tion ™ontrols thisF „he temper—ture must ˜e kept low enough to keep the monol—yer on the surf—™e until the re—™tion with the se™ond re—™t—nt o™™ursD ˜ut high enough to reEev—por—te or ˜re—k the ™hemisorption ˜ondF „he ™ontrol of — monol—yer ™—n further ˜e in)uen™ed with the input of extr— energy su™h —s …† irr—di—tion or l—ser ˜e—msF „he gre—ter the di'eren™e ˜etween the ˜ond energy of — monol—yer —nd the ˜ond energies of the su˜sequent l—yersD the ˜etter the selfE™ontrolling ™h—r—™teristi™s of the pro™essF f—si™—llyD the evh te™hnique depends on the di'eren™e ˜etween ™hemisorption —nd physisorptionF €hE ysisorption involves the we—k v—n der ‡——l9s for™esD where—s ™hemisorption involves the form—tion of rel—E tively strong ™hemi™—l ˜onds —nd requires some —™tiv—tion energyD therefore it m—y ˜e slow —nd not —lw—ys reversi˜leF e˜ove ™ert—in temper—tures ™hemisorption domin—tes —nd it is —t this temper—ture evh oper—tes ˜estF elsoD ™hemisorption is the re—son th—t the pro™ess is selfE™ontrolling —nd insensitive to pressure —nd su˜str—te ™h—nges ˜e™—use only one —tomi™ or mole™ul—r l—yer ™—n —dsor˜ —t the s—me timeF 5.3 Equipment for the ALD process iquipment used in the evh pro™ess m—y ˜e ™l—ssi(ed in terms of their working pressure @v—™uumD low pressureD —tmospheri™ pressureAD method of pulsing the pre™ursors @moving su˜str—te or v—lve sour™esA or —™™ording to the types of sour™esF ƒever—l system types —re dis™ussedF sn — typi™—l moving su˜str—te evh growth system @pigure SFTA the su˜str—teD lo™—ted in the re™ess p—rt of the sus™eptorD is ™ontinuously rot—ted —nd ™uts through stre—ms of the g—seous pre™ursorsD in this ™—seD trimethylg—llium ‘„wqD q—@gr3 A3 “ —nd —rsine @esr3 AF „hese g—seous pre™ursors —re introdu™ed through sep—r—te lines —nd the g—ses ™ome in ™ont—™t with the su˜str—te only when it revolves under the inlet tu˜eF „his ™y™le is repe—ted until the required thi™kness of q—es is —™hievedF „he exposure time to e—™h of the g—s stre—ms is —˜out HFQ sF .2.

4 Requirements for ALD growth ƒever—l p—r—meters must ˜e t—ken into —™™ount in order to —ssure su™™essful evh growthF „hese in™lude the physi™—l —nd ™hemi™—l properties of the sour™e m—teri—lsD their pulsing into the re—™torD their inter—™tion with the su˜str—te —nd e—™h otherD —nd the thermodyn—mi™s —nd vol—tility of the (lm itselfF ƒour™e mole™ules used in evh ™—n ˜e either element—l or —n inorg—ni™D org—ni™D or org—nomet—lli™ ™omE poundF „he ™hemi™—l n—ture of the pre™ursor is insigni(™—nt —s long —s it possesses the following propertiesF . Adapted from M. M.6: evh m—y ˜e ™—rried out in — v—™uum system using —n ultr—Ehigh v—™uum with — mov—˜le su˜str—te holder —nd g—seous v—lvingF sn this m—nner it m—y ˜e —lso equipped with —n inEsitu viih system for the dire™t o˜serv—tion of surf—™e —tom ™on(gur—tions —nd other systems su™h —s ˆ€ƒD …€ƒD —nd eiƒ for surf—™e —n—lysisF e l—ter—l )ow system m—y —lso ˜e employed for su™™essful evi depositionF „his uses —n inert g—s )ow for sever—l fun™tionsY it tr—nsports the re—™t—ntsD it prevents pump oil from entering the re—™tion zoneD it v—lves the sour™es —nd it purges the deposition site ˜etween pulsesF snert g—s v—lving h—s m—ny —dv—nt—ges —s it ™—n ˜e used —t ultr— high temper—tures where me™h—ni™—l v—lves m—y f—il —nd it does not ™orrode —s me™h—ni™—l v—lves would in the presen™e of h—lidesF „his method is ˜—sed on the f—™t th—t —s the inert g—s is )owing through the feeding tu˜e from the sour™e to the re—™tion ™h—m˜erD it ˜lo™ks the )ow of the sour™esF elthough in this system the front end of the su˜str—te re™eives — higher )ux density th—n the downEstre—m endD — uniform growth r—te o™™urs —s long —s the s—tur—tion l—yer of the monoform—tion predomin—tesF „his l—ter—l )ow system e'e™tively utilizes the s—tur—tion me™h—nism of — monol—yer form—tion o˜t—ined in eviF hepending on the properties of the pre™ursors usedD —nd on the growth temper—tureD v—rious growth systems m—y ˜e used for eviF 5. Figure 5.IUP CHAPTER 5.. 1681. Lett. Tischler and S. Bedair. A. Phys. 1986. THIN FILM GROWTH A typical moving substrate ALD growth system used to grow GaAs lms.2. Appl. 48.

5 Advantages of ALD etomi™ l—yer deposition provides —n e—sy w—y to produ™e uniformD ™ryst—llineD high qu—lity thin (lmsF st h—s prim—rily ˜een dire™ted tow—rds epit—xi—l growth of sssE† @IQEISA —nd ssE† @IPEITA ™ompoundsD espe™i—lly to l—yered stru™tures su™h —s superl—tti™es —nd super—lloysF „his —ppli™—tion is due to the gre—test —dv—nt—ge of this methodD it is ™ontroll—˜le to —n —™™ur—™y of — single —tomi™ l—yer ˜e™—use of s—tur—ted surf—™e re—™tionsF xot only th—tD ˜ut it produ™es epit—xi—l l—yers th—t —re uniform over l—rge —re—sD even on nonEpl—n—r surf—™esD —t temper—tures lower th—n those used in ™onvention—l epit—xi—l growthF enother —dv—nt—ge to this method th—t m—y ˜e most import—nt for future —ppli™—tionsD is the vers—tility —sso™i—ted with the pro™essF st is possi˜le to grow di'erent thin (lms ˜y ™hoosing suit—˜le st—rting m—teri—ls —mong the thous—nds of —v—il—˜le ™hemi™—l ™ompoundsF €rovided th—t the thermodyn—mi™s —re f—vor—˜leD the —djustment of the re—™tion ™onditions is — rel—tively e—sy t—sk ˜e™—use the pro™ess is insensitive to sm—ll ™h—nges in temper—ture —nd pressure due to its rel—tively l—rge pro™essing windowF „here —re —lso no limits in prin™iple to the size —nd sh—pe of the su˜str—tesF yne —dv—nt—ge th—t is result—nt from the selfElimiting growth me™h—nism is th—t the (n—l thi™kness of the (lm is dependent only upon the num˜er of deposition ™y™les —nd the l—tti™e ™onst—nt of the m—teri—lD —nd ™—n ˜e reprodu™ed —nd ™ontrolledF „he thi™kness is independent of the p—rti—l pressures of the pre™ursors —nd growth temper—tureF …nder ide—l ™onditionsD the uniformity —nd the reprodu™i˜ility of the (lms —re ex™ellentF evi —lso h—s the potenti—l to grow very —˜rupt heterostru™tures —nd very thin l—yers —nd these properties —re in dem—nd for some —ppli™—tions su™h —s superl—tti™es —nd qu—ntum wellsF 5.2. RevFD IWVWD 89D IQIUF wF ‚it—l— —nd wF veskelD NanotechnologyD IWWWD 10D IWF wF €ess—D €F ruttunenD —nd wF eF rerm—nD J.6 Bibliography • • • • • hF gF fr—dleyD Chem. LettFD IWVTD 48D ITVIF . Appl. PhysFD IWVQD 54D THRUF „F ƒuntol— —nd tF entsonD Method for producing compound thin lmsD …FƒF €—tent RDHSVDRQH @IWUUAF wF eF „is™hler —nd ƒF wF fed—irD Appl.2.IUQ st must ˜e — g—s or must vol—tilize —t — re—son—˜le temper—ture produ™ing su0™ient v—por pressureF „he v—por pressure must ˜e high enough to (ll the su˜str—te —re— so th—t the monol—yer ™hemisorption ™—n o™™ur in — re—son—˜le length of timeF xote th—t prolonged exposure to the su˜str—te ™—n ™—use the pre™ursor to ™ondense on the surf—™e hindering the growthF ghemi™—l inter—™tion ˜etween the two pre™ursors prior to ™hemisorption on the surf—™e is —lso undesiredF „his m—y ˜e over™ome ˜y purging the surf—™e with —n inert g—s or hydrogen ˜etween the pulsesF „he inert g—s not only sep—r—tes the re—™t—nt pulses ˜ut —lso ™le—ns out the re—™tion —re— ˜y removing ex™ess mole™ulesF elsoD the sour™e mole™ules should not de™ompose on the su˜str—te inste—d of ™hemisor˜ingF „he de™omposition of the pre™ursor le—ds to un™ontrolled growth of the (lm —nd this defe—ts the purpose of evh —s it no longer is selfE™ontrolledD l—yerE˜yEl—yer growth —nd the qu—lity of the (lm plummetsF sn gener—lD temper—ture rem—ins the most import—nt p—r—meter in the evh pro™essF „here exists — proE ™essing window for ide—l growth of monol—yersF „he temper—ture ˜eh—vior of the r—te of growth in monol—yer units per ™y™le gives — (rst indi™—tion of the limiting me™h—nisms of —n evh pro™essF sf the temper—ture f—lls too lowD the re—™t—nt m—y ™ondense or the energy of —™tiv—tion required for the surf—™e re—™tion m—y not ˜e —tt—inedF sf the temper—ture is too highD then the pre™ursor m—y de™ompose or the monol—yer m—y ev—por—te resulting in poor evh growthF sn the —ppropri—te temper—ture windowD full monol—yer s—tur—tion o™™urs me—ning th—t —ll ˜onding sites —re o™™upied —nd — growth r—te of one l—tti™e unit per ™y™le is o˜servedF sf the s—tur—tion density is ˜elow oneD sever—l f—™tors m—y ™ontri˜ute to thisF „hese in™lude —n oversized re—™t—nt mole™uleD surf—™e re™onstru™tionD or the ˜ond strength of —n —dsor˜ed surf—™e —tom is higher when the neigh˜oring sites —re uno™™upiedF „hen the lower s—tur—tion density m—y ˜e thermodyn—mi™—lly f—voredF sf the s—tur—tion density is —˜ove oneD then the unde™omposed pre™ursor mole™ules form the monol—yerF qener—llyD ide—l growth o™™urs when the temper—ture is set where the s—tur—tion density is oneF 5. Phys.

3. . THIN FILM GROWTH 3 5.2/>.2 Kinetics of CVD e norm—l g†h pro™ess involves ™omplex )ow dyn—mi™s sin™e g—ses —re )owing into the re—™torD re—™tingD —nd then ˜yEprodu™ts —re exh—usted out of the re—™torF „he sequen™e of events during — g†h re—™tion —re shown in pigure SFU —nd —s followsX IA €re™ursor g—ses input into the ™h—m˜er ˜y pressurized g—s linesF PA w—ss tr—nsport of pre™ursors from the m—in )ow region to the su˜str—te through the ˜ound—ry l—yer @pigure SFU—AY QA edsorption of pre™ursors on the su˜str—te @norm—lly he—tedA @pigure SFU˜AF RA ghemi™—l re—™tion on the surf—™e @pigure SFU™A SA etoms di'use on the surf—™e to growth sitesF TA hesorption of ˜yEprodu™ts of the re—™tions @pigure SFUdAF UA w—ss tr—nsport of ˜yEprodu™ts to the m—in )ow region @pigure SFUeAF 3 This content is available online at <http://cnx.1 Introduction ghemi™—l v—por deposition @g†hA is — deposition pro™ess where ™hemi™—l pre™ursors —re tr—nsported in the v—por ph—se to de™ompose on — he—ted su˜str—te to form — (lmF „he (lms m—y ˜e epit—xi—lD poly™ryst—lline or —morphous depending on the m—teri—ls —nd re—™tor ™onditionsF g†h h—s ˜e™ome the m—jor method of (lm deposition for the semi™ondu™tor industry due to its high throughputD high purityD —nd low ™ost of oper—tionF g†h is —lso ™ommonly used in optoele™troni™s —ppli™—tionsD opti™—l ™o—tingsD —nd ™o—tings of we—r resist—nt p—rtsF g†h h—s m—ny —dv—nt—ges over physi™—l v—por deposition @€†hA pro™esses su™h —s mole™ul—r ˜e—m ev—por—tion —nd sputteringF pirstlyD the pressures used in g†h —llow ™o—ting of three dimension—l stru™tures with l—rge —spe™t r—tiosF ƒin™e ev—por—tion pro™esses —re very dire™tion—lD €†h pro™esses —re typi™—lly line of sight depositions th—t m—y not give ™omplete ™over—ge due to sh—dowing from t—ll stru™turesF ƒe™ondlyD high pre™ursor )ow r—tes in g†h give deposition r—tes sever—l times higher th—n €†hF elsoD the g†h re—™tor is rel—tively simple —nd ™—n ˜e s™—led to (t sever—l su˜str—tesF …ltr—Ehigh v—™uum is not needed for g†h —nd ™h—nges or —dditions of pre™ursors is —n e—sy t—skF purthermoreD v—rying ev—por—tion r—tes m—ke stoi™hiometry h—rd to ™ontrol in physi™—l depositionF ‡hile for g†h stoi™hiometry is more e—sily ™ontrolled ˜y monitoring )ow r—tes of pre™ursorsF yther —dv—nt—ges of g†h in™lude growth of high purity (lms —nd the —˜ility to f—˜ri™—te —˜rupt jun™tionsF „here —reD howeverD some dis—dv—nt—ges of g†h th—t m—ke €†h more —ttr—™tive for some —ppli™—tionsF righ deposition temper—tures for some g†h pro™esses @often gre—ter th—n THH ◦ gA —re often unsuit—˜le for stru™tures —lre—dy f—˜ri™—ted on su˜str—tesF elthough with some m—teri—lsD use of pl—sm—Eenh—n™ed g†h or met—lEorg—ni™ pre™ursors m—y redu™e deposition temper—turesF enother dis—dv—nt—ge is th—t g†h pre™ursors —re often h—z—rdous or toxi™ —nd the ˜yEprodu™ts of these pre™ursors m—y —lso ˜e toxi™F „herefore extr— steps h—ve to ˜e t—ken in the h—ndling of the pre™ursors —nd in the tre—tment of the re—™tor exh—ustF elsoD m—ny pre™ursors for g†hD espe™i—lly the met—lEorg—ni™sD —re rel—tively expensiveF pin—llyD the g†h pro™ess ™ont—ins — l—rge num˜er of p—r—meters th—t must ˜e —™™ur—tely —nd reprodu™i˜ly optimized to produ™e good (lmsF Chemical Vapor Deposition note: Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of ƒ™ott ƒtokesF „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of 5.IUR CHAPTER 5.

B. Stringfellow. Pierson. (b) adsorption of reactants on substrate.7: 5. Noyes Publications. and (e) diusion out of by-products through boundary layer. O. Handbook of Chemical Vapor Deposition. (c) chemical reaction takes place. Adapted from H.2.IUS Sequence of events during CVD: (a) diusion of reactants through boundary layer. (d) desorption of adsorbed species. New York (1994). . .3. Figure 5.8: Organometallic Vapor-Phase Epitaxy: Theory and Practice Development of boundary layer in a horizontal reactor. Park Ridge (1992). Adapted from G.1 The boundary layer q—s )ow in — g†h re—™tor is gener—lly l—min—rD —lthough in some ™—ses he—ting of the ™h—m˜er w—lls will ™re—te ™onve™tion ™urrentsF „he ™omplete pro˜lem of g—s )ow through the system is too ™omplex to ˜e des™ri˜ed hereY howeverD —ssuming we h—ve l—min—r )ow @often — s—fe —ssumptionA the g—s velo™ity —t the ™h—m˜er w—lls will ˜e zeroF fetween the w—ll @zero velo™ityA —nd the ˜ulk g—s velo™ity there is — ˜ound—ry l—yerF „he ˜ound—ry l—yer thi™kness in™re—ses with lowered g—s velo™ity —nd the dist—n™e from the tu˜e inlet @pigure SFVAF ‚e—™t—nt g—ses )owing in the ˜ulk must di'use through the ˜ound—ry l—yer to re—™h the su˜str—te surf—™eF yftenD the sus™eptor is tilted to p—rti—lly ™ompens—te for the in™re—sing ˜ound—ryEl—yer thi™kness —nd ™on™entr—tion pro(leF Figure 5. Academic Press.

Adapted from H. Noyes Publications. Handbook of Chem- e deposition limited ˜y m—ss tr—nsport is ™ontrolled ˜y the di'usion of re—™t—nts through the ˜ound—ry l—yer —nd di'usion of ˜yEprodu™ts out of the ˜ound—ry l—yerF w—ss tr—nsport limits re—™tions when the temper—ture —nd pressure —re highF „hese ™onditions in™re—ses the thi™kness of the ˜ound—ry l—yer —nd m—ke it h—rder for g—ses to di'use through @pigure SFIHAF sn —dditionD de™omposition of the re—™t—nts is typi™—lly qui™ker sin™e the su˜str—te is —t — higher temper—tureF ‡hen m—ss tr—nsport limits the growthD either in™re—sing the g—s velo™ity or rot—ting the su˜str—te during growth will de™re—se the ˜ound—ry l—yer —nd in™re—se the growth r—teF . . Pierson. Park Ridge (1992).9: ical Vapor Deposition Surface reaction limited growth in CVD.2 Rate limiting steps CHAPTER 5. O. THIN FILM GROWTH huring g†h the growth r—te of the (lm is limited ˜y either surf—™e re—™tion kineti™sD m—ss tr—nsport @di'uE sionA of pre™ursors to the su˜str—teD or the feed r—te of the pre™ursorsF ƒurf—™e re—™tion ™ontrols the r—te when growth o™™urs —t low temper—tures @where the re—™tion o™™urs slowlyA —nd —lso domin—tes —t low pressures @where the ˜ound—ry l—yer is thin —nd re—™t—nts e—sily di'use to the surf—™eAD see pigure SFWF ƒin™e re—™t—nts e—sily di'use through the ˜ound—ry l—yerD the —mount of re—™t—nt —t the surf—™e is independent of re—™tor pressureF „hereforeD it is the re—™tions —nd motions of the pre™ursors —dsor˜ed on the surf—™e whi™h will determine the over—ll growth r—te of the (lmF e sign of surf—™e re—™tion limited growth would ˜e dependen™e of the growth r—te on su˜str—te orient—tionD sin™e the orient—tion would ™ert—inly not —'e™t the thermodyn—mi™s or m—ss tr—nsport of the systemF Figure 5.2.3.IUT 5.

L. Handbook of peed r—te limits the deposition when ne—rly —ll the re—™t—nt is ™onsumed in the ™h—m˜erF „he feed r—te is more import—nt for — hot w—ll re—™tor sin™e the he—ted w—lls will de™ompose — l—rge —mount of the pre™ursorF gold w—ll re—™tors tend to h—ve higher deposition r—tes sin™e the re—™t—nts —re not depleted ˜y the w—llsF e plot of growth r—te versus temper—tureD known —s —n errhenius plotD ™—n ˜e used to determine the r—te limiting step of — re—™tion @pigure SFIIAF w—ss tr—nsport limits re—™tions —t high temper—tures su™h th—t growth r—te in™re—ses with p—rti—l pressures of re—™t—ntsD ˜ut is ™onst—nt with temper—tureF ƒurf—™e re—™tion kineti™s domin—tes —t low temper—tures where the growth r—te in™re—ses with temper—tureD ˜ut is ™onst—nt with pressures of re—™t—ntsF peed r—te limited re—™tions —re independent of temper—tureD sin™e it is the r—te of g—s delivery th—t is limiting the re—™tionF „he errhenius plot will show where the tr—nsition ˜etween the m—ss tr—nsport limited —nd the surf—™e kineti™s limited growth o™™urs in the temper—ture regimeF Figure 5. Vossen and W. Academic Press. J. O. Adapted from H.IUU Figure 5. Thin sn™re—ses in re—™t—nt ™on™entr—tions will to — point in™re—se the deposition r—teF roweverD —t very high re—™t—nt ™on™entr—tionsD g—s ph—se nu™le—tion will o™™ur —nd the growth r—te will drop @pigure SFIPAF ƒlow deposition in — g†h re—™tor ™—n often ˜e —ttri˜uted to either g—s ph—se nu™le—tionD pre™ursor depletion due to hot w—llsD thi™k ˜ound—ry l—yer form—tionD low temper—tureD or low pre™ursor v—por pressureF . in . Kern. Park Ridge (1992). . Noyes Publications.10: Chemical Vapor Deposition Mass transport limited growth in CVD. Eden. New York (1991). Adapted from J.11: Film Processes II Dependence of CVD deposition rate on temperature. G. Pierson. Eds.

12: Demonstration of deposition rate on reactant concentration for CVD deposition.3 CVD systems 5. J. New York (1991). Academic Press. Adapted from J. Kern. Eden.13: Schematic representation of a bubbler for liquid precursors. 5. Eds. in Thin Film Processes II.3. Vossen and W. G. L.3.IUV CHAPTER 5.1 Precursor delivery plow of re—™t—nts into the re—™tor must ˜e ™losely monitored to ™ontrol stoi™hiometry —nd growth r—teF €re™ursor delivery is very import—nt sin™e in m—ny ™—ses the )ow r—te ™—n limit the depositionF por low v—por pressure solidsD — ™—rrier g—s is p—ssed over or through — ˜ed of the he—ted solid to tr—nsport the v—por into the re—™torF q—s )ow lines —re usu—lly he—ted to redu™e ™ondens—tion of the v—por in the )ow linesF sn the ™—se of g—s pre™ursorsD m—ss )owmeters e—sily g—uge —nd ™ontrol the )ow r—tesF viquid pre™ursors —re norm—lly he—ted in — ˜u˜˜ler to —™hieve — desired v—por pressure @pigure SFIQAF Figure 5. THIN FILM GROWTH Figure 5. en inert g—s su™h —s hydrogen is ˜u˜˜led through the liquid —nd ˜y ™—l™ul—ting the v—por pressure of the re—™t—nt —nd monitoring the )ow r—te of the hydrogenD the )ow r—te of the pre™ursor is ™ontrolled ˜y using @SFIAD where MO is the )ow r—te of the met—lEorg—ni™ pre™ursorD H2 is the )ow r—te of hydrogen through the ˜u˜˜lerD €MO is the v—por pressure of the met—lEorg—ni™ —t the ˜u˜˜ler temper—tureD —nd €B is .3.

2 Thermal CVD reactors sn therm—l g†h temper—tures —s high —s PHHH ◦ g m—y ˜e needed to therm—lly de™ompose the pre™ursorsF re—ting is norm—lly —™™omplished ˜y use of resistive he—tingD r—dio frequen™y @rfA indu™tion he—tingD or r—di—nt he—tingF „here —re two ˜—si™ types of re—™tors for therm—l g†hX the hot w—ll re—™tor —nd the ™old w—ll re—™torF e hot w—ll re—™tor is —n isotherm—l furn—™e into whi™h the su˜str—tes —re pl—™edF rot w—ll re—™tors —re typi™—lly very l—rge —nd depositions —re done on sever—l su˜str—tes —t on™eF ƒin™e the whole ™h—m˜er is he—tedD pre™ise temper—ture ™ontrol ™—n ˜e —™hieved with ™orre™t furn—™e designF e dis—dv—nt—ge of the hot w—ll ™on(gur—tion is th—t deposition o™™urs on the w—lls of the ™h—m˜er —s well —s on the su˜str—teF es — ™onsequen™eD hot w—ll re—™tors must ˜e frequently ™le—ned to redu™e )—king of p—rti™les from the w—lls whi™h m—y ™ont—min—te the su˜str—tesF purthermoreD re—™tions in the he—ted g—s —nd —t the w—lls deplete the re—™t—nts —nd ™—n result in feed r—te limited growthF pigure SFIS shows — typi™—l low pressure hot w—ll g†h re—™torF .IUW the pressure of the ˜u˜˜lerF @SFIA enother method of introdu™ing liquid pre™ursors involves )—sh v—poriz—tion where the liquid is p—ssed into — )—sk he—ted —˜ove the ˜oiling point of the liquidF „he g—s v—por is then p—ssed through he—ted lines to the g†h ™h—m˜erF yftenD — ™—rrier g—s is —dded to provide — (xed )ow r—te into the re—™torF „his method of pre™ursor introdu™tion is useful when the pre™ursor will de™ompose if he—ted over timeF e simil—r te™hnique ™—lled spr—y pyrolysis introdu™es the pre™ursors in the form of —erosol dropletsF „he droplets ev—por—te in the ™h—m˜er from the he—ted g—s —˜ove the su˜str—te or he—ted ™h—m˜er w—lls @pigure SFIRAF „hen the re—™tion pro™eeds —s — norm—l g†h pro™essF Schematic representation of a typical aerosol delivery system for CVD precursors. The Chemistry of Metal CVD.14: 5.3. Adapted from T. Figure 5. Kodas and M. T. VCH. New York (1994).3. Hamton-Smith. J.

Adapted from H.3. Pierson.3 Plasma-enhanced CVD €l—sm—s —re gener—ted for — v—riety of thin (lm pro™esses in™luding sputteringD et™hingD —shingD —nd pl—sm—E enh—n™ed g†hF €l—sm—Eenh—n™ed g†h @€ig†hAD sometimes ™—lled pl—sm—E—ssisted @€eg†hAD h—s the —dv—nt—ge th—t pl—sm— —™tiv—ted re—™tions o™™ur —t mu™h lower temper—tures ™omp—red to those in therm—l g†hF por ex—mpleD the therm—l g†h of sili™on nitride o™™urs ˜etween UHH E WHH ◦ gD the equiv—lent €ig†h pro™ess is —™™omplished ˜etween PSH E QSH ◦ gF e pl—sm— is — p—rti—lly ionized g—s ™onsisting of ele™trons —nd ionsF „ypi™—l ioniz—tion fr—™tions of IH-5 to -1 IH —re en™ountered in pro™ess re—™torsF €l—sm—s —re ele™tri™—lly ™ondu™tive with the prim—ry ™h—rge ™—rriers ˜eing the ele™tronsF „he light m—ss of the ele™tron —llows it to respond mu™h more qui™kly to ™h—nges in the (eld th—n the he—vier ionsF wost pl—sm—s used for €ig†h —re gener—ted using — rf ele™tri™ (eldF sn the high frequen™y ele™tri™ (eldD the light ele™trons —re qui™kly —™™eler—ted ˜y the (eld ˜ut do not in™re—se the temper—ture of the pl—sm— ˜e™—use of their low m—ssF „he he—vy ions ™—nnot respond to the qui™k ™h—nges . sn — ™old w—ll re—™tor only the su˜str—te is he—tedD usu—lly ˜y indu™tion or r—di—nt he—tingF ƒin™e most g†h re—™tions —re endothermi™D deposition is preferenti—lly on the —re— of highest temper—tureF es — resultD deposition is only on the su˜str—te —nd the ™ooler re—™tor w—lls st—y ™le—nF gold w—ll g†h h—s two m—in —dv—nt—ges over the hot w—ll ™on(gur—tionF pirstD p—rti™ul—te ™ont—min—tion is redu™ed sin™e there —re no deposits formed on the w—lls of the re—™torF ƒe™ondD sin™e de™omposition only o™™urs on the su˜str—te there is no depletion of sour™e g—ses due to re—™tion on the w—llsF roweverD hot w—ll re—™tors tend to h—ve higher throughput sin™e the designs more e—sily —™™ommod—te multiple w—fer ™on(gur—tionsF „he (n—l issue in design of — therm—l g†h re—™tor is the oper—ting pressureF „he pressure of the re—™tor h—s — l—rge e'e™t on the r—te limiting step of the depositionF etmospheri™ pressure re—™tors h—ve — l—rge ˜ound—ry l—yer @pigure SFIHA —nd nonEuniform di'usion of re—™t—nts through the ˜ound—ry l—yer often results in nonEuniform (lm ™ompositions —™ross the w—ferF gonverselyD low pressure re—™tors h—ve — ne—rly nonEexistent ˜ound—ry l—ter —nd re—™t—nts e—sily di'use to the su˜str—te @pigure SFWAF roweverD the di0™ulty in m—int—ining — uniform temper—ture pro(le —™ross the w—fer ™—n result in thi™kness nonEuniformities sin™e the deposition r—te in low pressure re—™tors is strongly temper—ture dependentF g—reful studies of the )ow dyn—mi™s —nd temper—ture pro(les of g†h re—™tors —re —lw—ys ™—rried out in order to —™hieve uniform m—teri—l depositionsF 5. Handbook of Chemical Vapor Deposition.15: Schematic of a typical low pressure hot wall CVD reactor used in coating silicon substrates.3. Park Ridge (1992). THIN FILM GROWTH Figure 5. Noyes Publications.IVH CHAPTER 5. O.

Adapted from M. . New York (1992). Film Deposition by Plasma e ˜—si™ €ig†h re—™tor is shown in pigure SFIUF „he w—fer ™hu™k —™ts —s the lower ele™trode —nd is norm—lly pl—™ed —t ground potenti—lF q—ses —re either introdu™ed r—di—lly —t the edges of the re—™tor —nd pumped out from the ™enterD or g—ses ™—n ˜e introdu™ed from the ™enter —nd pumped —t the edges —s shown in pigure SFIUF „he m—gneti™ drive —llows rot—tion of the w—fers during pro™essing to r—ndomize su˜str—te positionF ƒome newer re—™tors introdu™e the g—ses through holes drilled in the upper ele™trodeF „his method of g—s introdu™tion gives — more uniform pl—sm— distri˜utionF .IVI in dire™tion —nd therefore their temper—ture st—ys lowF ile™tron energies in the pl—sm— h—ve — w—xwelli—n distri˜ution in the HFI ! PH e† r—ngeF „hese energies —re su0™iently high to ex™ite mole™ules or ˜re—k ™hemi™—l ˜onds in ™ollisions ˜etween ele™trons —nd g—s mole™ulesF „he high energy ele™trons inel—sti™—lly ™ollide with g—s mole™ules resulting in ex™it—tion or ioniz—tionF „he re—™tive spe™ies gener—ted ˜y the ™ollisions do not h—ve the energy ˜—rriers to re—™tions th—t the p—rent pre™ursors doF „hereforeD the re—™tive ions —re —˜le to form (lms —t temper—tures mu™h lower th—n those required for therm—l g†hF „he gener—l re—™tion sequen™e for €ig†h is shown in pigure SFITF sn —ddition to the pro™esses th—t o™™ur in therm—l g†hD re—™tive spe™ies resulting from ele™tron disso™i—tion of p—rent mole™ules —lso di'use to the surf—™eF „he re—™tive spe™ies h—ve lower —™tiv—tion energies for ™hemi™—l re—™tions —nd usu—lly h—ve higher sti™king ™oe0™ients to the su˜str—teF „hereforeD the €ig†h re—™tion is domin—ted ˜y the re—™tive spe™ies on the surf—™e —nd not —ny of the the p—rent pre™ursor mole™ules th—t —lso di'use to the surf—™eF Figure 5. Springer-Verlag. Konuma.16: Techniques Reaction sequence in PECVD.

4 Photochemical CVD €hoto™hemi™—l g†h uses the energy of photons to initi—te the ™hemi™—l re—™tionsF €hotodisso™i—tion of the ™hemi™—l pre™ursor involves the —˜sorption of one or more photons resulting in the ˜re—king of — ™hemi™—l ˜ondF „he most ™ommon pre™ursors for photoE—ssisted deposition —re the hydridesD ™—r˜onylsD —nd the —lkylsF „he disso™i—tion of dimethylzin™ ˜y @SFPAD — photon ™re—tes — zin™ r—di™—l —nd — methyl r—di™—l @. . Noyes Publications. THIN FILM GROWTH Figure 5.IVP CHAPTER 5. €l—sm— g†h h—s numerous —dv—nt—ges over therm—l g†hF y˜viously the redu™ed deposition temper—ture is — ˜onus for the semi™ondu™tor industry whi™h must worry —˜out dop—nt di'usion —nd met—l inter™onne™ts melting —t the temper—tures required for therm—l g†hF elsoD the low pressures @˜etween HFI E IH „orrA required for sust—ining — pl—sm— result in surf—™e kineti™s ™ontrolling the re—™tion —nd therefore gre—ter (lm uniformityF e dis—dv—nt—ge of pl—sm— g†h is th—t it is often di0™ult to ™ontrol stoi™hiometry due to v—ri—tions in ˜ond strengths of v—rious pre™ursorsF por ex—mpleD €ig†h (lms of sili™on nitride tend to ˜e sili™on ri™h ˜e™—use of the rel—tive ˜ond strength of x2 rel—tive to the ƒiEr ˜ondF eddition—llyD some (lms m—y ˜e e—sily d—m—ged ˜y ion ˜om˜—rdment from the pl—sm—F 5.17: Handbook of Chemical Vapor Deposition Schematic representation of a radial ow PECVD reactor.3. Adapted from H. O.3. Park Ridge (1992). Pierson. gr3 A th—t will re—™t with hydrogen in the re—™tor to produ™e meth—neF @SFPA vike sever—l met—lEorg—ni™sD dimethylzin™ is disso™i—ted ˜y the —˜sorption of only one …† photonF roweverD some pre™ursors require —˜sorption of more th—n one photon to ™ompletely disso™i—teF „here —re two ˜—si™ ™on(gur—tions for photo™hemi™—l g†hF „he (rst method uses — l—ser prim—rily —s — lo™—lized he—t sour™eF „he se™ond method uses high energy photons to de™ompose the re—™t—nts on or ne—r the growth surf—™eF sn therm—l l—ser g†hD sometimes referred to —s l—ser pyrolysisD the l—ser is used to he—t — su˜str—te th—t —˜sor˜s the l—ser photonsF v—ser he—ting of su˜str—tes is — very lo™—lized pro™ess —nd deposition o™™urs .

J.18: Thin Film Processes II Parallel (a) and perpendicular (b) irradiation in laser CVD. New York (1991). Eden. Kern. Eds.IVQ sele™tively on the illumin—ted portions of the su˜str—tesF ix™ept for the method of he—tingD l—ser g†h is identi™—l to therm—l g†hF „he l—ser g†h method h—s the potenti—l to ˜e used for dire™t writing of fe—tures with rel—tively high resolutionF „he l—ter—l extent of (lm growth when the su˜str—te is illumin—ted ˜y — l—ser is determined not only ˜y the spot size of the l—serD ˜ut ˜y the therm—l ™ondu™tivity of the su˜str—teF e v—ri—tion of l—ser pyrolysis uses — l—ser to he—t the g—s mole™ules su™h th—t they —re fr—gmented ˜y therm—l pro™essesF €hoto™hemi™—l e'e™ts ™—n ˜e indu™ed ˜y — l—ser if the pre™ursor mole™ules —˜sor˜ —t the l—ser w—velengthF …† photons h—ve su0™ient energy to ˜re—k the ˜onds in the pre™ursor ™hemi™—lsF v—serE—ssisted g†h @veg†hA uses — l—serD usu—lly —n eximer l—serD to provide the high energy photons needed to ˜re—k the ˜onds in the pre™ursor mole™ulesF pigure SFIV shows two geometries for veg†hF por the perpendi™ul—r illumin—tion the photo™hemi™—l e'e™ts gener—lly o™™ur in the —dsor˜ed —dl—yer on the su˜str—teF €erpendi™ul—r irr—di—tion is often done using — …† l—mp inste—d of — l—ser so th—t unw—nted su˜str—te he—ting is not produ™ed ˜y the light sour™eF „he p—r—llel illumin—tion ™on(gur—tion h—s the ˜ene(t th—t re—™tion ˜yEprodu™ts —re produ™ed further from the growth surf—™e —nd h—ve less ™h—n™e of ˜eing in™orpor—ted into the growing (lmF „he m—in ˜ene(t of veg†h is th—t ne—rly no he—t is required for deposition of high qu—lity (lmsF Figure 5. . Adapted from J. in . L. G. Vossen and W. Academic Press.

4. THIN FILM GROWTH en —ppli™—tion of l—ser photolysis is photonu™le—tionF €hotonu™le—tion is the pro™ess ˜y whi™h — ™hemisor˜ed —dl—yer of met—l pre™ursors is photolyzed ˜y the l—ser to ™re—te — nu™le—tion site for further growthF €hotonu™le—tion is useful in promoting growth on su˜str—tes th—t h—ve sm—ll sti™king ™oe0™ients for g—s ph—se met—l —tomsF fy ˜eginning the nu™le—tion pro™ess with photonu™le—tion the n—tur—l ˜—rrier to surf—™e nu™le—tion on the su˜str—te is over™omeF Liquid Phase Deposition 5.3. .4 Bibliography • tF qF idenD in Thin Film Processes IID idsF tF vF †ossen —nd ‡F uernD e™—demi™ €ressD xew ‰ork @IWWIAF • „F „F uod—s —nd wF tF r—mtonEƒmithD The Chemistry of Metal CVDD †grD xew ‰ork @IWWRAF • wF uonum—D Film Deposition by Plasma TechniquesD ƒpringerE†erl—gD xew ‰ork @IWWPAF • rF yF €iersonD Handbook of Chemical Vapor DepositionD xoyes €u˜li™—tionsD €—rk ‚idge @IWWPAF • ‚F ‚eif —nd ‡F uernD in Thin Film Processes IID idsF tF vF †ossen —nd ‡F uernD e™—demi™ €ressD xew ‰ork @IWWIAF • qF fF ƒtringfellowD Organometallic Vapor-Phase Epitaxy: Theory and PracticeD e™—demi™ €ressD xew ‰ork @IWWRAF 5.IVR CHAPTER 5.1 Introduction 4 ƒili™on dioxide @sili™—D ƒiy2 A h—s ˜een the most rese—r™hed ™hemi™—l ™ompound —p—rt from w—terF ƒili™— h—s ˜een used throughout historyD for ex—mpleD )intD whi™h when sh—rpened formed one of hum—nities (rst toolsF gryst—lline sili™—D or s—ndD w—s melted into gl—ss —s e—rly —s SHHH fFgFD ˜irthing — te™hnology th—t h—s g—ined sophisti™—tion in modern timesF ƒili™on is the se™ond most plentiful element in the i—rth9s ™rustD the most plentiful ˜eing oxygenF st is thus surprising th—t it w—s not until IVHH th—t sili™— w—s n—med — ™ompound ˜y ƒir rumphry h—vyF reD howeverD f—iled to isol—te its ™omponents vi— ele™trolysisD —nd it is tons t—™o˜ ferzelius who is thus ™redited with dis™overing sili™— in IVPRF re he—ted pot—ssium )uorosili™—te ¨ with pot—ssium met—l —ndD —fter purifying the produ™t of this re—™tion with w—terD produ™ed —morphous sili™— powderF „he most ™ommon forms of sili™— employed in industry in™lude αEqu—rtzD vitreous sili™—D sili™— gelD fumed sili™— —nd di—tom—™eous e—rthF ƒyntheti™ qu—rtz is hydrotherm—lly grown from — seed ™ryst—lD with —queous x—yr —nd vitreous ƒiy2 D —t RHH ◦ g —nd IFU k˜—rF fe™—use it is — piezoele™tri™ m—teri—lD it is used in ™ryst—l os™ill—torsD tr—nsdu™ersD pi™kups —nd (lters for frequen™y ™ontrol —nd modul—tionF †itreous sili™— is super ™ooled liquid sili™— used in l—˜or—tory gl—ssw—reD prote™tive tu˜ing she—ths —nd v—por grown (lmsF ƒili™— gel is formed from the re—™tion of —queous sodium sili™—te with —™idD —fter whi™h it is w—shed —nd dehydr—tedF ƒili™— gel is —n ex™eption—lly porous m—teri—l with numerous —ppli™—tions in™luding use —s — dessi™—ntD ™hrom—togr—phi™ supportD ™—t—lyst su˜str—te —nd insul—torF €yrogeni™ or fumed sili™— is produ™ed ˜y the high temper—ture hydrolysisD in —n oxyhydrogen )—meD of ƒigl4 F sts —ppli™—tions in™lude use —s — thi™kening —gent —nd reinfor™ing (ller in polymersF hi—tom—™eous e—rthD the e™toEskeletons of tiny uni™ellul—r m—rine —lg—e ™—lled di—tomsD is mined from v—st deposits in iurope —nd xorth emeri™—F sts prim—ry use is in (ltr—tionF eddition—l —ppli™—tions in™lude use —s —n —˜r—siveD insul—torD (ller —nd — lightweight —ggreg—teF wethods of ™olloid—l growth —nd thin (lm deposition of —morphous sili™— h—ve ˜een investig—ted sin™e IWPSF „he two most ™ommon —nd wellEinvestig—ted methods of forming ƒiy2 in — sol or —s — (lm or ™o—ting —re ™ondens—tion of —lkoxysil—nes @known —s the ƒto˜er methodA —nd hydrolysis of met—l —lkoxides @the sler or dense sili™— ‘hƒ“ pro™essAF 4 This content is available online at <http://cnx.1/>.

2 Liquid phase deposition (LPD) v€h is — method for the nonEele™tro™hemi™—l produ™tion of poly™ryst—lline ™er—mi™ (lms —t low temper—E turesF v€hD —long with other —queous solution methods ‘™hemi™—l ˜—th deposition @gfhAD su™™essive ion l—yer —dsorption —nd re—™tion @ƒsve‚A —nd ele™troless deposition @ihA with ™—t—lyst“ h—s developed —s — potenti—l su˜stitute for v—porEph—se —nd ™hemi™—lEpre™ursor systemsF equeous solution methods —re not dependent on v—™uum systems or glove ˜oxesD —nd the use of e—sily —™quired re—gents redu™es reli—n™e on exE pensive or sensitive org—nomet—lli™ pre™ursorsF „husD v€h holds potenti—l for redu™ed produ™tion ™osts —nd environment—l imp—™tF pilms m—y ˜e deposited on su˜str—tes th—t might not ˜e ™hemi™—lly or me™h—ni™—lly st—˜le —t higher temper—turesF sn —dditionD the use of liquid —s — deposition medium —llows ™o—ting of nonE pl—n—r su˜str—tesD exp—nding the r—nge of su˜str—tes th—t —re ™—p—˜le of ˜eing ™o—tedF equeous deposition te™hniques h—ve not re—™hed the level of m—tur—tion th—t v—porEph—se te™hniques h—ve in respe™t to — high level of ™ontrol over ™ompositionD mi™rostru™ture —nd growth r—tes of the resulting (lmsD ˜ut their prospe™t m—kes them —ttr—™tive for rese—r™hF v€h gener—lly refers to the form—tion of oxide thin (lmsD the most ™ommon ˜eing ƒiy2 D from —n —queous solution of — met—lE)uoro ™omplex ‘wpn “m-n D whi™h is slowly hydrolyzed using w—terD ˜ori™ —™id or —luminum met—lF eddition of w—ter drives pre™ipit—tion of the oxideF fori™ —™id —nd —luminum work —s )uoride s™—vengersD r—pidly we—kening the )uoro ™omplex —nd pre™ipit—ting the oxideF „hese re—™t—nts —re —dded either drop wise or outrightD ˜oth methods —llowing for high ™ontrol of the hydrolysis re—™tion —nd of the solution9s supers—tur—tionF pilm form—tion is —™™omplished from highly —™idi™ solutionsD in ™ontr—st to the ˜—si™ or we—kly —™idi™ solutions used in ™hemi™—l ˜—th depositionF e generi™ des™ription of the v€h re—™tion is shown in @SFQAD where m is the ™h—rge on the met—l ™—tionF sf the ™on™entr—tion of w—ter is in™re—sed or the ™on™entr—tion of hydro)uori™ —™id @rpA is de™re—sedD the equili˜rium will ˜e shifted tow—rd the oxideF …se of ˜ori™ —™id or —luminum met—l will —™™omplish the l—tterD see @SFRA —nd @SFSAF „he most popul—r of these methods for —™™omplishing oxide form—tion h—s ˜een through the —ddition of ˜ori™ —™idF @SFQA @SFRA @SFSA „he (rst p—tent using liquid ph—se deposition @v€hA of sili™on dioxide vi— )uorosili™i™ —™id solutions @r2 ƒip6 A w—s gr—nted to the ‚—dio gorpor—tion of emeri™— @‚geA in IWSHF ‚ge used v€h —s — method for ™o—ting —ntiEre)e™tive (lms on gl—ssD ˜ut the p—tent promised further —ppli™—tionsF ƒin™e this initi—l p—tent there h—ve ˜een m—ny further p—tents —nd p—pers utilizing this methodD in v—ri—˜le formsD to ™o—t su˜str—tesD usu—lly sili™onD with sili™on dioxideF „he impetus ˜ehind this work is to ™re—te —n —ltern—tive to the growth of insul—tor ™o—tings ˜y therm—l oxid—tion or ™hemi™—l v—por deposition @g†hA for pl—n—r sili™on ™hip te™hnologyF „herm—l oxid—tion —nd g†h —re performed —t elev—ted temper—turesD requiring — higher output of energy —nd more ™ompli™—ted instrument—tion th—n th—t of v€hF „he most simple —nd eleg—nt of the v€h methods uses only w—ter to ™—t—lyze sili™— thin (lm growth on sili™on from — solution of )uorosili™i™ —™id supers—tur—ted with sili™on dioxideD @SFTAF @SFTA „he —mount of w—ter re—™ted with the supers—tur—ted )uorosili™i™ —™id solution ™ontrols ˜oth the growth r—te —nd in™orpor—tion of )uorine into the resulting sili™— m—trixF foth growth r—te —nd )uorine ™ontent in™re—se with in™re—sed —ddition of w—terF …ltim—tely this dilution —'e™ts the opti™—l properties of the resulting sili™— (lmY —n in™re—sed —mount of )uorine de™re—ses its diele™tri™ ™onst—nt @—nd thus its refr—™tive indexAF .4.IVS 5.

THIN FILM GROWTH „o ensure — uniform (lm growth with v€hD the prep—r—tion of the surf—™e to ˜e ™o—ted is of utmost import—n™eF ƒuit—˜le tre—tments m—y involve the form—tion of surf—™e hydroxidesD the preEdeposition or selfE —ssem˜ly of —n —ppropri—te seed l—yerF „he most e0™ient ™over—ge is seen with sili™on surf—™es fun™tion—lized with hydroxy @EyrA groups prior to immersion in the growth solutionF „his ™—n ˜e —™hieved through —ppropri—te et™hing of the sili™on surf—™eF st is proposed th—t the sil—nol @ƒiEyrA groups —™t to seed the growth of the sili™— (lm through ™ondens—tion re—™tions with the sili™i™ —™id formed in the growth solutionF vee —nd ™oEworkers —nd romm— sep—r—tely propose th—t intermedi—teD hydrolyzed spe™iesD ƒipn @yrA4-n @n < RAD —re formed ˜y the re—™tion shown in @SFUAF e™™ording to veeD these spe™ies then re—™t with the su˜str—te surf—™e to form — (lmF romm— proposes th—t )uorineE™ont—ining silox—nes —re su˜sequently formedD whi™h —dsor˜ onto the surf—™e where ™ondens—tion —nd ˜onding o™™urs ˜etween the oligomers —nd surf—™e hydroxyl groupsF „he former me™h—nism implies — mole™ul—r growth me™h—nismD where—s the l—tter implies homogeneous nu™le—tion with su˜sequent depositionF @SFUA sn ™on™entr—ted )uorosili™i™ —™id solutions sili™— ™—n ˜e dissolved to well ˜eyond its solu˜ilityD forming )uorosili™on ™omplexes su™h —s ‘ƒip6 Fƒip4 “ form tetr—)uorosili™—te @ƒip4 A —nd w—terD @SFWAF rydrolysis of the ƒip4 will then yield the hex—)uorosili™—te —nionD protons —nd sili™i™ —™idD @SFIHAF @SFVA @SFWA @SFIHA ƒili™i™ —™id is —dsor˜ed onto the surf—™e of the su˜str—te th—t h—s ˜een introdu™ed into the growth solutionF wole™ul—r growth of sili™— on the su˜str—te surf—™e is initi—lized in —n —™id ™—t—lyzed dehydr—tion ˜etween the sili™i™ —™id —nd the sil—nol groups on the su˜str—te surf—™eF ƒiEyEƒi ˜onds —re formedD resulting in —n initi—l sili™— ™o—ting of the surf—™eF pollowing re—™tions ˜etween the initi—l sili™— ™o—ting —nd the monosili™i™ —™id in solution result in further sili™— deposition —nd growthF fe™—use of the presen™e of rp in the solutionD the surf—™e —nd growing sili™— m—trix is su˜je™t to —tt—™k —™™ording to the re—™tion in @SFIIAF „his expl—ins the in™orpor—tion of — qu—ntity of )uorine into the sili™— (lmF eddition—llyD it reve—ls th—t — ™ert—in —mount of sili™— et™hing o™™urs —long with growthF fe™—use of the prev—len™e of the sili™i™ —™id in the solutionD howeverD deposition is predomin—ntF @SFIIA „his proposed me™h—nismD whi™h is more in depth th—n those proposed ˜y vee —nd romm—D elu™id—tes wh—t is experiment—lly provenF „he deposition r—te of the sili™— in™re—ses with —ddition of r2 y ˜e™—use the nu™leophili™ —tt—™k of the )uorosili™on ™omplex is then —ugmentedD in™re—sing the ™on™entr—tion of sili™i™ —™id in the growth solutionF „he r2 y —ddition in™re—ses the re—™tion r—te —nd thus the ™on™entr—tion of rp in the growth solutionD resulting in gre—ter in™orpor—tion of )uorine into the sili™— m—trix ˜e™—use of rp —tt—™k of the deposited (lmF eddition—llyD ‰eh9s me™h—nism supports — mole™ul—r growth modelD iFeFD heterogeneous growthD whi™h represents — ™onsensus of the ˜ody of rese—r™h performed thus f—rF sn — solution with dissolved ™er—mi™ pre™ursorsD nu™le—tion —nd growth will o™™ur either in solution @homogenous nu™le—tionA or on the surf—™es of introdu™ed solid ph—ses @heterogeneous nu™le—tionAF ƒu™™essful .D @SFVAF „he ˜ridged )uorosili™on ™omplex h—s ele™tron de(™ient sili™on ˜e™—use of the high ele™troneg—tivity of the ˜onded )uorinesD ™re—ting we—k ƒiEp ˜ondsF „hese ˜onds —re then prone to nu™leophili™ —tt—™k ˜y w—terF „he )uorine ion @p.D ƒip4 —nd rpF „he high —™idity of the solution then —llows protons to re—™t with ‘ƒip4 @yrA2 “2.IVT CHAPTER 5.A ™om˜ines with the proton in this re—™tion to form hydro)uori™ —™id @rpAF „he produ™t of this re—™tion ™—n then re—™t further with w—ter to yield ‘ƒip4 @yrA2 “2.

Liu. Science. A.2.1 Comparing LPD to sol-gel en —ltern—tive method to v€h for forming sili™— thin (lms is the solEgel methodF e sol is — ™olloid—l dispersion of p—rti™les in — liquidF e gel is — m—teri—l th—t ™ont—ins — ™ontinuous solid m—trix en™losing — ™ontinuous liquid ph—seF „he liquid inhi˜its the solid from ™oll—psing —nd the solid impedes rele—se of the liquidF e form—l de(nition of solEgel pro™essing is the growth of ™olloid—l p—rti™les —nd their linking together to form . Figure 5. J. Campbell. J. P.4.19: ƒili™— ™—n ˜e dissolved in )uorosili™i™ —™id to well —˜ove its solu˜ility in w—terD whi™h is —pproxim—tely PPH ppm @mgGvAF hepending on the ™on™entr—tion of the )uorosili™i™ —™id solutionD it ™—n ™ont—in up to PH7 more sili™— th—n is implied ˜y the formul— r2 ƒip6 F efter s—tur—tion of the solution with ƒiy2 D the solv—ted spe™ies is — mixture of )uorosili™—tesD whi™h re—™ts —s expl—ined e—rlierF st must ˜e emph—sized th—t —ddition of w—ter in this re—™tion is not simply dilutionD ˜ut is the —ddition of — re—™t—ntD whi™h pl—™es the solution in — met—st—˜le st—te @the ˜lue —re— in pigure SFIWA in prep—r—tion for the introdu™tion of — suit—˜le surf—™e to seed the growth of sili™—F enother import—nt f—™tor in solution growth methods is interf—™i—l energyF ‡hen — su˜str—te with lower interf—™i—l energy th—n th—t of — growing homogeneous nu™leus is introdu™ed into — growth solutionD heterogeneous growth is f—voredF „husD — seeded growth me™h—nism ˜y de(nition introdu™es — su˜str—te of lower interf—™i—l energy into — supers—tur—ted solutionD f—™ilit—ting heterogeneous growthF vower interf—™i—l energies ™—n ˜e — produ™t of surf—™e modi(™—tionD —s well —s — property of the m—teri—ls9 n—tur—l st—teF 5. Song. McVay. Tarasevich. 264. 1994. A.IVU (lm form—tion relies on the promotion of heterogeneous nu™le—tionF ƒolu˜ility gener—lly depends on the solution pr —nd the ™on™entr—tion of the spe™ies in solutionF es the solution ™rosses over from — solv—ted st—te to — st—te of supers—tur—tionD (lm form—tion ™—n o™™urF st is vit—l to —ssure th—t the st—te of supers—tur—tion is one th—t promotes (lm growth —nd not homogeneous nu™le—tion —nd pre™ipit—tionF „his ™on™ept is illustr—ted in pigure SFIWF Idealized solubility diagram for lm forming species in water. Adapted from B. Fryxall. 48. J. Gra. Bunker. L. G. L. C. E. L. and G. C. Rieke. B. Virden. G. W.

3 Bibliography • fF gF funkerD €F gF ‚iekeD fF tF „—r—sevi™hD eF eF g—mp˜ellD qF iF pryx—llD qF vF qr—'D vF ƒongD tF viuD tF ‡F †irdenD —nd qF vF w™†—yD ScienceD IWWRD 264D RVF • €FErF gh—ngD gFE„F ru—ngD —nd tFEƒF ƒhieD J. Soc.D IWWQD 140D PRIHF • ‚F uF slerD The Chemistry of Silica Solubility.D IWWUD 144D IIRRF • tFEƒF ghou —nd ƒFEgF veeD J. Electrochem. Colloid and Surface Properties.D IWTVD 26D TPF • hF ‡hitehouseD Glass of the Roman EmpireD gorning @IWVVAF . Electrochem.D IWWRD 141D QPIRF • „F romm—D „F u—tohD ‰F ‰—m—d—D —nd ‰F wur—oD J. SciFD PHHUD 42D UQVIF • „F xiesen —nd wF ‚F he quireD J. Soc. ElectroceramicsD PHHID 6D ITWF • xF yz—w—D ‰F uum—z—w—D —nd „F ‰—oD Thin Solid FilmsD PHHPD 418D IHPF • ‡F ƒto˜erD eF pinkD —nd iF fohnD J. Colloid Interface Sci. and BiochemistryD tohn ‡iley 8 ƒons @IWUWAF • rF ‚F t—fryD iF eF ‡hitsittD —nd eF ‚F f—rronD J. THIN FILM GROWTH — gelF „his method des™ri˜es ˜oth the hydrolysis —nd ™ondens—tion of sili™on —lkoxides —nd the hydrolysis —nd ™ondens—tion of —queous sili™—tes @the hƒ pro™essAF sn the hydrolysis of sili™on —lkoxidesD —n —lkoxide group is repl—™ed with — hydroxyl groupD @SFIPAF purther ™ondens—tion re—™tions ˜etween —lkoxyl groups or hydroxyl groups produ™e silox—ne ˜ondsD see @SFIQA —nd @SFIRAF @SFIPA @SFIQA @SFIRA „etr—methoxysil—ne ‘ƒi@yweA4 D „wyƒ“ —nd tetr—ethylorthoxysil—ne ‘ƒi@yitA4 D „iyƒ“ —re the most ™omE monly used pre™ursors in sili™— solEgel pro™essingF „he —lkoxides —re hydrolyzed in their p—rent —l™oholsD with — miner—l —™id or ˜—se ™—t—lystD produ™ing sili™—te gels th—t ™—n ˜e deposited —s ™o—tingsF „he ƒto˜er methodD whi™h utilizes this ™hemistryD relies on homogeneous nu™le—tion to produ™e monodisperse solsF sler9s hƒ method of sili™— (lm form—tion w—s origin—lly p—tented —s — pigment ™o—ting to in™re—se disE persi˜ility of tit—ni— p—rti™les for use in the p—int industryF „he hƒ method is ˜—sed on the —queous ™hemistry of sili™— —nd t—kes —dv—nt—ge of the spe™ies present in solution —t v—rying prF felow pr U threeEdimension—l gel networks —re formedF e˜ove pr U sili™— surf—™es —re quite neg—tively ™h—rged @@SFISAAD so th—t p—rti™le growth o™™urs without —ggreg—tionF „he isoele™tri™ point of sili™— is pr PF ‚e—™tions —˜ove —nd ˜elow pr P —re thought to o™™ur through ˜imole™ul—r nu™leophili™ ™ondens—tion me™h—nismsF e˜ove pr P —n —nioni™ spe™ies —tt—™ks — neutr—l spe™ies @@SFITAA —nd ˜elow pr P ™ondens—tion involves — proton—ted sil—nol @@SFIUAAF „he hƒ pro™ess h—s ˜een utilized extensively in solEgel ™o—ting te™hnology —nd —s — growth method for monodisperse —nd polydisperse solsF @SFISA @SFITA @SFIUA 5. Mater.IVV CHAPTER 5.4. Soc. Electrochem. Polymerization.

Electrochem.D IWWRD 141D QIUUF . Colloid Interface SciFD PHHSD 287D QIVF gFEpF ‰ehD gFEvF ghenD —nd qFErF vinD J.IVW • • • • iF eF ‡hitsitt —nd eF ‚F f—rronD Nano LettFD PHHQD 3D UUSF iF eF ‡hitsitt —nd eF ‚F f—rronD Chem. Soc. CommunFD PHHQD IHRPF iF eF ‡hitsitt —nd eF ‚F f—rronD J.


org/content/m27846/1.1 Selecting a Molecular Precursor for Chemical Vapor Deposition 6.1. IWI .Chapter 6 Chemical Vapor Deposition 6.1 Introduction „he proven utility of ™hemi™—l v—por deposition @g†hA in — wide r—nge of ele™troni™ m—teri—ls systems @semi™ondu™torsD ™ondu™torsD —nd insul—torsA h—s driven rese—r™h e'orts to investig—te the potenti—l for thin (lm growth of other m—teri—lsD in™ludingX high temper—ture super™ondu™ting met—l oxidesD piezoele™tri™ m—teri—lD et™F woreoverD g†h potenti—lly is well suited for the prep—r—tion of thin (lms on — wide r—nge of su˜str—tesD in™luding those of nonpl—n—r geometriesF g†h o'ers the —dv—nt—ges of mild pro™ess ™onditions @iFeFD low temper—turesAD ™ontrol over mi™rostru™ture —nd ™ompositionD high deposition r—tesD —nd possi˜le l—rge s™—le pro™essingF es with —ny g†h pro™essD howeverD the ™riti™—l f—™tor in the deposition pro™ess h—s ˜een the sele™tion of pre™ursors with suit—˜le tr—nsport propertiesF 1 6.2 Factors in selecting a CVD precursor molecule „he following properties —re —mong those th—t must ˜e ™onsidered when sele™ting suit—˜le ™—ndid—tes for — g†h pre™ursorX IF „he pre™ursor should ˜e either — liquid or — solidD with su0™ient v—por pressure —nd m—ss tr—nsport —t the desired temper—tureD prefer—˜ly ˜elow PHH ◦ gF viquids —re preferred over solidsD due to the di0™ulty of m—int—ining — ™onst—nt )ux of sour™e v—pors over — nonEequili˜rium per™ol—tion @solidA pro™essF ƒu™h nonE˜u˜˜ling pro™esses —re — fun™tion of surf—™e —re—D — nonE™onst—nt v—ri—˜le with respe™t ˜oth to time —nd p—rti™le sizeF „he upper temper—ture limit is not di™t—ted ˜y ™hemi™—l f—™torsY r—therD it is — limit—tion imposed ˜y the st—˜ility of the m—ss )ow ™ontrollers —nd pneum—ti™ v—lves utilized in ™ommer™i—l deposition equipmentF st must ˜e stressed th—t while the —™hievement of —n optimum v—por pressure for e0™ient utiliz—tion —s —n industri—lly pr—™ti™—˜le sour™e providing high (lm growth r—tes @>IH „orr —t PS ◦ gA is — worthy go—lD the us—˜le pressure regimes —re those in whi™h ev—lu—tion ™—n ˜e ™—rried out on ™ompounds whi™h exhi˜it v—por pressures ex™eeding I „orr —t IHH ◦ gF PF „he pre™ursor must ˜e ™hemi™—lly —nd therm—lly st—˜le in the region ˜ordered ˜y the ev—por—tion —nd tr—nsport temper—turesD even —fter prolonged useF i—rly workers were pl—gued ˜y irreprodu™i˜le (lm growth results ™—used ˜y prem—ture de™omposition of sour™e ™ompounds in the ˜u˜˜lerD in tr—nsfer linesD —ndD ˜—si™—lly everywhere except on the su˜str—teF ƒu™h experien™es —re to ˜e —voided3 QF fy its very n—tureD g†h dem—nds — de™ompos—˜le pre™ursorF „his gener—lly is —™™omplished therm—llyY howeverD the pl—sm—Eenh—n™ed growth regime h—s seen mu™h improvementF sn —dditionD photolyti™ pro™esses h—ve tremendous potenti—lF xeverthelessD the pre™ursor must ˜e therm—lly ro˜ust until deposition conditions are employedF 1 This content is available online at <http://cnx.1/>.1.

.2/>.1 Introduction wet—l ™ompounds —nd ™omplexes —re inv—lu—˜le pre™ursors for the ™hemi™—l v—por deposition @g†hA of met—l —nd nonEmet—l thin (lmsF sn gener—lD the pre™ursor ™ompounds —re ™hosen on the ˜—sis of their rel—tive vol—tility —nd their —˜ility to de™ompose to the desired m—teri—l under — suit—˜le temper—ture regimeF …nfortun—telyD m—ny re—dily o˜t—in—˜le @™ommer™i—lly —v—il—˜leA ™ompounds —re not of su0™ient vol—tility to m—ke them suit—˜le for g†h —ppli™—tionsF „husD — prediction of the vol—tility of — met—lEorg—ni™ ™ompounds —s — fun™tion of its lig—nd identity —nd mole™ul—r stru™ture would ˜e desir—˜le in order to determine the suit—˜ility of su™h ™ompounds —s g†h pre™ursorsF iqu—lly import—nt would ˜e — method to determine the v—por pressure of — potenti—l g†h pre™ursor —s well —s its optimum temper—ture of su˜lim—tionF st h—s ˜een o˜served th—t for org—ni™ ™ompounds it w—s determined th—t — rough proportion—lity exists ˜etween — ™ompound9s melting point —nd su˜lim—tion enth—lpyY howeverD signi(™—nt devi—tion is o˜served for inorg—ni™ ™ompoundsF inth—lpies of su˜lim—tion for met—lEorg—ni™ ™ompounds h—ve ˜een previously determined through — v—riE ety of methodsD most ™ommonly from v—por pressure me—surements using ™omplex experiment—l systems su™h —s unudsen e'usionD temper—ture drop mi™ro™—lorimetry —ndD more re™entlyD di'erenti—l s™—nning ™—lorimeE try @hƒgAF roweverD the me—sured v—lues —re highly dependent on the experiment—l pro™edure utilizedF por ex—mpleD the reported su˜lim—tion enth—lpy of el@—™—™A3 @pigure TFI—D where w a elD n a QA v—ries from RUFQ to IPT ktGmolF 2 This content is available online at <http://cnx. CHEMICAL VAPOR DEPOSITION RF „he pre™ursor should ˜e rel—tively e—sy to synthesizeD ensuring su0™ient —v—il—˜ility of m—teri—l for testing —nd f—˜ri™—tionF st —lso is import—nt th—t the synthesis of the ™ompound ˜e reprodu™i˜leF st should ˜e simple to prep—re —nd purify to — rel—tively high level of purityF st should ˜e nonEtoxi™ —nd environmentally friendly @iFeFD —s low — toxi™ity —s ™—n ˜e —tt—inedD given the fund—ment—l toxi™ity of p—rti™ul—r elements su™h —s mer™uryD th—lliumD ˜—riumD et™FAF st should ˜e routine to reprodu™e —nd s™—leEup the prep—r—tion for further development—l studiesF st should utilize re—dily —v—il—˜le st—rting re—gentsD —nd pro™eed ˜y — minimum num˜er of ™hemi™—l tr—nsform—tions in order to minimize the ™ostF SF hue to h—ndling ™onsider—tionsD the sour™e should ˜e oxid—tivelyD hydrolyti™—llyD therm—lly —nd phoE to™hemi™—lly st—˜le under norm—l stor—ge ™onditionsD in —ddition the pre™usor should resist oligomerE iz—tion @in the solidD liquidD or g—seous st—tesAF st is worth noting th—t pr—™titioners of met—l org—ni™ g†h @wyg†hAD espe™i—lly for IQEIS m—teri—ls h—ve of ne™essity ˜e™ome expert in the h—ndling of very toxi™D highly —ir sensitive m—teri—lsF ristori™—llyD rese—r™hers were limited in their ™hoi™es of pre™ursors to those th—t were re—dily known —nd ™ommer™i—lly —v—il—˜leF st must ˜e emph—sized th—t none of these previously known ™ompounds h—d ˜een designed spe™i(™—lly to serve —s v—por ph—se tr—nsport mole™ules for the —sso™i—ted elementF „husD the s™ope w—s often limited to wh—t w—s ™ommer™i—lly —v—il—˜leF roweverD —s new ™ompounds h—ve now ˜een m—de with the spe™i(™ go—l of providing ide—l g†h pre™ursors the ™hoi™e to —™—demi— —nd industry h—s in™re—sedF 6.2 Determination of Sublimation Enthalpy and Vapor Pressure for Inorganic and Metal-Organic Compounds by Thermogravimetric Analysis 2 Bibliography • qF fF ƒtringfellowD Organometallic Vapor Phase Epitaxy: Theory and PracticeD e™—demi™ €ressD xew ‰ork @IWVWAF 6.IWP CHAPTER

and (c) hexauoroacetylacetonate (hfac).IWQ Structure of a typical metal β -diketonate complex.2. (b) triuoro acetylacetonate (tfac). (a) acetylacetonate (acac).1: „hermogr—vimetri™ —n—lysis o'ers — simple —nd reprodu™i˜le method for the determin—tion of the v—por pressure of — potenti—l g†h pre™ursor —s well —s its enth—lpy of su˜lim—tionF 6.2 Determination of sublimation enthalpy „he enth—lpy of su˜lim—tion is — qu—ntit—tive me—sure of the vol—tility of — p—rti™ul—r solidF „his inform—tion is useful when ™onsidering the fe—si˜ility of — p—rti™ul—r pre™ursor for g†h —ppli™—tionsF en ide—l su˜lim—tion pro™ess involves no ™ompound de™omposition —nd only results in — solidEg—s ph—se ™h—ngeD iFeFD @TFIAF @TFIA ƒin™e ph—se ™h—nges —re thermodyn—mi™ pro™esses following zeroEorder kineti™sD the ev—por—tion r—te or r—te of m—ss loss ˜y su˜lim—tion @msub AD —t — ™onst—nt temper—ture @„AD is ™onst—nt —t — given temper—tureD @TFPAF „hereforeD the msub v—lues m—y ˜e dire™tly determined from the line—r m—ss loss of the „qe d—t— in isotherm—l regionsF @TFPA „he thermogr—vimetri™ —nd di'erenti—l therm—l —n—lysis of the ™ompound under study is performed to determine the temper—ture of su˜lim—tion —nd therm—l events su™h —s meltingF pigure TFP shows — typi™—l „qGh„e plot for — g—llium ™h—l™ogenide ™u˜—ne ™ompound @pigure TFQAF . Figure 6.

6. whose structure is shown in Figure 6. G. and A. Mater. G. Barron. CMe2 Et. 796.2: A typical thermogravimetric/dierential thermal analysis (TG/DTA) analysis of [(EtMe2 C)GaSe]4 .3: Structure of gallium chalcogenide cubane compound. CHEMICAL VAPOR DEPOSITION 6. R.1 Data collection sn — typi™—l experiment S E IH mg of s—mple is used with — he—ting r—te of ™—F S ◦ gGmin up to under either — PHHEQHH mvGmin inert @x2 or erA g—s )ow or — dyn—mi™ v—™uum @caF HFP „orr if using — typi™—l v—™uum pumpAF „he —rgon )ow r—te w—s set to WHFH mvGmin —nd w—s ™—refully monitored to ensure — ste—dy )ow r—te during runs —nd —n identi™—l )ow r—te from one set of d—t— to the nextF yn™e the temper—ture r—nge is de(nedD the „qe is run with — preprogr—mmed temper—ture pro(le @pigure TFRAF st h—s ˜een found th—t su0™ient d—t— ™—n ˜e o˜t—ined if e—™h isotherm—l m—ss loss is monitored over — period @˜etween U —nd IH minutes is found to ˜e su0™ientA ˜efore moving to the next temper—ture pl—te—uF sn —ll ™—ses it is import—nt to ™on(rm th—t the m—ss loss —t — given temper—ture is line—rF sf it is . 3. Bott. Gillan. CEt3 . Chem. 9.2. Figure Figure 6. and R = CMe3 .IWR CHAPTER 6.2.3. S. Adapted from E. where E = S.. CEt2 Me. Se. 1997.

IWS notD this ™—n ˜e due to either @—A temper—ture st—˜iliz—tion h—d not o™™urred —nd so longer times should ˜e spent —t e—™h isothermD or @˜A de™omposition is o™™urring —long with su˜lim—tionD —nd lower temper—ture r—nges must ˜e usedF „he slope of e—™h m—ss drop is me—sured —nd used to ™—l™ul—te su˜lim—tion enth—lpies —s dis™ussed ˜elowF Figure 6. es —n illustr—tive ex—mpleD pigure TFS displ—ys the d—t— for the m—ss loss of gr@—™—™A3 @pigure TFI—D where w a grD n a QA —t three isotherm—l regions under — ™onst—nt —rgon )owF i—™h isotherm—l d—t— set should exhi˜it — line—r rel—tionF es expe™ted for —n endotherm—l ph—se ™h—ngeD the line—r slopeD equ—l to msub D in™re—ses with in™re—sing temper—tureF .4: A typical temperature prole for determination of isothermal mass loss rate.

Barron. Optics Electron. Fahlman and A. R. 10.IWT CHAPTER 6. 223. ƒ—mples of iron —™etyl—™eton—te @pigure TFI—D where w a peD n a QA m—y ˜e used —s — ™—li˜r—tion st—nd—rd through ∆rsub determin—tions ˜efore e—™h d—y of useF sf the me—sured v—lue of the su˜lim—tion enth—lpy for pe@—™—™A3 is found to di'er from the liter—ture v—lue ˜y more th—n S7D the s—mple is reE—n—lyzed —nd the )ow r—tes —re optimized until —n —ppropri—te v—lue is o˜t—inedF ynly —fter su™h — ™—li˜r—tion is optimized should other ™omplexes ˜e —n—lyzedF st is import—nt to note th—t while sm—ll —mounts @< IH7A of invol—tile impurities will not interfere with the ∆rsub —n—lysisD ™ompetitively vol—tile impurities will produ™e higher —pp—rent su˜lim—tion r—tesF note: st is import—nt to dis™uss —t this point the v—rious f—™tors th—t must ˜e ™ontrolled in order to o˜t—in me—ningful @usefulA msub d—t— from „qe d—t—F IF „he su˜lim—tion r—te is independent of the —mount of m—teri—l used ˜ut m—y exhi˜it some dependen™e on the )ow r—te of —n inert ™—rrier g—sD sin™e this will —'e™t the equili˜rium ™on™entr—tion of the ™u˜—ne in the v—por ph—seF ‡hile little v—ri—tion w—s o˜served we de™ided th—t for ™onsisten™y msub v—lues should ˜e derived from v—™uum experiments onlyF PF „he surf—™e —re— of the solid in — given experiment should rem—in —pproxim—tely ™onst—ntY otherwise the su˜lim—tion r—te @iFeFD m—ssGtimeA —t di'erent temper—tures ™—nnot ˜e ™omp—redD sin™e —s the rel—tive surf—™e —re— of — given ™ryst—llite de™re—ses during the experiment the —pp—rent su˜lim—tion r—te will —lso de™re—seF „o minimize this pro˜lemD d—t— w—s t—ken over — sm—ll temper—ture r—nges @caF QH ◦ gAD —nd over—ll su˜lim—tion w—s kept low @caF PS7 m—ss loss representing — surf—™e —re— ™h—nge of less th—n IS7AF sn experiments where signi(™—nt surf—™e —re— ™h—nges o™™urred the v—lues of msub devi—ted signi(™—ntly from line—rity on — log@msub A versus IG„ plotF QF „he ™ompound ˜eing —n—lyzed must not de™ompose to —ny signi(™—nt degreeD ˜e™—use the m—ss ™h—nges due to de™omposition will ™—use — redu™tion in the —pp—rent msub v—lueD produ™ing erroneous resultsF ‡ith — simult—neous „qGh„e system it is possi˜le to o˜serve exothermi™ events if de™omposition o™™ursD however the ™le—rest indi™—tion is shown ˜y the m—ss loss versus time ™urves whi™h —re no longer line—r ˜ut exhi˜it exponenti—l de™—ys ™h—r—™teristi™ of (rst or se™ond order de™omposition pro™essesF .5: Plot of TGA results for Cr(acac)3 performed at dierent isothermal regions. Adapted from B. Mater.. Adv. D. CHEMICAL VAPOR DEPOSITION Figure 6. 2000.

10.6: Plot of log(msub T ) versus 1/T and the determination of the ∆Hsub (112.2.6 kJ/mol) for Fe(acac)3 (R2 = 0. D. 2000.IWU 6.9989). „—˜le TFI lists the typi™—l results using the „qe method for — v—riety of met—l β Ediketon—tesD while „—˜le TFP lists simil—r v—lues o˜t—ined for g—llium ™h—l™ogenide ™u˜—ne ™ompoundsF . Barron. Mater. Fahlman and A.2. Adapted from B..2 Data analysis „he ˜—sis of —n—lyzing isotherm—l „qe d—t— involves using the gl—usiusEgl—peyron rel—tion ˜etween v—por pressure @pA —nd temper—ture @„AD @TFQAD where ∆rsub is the enth—lpy of su˜lim—tion —nd ‚ is the g—s ™onst—nt @VFQIR tGuFmolAF @TFQA ƒin™e msu˜ d—t— —re o˜t—ined from „qe d—t—D it is ne™ess—ry to utilize the v—ngmuir equ—tionD @TFRAD th—t rel—tes the v—por pressure of — solid with its su˜lim—tion r—teF @TFRA efter integr—ting @TFQA in log formD su˜stituting in @TFRAD —nd ™onsolid—ting the ™onst—ntsD one o˜t—ins the useful equ—lityD @TFSAF @TFSA ren™eD the line—r slope of — log@msub „ A versus IG„ plot yields ∆rsub F en ex—mple of — typi™—l plot —nd the ™orresponding ∆rsub v—lue is shown in pigure TFTF sn —dditionD the y inter™ept of su™h — plot provides — v—lue for „sub D the ™—l™ul—ted su˜lim—tion temper—ture —t —tmospheri™ pressureF 1/2 1/2 Figure 6. R. 223. Optics Electron. Adv.

1X ƒele™ted thermodyn—mi™ d—t— for met—l β Ediketon—te ™ompounds determined from thermogr—vimetri™ —n—lysisF h—t— from fF hF p—hlm—n —nd eF ‚F f—rronD Adv. CHEMICAL VAPOR DEPOSITION ∆Hsub (kJ/mol) ∆Ssub Tsub calc. Tsub calc. IWWUD 9D QD UWTF e ™ommon method used to enh—n™e pre™ursor vol—tility —nd ™orresponding e0™—™y for g†h —ppli™—tions is to in™orpor—te p—rti—lly @pigure TFI˜A or fully @pigure TFI™A )uorin—ted lig—ndsF es m—y ˜e seen from „—˜le TFI this su˜stitution does results in signi(™—nt de™re—se in the ∆rsub D —nd thus in™re—sed vol—tilityF „he o˜served enh—n™ement in vol—tility m—y ˜e r—tion—lized either ˜y —n in™re—sed —mount of intermole™ul—r repulsion due to the —ddition—l lone p—irs or th—t the redu™ed pol—riz—˜ility of )uorine @rel—tive to hydrogenA ™—uses )uorin—ted lig—nds to h—ve less intermole™ul—r —ttr—™tive inter—™tionsF .mol) el@—™—™A3 el@tf—™A3 el@hf—™A3 gr@—™—™A3 gr@tf—™A3 gr@hf—™A3 pe@—™—™A3 pe@tf—™A3 pe@hf—™A3 go@—™—™A3 go@tf—™A3 go@hf—™A3 WQ UR SP WI UI RT IIP WT TH IQV IIW UQ PPH IWP ISP PIT IVT IQR PSW PRQ ITW QII PWS PHH ISH III UH IRV IHW TW ITI IPI VI IUH IQI WH QFPTI WFUIS PWFIPH QFQPV WFWIH PWFSII PFUVI VFQRH PSFHPI IFHSW QFQIW WFIQP Table 6. ( ◦ C) Calculated vapor pressure @ 150 ◦ C (Torr) (J/K. Mater.2X ƒele™ted thermodyn—mi™ d—t— for g—llium ™h—l™ogenide ™u˜—ne ™ompounds determined from thermogr—vimetri™ —n—lysisF h—t— from iF qF qill—nD ƒF qF fottD —nd eF ‚F f—rronD Chem. ( ◦ C) Calculated vapor pressure @ 150 ◦ C (Torr) ‘@we3 gAq—ƒ“4 ‘@itwe2 gAq—ƒ“4 ‘@it2 wegAq—ƒ“4 ‘@it3 gAq—ƒ“4 ‘@we3 gAq—ƒeA“4 ‘@itwe2 gAq—ƒe“4 ‘@it2 wegAq—ƒe“4 ‘@it3 gAq—ƒe“4 IIH IPR IQU IRW IIW IQU IRU IST QHH QQH QQW QQQ QHS QRR QSW QQW WR IHP IQI IUS IIT IPR IQT IVW PPFUS IVFVW IFIUQ HFHIV QFTTV PFSTP HFVIS HFHHS Table 6.IWV Compound CHAPTER 6. Optics ElectronFD PHHHD 10D PPQF Compound ∆Hsub (kJ/mol) ∆Ssub mol) (J/K.. Mater.

Adapted from E. Chem. 9. R. Gillan.3 Determination of sublimation entropy „he entropy of su˜lim—tion is re—dily ™—l™ul—ted from the ∆rsub —nd the ™—l™ul—ted „sub d—t—D @TFTAF @TFTA „—˜le TFI —nd „—˜le TFP show typi™—l v—lues for met—l β Ediketon—te ™ompounds —nd g—llium ™h—l™ogenide ™u˜—ne ™ompoundsD respe™tivelyF „he r—nge o˜served for g—llium ™h—l™ogenide ™u˜—ne ™ompounds @∆ƒsub a QQH ±PH tGuFmolA is slightly l—rger th—n v—lues reported for the met—l β Ediketon—tes ™ompounds @∆ƒsub a IQH E QQH tGuFmolA —nd org—ni™ ™ompounds @IHH E PHH tGuFmolAD —s would ˜e expe™ted for — tr—nsform—tion giving tr—nsl—tion—l —nd intern—l degrees of freedomF por —ny p—rti™ul—r ™h—l™ogenideD iFeFD ‘@‚Aq—ƒ“4 D the lowest ∆ƒsub —re o˜served for the we3 g deriv—tivesD —nd the l—rgest ∆ƒsub for the it2 weg deriv—tivesD see „—˜le TFPF „his is in line with the rel—tive in™re—se in the modes of freedom for the —lkyl groups in the —˜sen™e of ™ryst—l p—™king for™esF 6. Mater.. Barron.2.7: A plot of calculated vapor pressure (Torr) against temperature (K) for [(Me3 C)GaS]4 .4 Determination of vapor pressure ‡hile the su˜lim—tion temper—ture is —n import—nt p—r—meter to determine the suit—˜ility of — potenti—l pre™ursor ™ompounds for g†hD it is often prefer—˜le to express — ™ompound9s vol—tility in terms of its v—por pressureF roweverD while it is rel—tively str—ightforw—rd to determine the v—por pressure of — liquid or g—sD me—surements of solids —re di0™ult @eFgFD use of the isotenis™opi™ methodA —nd few l—˜or—tories —re equipped to perform su™h experimentsF qiven th—t „qe —pp—r—tus —re in™re—singly —™™essi˜leD it would therefore ˜e desir—˜le to h—ve — simple method for v—por pressure determin—tion th—t ™—n ˜e —™™omplished on — „qeF ƒu˜stitution of @TFPA into @TFRA —llows for the ™—l™ul—tion of the v—por pressure @pA —s — fun™tion of temper—ture @„AF por ex—mpleD pigure TFU shows the ™—l™ul—ted temper—ture dependen™e of the v—por pressure for ‘@we3 gAq—ƒ“4 F „he ™—l™ul—ted v—por pressures —t ISH ◦ g for met—l β Ediketon—tes ™ompounds —nd g—llium ™h—l™ogenide ™u˜—ne ™ompounds —re given in „—˜le TFI —nd „—˜le TFPF Figure 6. 796. Bott. G. G. and A. 3.IWW 6. .2. S. 1997.

3/>. Thermodyn. Mater. Chem.1 Synthesis €hosphine @€r3 A is prep—red ˜y the re—™tion of element—l phosphorus @€4 A with w—terD @TFUAF …ltr— pure phosphine th—t is used ˜y the ele™troni™s industry is prep—red ˜y the therm—l disproportion—tion of phosE phorous —™idD @TFVAF @TFUA @TFVA ersine ™—n ˜e prep—red ˜y the redu™tion of the ™hlorideD @TFWA or @TFIHAF „he ™orresponding syntheses ™—n —lso ˜e used for sti˜ine —nd ˜ismuthineF @TFWA @TFIHA „he hydrolysis of ™—l™ium phosphide or —rsenide ™—n —lso gener—te the trihydridesF 3 This content is available online at <http://cnx. Sth edFD ‡F rF preem—nD xew ‰ork @IWWRAF qF fee™h —nd ‚F wF vinton˜onD Thermochim. IWUID 3D WUF fF hF p—hlm—n —nd eF ‚F f—rronD Adv.3 13-15 (III-V) Semiconductor Chemical Vapor Deposition 6. Mater. IWWQD 13D IPSF tF €F wurr—yD uF tF g—vell —nd tF yF rillD Thermochim. IWVVD 124D PPWF 6. CHEMICAL VAPOR DEPOSITION „he „qe —ppro—™h to show re—son—˜le —greement with previous me—surementsF por ex—mpleD while the v—lue ™—l™ul—ted for pe@—™—™A3 @PFUV „orr d IIQ ◦ gA is slightly higher th—n th—t me—sured dire™tly ˜y the isotenis™opi™ method @HFSQ „orr d IIQ ◦ gAY howeverD it should ˜e noted th—t me—surements using the su˜lim—tion ˜ul˜ method o˜t—ined v—lues mu™h lower @V x IH-3 „orr d IIQ ◦ gAF „he „qe method o'ers — suit—˜le —ltern—tive to ™onvention—l @dire™tA me—surements of v—por pressureF 6. Chem. Optics ElectronFD PHHHD 10D PPQF iF qF qill—nD ƒF qF fottD —nd eF ‚F f—rronD Chem.1.5 Bibliography • • • • • • • • • €F ‡F etkinsD Physical Chemistry.3. IWWRD 247D IWQF vF eF „orresEqomezD qF f—rreiroE‚odriquezD —nd eF q—l—rz—Ewondr—gonD Thermochim. Acta. . IWWUD 9D QD UWTF tF yF rill —nd tF €F wurr—yD Rev.1 Phosphine and Arsine 3 fe™—use of their use in met—l org—ni™ ™hemi™—l v—por deposition @wyg†hA of IQEIS @sssE†A semi™ondu™tor ™ompounds phosphine @€r3 A —nd —rsine @esr3 A —re prep—red on —n industri—l s™—leF 6. Acta.. IWVHD 36D WUF wF eF †F ‚i˜eiro d— ƒilv— —nd wF vF gF gF rF perr—oD J. IWWRD 26D QISF ‚F ƒ—˜˜—hD hF „—˜etD ƒF fel——diD Thermochim. Acta.2..3. Acta.PHH CHAPTER 6..

3.1.1 Gutzeit test „he qutzeit test is the ™h—r—™teristi™ test for —rseni™ —nd involves the re—™tion of —rsine with eg+ F ersine is gener—ted ˜y redu™tion of —queous —rseni™ ™ompoundsD typi™—lly —rsenitesD with n in the presen™e of r2 ƒy4 F „he evolved g—seous esr3 is then exposed to silver nitr—te either —s powder or —s — solutionF ‡ith solid egxy3 D esr3 re—™ts to produ™e yellow eg3 esxy3 D while with — solution of egxy3 ˜l—™k eg3 es is formedF 6.1.—t high prD with equili˜rium ™onst—nts ub a R x IH-28 —nd ua a RIFT x IH-29 D respe™tivelyF ersine h—s simil—r solu˜ility in w—ter to th—t of phosphine @iFeFD UH mgGIHH mvAD —nd esr3 is gener—lly ™onsidered nonE˜—si™D ˜ut it ™—n ˜e proton—ted ˜y super—™ids to give isol—˜le s—lts of esr4 + F ersine is re—dily oxidized in —irD @TFIIAF @TFIIA ersine will re—™t violently in presen™e of strong oxidizing —gentsD su™h —s pot—ssium perm—ng—n—teD sodium hypo™hlorite or nitri™ —™idF ersine de™omposes the its ™onstituent elements upon he—ting to PSH E QHH ◦ gF 6.3.3 Reactions €hosphine is only slightly solu˜le in w—ter @QIFP mgGIHH mvA ˜ut it is re—dily solu˜le in nonEpol—r solventsF €hosphine —™ts —s neither —n —™id nor — ˜—se in w—terY howeverD proton ex™h—nge pro™eeds vi— the phosphoE nium ion @€r4 + A in —™idi™ solutions —nd vi— €r2 .3.3.2 Structure „he phosphorus in phosphine —dopts sp3 hy˜ridiz—tionD —nd thus phosphine h—s —n um˜rell— stru™ture @pigE ure TFV—A due to the stereo™hemi™—lly —™tive lone p—irF „he ˜—rrier to inversion of the um˜rell— @ia a ISS ktGmolA is mu™h higher th—n th—t in —mmoni— @ia a PR ktGmolAF €utting this di'eren™e in ™ontextD —mmoE ni—9s inversion r—te is IH11 while th—t of phosphine is IH3 F es — ™onsequen™e it is possi˜le to isol—te ™hir—l org—nophosphines @€‚‚9‚4AF ersine —dopts the —n—logous stru™ture @pigure TFV˜AF Figure 6.PHI 6. 6.8: The structures of (a) phosphine and (b) arsine. Hazards €ure phosphine is odorlessD ˜ut te™hni™—l gr—de phosphine h—s — highly unple—s—nt odor like g—rli™ or rotting (shD due to the presen™e of su˜stituted phosphine —nd diphosphine @€2 r4 AF „he presen™e of €2 r4 —lso ™—uses spont—neous ™om˜ustion in —irF €hosphine is highly toxi™Y symptoms in™lude p—in in the ™hestD — sens—tion of ™oldnessD vertigoD shortness of ˜re—thD —nd —t higher ™on™entr—tions lung d—m—geD ™onvulsions —nd de—thF „he re™ommended limit @‚vA is HFQ ppmF .

.1 Introduction €rep—r—tion of epit—xi—l thin (lms of sssE† @IQEISA ™ompound semi™ondu™tors @not—˜ly q—esA for —ppli™—tions in —dv—n™ed ele™troni™ devi™es ˜e™—me — re—listi™ te™hnology through the development of met—l org—ni™ ™hemi™—l v—por deposition @wyg†hA pro™esses —nd te™hniquesF „he pro™esses m—inly involves the therm—l de™omposition of met—l —lkyls —ndGor met—l hydridesF sn IWTV w—n—sevit —t the ‚o™kwell gorpor—tion w—s the (rst to pu˜lish on wyg†h for the epit—xi—l growth of q—esF „his followed his pioneering work in IWTQ with the epit—xi—l growth of sili™on on s—pphireF „he (rst pu˜li™—tion used triethylg—llium ‘q—@gr2 gr3 A3 “ —nd —rsine @esr3 A in —n open tu˜e with hydrogen —s the ™—rrier g—sF w—n—sevit —™tu—lly ™oined the phr—se wyg†h —nd sin™e this semin—l work there h—ve ˜een numerous —ttempts to improve —nd exp—nd wyg†h for the f—˜ri™—tion of q—esF ƒever—l pro™essesD p—rtly in seriesD p—rtly in p—r—llel t—ke pl—™e during the growth ˜y g†hF „hey —re presented s™hem—ti™—lly in pigure TFWF „he rel—tive import—n™e of e—™h of them depends on the ™hemi™—l n—ture of the spe™ies involved —nd the design of the re—™tor usedF „he —™tu—l growth r—te is determined ˜y the slowest pro™ess in the series of events needed to ™ome to depositionF 4 This content is available online at <http://cnx.2. Anorg. CHEMICAL VAPOR DEPOSITION ersine is — ™olorless odorless g—s th—t is highly toxi™ ˜y inh—l—tionF ywing to oxid—tion ˜y —ir it is possi˜le to smell — slightD g—rli™Elike s™ent when —rsine is present —t —˜out HFS ppmF ersine —tt—™ks hemoglo˜in in the red ˜lood ™ellsD ™—using them to ˜e destroyed ˜y the ˜odyF purther d—m—ge is ™—used to the kidney —nd liverF ixposure to —rsine ™on™entr—tions of PSH ppm is r—pidly f—t—lX ™on™entr—tions of PS ! QH ppm —re f—t—l for QH min exposureD —nd ™on™entr—tions of IH ppm ™—n ˜e f—t—l —t longer exposure timesF ƒymptoms of poisoning —ppe—r —fter exposure to ™on™entr—tions of HFS ppm —nd the re™ommended limit @‚vA is —s low —s HFHS ppmF 6.6/>.2 Mechanism of the Metal Organic Chemical Vapor Deposition of Gallium Arsenide 4 6.PHP CHAPTER 6.5 Bibliography • ‚F winkwitzD eF uorn—thD ‡F ƒ—wodnyD —nd rF rärtnerD Z. Chem.D IWWRD 620D USQF Allg.1.

3.9: gonvention—llyD the met—l org—ni™ ™hemi™—l v—por deposition @wyg†hA growth of q—es involves the pyrolysis of — v—por ph—se mixture of —rsine —ndD most ™ommonlyD trimethylg—llium ‘q—@gr3 A3 D „wq“ —nd triethylg—llium ‘q—@gr2 gr3 A3 D „iq“F „r—dition—llyD growth is ™—rried out in — ™oldEw—ll qu—rtz re—™tor in )owing r2 —t —tmospheri™ or low pressureF „he su˜str—te is he—ted to temper—tures RHH E VHH ◦ gD typi™—lly ˜y ‚p he—ting of — gr—phite sus™eptorF „r—nsport of the met—lEorg—ni™s to the growth zone is —™hieved ˜y ˜u˜˜ling — ™—rrier g—s @eFgFD r2 A through the liquid sour™es th—t —re in held temper—tureE™ontrolled ˜u˜˜lersF 6.2 Reaction mechanism ‡hile the over—ll re—™tion @where ‚ a gr3 or gr2 gr3 A ™—n ˜e des™ri˜ed ˜y @TFIPAF @TFIPA „he n—ture of the re—™tion is mu™h more ™omplexF prom e—rly studies it w—s thought th—t free q— —toms —re formed ˜y pyrolysis of „wq —nd es4 mole™ules —re formed ˜y pyrolysis of esr3 —nd these spe™ies re™om˜ine on the su˜str—te surf—™e in —n irreversi˜le re—™tion to form q—esF elthough — vewis —™idE˜—se ™omplex formed ˜etween „wq —nd esr3 is possi˜leD it is now known th—t if there is —ny intermedi—te re—™tion ˜etween the „wq —nd esr3 D the produ™t is unst—˜leF roweverD e—rly work indi™—ted th—t free q—es mole™ules resulted from the de™omposition of — „wqFesr3 intermedi—te —nd th—t the he—ted surf—™e ™ontri˜uted to the re—™tionF st w—s su˜sequently suggested th—t the re—™tion o™™urs ˜y sep—r—te pyrolysis of the re—™t—nts —nd — ™om˜in—tion of individu—l q— —nd es —toms —t the surf—™e or just —˜ove itF pin—llyD eviden™e h—s —lso ˜een found for „wq pyrolysis followed ˜y di'usion through — ˜ound—ry l—yer —nd for esr3 pyrolysis ™—t—lyzed ˜y the q—es surf—™eF „here —re sever—l di'erent kinds of potenti—l re—™tions o™™uring in the g†h re—™tion ™h—m˜erD n—melyD lig—nd disso™i—tionD lig—nd —sso™i—tionD D redu™tive elimin—tionD oxid—tive —dditionD β Ehydride elimin—tionD et™F ƒome of them —re listed in the following equ—tionsX @TFIQA . Jensen and W. Eds. Academic Press. New York (1991). Kern. J. Vossen and W.PHQ Schematic representation of the fundamental transport and reaction steps underlying MOCVD. Adapted from K. in Thin Film Processes II. Kern. L. Figure 6.2. F.

3. CHEMICAL VAPOR DEPOSITION @TFIRA @TFISA @TFITA @TFIUA @TFIVA 6.3.2.PHR CHAPTER Using ALE studies as insight for MOCVD qiven the stepwise —nd presum—˜ly simpli(ed me™h—nism for —tomi™ l—yer epit—xy @eviA growth of q—esD — num˜er of me™h—nisti™ studies h—ve ˜een undert—ken of evi using „wq —nd esr3 to provide insight into the ™omp—r—˜le wyg†h re—™tionsF xishiz—w— —nd uur—˜—y—shi proposed th—t — gr3 Etermin—ted q—es surf—™e inhi˜its further heterogeneous de™omposition of „wq —nd selfElimits the growth r—te to one monol—yerG™y™leF ‡hileD ˆEr—y photoele™tron spe™tros™opy @ˆ€ƒA studies showed th—t no ™—r˜on w—s o˜served on — q—es surE f—™e re—™ted with „wqF purthermoreD the s—me selfElimiting growth w—s seen in in evi using — met—lorg—ni™ mole™ul—r ˜e—m epit—xy @wywfiA with „wq —nd esr3 F st w—s reported th—t — tr—nsient surf—™e re™onE stru™tion is o˜serv—˜le ˜y re)e™tion highEenergy ele™tron di'r—™tion @‚riihA during the evi of q—es in wywfiF st w—s suggested th—t this stru™ture is ™—used ˜y gr3 Etermin—tion —nd the selfElimit—tion of the growth r—te is —ttri˜uted to this stru™tureF roweverD me—surement of the desorption of gr3 ˜y me—ns of — ™om˜in—tion of pulsed mole™ul—r ˜e—ms —nd timeEresolved m—ss spe™trometryD indi™—tes th—t gr3 desorption is too f—st to —ttri˜ute the selfElimit—tion to the gr3 Etermin—ted surf—™eF ƒu˜sequentlyD investig—tions of the pyrolysis of „wq on — @IHHAq—es surf—™e ˜y the surf—™e photoE—˜sorption method @ƒ€eA —llowed for the dire™t o˜serv—tion of gr3 desorption from — q—es surf—™e re—™ted with „wqF prom the me—sured gr3 desorption kineti™sD it w—s shown th—t the gr3 Etermin—ted surf—™es ™—uses the selfElimit—tion of the growth r—te in evi ˜e™—use the ex™ess „wq ™—nnot —dsor˜F ell this rese—r™h helped people to visu—lize the re—l re—™tion me™h—nism in the form—tion of q—es ˜y wyg†h methodsD in whi™h the de™ompositionD di'usion —nd surf—™e re—™tion inter—™t with e—™h other —nd result in — mu™h more ™ompli™—ted re—™tion me™h—nismF 6.2 Gas phase reaction: pyrolysis of TMG and AsH3 sn the „wqGr2 systemD there is —lmost no re—™tions —t — temper—ture ˜elow RSH ◦ gD where—s the re—™tion of „wq with r2 —lmost ™ompletely ™h—nged into gr4 —nd q— —t — temper—ture —˜ove THH ◦ gD @TFIWAF @TFIWA es for the esr3 de™ompositionD without —ny deposition of q— or q—es in the re—™torD the pyrolysis of esr3 pro™eeded ˜—rely —t — temper—ture ˜elow THH ◦ gD howeverD it pro™eeded ne—rly ™ompletely —t — temper—ture —˜ove USH ◦ gF sn the esr3 Gr2 system with the „wq introdu™ed previouslyD the de™omposition of esr3 w—s l—rgely enh—n™ed even —t — temper—ture ˜elow THH ◦ gF „he de™omposition of esr3 seems to ˜e —'e™ted .2.

2.PHS sensitively ˜y the deposited q—es or q—F „his phenomenon m—y ˜e ™on™luded to ˜e ™—used ˜y the ™—t—lyti™ —™tion ˜y q—es or q—F „he re—™tion —t — temper—ture ˜elow THH ◦ g ™—n ˜e des™ri˜ed —s shown in @TFPHAD ˜ut —t — temper—ture —˜ove THH ◦ gD pyrolysis of esr3 ™—n o™™ur even without q—es or q—D @TFPIAF @TFPHA @TFPIA 6. (ad) —nd q—@gr3 A3(ad) do not re—™t with esr3 in the „wqEesr3 systemF wonomole™ul—r l—yer growth is limited ˜y the form—tion of q—gr3 —nd its re—™tion with esr3 F .3 Adsorption and surface reactions prom the temper—ture dependent me—surements of the desorption spe™trum from — surf—™e on whi™h „wq w—s suppliedD it w—s estim—ted th—t the surf—™eE—dsor˜ed spe™ies w—s q— —t the high temper—ture region of „sub > SHH ◦ gD q—gr3 —t the r—nge of QSH ◦ g < „sub < SHH ◦ gD —nd q—@gr3 A2 —nd q—@gr3 A3 —t the r—nge of „sub < QSH ◦ gF „he re—™tionsD where @—dA me—ns the —dsor˜ed st—te of the mole™ulesD —reX @TFPPA @TFPQA @TFPRA @TFPSA ‡hen esr3 is suppliedD the re—™tions with these —dsor˜—tes —reX @TFPTA @TFPUA @TFPVA @TFPWA st w—s o˜served th—t there is no growth in the r—nge of „sub < QSH ◦ gD iFeFD q—@gr3 A2 .3.2.

2.PHT 6. CHEMICAL VAPOR DEPOSITION et lower temper—ture @QSH E SHH ◦ gAD equiv—lently low energyD „wq de™ompose in the g—s ph—se to q—@gr3 A2 —nd methyl r—di™—lD @TFQHAF @TFQHA efter the (rst lig—nd disso™i—tionD there —re two di'erent p—thw—ysD in the (rstD the q—@gr3 A2 keeps deE ™omposing into q—gr3 —nd —nother methyl group when it is —t the g—sEsu˜str—te interf—™eD @TFQIAD —nd then further de™omposes into free g—llium —toms on the su˜str—te surf—™eD @TFQPAF sn the se™ond re—™tionD the q—@gr3 A2 de™omposes dire™tly into q— —nd gr3 Egr3 ˜y redu™tive elimin—tionD @TFQQAF @TFQIA @TFQPA @TFQQA et high temper—ture @> SHH gAD the „wq de™omposes into q—@gr3 A —nd two methyl groups inste—d of the stepEwise de™omposition —t lower temper—tureD @TFQRAD —nd the q—@gr3 A further de™omposes into free q— —toms —t the su˜str—te surf—™eD @TFQSAF ◦ @TFQRA @TFQSA „he de™omposition of esr3 forms —n —rseni™ ™loud in the re—™tion ™h—m˜erF „he de™omposition is —lso stepEwiseX @TFQTA @TFQUA @TFQVA „he methyl groups in the surf—™e q—@gr3 A mole™ules —re removed ˜y the form—tion of meth—ne with —tomi™ hydrogen from the de™omposition of esr3 D @TFQWAF @TFQWA .3.2.4 Overall reaction pathway CHAPTER 6.

Crys.D IWVWD 54D TSTF • wF ‚F veys —nd rF †eenvlietD J.PHU 6. Phys. GrowthD IWVID 55D IRSF • …F wemmert —nd wF vF ‰uD Appl.5 Kinetics for other systems snvestig—tions h—ve ˜een reported for the me™h—nism of the growth of q—es using triethylg—llium ‘q—@gr2 gr3 A3 D „iq“ —nd „wq with trimethyl—rsene ‘es@gr3 A3 D „we“D triethyl—rsene ‘es@gr2 gr3 A3 D „ie“D tertE˜utyl—rsine {‘@gr3 A3 g“esr2 D „fe}D —nd phenyl—rsine ‘@g6 r5 Aesr2 “F „he experiments were ™ondu™ted in — wyg†h re—™tor equipped with — re™ording mi™ro˜—l—n™e for inEsitu growth r—te me—sureE mentsF por ex—mpleD the kineti™s of the growth of q—es were investig—ted ˜y me—suring growth r—te —s — fun™tion of temper—ture using the mi™ro˜—l—n™e re—™tor while holding the p—rti—l pressure of g—llium pre™urE sor @eFgFD „wqA —nd —rseni™ pre™ursor ‘eFgFD es@gr3 A3 “ ™onst—nt —t HFHI —nd HFHS „orrD respe™tivelyF „hree di'erent )ow r—tes were used to determine the in)uen™e of the g—s residen™e timeF „he growth r—te of q—es with „wq —nd es@gr2 gr3 A3 is higher —s ™omp—red with the growth from „wq —nd es@gr3 A3 ˜e™—use of the lower therm—l st—˜ility of es@gr2 gr3 A3 th—n es@gr3 A3 F foth of the two growth r—tes showed — strong dependen™e on the residen™e timeF ƒimil—rlyD the kineti™ ˜eh—viors of the „wqG„fe —nd „iqG„fe system were investig—ted under the s—me ™onditions —s the „we —nd „ie studiesF „here —re two distin™t regions of growthF por „wqG„feD the deposition r—te is independent —t low temper—ture —nd in the intermedi—te temper—ture @—round THH ◦ gA the dependen™e of the growth r—te on the tot—l )ow r—te is signi(™—ntF „his me—ns th—t the growth —t the lower temper—ture is ™ontrolled ˜y surf—™e re—™tionsF „he „iqG„fe system showed — simil—r ˜eh—vior ex™ept th—t the m—ximum growth r—te o™™urs —round RSH ◦ g while it is —round USH ◦ g for „wqG„fe systemF elsoD the growth of „wqG@g6 r5 Aesr2 w—s studied on the s—me ™onditions —s for the we3 q—Gt fuesr2 systemF st w—s reported th—t the di'eren™e in the growth r—te —t v—rious )ow r—tes w—s rel—ted to — ™om˜in—tion of p—r—siti™ re—™tions —nd depletion e'e™ts from depositionF prom the ™omp—rison of the d—t—D it is dedu™ed th—t the e'e™t of p—r—siti™ re—™tions is slightly sm—ller for @g6 r5 Aesr2 th—n for „feF „wo possi˜le me™h—nisms for the dependen™e of growth r—te on )ow r—te were proposedF „he (rstD m—ssEtr—nsfer limit—tion w—s thought to ˜e unlikely ˜e™—use of the high di'usivity of the g—llium pre™ursors —t I „orr @™—F QSH ™m2 GsAF „he se™ondD —lso the more likely expl—n—tion for the o˜served growthEr—te dependen™e on )ow r—tes is g—sEph—se depletion ™—use ˜y the p—r—siti™ re—™tionsF ƒin™e the growth e0™ien™y is high @RI7 —t UHH ◦ gAD the loss of pre™ursor from the g—s ph—se will dire™tly —'e™t the growth r—teF st w—s eviden™ed ˜y the di'eren™es in the growth r—tes ˜etween split —nd ™om˜ined feed stre—msF „he growth r—te is lower when the re—gents —re ™om˜ined upstre—m of the re—™tor th—n when they —re ™om˜ined inside the re—™tor @split stre—mAF st ís suggested th—t the experiment—l o˜serv—tions ™—n ˜e expl—ined ˜y — model ˜—sed on the reversi˜le form—tion of —n —ddu™t —nd the de™omposition of this —ddu™t to useless polymeri™ m—teri—l ™ompeting with the growth of q—esF st ™—n ˜e written in the form shown in @TFRHA where kf —nd kr —re the forw—rd —nd reverse r—te ™onst—nts for —ddu™t form—tionD respe™tivelyD kd is the r—te ™onst—nt for the irreversi˜le de™omposition of the —ddu™t to polymerD —nd ks is the surf—™e re—™tion r—te ™onst—nt for the growth of q—esF st is o˜vious th—t e—™h step involves sever—l element—ry re—™tionsD ˜ut there were insu0™ient d—t— to provide —ny more det—ilF @TFRHA 6.3.2. Phys. Lett.D IWVWD 55D IPRRF • rF sshiiD rF yhnoD uF w—tsuz—ki —nd rF r—seg—w—D J.3 Bibliography • „F rF ghiuD Appl. GrowthD IWWID 115D QSQF • uF uod—m—D wF yzekiD uF wo™hizukiD —nd xF yhtsuk—D Appl. Crys. Phys.2.D IWWHD 56DIVVQF . Crys. GrowthD IWVWD 95D IQPF • uF pF tensen —nd ‡F uernD in „hin pilm €ro™esses ssD idsF tF vF †ossen —nd ‡F uernD e™—demi™ €ressD xew ‰ork @IWWIAF • xF uo˜—y—shiD ‰F ‰—m—u™hiD —nd ‰F rorikoshiD J.2. Lett.3. Lett.

1.2 Deposition variables „he requirements of g†h (lms for ele™troni™ devi™e —ppli™—tions h—ve ˜e™ome in™re—singly more stringent —s devi™e sizes —re ™ontinu—lly redu™edF pilm thi™kness must ˜e uniform —™ross —n entire w—ferD iFeFD ˜etter 5 This content is available online at <http://cnx.3 X gomp—rison of di'erent deposition methods for ƒiy2 thin (lmsF 6. .1 Chemical Vapor Deposition of Silica Thin Films 6. Mater.4/>. SocFD IWUUD 124D STWF ‡—t—n—˜eD „F ssuD wF r—t—D „F u—mijohD —nd ‰F u—t—y—m—D Japan.4.D IWWHD 2D QWF hF tF ƒ™hyer —nd wF eF ‚ingD J.1.1 Deposition methods sn reg—rd to the g†h of insul—ting (lms in gener—lD —nd sili™— (lms in p—rti™ul—rD three gener—l re—™tors —re presently usedX —tmospheri™ pressure g†h @e€g†hAD low —nd medium temper—ture low pressure g†h @v€g†hAD —nd pl—sm—Eenh—n™ed g†h @€ig†hAF v€g†h is often further divided into low —nd high temE per—turesF e€g†h systems —llow for high throughput —nd even ™ontinuous oper—tionD while v€g†h provides for superior ™onform—l step ™over—ge —nd ˜etter (lm homogeneityF €ig†h h—s ˜een tr—dition—lly used where low temper—tures —re requiredD howeverD (lm qu—lity is often poorF es ™omp—red to €ig†hD photoE—ssisted g†h h—s the —ddition—l —dv—nt—ge of highly sele™tive depositionD —lthough it h—s ˜een little used in ™ommer™i—l systemsF „—˜le TFQ summ—rizes the —dv—nt—ges —nd dis—dv—nt—ges of e—™h type of g†h system ™ommer™i—lly used for ƒiy2 (lmsF Atmospheric pressure CVD Low temperature LPCVD Medium temperature LPCVD Plasma enhanced CVD „emper—ture @ ◦ gA „hroughput ƒtep ™over—ge pilm properties …ses QHH E SHH high poor good p—ssiv—tionD insuE l—tion QHH E SHH high poor good p—ssiv—tionD insuE l—tion SHH E WHH high ™onform—l ex™ellent insul—tion IHH E QSH low poor poor p—ssiv—tionD insuE l—tion Table 6.1. Electrochem.4 Oxide Chemical Vapor Deposition 6. GrowthF IWVVD 93D IQPF „F ‚F ymste—d —nd uF pF tensenD Chem.1 General considerations 5 fefore des™ri˜ing individu—l ™hemi™—l v—por deposition @g†hA systems for the deposition of sili™— thin (lmsD it is worth outlining gener—l ™onsider—tions to ˜e t—ken into —™™ount with reg—rd to the growth ˜y g†h of —ny insul—ting (lmX the type of g†h methodD deposition v—ri—˜lesD —nd limit—tions of the pre™ursorF 6.4. BD IWVWD 48D WUF ‰F h—ngD ‡F wF gle—verD wF ƒtukeD —nd eF ‚F f—rronD Appl. Phys.1.PHV CHAPTER 6. Phys.4. Crys.4. CHEMICAL VAPOR DEPOSITION tF xishiz—w— —nd „F uur—˜—y—shiD J. AD IWWPD 55D PTIF • • • • • • 6.1. PhysFD IWVWD 28D vIHVHF ‰F h—ngD „hF feuerm—nnD —nd wF ƒtukeD Appl. Appl.

4. 6.PHW th—n ±I7F „he stru™ture of the (lm —nd its ™omposition must ˜e ™ontrolled —nd reprodu™i˜leD ˜oth on — single w—ferD —s well —s ˜etween w—fer s—mplesF st is —lso desir—˜le th—t the pro™ess is s—feD inexpensiveD —nd e—sily —utom—tedF e num˜er of v—ri—˜les determine the qu—lity —nd r—te of (lm growth for —ny m—teri—lF sn gener—lD the deposition r—te in™re—ses with in™re—sed temper—ture —nd follows the errhenius equ—tionD @TFRIAD where ‚ is the deposition r—teD ia is the —™tiv—tion energyD „ is the temper—ture @uAD e is the frequen™y f—™torD —nd k is foltzm—nn9s ™onst—nt @IFQVI x IH-23 tGuAF @TFRIA et the high temper—tures the r—te of deposition ˜e™omes m—ss tr—nsport limitedF we—ningD the r—te of surf—™e re—™tion is f—ster th—n the r—te —t whi™h pre™ursors —re tr—nsported to the surf—™eF sn multiple sour™e systemsD the (lm growth r—te is dependent on the v—por ph—se ™on™entr—tion @or p—rti—l pressureA of e—™h of the re—™t—ntsD ˜ut in ™ert—in ™—ses the r—tio of re—™t—nts is —lso import—ntD eFgFD the ƒir4 Gy2 growth of ƒiy2 F ƒurf—™e ™—t—lyzed re—™tions ™—n —lso —lter the deposition r—teF ƒu™h —s the nonEline—r dependen™e of the deposition r—te of ƒiy2 on the p—rti—l pressure of ƒi@yitA4 F q—s depletion m—y —lso ˜e signi(™—nt requiring either — therm—l r—mp in the ™h—m˜er —ndGor spe™i—l re—™tor designsF „he ne™ess—ry in™orpor—tion of dop—nts usu—lly lowers deposition r—tesD due to ™ompetitive surf—™e ˜indingF por the —ppli™—tions of insul—ting m—teri—ls —s isol—tion l—yersD —n import—nt ™onsider—tion is step ™over—geX whether — ™o—ting is uniform with respe™t to the surf—™eF pigure TFIH— shows — s™hem—ti™ of — ™ompletely uniform or ™onform—l step ™over—ge of — tren™h @su™h —s o™™urs ˜etween isol—ted devi™esA where the (lm thi™kness —long the w—lls is the s—me —s the (lm thi™kness —t the ˜ottom of the stepF …niform step ™over—ge results when re—™t—nts or re—™tive intermedi—tes —re —˜le to migr—te r—pidly —long the surf—™e ˜efore re—™tingF ‡hen the re—™t—nts —dsor˜ —nd re—™t without signi(™—nt surf—™e migr—tionD deposition is dependent on the me—n free p—th of the g—sF pigure TFIH˜ shows —n ex—mple of minim—l surf—™e migr—tion —nd — short me—n free p—thF por ƒiy2 (lm growth v€g†h h—s highly uniform ™over—ge @pigure TFIH—A —nd €ig†h poor step ™over—ge @pigure TFIH˜AF Figure 6.1.10: Step coverage of deposited lms with (a) uniform coverage resulting from rapid surface migration and (b) nonconformal step coverage due to no surface migration.3 Precursor considerations „he gener—l requirements for —ny g†h pre™ursor h—ve ˜een —dequ—tely reviewed elsewhereD —nd will not ˜e ™overed hereF roweverD m—ny of the g—ses —nd org—nomet—lli™s used to deposit diele™tri™ (lms —re h—z—rdousF „he s—fety pro˜lems —re more severe for v€g†h ˜e™—use the pro™ess often uses no diluent g—s su™h —s —rgon or nitrogenF „—˜le TFR lists the ˜oiling point —nd h—z—rds of ™ommon inorg—ni™ —nd org—nomet—lli™ pre™ursor .1.

2 CVD silica (SiO2 ) „he pro™essing sequen™e for sili™on dioxide @ƒiy2 A used depends on its spe™i(™ useF g†h pro™esses for ƒiy2 (lms ™—n ˜e ™h—r—™terized ˜y either the ™hemi™—l re—™tion typeD the growth pressureD or the deposition temper—tureF „he ™hoi™e of route is often di™t—ted ˜y requirements of the therm—l st—˜ility of the su˜str—te or the ™onform—lityF „—˜le TFS summ—rizes sele™ted properties of ƒiy2 grown ˜y v—rious g†h methodsD in ™omp—rison to th—t of therm—lly grown sili™—F sn gener—lD sili™— grown —t high temper—tures resem˜le therm—lly grown n—tive ƒiy2 F roweverD the use of —luminum met—lliz—tion requires low temper—ture deposition of sili™—F Deposition Plasma ◦ SiH4 + O2 Si(OEt)4 SiCl2 H2 + N2 O Thermal „emper—ture @ gA gomposition ƒtep ™over—ge „herm—l st—˜ility ‚efr—™tive idex hiele™tri™ ™onst—nt Table 6.9 @rA nonE™onform—l loses r IFRU RFW RSH ƒiy2 @rA nonE™onform—l densi(es IFRR RFQ UHH ƒiy2 ™onform—l st—˜le IFRT RFH WHH ƒiy2 @glA ™onform—l loses gl IFRT RFH IHHH ƒiy2 ™onform—l st—˜le IFRT QFW X gomp—rison of physi™—l properties of ƒiy2 grown ˜y ™ommer™i—l g†h methodsF .4 xr3 er esr3 f2 r6 ƒigl2 r2 r2 x2 x2 y y2 €r3 ƒir4 EQQFQS EIVSFU ESS EWPFS VFQ EPSPFV EPHWFVT EVVFS EIVPFWTP EVUFU EIIIFV toxi™D ™orrosive inert toxi™ toxi™D )—mm—˜le toxi™D )—mm—˜le )—mm—˜le inert oxidizer oxidizer toxi™D €2 r4 impuritiesD )—mm—˜le )—mm—˜leD toxi™ X €hysi™—l —nd h—z—rd properties of ™ommon g—seous sour™es for g†h of diele™tri™ m—teri—lsF sn prin™ipleD the deposition of — ƒiy2 D or sili™—D thin (lm ˜y g†h requires two ™hemi™—l sour™esX the element @or elementsA in questionD —nd —n oxygen sour™eF ‡hile dioxygen @y2 A is suit—˜le for m—ny —ppli™—E tionsD its re—™tions m—y ˜e too f—st or too slow for optimum (lm growthD requiring th—t —ltern—tive oxygen sour™es ˜e usedD eFgFD nitrous oxide @x2 yA —nd ozone @y3 AF e ™ommon nonEoxidizing oxygen sour™e is w—terF e more —dv—nt—geous —ppro—™h is to in™orpor—te oxygen into the lig—nd environment of the pre™ursorD —nd ende—vor to preserve su™h —n inter—™tion int—™t from the sour™e mole™ule into the ultim—te (lmY su™h — sour™e is often termed — 4singleEsour™e4 pre™ursorF 6.4.PIH CHAPTER 6.1.5 PHH ƒiy1. CHEMICAL VAPOR DEPOSITION sour™es for g†h of ƒiy2 —nd doped sili™—F w—ny of the pre™ursors re—™t with —ir to form solid produ™tsD thus le—ks ™—n ™—use p—rti™les to form in the ™h—m˜er —nd g—s linesF Gas Formula Bpt ( ◦ C) Hazard —mmoni— —rgon —rsine di˜or—ne di™hlorosil—ne hydrogen nitrogen nitrous oxide oxygen phosphine sil—ne Table 6.

1.PII 6.2.1 CVD from hydrides „he most widely used method for ƒiy2 thin (lm g†h is the oxid—tion of sil—ne @ƒir4 AD (rst developed in IWTU for e€g†hF xonethelessD v€g†h systems h—ve sin™e ˜e™ome in™re—singly employedD —nd ex™eption—lly high growth r—tes @QHDHHH ÅGminA h—ve ˜een o˜t—ined ˜y the use of r—pid therm—l g†hF „he ™hemi™—l re—™tion for ƒiy2 deposition from ƒir4 isX @TFRPA et high oxygen p—rti—l pressures —n —ltern—tive re—™tion o™™ursD resulting in the form—tion of w—terF @TFRQA ‡hile these re—™tions —ppe—rs simpleD the det—iled me™h—nism involves — ™omplex ˜r—n™hingE™h—in sequen™e of re—™tionsF „he —pp—rent —™tiv—tion energy is low @< RI ktGmolA —s — ™onsequen™e of its heterogeneous n—tureD —nd involves ˜oth surf—™e —dsorption —nd surf—™e ™—t—lysisF xitrous oxide @x2 yA ™—n ˜e used —s —n —ltern—tive oxygen sour™e to y2 D —™™ording to the over—ll re—™tionD @TFRRAF @TFRRA e simple kineti™ s™heme h—s ˜een developed to expl—in m—ny of the o˜served —spe™ts of ƒir4 Ex2 y growthF st w—s suggested th—t the re—™tion is initi—ted ˜y de™omposition of x2 yD @TFRSAD gener—ting —n oxygen r—di™—l whi™h ™—n —˜str—™t hydrogen from sil—ne forming — hydroxyl r—di™—lD @TFRTAD th—t ™—n re—™t further with sil—neD @TFRUAF @TFRSA @TFRTA @TFRUA ividen™e for the re—™tion of the yr r—di™—l to form w—ter is the form—tion of — sm—ll qu—ntity of w—ter o˜served during the oxid—tion of ƒir4 F ƒilyl r—di™—ls —re oxidized ˜y x2 y to form siloxy r—di™—lsD @TFRVAD whi™h provide — suit—˜le prop—g—tion stepD @TFRWAF @TFRVA @TFRWA st h—s ˜een proposed th—t the sil—nol @ƒir3 yrA is the penultim—te (lm pre™ursorF „he ƒir4 Ey2 —nd ƒir4 Ex2 y routes to ƒiy2 thin (lms —re perh—ps the most widely studied photo™hemi™—l g†h system of —ll diele™tri™sF €hotoEg†h of ƒiy2 provides — suit—˜le route to deposition —t low su˜str—te temper—turesD there˜y —voiding potenti—l therm—l e'e™ts of w—fer w—rp—ge —nd deleterious dop—nt redistriE ˜utionF sn —dditionD unlike other low temper—ture methods su™h —s e€g†h —nd €ig†hD photoEg†h often provides good purity of (lmsF e summ—ry of ™ommon sil—ne g†h systems is given in „—˜le TFTF .4.

4. ( ◦ C) Growth (Å/min) rate y2 y2 y2 y2 x2 y x2 y x2 y x2 y Table 6.1.4.PIP Oxygen source Carrier (diluent) gas CHAPTER CHEMICAL VAPOR DEPOSITION CVD method Deposition temp.3 CVD from tetraethoxylsilane (TEOS) „he (rst g†h pro™ess to ˜e introdu™ed into semi™ondu™tor te™hnology in IWTI w—s th—t involving the pyrolE ysis of tetr—ethoxysil—neD ƒi@yitA4 @™ommonly ™—lled „iyƒ from tetr—ethylorthosili™—teAF heposition o™™urs —t —n optimum temper—ture —round USH ◦ gF roweverD under v€g†h ™onditionsD the growth temper—ture ™—n ˜e signi(™—ntly lowered @> THH ◦ gAF „he high temper—ture growth of ƒiy2 from „iyƒ involves no extern—l oxygen sour™eF hisso™i—tive —dsorption studies indi™—te th—t de™omposition of the „iyƒEderived surf—™e ˜ound diE —nd triEethoxysilox—nes is the dire™t sour™e of the ethyleneF €ig†h signi(™—ntly lowers deposition temper—tures using „iyƒD ˜ut requires the —ddition of y2 to remove ™—r˜on ™ont—min—tionD vi— the form—tion of g—seous gy —nd gy2 D whi™h —re su˜sequently not in™orE por—ted within the (lmF elthough deposition —s low —s IHH ◦ g m—y ˜e o˜t—inedD the (lm resistivity in™re—ses ˜y three orders of m—gnitude ˜y depositing —t PHH ◦ gY ˜eing IH16 ΩF™mD with — ˜re—kdown strength of U x IH6 †G™mF eddition of y2 for e€g†h growth does not de™re—se the deposition temper—tureD howeverD if ozone @y3 A is used —s the oxid—tion sour™eD deposition temper—tures —s low —s QHH ◦ g m—y ˜e o˜t—ined for uniform ™r—™kEfree (lmsF st h—s ˜een postul—ted th—t the ozone tr—ps the „iyƒ mole™ule on the surf—™e —s it re—™ts with the ethoxy su˜stituentD providing — lower energy p—thw—y @„iyƒEy3 d SS ktGmol versus „iyƒEy2 d PQH ktGmol —nd „iyƒ only d IWH ktGmolAF „here —re signi(™—nt —dv—nt—ges of the „iyƒGy3 systemD for ex—mple the superior step ™over—ge it providesF purthermoreD (lms h—ve low stress —nd low p—rti™le ™ont—min—tionF yn this ˜—sis the „iyƒGy3 system h—s ˜e™ome widely used for sili™—D —s well —s sili™—te gl—ssesF .2 CVD from halides „he most widely used pro™ess of the high temper—ture growth of ƒiy2 ˜y v€g†h involves the x2 y oxid—tion of di™hlorosil—neD ƒigl2 r2 D @TFSHAF @TFSHA heposition —t WHH E WIS g —llows for growth of ƒiy2 (lms —t caF IPH ÅGminY howeverD these (lms —re ™ont—min—ted with glF eddition of sm—ll —mounts of y2 is ne™ess—ry to remove the ™hlorineF ‡hile €ig†h h—s ˜een employed utility h—lide pre™ursorsD the —˜ility of sm—ll qu—ntities of )uorine to improve the ele™tri™—l properties of ƒiy2 h—s prompted investig—tion of the use of ƒip4 —s — suit—˜le sour™eF ◦ 6.6 x2 er erGx2 er x2 x2 x2 er e€g†h v€g†h v€g†h €ig†h e€g†h v€g†h v€g†h €ig†h QSH E RUS IHH E SSH PS E SHH PS E PHH RWH E TWH UHH E VTH PS E QSH IHH E PHH IHH E IRDHHH IHH E QHDHHH IH E RSH PHH E WHH PHH E IDPHH caF SH U E IVH VH E VHH X €re™ursors —nd deposition ™onditions for ƒiy2 g†h using sil—ne @ƒir4 AF 6.

11: en interesting ™on™ept h—s ˜een to preform the EƒiEyEƒiE fr—mework in the pre™ursorF sn this reg—rdD the novel pre™ursor „8 Ehydridospherosilox—ne @r8 ƒi8 y12 D pigure TFIIdA gives smooth —morphous stoi™hiometri™ ƒiy2 —t RSH E SPS ◦ g ˜y v€g†hF „he de™omposition me™h—nism in the presen™e of —dded oxygen involves the loss of w—terD @TFSIAF s‚ studies indi™—te th—t the ƒiEyEƒi ˜onds —re preserved during depositionF ‡hile (lms —re of high qu—lityD the present synthesis of r8 ƒi8 y12 is of low yield @caF PI7AD m—king it ™urrently impr—™ti™—l for l—rge s™—le pro™essingF @TFSIA .4.2. Figure 6.PIQ 6.1.4 CVD from other organosilicon precursors e wide r—nge of —ltern—tive sili™on sour™es h—s ˜een investig—tedD espe™i—lly with reg—rd to either lower temper—ture deposition —ndGor pre™ursors with gre—ter —m˜ient st—˜ilityF hiethylsil—ne @it2 ƒir2 AD IDREdisl—˜ut—ne @hfƒD r3 ƒigr2 gr2 ƒir3 AD PDRDTDVEtetr—methyl™y™lotetr—silox—ne @„wg„ƒD pigure TFII—D where ‚ a gr3 AD —nd PDRDTDVEtetr—ethyl™y™lotetr—silox—ne @„ig„ƒD pigure TFII—D where ‚ a g2 r5 AD h—ve ˜een used in ™onjun™tion with y2 over deposition temper—tures of IHH E THH ◦ gD depending on the pre™ursorF hi—™etoxydiEtertE˜utyl sil—ne @hehfƒD pigure TFII˜A h—s ˜een used without —ddition—l oxid—tion sour™esF righ qu—lity sili™on oxide h—s ˜een grown —t QHH ◦ g ˜y e€g†h using the —mido pre™ursorD ƒi@xwe2 A4 @pigure TFII™AF Alternative organometallic silicon sources that have been investigated for the growth of silica thin lms.

Figure 6.4.1. CHEMICAL VAPOR DEPOSITION forosili™—te gl—sses @fƒqAD phosphosili™—te gl—sses @€ƒqA —nd ˜orophosphosili™—te gl—sses @f€ƒqA —re freE quently used —s insul—ting l—yers sep—r—ting ™ondu™ting l—yersF „hese gl—sses h—ve lower intrinsi™ stressD lower melting temper—tures —nd ˜etter diele™tri™ properties th—n ƒiy2 itselfF €ƒq —nd f€ƒq h—ve the —dded property of gettering —nd immo˜ilizing dop—ntsF €—rti™ul—rly import—nt is the gettering of sodium ionsD whi™h —re — sour™e of interf—™e tr—psF „he low temper—ture molten properties of fƒqD €ƒqD —nd f€ƒq gl—sses —llow for the smoothing of the devi™e topogr—phy ˜y vis™ous therm—l fusion to ™onvert —˜rupt steps to more gr—du—lly t—pered steps @pigure TFIP—A —s well —s pl—n—riz—tion of ™omplex topologies @pigure TFIP˜AD en—˜ling deposition of ™ontinuous met—l l—yersF „his pro™ess is ™ommonly ™—lled €Egl—ss )owF „he ˜oron —nd phosphorous ™ontents of the sili™—te gl—sses v—ryD depending on the —ppli™—tionD typi™—lly ˜eing from P to V weight per ™entF Schematic cross section of BPSG as deposited (a) and after annealing (b).3 CVD silicate glasses CHAPTER 6.PIR 6. showing the ow causing a decrease in the angle of the BPSG going over the step.12: „he —dv—nt—ge of f€ƒq over €ƒq is th—t )ow o™™urs over the temper—ture r—nge of USH E WSH ◦ gD depending on the rel—tive € —nd f ™ontent @—s opposed to WSH E IIIH ◦ g for €ƒqAF vowering of the )ow temper—ture is required to minimize dop—nt migr—tion in †vƒs devi™esF gonverselyD the dis—dv—nt—ges of f€ƒq versus €ƒq in™lude the form—tion of ˜u˜˜les of vol—tile phosphorous oxides —nd ™ryst—llites of ˜oronE ri™h ph—sesF sfD howeverD the dop—nt ™on™entr—tion is ™ontrolledD these e'e™ts ™—n ˜e minimizedF ersenosili™—tes @esƒqA were employed origin—lly in sili™on devi™e te™hnology —s —n —rseni™ dop—nt sour™e for pl—n—r su˜str—tes prior to the —dvent of l—rge s™—le ion impl—nt—tion whi™h h—s l—rgely removed the need for esƒq in doping —ppli™—tionsF roweverD with …vƒs sili™on ™ir™uit f—˜ri™—tionD the requirement for doping of deep tren™hes @in—™™essi˜le to ion impl—nt—tionA h—s witnessed the reEemergen™e of interest in esƒq (lmsF „he g†h growth of sili™—te gl—sses follows th—t of ƒiy2 D with ƒir4 —nd „iyƒ ˜eing the most ™ommonly employed sili™on pre™ursorsF e summ—ry of ™ommon g†h pre™ursor systems for sili™—te gl—sses is given in „—˜le TFUF .

3.PIS Precursors CVD method Deposition temp.1.1 CVD from hydrides pilms of fƒqD €ƒqD —nd f€ƒq m—y —ll ˜e grown from ƒir4 D y2 —nd f2 r6 —ndGor €r3 D —t QHH E TSH ◦ gF por e€g†hD the re—™t—nts —re diluted with —n inert g—s su™h —s nitrogenD —nd the y2 Ghydride mol—r r—tio is ™—refully ™ontrolled to m—ximize growth r—te —nd dop—nt ™on™entr—tion @v—lues of I to IHH —re used depending on the —ppli™—tionAF yrdin—rilyD the dop—nt ™on™entr—tion for ˜oth fƒq —nd €ƒq de™re—ses with in™re—sed temper—tureF roweverD some reports indi™—te —n in™re—se in ˜oron ™ontent with in™re—sed temper—tureF pilm growth of f€ƒq w—s found to o™™ur in two temper—ture regionsF heposition —t low temper—ture @PUH E QTH ◦ gA o™™urred vi— — surf—™e re—™tion r—te limiting growth @ia a QW k™—lGmolAD while —t higher temper—ture @QSH E RSH ◦ gAD — m—ssEtr—nsport r—te limited re—™tion region is o˜served @ia a UFT k™—lGmolAF v€g†h of fƒq —nd €ƒq is ™ondu™ted —t RSH E SSH ◦ g with —n y2 Xhydride r—tio of IXIFSF gonverselyD —n y2 Xhydride r—tio of IFSXI provides the optimum growth ™onditions for f€ƒq over the s—me temper—ture r—ngeF „he phosphorous in €ƒq (lms w—s found to exist —s — mixture of €2 y5 —nd €2 y3 D howeverD the l—tter ™—n ˜e minimized under the ™orre™t deposition ™onditionsF ƒome di0™ulties h—ve ˜een reported for the use of f2 r6 due to its therm—l inst—˜ilityF ƒu˜stitution of f2 r6 with fgl3 o˜vi—tes this pro˜lemD —lthough the resulting (lms —re inv—ri—˜ly ™ont—min—ted with I weight per ™ent ™hlorideF . ( ◦ C) Applications ƒir4 Gf2 r6 ƒir4 Gf2 r6 ƒir4 G€r3 ƒir4 G€r3 ƒir4 Gf2 r6 G€r3 ƒir4 Gf2 r6 G€r3 ƒir4 Gesr3 „iyƒGf@yweA3 „iyƒGf@yweA3 „iyƒGf@yitA3 „iyƒGf@yitA3 „iyƒG€r3 „iyƒGya€@yweA3 „iyƒG€@yweA3 „iyƒGya€@yweA3 „iyƒGf@yweA3 G€r3 „iyƒGf@yweA3 G€@yweA3 „iyƒGf@yweA3 Gya€@yweA3 „iyƒGesgl3 „iyƒGes@yitA3 „iyƒGyaes@yitA3 Table 6.7 e€g†h v€g†h e€g†h v€g†h e€g†h v€g†h e€g†h e€g†h v€g†h e€g†h v€g†h v€g†h e€g†h v€g†h v€g†h v€g†h v€g†h v€g†h e€g†h v€g†h v€g†h QHH E RSH QSH E RHH QHH E RSH QSH E RHH QHH E RSH QSH E RHH SHH E UHH TSH E UQH SHH E USH RUS E VHH SHH E USH TSH QHH E VHH SHH E USH SHH E VHH TPH E VHH TUS E USH TVH SHH E UHH UHH E UQH UHH E UQH good step ™over—ge E E )ow gl—ss E E E di'usion sour™e tren™h (lling di'usion sour™e di'usion sour™e )ow gl—ss )ow gl—ss di'usion sour™e )ow gl—ss tren™h (lling )ow gl—ss )ow gl—ss di'usion sour™e tren™h doping tren™h doping X €re™ursors —nd deposition ™onditions for g†h of ˜orosili™—te gl—ss @fƒqAD phososili™—te gl—ss @€ƒqAD ˜orophosphosili™—te gl—ss @f€ƒqA —nd —rsenosili™—tes @esƒqA thin (lmsF 6.4.

Optics Electron. Electrochem.D IWWHD 137D ISHIF 6. Electrochem.1 Alumina 6 elumin—D el2 y3 D exists —s multiple ™ryst—lline formsD howeverD the two most import—nt —re the α —nd γ formsF αEel2 y3 @™orundumA is st—˜le —t high temper—tures —nd its stru™ture ™onsists of — hex—gon—l ™loseEp—™ked —rr—y of oxide @y2.2 Chemical Vapor Deposition of Alumina 6. Soc. Soc.4. IWVHD 23D IHRF • eF ‚F f—rron —nd ‡F ƒF ‚eesD trFD Adv.D IWWHD 137D PVVQF • ‚F eF vevy —nd uF x—ss—uD J.1.1. IWTUD 28D ISQF • gF €—veles™uD tF €F w™†ittieD gF gh—ngD uF gF ƒ—r—sw—tD —nd tF ‰F veongD Thin Solid FilmsD IWWPD 217D TVF • tF hF gh—ppleEƒokolD gF tF qiunt—D —nd ‚F qF qordonD J. Mater.D IWWQD 2D PUIF • xF qoldsmith —nd ‡F uernD RCA Rev. CHEMICAL VAPOR DEPOSITION ersenosili™—te gl—ss @esƒqA thin (lms —re gener—lly grown ˜y e€g†h using —rsine @esrQAY the use of whi™h is ˜eing limited due to its high toxi™ityF roweverD —rsine inhi˜its the g—s ph—se re—™tions ˜etween ƒir4 —nd y2 D su™h th—t (lm grown from ƒir4 Gesr3 Gy2 show improved step ™over—ge —t high deposition r—tesF 6.. Soc.PIT CHAPTER 6.3. SocFD IWTID 108D RUVF • uF pujinoD ‰F xishimotoD xF „okum—suD —nd uF w—ed—D J.A ions with the el3+ ions o™™upying o™t—hedr—l intersti™esF sn ™ontr—stD γ Eel2 y3 h—s — defe™t spinel stru™tureD re—dily t—kes up w—ter —nd dissolves in —™idF hespite the potenti—l dis—dv—nt—ges of γ Eel2 y3 there is — preferen™e for its deposition on sili™on su˜str—tes ˜e™—use of the two di'erent l—tti™eE m—t™hing rel—tionships of γ Eel2 y3 @IHHA on ƒi@IHHAF „hese —re shown —s s™hem—ti™ di—gr—ms in pigure TFIQF e summ—ry of g†h pre™ursor systems for el2 y3 is given in „—˜le TFVF 6 This content is available online at <http://cnx. Electrochem.4. Electrochem.5/>.2. .2 CVD from metal organic precursors es with ƒiy2 depositionD see —˜oveD there h—s ˜een — trend tow—rds the repl—™ement of ƒir4 with „iyƒ on —™™ount of its —˜ility to produ™e highly ™onform—l ™o—tingsF „his is p—rti™ul—rly —ttr—™tive with respe™t to tren™h (llingF purthermoreD (lms of doped ƒiy2 gl—sses h—ve ˜een o˜t—ined using ˜oth e€g†h —nd v€g†h @typi™—lly ˜elow Q „orrAD with — wide v—riety of dop—nt elements in™ludingX ˜oronD phosphorousD —nd —rseni™D in™luding —ntimonyD tinD —nd zin™F foronE™ont—ining gl—sses —re gener—lly grown using either trimethyl˜or—teD f@yweA3 D or triethyl˜or—teD f@yitA3 D —lthough the multiEelement sour™eD tris @trimethylsilylA˜or—teD f@yƒiwe3 A3 D h—s ˜een employed for ˜oth sili™on —nd ˜oron in f€ƒq thin (lm growthF ƒimil—rlyD where—s €r3 m—y ˜e used —s the phosphoE rous sour™eD trimethylphosphiteD €@yweA3 D —nd trimethylphosph—teD ya€@yweA3 D —re preferredF vikewiseD triethoxy—rsineD es@yitA3 D —nd triethyl—rsen—teD yaes@yitA3 D h—ve ˜een employed for esƒq growthF „he ™oEre—™tion of „iyƒ with org—no˜oron —nd org—nophosphorous ™ompounds —llows for deposition —t lower temper—tures @SHH E TSH ◦ gA th—n for hydride growth of ™omp—r—˜le r—tesF roweverD v€g†hD using —n —ll org—nomet—lli™ —ppro—™hD requires €@yweA3 ˜e™—use the low re—™tivity of ya€@yweA3 prevents signi(™—nt phosphorus in™orpor—tionF elthough prem—ture de™omposition of €@yweA3 o™™urs —t THH ◦ g @le—ding to nonEuniform growthAD deposition —t SSH ◦ g results in high (lm uniformity —t re—son—˜le deposition r—tesF 6.4 Bibliography • ‡F uern —nd †F ƒF f—nD in Thin Film ProcessesD idsF tF vF †ossenD ‡F uernD e™—demi™ €ressD xew ‰ork @IWUVAF • wF vF r—mmodD Sold State Technol. SocFD IWVUD 136D PWWQF • €F qonzálezD hF pernándezD tF €ouD iF q—r™í—D tF ƒerr—D fF veónD —nd wF €érezEemorD Thin Solid FilmsD IWWPD 218D IUHF • iF vF tord—nD J.D IWVTD 133D IRIUF • vF uF ‡hiteD tF wF ƒh—wD ‡F eF uuryloD —nd xF wiszkowskiD J.4.4.

Aluminum precursor Oxygen source Carrier gas CVD method Deposition temp.13: Schematic diagram of the crystallographic relations of γ -Al2 O3 on Si(100): (a) γ -Al2 O3 (100)||Si(100).PIU Figure 6. Rees. R. Jr.. and (b) γ -Al2 O3 (100)||Si(110). VCH. Barron. S. ( ◦ C) Comments elgl3 gy2 Gr2 r2 or x2 e€g†h UHH E WHH —morphous @UHHAD ™rysE t—lline @VSH E WHHA depF r—te highly deE pendent on g—sEph—se ™on™F el —nd y2 elwe3 y2 x2 or re e€g†h QSH E QVH continued on next page . CVD of Non-Metals. Ed. New York (1996). W. Adapted from A.

4.1.2.PIV elwe3 y2 x2 CHAPTER 6.4. CHEMICAL VAPOR DEPOSITION v€g†h QUS pl—sm—E enh—n™edD IH ‡ lower qu—lity th—n with y2 good p—ssiv—E tion properties of ƒi wyƒ deE vi™es pl—sm—E enh—n™edD elwe3 elwe3 x2 y x2 y x2 or re x2 e€g†h v€g†h IHH E TTH WSH E IHSH elwe3 el@yi €rA3 el@y €rA3 el@y €rA3 el@—™—™A3 el@—™—™A3 el@—™—™A3 i i x2 y y2 y2 x2 y —ir y2 —nd r2 y re x2 x2 er x2 x2 er €ig†h e€g†h v€g†h v€g†h e€g†h e€g†h v€g†h IPH E QHH RPH E THH PSH E RSH PHH E USH RPH E RSH PSH E THH PQH E SSH epit—xi—l on ƒi high g ™ontent signi(™—nt ™ontent g growth r—te inE depF of r2 y ˜ut (lm qu—lE ity depF on r2 y Table 6.1 CVD from halides „he initi—l use of gy2 Gr2 —s — hydrolysis sour™e for the g†h of ƒiy2 from ƒigl4 D led to the —n—logous deposition of el2 y3 from elgl3 D iFeFD @TFSPA heposition in the temper—ture r—nge UHH E WHH ◦ g w—s found to yield (lms with optimum diele™tri™ propertiesD ˜ut (lms deposited ˜elow UHH ◦ g ™ont—ined signi(™—nt ™hloride impuritiesF st h—s ˜een determined th—t r2 y v—porD formed from r2 —nd gy2 D —™ts —s the oxygen donorD —nd not the gy2 F „he ™ryst—l form of the g†hE grown —lumin— (lms w—s found to depend on the deposition temper—tureY (lms grown ˜elow WHH ◦ g were γ Eel2 y3 D while those grown —t IPHH ◦ g were αEel2 y3 D in —™™ord with the known ph—se di—gr—m for this m—teri—lF 6.2.2 CVD from trimethylaluminum (TMA) elthough trimethyl—luminumD elwe3 @„weAD re—™ts r—pidly with w—ter to yield el2 y3 D the re—™tion is highly exothermi™ @EIPRQ ktGmolA —nd thus di0™ult to ™ontrolF „he oxygen gettering properties of —luminum met—lD howeverD ™—n ˜e employed in the ™ontrolled wyg†h growth of el2 y3 F „he ™ommon deposition ™onditions employed for g†h of el2 y3 from elwe3 —re simil—r to those used for —luminumEmet—l g†hD ˜ut with the —ddition of —n oxygen sour™eD either y2 or x2 yF pilms grown ˜y e€g†h using x2 y —re of inferior qu—lity to those employing y2 D due to their exhi˜iting some opti™—l —˜sorption in the visi˜le w—velength regionF „he growth of high qu—lity (lms using either .8 X €re™ursors —nd deposition ™onditions for el2 y3 g†hF 6.1.

3 CVD from alkoxides and β -diketonates „he pyrophori™ n—ture of elwe3 urged investig—tions into —ltern—tive pre™ursorsD in p—rti™ul—r those whi™h —lre—dy ™ont—in oxygenF eltern—tive pre™ursors might —lso provide possi˜le routes to elimin—te ™—r˜on ™onE t—min—tionF qiven the su™™essful use of „iyƒ in ƒiy2 thin (lm growthD —n —n—logous —lkoxide pre™ursor —ppro—™h is logi™—lF „he (rst report of el2 y3 (lms grown ˜y g†h used —n —luminum —lkoxide pre™ursorsF eluminum trisEiso EpropoxideD el@yi €rA3 D is — ™ommer™i—lly —v—il—˜le inexpensive —lkoxide pre™ursor ™omE poundF heposition m—y ˜e ™—rriedEout ˜y either e€g†h or v€g†hD using oxygen —s —n —ddition—l oxid—tion sour™e to ensure low ™—r˜on ™ont—min—tionF st is —dventitious to use v€g†h @IH „orrA growth to inhi˜it g—s ph—se homogeneous re—™tionsD ™—using form—tion of — powdery depositF „he use of lower ™h—m˜er pressures @Q „orrA —nd x2 y —s the oxide sour™e provided su0™ient improvement in (lm qu—lity to —llow for devi™e f—˜ri™—tionF „he deposition of el2 y3 (lms from the pyrolysis of —luminum —™etyl—™eton—teD el@—™—™A3 @pigure TFIR—AD h—s ˜een widely investig—ted using ˜oth e€g†h —nd v€g†hF „he per™eived —dv—nt—ge of el@—™—™A3 over other —luminum pre™ursors in™ludes loweredEtoxi™ityD good st—˜ility —t room temper—tureD e—sy h—ndlingD high vol—tility —t elev—ted temper—turesD —nd low ™ostF roweverD the qu—lity of (lms w—s origin—lly poorY ™—r˜on ˜eing the m—in ™ont—min—nt resulting from the thermolysis —nd in™orpor—tion of —™etone —nd ™—r˜on dioxide formed upon therm—l de™omposition @pigure TFISAF Figure oxygen sour™e is highly dependent on the g—s ph—se ™on™entr—tions of —luminum —nd oxygenF purther improvements in (lm qu—lity —re o˜served with the use of — temper—ture gr—dient in the ™h—m˜ers deposition zoneF ettempts to lower the deposition temper—ture employing €ig†h h—ve ˜een gener—lly su™™essfulF rowE everD — det—iled spe™tros™opi™ study showed th—t the use of x2 y —s the oxygen sour™e resulted in signi(™—nt ™—r˜on —nd hydrogen in™orpor—tion —t low temper—tures @IPH E QHH ◦ gAF „he ™—r˜on —nd hydrogen ™ont—miE n—tion —re lowered —t high deposition temper—tureD —nd ™ompletely removed ˜y — postEdeposition tre—tment under y2 F st w—s proposed th—t the ™—r˜on in™orpor—ted in the (lms is in the ™hemi™—l form of elEgr3 or elEg@yAyrD while hydrogen exists —s elEyr moieties within the (lmF €hotoE—ssisted g†h of el2 y3 from elwe3 h—s ˜een reported to provide very high growth r—tes @PHHH ÅGminA —nd give (lms with ele™tri™—l properties ™omp—r—˜le to (lms deposited using therm—l or pl—sm— te™hniquesF srr—di—tion with — PRV nm @urpA l—ser sour™e —llowed for uniform deposition —™ross — Q4 w—ferF roweverD use of IWQ nm @erpA irr—di—tion required dilution of the elwe3 ™on™entr—tion to —void nonEuniform (lm growthF 6.14: Aluminum β -diketonate precursors. .

62. J. M.2. G. Charles. Chem.15: Gaseous decomposition products from the pyrolysis of Al(acac)3 as a function of pyrolysis temperature (Data from J. Von Hoene. and W. sn™omplete oxid—tion of the (lm m—y ˜e re—dily solved ˜y the —ddition of w—ter v—por to the ™—rrier g—s stre—mY pure ™—r˜onEfree (lms ˜eing grown —t temper—tures —s low —s PQH ◦ gF sn f—™tD w—ter v—por pl—ys —n import—nt role in the (lm growth kineti™sD (lm purityD —nd the surf—™e morphology of the grown (lmsF ‡hile the growth r—te is un—'e™ted ˜y the —ddition of w—ter v—porD its in)uen™e on the surf—™e morphology is signi(™—ntF pilms grown without w—ter v—por on the el2 y3 surf—™e is rough with p—rti™ul—tesF sn ™ontr—stD (lms grown with w—ter v—por —re mirror smoothF e system—ti™ study of the kineti™s of v—poriz—tion of el@—™—™A3 —long with )uorin—ted —luminum β E diketon—te ™omplexesD el@tf—™A3 @pigure TFIR˜A —nd el@hf—™A3 @pigure TFIR™AD h—s ˜een reportedD —nd the s—tur—tion v—por pressures determined —t US E IUS ◦ gF 6. CHEMICAL VAPOR DEPOSITION Figure 6. 1098).PPH CHAPTER 6. Hickam. Phys..2 Aluminum silicates „he high diele™tri™ ™onst—ntD ™hemi™—l st—˜ility —nd refr—™tory ™h—r—™ter of —luminosili™—tesD @el2 y3 Ax @ƒiy2 Ay D m—kes them useful —s p—™k—ging m—teri—ls in sg ™hip m—nuf—™tureF wullite @Qel2 y3 FPƒiy2 A prep—red ˜y solE gel te™hniquesD is often used —s —n en™—psul—nt for —™tive devi™es —nd thinE(lm ™omponentsF emorphous —lumin—Esili™— (lms h—ve —lso ˜een proposed —s insul—tors in multilevel inter™onne™tionsD sin™e they do not su'er the temper—ture inst—˜ility of —lumin— (lms ret—in the desir—˜le insul—ting ™h—r—™teristi™sF …nder ™ert—in ™onditions of growth —nd f—˜ri™—tionD sili™— m—y ™ryst—llizeD there˜y —llowing di'usion of oxygen —nd impurities —long gr—in ˜ound—ries to the sili™on su˜str—te underne—thF ƒu™h unw—nted re—™tions —re ™—t—strophi™ to the ele™troni™ properties of the devi™eF „he retention of —morphous stru™ture over — l—rger temper—ture r—nge of sili™on ri™h —lumin—Esili™— (lms o'ers — possi˜le solution to this deleterious di'usionF „hin (lms of mixed met—l oxides —re usu—lly o˜t—ined from — mixture of two di'erent kinds of —lkoxide pre™ursorsF roweverD this method su'ers from pro˜lems with stoi™hiometry ™ontrol sin™e extensive e'orts must ˜e m—de to ™ontrol the v—por ph—se ™on™entr—tion of two pre™ursors with often dissimil—r v—por presE suresF elso of import here is the ne—r impossi˜le t—sk of m—t™hing r—tes of hydrolysisGoxid—tion to give 4pure4D nonEph—se segreg—ted (lmsD iFeFD those h—ving — homogeneous ™omposition —nd stru™tureF sn —n e'ort .4. 1958. R.

Mater.16: Precursors for aluminum silicate thin lms. „he elGƒi r—tio of thin (lms growth ˜y e€g†h using ‘el@yƒiit3 A3 “2 —t RPH E SSH ◦ gD w—s found to ˜e dependent on the deposition temper—ture —nd the ™—rrier g—s ™omposition @y2 GerAF „his temper—ture —nd oxygenEdependent v—ri—tion in the (lm ™omposition suggests th—t two ™ompeting pre™ursor de™omposition p—thw—ys —re presentF IF heposition in the —˜sen™e of y2 D is simil—r to th—t o˜served for the de™omposition of el@yi €rA2 @yƒiwe3 A under x2 D —nd would imply th—t the (lm ™omposition is determined ˜y the temper—tureEdependent tenden™ies of the elEyEƒi ˜onds to ™le—veF PF „he temper—tureEindependent oxid—tive de™omposition of the pre™ursorF ‡hile it is possi˜le to prep—re (lms ri™her in ƒi using ‘el@yƒiit3 A3 “2 r—ther th—n el@yi €rA2 @yƒiwe3 AD the elXƒi r—tio is unfortun—tely not e—sily ™ontrolled simply ˜y the num˜er of siloxy lig—nds per —luminum in the pre™ursorF pilms grown from the singleEsour™e pre™ursor el@yi €rA2 @yƒiwe3 A ™ryst—llize to ky—niteD el2 ƒiy5 D where—s those grown from ‘el@yƒiit3 A3 “2 rem—ined —morphous even —fter —nne—lingF 6. Optics Electron. Chem.PPI to solve these pro˜lemsD rese—r™h e'ort h—s ˜een —imed —t singleEsour™e pre™ursorsD iFeFD those ™ont—ining ˜oth —luminum —nd sili™onF „he (rst study of singleEsour™e pre™ursors for @el2 y3 Ax @ƒiy2 Ay (lms employed the monoEsiloxide ™omplex el@yi €rA2 @yƒiwe3 A @pigure TFIT—AF roweverD it w—s found th—t ex™ept for deposition —t very high temper—E tures @> WHH ◦ gA the deposited (lms this monoEsiloxide ™ompound were —luminumEri™h @elGƒi a IFQ E PFIA —nd thus showed therm—l inst—˜ility in the insul—ting properties ™—used ˜y ™ryst—lliz—tion in the (lmsF st would —ppe—r th—t in order for sili™onEri™h —lumin—Esili™— (lms to ˜e grown more silox—ne su˜stituents —re requiredD eFgFD the tris Esiloxy —luminum ™omplex ‘el@yƒiit3 A3 “2 @pigure TFIT˜AF Figure 6. Lett.2. Lett.D IWTVD 115D IHWRF • „F w—ruy—m— —nd „F x—k—iD Appl.D IWWID 58D PHUWF • uF ƒ—w—d—D wF sshid—D „F x—k—mur—D —nd xF yht—keD Appl. Mater. Chem. Phys. Phys. Electronic Mater.D IWWID 1 DIRQF • uF wF qustin —nd ‚F qF qordonD J.D IWVVD 17D SHWF • gF v—ndryD vF uF ghe—th—mD eF xF w—™snnesD —nd eF ‚F f—rronD Adv.D IWVVD 52D ITUQF • tF †on roeneD ‚F qF gh—rlesD —nd ‡F wF ri™k—mD J. Phys.D IWWPD 1D QF • ‰F x—k—ido —nd ƒF „oyoshim—D J.4.3 Bibliography • eF ‡F ep˜lettD vF uF ghe—th—mD —nd eF ‚F f—rronD J. Soc. Electrochem.D IWSVD 62D IHWVF .

2.5 Nitride Chemical Vapor Deposition 6.2 Chemical Vapor Deposition of Silicon Nitride and Oxynitride Introduction to Nitride Chemical Vapor Deposition 7 „he refr—™tory n—ture —nd high diele™tri™ properties of m—ny nitrides m—ke them —ttr—™tive for ™hemi™—l —nd ele™troni™ p—ssiv—tionF es — ™onsequen™e sili™on nitride h—s ˜e™ome the st—nd—rd within the semi™ondu™tor industryD —s ˜oth —n en™—psul—tion l—yer —nd —s —n et™h m—skF sn — simil—r m—nner to oxide growth ˜y ™hemi™—l v—por deposition @g†hAD two sour™es —re gener—lly required for ˜in—ry nitride g†hX the element of ™hoi™e —nd — nitrogen sour™eF roweverD unlike the g†h of oxidesD element—l nitrogen @x2 A is not re—™tiveD even —t elev—ted temper—turesD there˜y requiring pl—sm— enh—n™ementF iven with pl—sm— enh—n™ed g†h @€ig†hAD x2 does not yield high qu—lity (lmsF es — su˜stitute for x2 D —mmoni— @xr3 A h—s found gener—l —™™ept—n™e —s — suit—˜le nitrogen sour™eF st is — g—sD re—dily puri(ed —nd ™he—pD howeverD it is of low re—™tivity —t low temper—turesF €ig†h h—s therefore found f—vor for low temper—ture xr3 E˜—sed pre™ursor systemsF ‚e™ent —ttempts to lower deposition temper—tures h—ve in™luded the use of more re—™tive sour™es @eFgFD r2 xxr2 A —nd pre™ursors ™ont—ining nitrogen —s — ™oordin—ted lig—ndF €ro˜—˜ly the most import—nt dis™overy with respe™t to nitride deposition is the use of — tr—ns—min—tion re—™tion ˜etween —mido ™ompounds —nd —mmoni— @@TFSQAAF @TFSQA 6. .5.1.PPP CHAPTER 6.1 Introduction 8 ƒtoi™hiometri™ sili™on nitride @ƒi3 x4 A is used for ™hemi™—l p—ssiv—tion —nd en™—psul—tion of sili™on ˜ipol—r —nd met—l oxide semi™ondu™tor @wyƒA devi™esD ˜e™—use of its extremely good ˜—rrier properties for w—ter —nd sodium ion di'usionF ‡—ter ™—uses devi™e met—lliz—tion to ™orrodeD —nd sodium ™—uses devi™es to ˜e™ome ele™tri™—lly unst—˜leF ƒili™on nitride is —lso used —s — m—sk for the sele™tive oxid—tion of sili™onD —nd —s — strong diele™tri™ in wxyƒ @met—lEnitrideEoxideEsili™onA stru™turesF „he use of ion impl—nt—tion for the form—tion of —™tive l—yers in q—es wiƒpi„ devi™es @pigure TFIUA —llow for ™ontrol of the —™tive l—yer thi™kness —nd doping densityF ƒin™e impl—nt—tion ™—uses stru™tur—l disorderD the ™ryst—l l—tti™e of the q—es must ˜e su˜je™ted to — post impl—nt—tion r—pid therm—l —nne—l step to rep—ir the d—m—ge —nd to —™tiv—te the impl—nted spe™iesF „he required —nne—ling temper—ture @> VHH ◦ gA is higher th—n the temper—ture —t whi™h q—es de™omposesF ƒili™on nitride en™—psul—tion is used to prevent su™h disso™i—tionF ƒili™on nitride is —lso used for the (n—l en™—psul—tion of q—es wiƒpi„ devi™es @pigure TFIUAF 7 8 This content is available online at <http://cnx.5.1/>.org/content/m26117/1. This content is available online at <http://cnx.1/>.1 Bibliography • hF wF ro'm—nD PolyhedronD IWWRD 13D IITWF 6.5. CHEMICAL VAPOR DEPOSITION 6.

17: Schematic diagrams of a GaAs metal-semiconductor eld eect transistor (MESFET).PPQ Figure 6.. NY (1996). Jr. Barron. in CVD of Nonmetals.9 UHH E VHH ƒi3 x4 @rA HFUS REV TEU PFHI IHIT S PSH E QSH ƒixx ry HFV E IFP PH E PS TEW IFV E PFS IHT E IHIS RES X ƒumm—ry of the properties of sili™on nitride grown in typi™—l ™ommer™i—l systemsF yne of the dis—dv—nt—ges of ƒi3 x4 is its high diele™tri™ ™onst—nt th—t m—y limit devi™e speed —t higher oper—ting frequen™iesF st is hoped th—t sili™on oxynitride @ƒiyxA (lms will exhi˜it the ˜est properties of ƒiQxR —nd ƒiy2 D n—mely the p—ssiv—tion —nd me™h—ni™—l properties of ƒi3 x4 —nd the low diele™tri™ ™onst—nt —nd low stress of ƒiy2 F e summ—ry of some typi™—l g†h systems for sili™on nitride is given in „—˜le TFIHF Silicon cursor preNitrogen source Carrier gas CVD method Deposition temp. Adapted from A. W. Ed. Wiley. Rees. S. ( ◦ C) Comment continued on next page . „he deposition of ƒi3 x4 is — ˜ro—dly pr—™ti™ed industri—l pro™ess using either grown ˜y low pressure g†h @v€g†hA or pl—sm— enh—n™ed g†h @€ig†hA with ™omp—r—˜le properties for the grown (lms @„—˜le TFWAF Deposition LPCVD PECVD qrowth temper—ture @ ◦ gA gomposition ƒiGx r—tio etom7 r hiele™tri™ ™onst—nt ‚efr—™tive index ‚esistivity @ΩF™mA f—nd g—p @e†A Table 6. R.

5.PPR ƒir4 ƒir4 ƒir4 ƒigl2 r2 ƒi2 gl6 it2 ƒir2 ‚ƒi@x3 A3 @‚ a itD t fuA weƒir@xrAn ƒi@xwe2 A4-n rn ƒi@xwe2 A4-n rn xr3 xr3 x2 xr3 xr3 xr3 E x2 erGx2 x2 x2 E E E CHAPTER 6.2 CVD of silicon nitride from hydrides and chlorides „he (rst ™ommer™i—l growth of sili™on nitride w—s ˜y the re—™tion of ƒir4 —nd xr3 ˜y either —tmospheri™ pressure g†h @e€g†hA or €ig†hF pilm growth using e€g†h is slower —nd requires higher temper—tures —nd so it h—s ˜een gener—lly suppl—nted ˜y pl—sm— growthD howeverD (lm qu—lity for e€g†h is higher due to the lower hydrogen ™ontentF ‡hile therm—lly grown (lms —re ™lose to stoi™hiometri™D €ig†h (lms h—ve — ™omposition in whi™h the ƒGx r—tio is o˜served to v—ry from HFU E IFIF „he nonEstoi™hiometri™ n—ture of €ig†h (lms is expl—ined ˜y the in™orpor—tion of signi(™—nt hydrogen in the (lms @IH E QH7AF €ig†h of ƒixx using ƒir4 Gx2 le—ds to ele™troni™—lly le—ky (lms due to the porous n—ture of the (lmsD howeverD if —n ele™tron ™y™lotron reson—n™e @ig‚A pl—sm— is employedD ƒixx (lms of high qu—lity m—y ˜e deposited on —m˜ient temper—ture su˜str—tesF „he more re™ent ™ommer™i—l methods for sili™on nitride deposition involves v€g†h using ƒigl2 r2 —s the sili™on sour™e in ™om˜in—tion with xr3 —t UHH E WHH ◦ gF „he redu™ed pressure of v€g†h h—s the —dv—nt—ges of high purityD low hydrogen ™ontentD stoi™hiometri™ (lmsD with — high degree of uniformityD —nd — high w—fer throughputF st is for these re—sons th—t v€g†h is now the method of ™hoi™e in ™ommer™i—l systemsF e l—rge ex™ess of xr3 is therefore used in ™ommer™i—l systems to o˜t—in stoi™hiometri™ (lmsF ƒili™on nitride h—s —lso ˜een prep—red from ƒigl4 Gxr4 D ƒifr4 Gxr3 D —ndD more re™entlyD ƒi2 gl6 Gxr3 F ƒili™on oxynitride @ƒiyxA m—y ˜e prep—red ˜y the use of —ny of the pre™ursors used for sili™on nitride with the —ddition of either x2 y or xy —s —n oxygen sour™eF „he ™omposition —nd properties of the ƒiyx xy (lms m—y ˜e v—ried from ƒiy2 Elike to ƒi3 x4 Elike ˜y the v—ri—tion of the re—™t—nt )ow r—tesF ƒigl2 r2 g—s plum˜ing to — v€g†h re—™tor must ˜e therm—lly insul—ted to prevent ™ondens—tion th—t would otherwise le—d to h—zy deposits on the (lmF „he vol—tile ˜yEprodu™ts from g†h produ™e xr4 gl —t the exh—ust of the re—™tion tu˜eD —nd in the plum˜ing —nd pumping systemF st would ˜e desir—˜leD thereforeD to (nd —n —ltern—tiveD ™hlorineEfree sili™on sour™e with none of the toxi™ity or pyrophori™ity pro˜lems —sso™i—ted with ƒir4 F st is for this re—son th—t org—nosili™on ™ompounds h—ve ˜een investig—tedF .2. CHEMICAL VAPOR DEPOSITION e€g†h €ig†h €ig†h v€g†h v€g†h v€g†h v€g†h UH E WHH PH E THH UH E QHH UHH E WHH RSH E VSH TSH E UPS RSH E THH g impurities h—nger pre™ursor explosive ƒigni(™—nt ™ontent ƒigni(™—nt ™ontent ! gommer™i—l pro™ess €orous (lms gommer™i—l pro™ess E E xr3 xr3 Gr2 re re e€g†h e€g†h e€g†h THH E VHH THH E USH THH E USH g g xo g ™ont—miE n—tion Table 6.10 X €re™ursors —nd deposition ™onditions for ƒi3 x4 g†hF 6.

Electron.5.2. Electrochem. A.1 Introduction 9 eluminum nitride @elxA h—s potenti—l for signi(™—nt —ppli™—tions in mi™roele™troni™ —nd opti™—l devi™esF st h—s — l—rge dire™t ˜—ndg—p @ig.D IWVQD 130D RSHF • gF „F x—˜er —nd qF gF vo™kwoodD in Semiconductor SiliconD idsF rF ‚F ru' —nd ‚F ‚F furgessF „he ile™tro™hemi™—l ƒo™ietyD ƒoft˜ound €ro™eedings ƒeriesD €rin™etonD xt @IWUQAF • tF iF ƒ™hoenholtzD hF ‡F ressD Thin Solid FilmsD IWVUD 148D PVSF 6. Soc.2.4 Bibliography • tF gF f—r˜ourD rF tF ƒteinD yF eF €opovD wF ‰oderD —nd gFeF yuttenD J. Technol.2. .5.1 CVD from silicon-nitrogen compounds „he in™orpor—tion of ™—r˜on into sili™on nitride (lms is — persistent pro˜lem of org—nosili™on pre™ursorsF ƒever—l studies h—ve ˜een —imed —t developing single sour™e pre™ursors ™ont—ining — ƒiEx ˜ond r—ther th—n ƒiEg ˜ondsF €oly—zidosil—nesD ‚n ƒi@x3 A4-n D —re low in ™—r˜on —nd hydrogenD re—son—˜ly vol—tileD —nd ™ont—in highly —™tiv—ted nitrogenD howeverD they represent — signi(™—nt explosive h—z—rdX they are explosive with an equivalent force to TNTF pilms deposited using itƒi@x3 A3 —nd @tfuAƒi@x3 A3 showed promiseD despite the o˜serv—tion of oxygen —nd ™—r˜onF €yrolyti™ studies on the —zide pre™ursors suggest th—t the prim—ry de™omposition step is the loss of dinitrogenD whi™h is followed ˜y migr—tion of the —lkyl onto the rem—ining nitrogenD @TFSRAF „he f—™t th—t neither the —ddition of xr3 or r2 in)uen™e the (lm deposition r—te suggest th—t the intr—mole™ul—r nitride form—tion pro™ess is f—stD rel—tive to re—™tion with xr3 D or hydrogen—tionF @TFSRA g—r˜on in™orpor—tion is —lso o˜served for the e€g†h deposition from ƒi@xwe2 An r4-n @n a P E RAF roweverD using the ro'm—n tr—ns—min—tion re—™tionD deposition in the presen™e of xr3 ™ompletely removed ™—r˜on in™orpor—tion into the stoi™hiometri™ ƒi3 x4 (lmF prom p„s‚ d—t—D the hydrogen ™ontent w—s estim—ted to ˜e V E IH —tom per™entF ‡hile the ƒi@xwe2 An r4-n Gxr3 system does not provide su˜st—nti—lly lower temE per—tures th—n e€g†h using ƒir4 Gxr3 growth r—tes —re signi(™—ntly higherF …nlike the —zide pre™ursorsD ƒi@xwe2 An r4-n —re e—sier to h—ndle th—n either ƒir4 or ƒigl2 r2 F 6.5.3 CVD from organosilicon precursors hiethylsil—neD it2 ƒir2 D h—s shown promise —s — repl—™ement for ƒir4 in the low temper—ture v€g†h of ƒiy2 D —nd h—s ˜een investig—ted —s — sour™e for ƒixx —nd ƒiyx xy (lmsF heposition ˜y v€g†h in the presen™e of xrQ produ™es ƒixx (lmsD in whi™h the ™—r˜on ™ont—min—tion @R E W7A depends on the p—rti—l pressure of the it2 ƒir2 F „he presen™e of ™—r˜on r—ises the refr—™tive index @PFHPS E PFPVA with respe™t to tr—dition—l v€g†h (lms @PFHIAF wixtures of it2 ƒir2 D xr3 D —nd x2 y deposit ƒiyx xy (lms where the ™omposition is ™ontrolled ˜y the xr3 Xx2 y r—tioF 6.dir a TFPV e†AD extremely high melting point @QHHH ◦ gAD high therm—l 9 This content is available online at <http://cnx.3 Chemical Vapor Deposition of Aluminum Nitride 6.PPS 6.3.3. Vac.1/>. DevicesD IWUVD 25D SVUF • hF wF ro'm—nD PolyhedronD IWWRD 13D IITWF • ‡F uellnerD rF uniepk—mpD hF ‚epowD wF reinzelD —nd rF forolek—D Solid State IWWID 9D RVHF • tF eF riggensD ‚F vF uuv—sD pF rF iisenD —nd hF ‚F ghenD IEEE Trans.D IWUUD 20D RSWF • „F w—kinoD J. Sci.5.

PPT CHAPTER 6. ( ◦ C) Comments elgl3 @xr3 A elfr3 elfr3 elwe3 elwe3 elwe3 E xr3 x2 xr3 xr3 preE™r—™ked xr3 t i x2 x2 x2 r2 re r2 Gre v€g†h e€g†h v€g†h v€g†h e€g†h e€g†h UHH E IRHH RHH E WHH SPH E STH IPHH QSH E RHH QIH E RTH xr4 gl present fr present oriented growth xEr —nd elxE x ˜onds deE te™ted high g ™ontentD low x very high ™ontent g elwe3 elwe3 ‘‚2 el@xr2 A“3 @‚ a weD itA ‘‚2 elx3 “3 @‚ a weD itA el@xwe2 A3 fuxr2 €rxr2 or r2 r2 r2 e€g†h e€g†h v€g†h RHH E THH QHH E RSH RHH E VHH we3 ƒix3 poor (lm qu—lE ityD high g ™onE tent unre—™ted preE ™ursor present on (lm —morphous IHH E PHH ◦ gD ™rysE t—lline QHH E SHH ◦ g E v€g†h RHH E SHH xr3 re e€g†h IHH E SHH Table 6.5.11 X €re™ursors —nd deposition ™onditions for elx g†hF 6.2 CVD from halides „he o˜serv—tion th—t elx powder m—y ˜e produ™ed upon the therm—l de™omposition of the elgl3 @xr3 A ™omplexD prompted initi—l studies on the use of elgl3 Gxr3 for the g†h of elx (lmsF sniti—llyD the low vol—tility of elgl3 @— polymeri™ ™h—in stru™tureA required th—t the elgl3 @xr3 A ™omplex to ˜e used —s — single pre™ursorF vow pressure g†h @v€g†hA —t S EIH „orr resulted in deposition of elx (lmsD —lthough . CHEMICAL VAPOR DEPOSITION ™ondu™tivity @PFT ‡G™mFuAD —nd — l—rge diele™tri™ ™onst—nt @ε a WFIRAF sn present ™ommer™i—l mi™roele™troni™ devi™esD elx is used most often —s — p—™k—ging m—teri—lD —llowing for the ™onstru™tion of ™omplex p—™k—ges with m—ny sign—lD groundD powerD ˜ondingD —nd se—ling l—yersF eluminum nitride is espe™i—lly useful for high power —ppli™—tions due to its enh—n™ed therm—l ™ondu™tivityF ghemi™—l v—por deposition @g†hA grown thin (lms of elx h—ve ˜een ™entered upon its use —s — high g—teEinsul—tion l—yer for wsƒ devi™esD —nd — diele™tri™ in highEperform—n™e ™—p—™itorsF yne —ddition—l property of elx th—t m—kes it — promising insul—ting m—teri—l for ˜oth ƒi —nd q—es devi™es is th—t its therm—l exp—nsion ™oe0™ient is —lmost identi™—l to ˜oth of these semi™ondu™torsF „he l—™k of — suit—˜ly vol—tile homolepti™ hydride for —luminum @elr3 is —n invol—tile polymeri™ spe™iesA led to the —ppli™—tion of —luminum h—lides —nd org—nomet—lli™ ™ompounds —s pre™ursorsF e summ—ry of sele™ted pre™ursor ™om˜in—tions is given in „—˜le TFIIF Aluminum precursor Nitrogen source Carrier gas CVD method Deposition temp.3.

PPU (lms deposited ˜elow IHHH ◦ g were ™ont—min—ted with xr4 glD —nd —ll the (lms ™ont—ined ™hlorineF pilms with re—son—˜le ele™tri™—l properties were prep—red ˜y the use of the more vol—tile tris E—mmoni— ™omplexD elgl3 @xr3 A3 F „he diele™tri™ ™onst—nt for (lms grown —t VHH E IHHH ◦ g @IIFSA is higher th—n ˜ulk elx @WFIRA —nd —lso th—n th—t of the (lms grown —t IIHH ◦ g @VFIAF ell the (lms were poly™ryst—lline with the gr—in size in™re—sing with in™re—sing deposition temper—tures —nd preferred orient—tion w—s o˜served only for the (lms grown ˜elow IHHH ◦ gF eluminum ˜romide is — dimeri™ vol—tile ™ompoundD ‘fr2 el@µEfrA“2 D —nd is more —ttr—™tive —s — g†h sour™eD th—n elgl3 F heposition of elx (lms ™—n ˜e —™™omplished using elfr3 —nd xr3 in —n e€g†h system with r2 —s the ™—rrier g—sF „he me™h—nism of (lm growth h—s ˜een proposed @pigure TFIVAF Figure CVD from aluminum alkyls f—sed upon the su™™essful met—l org—ni™ g†h @wyg†hA growth of elq—es using the —lkyl deriv—tivesD el‚3 D it w—s logi™—l to extend wyg†h to —luminum nitrideF sniti—l studies were performed using elwe3 —nd xr3 with r2 ™—rrier g—sF ‡hile these (lms —re gener—lly of high qu—lityD the temper—ture of deposition is in™omp—ti˜le with semi™ondu™tor pro™essing @˜eing —˜ove ˜oth the melting point of most met—lliz—tion —lloys —nd the temper—ture —t whi™h dop—nt migr—tion ˜e™omes deleteriousAF vower temper—tures @—s low —s QSH ◦ gA were exploredD however signi(™—nt preEre—™tion w—s o˜served ˜etween elwe3 —nd xr3 Y ™—using depletion of the re—™t—nts in the deposition zoneD redu™ing the growth r—te —nd le—ding to nonEuniform depositsF „wo routes h—ve ˜een investig—ted ˜y whi™h this pro˜lem ™—n ˜e ™ir™umventedF €ig†h su™™essfully lowers the deposition temper—tureD —lthoughD degr—d—tion of the su˜str—te surf—™e ˜y ion ˜om˜—rdment is — signi(™—nt dr—w˜—™kF qiven th—t it is the —mmoni— de™omposition th—t represents the highest energy pro™essD preE™r—™king should lower the over—ll deposition temper—tureF „his is indeed o˜served for the elwe3 Gxr3 E˜—sed elx system where growth is —™hieved —s low —s SVR ◦ g if the xr3 is ™—t—lyti™—lly ™r—™ked over — he—ted tungsten (l—ment @IURU ◦ gAF sn f—™tD with ™—t—lyti™ preE™r—™kingD deposition r—tes were o˜served to ˜e —n order of m—gnitude gre—ter th—n for €ig†h —t the s—me temper—turesD resulting in (lms th—t were ™ryst—lline with ™olumn—r growthF por this —ppro—™h to lowEtemper—ture wyg†h growth of elx the only m—jor dr—w˜—™k is the presen™e of residu—l xEr —nd elxEx groups dete™ted ˜y p„Es‚F ghemi™—l solutions to the high st—˜ility of xr3 h—ve prim—rily ™entered upon the use of —ltern—tive nitrogen sour™esF „he use of the vol—tile nitrogen sour™e hydr—zine @x2 r4 AD h—s —llowed for the growth .18: Mechanism of APCVD lm growth of AlN using AlBr3 and NH3 . hue to the high temper—tures required @USH ◦ gA for good qu—lity elx (lm growth from elfr3 D €ig†h w—s investig—tedF …sing —n elfr3 Er2 Ex2 g—s mixture —nd — PRSH wrz mi™row—ve @IHH E IHHH ‡A pl—sm— sour™eD elx (lms were grownF „he m—ximum deposition r—te o™™urred with —n x2 Gelfr3 r—tio of caF PH —nd — su˜str—te temper—ture caF THH ◦ gF 6.

4 CVD from aluminum amide and related compounds „he re—™tion ˜etween —luminum —lkyls —nd —mines @@TFSSAAD —s well —s the form—tion of elx powders from the pyrolysis of elwe3 @xr3 A @@TFSTAAD le—d to the misguided ™on™ept th—t the route to highEpurity elx would ˜e through the soE™—lled single sour™e pre™ursor routeF @TFSSA @TFSTA „he trimeri™ dimethyl—luminum —mideD ‘we2 el@xr2 A“3 @pigure TFPH—AD w—s origin—lly used —s — single sour™e pre™ursor for growth of elx under v€g†h ™onditions using — hot w—lled re—™torD —lthough su˜sequent deposition w—s —lso demonstr—ted in — ™old w—lled systemF pilm qu—lity w—s never demonstr—ted for ele™troni™ —ppli™—tionsD ˜ut the (lms showed promise —s (˜er ™o—tings for ™ompositesF „he ™on™ept of using — trimeri™ . J.5..3.. Bartram. Michalske. Mater. 5. and R. Paine.19: 6. A. Rogers. Figure 6.PPV CHAPTER 6. T. CHEMICAL VAPOR DEPOSITION of elx —t temper—tures —s low —s PPH ◦ gD howeverD hydr—zine is extremely toxi™ —nd highly unst—˜leD restri™ting its ™ommer™i—l —ppli™—tionF €rim—ry —minesD su™h —s t fuxr2 or i €rxr2 D —llow for deposition —t modest temper—tures @RHH E THH ◦ gAF „he high ™—r˜on in™orpor—tionD —s high —s IU7 pre™ludes their —doptionF e simil—r pro˜lem is o˜served with the use of trimethylsilyl—zideD we3 ƒix3 F „he presen™e of ™—r˜on ™ont—min—tion in the deposition of el (lms —nd elq—es epit—xi—l l—yers h—s ˜een —ttri˜uted to the use of elwe3 F „herefore —ttempts h—ve ˜een m—de to use —ltern—tive —luminum pre™ursorsF snterest in the me™h—nism of nu™le—tion —nd —tomi™ l—yer growth of elx h—s prompted sever—l me™h—nisti™ studies of the form—tion of elEx ˜onds on the growth surf—™eF ell the studies ™on™urred th—t the me™h—nism involves — stepEwise re—™tion where the —mide @Exr2 EA groups form ™ov—lent ˜onds to —luminum irrespe™tive of su˜str—teF e s™hem—ti™ represent—tion of the pro™ess is shown in pigure TFIWF A schematic representation of the proposed step-wise reaction involving the formation of amide (-NH2 -) groups covalently bound to aluminum during the MOCVD growth of AlN using AlMe3 /NH3 . 1993. W. Chem. T. Jr. 1424). E. (Adapted from M.

pollowing the e—rly reports of single sour™e pre™ursor routesD — wide r—nge of ™ompounds h—ve ˜een investig—tedD in™luding ‘el@x‚2 A3 “2 D ‘rel@x‚2 A2 “2 @‚ a weD itAD —nd ‘we2 elx@i €rA2 “2 D —ll of whi™h g—ve elxD ˜ut none of these pre™ursors give (lms of superior qu—lity ™omp—r—˜le to th—t o˜t—ined from tr—dition—l g†hF sn p—rti™ul—rD the (lms ™ont—ined signi(™—nt ™—r˜on ™ont—min—tionD prompting further investig—tions into the e0™—™y ofD xEg ˜ond freeD di—lkyl—luminum —zidesD ‘‚2 el@x3 A“3 D —s v€g†h pre™ursorsF ‡hile —luminum tris E—midesD el@x‚2 A3 were shown to give ™—r˜onE™ont—min—ted (lmsD e€g†h ™—rriedE out with xr3 —s the ™—rrier g—s results in ™—r˜onEfree elx (lm growth —s low —s IHH ◦ gF „he re—son for the deposition of high qu—lity (lms —t su™h low temper—tures resides with the ro'm—n tr—ns—min—tion re—™tion ˜etween the prim—ry —mido unit —nd —mmoni—F „he ™ryst—llinityD ˜—ndg—p —nd refr—™tive index for the elx grown ˜y e€g†h using ‘el@xwe2 A3 “2 —nd xr3 —re dependent on the deposition temper—tureF pilms grown —t IHH E PHH ◦ g —re —morphous —nd h—ve — low ˜—ndg—p —nd low refr—™tive indexF e˜ove QHH ◦ gD the (lms —re ™ryst—llineD —nd h—ve — refr—™tive index ™lose to th—t of ˜ulk elx @IFWW E PFHPAD with — ˜—ndg—p @≤ SFUU e†A —ppro—™hing the v—lues reported for poly™ryst—lline elx @SFV E SFW e†AF 6.d) observed by TOF-mass spectrometry.3. Electrochem.D IWUID 118D IVTRF .PPW single sour™e pre™ursor for elx w—s derived from the o˜serv—tion of el3 x3 ™y™les —s the sm—llest stru™tur—l fr—gment in wurtzite elxF roweverD det—iled me™h—nisti™ studies indi™—te th—t under g—s ph—se thermolysis the trimeri™ pre™ursor ‘we2 el@xr2 A“3 is in equili˜rium with @or de™omposes toA dimeri™ @pigure TFPH˜A —nd monomeri™ @pigure TFPH™A ™ompoundsF purthermoreD nitrogenEpoor spe™ies @pigure TFPHdA were —lso o˜served ˜y „ypEm—ss spe™trometryF Figure 6. Electrochem.5 Bibliography • • • • tF vF hupuie —nd iF qul—riD J. Vac.20: The trimeric dimethylaluminum amide (a) used as a single source precursor for growth of AlN. Technol.5. AD IWWPD 10D IVF hF wF ro'm—nD PolyhedronD IWWRD 13D IITWF vF †F snterr—nteD ‡F veeD wF w™gonnellD xF vewisD —nd iF r—llD J. Soc.D IWVWD 136D RUPF rF wF w—n—sevitD pF wF irdm—nnD —nd ‡F sF ƒimpsonD J. Soc. and the decomposition products (b . Sci.

PQH CHAPTER 6. Appl.56 p2 is —lmost perfe™tly l—tti™eEm—t™hed to q—esF …nfortun—telyD the therm—l exp—nsion ™oe0™ient di'eren™es ˜etween q—es —nd g—p2 Eƒrp2 produ™e str—ins —t the (lmGsu˜str—te interf—™e under high temper—ture growth ™onditionsF „he solution to this l—tter pro˜lem lies in the low temper—ture deposition of g—p2 Eƒrp2 ˜y g†hF Compound Lattice constant (Å) g—p2 ƒrp2 f—p2 q—es Table IWWHD 29D vQSVF 6.D IWVHD 127D ISQPF • ‰F ƒomenoD wF ƒ—s—kiD —nd „F rir—iD Jpn. Phys. Electrochem.6 Metal Organic Chemical Vapor Deposition of Calcium Fluoride 10 „he ™hemi™—l v—por deposition @g†hA of met—l )uorides h—s ˜een mu™h less studied th—n th—t of oxidesD pni™tidesD or ™h—lgogenidesF es m—y ˜e expe™ted where — vol—tile )uoride pre™ursor is —v—il—˜le then suit—˜le (lms m—y ˜e grownF por ex—mpleD qroup S @†D x˜D „—AD T @woD ‡AD —nd U @‚eA tr—nsition met—ls —re re—dily deposited from )uorideEhydrogen mixturesF ‡hile the use of )uorine is dis™our—ged on s—fety groundsD m—ny of the )uorin—ted —lkoxide or β Ediketon—te lig—nds employed for met—l oxide met—l org—ni™ ™hemi™—l v—por deposition @wyg†hA —re predisposed to depositing met—l )uoridesF „he use of )uorine su˜stituted deriv—tives is ˜e™—use they —re often more vol—tile th—n their hydro™—r˜on —n—logsD —nd therefore re—dily used for ˜oth —tmospheri™ —nd low pressure g†hF „o minimize the unw—nted form—tion of met—l )uoridesD w—ter v—por is in™orpor—ted in the g—s stre—mD —nd it is ™ommon to perform postEdeposition hydrolyti™ —nne—lsF roweverD there exist — num˜er of —ppli™—tions where )uorides —re requiredF por ex—mpleD the highly insul—ting n—ture of g—p2 —nd ƒrp2 h—s prompted investig—tions into their use —s — g—te insul—tor in q—esE˜—sed met—l insul—tor semi™ondu™tor (eld e'e™t tr—nsistor @wsƒpi„A devi™esF st should ˜e noted th—t while g—p2 is — good insul—torD the g—p2 Gq—es interf—™e h—s — high interf—™e tr—p densityD requiring — p—ssiv—tion ˜u'er l—yer to ˜e deposited on q—es prior to g—p2 growthF yne of the di0™ulties with the use of g—p2 @—nd ƒrp2 A on q—es is the l—tti™e mism—t™h @„—˜le TFIPAD ˜ut this m—y ˜e minimized ˜y the use of solid solutions ˜etween g—p2 Eƒrp2 F „he ™omposition g—0. CHEMICAL VAPOR DEPOSITION • ‰F €—ule—uD eF foutevilleD tFtF r—ntzpergueD tF g ‚emyD —nd eF g—™h—rdD J.12 SFRT SFVT TFPH SFTSQP X v—tti™e p—r—meters of qroup P @ssA )uorides in ™omp—rison with q—esF €oly™ryst—lline g—p2 m—y ˜e grown ˜y the pyrolyti™ de™omposition of g—@g5 we5 A2 @pigure TFPI—A in either ƒip4 or xp3 F heposition —t ISH ◦ g results in poly™ryst—lline (lms with high levels of ™—r˜on @IV7A —nd oxygen @U7A impurities limiting the (lms usefulness in ele™troni™ —ppli™—tionsF roweverD signi(™—ntly higher purity (lms m—y ˜e grown —t IHH ¦g using the photoE—ssisted de™omposition of g—@hf—™A2 @pigure TFPI˜AF „hese (lms were deposited —t QH ÅGmin —nd showed — high degree of ™ryst—llogr—phi™ preferred orient—tionF 10 This content is available online at <http://cnx. J. Soc. .3/>.44 ƒr0.

22: 6. A. Apen. D. Chiang. Caulton. Smith. W. Chem. 1684). „he me™h—nism en—˜eling )uoride tr—nsfer to the met—l @from the ™—r˜on of )uorin—ted —lkoxide ligE —ndsA h—s ˜een investig—tedF wyg†h employing ‘x—@y‚f A“4 —nd r@y‚f A4 ‘y‚f a ygr@gp3 A2 —nd ygwe3-n @gp3 An D n a I E Q“ gives x—p —nd rp4 (lmsD respe™tivelyD with vol—tile )uoro™—r˜on sideEprodu™tsF en—lysis of the org—ni™ sideEprodu™ts indi™—ted th—t de™omposition o™™urs ˜y tr—nsfer of )uorine to the met—l in ™onjun™tion with — IDPEmigr—tion of — residu—l group on the —lkoxideD to form — ketone @pigure TFPPAF „he migr—tion is in™re—singly f—™ile in the order gp3 gr3 ≤ rF „he initi—l wEp ˜ond form—tion h—s ˜een proposed to ˜e —s — ™onsequen™e of the ™lose w. -C. p —gosti™ inter—™tions o˜served for some )uoro—lkoxide —nd )uoroEβ Ediketon—tesF Proposed mechanism for the decomposition of uorinated alkoxide compounds. G. D. (Adapted from J.PQI Figure 6. -P.1 Bibliography • eF ‚F f—rronD in CVD of NonmetalsD ‡F ƒF ‚eesD trF @edAD ‡ileyD xew ‰ork @IWWTAF . 1994. E.. C.6.21: CaF2 MOCVD precursors. C. V. 6.. K. Figure 6. Mater. Samuels. Yu.. Baxter.

7. Mater.1 Introduction ghemi™—l v—por deposition @g†hA is — pro™ess for depositing solid elements —nd ™ompounds ˜y re—™tions of g—sEph—se mole™ul—r pre™ursorsF heposition of — m—jority of the solid elements —nd — l—rge —nd everEgrowing num˜er of ™ompounds is possi˜le ˜y g†hF wost met—lliz—tion for mi™roele™troni™s tod—y is performed ˜y the physi™—l v—por deposition @€†hA proE ™esses of ev—por—tion —nd sputteringD whi™h —re often ™on™eptu—lly —nd experiment—lly more str—ightforw—rd th—n g†hF roweverD the in™re—sing import—n™e of g†h is due to — l—rge degree to the —dv—nt—ges th—t it holds over physi™—l v—por depositionF poremost —mong these —re the —dv—nt—ges of ™onform—l ™over—ge —nd sele™tivityF ƒputtering —nd ev—por—tion —re ˜y their n—ture lineEofEsight deposition pro™esses in whi™h the su˜str—te to ˜e ™o—ted must ˜e pl—™ed dire™tly in front of the €†h sour™eF sn ™ontr—stD g†h —llows —ny su˜str—te to ˜e ™o—ted th—t is in — region of su0™ient pre™ursor p—rti—l pressureF „his —llows the uniform ™o—ting of sever—l su˜str—te w—fers —t on™eD of ˜oth sides of — su˜str—te w—ferD or of — su˜str—te of l—rge size —ndGor ™omplex sh—peF „he €†h te™hniques ™le—rly will —lso deposit met—l on —ny surf—™e th—t is in line of sightF yn the other h—ndD it is possi˜le to deposit sele™tively on some su˜str—te m—teri—ls in the presen™e of others using g†hD ˜e™—use the deposition is ™ontrolled ˜y the surf—™e ™hemistry of the pre™ursorGsu˜str—te p—irF „husD it m—y ˜e possi˜leD for ex—mpleD to synthesize — g†h pre™ursor th—t under ™ert—in ™onditions will deposit on met—ls ˜ut not on —n insul—ting m—teri—l su™h —s ƒiy2 D —nd to exploit this sele™tivityD for ex—mpleD in the f—˜ri™—tion of — very l—rgeEs™—le integr—ted @†vƒsA ™ir™uitF st should —lso ˜e pointed out th—tD unlike some €†h —ppli™—tionsD g†h does not ™—use r—di—tion d—m—ge of the su˜str—teF ƒin™e the IWTHsD there h—s ˜een ™onsider—˜le interest in the —ppli™—tion of met—l g†h for thinE(lm deposition for met—lliz—tion of integr—ted ™ir™uitsF ‚ese—r™h on the therm—l g†h of ™opper is motiv—ted ˜y the f—™t th—t ™opper h—s physi™—l properties th—t m—y m—ke it superior to either tungsten or —luminum in ™ert—in mi™roele™troni™s —ppli™—tionsF „he resistivity of ™opper @IFTU m‡F™mA is mu™h lower th—n th—t of tungsten @SFT m‡F™mA —nd signi(™—ntly lower th—n th—t of —luminum @PFU m‡F™mAF „his immedi—tely suggests th—t ™opper ™ould ˜e — superior m—teri—l for m—king met—l inter™onne™tsD espe™i—lly in devi™es where rel—tively long inter™onne™ts —re requiredF „he ele™tromigr—tion resist—n™e of ™opper is higher th—n th—t of —luminum ˜y four orders of m—gnitudeF gopper h—s in™re—sed resist—n™e to stressEindu™ed void—ge due to its higher melting point versus —luminumF „here —re —lso reported —dv—nt—ges for ™opper rel—ted devi™e perform—n™e su™h —s gre—ter speed —nd redu™ed ™ross t—lk —nd sm—ller ‚g time ™onst—ntsF yn the wholeD the ™om˜in—tion of superior resistivity —nd intermedi—te reli—˜ility properties m—kes ™opper — promising m—teri—l for m—ny —ppli™—tionsD provide th—t suit—˜le g†h pro™esses ™—n ˜e devisedF 6.1 Applications of metal CVD „here —re — num˜er of potenti—l mi™roele™troni™ —ppli™—tions for met—l g†hD in™luding g—te met—lliz—tion @deposit on semi™ondu™torAD ™ont—™t met—lliz—tion @deposit on semi™ondu™torAD di'usion ˜—rrier met—lliz—tion 11 This content is available online at <http://cnx. Engl.4/>. Opt.PQP CHAPTER 6. Mater.7 Precursors for Chemical Vapor Deposition of Copper note: 11 Electronic MaterialsF „his module w—s prep—red with the —ssist—n™e of ‡ei h—oF „his module w—s developed —s p—rt of the ‚i™e …niversity ™ourse griwERWTX Chemistry of 6. PhysFD IWVUD 61D PRIHF • tF eF ƒ—muelsD ‡F EgF ghi—ngD gF E€F ‰uD iF epenD hF gF ƒmithD hF †F f—xterD uF qF g—ultonD Chem. Adv.1. Appl. Electron. IWVWD 28D ISVIF 6. MaterFD IWWRD 6D ITVRF • ‡F †ereD uF tF w—™keyD hF gF ‚odw—yD €F gF ƒmithD hF w prigoD hF gF fr—dleyD Angew. CHEMICAL VAPOR DEPOSITION • fF hF p—hlm—n —nd eF ‚F f—rronD Adv.7. Int. Chem. .D PHHHD 10D PPQF • rF rer—lF vF fern—rdD eF ‚o™herD gF pont—ineD eF wunozEt—gueD J.

2 Copper CVD „he ™hemi™—l v—por deposition of ™opper origin—lly su'ered from — l—™k of re—dily —v—il—˜le ™opper ™ompounds with the requisite properties to serve —s g†h pre™ursorsF „he su™™essful development of — te™hnologi™—lly useful ™opper g†h pro™ess requires (rst —nd foremost the design —nd synthesis of — ™opper pre™ursor whi™h is vol—tileD iFeFD possesses —n —ppre™i—˜le v—por pressure —nd v—poriz—tion r—te to —llow e—se in tr—nsport—tion to the re—™tion zone —nd deposition —t high growth r—tesF sts de™omposition me™h—nism@sA should prefer—˜ly ˜e str—ightforw—rd —nd le—d to the form—tion of pure ™opper —nd vol—tile ˜yEprodu™ts th—t —re nonre—™tive —nd ™—n ˜e ™le—nly removed from the re—™tion zone to prevent (lmD su˜str—teD —nd re—™tor ™ont—min—tionF q—seous or liquid sour™es —re preferred to solid sour™es to —void undesir—˜le v—ri—tions in v—poriz—tion r—tes ˜e™—use of surf—™eE—re— ™h—nges during ev—por—tion of solid sour™es —nd to permit high levels of reprodu™i˜ility —nd ™ontrol in sour™e deliveryF yther desir—˜le fe—tures in pre™ursor sele™tion in™lude ™hemi™—l —nd therm—l st—˜ility to —llow extended shelf life —nd e—se in tr—nsport —nd h—ndlingD rel—tive s—fety to minimize the industri—l —nd environment—l imp—™t of pro™essing —nd dispos—lD —nd low synthesis —nd produ™tion ™osts to ensure —n e™onomi™—lly vi—˜le pro™essF ƒever—l ™l—sses of inorg—ni™ —nd met—lorg—ni™ sour™es h—ve ˜een explored —s ™opper sour™esF snorg—ni™ pre™ursors for ™opper g†h used hydrogen redu™tion of ™opper h—lide sour™es of the type guˆ or guˆ2 D where ˆ is ™hlorine @glA or )uorine @pAX P guˆ C r2 → P gu C P rˆ guˆ2 C r2 → gu C P rˆ „he vol—tility of ™opper h—lides is lowD the re—™tions involved require prohi˜itively high temper—tures @RHH E IPHH ◦ gAD le—d to the produ™tion of ™orrosive ˜yEprodu™ts su™h —s hydro™hlori™ —nd hydro)uori™ —™ids @rgl —nd rpAD —nd produ™e deposits with l—rge ™on™entr—tions of h—lide ™ont—min—ntsF we—nwhileD the explor—tion of met—lorg—ni™ ™hemistries h—s involved v—rious ™opper@ssA —nd ™opper@sA sour™e pre™ursorsD with signi(™—nt —dv—nt—ges over inorg—ni™ pre™ursorsF 6.7.PQQ @deposit on semi™ondu™torAD inter™onne™t met—lliz—tion @deposit on insul—tor —nd ™ondu™tor or semi™ondu™E torAF wost of the relev—nt fe—tures of met—l g†h —re found in the inter™onne™t —nd vi— (ll —ppli™—tionsD whi™h we ˜rie)y des™ri˜e hereF „here —re ˜—si™—lly two types of met—l g†h pro™esses th—t m—y o™™urX @IA fl—nket or nonsele™tive depositionD in whi™h deposition pro™eeds uniformly over — v—riety of surf—™esF @PA ƒele™tive deposition in whi™h deposition only o™™urs on ™ert—in types of surf—™es @usu—lly semi™ondu™tors or ™ondu™torsD ˜ut not insul—torsAF e prim—ry —ppli™—tion of ˜l—nket met—l g†h is for inter™onne™tsF „he ™onform—l n—ture of the g†h pro™ess is one of the key —dv—nt—ges of g†h over €†h —nd is — driving for™e for its rese—r™h —nd developmentF „he degree of ™onform—lity is usu—lly des™ri˜ed —s the step ™over—geD whi™h is norm—lly de(ned —s the r—tio of the deposit thi™kness on the step sidew—ll to the deposit thi™kness on the top surf—™eF enother —ppli™—tion for ˜l—nket met—l g†h is vi— hole (lling to pl—n—rize e—™h level for su˜sequent pro™essingD „his is —™hieved ˜y depositing — ™onform—l (lm —nd et™hing ˜—™k to the insul—tor surf—™eD le—ving the met—l plug int—™tF enother unique —spe™t of g†h is its potenti—l to deposit (lms sele™tivelyD whi™h would elimin—te sever—l pro™essing steps required to perform the s—me t—skF „he prim—ry —ppli™—tion for sele™tive met—l g†h would ˜e for vi— hole (llingF sde—llyD deposition only o™™urs on exposed ™ondu™tor or semi™ondu™tor surf—™esD so (lling of the vi— hole is —™hieved in — single stepF From Cu(II) precursors 6.7.1 Volatile Cu(II) compounds gopper w—s known to form very few st—˜leD vol—tile —lkyl or ™—r˜onyl ™ompoundsF „his w—s thought to elimE in—te the two m—jor ™l—sses of ™ompounds used in most existing pro™esses for g†h of met—ls or ™ompound semi™ondu™torsF gopper h—lides h—ve ˜een used for ™hemi™—l v—por tr—nsport growth of guE™ont—ining semiE ™ondu™tor ™ryst—lsF fut the ev—por—tion temper—tures needed for ™opper h—lides —re mu™h higher th—n those .

. ( ◦ C) Deposition temp.13 IVH E PHH VH E WS IQS E ITH IHH IHH E PVU VS E IHS PHR PPS E PSH PSH E QHH PSH E QHH RHH RHH QHH E RHH RHH PUH E QSH RSH r2 Ger r2 r2 none none r2 r2 r2 r2 UTH UTH UTH <IH-2 <HFQ IH-3 E UTH UQH IH E UH UQH X ƒtudies of gu g†h using gu@ssA ™ompoundF ed—pted from „F uod—s —nd wF r—mpdenEƒmithD The Chemistry of Metal CVDD †gr €u˜lishers sn™FD xew ‰orkD x‰ @IWWRAF Figure 6. ( ◦ C) Carrier gas Reactor pressure (Torr) gu@—™—™A2 gu@hf—™A2 gu@tf—™A2 gu@dpmA2 gu@ppmA2 gu@fodA2 gu@—™imA2 gu@non—EpA2 gu@—™enA2 Table 6.23: Structures of Cu(II) compounds studied as CVD precursors. CHEMICAL VAPOR DEPOSITION needed for met—lEorg—ni™ ™ompoundsF pilm purity —nd resistivity were —lso — pro˜lemD possi˜ly re)e™ting the high re—™tivity of ƒi su˜str—tes with met—l h—lidesF gu@ssA ™ompounds th—t h—ve ˜een studied —s g†h pre™ursors —re listed in „—˜le TFIQF „he stru™tur—l formul—s of these ™ompounds —re shown in pigure TFPQ —long with the lig—nd —˜˜revi—tions in „—˜le TFIRF i—™h ™ompound ™ont—ins — ™entr—l gu@ssA —tom ˜onded to two singly ™h—rged β Ediketon—te or β Eketoimin—te lig—ndsF wost of them —re st—˜leD e—sy to synthesizeD tr—nsport —nd h—ndleF Compound Evaporation temp.PQR CHAPTER 6.

7.14 gr3 gp3 gr3 g@gr3 A3 g@gr3 A3 g@gr3 A3 gr3 gp3 gr3 gr3 gp3 gp3 g@gr3 A3 gp2 gp3 gp2 gp2 gp3 r gr2 gp3 E — — — — — — ˜ ˜ ™ X vig—nd —˜˜revi—tions for the stru™tures shown in pigure TFPQF ettention h—s fo™used on gu@ssA β Ediketon—te ‘iFeFD gu@tf—™A2 D gu@hf—™A2 “ —nd gu@ssA β Eketoimin—te ‘iFeFD gu@—™imA2 D gu@—™enA2 “F en import—nt ™h—r—™teristi™ of gu@ssA ™ompounds —s g†h pre™ursors is the use of he—vily )uorin—ted lig—nd su™h —s gu@tf—™A2 —nd gu@hf—™A2 versus gu@—™—™A2 F „he m—in e'ort of )uorine su˜stitution is — signi(™—nt in™re—se in the vol—tility of the ™omplexF 6. 1.3 Reaction mechanism ƒt—rting from the experiment—l resultsD — list of possi˜le steps for gu g†h vi— r2 redu™tion of gu@ssA ™ompounds would in™lude the followingsD where remov—l of —dsor˜ed lig—nd from the surf—™e is ˜elieved to ˜e the r—te limiting stepX gu@ssAv2 @gA → gu@sA C P v.3.PQS Ligand abbreviation R1 R2 Structural type —™—™ hf—™ tf—™ dpm ppm fod —™im non—Ep —™en Table 6.2. @—dsA v.7.2.3. 2) gu@hf—™A2 is ˜y f—r the most extensively studied of the gu@ssA g†h pre™ursorsF €rep—r—tions in —queous solutions yield the yellowEgreen dihydr—teD gu@hf—™A2 ·Pr2 yF „his is st—˜le in very humid —ir or —t lower temper—tures ˜ut slowly loses one mole™ule of w—ter under typi™—l l—˜or—tory ™onditions to form the gr—ssE green monohydr—teD gu@hf—™A2 ·r2 yF „he monohydr—teD whi™h is ™ommer™i—lly —v—il—˜leD ™—n ˜e su˜limed un™h—nged —nd melts —t IQQ ! IQT ◦ gF wore vigorous drying over ™on™entr—ted r2 ƒy4 produ™es the purple —nhydrous ™ompound gu@hf—™A2 @mp a WS ! WV ◦ gAF „he purple m—teri—l is hydros™opi™D ™onverting re—dily into the monohydr—teF yther β Ediketon—te gu@ssA ™omplexes —re prep—red ˜y the simil—r methodF 6.2 Synthesis of Cu(II) precursors 6.7. @—dsA → rv@gA where v represents —ny of the singly ™h—rged β Ediketon—te or β Eketoimin—te lig—nds des™ri˜ed ˜eforeF „his me™h—nism gives — ™le—r expl—n—tion of the import—n™e of hydrogen ˜eing presentX in the —˜sen™e of hydrogenD .1 Cu(hfac)2 ·nH2 O (n = 0.2 Schi-base complexes ƒ™hi'E˜—se ™omplexes in™lude gu@—™imA2 D gu@—™enA —nd gu@non—EpA2 F „he (rst two of these ™—n ˜e prep—red ˜y mixing gu@xr3 A4 2+ @—qA with the pure lig—nd —nd ˜y —dding freshly prep—red solid gu@yrA2 to — solution of the lig—nd in —™etoneF „he synthesis of gu@non—EpA2 D on the other h—ndD involved two import—nt developmentsX the introdu™tion of the silyl enol ether route to the lig—nd —nd its ™onversion inEsitu into the desired pre™ursorF „he new —ppro—™h to the lig—nd w—s required ˜e™—useD in ™ontr—st to nonE)uorin—ted ˜Ediketon—tesD r@hf—™A re—™ts with —mines to produ™e s—ltsF 6.3. @—dsA r2 @gA → P r.3. @—dsA C r.7. Precursor design „he gu@sA ™ompounds th—t h—ve ˜een investig—ted —re des™ri˜ed in pigure TFPRF „hese spe™ies ™—n ˜e ˜ro—dly divided into two ™l—ssesD guˆ —nd ˆguvn D where ˆ is — unineg—tive lig—nd —nd v is — neutr—l vewis ˜—se ele™tron p—ir donorF „he ˆguvn ™l—ss ™—n ˜e further su˜divided —™™ording to the n—ture of ˆ —nd vF Figure 6. Hampden-Smith. NY (1994). CHEMICAL VAPOR DEPOSITION rv ™—nnot desor˜ ™le—nly into the g—s ph—se —nd lig—nd will tend to de™ompose on the surf—™eD resulting in impurity in™orpor—tion into the growing (lmF „he me™h—nism is —lso supported ˜y the o˜serv—tion th—t the deposition re—™tion is enh—n™ed ˜y the —ddition of —l™ohol ™ont—ining β Ehydrogen to the re—™tion mixtureF wore re™entlyD the fo™us h—s shifted to gu@sA ™ompounds in™luding gu@sA ™y™lopent—dienyls —nd gu@sA β Ediketon—teF „he gu@sA β Ediketon—te in p—rti™ul—r show gre—t promise —s gu g†h pre™ursors —nd h—ve superseded the gu@ssA β Ediketon—te —s the ˜est f—mily of pre™ursors ™urrently —v—il—˜leF 6. . New York.24: The Chemistry of Metal CVD Copper(I) precursors used for CVD.. gompounds of gener—l formul— guˆ —re likely to ˜e oligomeri™ resulting in — rel—tively low v—por pressureF „he presen™e of — neutr—l donor lig—ndD vD is likely to redu™e the extent of oligomeriz—tion ™omp—red to guˆ ˜y o™™upying v—™—nt ™oordin—tion sitesF wet—l —lkoxide ™ompounds —re expe™ted to undergo therm—l de™omposition ˜y ™le—v—ge of either wEy or yEg ˜ondsF yrg—noE™opper@sA ™ompoundsD ‚guvD where ‚ is —lkylD —re therm—lly unst—˜leD ˜ut ™y™lopent—dienyl ™ompounds —re likely to ˜e more ro˜ust due to the π E˜onding of the ™y™lopent—dienyl lig—nd to the ™opper ™enterF et the s—me timeD the ™y™lopent—dienyl lig—nd is steri™—lly dem—ndingD o™™upies three ™oordin—tion sites —t the met—l ™enterD —nd there˜y redu™es the desire for oligomeriz—tionF sn gener—lD — ™y™lopent—dienyl lig—nd is — poor ™hoi™e to support g†h pre™ursorsD espe™i—lly with ele™tropositive met—lsD ˜e™—use this lig—nd is unlikely to ˜e li—˜leF gompounds in the f—mily ˆguv2 D where ˆ is — h—lide —nd v is — triorg—nophosE phineD exhi˜it rel—tively high vol—tility ˜ut —re therm—lly st—˜le with respe™t to form—tion of ™opper —t low temper—turesF „hese spe™ies —re therefore suit—˜le —s produ™ts of et™hing re—™tions of ™opper (lmsF .PQT CHAPTER 6. VCH Publishers Inc. Adapted from T. Kodas and M.4 From Cu(I) precursors 6.

5 Selectivity ƒele™tivity deposition h—s ˜een studied in ˜oth hotE —nd ™oldEw—ll g†h re—™tors —s — fun™tion of the n—ture of the su˜str—teD the temper—ture of the su˜str—te —nd the n—ture of the ™opper su˜stituentsF ƒele™tivity h—s .25: „husD the st—rting m—teri—l —™ts —s its own redu™ing —gent —nd no extern—l redu™ing —gent su™h —s r2 is requiredF enother —dv—nt—ge of the gu@sA β Ediketon—tes over the gu@ssA β Ediketon—tes is th—t in the former the lig—nd v ™—n ˜e v—ried system—ti™—llyD —llowing the synthesis of — whole series of di'erent ˜ut ™losely rel—ted ™ompoundsF 6. Hampden-Smith. New York. VCH Publishers Inc.PQU e num˜er of rese—r™hers h—ve demonstr—ted the potenti—l of — series of β Ediketon—te gu@sA ™ompoundsD @β Ediketon—teAguvn D where v is vewis ˜—se —nd n a I or PD th—t ful(ll most of the ™riteri— outlined for pre™ursor design ˜eforeF „hese spe™ies were ™hosen —s ™opper pre™ursors for the following re—sonsX • „hey ™ont—in the β Ediketon—te lig—nd whi™h gener—lly imp—rts vol—tility to met—lEorg—ni™ ™omplexesD p—rti™ul—rly when )uorin—tedD —s — result of — redu™tion in hydrogenE˜onding in the solidEst—teF • „hey —re ™—p—˜le of system—ti™ su˜stitution through ˜oth the β Ediketon—te —nd vewis ˜—se lig—nds to t—ilor vol—tility —nd re—™tivityF • vewis ˜—ses su™h —s phosphinesD ole(ns —nd —lkynes —re unlikely to therm—lly de™ompose —t temper—E tures where ™opper deposition o™™ursF • „hese pre™ursors ™—n deposit ™opper vi— therm—lly indu™ed disproportion—tion re—™tions —nd no lig—nd de™omposition is required sin™e the vol—tile vewis ˜—se the gu@ssA disproportion—tion produ™ts —re tr—nsported out of the re—™tor int—™t —t the disproportion—tion temper—tureF 6. Adapted from T. Kodas and M.4. NY (1994).7.. The Chemistry of Metal CVD.7. Figure 6.2 Reaction mechanism e gener—l fe—ture of the re—™tions of gu@sA pre™ursors is th—t they therm—lly disproportion—teD — me™h—E nism likely to ˜e responsi˜le for the high purity of the ™opper (lms o˜served sin™e lig—nd de™omposition does not o™™urF „he disproportion—tion me™h—nism is shown in pigure TFPS for @β Ediketon—teAguvF „he unique ™—p—˜ilities of this ™l—ss of ™ompounds result from this re—™tion me™h—nism ˜y whi™h they deposit ™opperF „his me™h—nism is ˜—sed on the disso™i—tive —dsorption of the pre™ursor to form gu@hf—™A —nd vD disproportion—tion to form gu@hf—™A2 —nd gu —nd desorption of gu@hf—™A2 —nd vF Schematic diagram of the disproportionation mechanism.

CHEMICAL VAPOR DEPOSITION usu—lly ˜een ev—lu—ted ˜y using ƒi su˜str—tes on whi™h ƒiy2 h—s ˜een grown —nd p—tterned with v—rious met—ls ˜y either ele™tronE˜e—m depositionD g†h or sputteringF ‚ese—r™h h—s suggested th—t sele™tivity on met—lli™ surf—™es is —ttri˜ut—˜le to the ˜iomole™ul—r disproportion—tion re—™tion involved in pre™ursor de™ompositionF 6.D IWWPD 139D QPWSF • tF tF t—rvisD ‚F €e—r™eD —nd wF pF v—ppertD J. IWWHD 19D PUIF • „F uod—s —nd wF r—mpdenEƒmithD The Chemistry of Metal CVDD †gr €u˜lishers sn™FD xew ‰orkD x‰ @IWWRAF • gF pF €owellD tF rF yxleyD —nd tF wF flo™her trFD Vapor DepositionD tohn ‡ileyD xew ‰ork @IWTTAF • ƒF ƒhingu˜—r—D ‰F x—k—s—kiD —nd rF u—nekoD Appl. Electronic Mater.PQV CHAPTER 6. Soc. Electrochem. Soc. IWWID 58D RPF .6 Bibliography • tF ‚F greightonD —nd tF iF €—rmeterD Critical Review in Solid State and Materials ScienceD IWWQD 18D IUSF • vF rF hu˜ois —nd fF ‚F eg—rskiD J. Lett. Phys..7.D Dalton Trans..D IWUUD WWWF • eF iF u—loyerosD eF pengD tF q—rh—rtD uF gF frooksD ƒF uF qhoshD eF xF ƒ—zen—D —nd pF vuehersD J. Chem.

PQW .1 Rutherford Backscattering of Thin Films 7.1 Introduction yne of the m—in rese—r™h interests of the semi™ondu™tor industry is to improve the perform—n™e of semiE ™ondu™ting devi™es —nd to ™onstru™t new m—teri—ls with redu™ed size or thi™kness th—t h—ve potenti—l —pE pli™—tion in tr—nsistors —nd mi™roele™troni™ devi™esF roweverD the most signi(™—nt ™h—llenge reg—rding thin (lm semi™ondu™tor m—teri—ls is me—surementF €roperties su™h —s the thi™knessD ™omposition —t the surE f—™eD —nd ™ont—min—tionD —ll —re ™riti™—l p—r—meters of the thin (lmsF „o —ddress these issuesD we need —n —n—lyti™—l te™hnique whi™h ™—n me—sure —™™ur—tely through the depth of the of the semi™ondu™tor surf—™e without destru™tion of the m—teri—lF ‚utherford ˜—™ks™—ttering spe™tros™opy is — unique —n—lysis method for this purposeF st ™—n give us inform—tion reg—rding inEdepth pro(ling in — nonEdestru™tive m—nnerF rowE ever ˆEr—y photo ele™tron spe™tros™opy @ˆ€ƒAD energy dispersive ˆEr—y —n—lysis @ihˆA —nd euger ele™tron spe™tros™opy —re —lso —˜le to study the depthEpro(le of semi™ondu™tor (lmsF „—˜le UFI demonstr—tes the ™omp—rison ˜etween those te™hniques with ‚fƒF Method Destructive Incident particle Outgoing Particle Detection limit Depth lution reso1 ‚fƒ ˆ€ƒ ihˆ euger xo ‰es ‰es ‰es Table 7.Chapter 7 Materials Characterization son ˆEr—y photon ile™tron ile™tron son ile™tron ˆEr—y photon ile™tron ∼I ∼HFIEI ∼HFI ∼HFIEI IH nm ∼I µm IFS nm IFS nm X gomp—rison ˜etween di'erent thin (lm —n—lysis te™hniquesF 7.2 Basic concept of Rutherford backscattering spectroscopy et — ˜—si™ levelD ‚fƒ demonstr—tes the ele™trost—ti™ repulsion ˜etween high energy in™ident ions —nd t—rE get nu™leiF „he spe™imen under study is ˜om˜—rded with monoenergeti™ ˜e—m of 4 re+ p—rti™les —nd the ˜—™ks™—ttered p—rti™les —re dete™ted ˜y the dete™torE—n—lysis system whi™h me—sures the energies of the p—rE ti™lesF huring the ™ollisionD energy is tr—nsferred from the in™ident p—rti™le to the t—rget spe™imen —tomsY the ™h—nge in energy of the s™—ttered p—rti™le depends on the m—sses of in™oming —nd t—rget —tomsF por —n 1 This content is available online at <http://cnx.3/>.

PRH CHAPTER 7. MATERIALS CHARACTERIZATION in™ident p—rti™le of m—ss w1 D the energy is i0 while the m—ss of the t—rget —tom is w2 F efter the ™ollisionD the residu—l energy i of the p—rti™le s™—ttered —t —ngle Ø ™—n ˜e expressed —sX where k is the kinem—ti™ s™—ttering f—™torD whi™h is —™tu—lly the energy r—tio of the p—rti™le ˜efore —nd —fter the ™ollisionF ƒin™e k depends on the m—sses of the in™ident p—rti™le —nd t—rget —tom —nd the s™—ttering —ngleD the energy of the s™—ttered p—rti™le is —lso determined ˜y these three p—r—metersF e simpli(ed l—yout of ˜—™ks™—ttering experiment is shown in pigure I @pigure UFIAF Figure 7.1: Schematic representation of the experimental setup for Rutherford backscattering analysis. „he pro˜—˜ility of — s™—ttering event ™—n ˜e des™ri˜ed ˜y the di'erenti—l s™—ttering ™ross se™tion of — t—rget —tom for s™—ttering —n in™oming p—rti™le through the —ngle Ø into di'erenti—l solid —ngle —s followsD where d σ R is the e'e™tive di'erenti—l ™ross se™tion for the s™—ttering of — p—rti™leF „he —˜ove equ—tion m—y looks ™ompli™—ted ˜ut it ™onveys the mess—ge th—t the pro˜—˜ility of s™—ttering event ™—n ˜e expressed —s — fun™tion of s™—ttering ™ross se™tion whi™h is proportion—l to the z when — p—rti™le with ™h—rge ze —ppro—™hes the t—rget —tom with ™h—rge eF relium ions not s™—ttered —t the surf—™e lose energy —s they tr—verse the solidF „hey lose energy due to inter—™tion with ele™trons in the t—rgetF efter ™ollision the re p—rti™les lose further energy on their w—y out to the dete™torF ‡e need to know two qu—ntities to me—sure the energy lossD the dist—n™e ∆t th—t the p—rti™les penetr—te into the t—rget —nd the energy loss ∆i in this dist—n™e pigure UFPF „he r—te of energy loss .

incident beam loses energy through interaction with electrons ∆Ein . Figure 7. Mayer. Feldman and J. Adapted from L.2: sn thin (lm —n—lysisD it is ™onvenient to —ssume th—t tot—l energy loss ∆i into depth t is only proportion—l to t for — given t—rgetF „his —ssumption —llows — simple deriv—tion of energy loss in ˜—™ks™—ttering —s more ™omplete —n—lysis requires m—ny numeri™—l te™hniquesF sn ™onst—nt dE Gdx —pproxim—tionD tot—l energy loss ˜e™omes line—rly rel—ted to depth tD pigure UFQF . Then energy lost occurs due to scattering Ec . First. Finally outgoing beam loses energy for interaction with electrons ∆Eout . New York (1986).PRI or stopping power is — ™riti™—l ™omponent in ˜—™ks™—ttering experiments —s it determines the depth pro(le in — given experimentF Components of energy loss for a ion beam that scatters from depth t. North Holland-Elsevier. Fundamentals of Surface and Thin Film Analysis . W. C.

PRP CHAPTER 7.3: Variation of energy loss with the depth of the target in constant dE/dx approximation.1.3 Experimental set-up „he —pp—r—tus for ‚utherford ˜—™ks™—ttering —n—lysis of thin solid surf—™e typi™—lly ™onsist of three ™ompoE nentsX IF e sour™e of helium ionsF PF en —™™eler—tor to energize the helium ionsF QF e dete™tor to me—sure the energy of s™—ttered ionsF „here —re two types of —™™eler—torGion sour™e —v—il—˜leF sn single st—ge —™™eler—torD the re+ sour™e is pl—™ed within —n insul—ting g—sE(lled t—nk @pigure UFRAF st is di0™ult to inst—ll new ion sour™e when it is exh—usted in this type of —™™eler—torF woreoverD it is —lso di0™ult to —™hieve p—rti™les with energy mu™h more th—n I we† sin™e it is di0™ult to —pply high volt—ges in this type of systemF . MATERIALS CHARACTERIZATION Figure 7. 7.

5: Schematic representation of a tandem re++ F „he positive ions —re further —™™eler—ted tow—rd ground due to ™olum˜i™ repulsion from positive termin—lF „his —rr—ngement ™—n —™hieve highly —™™eler—ted re++ ions @∼ PFPS we†A with moder—te volt—ge of USH k†F Figure 7.PRQ Figure 7.4: Schematic representation of a single stage accelerator. enother v—ri—tion is t—ndem —™™eler—torF rere the ion sour™e is —t ground —nd produ™es neg—tive ionF „he positive termin—l is lo™—ted is —t the ™enter of the —™™eler—tion tu˜e @pigure UFSAF sniti—lly the neg—tive ion is —™™eler—ted from ground to termin—lF et termin—l twoEele™tron stripping pro™ess ™onverts the re. €—rti™les th—t —re ˜—™ks™—ttered ˜y surf—™e —toms of the ˜om˜—rded spe™imen —re dete™ted ˜y — surf—™e ˜—rrier dete™torF „he surf—™e ˜—rrier dete™tor is — thin l—yer of pEtype sili™on on the nEtype su˜str—te resulting pEn jun™tionF ‡hen the s™—ttered ions ex™h—nge energy with the ele™trons on the surf—™e of the dete™tor upon re—™hing the dete™torD ele™trons get promoted from the v—len™e ˜—nd to the ™ondu™tion ˜—ndF „husD e—™h ex™h—nge of energy ™re—tes ele™tronEhole p—irsF „he energy of s™—ttered ions is dete™ted ˜y simply ™ounting the num˜er of ele™tronEhole p—irsF „he energy resolution of the surf—™e ˜—rrier dete™tor in — st—nd—rd ‚fƒ experiment is IP E PH ke†F „he surf—™e ˜—rrier dete™tor is gener—lly set ˜etween WH ◦ —nd IUH ◦ to the in™ident ˜e—mF pilms —re usu—lly set norm—l to the in™ident ˜e—mF e simple l—yout is shown in pigure UFTF .

1. Figure 7. MATERIALS CHARACTERIZATION Schematic representation general setup where the surface barrier detector is placed at angle of 165 to the extrapolated incident beam.6: ◦ 7.4 Depth prole analysis es st—ted e—rlierD it is — good —pproxim—tion in thin (lm —n—lysis th—t the tot—l energy loss ∆i is proportion—l to depth tF ‡ith this —pproxim—tionD we ™—n derive the rel—tion ˜etween energy width ∆i of the sign—l from — (lm of thi™kness ∆t —s followsD ∆i a ∆t@k diGdx in C IG™osØ diGdx out A where Ø a l—˜ s™—ttering —ngleF st is worth noting th—t k is the kinem—ti™ f—™tor de(ned in equ—tion —˜ove —nd the su˜s™ripts in —nd out indi™—te the energies —t whi™h the r—te of loss of energy or diGdx is ev—lu—tedF es —n ex—mpleD we ™onsider the ˜—™ks™—ttering spe™trumD —t s™—ttering —ngle IUH ◦ D for P we† re++ in™idents on sili™on l—yer deposited onto P mm thi™k nio˜ium su˜str—te pigure UFUF .PRR CHAPTER 7.

Donovan. Figure 7. Thin Solid Films. Stupik.7: „he energy loss r—te of in™oming re++ or diGdx —long inw—rd p—th in element—l ƒi is ≈PRFT e†GÅ —t P we† —nd is ≈PT e†GÅ for the outgoing p—rti™le —t IFIP we† @ƒin™e u of ƒi is HFST when the s™—ttering —ngle is IUH ◦ D energy of the outgoing p—rti™le would ˜e equ—l to P x HFST or IFIP we†A F eg—in the v—lue of ∆iSi is ≈IQQFQ ke†F €utting the v—lues into —˜ove equ—tion we get ∆t ≈ IQQFQ ke†G@HFST B PRFT e†GÅ C IG™os IUH ◦ B PT e†GÅA a IQQFQ ke†G@IQFUU e†GÅ C PWGFWVS e†GÅA a IQQFQ ke†G RHFIU e†GÅ a QQIV ÅF ren™e — ƒi l—yer of ™—F QQHH Å thi™kness h—s ˜een deposited on the nio˜ium su˜str—teF rowever we need to remem˜er th—t the v—lue of diGdx is —pproxim—ted in this ™—l™ul—tionF 7. R. Barron.1. Nastasi. D. M.0 MeV He ions incident on a silicon thin lm deposited onto a niobium substrate. 138. 207. A. Jervis and M. R. M.5 Quantitative Analysis sn —ddition to depth pro(le —n—lysisD we ™—n study the ™omposition of —n element qu—ntit—tively ˜y ˜—™ks™—tE tering spe™tros™opyF „he ˜—si™ equ—tion for qu—ntit—tive —n—lysis is ‰ a σ F ΩF F x∆t . Adapted from P. T. 1992.PRS The backscattering spectrum for 2.

PRT CHAPTER 7. 207. Donovan. MATERIALS CHARACTERIZATION ‡here ‰ is the yield of s™—ttered ions from — thin l—yer of thi™kness ∆tD  is the num˜er of in™ident ions —nd Ω is the dete™tor solid —ngleD —nd x∆t is the num˜er of spe™imen —toms @—tomG™m2 AF shows the ‚fƒ spe™trum for — s—mple of sili™on deposited on — nio˜ium su˜str—te —nd su˜je™ted to l—ser mixingF „he x˜ h—s re—™ted with the sili™on to form — x˜ƒi2 interph—se l—yerF „he x˜ sign—l h—s ˜ro—dened —fter the re—™tion —s show in F Backscattering spectra of Si diused into Nb and Si as deposited on Nb substrate. A. Barron. R. D. Stupik. Nastasi. Figure 7. M. T. 138.8: ‡e ™—n use r—tio of the heights rSi GrNb of the ˜—™ks™—ttering spe™trum —fter form—tion of x˜ƒi2 to determine the ™omposition of the sili™ide l—yerF „he stoi™hiometri™ r—tio of x˜ —nd ƒi ™—n ˜e —pproxim—ted —sD xSi GxNb ≈ ‘rSi B σ Si “G‘rNb B σ Nb “ ren™e the ™on™entr—tion of ƒi —nd x˜ ™—n ˜e determined if we ™—n know the —ppropri—te ™ross se™tions σ Si —nd σ Nb F rowever the yield in the ˜—™ks™—ttering spe™tr— is ˜etter represented —s the produ™t of sign—l height —nd the energy width ∆iF „hus stoi™hiometri™ r—tio ™—n ˜e ˜etter —pproxim—ted —s xSi GxNb ≈ ‘rSi B ∆iSi B σ Si “G‘rNb B ∆iNb B σ Nb “ . R. 1992. Jervis and M. M. Adapted from P. Thin Solid Films.

8 Bibliography • vF gF peldm—n —nd tF ‡F w—yerD Fundamentals of Surface and Thin Film AnalysisD xorth roll—ndE ilsevierD xew ‰ork @IWVTAF • Ion Spectroscopies for Surface AnalysisD idF eF ‡F gz—ndern— —nd hF wF rer™ulesD €lenum €ress @xew ‰orkAD IWWIF • €F hF ƒtupikD wF wF honov—nD eF ‚ f—rronD „F ‚F tervisD —nd wF x—st—siD Thin Solid FilmsD IWWPD 207D IQV 7.1 Introduction „he pro™esses whi™h o™™ur —t the surf—™es of ™ryst—ls depend on m—ny extern—l —nd intern—l f—™tors su™h —s ™ryst—l stru™ture —nd ™ompositionD ™onditions of — medium where the ™ryst—l surf—™e exists —nd othersF „he —ppe—r—n™e of — ™ryst—l surf—™e is the result of ™omplexity of inter—™tions ˜etween the ™ryst—l surf—™e —nd the environmentF „he me™h—nisms of surf—™e pro™esses su™h —s dissolution or growth —re studied ˜y the physi™—l ™hemistry of surf—™esF „here —re — lot of ™omput—tion—l te™hniques whi™h —llows us to predi™t the ™h—nging of surf—™e morphology of di'erent miner—ls whi™h —re in)uen™ed ˜y di'erent ™onditions su™h —s temper—tureD pressureD pr —nd ™hemi™—l ™omposition of solution re—™ting with the surf—™eF por ex—mpleD wonte g—rlo method is widely used to simul—te the dissolution or growth of ™ryst—lsF roweverD the theoreti™—l models of surf—™e pro™esses need to ˜e veri(ed ˜y n—tur—l o˜serv—tionsF ‡e ™—n extr—™t — lot of useful inform—tion —˜out the surf—™e pro™esses through studying the ™h—nging of ™ryst—l surf—™e stru™ture under in)uen™e of environment—l ™onditionsF „he ™h—nges in surf—™e stru™ture ™—n ˜e studied through the o˜serv—tion of ™ryst—l surf—™e topogr—phyF „he topogr—phy ™—n ˜e dire™tly o˜served m—™ros™opi™—lly or ˜y using mi™ros™opi™ te™hniquesF wi™ros™opi™ o˜serv—tion —llows us to study even very sm—ll ™h—nges —nd estim—te the r—te of pro™esses ˜y o˜serving ™h—nging the ™ryst—l surf—™e topogr—phy in timeF wu™h l—˜or—tory worked under the re™onstru™tion of surf—™e ™h—nges —nd interpret—tion of dissolution —nd pre™ipit—tion kineti™s of ™ryst—lsF snvention of epw m—de possi˜le to monitor ™h—nges of surf—™e stru™ture during dissolution or growthF roweverD to dete™t —nd qu—ntify the results of dissolution pro™esses or growth it is ne™ess—ry to determine surf—™e —re— ™h—nges over — signi(™—ntly l—rger (eld of view th—n epw ™—n 2 This content is available online at <http://cnx.1.4/> The Application of VSI (Vertical Scanning Interferometry) to the Study of Crystal Surface Processes 2 7.6 Limitations st is of interest to underst—nd the limit—tions of the ˜—™ks™—ttering te™hnique in terms of the ™omp—rison with other thin (lm —n—lysis te™hnique su™h —s eiƒD ˆ€ƒ —nd ƒswƒ @„—˜le UFIAF eiƒ h—s ˜etter m—ss resolutionD l—ter—l resolution —nd depth resolution th—n ‚fƒF fut eiƒ su'ers from sputtering —rtif—™tsF gomp—red to ‚fƒD ƒswƒ h—s ˜etter sensitivityF ‚fƒ does not provide —ny ™hemi™—l ˜onding inform—tion whi™h we ™—n get from ˆ€ƒF eg—inD sputtering —rtif—™t pro˜lems —re —lso —sso™i—ted in ˆ€ƒF „he strength of ‚fƒ lies in qu—ntit—tive —n—lysisF roweverD ™onvention—l ‚fƒ systems ™—nnot —n—lyze ultr—thin (lms sin™e the depth resolution is only —˜out IH nm using surf—™e ˜—rrier dete™torF 7.7 Summary ‚utherford f—™ks™—ttering —n—lysis is — str—ightforw—rd te™hnique to determine the thi™kness —nd ™omposition of thin (lms @< RHHH ÅAF ere—s th—t h—ve ˜een l—tely explored —re the use of ˜—™ks™—ttering te™hnique in ™omposition determin—tion of new super™ondu™tor oxidesY —n—lysis of l—tti™e mism—t™hed epit—xi—l l—yersD —nd —s — pro˜e of thin (lm morphology —nd surf—™e ™lusteringF 7.PRU 7.1. .

y.2 Physical principles of optical interferometry ypti™—l interferometry —llows us to m—ke extremely —™™ur—te me—surements —nd h—s ˜een used —s — l—˜oE r—tory te™hnique for —lmost — hundred ye—rsF „hom—s ‰oung o˜served interferen™e of light —nd me—sured the w—velength of light in —n experimentD performed —round IVHIF „his experiment g—ve —n eviden™e of ‰oung9s —rguments for the w—ve model for lightF „he dis™overy of interferen™e g—ve — ˜—sis to development of interferomertry te™hniques widely su™™essfully used —s in mi™ros™opi™ investig—tionsD —s in —stronomi™ investig—tionsF „he physi™—l prin™iples of opti™—l interferometry exploit the w—ve properties of lightF vight ™—n ˜e thought —s ele™trom—gneti™ w—ve prop—g—ting through sp—™eF sf we —ssume th—t we —re de—ling with — line—rly pol—rized w—ve prop—g—ting in — v—™uum in z dire™tionD ele™tri™ (eld i ™—n ˜e represented ˜y — sinusoid—l fun™tion of dist—n™e —nd timeF E (x. y. y. MATERIALS CHARACTERIZATION provideF wore re™entlyD verti™—l s™—nning interferometry @†ƒsA h—s ˜een developed —s new tool to distinguish —nd tr—™e the re—™tive p—rts of ™ryst—l surf—™esF †ƒs —nd epw —re ™omplement—ry te™hniques —nd pr—™ti™—lly well suited to dete™t surf—™e ™h—ngesF †ƒs te™hnique provides — method for qu—nti(™—tion of surf—™e topogr—phy —t the —ngstrom to n—nometer levelF „imeEdependent †ƒs me—surements ™—n ˜e used to study the surf—™eEnorm—l retre—t —™ross ™ryst—l —nd other solid surf—™es during dissolution pro™essF „hereforeD †ƒs ™—n ˜e used to dire™tly —nd nondire™tly me—sure miner—l dissolution r—tes with high pre™isionF en—logi™—llyD †ƒs ™—n ˜e used to study kineti™s of ™ryst—l growthF 7. t) = ‚e{aexp (iϕ) exp (iωt)} = ‚e{Aexp (iωt)} @UFQA where ϕ = 2πz/λ —nd A = exp (−iϕ) is known —s the ™omplex —mplitudeF sf n is — refr—™tive index of — medium where the light prop—g—tesD the light w—ve tr—verses — dist—n™e d in su™h — mediumF „he equiv—lent opti™—l p—th in this ™—se is p=n·d @UFRA ‡hen two light w—ves —re superposedD the result intensity —t —ny point depends on whether reinfor™e or ™—n™el e—™h other @pigure UFWAF „his is well known phenomenon of interferen™eF ‡e will —ssume th—t two w—ves —re prop—g—ting in the s—me dire™tion —nd —re pol—rized with their (eld ve™tors in the s—me pl—neF ‡e will —lso —ssume th—t they h—ve the s—me frequen™yF „he ™omplex —mplitude —t —ny point in the interferen™e p—ttern is then the sum of the ™omplex —mplitudes of the two w—vesD so th—t we ™—n writeD A = A1 + A2 @UFSA where A1 = a1 exp (−iϕ1 ) —nd A2 = a2 exp (−iϕ2 ) —re the ™omplex —mplitudes of two w—vesF „he result—nt intensity isD thereforeD I = | A | = I1 + I2 + 2 (I1 I2 ) 2 1/2 ™os∆ϕ @UFTA . z. t) = a™os ωt − kz @UFPA where ω = 2πv is the ™ir™ul—r frequen™yD —nd k = 2π/λ is the prop—g—tion ™onst—ntF vet9s —lso tr—nsform this se™ond equ—tion into — ™omplex exponenti—l formD E (x. t) = a™os [2π (vt − z/λ)] @UFIA ‡here a is the —mplitude of the light w—veD v is the frequen™yD —nd λ is its w—velengthF „he term within the squ—re ˜r—™kets is ™—lled the ph—se of the w—veF vet9s rewrite this equ—tion in more ™omp—™t formD E (x. z.2. z.PRV CHAPTER 7.

The value of this amplitude depends on phase dierence between two original waves. the amplitude of resulting wave will increase or decrease.PRW where I1 —nd I2 —re the intensities of two w—ves —™ting sep—r—telyD —nd ∆ϕ = ϕ1 − ϕ2 is the ph—se di'eren™e ˜etween themF sf the two w—ves —re derived from — ™ommon sour™eD the ph—se di'eren™e ™orresponds to —n opti™—l p—th di'eren™eD ∆p = (λ/2π) ∆ϕ @UFUA The scheme of interferometric wave interaction when two waves interact with each other.9: sf ∆ϕD the ph—se di'eren™e ˜etween the ˜e—msD v—ries line—rly —™ross the (eld of viewD the intensity v—ries ™osinusoid—llyD giving rise to —ltern—ting light —nd d—rk ˜—nds or fringes @pigure UFWAF „he intensity in —n interferen™e p—ttern h—s its m—ximum v—lue Imax = I1 + I2 + 2 (I1 I2 ) when ∆ϕ = 2mπ D where m is —n integer —nd its minimum v—lue 1/2 @UFVA Imin = I1 + I2 − 2 (I1 I2 ) 1/2 @UFWA when ∆ϕ = (2m + 1) π F „he prin™iple of interferometry is widely used to develop m—ny types of interferometri™ set upsF yne of the e—rliest set ups is wi™helson interferometryF „he ide— of this interferometry is quite simpleX interferen™e . Figure 7.

m = 0. MATERIALS CHARACTERIZATION fringes —re produ™ed ˜y splitting — ˜e—m of mono™hrom—ti™ light so th—t one ˜e—m strikes — (xed mirror —nd the other — mov—˜le mirrorF en interferen™e p—ttern results when the re)e™ted ˜e—ms —re ˜rought ˜—™k togetherF „he wi™helson interferometri™ s™heme is shown in pigure UFIHF Figure 7. „he di'eren™e of p—th lengths ˜etween two ˜e—ms is Px ˜e™—use ˜e—ms tr—verse the design—ted dist—n™es twi™eF „he interferen™e o™™urs when the p—th di'eren™e is equ—l to integer num˜ers of w—velengthsD ∆p = 2x = mλ. ±1. ±2FFF @UFIHA wodern interferometri™ systems —re more ™ompli™—tedF …sing spe™i—l ph—seEme—surement te™hniques they ™—p—˜le to perform mu™h more —™™ur—te height me—surements th—n ™—n ˜e o˜t—ined just ˜y dire™tly looking —t the interferen™e fringes —nd me—suring how they dep—rt from ˜eing str—ight —nd equ—lly sp—™edF „ypi™—lly interferometri™ system ™onsist of lights sour™eD ˜e—msplitterD o˜je™tive systemD system of registr—tion of sign—ls —nd tr—nsform—tion into digit—l form—t —nd ™omputer whi™h pro™ess d—t—F †erti™—l s™—nning interferometry is ™ont—ins —ll these p—rtsF pigure UFII shows — ™on(gur—tion of †ƒs interferometri™ systemF .10: Schematic representation of a Michelson interferometry set-up.PSH CHAPTER 7.

w—ny of modern interferometri™ systems use wir—u o˜je™tive in their ™onstru™tionsF wire—u o˜je™tive is ˜—sed on — wi™helson interferometerF „his o˜je™tive ™onsists of — lensD — referen™e mirror —nd — ˜e—msplitterF „he ide— of getting interfering ˜e—ms is simpleX two ˜e—ms @red linesA tr—vel —long the opti™—l —xisF „hen they —re re)e™ted from the referen™e surf—™e —nd the s—mple surf—™e respe™tively @˜lue linesAF efter this these ˜e—ms —re re™om˜ined to interfere with e—™h otherF en illumin—tion or light sour™e system is used to dire™t light onto — s—mple surf—™e through — ™u˜e ˜e—m splitter —nd the wire—u o˜je™tiveF „he s—mple surf—™e within the (eld of view of the o˜je™tive is uniformly illumin—ted ˜y those ˜e—ms with di'erent in™iden™e —nglesF eny point on the s—mple surf—™e ™—n re)e™t those in™ident ˜e—ms in the form of divergent ™oneF ƒimil—rlyD the point on the referen™e symmetri™—l with th—t on the s—mple surf—™e —lso re)e™ts those illumin—ted ˜e—ms in the s—me formF „he wire—u o˜je™tive dire™ts the ˜e—ms re)e™ted of the referen™e —nd the s—mple surf—™e onto — ggh @™h—rgeE™oupled devi™eA sensor through — tu˜e lensF „he ggh sensor is —n —n—log shift register th—t en—˜les the tr—nsport—tion of —n—log sign—ls @ele™tri™ ™h—rgesA through su™™essive st—ges @™—p—™itorsAD ™ontrolled ˜y — ™lo™k sign—lF „he resulting interferen™e fringe p—ttern is dete™ted ˜y ggh sensor —nd the ™orresponding sign—l is digitized ˜y — fr—me gr—˜˜er for further pro™essing with — ™omputerF „he dist—n™e ˜etween — minimum —nd — m—ximum of the interferogr—m produ™ed ˜y two ˜e—ms re)e™ted from the referen™e —nd s—mple surf—™e is knownF „h—t isD ex—™tly h—lf the w—velength of the light sour™eF „hereforeD with — simple interferogr—m the verti™—l resolution of the te™hnique would ˜e —lso limited to λGPF sf we will use — l—ser light —s — light sour™e with — w—velength of QHH nm the resolution would ˜e only ISH .11: Schematic representation of the Vertical scanning interferometry (VSI) system.PSI Figure 7.

y) sinα (x. Figure 7. y) B (x. y) = I1 (x. y) = I1 (x. y) + I2 (x. y) − I2 (x. MATERIALS CHARACTERIZATION nmF „his resolution is not good enough for — det—iled ne—rE—tomi™ s™—le investig—tion of ™ryst—l surf—™esF portun—telyD the verti™—l resolution of the te™hnique ™—n ˜e improved signi(™—ntly ˜y moving either the referen™e or the s—mple ˜y — fr—™tion of the w—velength of the lightF sn this w—yD sever—l interferogr—ms —re produ™edF „hen they —re —ll overl—yedD —nd their ph—se shifts ™omp—red ˜y the ™omputer softw—re pigure UFIPF „his method is widely known —s ph—se shift interferometry @€ƒsAF Sketch illustrating phase-shift technology. y)D B(x. y) —nd D(x. y) to the resulting interferen™e light intensities whi™h —re ™orresponded to ph—seEshifting steps of HD π / PD π —nd Qπ / PF „hese intensities ™—n ˜e o˜t—ined ˜y moving the referen™e mirror through displ—™ements of λ/ VD λ/ R —nd Qλ/ VD respe™tivelyF „he equ—tions for the resulting intensities would ˜eX A (x. y) @UFIIA @UFIPA .PSP CHAPTER 7. y) ™osα (x. y) is re™orded ˜y using the ggh ™—mer—F vet9s —ssign A(x.12: wost opti™—l testing interferometers now use ph—seEshifting te™hniques not only ˜e™—use of high resolution ˜ut —lso ˜e™—use ph—seEshifting is — high —™™ur—™y r—pid w—y of getting the interferogr—m inform—tion into the ™omputerF elso us—ge of this te™hnique m—kes the inherent noise in the d—t— t—king pro™ess very lowF es the result in — good environment —ngstrom or su˜E—ngstrom surf—™e height me—surements ™—n ˜e performedF es it w—s s—id —˜oveD in ph—seEshifting interferometry the ph—se di'eren™e ˜etween the interfering ˜e—ms is ™h—nged —t — ™onst—nt r—te —s the dete™tor is re—d outF yn™e the ph—se is determined —™ross the interferen™e (eldD the ™orresponding height distri˜ution on the s—mple surf—™e ™—n ˜e determinedF „he ph—se distri˜ution φ(x. The sample is continuously moved along the vertical axes in order to scan surface topography. All interferograms are automatically overlayed using computer software. y)D C(x.

y) + I2 (x. y) @UFIQA @UFIRA where I1 (x. y)D on the test surf—™e is given ˜y λ ϕ (x. y) = I1 (x. y) sinα (x.PSQ C (x. y) − I2 (x. y) D (x. y) − C (x. y) ™osα (x. y) of — s—mple surf—™e will ˜e given ˜y the rel—tionX ϕ (x. y)—nd I2 (x. y) —re two overl—pping ˜e—ms from two symmetri™ points on the test surf—™e —nd the referen™e respe™tivelyF ƒolving equ—tions @UFIIA!@UFIRAD the ph—se m—p φ(x. y) @UFISA yn™e the ph—seis determined —™ross the interferen™e (eld pixel ˜y pixel on — twoEdimension—l ggh —rr—yD the lo™—l height distri˜ution/ ™ontourD h(x. y) @UFITA 4π xorm—lly the resulted fringe ™—n ˜e in the form of — line—r fringe p—ttern ˜y —djusting the rel—tive position ˜etween the referen™e mirror —nd s—mple surf—™esF ren™e —ny distorted interferen™e fringe would indi™—te — lo™—l pro(le/ ™ontour of the test surf—™eF st is import—nt to note th—t the wire—u o˜je™tive is mounted on — ™—p—™itive ™losedEloop ™ontrolled €„ @piezoele™tri™ —™tu—torA —s to en—˜le ph—se shifting to ˜e —™™ur—tely implementedF „he €„ is ˜—sed on piezoele™tri™ e'e™t referred to the ele™tri™ potenti—l gener—ted ˜y —pplying pressure to piezoele™tri™ m—teri—lF „his type of m—teri—ls is used to ™onvert ele™tri™—l energy to me™h—ni™—l energy —nd vi™eEvers—F „he pre™ise motion th—t results when —n ele™tri™ potenti—l is —pplied to — piezoele™tri™ m—teri—l h—s —n import—n™e for n—nopositioningF e™tu—tors using the piezo e'e™t h—ve ˜een ™ommer™i—lly —v—il—˜le for QS ye—rs —nd in th—t time h—ve tr—nsformed the world of pre™ision positioning —nd motion ™ontrolF †erti™—l s™—nning interferometer —lso h—s —nother n—meY whiteElight interferometry @‡vsA ˜e™—use of using the white light —s — sour™e of lightF ‡ith this type of sour™e — sep—r—te fringe system is produ™ed for e—™h w—velengthD —nd the result—nt intensity —t —ny point of ex—mined surf—™e is o˜t—ined ˜y summing these individu—l p—tternsF hue to the ˜ro—d ˜—ndwidth of the sour™e the ™oherent length v of the sour™e is shortX h (x. y) = I1 (x. y) − D (x. y) = B (x. y) = λ2 @UFIUA n∆λ where λ is the ™enter w—velengthD n is the refr—™tive index of the mediumD ∆λ is the spe™tr—l width of the sour™eF sn this w—y good ™ontr—st fringes ™—n ˜e o˜t—ined only when the lengths of interfering ˜e—ms p—thw—ys —re ™losed to e—™h otherF sf we will v—ry the length of — p—thw—y of — ˜e—m re)e™ted from s—mpleD the height of — s—mple ™—n ˜e determined ˜y looking —t the position for whi™h — fringe ™ontr—st is — m—ximumF sn this ™—se interferen™e p—ttern exist only over — very sh—llow depth of the surf—™eF ‡hen we v—ry — p—thw—y of s—mpleEre)e™ted ˜e—m we —lso move the s—mple in — verti™—l dire™tion in order to get the ph—se —t whi™h m—ximum intensity of fringes will ˜e —™hievedF „his ph—se will ˜e ™onverted in height of — point —t the s—mple surf—™eF „he ™om˜in—tion of ph—se shift te™hnology with whiteElight sour™e provides — very powerful tool to me—sure the topogr—phy of quite rough surf—™es with the —mplitude in heights —˜out —nd the pre™ision up to IEP nmF „hrough — developed softw—re p—™k—ge for qu—ntit—tively ev—lu—ting the resulting interferogr—mD the proposed system ™—n retrieve the surf—™e pro(le —nd topogr—phy of the s—mple o˜je™ts pigure UFIQF L= . y) A (x.

2.2. MATERIALS CHARACTERIZATION Figure 7. AFM and VSI ix™ept the interferometri™ methods des™ri˜ed —˜oveD there —re — sever—l other mi™ros™opi™ te™hniques for studying ™ryst—l surf—™e topogr—phyF „he most ™ommon —re s™—nning ele™tron mi™ros™opy @ƒiwA —nd —tomi™ for™e mi™ros™opy @epwAF ell these te™hniques —re used to o˜t—in inform—tion —˜out the surf—™e stru™tureF rowever they di'er from e—™h other ˜y the physi™—l prin™iples on whi™h they ˜—sedF 7.3.50x objective.1 Scanning electron microscopy ƒiw —llows us to o˜t—in im—ges of surf—™e topogr—phy with the resolution mu™h higher th—n the ™onvention—l light mi™ros™opes doF elso it is —˜le to provide inform—tion —˜out other surf—™e ™h—r—™teristi™s su™h —s ™hemi™—l ™ompositionD ele™tri™—l ™ondu™tivity et™D see pigure UFIRF ell types of d—t— —re gener—ted ˜y the re)e™ting of —™™eler—ted ele™tron ˜e—ms from the s—mple surf—™eF ‡hen ele™trons strike the s—mple surf—™eD they lose their energy ˜y repe—ted r—ndom s™—ttering —nd —dsorption within —n outer l—yer into the depth v—rying from IHH nm to S mi™ronsF .13: Example of muscovite surface topography. 7.3 A comparison of common methods to determine surface topography: SEM.PSR CHAPTER 7. obtained by using VSI.

2 Atomic force microscopy epw is — very popul—r tool to study surf—™e dissolutionF epw set up ™onsists of s™—nning — sh—rp tip on the end of — )exi˜le ™—ntilever whi™h moves —™ross — s—mple surf—™eF „he tips typi™—lly h—ve —n end r—dius of P to PH nmD depending on tip typeF ‡hen the tip tou™h the surf—™e the for™es of these inter—™tions le—ds to de)e™tion of — ™—ntileverF „he inter—™tion ˜etween tip —nd s—mple surf—™e involve me™h—ni™—l ™ont—™t for™esD v—n der ‡——ls for™esD ™—pill—ry for™esD ™hemi™—l ˜ondingD ele™trost—ti™ for™esD m—gneti™ for™es et™F „he de)e™tion of — ™—ntilever is usu—lly me—sured ˜y re)e™ting — l—ser ˜e—m o' the ˜—™k of the ™—ntilever into — split photodiode dete™torF e s™hem—ti™ dr—wing of epw ™—n ˜e seen in pigure UFISF „he two most ™ommonly used modes of oper—tion —re ™ont—™t mode epw —nd t—pping mode epwD whi™h —re ™ondu™ted in —ir or liquid environmentsF .3.2.14: Scheme of electron beam-sample interaction at SEM analysis „he thi™kness of this outer l—yer —lso knows —s inter—™tive l—yer depends on energy of ele™trons in the ˜e—mD ™omposition —nd density of — s—mpleF ‚esult of the inter—™tion ˜etween ele™tron ˜e—m —nd the surf—™e provides sever—l types of sign—lsF „he m—in type is se™ond—ry or inel—sti™ s™—ttered ele™tronsF „hey —re produ™ed —s — result of inter—™tion ˜etween the ˜e—m of ele™trons —nd we—kly ˜ound ele™trons in the ™ondu™tion ˜—nd of the s—mpleF ƒe™ond—ry ele™trons —re eje™ted from the kEor˜it—ls of —toms within the surf—™e l—yer of thi™kness —˜out — few n—nometersF „his is ˜e™—use se™ond—ry ele™trons —re low energy ele™trons @<SH e†AD so only those formed within the (rst few n—nometers of the s—mple surf—™e h—ve enough energy to es™—pe —nd ˜e dete™tedF ƒe™ond—ry ˜—™ks™—ttered ele™trons provide the most ™ommon sign—l to investig—te surf—™e topogr—phy with l—ter—l resolution up to HFR E HFU nmF righ energy ˜e—m ele™trons —re el—sti™ s™—ttered ˜—™k from the surf—™eF „his type of sign—l gives inforE m—tion —˜out ™hemi™—l ™omposition of the surf—™e ˜e™—use the energy of ˜—™ks™—ttered ele™trons depends on the weight of —toms within the inter—™tion l—yerF elso this type of ele™trons ™—n form se™ond—ry ele™trons —nd es™—pe from the surf—™e or tr—vel f—ther into the s—mple th—n the se™ond—ryF „he ƒiw im—ge formed is the result of the intensity of the se™ond—ry ele™tron emission from the s—mple —t e—™h xDy d—t— point during the s™—nning of the surf—™eF 7.PSS Figure 7.

2.3 Comparison of techniques ell te™hniques des™ri˜ed —˜ove —re widely used in studying of surf—™e n—noE —nd mi™romorphologyF roweverD e—™h method h—s its own limit—tions —nd the proper ™hoi™e of —n—lyti™—l te™hnique depends on fe—tures of —n—lyzed surf—™e —nd prim—ry go—ls of rese—r™hF ell these te™hniques —re ™—p—˜le to o˜t—in —n im—ge of — s—mple surf—™e with quite good resolutionF „he l—ter—l resolution of †ƒs is mu™h lessD then for other te™hniquesX ISH nm for †ƒs —nd HFS nm for epw —nd ¡ ƒiwF †erti™—l resolution of epw @HFS ÅA is ˜etter then for †ƒs @I E P nmAD however †ƒs is ™—p—˜le to me—sure — high verti™—l r—nge of heights @I mmA whi™h m—kes possi˜le to study even very rough surf—™esF yn the ™ontr—ryD epw —llows us to me—sure only quite smooth surf—™es ˜e™—use of its rel—tively sm—ll verti™—l s™—n r—nge @U µmAF ƒiw h—s less resolutionD th—n epw ˜e™—use it requires ™o—ting of — ™ondu™tive m—teri—l with the thi™kness within sever—l nmF „he signi(™—nt —dv—nt—ge of †ƒs is th—t it ™—n provide — l—rge (eld of view @VRS × TQH µm for IHx o˜je™tiveA of tested surf—™esF ‚e™ent studies of surf—™e roughness ™h—r—™teristi™s showed th—t the surf—™e roughness p—r—meters in™re—se with the in™re—sing (eld of view until — ™riti™—l size of PSHDHHH µm is re—™hedF „his v—lue is l—rger then the m—ximum (eld of view produ™ed ˜y epw @IHH × IHH µmA ˜ut ™—n ˜e e—sily o˜t—ined ˜y †ƒsF ƒiw is —lso ™—p—˜le to produ™e im—ges with l—rge (eld of viewF roweverD ƒiw is —˜le to provide only Ph im—ges from one s™—n while epw —nd †ƒs let us to o˜t—in Qh im—gesF st m—kes qu—ntit—tive . MATERIALS CHARACTERIZATION Figure 7. ‡orking under the ™ont—™t mode epw s™—ns the s—mple while monitoring the ™h—nge in ™—ntilever de)e™tion with the split photodiode dete™torF voop m—int—ins — ™onst—nt ™—ntilever re)e™tion ˜y verti™—lly moving the s™—nner to get — ™onst—nt sign—lF „he dist—n™e whi™h the s™—nner goes ˜y moving verti™—lly —t e—™h xDy d—t— point is stored ˜y the ™omputer to form the topogr—phi™ im—ge of the s—mple surf—™eF ‡orking under the t—pping mode epw os™ill—tes the ™—ntilever —t its reson—n™e frequen™y @typi™—lly∼QHH krzA —nd lightly t—ps the tip on the surf—™e during s™—nningF „he ele™trost—ti™ for™es in™re—se when tip gets ™lose to the s—mple surf—™eD therefore the —mplitude of the os™ill—tion de™re—sesF „he l—ser de)e™tion method is used to dete™t the —mplitude of ™—ntilever os™ill—tionF ƒimil—r to the ™ont—™t modeD feed˜—™k loop m—int—ins — ™onst—nt os™ill—tion —mplitude ˜y moving the s™—nner verti™—lly —t every xDy d—t— pointF ‚e™ording this movement forms the topogr—phi™—l im—geF „he —dv—nt—ge of t—pping mode over ™ont—™t mode is th—t it elimin—tes the l—ter—lD she—r for™es present in ™ont—™t modeF „his en—˜les t—pping mode to im—ge softD fr—gileD —nd —dhesive surf—™es without d—m—ging them while work under ™ont—™t mode —llows the d—m—ge to o™™urF 7.PST CHAPTER 7.3.15: Schematic drawing of an AFM apparatus.

2 HFSEIFP µm P nm VRS × TQH µm @IHx o˜E je™tiveA I mm E eir HFS nm HFS Å IHH × IHH µm IH µm E eirD liquid HFSEI nm ynly Ph im—ges IEP mm E ‚equired ™o—ting of — ™ondu™ted m—teri—l †—™uum X e ™omp—rison of †ƒs s—mple —nd resolution with epw —nd ƒiwF 7.PSU —n—lysis of surf—™e topogr—phy more ™ompli™—tedD for ex—mpleD topogr—phy of mem˜r—nes is studied ˜y ™ross se™tion —nd top view im—gesF VSI AFM SEM v—ter—l resolution †erti™—l resolution pield of view †erti™—l r—nge of s™—n €rep—r—tion of — s—mple ‚equired environment Table 7.4 The experimental studying of surface processes using microscopic techniques „he limit—tions of e—™h te™hnique des™ri˜ed —˜ove —re ™riti™—lly import—nt to ™hoose —ppropri—te te™hnique for studying surf—™e pro™essesF vet9s explore —ppli™—tion of these te™hniques to study dissolution of ™ryst—lsF ‡hen ™ryst—lline m—tter dissolves the ™h—nges of the ™ryst—l surf—™e topogr—phy ™—n ˜e o˜served ˜y using mi™ros™opi™ te™hniquesF sf we will —pply —n unre—™tive m—sk @sili™on for ex—mpleA on ™ryst—l surf—™e —nd pl—™e — ™ryst—lline s—mple into the experiment re—™tor then we get two types of surf—™esX dissolving —nd rem—ining the s—me or unre—™tedF efter some period of time the ™ryst—l surf—™e st—rts to dissolve —nd ™h—nge its zElevelF sn order to study these ™h—nges ex situ we ™—n pull out — s—mple from the re—™tion ™ell then remove — m—sk —nd me—sure the —ver—ge height di'eren™e ∆ h˜etween the unre—™ted —nd dissolved —re—sF „he —ver—ge heights of dissolved —nd unre—™ted —re—s —re o˜t—ined through digit—l pro™essing of d—t— o˜t—ined ˜y mi™ros™opesF „he velo™ity of norm—l surf—™e retre—t vSNR during the time interv—l ∆t is de(ned —s vSNR = ∆h ∆t hividing this velo™ity ˜y the mol—r volume V @™m3 GmolA gives — glo˜—l dissolution r—te in the f—mili—r units of moles per unit —re— per unit timeX Ψ vSNR @UFIVA V „his method —llows us to o˜t—in experiment—l v—lues of dissolution r—tes just ˜y pre™ise me—suring of —ver—ge surf—™e heightsF woreoverD using this method we ™—n me—sure lo™—l dissolution r—tes —t et™h pits ˜y monitoring ™h—nges in the volume —nd density of et™h pits —™ross the surf—™e over timeF †ƒs te™hnique is ™—p—˜le to perform these me—surements ˜e™—use of l—rge verti™—l r—nge of s™—nningF sn order to get pre™ise v—lues of r—tes whi™h —re not depend on o˜serving pl—™e of ™ryst—l surf—™e we need to me—sure enough l—rge —re—sF †ƒs te™hnique provides d—t— from —re—s whi™h —re l—rge enough to study surf—™es with heterogeneous dissolution dyn—mi™s —nd o˜t—in —ver—ge dissolution r—tesF „hereforeD †ƒs m—kes possi˜le to me—sure r—tes of norm—l surf—™e retre—t during the dissolution —nd o˜serve form—tionD growth —nd distri˜ution of et™h pits on the surf—™eF roweverD if the me™h—nism of dissolution is ™ontrolled ˜y dyn—mi™s of —tomi™ steps —nd kink sites within — smooth —tomi™ surf—™e —re—D the o˜serv—tion of the dissolution pro™ess need to use — more pre™ise te™hniqueF epw is ™—p—˜le to provide inform—tion —˜out ™h—nges in step morphology in situ when the dissolution R= .2.

Sci.PSV CHAPTER 7. J.D PHHUD 307D WSSF ‰F ‡y—rtD qF qeorgesD gF heumieD gF emr—D —nd €F woulin—D J.D PHHTD 17D TIUF eF vuttge —nd ‚F ƒF ervidsonD in Kinetics of water-rock interactionD idF ƒF fr—ntleyD tF uu˜i™kiD —nd eF ‡hiteD ƒpringer @PHHUAF vF h—ng —nd eF vuttgeD American MineralogistD PHHUD 92D IQITF gF pis™her eF —nd vuttgeD Am.D PHHRD 70D ITPUF eF gF v—s—g— —nd eF vuttgeD American MineralogistD PHHRD 89D SPUF uF tF h—vis —nd eF vuttgeD Am. Microbiol.D PHHSD 305D UPUF ƒF rF ‡—ng —nd „—yD Meas. Membrane Sci. J. J. Anal. Sci.D PHHVD 315D VPF „F gF †—im—kisD iF hF i™onomouD —nd gF gF „r—p—lisD J. Technol.5 Bibliography • • • • • • • • • • • • • eF gF v—s—g—D Kinetic Theory in the Earth SciencesF €rin™eton …nivF €ressD €rin™etonD xt @IWWVAF eF vuttgeD iF †F foltonD —nd eF gF v—s—g— eFgFD Am. Sci. Sci. MATERIALS CHARACTERIZATION o™™ursF por ex—mpleD immedi—te response of the dissolved surf—™e to the ™h—nging of environment—l ™onditions @™on™entr—tions of ions in the solutionD pr et™FA ™—n ˜e studied ˜y using epwF ƒiw is —lso used to ex—mine mi™ro —nd n—notexture of solid surf—™es —nd study dissolution pro™essesF „his method —llows us to o˜serve l—rge —re—s of ™ryst—l surf—™e with high resolution whi™h m—kes possi˜le to me—sure — high v—riety of surf—™esF „he signi(™—nt dis—dv—nt—ge of this method is the requirement to ™over ex—mine s—mple ˜y ™ondu™tive su˜st—n™e whi™h limits the resolution of ƒiwF „he other dis—dv—nt—ge of ƒiw is th—t the —n—lysis is ™ondu™ted in v—™uumF ‚e™ent te™hniqueD environment—l ƒiw or iƒiw over™omes these requirements —nd m—kes possi˜le even ex—mine liquids —nd ˜iologi™—l m—teri—lsF „he third dis—dv—nt—ge of this te™hnique is th—t it produ™es only Ph im—gesF „his ™re—tes some di0™ulties to me—sure ∆h within the dissolving —re—F yne of —dv—nt—ges of this te™hnique is th—t it is —˜le to me—sure not only surf—™e topogr—phy ˜ut —lso ™hemi™—l ™omposition —nd other surf—™e ™h—r—™teristi™s of the surf—™eF „his f—™t is used to monitor ™h—nging in ™hemi™—l ™omposition during the dissolutionF 7. Environ.D PHHVD 92D UVQF .D IWWWD 299D TSPF hF u—™zm—rekD VacuumD PHHID 62D QHQF €F r—rih—r—nF Optical interferometryD ƒe™ond editionD e™—demi™ press @PHHQA sƒfx HEIPEQIITQHEWF eF vuttge —nd €F qF gonr—dD Appl. Cal. Therm.2.

MaterFD IWWSD 7D IPTSF 8.1. This content is available online at <http://cnx.2/>.1 Bibliography • tF qop—l—krishn—nD Chem.2 Semiconductor Nanoparticles 2 „he most studied nonEoxide semi™ondu™tors —re ™—dmium ™h—l™ogenides @gdiD with i a sul(deD selenide —nd tellurideAF gdi n—no™ryst—ls were pro˜—˜ly the (rst m—teri—l used to demonstr—te qu—ntum size e'e™ts ™orresponding to — ™h—nge in the ele™troni™ stru™ture with sizeD iFeFD the in™re—se of the ˜—nd g—p energy with 1 2 This content is available online at < Introduction to Nanoparticle Synthesis 1 „he f—˜ri™—tion of n—nom—teri—ls with stri™t ™ontrol over sizeD sh—peD —nd ™ryst—lline stru™ture h—s inspired the —ppli™—tion of n—no™hemistry to numerous (elds in™luding ™—t—lysisD medi™ineD —nd ele™troni™sF „he use of n—nom—teri—ls in su™h —ppli™—tions —lso requires the development of methods for n—nop—rti™le —ssem˜ly or dispersion in v—rious medi—F e m—jority of studies h—ve ˜een —imed —t dispersion in —queous medi— —imed —t their use in medi™—l —ppli™—tions —nd studies of environment—l e'e™tsD howeverD the prin™iples of n—nop—rti™le f—˜ri™—tion —nd fun™tion—liz—tion of n—nop—rti™les tr—ns™ends their eventu—l —ppli™—tionF rereinD we review the most gener—l routes to n—nop—rti™les of the key types th—t m—y h—ve p—rti™ul—r —ppli™—tion within the oil —nd g—s industry for sensorD ™ompositeD or devi™e —ppli™—tionsF ƒynthesis methods for n—nop—rti™les —re typi™—lly grouped into two ™—tegoriesX topEdown —nd ˜ottomE upF „he (rst involves division of — m—ssive solid into sm—ller portionsF „his —ppro—™h m—y involve milling or —ttritionD ™hemi™—l methodsD —nd vol—tiliz—tion of — solid followed ˜y ™ondens—tion of the vol—tilized ™omponentsF „he se™ondD ˜ottomEupD method of n—nop—rti™le f—˜ri™—tion involves ™ondens—tion of —toms or mole™ul—r entities in — g—s ph—se or in solutionF „he l—tter —ppro—™h is f—r more popul—r in the synthesis of n—nop—rti™lesF hispersions of n—nop—rti™les —re intrinsi™—lly thermodyn—mi™—lly met—st—˜leD prim—rily due to their very high surf—™e —re—D whi™h represents — positive ™ontri˜ution to the free enth—lpy of the systemF sf the —™tiv—tion energies —re not su0™iently highD evolution of the n—nop—rti™le dispersion o™™urs ™—using —n in™re—se in n—nop—rti™le size —s typi(ed ˜y —n ystw—ld ripening pro™essF „husD highly dispersed n—nop—rti™les —re only kineti™—lly st—˜ilized —nd ™—nnot ˜e prep—red under ™onditions th—t ex™eed some thresholdD me—ning th—t soE™—lled softE™hemi™—l or  chemie duce  methods —re preferredF sn —dditionD the use of surf—™e st—˜iliz—tion is employed in m—ny n—nom—teri—ls to hinder sinteringD re™ryst—lliz—tion —nd —ggreg—tionF 8.Chapter 8 Nanotechnology 8.4/>.org/content/m22374/1. PSW .

the shorter the emitted wavelength of light.1: elthough ™—dmium ™h—l™ogenides —re the most studies semi™ondu™ting n—nop—rti™lesD the methodology for the form—tion of semi™ondu™ting n—nop—rti™les w—s (rst demonstr—ted independently for sn€ —nd q—esD eFgFD @VFIAF „his method h—s ˜een —d—pted for — r—nge of semi™ondu™tor n—nop—rti™lesF @VFIA sn the ™—se of gdiD dimethyl™—dmium gd@gr3 A2 is used —s — ™—dmium sour™e —nd ˜is@trimethylsilylAsul(deD @we3 ƒiA2 ƒD trio™tylphosphine selenide or telluride @„y€ƒeD „y€„eA serve —s sour™es of selenide in triE o™tylphosphine oxide @„y€yA used —s solvent —nd ™—pping mole™uleF „he mixture is he—ted —t PQHEPTH ◦ g over — few hours while modul—ting the temper—ture in response to ™h—nges in the size distri˜ution —s estim—ted from the —˜sorption spe™tr— of —liquots removed —t regul—r interv—lsF „hese p—rti™lesD ™—pped with „y€G„y€y mole™ulesD —re nonE—ggreg—ted @pigure VFPA —nd e—sily dispersi˜le in org—ni™ solvents forming opti™—lly ™le—r dispersionsF ‡hen simil—r syntheses —re performed in the presen™e of surf—™t—ntD strongly —nisotropi™ n—nop—rti™les —re o˜t—inedD eFgFD rodEsh—ped gdƒe n—nop—rti™les ™—n ˜e o˜t—inedF .PTH CHAPTER 8. green ∼520 nm. uorescing brightly. the smaller the dot. and orange ∼612 nm) due to the quantum dots' bandgap (and thus the wavelength of emitted light) depends strongly on the particle size. in three noticeable dierent colors (blue ∼481 nm. Figure 8. The "blue" quantum dots have the smallest particle size. as they are exposed to an ultraviolet lamp. dissolved in toluene. the "green" dots are slightly larger. NANOTECHNOLOGY the de™re—se in size of p—rti™les @pigure VFIAF „hese semi™ondu™tors n—no™ryst—ls —re ™ommonly synthesized ˜y therm—l de™omposition of —n org—nomet—lli™ pre™ursor dissolved in —n —nhydrous solvent ™ont—ining the sour™e of ™h—l™ogenide —nd — st—˜ilizing m—teri—l @polymer or ™—pping lig—ndAF ƒt—˜ilizing mole™ules ˜ound to the surf—™e of p—rti™les ™ontrol their growth —nd prevent p—rti™le —ggreg—tionF Picture of cadmium selenide (CdSe) quantum dots. and the "orange" dots are the largest.

Chem.2.D IWVWD 1D RF • ˆF ongD ‰F pengD ‡F unollD —nd rF w—nD J.1 Bibliography • gF ‚F ferryD Soc. Rev. Chem. Commun. .3.PTI Figure 8.D PHHPD 12D QQRQF • ‚F vF ‡ellsD gF qF €ittD eF „F w™€h—ilD eF €F €urdyD ƒF ‚F fF ƒh—(eez—dD —nd r—llo™k Chem. Soc. Chem.D PHHHD 122D IPUHHF • gF fF wurr—yD hF tF xorrisD —nd wF qF f—wendiD J. Soc.4/>. Chem.D IWTUD 161D VRVF • wF hF re—lyD €F iF v—i˜inisD €F hF ƒtupikD —nd eF ‚F f—rronD J. Chem.D PHHQD 125D IQSSWF 8. Soc. Am.2: TEM image of CdSe nanoparticles.D IWVWD QSWF • vF w—nn—D iF gF ƒ™herD —nd eF €F elivis—tosD J. Am. fe™—use gd@gr3 A2 is extremely toxi™D pyrophori™ —nd explosive —t elev—ted temper—tureD other gd sour™es h—ve ˜een usedF gdy —ppe—rs to ˜e —n interesting pre™ursorF gdy powder dissolves in „y€y —nd r€e or „h€e @tetr—de™ylphosphoni™ —™idA —t —˜out QHH ◦ g giving — ™olorless homogeneous solutionF fy introdu™ing selenium or tellurium dissolved in „y€D n—no™ryst—ls grow to the desired sizeF x—norods of gdƒe or gd„e ™—n —lso ˜e produ™ed ˜y using — gre—ter initi—l ™on™entr—tion of ™—dmium —s ™omp—red to re—™tions for n—nop—rti™lesF „his —ppro—™h h—s ˜een su™™essfully —pplied for synthesis of numerous other met—l ™h—l™ogenides in™luding nƒD nƒeD —nd n1-x gdx ƒF ƒimil—r pro™edures en—˜le the form—tion of wnƒD €dƒD xiƒD gu2 ƒ n—nop—rti™lesD n—no rodsD —nd n—no disksF 8. Am.1 Introduction 3 elthough n—nom—teri—ls h—d ˜een known for m—ny ye—rs prior to the report of g60 the (eld of n—nos™—le s™ien™e w—s undou˜tedly founded upon this semin—l dis™overyF €—rt of the re—son for this explosion in n—no™hemistry is th—t while ™—r˜on m—teri—ls r—nge from wellEde(ned n—no sized mole™ules @iFeFD g60 A to tu˜es with lengths of hundreds of mi™ronsD they do not exhi˜it the inst—˜ilities of other n—nom—teri—ls —s — result of the very high —™tiv—tion ˜—rriers to their stru™tur—l re—rr—ngementF es — ™onsequen™e they —re 3 This content is available online at <http://cnx. Am. Mater.D IWWQD 115D VUHTF • F eF €eng —nd ˆF €engD J.3 Carbon Nanomaterials 8. Soc. Chem.



highly st—˜le even in their unfun™tion—lized formsF hespite this r—nge of ™—r˜on n—nom—teri—ls possi˜le they exhi˜it ™ommon re—™tion ™hemistryX th—t of org—ni™ ™hemistryF „he previously unknown —llotrope of ™—r˜onX g60 D w—s dis™overed in IWVSD —nd in IWWTD gurlD urotoD —nd ƒm—lley were —w—rded the xo˜el €rize in ghemistry for the dis™overyF „he other —llotropes of ™—r˜on —re gr—phite @sp2 A —nd di—mond @sp3 AF g60 D ™ommonly known —s the ˜u™ky˜—ll or fu™kminsterfullereneD h—s — spheri™—l sh—pe ™omprising of highly pyr—mid—lized sp2 ™—r˜on —tomsF „he g60 v—ri—nt is often ™omp—red to the typi™—l so™™er foot˜—llD hen™e ˜u™ky˜—llF roweverD ™onfusinglyD this term is ™ommonly used for higher deriv—tivesF pullerenes —re simil—r in sheet stru™ture to gr—phite ˜ut they ™ont—in pent—gon—l @or sometimes hept—gon—lA rings th—t prevent the sheet from ˜eing pl—n—rF „he unusu—l stru™ture of g60 led to the introdu™tion of — new ™l—ss of mole™ules known —s fullerenesD whi™h now ™onstitute the third —llotrope of ™—r˜onF pullerenes —re ™ommonly de(ned —s —ny of — ™l—ss of ™losed hollow —rom—ti™ ™—r˜on ™ompounds th—t —re m—de up of twelve pent—gon—l —nd di'ering num˜ers of hex—gon—l f—™esF „he num˜er of ™—r˜on —toms in — fullerene r—nge from g60 to g70 D g76 D —nd higherF righer order fullerenes in™lude ™—r˜on n—notu˜es th—t ™—n ˜e des™ri˜ed —s fullerenes th—t h—ve ˜een stret™hed —long — rot—tion—l —xis to form — tu˜eF es — ™onsequen™e of di'eren™es in the ™hemistry of fullerenes su™h —s g60 —nd g70 —s ™omp—red to n—notu˜esD these will ˜e de—lt with sep—r—tely hereinF sn —ddition there h—ve —lso ˜een reports of n—nohorns —nd n—no(˜ersD howeverD these m—y ˜e ™onsidered —s v—ri—tions on the gener—l themeF st should ˜e noted th—t fullerenes —nd n—notu˜es h—ve ˜een shown to ˜e in )—mes produ™ed ˜y hydro™—r˜on ™om˜ustionF …nfortun—telyD these n—tur—lly o™™urring v—rieties ™—n ˜e highly irregul—r in size —nd qu—lityD —s well —s ˜eing formed in mixturesD m—king them unsuit—˜le for ˜oth rese—r™h —nd industri—l —ppli™—tionsF

8.3.2 Fullerenes
g—r˜onETH @g60 A is pro˜—˜ly the most studied individu—l type of n—nom—teri—lF „he spheri™—l sh—pe of g60 is ™onstru™ted from twelve pent—gons —nd twenty hex—gons —nd resem˜les — so™™er ˜—ll @pigure VFQ—AF „he next st—˜le higher fullerene is g70 @pigure VFQ˜A th—t is sh—ped like — rug˜y or emeri™—n foot˜—llF „he progression of higher fullerenes ™ontinues in the sequen™e g74 D g76 D g78 D et™F „he stru™tur—l rel—tionship ˜etween e—™h involves the —ddition of six mem˜ered ringsF w—them—ti™—lly @—nd ™hemi™—llyA two prin™iples de(ne the existen™e of — st—˜le fullereneD iFeFD iuler9s theorem —nd isol—ted pent—gon rule @s€‚AF iuler9s theorem st—tes th—t for the ™losure of e—™h spheri™—l networkD n @n ≥ PA hex—gons —nd IP pent—gons —re required while the s€‚ s—ys no two pent—gons m—y ˜e ™onne™ted dire™tly with e—™h other —s dest—˜iliz—tion is ™—used ˜y two —dj—™ent pent—gonsF

Figure 8.3:

Molecular structures of (a) C60 and (b) C70 .

elthough fullerenes —re ™omposed of sp2 ™—r˜ons in — simil—r m—nner to gr—phiteD fullerenes —re solu˜le in v—rious ™ommon org—ni™ solventsF hue to their hydropho˜i™ n—tureD fullerenes —re most solu˜le in gƒ2

PTQ @g60 a UFW mgGmvA —nd toluene @g60 a PFV mgGmvAF elthough fullerenes h—ve — ™onjug—ted systemD their —rom—ti™ity is distin™tive from ˜enzene th—t h—s —ll gEg ˜onds of equ—l lengthsD in fullerenes two distin™t ™l—sses of ˜onds existF „he shorter ˜onds —re —t the jun™tions of two hex—gons @‘TD T“ ˜ondsA —nd the longer ˜onds —t the jun™tions of — hex—gon —nd — pent—gon @‘SDT“ ˜ondsAF „his di'eren™e in ˜onding is responsi˜le for some of the o˜served re—™tivity of fullerenesF Synthesis of fullerenes

„he (rst o˜serv—tion of fullerenes w—s in mole™ul—r ˜e—m experiments —t ‚i™e …niversityF ƒu˜sequent studies demonstr—ted th—t g60 it w—s rel—tively e—sy to produ™e gr—ms of fullerenesF elthough the synthesis is rel—tively str—ightforw—rd fullerene puri(™—tion rem—ins — ™h—llenge —nd determines fullerene9s ™ommer™i—l pri™eF „he (rst method of produ™tion of me—sur—˜le qu—ntities of fullerenes used l—ser v—poriz—tion of ™—r˜on in —n inert —tmosphereD ˜ut this produ™ed mi™ros™opi™ —mounts of fullerenesF v—˜or—tory s™—les of fullerene —re prep—red ˜y the v—poriz—tion of ™—r˜on rods in — helium —tmosphereF gommer™i—l produ™tion ordin—rily employs — simple —™ or d™ —r™F „he fullerenes in the ˜l—™k soot ™olle™ted —re extr—™ted in toluene —nd puri(ed ˜y liquid ™hrom—togr—phyF „he m—gent— g60 ™omes o' the ™olumn (rstD followed ˜y the red g70 D —nd other higher fullerenesF iven though the me™h—nism of — ™—r˜on —r™ di'ers from th—t of — resistively he—ted ™—r˜on rod @˜e™—use it involves — pl—sm—A the re pressure for optimum g60 form—tion is very simil—rF e r—tio ˜etween the m—ss of fullerenes —nd the tot—l m—ss of ™—r˜on soot de(nes fullerene yieldF „he yields determined ˜y …†E†is —˜sorption —re —pproxim—tely RH7D IHEIS7D —nd IS7 in l—serD ele™tri™ —r™D —nd sol—r pro™essesF snterestinglyD the l—ser —˜l—tion te™hnique h—s ˜oth the highest yield —nd the lowest produ™tivity —ndD thereforeD — s™—leEup to — higher power is ™ostlyF „husD fullerene ™ommer™i—l produ™tion is — ™h—llenging t—skF „he world9s (rst ™omputer ™ontrolled fullerene produ™tion pl—nt is now oper—tion—l —t the wi‚ gorpor—tionD who pioneered the (rst ™ommer™i—l produ™tion of fullerene —nd fullerene produ™tsF Endohedral fullerenes

indohedr—l fullerenes —re fullerenes th—t h—ve in™orpor—ted in their inner sphere —tomsD ions or ™lustersF indohedr—l fullerenes —re gener—lly divided into two groupsX endohedr—l met—llofullerenes —nd nonEmet—l doped fullerenesF „he (rst endohedr—l met—llofullerenes w—s ™—lled v—dg60 F „he d sign in the n—me re)e™ts the notion of — sm—ll mole™ule tr—pped inside — shellF hoping fullerenes with met—ls t—kes pl—™e in-situ during the fullerene synthesis in —n —r™ re—™tor or vi— l—ser ev—por—tionF e wide r—nge of met—ls h—ve ˜een en™—sed inside — fullereneD iFeFD ƒ™D ‰D v—D geD f—D ƒrD uD …D rD —nd rfF …nfortun—telyD the synthesis of endohedr—l met—llofullerenes is unspe™i(™ ˜e™—use in —ddition — high yield of un(lled fullerenesD ™ompounds with di'erent ™—ge sizes —re prep—red @eFgFD v—dg60 or v—dg82 AF e ™h—r—™teristi™ of endohedr—l met—llofullerenes is th—t ele™trons will tr—nsfer from the met—l —tom to the fullerene ™—ge —nd th—t the met—l —tom t—kes — position o'E™enter in the ™—geF „he size of the ™h—rge tr—nsfer is not —lw—ys simple to determineD ˜ut it is usu—lly ˜etween P —nd Q units @eFgFD v—2 dg80 A ˜ut ™—n ˜e —s high —s T ele™trons @eFgFD ƒ™3 xdg80 AF „hese —nioni™ fullerene ™—ges —re very st—˜le mole™ules —nd do not h—ve the re—™tivity —sso™i—ted with ordin—ry empty fullerenes @see ˜elowAF „his l—™k of re—™tivity is utilized in — method to purify endohedr—l met—llofullerenes from empty fullerenesF „he endohedr—l redg60 —nd xedg60 form when g60 is exposed to — pressure of —round Q ˜—r of the —ppropri—te no˜le g—sesF …nder these ™onditions it w—s possi˜le to dope I in every TSHDHHH g60 ™—ges with — helium —tomF indohedr—l ™omplexes with reD xeD erD ur —nd ˆe —s well —s numerous —ddu™ts of the redg60 ™ompound h—ve —lso ˜een proven with oper—ting pressures of QHHH ˜—rs —nd in™orpor—tion of up to HFI 7 of the no˜le g—sesF „he isol—tion of xdg60 D xdg70 —nd €dg60 is very unusu—l —nd unlike the met—l deriv—tives no ™h—rge tr—nsfer of the pni™tide —tom in the ™enter to the ™—r˜on —toms of the ™—ge t—kes pl—™eF Chemically functionalized fullerenes

elthough fullerenes h—ve — ™onjug—ted —rom—ti™ system —ll the ™—r˜ons —re qu—tern—ry @iFeFD ™ont—ining no hydrogenAD whi™h results in m—king m—ny of the ™h—r—™teristi™ su˜stitution re—™tions of pl—n—r —rom—ti™s



impossi˜leF „husD only two types of ™hemi™—l tr—nsform—tions existX redox re—™tions —nd —ddition re—™tionsF yf theseD —ddition re—™tions h—ve the l—rgest syntheti™ v—lueF enother rem—rk—˜le fe—ture of fullerene —ddition ™hemistry is the thermodymi™s of the pro™essF ƒin™e the sp2 ™—r˜on —toms in — fullerene —re p—r—mid—lized there is signi(™—nt str—in energyF por ex—mpleD the str—in energy in g60 is ca V k™—lGmolD whi™h is VH7 of its he—t of form—tionF ƒo the relief of this str—in energy le—ding to sp3 hy˜ridized g —toms is the m—jor driving for™e for —ddition re—™tions @pigure VFRAF es — ™onsequen™eD most —dditions to fullerenes —re exothermi™ re—™tionsF

Figure 8.4:

Strain release after addition of reagent A to a pyramidalize carbon of C60 .

gy™li™ volt—mmetry @g†A studies show th—t g60 ™—n ˜e redu™ed —nd oxidized reversi˜ly up to T ele™trons with oneEele™tron tr—nsfer pro™essesF pulleride —nions ™—n ˜e gener—ted ˜y ele™tro™hemi™—l method —nd then ˜e used to synthesize ™ov—lent org—nofullerene deriv—tivesF elk—li met—ls ™—n ™hemi™—lly redu™e fullerene in solution —nd solid st—te to form wx g60 @x a Q E TAF g60 ™—n —lso ˜e redu™ed ˜y less ele™tropositive met—ls like mer™ury to form g60 - —nd g60 2- F sn —dditionD s—lts ™—n —lso ˜e synthesized with org—ni™ mole™ulesD for ex—mple ‘„hei+ “‘g60 - “ possesses interesting ele™troni™ —nd m—gneti™ ˜eh—viorF qeometri™ —nd ele™troni™ —n—lysis predi™ted th—t fullerene ˜eh—ves live —n ele™troEpoor ™onjug—ted polyE ole(nF sndeed g60 —nd g70 undergo — r—nge of nu™leophili™ re—™tions with ™—r˜onD nitrogenD phosphorous —nd oxygen nu™leophilesF gTH re—™ts re—dily with org—nolithium —nd qrign—rd ™ompounds to form —lkylD phenyl or —lk—nyl fullerenesF €ossi˜ly the most widely used —dditions to fullerene is the fingel re—™tion @pigure VFSAD where — ™—r˜on nu™leophileD gener—ted ˜y deproton—tion of αEh—lo m—lon—te esters or ketonesD is —dded to form — ™y™loprop—n—tion produ™tF „he αEh—lo esters —nd ketones ™—n —lso ˜e gener—ted in situ with s2 or gfr4 —nd — we—k ˜—se —s IDVEdi—z—˜i™y™lo‘SFRFH“undeEUene @hf…AF „he fingel re—™tion is ™onsidered one of the most vers—tile —nd e0™ient methods to fun™tion—lize g60 F

Figure 8.5:

Bingel reaction of C60 with 2-bromoethylmalonate.

gy™lo—ddition is —nother powerful tool to fun™tion—lize fullerenesD in p—rti™ul—r ˜e™—use of its sele™tivity with the TDT ˜ondsD limiting the possi˜le isomers @pigure VFTAF „he dienophili™ fe—ture of the ‘TDT“ dou˜le

PTS ˜onds of g60 en—˜les the mole™ule to undergo v—rious ™y™lo—ddition re—™tions in whi™h the mono—ddu™ts ™—n ˜e gener—ted in high yieldsF „he ˜est studies ™y™lo—dditon re—™tions of fullerene —re ‘QCP“ —dditions with di—zoderiv—tives —nd —zomethine ylides @€r—to re—™tionsAF sn this re—™tionD —zomethine ylides ™—n ˜e gener—ted in situ from ™ondens—tion of αE—mino —™ids with —ldehydes or ketonesD whi™h produ™e IDQ dipoles to further re—™t with g60 in good yields @pigure VFUAF rundreds of useful ˜uilding ˜lo™ks h—ve ˜een gener—ted ˜y those two methodsF „he €r—to re—™tions h—ve —lso ˜een su™™essfully —pplied to ™—r˜on n—notu˜esF

Geometrical shapes built onto a [6,6] ring junction: a) open, b) four-membered ring, c) ve-membered ring, and d) six-membered ring.
Figure 8.6:

Figure 8.7:

Prato reaction of C60 with N-methyglycine and paraformaldehyde.

„he oxid—tion of fullerenesD su™h —s g60 D h—s ˜een of in™re—sing interest with reg—rd to —ppli™—tions in photoele™tri™ devi™esD ˜iologi™—l systemsD —nd possi˜le remedi—tion of fullerenesF „he oxid—tion of g60 to g60 yn @n a ID PA m—y ˜e —™™omplished ˜y photooxid—tionD ozonolysisD —nd epoxid—tionF ‡ith e—™h of these methodsD there is — limit to the isol—˜le oxygen—ted produ™tD g60 yn with n < QF righly oxygen—ted fullerenesD g60 yn with Q ≤ n ≤ WD h—ve ˜een prep—red ˜y the ™—t—lyti™ oxid—tion of g60 with ‚ewey3 Gr2 y2 F

8.3.3 Carbon nanotubes
e key ˜re—kthrough in ™—r˜on n—no™hemistry ™—me in IWWQ with the report of needleElike tu˜es m—de exE ™lusively of ™—r˜onF „his m—teri—l ˜e™—me known —s ™—r˜on n—notu˜es @gx„sAF „here —re sever—l types of n—notu˜esF „he (rst dis™overy w—s of multi w—lled tu˜es @w‡x„sA resem˜ling m—ny pipes nested within e—™h otherF ƒhortly —fter w‡x„s were dis™overed single w—lled n—notu˜es @ƒ‡x„sA were o˜servedF ƒingle w—lled tu˜es resem˜le — single pipe th—t is potenti—lly ™—pped —t e—™h endF „he properties of single w—lled —nd multi w—lled tu˜es —re gener—lly the s—meD —lthough single w—lled tu˜es —re ˜elieved to h—ve superior me™h—ni™—l strength —nd therm—l —nd ele™tri™—l ™ondu™tivityY it is —lso more di0™ult to m—nuf—™ture themF



ƒingle w—lled ™—r˜on n—notu˜es @ƒ‡x„sA —re ˜y de(nition fullerene m—teri—lsF „heir stru™ture ™onsists of — gr—phene sheet rolled into — tu˜e —nd ™—pped ˜y h—lf — fullerene @pigure VFVAF „he ™—r˜on —toms in — ƒ‡x„D like those in — fullereneD —re spP hy˜ridizedF „he stru™ture of — n—notu˜e is —n—logous to t—king this gr—phene sheet —nd rolling it into — se—mless ™ylinderF „he di'erent types of ƒ‡x„s —re de(ned ˜y their di—meter —nd ™hir—lityF wost of the presently used singleEw—ll ™—r˜on n—notu˜es h—ve ˜een synthesized ˜y the pulsed l—ser v—poriz—tion methodD howeverD in™re—singly ƒ‡x„s —re prep—red ˜y v—por liquid solid ™—t—lyzed growthF

Structure of single walled carbon nanotubes (SWNTs) with (a) armchair, (b) zig-zag, and (c) chiral chirality.
Figure 8.8:

„he physi™—l properties of ƒ‡x„s h—ve m—de them —n extremely —ttr—™tive m—teri—l for the m—nuf—™turE ing of n—no devi™esF ƒ‡x„s h—ve ˜een shown to ˜e stronger th—n steel —s estim—tes for the ‰oung9s modulus —ppro—™hes I „p—F „heir ele™tri™—l ™ondu™t—n™e is ™omp—r—˜le to ™opper with —nti™ip—te ™urrent densities of up to IH13 eG™m2 —nd — resistivity —s low —s HFQR x IH-4 ΩF™m —t room temper—turesF pin—llyD they h—ve — high therm—l ™ondu™tivity @QHHH E THHH ‡FmGuAF „he ele™troni™ properties of — p—rti™ul—r ƒ‡x„ stru™ture —re ˜—sed on its ™hir—lity or twist in the stru™ture of the tu˜e whi™h is de(ned ˜y its n,m v—lueF „he v—lues of n —nd m determine the ™hir—lityD or 4twist4 of the n—notu˜eF „he ™hir—lity in turn —'e™ts the ™ondu™t—n™e of the n—notu˜eD its densityD its l—tti™e stru™tureD —nd other propertiesF e ƒ‡x„ is ™onsidered met—lli™ if the v—lue n-m is divisi˜le ˜y threeF ytherwiseD the n—notu˜e is semiE™ondu™tingF „he extern—l environment —lso h—s —n e'e™t on the ™ondu™t—n™e of — tu˜eD thus mole™ules su™h —s y2 —nd xr3 ™—n ™h—nge the over—ll ™ondu™t—n™e of — tu˜eD while the presen™e of met—ls h—ve ˜een shown to signi(™—ntly e'e™t the optoEele™troni™ properties of ƒ‡x„sF wulti w—lled ™—r˜on n—notu˜es @w‡x„sA r—nge from dou˜le w—lled x„sD through m—nyEw—lled x„s @pigure VFWA to ™—r˜on n—no(˜ersF g—r˜on n—no(˜ers —re the extreme of multi w—lled tu˜es @pigure VFIHA —nd they —re thi™ker —nd longer th—n either ƒ‡x„s or w‡x„sD h—ving — ™rossEse™tion—l of ™—F SHH Å2 —nd —re ˜etween IH to IHH µm in lengthF „hey h—ve ˜een used extensively in the ™onstru™tion of high strength ™ompositesF


Figure 8.9:

TEM image of an individual multi walled carbon nanotube (MWNTs). Copyright of Nanotech Innovations.

Figure 8.10:

SEM image of vapor grown carbon nanobers. Synthesis of carbon nanotubes

e r—nge of methodologies h—ve ˜een developed to produ™e n—notu˜es in size—˜le qu—ntitiesD in™luding —r™ dis™h—rgeD l—ser —˜l—tionD high pressure ™—r˜on monoxide @ri€™oAD —nd v—por liquid solid @†vƒA growthF ell

PTV CHAPTER 8. NANOTECHNOLOGY these pro™esses t—ke pl—™e in v—™uum or —t low pressure with — pro™ess g—sesD —lthough †vƒ growth ™—n t—ke pl—™e —t —tmospheri™ pressureF v—rge qu—ntities of n—notu˜es ™—n ˜e synthesized ˜y these methodsY —dv—n™es in ™—t—lysis —nd ™ontinuous growth pro™esses —re m—king ƒ‡x„s more ™ommer™i—lly vi—˜leF „he (rst o˜serv—tion of n—notu˜es w—s in the ™—r˜on soot formed during the —r™ dis™h—rge produ™tion of fullerenesF „he high temper—tures ™—used ˜y the dis™h—rge ™—used the ™—r˜on ™ont—ined in the neg—tive ele™trode to su˜lime —nd the gx„s —re deposited on the opposing ele™trodeF „u˜es produ™ed ˜y this method were initi—lly multi w—lled tu˜es @w‡x„sAF roweverD with the —ddition of ™o˜—lt to the v—porized ™—r˜onD it is possi˜le to grow single w—lled n—notu˜esF „his method it produ™es — mixture of ™omponentsD —nd requires further puri(™—tion to sep—r—te the gx„s from the soot —nd the residu—l ™—t—lyti™ met—lsF €rodu™ing gx„s in high yield depends on the uniformity of the pl—sm— —r™D —nd the temper—ture of the deposit forming on the ™—r˜on ele™trodeF righer yield —nd purity of ƒ‡x„s m—y ˜e prep—red ˜y the use of — du—lEpulsed l—serF ƒ‡x„s ™—n ˜e grown in — SH7 yield through dire™t v—poriz—tion of — goGxi doped gr—phite rod with — highEpowered l—ser in — tu˜e furn—™e oper—ting —t IPHH ◦ gF „he m—teri—l produ™ed ˜y this method —ppe—rs —s — m—t of ropesD IH E PH nm in di—meter —nd up to IHH µm or more in lengthF i—™h rope ™onsists of — ˜undle of ƒ‡x„sD —ligned —long — ™ommon —xisF fy v—rying the pro™ess p—r—meters su™h —s ™—t—lyst ™omposition —nd the growth temper—tureD the —ver—ge n—notu˜e di—meter —nd size distri˜ution ™—n ˜e v—riedF elthough —r™Edis™h—rge —nd l—ser v—poriz—tion —re ™urrently the prin™ip—l methods for o˜t—ining sm—ll qu—ntities of high qu—lity ƒ‡x„sD ˜oth methods su'er from dr—w˜—™ksF „he (rst is th—t they involve ev—por—ting the ™—r˜on sour™eD m—king s™—leEup on —n industri—l level di0™ult —nd energeti™—lly expensiveF „he se™ond issue rel—tes to the f—™t th—t v—poriz—tion methods grow ƒ‡x„s in highly t—ngled formsD mixed with unw—nted forms of ™—r˜on —ndGor met—l spe™iesF „he ƒ‡x„s thus produ™ed —re di0™ult to purifyD m—nipul—teD —nd —ssem˜le for ˜uilding n—notu˜eEdevi™e —r™hite™tures for pr—™ti™—l —ppli™—tionsF sn order to over™ome some of the di0™ulties of these highEenergy pro™essesD the ™hemi™—l ™—t—lysis method w—s developed in whi™h — hydro™—r˜on feedsto™k is used in ™om˜in—tion with — met—l ™—t—lystF „he ™—t—lyst is typi™—llyD ˜ut not limited to ironD ™ol˜—ltD or ironGmoly˜denumD it is he—ted under redu™ing ™onditions in the presen™e of — suit—˜le ™—r˜on feedsto™kD eFgFD ethyleneF „his method ™—n ˜e used for ˜oth ƒ‡x„s —nd w‡x„sY the form—tion of e—™h is ™ontrolled ˜y the identity of the ™—t—lyst —nd the re—™tion ™onditionsF e ™onvenient l—˜or—tory s™—le —pp—r—tus is —v—il—˜le from x—note™h snnov—tionsD sn™FD for the synthesis of highly uniformD ™onsistentD rese—r™h s—mple th—t uses preEweighed ™—t—lystG™—r˜on sour™e —mpoulesF „his systemD —llows for PHH mg s—mples of w‡x„s to ˜e prep—red for rese—r™h —nd testingF „he use of gy —s — feedsto™kD in pl—™e of — hydro™—r˜onD led to the development of the highEpressure ™—r˜on monoxide @ri€™oA pro™edure for ƒ‡x„ synthesisF fy this methodD it is possi˜le to produ™e gr—m qu—ntities of ƒ‡x„sD unfortun—telyD e'orts to s™—le ˜eyond th—t h—ve not met with ™omplete su™™essF sniti—lly developed for sm—llEs™—le investig—tions of ™—t—lyst —™tivityD v—por liquid solid @†vƒA growth of n—notu˜es h—s ˜een highly studiedD —nd now shows promise for l—rgeEs™—le produ™tion of n—notu˜esF ‚e™ent —ppro—™hes h—ve involved the use of wellEde(ned n—nop—rti™le or mole™ul—r pre™ursors —nd m—ny di'erent tr—nsition met—ls h—ve ˜een employedD ˜ut ironD ni™kelD —nd ™o˜—lt rem—in to ˜e the fo™us of most rese—r™hF „he n—notu˜es grow —t the sites of the met—l ™—t—lystY the ™—r˜onE™ont—ining g—s is ˜roken —p—rt —t the surf—™e of the ™—t—lyst p—rti™leD —nd the ™—r˜on is tr—nsported to the edges of the p—rti™leD where it forms the n—notu˜eF „he length of the tu˜e grown in surf—™e supported ™—t—lyst †vƒ systems —ppe—rs to ˜e dependent on the orient—tion of the growing tu˜e with the surf—™eF fy properly —djusting the surf—™e ™on™entr—tion —nd —ggreg—tion of the ™—t—lyst p—rti™les it is possi˜le to synthesize verti™—lly —ligned ™—r˜on n—notu˜esD iFeFD —s — ™—rpet perpendi™ul—r to the su˜str—teF yf the v—rious me—ns for n—notu˜e synthesisD the ™hemi™—l pro™esses show the gre—test promise for industri—l s™—le deposition in terms of its pri™eGunit r—tioF „here —re —ddition—l —dv—nt—ges to the †vƒ growthD whi™h unlike the other methods is ™—p—˜le of growing n—notu˜es dire™tly on — desired su˜str—teF „he growth sites —re ™ontroll—˜le ˜y ™—reful deposition of the ™—t—lystF eddition—llyD no other growth methods h—ve ˜een developed to produ™e verti™—lly —ligned ƒ‡x„sF .

3.11: Schematic description of various covalent functionalization strategies for SWNTs.2 Chemical functionalization of carbon nanotubes „he limit—tion of using ™—r˜on n—notu˜es in —ny pr—™ti™—l —ppli™—tions h—s ˜een its solu˜ilityY for ex—mple ƒ‡x„s h—ve little to no solu˜ility in most solvent due to the —ggreg—tion of the tu˜esF eggreg—tionGroping of n—notu˜es o™™urs —s — result of the high v—n der ‡——ls ˜inding energy of caF SHH e† per mm of tu˜e ™ont—™tF „he v—n der ‡——ls for™e ˜etween the tu˜es is so gre—tD th—t it t—ke tremendous energy to pry them —p—rtD m—king it very to m—ke ™om˜in—tion of n—notu˜es with other m—teri—ls su™h —s in ™omposite —ppli™—tionsF „he fun™tion—liz—tion of n—notu˜esD iFeFD the —tt—™hment of ™hemi™—l fun™tion—l groups provides the p—th to over™ome these ˜—rriersF pun™tion—liz—tion ™—n improve solu˜ility —s well —s pro™essi˜ilityD —nd h—s ˜een used to —lign the properties of n—notu˜es to those of other m—teri—lsF „he ™le—rest ex—mple of this is the —˜ility to solu˜ilize n—notu˜es in — v—riety of solventsD in™luding w—terF st is import—nt when dis™ussing fun™tion—liz—tion th—t — distin™tion is m—de ˜etween ™ov—lent —nd nonE™ov—lent fun™tion—liz—tionF gurrent methods for solu˜ilizing n—notu˜es without ™ov—lent fun™tion—liz—tion in™lude highly —rom—ti™ solventsD super —™idsD polymersD or surf—™t—ntsF xonE™ov—lent fun™tion—liz—tion is gener—lly on the ™on™ept of supr—mole™ul—r inter—™tions ˜etween the ƒ‡x„ —nd some m—™romole™ule —s — result of v—rious —dsorption for™esD su™h —s v—n der ‡——ls9 —nd π Est—™king inter—™tionsF „he ™hemi™—l spe™i—tion of the n—notu˜e itself is not —ltered —s — result of the inter—™tionF sn ™ontr—stD ™ov—lent fun™tion—liz—tion relies on the ™hemi™—l re—™tion —t either the sidew—ll or end of the ƒ‡x„F es m—y ˜e expe™ted the high —spe™t r—tio of n—notu˜es me—ns th—t sidew—ll fun™tion—liz—tion is mu™h more import—nt th—n the fun™tion—liz—tion of the ™—pF hire™t ™ov—lent sidew—ll fun™tion—liz—tion is —sso™i—ted with — ™h—nge of hy˜ridiz—tion from sp2 to sp2 —nd — simult—neous loss of ™onjug—tionF en —ltern—tive —ppro—™h to ™ov—lent fun™tion—liz—tion involves the re—™tion of defe™ts present @or gener—tedA in the stru™ture of the n—notu˜eF hefe™t sites ™—n ˜e the open ends —nd holes in the sidew—llsD —nd pent—gon —nd hept—gon irregul—rities in the hex—gon gr—phene fr—mework @often —sso™i—ted with ˜ends in the tu˜esAF ell these fun™tion—liz—tions —re exohedr—l deriv—tiz—tionsF „—king the hollow stru™ture of n—notu˜es into ™onsider—tionD endohedr—l fun™tion—liz—tion of ƒ‡x„s is possi˜leD iFeFD the (lling of the tu˜es with —toms or sm—ll mole™ulesF st is import—nt to note th—t ™ov—lent fun™tion—liz—tion methods h—ve one pro˜lem in ™ommonX extensive ™ov—lent fun™tion—liz—tion modi(es ƒ‡x„ properties ˜y disrupting the ™ontinuous π !system of ƒ‡x„sF †—rious —ppli™—tions of n—notu˜es require di'erentD spe™i(™ modi(™—tion to —™hieve desir—˜le physi™—l —nd ™hemi™—l properties of n—notu˜esF sn this reg—rdD ™ov—lent fun™tion—liz—tion provides — higher degree of (neEtuning the ™hemistry —nd physi™s of ƒ‡x„s th—n nonE™ov—lent fun™tion—liz—tionF …ntil nowD — v—riety of methods h—ve ˜een used to —™hieve the fun™tion—liz—tion of n—notu˜es @pigure VFIIAF Figure 8.PTW 8.3. „—king ™hemistry developed for g60 D ƒ‡x„s m—y ˜e fun™tion—lized using IDQ dipol—r —ddition of —zomeE thine ylidesF „he fun™tion—lized ƒ‡x„s —re solu˜le in most ™ommon org—ni™ solventsF „he —zomethine ylide fun™tion—liz—tion method w—s —lso used for the puri(™—tion of ƒ‡x„sF …nder ele™tro™hemi™—l ™onditionsD —ryl .

PUH CHAPTER 8. yne of the e—siest fun™tion—liz—tion routesD —nd — useful synthon for su˜sequent ™onversionsD is the )uorin—tion of ƒ‡x„sD using element—l )uorineF smport—ntlyD — gXp r—tios of up to PXI ™—n ˜e —™hieved without disruption of the tu˜ul—r stru™tureF „he )uorin—ted ƒ‡x„s @pEƒ‡x„sA proved to ˜e mu™h more solu˜le th—n pristine ƒ‡x„s in —l™ohols @I mgGmv in iso Eprop—nolAD hwp —nd other sele™ted org—ni™ solventsF ƒ™—nning tunneling mi™ros™opy @ƒ„wA reve—led th—t the )uorine formed ˜—nds of —pproxim—tely PH nmD while ™—l™ul—tions using hp„ reve—led IDP —ddition is more energeti™—lly prefer—˜le th—n IDR —dditionD whi™h h—s ˜een ™on(rmed ˜y solid st—te 13 g xw‚F pEƒ‡x„s m—ke highly )exi˜le synthons —nd su˜sequent el—˜or—tion h—s ˜een performed with org—no lithiumD qrign—rd re—gentsD —nd —minesF pun™tion—lized n—notu˜es ™—n ˜e ™h—r—™terized ˜y — v—riety of te™hniquesD su™h —s —tomi™ for™e mi™ros™opy @epwAD tr—nsmission ele™tron mi™ros™opy @„iwAD …†Evis spe™tros™opyD —nd ‚—m—n spe™tros™opyF gh—nges in the ‚—m—n spe™trum of — n—notu˜e s—mple ™—n indi™—te if fun™tion—liz—tion h—s o™™urredF €ristine tu˜es exhi˜it two distin™t ˜—ndsF „hey —re the r—di—l ˜re—thing mode @PQH ™m-1 A —nd the t—ngenti—l mode @ISWH ™m-1 AF ‡hen fun™tion—lizedD — new ˜—ndD ™—lled the disorder ˜—ndD —ppe—rs —t ca. NANOTECHNOLOGY di—zonium s—lts re—™t with ƒ‡x„s to —™hieve fun™tion—lized ƒ‡x„sD —ltern—tively the di—zonium ions m—y ˜e gener—ted in-situ from the ™orresponding —nilineD while — solvent free re—™tion provides the ˜est ™h—n™e for l—rgeEs™—le fun™tion—liz—tion this w—yF sn e—™h of these methods it is possi˜le to ™ontrol the —mount of fun™tion—liz—tion on the tu˜e ˜y v—rying re—™tion times —nd the re—gents usedY fun™tion—liz—tion —s high —s I group per every IH E PS ™—r˜on —toms is possi˜leF yrg—ni™ fun™tion—liz—tion through the use of —lkyl h—lidesD — r—di™—l p—thw—yD on tu˜es tre—ted with lithium in liquid —mmoni— o'ers — simple —nd )exi˜le route to — r—nge of fun™tion—l groupsF sn this re—™tionD fun™tion—liz—tion o™™urs on every IU ™—r˜onsF wost su™™ess h—s ˜een found when the tu˜es —re dode™yl—tedF „hese tu˜es —re solu˜le in ™hloroformD hwpD —nd „rpF „he —ddition of oxygen moieties to ƒ‡x„ sidew—lls ™—n ˜e —™hieved ˜y tre—tment with —™id or wet —ir oxid—tionD —nd ozonolysisF „he dire™t epoxid—tion of ƒ‡x„s m—y ˜e —™™omplished ˜y the dire™t re—™tion with — peroxide re—gentD or ™—t—lyti™—llyF g—t—lyti™ deEepoxid—tion @pigure VFIPA —llows for the qu—ntit—tive —n—lysis of sidew—ll epoxide —nd led to the surprising result th—t previously —ssumed pure ƒ‡x„s —™tu—lly ™ont—in caF I oxygen per PSH ™—r˜on —tomsF Figure 8.12: Catalytic oxidation and de-epoxidation of SWNTs.IQSH ™m-1 F „his ˜—nd is —ttri˜uted to sp3 Ehy˜ridized ™—r˜ons in the tu˜eF …nfortun—telyD while the presen™e of — signi(™—nt h mode is ™onsistent with sidew—ll fun™tion—liz—tion —nd the rel—tive intensity of h @disorderA mode versus the t—ngenti—l q mode @ISSH ! ITHH ™m-1 A is often used —s — me—sure of the level of su˜stitutionF roweverD it h—s ˜een shown th—t ‚—m—n is —n unreli—˜le method for determin—tion of the extent of fun™tion—liz—tion sin™e the rel—tive intensity of the h ˜—nd is —lso — fun™tion of the su˜stituents distri˜ution —s well —s ™on™entr—tionF .

Am.D IWWVD 296D IWSF • eF rirs™hD Angew.D PHHSD 127D ITPWPF • vF eF qirif—l™oD wF rod—kD —nd ‚F ƒF veeD Phys. Chem. Chem.3.D IWWSD 99D IHTWRF • tF rF r—fnerD wF tF fronikowskiD fF ‚F ez—mi—nD €F xikol—evD eF qF ‚inzlerD hF „F gol˜ertD uF eF ƒmithD —nd ‚F iF ƒm—lleyD Chem.D PHHRD 4D IPSUF . BD PHHHD 62D IQIHRF • „F quoD €F xikol—evD eF qF ‚inzlerD hF „ománekD hF „F gol˜ertD —nd ‚F iF ƒm—lleyD J. Chem. Soc.PUI ‚e™ent studies suggest th—t solid st—te 13 g xw‚ —re possi˜ly the only de(nitive method of demonstr—ting ™ov—lent —tt—™hment of p—rti™ul—r fun™tion—l groupsF 8. Soc. Rev. Chem. Sci.D PHHQD 125D IISTF • F qeD tF gF hu™h—mpD „F g—iD rF ‡F qi˜sonD —nd rF gF hornD J.3.D PHHUD 42D UQVIF • rF ‡F urotoD tF ‚F re—thD ƒF gF y9frienD ‚F pF gurlD —nd ‚F iF ƒm—lleyD NatureD IWVSD 318D ITPF • pF vi—ngD eF uF ƒ—d—n—D eF €eer—D tF gh—ttop—dhy—yD F quD ‚F rF r—ugeD —nd ‡F iF fillupsD Nano Lett. CD PHHUD 111D IUVIPF • gF eF hyke —nd tF wF „ourD J. Lett.D PHHPD 40D RHHPF • ƒF sijim— —nd „F s™hih—shiD NatureD IWWQD 363D THQF • rF ‚F t—fryD iF eF ‡hitsittD —nd eF ‚F f—rronD J.3 Coating carbon nanotubes: creating inorganic nanostructures pullerenesD n—notu˜es —nd n—no(˜ers represent suit—˜le su˜str—tes for the seeding other m—teri—ls su™h —s oxides —nd other miner—lsD —s well —s semi™ondu™torsF sn this reg—rdD the ™—r˜on n—nom—teri—l —™ts —s — seed point for the growth —s well —s — method of de(ning unusu—l —spe™t r—tiosF por ex—mpleD sili™— (˜ers ™—n ˜e prep—red ˜y — num˜er of methodsD ˜ut it is only through ™o—ting ƒ‡x„s th—t sili™— n—noE(˜ers with of mi™ron lengths with tens of n—nometers in di—meter m—y ˜e prep—redF ‡hile g60 itself does not re—dily seed the growth of inorg—ni™ m—teri—lsD liquid ph—se deposition of oxidesD su™h —s sili™—D in the presen™e of fullerenolD g60 @yrAn D results in the form—tion of uniform oxide spheresF st —ppe—rs the fullerenol —™ts —s ˜oth — re—gent —nd — physi™—l point for su˜sequent oxide growthD —nd it is g60 D or —n —ggreg—te of g60 D th—t is present within the spheri™—l p—rti™leF „he —ddition of fullerenol —lters the morphology —nd ™ryst—l ph—se of g—gy3 pre™ipit—tes from —queous solutionD resulting in the form—tion of spheri™—l fe—turesD SEpointed )ower sh—ped ™lustersD —nd tri—ngul—r ™ryst—ls —s opposed to the usu—l rhom˜i™ ™ryst—lsF sn —dditionD the met—Est—˜le v—terite ph—se is o˜served with the —ddition of g60 @yrAn F es noted —˜ove individu—l ƒ‡x„s m—y ˜e o˜t—ined in solution when en™—sed in — ™ylindri™—l mi™elle of — suit—˜le surf—™t—ntF „hese individu—lized n—notu˜es ™—n ˜e ™o—ted with — r—nge of inorg—ni™ m—teri—lsF viquid ph—se deposition @v€hA —ppe—rs to h—ve signi(™—nt —dv—nt—ges over other methods su™h —s in™orpor—ting surf—™ted ƒ‡x„s into — pre™er—mi™ m—trixD in situ growth of the ƒ‡x„ in —n oxide m—trixD —nd solEgel methodsF „he prim—ry —dv—nt—ge of v€h growth is th—t individu—l ƒ‡x„s m—y ˜e ™o—ted r—ther th—n ˜undles or ropesF por ex—mpleD ƒ‡x„s h—ve ˜een ™o—ted with sili™— ˜y liquid ph—se deposition @v€hA using — sili™—Gr2 ƒip6 solution —nd — surf—™t—ntEst—˜ilized solution of ƒ‡x„sF „he thi™kness of the ™o—ting is dependent on the re—™tion mixture ™on™entr—tion —nd the re—™tion timeF „he ƒ‡x„ ™ore ™—n ˜e removed ˜y thermolysis under oxidizing ™onditions to le—ve — sili™— n—no (˜erF st is interesting to note th—t the use of — surf—™t—nt is ™ounter produ™tive when using w‡x„s —nd †qpsD in this ™—se surf—™e —™tiv—tion of the n—notu˜e o'ers the suit—˜le growth initi—tionF €reEoxid—tion of the w‡x„ or †qp —llows for uniform ™o—tings to ˜e depositedF „he ™o—ted ƒ‡x„sD w‡x„sD —nd †qps ™—n ˜e su˜sequently re—™ted with suit—˜le surf—™e re—gents to imp—rt mis™i˜ility in —queous solutionsD gu—r gelsD —nd org—ni™ m—trixesF sn —ddition to simple oxidesD ™o—ted n—notu˜es h—ve ˜een prep—red with miner—ls su™h —s ™—r˜on—tes —nd semi™ondu™torsF 8. Phys.. Phys. Int. Mater.3. Am. Chem. Phys.4 Bibliography • ƒF wF f—™hiloD wF ƒF ƒtr—noD gF uittrellD ‚F rF r—ugeD ‚F iF ƒm—lleyD —nd ‚F fF ‡eism—nD ScienceD PHHPD 298D PQTIF • hF ƒF fethuneD gF rF ul—ngD wF ƒF de†riesD qF qorm—nD ‚F ƒ—voyD tF †—zquezD —nd ‚F feyersD NatureD IWWQD 363D THSF • tD tF fregeD gF q—ll—w—yD —nd eF ‚F f—rronD J. Ed.

4. Soc.4. Am.D PHHRD PVVRF • vF engD vF fF elem—nyD gF vF idw—rdsD —nd eF ‚F f—rronD Nano Res.D PHHQD 3D UUSF • tF ‰—ng —nd eF ‚F f—rronD Chem.D IWWPD 25D WVF • wF wF tF „re—™yD „F ‡F i˜˜esenD —nd tF wF qi˜sonD NatureD IWWTD 381D TUVF • iF eF ‡hitsitt —nd eF ‚F f—rronD Nano Lett.3/>.1 Introduction qr—phene is — oneE—tomEthi™k pl—n—r sheet of sp2 E˜onded ™—r˜on —toms th—t —re densely p—™ked in — honeyE ™om˜ ™ryst—l l—tti™e @pigure VFIQAF „he n—me ™omes from gr—phite —nd —lkeneY gr—phite itself ™onsists of m—ny gr—phene sheets st—™ked togetherF Figure 8. Chem. Mol. NANOTECHNOLOGY • hF ygrin —nd eF ‚F f—rronD J.D PHHTD 244D PTUF • hF ygrinD tF gh—ttop—dhy—yD eF uF ƒ—d—n—D iF fillupsD —nd eF ‚F f—rronD J. .org/content/m29187/1.2 Physical properties of graphene qr—phene h—s ˜een reported to h—ve — ‰oung9s modulus of I „€— —nd intrinsi™ strength of IQH q€Y simil—r to single w—lled ™—r˜on n—notu˜es @ƒ‡x„sAF „he ele™troni™ properties of gr—phene —lso h—ve some simil—rity with ™—r˜on n—notu˜esF qr—phene is — zeroE˜—ndg—p semi™ondu™torF ile™tron mo˜ility in gr—phene is extr—ordin—rily high @ISDHHH ™m2 G†Fs —t room temper—tureA —nd ˜—llisti™ ele™tron tr—nsport is reported to 4 This content is available online at <http://cnx.4 Graphene 4 8. Res. ƒingleEl—yer gr—phene n—nosheets were (rst ™h—r—™terized in PHHRD prep—red ˜y me™h—ni™—l exfoli—tion @the s™ot™hEt—pe methodA of ˜ulk gr—phiteF v—ter gr—phene w—s produ™ed ˜y epit—xi—l ™hemi™—l v—por deposition on sili™on ™—r˜ide —nd ni™kel su˜str—tesF wost re™entlyD gr—phene n—nori˜˜ons @qx‚sA h—ve ˜een prep—red ˜y the oxid—tive tre—tment of ™—r˜on n—notu˜es —nd ˜y pl—sm— et™hing of n—notu˜es em˜edded in polymer (lmsF 8.D PHHTD 128D IIQPPF • ‚F iF ƒm—lleyD Acc.PUP CHAPTER 8. Cat.D PHHVD 1D UPF 8. Chem. Commun. A: Chem.13: Idealized structure of a single graphene sheet.

Rice University (2009). PhD Thesis.PUQ ˜e on length s™—les ™omp—r—˜le to th—t of ƒ‡x„sF yne of the most promising —spe™ts of gr—phene involves the use of qx‚sF gutting —n individu—l gr—phene l—yer into — long strip ™—n yield semi™ondu™ting m—teri—ls where the ˜—ndg—p is tuned ˜y the width of the ri˜˜onF ‡hile gr—phene9s novel ele™troni™ —nd physi™—l properties gu—r—ntee this m—teri—l will ˜e studied for ye—rs to ™omeD there —re some fund—ment—l o˜st—™les yet to over™ome ˜efore gr—phene ˜—sed m—teri—ls ™—n ˜e fully utilizedF „he —forementioned methods of gr—phene prep—r—tion —re e'e™tiveY howeverD they —re impr—™ti™—l for l—rgeEs™—le m—nuf—™turingF „he most plentiful —nd inexpensive sour™e of gr—phene is ˜ulk gr—phiteF ghemi™—l methods for exfoli—tion of gr—phene from gr—phite provide the most re—listi™ —nd s™—l—˜le —ppro—™h to gr—phene m—teri—lsF qr—phene l—yers —re held together in gr—phite ˜y enormous v—n der ‡——ls for™esF yver™oming these for™es is the m—jor o˜st—™le to gr—phite exfoli—tionF „o d—teD ™hemi™—l e'orts —t gr—phite exfoli—tion h—ve ˜een fo™used prim—rily on inter™—l—tionD ™hemi™—l deriv—tiz—tionD therm—l exp—nsionD oxid—tionEredu™tionD the use of surf—™t—ntsD or some ™om˜in—tion of theseF 8.4.14: es gr—phite oxide is ele™tri™—lly insul—tingD it must ˜e ™onverted ˜y ™hemi™—l redu™tion to restore the ele™troni™ properties of gr—pheneF ghemi™—lly ™onverted gr—phene @ggqA is typi™—lly redu™ed ˜y hydr—zine or ˜orohydrideF „he properties of ggq ™—n never fully m—t™h those of gr—phene for two re—sonsX IF yxid—tion to qy introdu™es defe™tsF PF ghemi™—l redu™tion does not fully restore the gr—phiti™ stru™tureF . Adapted from C. Figure 8. Hamilton.3 Graphite oxide €ro˜—˜ly the most ™ommon route to gr—phene involves the produ™tion of gr—phite oxide @qyA ˜y extremely h—rsh oxid—tion ™hemistryF „he methods of ƒt—udenmeier or rummers —re most ™ommonly used to produ™e qyD — highly exfoli—ted m—teri—l th—t is dispersi˜le in w—terF „he stru™ture of qy h—s ˜een the su˜je™t of numerous studiesY it is known to ™ont—in epoxide fun™tion—l groups —long the ˜—s—l pl—ne of sheets —s well —s hydroxyl —nd ™—r˜oxyl moieties —long the edges @pigure VFIRAF sn ™ontr—st to other methods for the synthesis of qyD the the mEperoxy˜enzoi™ —™id @mEg€feA oxid—tion of mi™ro™ryst—lline syntheti™ gr—phite —t room temper—ture yields gr—phite epoxide in high yieldD without signi(™—nt —ddition—l defe™tsF Idealized structure proposed for graphene oxide (GO). E.

NANOTECHNOLOGY es would ˜e expe™tedD ggq is prone to —ggreg—tion unless st—˜ilizedF qr—phene m—teri—ls produ™ed from pristine gr—phite —void h—rsh oxid—tion to qy —nd su˜sequent @in™ompleteA redu™tionY thusD m—teri—ls proE du™ed —re potenti—lly mu™h ˜etter suited to ele™troni™s —ppli™—tionsF e ™—t—lyti™ —ppro—™h to the remov—l of epoxides from fullerenes —nd ƒ‡x„s h—s ˜een —pplied to gr—phene epoxide —nd qyF „re—tment of oxidized gr—phenes with methyltrioxorhenium @we‚ey3 D w„yA in the presE en™e of €€h3 results in the oxygen tr—nsferD to form ya€€h3 —nd —llow for qu—nti(™—tion of the gXy r—tioF 8.4.PUR CHAPTER 8.4 Homogeneous graphene dispersions en —ltern—te —ppro—™h to produ™ing gr—phene m—teri—ls involves the use of pristine gr—phite —s st—rting m—teri—lF „he fund—ment—l v—lue of su™h —n —ppro—™h lies in its —void—n™e of oxid—tion to qy —nd su˜seE quent @in™ompleteA redu™tionD there˜y preserving the desir—˜le ele™troni™ properties of gr—pheneF „here is pre™edent for exfoli—tion of pristine gr—phite in ne—t org—ni™ solvents without oxid—tion or surf—™t—ntsF st h—s ˜een reported th—t NDN Edimethylform—mide @hwpA dispersions of gr—phene —re possi˜leD ˜ut no det—iled ™h—r—™teriz—tion of the dispersions were reportedF sn ™ontr—stD golem—n —nd ™oworkers reported simil—r disE persions using N Emethylpyrrolidone @xw€AD resulting in individu—l sheets of gr—phene —t — ™on™entr—tion of ≤HFHI mgGmvF xw€ —nd hwp —re highly pol—r solventsD —nd not ide—l in ™—ses where re—™tion ™hemistry requires — nonpol—r mediumF purtherD they —re hygros™opi™D m—king their use pro˜lem—ti™ when w—ter must ˜e ex™luded from re—™tion mixturesF pin—llyD hwp is prone to therm—l —nd ™hemi™—l de™ompositionF ‚e™entlyD dispersions of gr—phene h—s ˜een reported in ortho Edi™hloro˜enzene @yhgfA using — wide r—nge of gr—phite sour™esF „he ™hoi™e of yhgf for gr—phite exfoli—tion w—s ˜—sed on sever—l ™riteri—X IF PF QF RF yhgf is — ™ommon re—™tion solvent for fullerenes —nd is known to form st—˜le ƒ‡x„ dispersionsF yhgf is — ™onvenient highE˜oiling —rom—ti™D —nd is ™omp—ti˜le with — v—riety of re—™tion ™hemistriesF yhgfD ˜eing —rom—ti™D is —˜le to inter—™t with gr—phene via π Eπ st—™kingF st h—s ˜een suggested th—t good solvents for gr—phite exfoli—tion should h—ve surf—™e tension v—lues of RH ! SH mtGm2 F yhgf h—s — surf—™e tension of QTFT mtGm2 D ™lose to the proposed r—ngeF qr—phite is re—dily exfoli—ted in yhgf with homogeniz—tion —nd soni™—tionF „hree st—rting m—teri—ls were su™™essfully dispersedX mi™ro™ryst—lline syntheti™D therm—lly exp—ndedD —nd highly ordered pyrolyti™ gr—phite @ry€qAF hispersions of mi™ro™ryst—lline syntheti™ gr—phite h—ve — ™on™entr—tion of HFHQ mgGmvD determined gr—vimetri™—llyF hispersions from exp—nded gr—phite —nd ry€q —re less ™on™entr—ted @HFHP mgGmvAF righ resolution tr—nsmission ele™tron mi™ros™opy @r‚„iwA shows mostly fewEl—yer gr—phene @n < SA with single l—yers —nd sm—ll )—kes st—™ked on top @pigure VFISAF v—rge gr—phiti™ dom—ins —re visi˜leY this is further supported ˜y sele™ted —re— ele™tron di'r—™tion @ƒeihA —nd f—st pourier tr—nsform @pp„A in sele™ted —re—sF etomi™ for™e mi™ros™ope @epwA im—ges of dispersions spr—yed onto sili™on su˜str—tes shows extremely thin )—kes with ne—rly —ll ˜elow IH nmF ever—ge height is U E IH nmF „he thinnest —re less th—n I nmD gr—phene monol—yersF v—ter—l dimensions of n—nosheets r—nge from IHH ! SHH nmF .

15: esEdeposited (lms ™—st from yhgf gr—phene show poor ele™tri™—l ™ondu™tivityD howeverD —fter v—™uum —nne—ling —t RHH ◦ g for IP hours the (lms improve v—stlyD h—ving sheet resist—n™es on the order of TH ΩGsqF fy ™omp—risonD gr—phene epit—xi—lly grown on xi h—s — reported sheet resist—n™e of PVH ΩGsqF 8.4. PhD Thesis. Rice University (2009). (c) selected area from (b) with FFT inset. Adapted from C. Hamilton.PUS TEM images of single layer graphene from HOPG dispersion.5 Covalent functionalization of graphene and graphite oxide „he ™ov—lent fun™tion—liz—tion of ƒ‡x„s is well est—˜lishedF ƒome routes to ™ov—lently fun™tion—lized ƒ‡x„s in™lude esteri(™—tionG —mid—tionD redu™tive —lkyl—tion @fillups re—™tionAD —nd tre—tment with —zomethine ylides @€r—to re—™tionAD di—zonium s—ltsD or nitrenesF gonverselyD the ™hemi™—l deriv—tiz—tion of gr—phene —nd qy is still rel—tively unexploredF ƒome methods previously demonstr—ted for ƒ‡x„s h—ve ˜een —d—pted to qy or gr—pheneF qy ™—rE ˜oxyli™ —™id groups h—ve ˜een ™onverted into —™yl ™hlorides followed ˜y —mid—tion with longE™h—in —minesF . (b) selected edge region from (a). E. Figure 8. (d) HRTEM of boxed region in (c) showing lattice fringes with FFT inset. (a) monolayer and few layer of graphene stacked with smaller akes.

NANOTECHNOLOGY eddition—llyD the ™oupling of prim—ry —mines —nd —mino —™ids vi— nu™leophili™ —tt—™k of qy epoxide groups h—s ˜een reportedF ‰et —nother route ™oupled iso™y—n—tes to ™—r˜oxyli™ —™id groups of qyF pun™tion—liz—tion of p—rti—lly redu™ed qy ˜y —ryldi—zonium s—lts h—s —lso ˜een demonstr—tedF „he fillups re—™tion h—s ˜een performed on the inter™—l—tion ™ompound pot—ssium gr—phite @g8 uAD —s well —s gr—phite )uorideD —nd most re™ently qyF qr—phene —lkyl—tion h—s ˜een —™™omplished ˜y tre—ting gr—phite )uoride with —lkyllithium re—gentsF yhgf dispersions of gr—phene m—y ˜e re—dily ™onverted to ™ov—lently fun™tion—lize gr—pheneF „herm—l de™omposition of ˜enzoyl peroxide is used to initi—te r—di™—l —ddition of —lkyl iodides to gr—phene in yhgf dispersionsF @VFPA eddition—llyD fun™tion—lized gr—phene with nitrenes gener—ted ˜y therm—l de™omposition of —ryl —zides @VFQA 8.PUT CHAPTER 8.D PHHVD 3D STQF • ‡F ƒF rummers —nd ‚F iF y'em—nD J. SocFD IWSVD 80D IQQWF • vF ti—oD vF h—ngD ˆF ‡—ngD qF hi—nkovD —nd rF h—iD NatureD PHHWD 458D VUUF • hF †F uosynkinD eF vF riggin˜oth—mD eF ƒinitskiiD tF ‚F vomed—D eF himievD fF uF €ri™eD —nd tF wF „ourD NatureD PHHWD 458D VUPF • hF viD wF fF wuellerD ƒF qiljeD ‚F fF u—nerD —nd qF qF ‡—ll—™eD Nat. SocFD PHHTD 128D UUPHF • ‰F ƒi —nd iF „F ƒ—mulskiD Nano LettFD PHHVD 8D ITUWF • vF ƒt—udenm—ierD Ber. Chem. Nanotechnol. NanotechnolFD PHHVD 3D IHIF • ƒF xiyogiD iF feky—rov—D wF iF stkisD tF vF w™‡illi—msD wF eF r—monD —nd ‚F gF r—ddonD J. Am. LettFD PHHVD 98D PHTVHSF • ‰F rern—ndezD †F xi™olosiD wF voty—D pF wF fligheD F ƒunD ƒF heD sF „F w™qovernD fF roll—ndD wF fyrneD ‰F uF qun9uoD tF tF fol—ndD €F xir—jD qF hues˜ergD ƒF urishn—murthyD ‚F qoodhueD tF rut™hinsonD †F ƒ™—rd—™iD eF gF perr—riD —nd tF xF golem—nD Nat.4. Am. SocFD PHHVD 130D SRIRF • qF id—D qF p—n™hiniD —nd wF ghhow—ll—D Nat.6 Bibliography • €F fl—keD €F hF frimi™om˜eD ‚F ‚F x—irD „F tF foothD hF ti—ngD pF ƒ™hedinD vF eF €onom—renkoD ƒF †F worozovD rF pF qleesonD iF ‡F rillD eF uF qeimD —nd uF ƒF xovoselovD Nano LettFD PHHVD 8D IUHRF • tF gh—ttop—dhy—yD eF wukherjeeD gF iF r—miltonD tFErF u—ngD ƒF gh—kr—˜ortyD ‡F quoD uF pF uellyD eF ‚F f—rronD —nd ‡F iF fillupsD J. NanotechnolFD PHHVD 3D PUHF • wF ‰F r—nD fF yzyilm—zD ‰F h—ngD —nd €F uimD Phys. Chem. Rev. Am. Dtsch. Chem. Chem. GesFD IVWVD 31D IRVIF .

16: „he —™tu—l positioning experiment w—s ™—rried out in the following pro™essF „he ni™kel met—l su˜str—te w—s prep—red ˜y ™y™les of —rgonEion sputteringD followed ˜y —nne—ling in — p—rti—l pressure of oxygen to 5 This content is available online at <http://cnx. Figure 8.5.PUU 8. a) STM tip move onto a target atom then change the voltage and current of the tip to apply a stronger interaction. b) Move the atom to a desire Rolling Molecules on Surfaces Under STM Imaging 8. c) After reaching the desire position. .1 Introduction to surface motions at the molecular level 5 es single mole™ule im—ging methods su™h —s s™—nning tunneling mi™ros™ope @ƒ„wAD —tomi™ for™e mi™ros™ope @epwAD —nd tr—nsmission ele™tron mi™ros™ope @„iwA developed in the p—st de™—desD s™ientists h—ve g—ined powerful tools to explore mole™ul—r stru™tures —nd ˜eh—viors in previously unknown —re—sF emong these im—ging methodsD ƒ„w is pro˜—˜ly the most suit—˜le one to o˜serve det—il —t mole™ul—r levelF ƒ„w ™—n oper—te in — wide r—nge of ™onditionsD provides very high resolutionD —nd —˜le to m—nipul—te mole™ul—r motions with the tipF en interesting e—rly ex—mple ™—me from sfw in IWWHD in whi™h the ƒ„w w—s used to position individu—l —toms for the (rst timeD spelling out 4sEfEw4 in ˆenon —tomsF „his work reve—led th—t o˜serv—tion —nd ™ontrol of single —toms —nd mole™ul—r motions on surf—™es were possi˜leF „he sfw workD —nd su˜sequent experimentsD relied on the f—™t th—t ƒ„w tip —lw—ys exerts — (nite for™e tow—rd —n —dsor˜—te —tom th—t ™ont—ins ˜oth v—n der ‡——ls —nd ele™trost—ti™ for™es w—s utilized for m—nipul—tion purposeF fy —djusting the position —nd the volt—ge of the tipD the inter—™tions ˜etween the tip —nd the t—rget mole™ule were ™h—ngedF „hereforeD —pplyingGrele—sing for™e to — single —tom —nd m—ke it move w—s possi˜le pigure VFITF Manipulation of STM tip toward a xenon atom.3/>. the tip released by switching back to the scanning voltage and current.

Nature. Schweizer.2 Surface rolling of molecules under the manipulation of STM tips es des™ri˜ed —˜oveD rolling motions —re most likely to ˜e o˜served on mole™ules h—ving high degree of symmetry —nd suit—˜le inter—™tions ˜etween themselves —nd the surf—™eF g60 is not only — highly symmetri™—l mole™ule ˜ut —lso re—dily im—ge—˜le under ƒ„w due to its sizeF „hese properties together m—ke g60 —nd its deriv—tives highly suit—˜le to study with reg—rds to surf—™eErolling motionF „he ƒ„w im—ging of g60 w—s (rst ™—rried out —t et uing gollegeD vondonF ƒimil—r to the —tom positioning experiment ˜y sfwD ƒ„w tip m—nipul—tion w—s —lso utilized to —™hieve g60 displ—™ementF „he tip tr—je™tory . 1990. K.PUV CHAPTER 8. ell motions on surf—™es —t the single mole™ule level ™—n ˜e des™ri˜ed —s ˜y the following @or ™om˜in—tion of the followingA modesX iF iiF iiiF ivF ƒlidingF roppingF ‚ollingF €ivotingF elthough the power of ƒ„w im—ging h—s ˜een demonstr—tedD im—ging of mole™ules themselves is still often — di0™ult t—skF „he su™™essful im—ging of the sfw work w—s —ttri˜uted to sele™tion of — he—vy —tomF yther syntheti™ org—ni™ mole™ules without he—vy —toms —re mu™h more di0™ult to ˜e im—ged under ƒ„wF hetermin—tions of the me™h—nism of mole™ul—r motion is —notherF fesides im—ging methods themselvesD other —uxili—ry methods su™h —s hp„ ™—l™ul—tions —nd im—ging of properly designed mole™ules —re required to determine the me™h—nism ˜y whi™h — p—rti™ul—r mole™ule moves —™ross — surf—™eF rereinD we —re p—rti™ul—rly interested in surf—™eErolling mole™ulesD iFeFD those th—t —re designed to roll on — surf—™eF st is str—ightforw—rd to im—gine th—t if we w—nt to ™onstru™t @—nd im—geA surf—™eErolling mole™ulesD we must think of m—king highly symmetri™—l stru™turesF sn —dditionD the m—gnitudes of inter—™tions ˜etween the mole™ules —nd the surf—™es h—ve to ˜e —dequ—teY otherwise the mole™ules will ˜e more sus™epti˜le to slideGhop or sti™k on the surf—™esD inste—d of rollingF es — resultD only very few mole™ules —re known ™—n roll —nd ˜e dete™ted on surf—™esF 8. Adapted from D.17: Manipulation of STM tip starting with a) randomly dosed xenon sample.5.move xenon atom to desire position. M. NANOTECHNOLOGY remove surf—™e ™—r˜on —nd other impuritiesF efter the ™le—ning pro™essD the s—mple w—s ™ooled to R uD —nd im—ged with the ƒ„w to ensure the qu—lity of surf—™eF „he ni™kel s—mple w—s then doped with xenonF en im—ge of the doped s—mple w—s t—ken —t ™onst—ntE™urrent s™—nning ™onditionsF i—™h xenon —tom —ppe—rs —s — lo™—ted r—ndomly IFT Å high ˜ump on the surf—™e @pigure VFIU—AF …nder the im—ging ™onditions @tip ˜i—s a HFHIH † with tunneling ™urrent IH-9 eA the inter—™tion of the xenon with the tip is too we—k to ™—use the position of the xenon —tom to ˜e pertur˜edF „o move —n —tomD the ƒ„w tip w—s pl—™ed on top of the —tom performing the pro™edure depi™ted in pigure VFIT to move it to its t—rgetF ‚epe—ting this pro™ess —g—in —nd —g—in led the rese—r™her to ˜uild of the stru™ture they desired pigure VFIU˜ —nd ™F Figure 8. and c) accomplishment of the manipulation. Eigler and E. 524. 344. b) under construction .

. b) 1-point interaction.PUW suggested th—t — rolling motion took into —™™ount the displ—™ement on the surf—™e of g60 F sn order to ™on(rm the hypothesisD the rese—r™hers —lso employed ab initio density fun™tion @hp„A ™—l™ul—tions with rolling model ˜ound—ry ™ondition @pigure VFIVAF „he ™—l™ul—tion result h—s supported their experiment—l resultF Figure 8. The light blue Si balls represent the rst layer of molecules the silicon surface. a) 2-point interaction.18: Proposed mechanism of C60 translation showing the alteration of C60 . A new interaction formed to complete part of the rolling motion. and the yellow balls are the second layer. „he results provided insights into the dyn—mi™—l response of ™ov—lently ˜ound mole™ules to m—nipul—tionF „he sequenti—l ˜re—king —nd reforming of highly dire™tion—l ™ov—lent ˜onds resulted in — dyn—mi™—l mole™E ul—r response in whi™h ˜ond ˜re—kingD rot—tionD —nd tr—nsl—tion —re intim—tely ™oupled in — rolling motion @pigure VFIWAD ˜ut not performing sliding or hopping motionF e tripty™ene wheeled dimeri™ mole™ule pigure VFIW w—s —lso synthesized for studying rolling motion under ƒ„wF „his 4tripodElike4 tripty™ene wheel ulike — ˜—ll like g60 mole™ule —lso demonstr—ted — rolling motion on the surf—™eF „he two tripty™ene units were ™onne™ted vi— — di—lkynyl —xleD for ˜oth desired mole™ule orient—tion sitting on surf—™e —nd dire™tion—l preferen™e of the rolling motionF ƒ„w ™ontrolling —nd im—ging w—s demonstr—tedD in™luding the me™h—nism pigure VFIWF . C60 can pivot on surface. a) . c) 2-point interaction. The left point interaction was dissociated during the interaction. surface interactions during rolling..c) The black spot on the C60 is moved during the manipulation.

only one rotation of a wheel can be induced (the direction of movement is marked by arrows). 8. Step 1 is the tip approach towards the molecule. It shows that.3 Single molecule nanocar under STM imaging enother use of ƒ„w im—ging —t single mole™ule im—ging is the single mole™ule n—no™—r ˜y the „our group —t ‚i™e …niversityF „he ™on™ept of — n—no™—r initi—lly employed the free rot—tion of — gEg single ˜ond ˜etween — spheri™—l g60 mole™ule —nd —n —lkyneD pigure VFPHF f—sed on this ™on™eptD —n —xle ™—n ˜e designed into whi™h —re mounted g60 wheels ™onne™ted with — ™h—ssis to ™onstru™t the n—no™—rF x—no™—rs with this design —re expe™ted to h—ve — dire™tion—l movement perpendi™ul—r to the —xleF …nfortun—telyD the (rst gener—tion n—no™—r @n—med n—notru™k pigure VFPIA en™ountered some di0™ulties in ƒ„w im—ging due to its ™hemi™—l inst—˜ility —nd insolu˜ilityF „hereforeD — new of design of n—no™—r ˜—sed on y€i h—s ˜een synthesized pigure VFPPF .5. NANOTECHNOLOGY Figure 8.19: Scheme of the rolling mechanism (left to right).PVH CHAPTER 8. step 2 is a 120 degree rotation of a wheel around its molecular axle and in step 3 the tip reaches the other side of the molecule. in principle.

M. M. Yao. Alemany. Guerrero. Sasaki. No rolling motion was observed under STM imaging due to its instability. J. F.-H. H. Soc. Chiu. K. 2006.. A. J. Copyright American Chemical Society (2006). The arrow indicates the rotational motion of C60 . Zhao. Morin. J. L. Y.PVI Structure of C60 wheels connecting to an alkyne. Kelly. The only possible rolling direction is perpendicular to the C-C single bond between C60 and the alkyne. Osgood.The double head arrow indicates the expected direction of nanocar movement.-F. J. L. Figure 8. Y. and J. Y. 4854. Chem. Yang. Am. T. Saudan. Y. Tour.21: . 128. Shirai. Figure 8.20: Structure of the nanotruck. insolubility and inseparable unreacted C60 . B.

5. 2005.1 nm (W x L). J. A. Figure 8. Kelly. The dimension of nanocar was 3. The bold double head arrow indicates the expected direction of nanocar movement. Copyright American Chemical Society (2005)..PVP CHAPTER 8.3 nm X 2. Y. Y.1 nm which enable direct observation of the orientation under STM imaging. Tour. NANOTECHNOLOGY Nanocar based on OPE structure. F. The size of the nanocar is 3.3 nm X 2. Nano Lett. and J. Alkoxy chains were attached to improve solubility and stability. 2330. OPE moiety is also separable from C60 . K.22: „he newly designed n—no™—r w—s studied with ƒ„wF ‡hen the n—no™—r w—s he—ted to ∼PHH ◦ gD noE ti™e—˜le displ—™ements of the n—no™—r were o˜served under sele™ted im—ges from — IH min ƒ„w experiment pigure VFPQF „he phenomenon th—t the n—no™—r moved only —t high temper—ture w—s —ttri˜uted their st—E ˜ility to — rel—tively strong —dhesion for™e ˜etween the fullerene wheels —nd the underlying goldF „he series of im—ges showed ˜oth pivot—l —nd tr—nsl—tion—l motions on the surf—™esF . M. Osgood. Shirai. Zhao.

J. Acquisition time of one image is approximately 1 min with (a  e) images were selected from a series spanning 10 min. A. b)  e) indicated translation interrupted by small-angle pivot perturbations. Y. 5.23: elthough liter—ture studies suggested th—t the g60 mole™ule rolls on the surf—™eD in the n—no™—r movement studies it is still not possi˜le to ™on™lusively ™on™lude th—t the n—no™—r moves on surf—™e ex™lusively vi— — rolling me™h—nismF roppingD sliding —nd other moving modes ™ould —lso ˜e responsi˜le for the movement of the n—no™—r sin™e the experiment w—s ™—rried out —t high temper—ture ™onditionsD m—king the g60 mole™ules more energeti™ to over™ome inter—™tions ˜etween surf—™esF „o t—™kle the question of the mode of tr—nsl—tionD — trimeri™ n—noEtri™y™le h—s ˜een synthesizedF sf the movement of fullereneEwheeled n—no™—r w—s ˜—sed on — hopping or sliding me™h—nismD the trimer should give . Figure 8.PVQ Pivotal and translational movement of OPE based nanocar. The conguration of the nanocar on surface can be determined by the distances of four wheels. a)  b) indicated the nanocar had made a 80 ◦ pivotal motion. Kelly. 2330. Zhao. Nano Lett. Osgood. 2005. F. K. Shirai. Copyright American Chemical Society (2005). Tour. and J.. M. Y.

PVR CHAPTER 8. NANOTECHNOLOGY o˜serv—˜le tr—nsl—tion—l motions like the fourEwheeled n—no™—rD howeverD if rolling is the oper—˜le motion then the n—noEtri™y™le should rot—te on —n —xisD ˜ut not tr—nsl—te —™ross the surf—™eF „he result of the im—ging experiment of the trimer —t ∼PHH ◦ g @pigure VFPRDA yielded very sm—ll —nd insigni(™—nt tr—nsl—tion—l displ—™ements in ™omp—rison to REwheel n—no™—r @pigure VFPQAF „he trimeri™ QEwheel n—no™—r showed some pivoting motions in the im—gesF „his motion type ™—n ˜e —ttri˜uted to the dire™tion—l preferen™es of the wheels mounted on the trimer ™—using the ™—r to rot—teF ell the experiment—l results suggested th—t — g60 E˜—sed n—no™—r moves vi— — rolling motion r—ther th—n hopping —nd slidingF sn —dditionD the f—™t th—t the therm—lly driven n—no™—r only moves in high temper—ture —lso suggests th—t four g60 h—ve very strong inter—™tions to the surf—™eF .

A. 2005.d) Pivot motions of circled trimered were shown in the series of images.PVS Pivot motion of the trimer. a) . F. Nano Lett. 2330. K. Y. No signicant translation were observed in comparison to the nanocar. Osgood. Zhao. Shirai. Tour. J. Figure 8.. M. 5. Y. and J. Copyright American Chemical Society (2005). Kelly.24: .

Am.D PHHTD 128D RVSRF . NANOTECHNOLOGY 8.5.D PHHUD 2D WSF • ‰F ƒhir—iD eF tF ysgoodD ‰F h—oD uF pF uellyD —nd tF wF „ourD Nano Lett. Soc. Chem.PVT CHAPTER 8. Nanotechnol.D PHHSD 5D PQQHF • ‰F ƒhir—iD eF tF ysgoodD ‰F h—oD ‰F ‰—oD vF ƒ—ud—nD rF ‰—ngD ‰FErF ghiuD vF fF elem—nyD „F ƒ—s—kiD tFEpF worinD tF wF querreroD uF pF uellyD —nd tF wF „ourD J.4 Bibliography • hF wF iigler —nd iF uF ƒ™hweizerD NatureD IWWHD 344D SPRF • vF qrillD uF ErF ‚iederD pF wores™oD qF ‚—penneD ƒF ƒtojkovi™D ˆF foujuD —nd gF to—™himD Nat.

org/content/m14503/1.3/>.1 What is a semiconductor? „he semi™ondu™tor industry is one of the f—stest growing m—nuf—™turing se™tors in not only the …nited ƒt—tes ˜ut —lso in the worldF e™™ording to the emeri™—n ile™troni™s esso™i—tionD the domesti™ s—les of ele™troni™ ™omponents h—ve skyro™ketedD jumping from 6IPU ˜illion to 6QHT ˜illion over the ™ourse of the IWVH9sF sn the (rst three qu—rters of the PHHQ (s™—l ye—r —loneD the export of te™hnology goods from the …nited ƒt—tes in™re—sed ˜y 6IW ˜illion ‘I“F „he word semi™ondu™tor te™hni™—lly refers to —ny mem˜er of — ™l—ss of solidD ™ryst—lline m—teri—ls th—t is ™h—r—™terized ˜y —n ele™tri™—l ™ondu™tivity ˜etter th—n th—t of insul—tors @eFgFD pl—sti™A ˜ut less th—n th—t of good ™ondu™tors @eFgFD ™opperA ‘P“F ƒemi™ondu™tors —re p—rti™ul—rly useful —s — ˜—se m—teri—l in the m—nuf—™turing of ™omputer ™hipsD —nd the term semi™ondu™tor h—s —™tu—lly ™ome to ˜e synonymous with the ™omputer ™hipsD themselvesF roweverD semi™ondu™tors —re not only used in ™omputersF gomputers only m—ke up RR7 of entire industry ™onsumption @see pigure WFIAF ƒemi™ondu™tors —re —lso used for milit—ryD —utomotiveD industri—lD ™ommuni™—tionsD —nd other ™onsumer purposesF 1 2 This content is available online at <http://cnx.1 The Environmental Impact of the Manufacturing of Seminconductors 1 4„his module w—s developed —s p—rt of — ‚i™e …niversity gl—ss ™—lled 4x—note™hnologyX gontent —nd gontext2 4initi—lly funded ˜y the x—tion—l ƒ™ien™e pound—tion under qr—nt xoF iigE HRHUPQUF st w—s ™on™eivedD rese—r™hedD written —nd edited ˜y students in the p—ll PHHS version of the ™l—ssD —nd reviewed ˜y p—rti™ip—ting professorsF4 note: 9.Chapter 9 Economic and Environmental Issues PVU . http://frazer.1.rice.

1: Relative consumption of semiconductors by industry [3].2 Why is nanotechnology important to the semiconductor industry? wu™h of the study of n—note™hnology h—s ˜een ™entered on the m—nuf—™turing of semi™ondu™torsF „hough there —re — num˜er of highly —nti™ip—ted —ppli™—tions for n—note™hnology in other (eldsD not—˜ly in medi™ine —nd in ˜iote™hnologyD the most t—ngi˜le results thus f—r ™—n ˜e —rgued to h—ve ˜een —™hieved in the semiE ™ondu™tor industryF . ECONOMIC AND ENVIRONMENTAL ISSUES Figure 9. ƒemi™ondu™tors seem to ˜e —nywhere —nd everywhere throughout our everyd—y livesD yet it is surprising how little most people know —˜out how they —™tu—lly work or —˜out the potenti—lly dev—st—ting e'e™ts their m—nuf—™turing ™—n h—ve on the environment —nd hum—n he—lthF 9.PVV CHAPTER 9.1.

PVW Figure 9.2: An example of a semiconductor (photo from PEAK).3 How are semiconductors manufactured? „od—y9s semi™ondu™tors —re usu—lly ™omposed of sili™onD —nd they —re m—nuf—™tured in — pro™edure th—t ™om˜ines the f—mili—r with the ˜iz—rreY some steps th—t —re involved in the pro™ess —re —s everyd—y —s developing — roll of photogr—phi™ (lm while others seem —s if they would ˜e ˜etter suited to t—ke pl—™e on — sp—™eshipF „hese semi™ondu™tors —ppe—r to the n—ked eye —s ˜eing sm—ll —nd )—tD ˜ut they —re —™tu—lly threeE dimension—l s—ndwi™hes th—t —re ten to twenty l—yers thi™kF st ™—n t—ke more th—n two dozen steps —nd up to two full months to produ™e — single one of these sili™on s—ndwi™hesF ƒome of the ˜—si™ —nd more essenti—l .1. por ex—mpleD sntel re™ently unveiled its (rst produ™ts ˜—sed on — gener—tion of WHEn—nometer pro™ess te™hnologyD —nd its rese—r™hes —nd engineers h—ve ˜uilt —nd tested prototype tr—nsistors —ll the w—y down to the PPEn—nometer r—ngeF gurrentlyD sntel s™ientists —nd engineers —re working on identifying new m—teri—ls su™h —s ™—r˜on n—notu˜es —nd n—nowires to repl—™e ™urrent tr—nsistorsD —nd in p—rti™ul—r they hope to develop — triEg—te tr—nsistor —ppro—™h th—t would en—˜le ™hip designers to ˜uild tr—nsistors ˜elow the PPEn—nometer r—nge ‘R“F ‡ith the —dvent of n—note™hnologyD these tr—nsistors —re ˜e™oming even f—ster —nd more powerfulD —nd in —™™ord—n™e with the l—w of —™™eler—ting returnsD the industry h—s ˜een produ™ing sm—ller tr—nsistors —t lower ™osts with e—™h —nd every p—ssing ye—rF es these semi™ondu™tors ˜e™ome sm—ller —nd sm—llerD they —re qui™kly —nd surely pushing tow—rds the limits of the n—noEre—lmF „hese innov—tionsD howeverD do not ™ome without their f—ir sh—re of ™h—llengesF €hysi™—l issues th—t —re not pro˜lem—ti™ —t the mi™ron s™—le —rise —t the n—noEs™—le due to the emergen™e of qu—ntum e'e™tsD —nd in mu™h the s—me w—y th—t opti™—l mi™ros™opy ™—nnot ˜e utilized —t the n—noEs™—leD the semi™ondu™tor industry is f—st —ppro—™hing — simil—r di'r—™tion limitF ypti™—l lithogr—phyD for inst—n™eD — pro™ess th—t uses the properties of light to et™h tr—nsistors onto w—fers of sili™onD will soon re—™h its limitF et its most ˜—si™ levelD n—note™hnology involves pushing individu—l —toms together one ˜y oneF ƒin™e —pproxim—tely IFU ˜illion tr—nsistors —re required for — single ™hipD this is o˜viously not — re—listi™ method for m—ss produ™tionF …nless —n —ltern—tive method for produ™tion or — solution to this pro˜lem is foundD the development —nd m—nuf—™turing of tr—nsistors —re expe™ted to hit — prover˜i—l ˜ri™k w—ll ˜y the ye—r PHISF „his is the re—son th—t rese—r™h in n—note™hnology is so import—nt for the world —nd future of semi™ondu™torsF 9.

3: An artist's illustration of a stepper (image from Solid State Electronics). rundreds of ™opies of the ™hip —re et™hed onto the w—fer until the entire surf—™e h—s ˜een exposedF yn™e this pro™ess is ™ompleteD the entire w—fer is su˜merged into —n et™hing ˜—thD whi™h w—shes —w—y —ny p—rts of the photoresist th—t rem—in unexposed —long with the insul—ting ™hemi™—ls underne—thF „he h—rdened —re—s of the photoresistD howeverD rem—in —nd prote™t the l—yers of m—teri—l underne—th themF „his pro™ess of depositing ™hemi™—lsD ™o—ting with — photoresistD exposure to light over — (lm m—skD —nd et™hing —nd w—shing —w—y is repe—ted more th—n — dozen timesF „he result is —n el—˜or—teD threeEdimension—l ™onstru™tion of .PWH CHAPTER 9. ECONOMIC AND ENVIRONMENTAL ISSUES steps involved in the m—nuf—™turing pro™ess of sili™on ™hips —re ˜rie)y det—iled ˜elowF pirstD sili™on ™ryst—ls —re melted in — v—t —nd puri(ed to WWFWWWW7 purityF „he molten sili™on is dr—wn into longD he—vyD ™ylindri™—l ingotsD whi™h —re then ™ut into thin sli™es ™—lled w—fers—˜out the thi™kness of — ˜usiness ™—rdF yne side of e—™h w—fer must ˜e polished —˜solutely smoothF „his pro™ess is ™—lled ™hemi™—lEme™h—ni™—l polishingD —nd it involves ˜—thing the w—fers in spe™i—l —˜r—sive ™hemi™—lsF efter ™hemi™—lEme™h—ni™—l polE ishingD imperfe™tions ™—nnot ˜e dete™ted on the w—fers even with the —id of — l—˜or—tory mi™ros™opeF efter — w—fer is polishedD l—yers of m—teri—l must ˜e st—™ked on top of the sili™on w—fer ˜—seF snsul—ting l—yers —re l—id down in —ltern—tion with ™ondu™ting l—yers in — pro™ess ™—lled depositionF „his is often —™hieved ˜y spr—ying the ™hemi™—ls dire™tly onto the surf—™e of the w—fer through ™hemi™—l v—por depositionF pollowing depositionD the w—fer is ™o—ted with —nother l—yer of ™hemi™—ls ™—lled — photoresist th—t is sensitive to lightF xextD — m—™hine ™—lled — stepper @pigure WFQA is ™—li˜r—ted to proje™t —n extremely (ne —nd fo™used im—ge through — spe™i—l type of reti™le (lm in — m—nner simil—r to th—t of — simple slide proje™torF „he light th—t is tr—nsmitted through the reti™le is proje™ted onto the photoresist l—yerD whi™h re—™ts to the light —nd ˜egins to h—rdenF ell of the p—rts of the w—fer exposed to this light h—rden into — tough ™rust while the p—rts in sh—dow rem—in softF „his p—rti™ul—r step is known ˜y the n—me of photoele™tro™hemi™—l et™hing ˜e™—use it —™hieves —n et™hing e'e™tD resulting in — ™hipF Figure 9.

wost if not —ll surf—™es inside these ™le—n rooms —re ™omposed of st—inless steelD —nd these surf—™es —re sloped whenever possi˜le or perfor—ted ˜y gr—ting to —void giving dust — pl—™e to settleF „he —ir is (ltered through ˜oth the ™eiling —nd the )oor to remove p—rti™les th—t —re down to IGIHH the width of — hum—n h—irF vighting is ™h—r—™teristi™—lly ˜right —nd slightly yellowish to prevent mildew from forming ˜ehind equipment or in re™essed ™ornersD —nd even the workers in — ™le—n room must ˜e —˜solutely spotlessF ‡orkers in these rooms must ˜e ™overed from he—d to toe in ˜unny suits th—t ™ompletely se—l the ˜ody in — ˜ulky suitD helmetD ˜—ttery p—™kD glovesD —nd ˜ootsF yn™e se—led in these suitsD the workers often look more like sp—™e explorers in — s™ien™e (™tion movie th—n ™omputer ™hip employeesD ˜ut in order to even enter the st—inless steel lo™ker room to suit up to ˜egin withD they must (rst p—ss through — series of —ir lo™k doorsD st—nd under — num˜er of —ir showers th—t —™tu—lly ˜low dust o' of ™lothingD —nd w—lk —™ross — sti™ky )oor m—tting th—t removes grime from the ˜ottom of shoesF ƒemi™ondu™torEm—nuf—™turing ™omp—nies often portr—y their f—˜ri™—tion f—™ilities —s ˜eing ™le—nD environE ment—lly friendlyD —nd ™onspi™uously free of the ˜l—™kD ˜illowing smokest—™ks th—t h—ve ™ome to ˜e —sso™i—ted .4 What is a clean room? e typi™—l semi™ondu™tor f—˜ri™—tion f—™ilityD or f—˜ in industry j—rgonD looks like — norm—l twoE or threeE story o0™e ˜uilding from the outsideD —nd most of the interior sp—™e is devoted to one or more ™le—n roomsD in whi™h the semi™ondu™tors —re —™tu—lly m—deF e ™le—n room is designed with — f—n—ti™—l —ttention to det—il —imed tow—rds keeping the room imm—™ul—te —nd dustEfree @pigure WFRAF Figure 9.1.PWI interlo™king sili™on wiresF „his produ™t is then ™o—ted with —nother insul—ting l—yer —nd is pl—ted with — thin l—yer of met—lD usu—lly either —luminum or ™opperF ‰et —nother photoresist is l—id down on top of this met—l pl—tingD —nd —fter the w—fer is exposed in — stepperD the pro™ess repe—ts with —nother l—yer of met—lF efter this step h—s ˜een repe—ted sever—l more timesD — (n—l w—sh step is performedD —nd — (nished semi™ondu™tor produ™t rolls o' the —ssem˜ly lineD —t l—stF 9.4: An industry clean room at AP Tech (photo from Napa Gateway).

Figure 9.PWP CHAPTER 9.5: „he devi™es ˜eing ˜uilt —t semi™ondu™tor f—˜ri™—tion f—™ilities —re superEsensitive to environment—l ™onE t—min—ntsF fe™—use e—™h ™hip t—kes dozens of tr—ined personnel sever—l weeks to ™ompleteD —n enormous —mount of time —nd e'ort is expended to produ™e — single w—ferF „he industry m—y pride itself on its perE fe™tly imm—™ul—te l—˜or—tories —nd its ˜unnyEsuited workersD ˜ut it should ˜e noted th—t the ˜unny suits —re not designed to prote™t their we—rers from h—z—rdous m—teri—ls ˜ut r—ther to prote™t the —™tu—l semiE ™ondu™tor produ™ts from ™oming into ™ont—™t with dirtD h—irD )—kes of skinD —nd other ™ont—min—nts th—t ™—n ˜e shed from hum—n ˜odiesF „hey prote™t the sili™on w—fers from the peopleD not the people from the ™hemi™—lsF . ECONOMIC AND ENVIRONMENTAL ISSUES with the pl—nts —nd f—™tories of other m—jor industriesF „hese f—™ilities produ™e no visi˜le pollution —nd ™erE t—inly do not —ppe—r to pose —ny he—lth or environment—l risksF sn truthD the term ™le—n roomD itself is more th—n just — ˜it of —n underst—tementF sndustry exe™utives often ˜o—st th—t their ™le—n rooms —re from IDHHH times to IHDHHH times ™le—ner —nd more s—nit—ry th—n —ny hospit—l oper—ting roomF 9.1.5 What are the health risks involved in the semiconductor industry? „he use of sterile te™hniques —nd the f—stidious —ttention devoted to ™le—nliness in the semi™ondu™tor industry m—y perpetu—te the illusion th—t the m—nuf—™turing of semi™ondu™tors is — s—fe —nd sterile pro™essF roweverD —s — r—pidly growing ˜ody of eviden™e ™ontinues to suggestD h—rdly —nything ™ould ˜e further from the truth @pigure WFSAF „he question of worker s—fety —nd ™hemi™—l ™ont—min—tion —t ™hipEm—king pl—nts h—s re™eived —n in™re—sing —mount of —ttention over the ™ourse of the p—st de™—deF Chemicals used in the manufacturing of semiconductors are known to have toxic eects (image from FARSHA).

PWQ vee xe—lD the he—d of s—fetyD he—lthD —nd environment—l —'—irs for the ƒemi™ondu™tor sndustry essoE ™i—tionD h—s ˜een quoted —s s—yingD „his is —n environment th—t is ™le—ner th—n —n oper—ting room —t — hospit—lF roweverD this ˜o—st is ™urrently ˜eing ™h—llenged ˜y industry workersD government s™ientistsD —nd o™™up—tion—lEhe—lth experts —™ross the ™ountry —nd worldwideF sndustri—l hygiene h—s —lw—ys ˜een —n issue in the semi™ondu™tor industryF w—ny of the ™hemi™—ls involved in the m—nuf—™turing pro™ess of semi™ondu™tors —re known hum—n ™—r™inogens or pose some other serious he—lth risk if not ™ont—ined properlyF „—˜le WFI lists ten of the h—z—rdous ™hemi™—ls most ™ommonly used in m—nuf—™turing semi™ondu™tors —long with their known e'e™ts on hum—n he—lthF Chemical name Role in manufacturing process Health problems linked to exposure e™etone ghemi™—lEme™h—ni™—l polishing of sili™on w—fers xoseD thro—tD lungD —nd eye irriE t—tionD d—m—ge to the skinD ™onE fusionD un™ons™iousnessD possi˜le ™om— x—use—D deliriumD vomitingD dysE pepsi—D di—rrhe—D de™re—se in eryE thro™yte —nd leuko™yte produ™E tionD —˜norm—l he—rt rhythmD ˜lood vessel d—m—geD extensive tissue d—m—ge to nervesD stomE —™hD intestineD —nd skinD known hum—n ™—r™inogen for lung ™—nE ™er re—d—™heD m—l—iseD we—knessD vertigoD dyspne—D n—use—D —˜domE in—l —nd ˜—™k p—inD j—undi™eD peE ripher—l neurop—thyD —nemi— h—m—ge to ˜one m—rrowD —neE mi—D ex™essive ˜leedingD immune system e'e™tsD in™re—sed ™h—n™e of infe™tionD reprodu™tive e'e™tsD known hum—n ™—r™inogen for leukemi— continued on next page erseni™ sn™re—ses ™ondu™tivity of semiE ™ondu™tor m—teri—l ersine ghemi™—l v—por deposition fenzene €hotoele™tro™hemi™—l et™hing .

PWR g—dmium CHAPTER 9.1 X ghemi™—ls of ™on™ern in the semi™ondu™tor industry ‘S“F ƒever—l semi™ondu™tor m—nuf—™turers in™luding x—tion—l ƒemi™ondu™tor —nd sfw h—ve ˜een ™ited in the p—st for holes in their s—fety pro™edures —nd h—ve ˜een ordered to tighten their h—ndling of ™—r™inogeni™ —nd toxi™ m—teri—lsF sn IWWTD IIU former employees of sfw —nd the f—milies of II workers who h—d died of ™—n™er (led suit —g—inst the ™hemi™—l m—nuf—™turers i—stm—n uod—k gomp—nyD …nion g—r˜ide gorpor—tionD tF „F f—kerD —nd u„s ghemi™—lsD ™l—iming th—t they h—d su'ered —dverse he—lth e'e™ts —s — result of exposure to h—z—rdous ™hemi™—ls on the jo˜ in the semi™ondu™tor industry ‘S“F „he l—wsuit w—s (led in xew ‰orkD whi™h prevented the employees from suing sfw dire™tlyF e sep—r—te group of former sfw workers who h—d developed ™—n™er (led suit —g—inst the ™omp—ny in g—liforni—D —lleging th—t they h—d ˜een exposed to unhe—lthy doses of ™—r™inogeni™ ™hemi™—ls over the p—st three de™—desF ‡itnesses who testi(ed in depositions in the xew ‰ork . ECONOMIC AND ENVIRONMENTAL ISSUES gre—tes holes in sili™on l—tti™e to ™re—te e'e™t of positive ™h—rge h—m—ge to lungsD ren—l dysfun™E tionD immedi—te hep—ti™ injuryD ˜one defe™tsD hypertensionD reE produ™tive toxi™ityD ter—togeni™E ityD known hum—n ™—r™inogen for lung —nd prost—te ™—n™er righly ™orrosiveD severe eye —nd skin ˜urnsD ™onjun™tivitisD derE m—titisD respir—tory irrit—tion h—m—ge to ren—lD reprodu™tiveD —nd immune systemsD spont—E neous —˜ortionD prem—ture ˜irthD low ˜irth weightD le—rning de(™its in ™hildrenD —nemi—D memory efE fe™tsD dementi—D de™re—sed re—™E tion timeD de™re—sed ment—l —˜ilE ity re—d—™heD ™entr—l nervous sysE tem depressionD poor equili˜riumD eyeD noseD thro—tD —nd skin irrit—E tionD ™—rdi—™ —rrhythmi— ‡e—knessD ™onfusionD memory lossD n—use—D perm—nent d—mE —ge to ˜r—inD spee™hD visionD —nd he—ring pro˜lemsD loss of mus™le ™ontrolD poor ˜—l—n™eD neurologE i™—l pro˜lems —nd ret—rd—tion of growth in ™hildrenD suspe™ted huE m—n ™—r™inogen for lung —nd liver ™—n™er srrit—tion of skinD eyesD —nd resE pir—tory tr—™tD dizzinessD drowsiE nessD spee™h —nd he—ring imE p—irmentD kidney dise—seD ˜lood disordersD strokeD di—˜etesD susE pe™ted hum—n ™—r™inogen for reE n—l ™—n™er rydro™hlori™ —™id €hotoele™tro™hemi™—l et™hing ve—d ile™tropl—ted soldering wethyl ™hloroform ‡—shing „oluene ghemi™—l v—por deposition „ri™hloroethylene ‡—shing Table 9.

6: Center).PWS st—te ™ourt in ‡est™hester gounty des™ri˜ed how monitors th—t were supposed to w—rn workers of toxi™ le—ks often did not fun™tion ˜e™—use of ™orrosion from —™ids —nd w—terF „hey —lso —lleged th—t supervisors sometimes shut down monitors to m—int—in produ™tion r—tesF ‡hen they lodged ™ompl—ints with senior o0™i—ls in the ™omp—nyD they ™l—im to h—ve ˜een told not to m—ke w—ves ‘T“F we—nwhileD UH fem—le workers in ƒ™otl—nd sued x—tion—l ƒemi™ondu™tor gorpor—tionD —nother …FƒFE˜—sed ™omp—nyD ™l—iming th—t theyD tooD were exposed to ™—r™inogens on the jo˜F „hese l—wsuits —nd the resulting pu˜li™ity prompted — ground˜re—king study ˜y the re—lth —nd ƒ—fety ixe™utiveD whi™h ™ommissioned — ™ommittee to investig—te these —lleg—tions ‘U“F „he ™ommittee found th—t there were indeed unusu—lly high levels of ˜re—st —nd other kinds of ™—n™er —mong workers —t x—tion—l ƒemi™ondu™tor9s f—˜ri™—tion f—™ility in qreeno™kD ƒ™otl—ndF „he ™ommittee ™on™luded th—t the ™omp—ny h—d f—iled to ensure th—t the lo™—l exh—ust ventil—tion systems —dequ—tely ™ontrolled the potenti—l exposure of employees to hydro)uori™ —™id —nd sulphuri™ —™id fumes —nd to —rseni™ dustF „hese (ndings proved to ˜e extremely em˜—rr—ssing for the ™omp—ny —nd for the industryF e™™ording to —n o0™i—l st—tement rele—sed ˜y sr— veightonD —™ting region—l —dministr—tor of the xew ingl—nd ˜r—n™h of the …FƒF invironment—l €rote™tion egen™yD x—tion—l ƒemi™ondu™tor is — ˜ig ˜usiness th—t uses — l—rge —mount of h—rmful ™hemi™—ls —nd other m—teri—lsF yur h—z—rdous w—ste regul—tions were ™re—ted to properly monitor d—ngerous ™hemi™—ls —nd prevent spillsF sn order for it to workD it is import—nt ˜usinesses to ™omply with —ll of the regul—tionsF ‡hen ™omp—nies f—il to do this they —re potenti—lly putting people ! their employees —nd neigh˜ors ! —t risk ‘V“F woreoverD — study of (fteen semi™ondu™tor m—nuf—™turers pu˜lished in the he™em˜er IWWS issue of the emeri™—n tourn—l of sndependent wedi™ine showed th—t women working in the soE™—lled ™le—n rooms of the semi™ondu™tor f—˜s su'ered from — IR7 mis™—rri—ge r—teF Figure 9. Protesters at a rally staged against IBM (photo from San Francisco Independent Media „he m—in pro˜lem in prose™ution is th—t the industry does not h—ve — single over—r™hing —nd de(nitive pro™ess for m—nuf—™turingD —nd it is di0™ult to pinpoint one p—rti™ul—r ™ompound —s ™—using — ™ert—in he—lth pro˜lem ˜e™—use some pl—nts use —s m—ny —s QHH ™hemi™—lsF elsoD m—ny of the m—nuf—™turing pro™esses t—ke .

ECONOMIC AND ENVIRONMENTAL ISSUES pl—™e in ™losed systemsD so exposure to h—rmful su˜st—n™es is often di0™ult to dete™t unless monitored on — d—ily ˜—sisF ixe™utives —nd spokespeople for the semi™ondu™tor industry m—int—in th—t —ny ™hip workers9 ™—n™ers —nd other medi™—l pro˜lems —re more likely due to f—™tors unrel—ted to the jo˜D su™h —s f—mily historyD drinkingD smokingD or e—ting h—˜itsF „hey —lso s—y th—t over the ye—rsD —s —w—reness of ™hemi™—l h—z—rds h—s grownD they h—ve m—de e'orts to ph—se out toxi™ ™hemi™—ls —nd to lower exposure to othersF „hey insist th—t they use st—teEofEtheE—rt pro™ess equipment —nd ™hemi™—l tr—nsfer systems th—t limit or prevent physi™—l exposure to ™hemi™—ls —nd point out th—t the su˜st—n™es used in the semi™ondu™tor industry —re used in other industries without — m—jor he—lth or s—fety pro˜lemF 9.PWT CHAPTER 9.1.6 What environmental risks are involved? sn theoryD —ttention to ™le—nliness is in the m—nuf—™turer9s ˜est interest not only from — he—lth perspe™tive ˜ut —lso from —n e™onomi™F w—ny ™hemi™—ls used in the produ™tion pro™ess —re not expensive in —nd of themselvesY howeverD the ™ost of m—int—ining these m—teri—ls in —n ultr—E™le—n st—te ™—n ˜e quite highF „his en™our—ges the ™lose monitoring of us—geD the minimiz—tion of ™onsumptionD —nd the development of re™y™ling —nd repro™essing te™hniquesF elsoD the rising ™osts of ™hemi™—l dispos—l —re prompting ™omp—nies to ™ondu™t rese—r™h into —ltern—tives th—t use more environment—lly friendly methods —nd m—teri—lsF sndividu—l ™omp—nies —nd worldwide tr—de —sso™i—tions were —™tive in redu™ing the use —nd emission of greenhouse g—ses during the IWWH9sD —nd the industry —s — whole h—s su˜st—nti—lly redu™ed emissions over the l—st twenty ye—rsF xonethelessD there h—s ˜een — history of environment—l pro˜lems linked to the industry in ƒili™on †—lley —nd other te™hnology ™entersF „o ˜egin withD — tremendous —mount of r—w m—teri—ls is invested in the m—nuf—™turing of semi™ondu™tors every ye—rF woreoverD — typi™—l f—™ility produ™ing semi™ondu™tors on sixEin™h w—fers reportedly uses not only PRHDHHH kilow—tt hours of ele™tri™ity ˜ut —lso over P million g—llons of w—ter every d—y ‘W“F xewer f—™ilities th—t produ™e eightEin™h —nd twelveEin™h w—fers ™onsume even moreD with some estim—tes going —s high —s (ve million g—llons of w—ter d—ilyF ‡hile re™y™ling —nd reusing of w—ter does o™™urD extensive ™hemi™—l tre—tment is required for remedi—tionD —nd in dry or desert —re—s su™h —s el˜uquerqueD xew wexi™oD home to pl—nts for wotorol—D €hilips ƒemi™ondu™torD ellied ƒign—l —nd ƒigneti™sD sntelD —nd other highEte™h (rmsD the high ™onsumption of w—ter ne™ess—ry for the m—nuf—™turing of semi™ondu™tors ™—n pose —n espe™i—lly signi(™—nt dr—in on —n —lre—dy s™—r™e n—tur—l resour™e ‘IH“F „he existen™e of e™onomi™ m—inst—ys in™luding the mining industry —nd the est—˜lished presen™es of ƒ—ndi— x—tion—l v—˜or—tories —nd the vos el—mos x—tion—l v—˜or—tory m—ke xew wexi™o —n —ttr—™tive lo™—tion for highEte™h ten—ntsF roweverD the opening of f—˜ri™—tion f—™ilities in the st—te le—ves its f—rmers —nd r—n™hers in ™onst—nt ™ompetition with the ™orpor—tions for rights to w—ter ™onsumptionF yn —ver—geD the m—nuf—™turing of just IGVEin™h of — sili™on w—fer requires —˜out QDUVU g—llons of w—stew—terD not to mention PU pounds of ™hemi™—ls —nd PW ™u˜i™ feet of h—z—rdous g—ses ‘II“F .

7: gont—min—tion h—s —lso ˜een —n issue in —re—s surrounding f—˜ri™—tion pl—ntsF hrinking w—ter w—s found to ˜e ™ont—min—ted with tri™hloroeth—ne —nd preonD toxins ™ommonly used in the semi™ondu™tor industryD in ƒ—n toseD g—liforni— in IWVI ‘IP“F „hese toxins were l—ter suspe™ted to ˜e the ™—use of ˜irth defe™ts of m—ny ™hildren in the —re—F „he ™ulprits were p—ir™hild ƒemi™ondu™tor —nd sfwF „he ™omp—nies9 underground stor—ge t—nks were found to h—ve le—ked tens of thous—nds of g—llons of the toxi™ solvents into the groundF „here —re — num˜er of semi™ondu™torErel—ted i€e ™le—nup sites in ƒili™on †—lleyD —nd there h—ve ˜een ™on™erns r—ised —˜out the ™umul—tive —ir —nd groundw—ter pollution in ƒili™on †—lleyD —s wellF enother —re— of ™on™ern is the eventu—l f—te of dis™—rded ele™troni™ systems su™h —s ™omputersD p—gersD mo˜ile phonesD —nd televisions th—t ™ont—in semi™ondu™tor devi™esF €erson—l ™omputers in p—rti™ul—r —re espe™i—lly pro˜lem—ti™ ˜e™—use they ˜e™ome o˜solete f—irly r—pidly —nd lose —lmost —ll of their m—rket v—lue within (ve or ten ye—rs —fter their d—te of m—nuf—™tureF „ens of millions of €g9s —re sold in the …nited ƒt—tes e—™h ye—rD —nd they pose —n environment—l risk not only through their sheer ˜ulk in ™ity dumps —nd l—nd(lls ˜ut —lso ˜e™—use their semi™ondu™ting devi™es often ™ont—in signi(™—nt —mounts of he—vy met—lsD in™luding le—d —nd other potenti—lly h—z—rdous su˜st—n™esF 9.1.PWU A community near Sutter Creek. Figure 9. Hawes.7 Why don't we hear more about this on the news? e™ross the …nited ƒt—tesD —pproxim—tely TH7 of the m—nuf—™turing f—™ilities for semi™ondu™tor devi™es —re lo™—ted in six st—tesF „hese st—tes listed in des™ending order —re g—liforni—D „ex—sD w—ss—™husettsD xew ‰orkD sllinoisD —nd €ennsylv—ni—F „he industry —ppe—rs to ˜e ™on™entr—ted in these p—rti™ul—r lo™—tions in p—rt ˜e™—use they —re ne—r the prim—ry usersD tr—nsport—tion routesD —nd experts in the (eldD ˜ut people of —ll —ges in —ll (fty st—tes —re imp—™ted ˜y semi™ondu™tor te™hnologyF gonsumerism of semi™ondu™tor produ™ts is only expe™ted to in™re—se in ™oming ye—rsF eppleD for inst—n™eD expe™ts to h—ve sold PQFT million i€odsD devi™es th—t rely on semi™ondu™tor te™hnologyD ˜y the ye—r PHHTF sf semi™ondu™tors —re so u˜iquitous in our d—yEtoEd—y livesD why is there so little —w—reness —˜out the serious environment—l —nd he—lth risks th—t —re involved in their m—nuf—™turing pro™essc €—rt of the pro˜lem is th—t little is known —˜out the longEterm he—lth or environment—l ™onsequen™es of exposure to the ™hemi™—ls th—t —re used in the pro™essF fe™—use the semi™ondu™tor industry is still rel—tively newD not m—ny studies . & Audet). California that has been designated as an EPA Superfund site as a result of arsenic contamination (photo from Alexander.

1.PWV CHAPTER .1.phptr. ECONOMIC AND ENVIRONMENTAL ISSUES h—ve ˜een ™ondu™ted on this topi™D —nd existing d—t— is often in™on™lusiveF „his ˜eing s—idD some s™ientists predi™t th—t the ™—n™er r—te in the sili™on ™hip industry will rise signi(™—ntly in the future ˜e™—use ™—n™er ™—n t—ke —s long —s PHEPS ye—rs to m—nifest itself in popul—tions of exposed workersF „he i€e does h—ve regul—tions in e'e™t th—t —re —imed tow—rd the purpose of ™ontrolling the levels of ™ont—min—nts rele—sed —nd minimizing hum—n —nd environment—l exposure to themF roweverD ™urrent regul—tions do not m—nd—te th—t emeri™—n ™omp—nies report on o'shore m—nuf—™turingF „hereforeD even —s medi— ™over—ge —nd gener—l —w—reness in™re—seD ™omp—nies ™—n simply outsour™e more —nd more of their f—˜ri™—tion f—™ilities toD for ex—mpleD ƒouthe—st esi—F ƒome ™omp—niesD in f—™tD h—ve ˜egun to do soD —nd there h—ve even —lre—dy ˜een studies ™ondu™ted on the he—lth issues of workers in the ele™troni™s —nd semi™ondu™tor industries of ƒing—pore —nd w—l—ysi— ‘IQ“F „husD ™h—nges in how —nd where semi™ondu™tor (rms m—nuf—™ture ™hips ™urrently outstrip the present —˜ility of the …nited ƒt—tes government —nd medi— institutions to tr—™k —nd monitor their potenti—l thre—ts to hum—ns —nd the environmentF sf this situ—tion is to ™h—nge for the ˜etter in the ne—r futureD it is ™le—r th—t r—di™—l reforms will need to t—ke pl—™e on — num˜er of di'erent levelsF roweverD the whoD wh—tD whenD whereD —nd whyD so to spe—kD of th—t reform rem—ins to ˜e —ddressedF 9.9 Endnotes IF wF u—zmier™z—k —nd tF t—mesF sndustry h—t— 8 €u˜li™—tionsX …FƒF righE„e™h ixE portsD PHHHEPHHRF IT xovF PHHRF emeri™—n ile™troni™s esso™i—tionF IU y™tF PHHS<httpXGGwwwF—e—netForgG€u˜li™—tionsGidjl•ushighte™hexportsIPHRF—sp>F PF tF „urleyD „he issenti—l quide to ƒemi™ondu™torsF …pper ƒ—ddle ‚iverD xew terseyX €renti™e r—ll €rofession—l „e™hni™—l ‚eferen™eD PHHQF QF tF „urleyD „he issenti—l quide to ƒemi™ondu™torsF …pper ƒ—ddle ‚iverD xew terseyX €renti™e r—ll €rofession—l „e™hni™—l ‚eferen™eD PHHQF prom €renti™e r—ll3 RF sfw ‚ese—r™h x—note™hnology romep—geF sfwF IT y™tF PHHS <httpXGGdominoFrese—r™hFi˜mF™omG™ommGrese—r™hFnsfGp—gesGrFn—note™hFhtml>F SF ‚F ghepesiukD ‡here the ghips p—llX invironment—l re—lth in the ƒemi™ondu™tor sndustryF inviE ronment—l re—lth €erspe™tives IHU @IWWWAX RSPERSUF TF ‚i™h—rdsD sndustry gh—llengeX gomputerEghip €l—nts eren9t —s ƒ—fe end gle—n es filledD ƒome ƒ—y ! ‡omen —t ƒ™ottish p—™tory „ell of ƒpills —nd pumesD p—™e rost of wedi™—l slls ! pirms ‡on9t relp ho — ƒtudyF ‡—ll ƒtreet tourn—l S y™tF IWWVD e—stern edFX eIF UF eF re—vensD ghip €l—nts „—ke re—t por „oxi™sF IR t—nF PHHQF ‡ired xewsF IQ y™tF PHHSD <httpXGGwwwFwiredF™omGnewsGte™hnologyGHDIPVPDSUIWIDHHFhtml> VF wF wer™h—ntD w—ine ƒemi™ondu™tor €l—nt pined por r—z—rdous ‡—ste †iol—tionsF fostonX …FƒF invironment—l €rote™tion egen™yD €ress y0™eD PHHIF WF €F hunnD gle—nliness yutsideD ƒome sssues yutsideF P y™tF PHHHF „he pound—tion for emeri™—n gommuni™—tionsF IQ y™tF PHHS <httpXGGwwwFf—™snetForgGtoolsGs™i•te™hGte™hG™ommunityGenvironPFphpQ> 3 http://www.8 Discussion questions • row m—ny ele™troni™s produ™ts do you use on — d—yEtoEd—y ˜—sisc row m—ny of these produ™ts ™ont—in semi™ondu™torsc • ‡ho do you think is ultim—tely responsi˜le for initi—ting reformc „he governmentc „he ™orpor—tionc „he ™onsumerc • ho you think th—t the he—lth —nd environment—l in™idents rel—ted to semi™ondu™tor m—nuf—™turing will rem—in isol—ted in™identsc yr do you think th—t these in™idents will ˜e™ome epidemi™ in the futurec • ho you think th—t n—note™hnology will help the pro˜lem or m—ke the pro˜lem worsec 9.

PWW IHF tF w—zurekD w—king wi™ro™hipsX €oli™yD qlo˜—liz—tionD —nd i™onomi™ ‚estru™turing in the ƒemi™onE du™tor sndustryF g—m˜ridgeD w—ss—™husettsX ws„ €ressD IWWWF IIF gF r—yhurstD „oxi™ „e™hnologyX ile™troni™s —nd the ƒili™on †—lleyF iX the invironment—l w—g—zine w—yEtunF IWWUX RF IPF fF €imentelD „he †—lley9s „oxi™ ristoryF ƒ—n pr—n™is™o ghroni™le QH t—nF PHHRD (n—l edFX fIF IQF †F vinD re—lthD ‡omen9s ‡orkD —nd sndustri—liz—tionX ƒemi™ondu™tor ‡orkers in ƒing—pore —nd w—l—ysi—F xew ‰orkX q—rl—nd €u˜lishingD sn™FD IWWIF .

QHH INDEX Index of Keywords and Terms —re listed ˜y the se™tion with th—t keyword @p—ge num˜ers —re in p—renthesesAF ueywords do not ne™ess—rily —ppe—r in the text of the p—geF „hey —re merely —sso™i—ted with th—t se™tionF Ex. —pplesD Ÿ IFI @IA Terms —re referen™ed ˜y the p—ge they —ppe—r onF Ex. —pplesD I Keywords A —™—™D Ÿ TFP@IWPAD Ÿ TFU@PQPA —™eti™ —™idD Ÿ RFI@IIQA —™etyl—™eton—teD Ÿ TFP@IWPA —™idD Ÿ RFI@IIQAD Ÿ RFU@IRUAD Ÿ TFQFI@PHHA epwD Ÿ UFP@PRUAD Ÿ VFQ@PTIAD Ÿ VFR@PUPAD Ÿ VFS@PUUA elPyQD Ÿ TFRFP@PITA elglQD Ÿ TFSFQ@PPSA evhD Ÿ SFP@ITWA eviD Ÿ SFP@ITWAD Ÿ TFQFP@PHPA —lk—lineD Ÿ RFI@IIQA —lkoxideD Ÿ QFQ@IHIAD Ÿ TFT@PQHA —llowed st—teD Ÿ IFI@QA —lloyD Ÿ IFS@QVAD Ÿ RFW@ITHAD Ÿ SFI@ITQA elweQD Ÿ TFSFQ@PPSA elxD Ÿ TFSFQ@PPSA —lumin—D Ÿ QFQ@IHIAD Ÿ TFRFP@PITA —luminumD Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ PFS@TTAD Ÿ QFP@VWAD Ÿ QFQ@IHIAD Ÿ RFW@ITHAD Ÿ SFR@IVRA —luminum nitrideD Ÿ TFSFQ@PPSA —luminum sili™—teD Ÿ TFRFP@PITA —m˜ipol—rD Ÿ IFQ@ITA —mideD Ÿ TFSFQ@PPSA —mmoni—D Ÿ TFQFI@PHHAD Ÿ TFRFI@PHVAD Ÿ TFSFI@PPPAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSA —morphousD Ÿ QFR@IHRAD Ÿ SFP@ITWAD Ÿ SFR@IVRA —nisotropi™D Ÿ RFI@IIQA —nne—lingD IQH —nnul—rD Ÿ RFI@IIQA —nodeD Ÿ PFS@TTA —ntimonyD Ÿ IFS@QVAD Ÿ QFP@VWA —ntisiteD Ÿ IFR@PHA e€g†hD Ÿ TFRFI@PHVAD Ÿ TFRFP@PITAD Ÿ TFSFP@PPPA e‚D Ÿ PFU@UVA —rgonD Ÿ RFW@ITHAD Ÿ TFP@IWPAD Ÿ TFRFI@PHVA errheniusD Ÿ SFQ@IURA —rseni™D Ÿ PFR@TPAD Ÿ PFT@USAD Ÿ QFI@VSAD Ÿ QFP@VWAD Ÿ SFI@ITQAD Ÿ TFQFI@PHHAD Ÿ TFQFP@PHPA —rsenideD Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ QFI@VSAD Ÿ TFQFI@PHHA —rsineD Ÿ SFP@ITWAD Ÿ TFQFI@PHHAD Ÿ TFQFP@PHPAD Ÿ TFRFI@PHVA esD Ÿ QFP@VWA —tomD Ÿ IFR@PHA —tom densityD Ÿ IFR@PHAD Ÿ IFS@QVA —tom positionsD Ÿ IFR@PHA —tomi™ l—yer depositionD Ÿ SFP@ITWA —tomi™ l—yer epit—xyD Ÿ SFP@ITWA eugerD Ÿ SFI@ITQA B ˜—ndD Ÿ IFI@QA ˜—nd di—gr—mD IR ˜—nd g—pD Ÿ PFI@SIAD Ÿ PFR@TPAD Ÿ PFS@TTAD Ÿ QFI@VSA ˜—ng g—pD Ÿ IFI@QAD Ÿ IFP@WA ˜—seD Ÿ PFI@SIA ˜—tteryD Ÿ PFP@SQAD Ÿ PFQ@SVA ˜—uxiteD Ÿ QFI@VSAD Ÿ QFP@VWAD Ÿ QFQ@IHIA ˜i—sD Ÿ PFI@SIA ˜inderD Ÿ QFQ@IHIA fingel re—™tionD Ÿ VFQ@PTIA ˜ipol—rD Ÿ PFI@SIA ˜isE—ryl—zideD Ÿ RFU@IRUA ˜is—zideD Ÿ RFU@IRUA ˜odyE™enteredD Ÿ IFR@PHA ˜oehmiteD Ÿ QFQ@IHIA ˜oiling pointD Ÿ TFRFI@PHVA ˜ond energyD Ÿ SFP@ITWA ˜ori™ —™idD Ÿ SFR@IVRA ˜oronD Ÿ QFI@VSAD Ÿ QFP@VWAD Ÿ RFV@ISQA ˜oron nitrideD Ÿ SFI@ITQA ˜orophosphorosili™—teD Ÿ RFQ@IQHA ˜ottomEupD Ÿ VFI@PSWA ˜ound—ry l—yerD Ÿ SFQ@IURA f€ƒqD Ÿ RFQ@IQHA fr—v—is l—tti™eD Ÿ IFR@PHA fridgm—nD Ÿ QFI@VSA ˜u˜˜lerD Ÿ SFQ@IURAD Ÿ TFI@IWIA fu™ky˜—llD Ÿ VFQ@PTIA ˜ulkD Ÿ IFR@PHA ˜yprodu™tD Ÿ QFP@VWA .

INDEX QHI ™o—tingD Ÿ PFU@UVAD Ÿ QFR@IHRA ™o˜—ltD Ÿ QFP@VWA ™oheren™eD Ÿ PFT@USA ™okeD Ÿ QFP@VWA ™olle™torD Ÿ PFI@SIA ™olorD Ÿ PFS@TTA ™omplexeD Ÿ TFP@IWPA ™ompoundD Ÿ IFR@PHAD Ÿ TFP@IWPA ™ondu™tionD Ÿ IFI@QA ™ondu™tion ˜—ndD Ÿ IFP@WAD Ÿ RFR@IQRA ™onjug—tedD Ÿ PFS@TTA ™oordin—tion num˜erD Ÿ IFR@PHA ™opperD Ÿ IFR@PHAD Ÿ QFP@VWAD Ÿ TFU@PQPA ™orundumD Ÿ QFQ@IHIAD Ÿ TFRFP@PITA goulom˜D Ÿ PFQ@SVA g€…D Ÿ RFQ@IQHA gr—™ker ™ellD Ÿ SFI@ITQA ™riti™—l dimensionD Ÿ RFT@IRQA ™roppingD Ÿ RFI@IIQA ™rossElinkingD Ÿ RFU@IRUA ™ryst—lD Ÿ IFR@PHAD Ÿ QFI@VSAD Ÿ QFR@IHRAD Ÿ SFI@ITQAD Ÿ SFP@ITWA ™ryst—l —xesD Ÿ IFR@PHA ™ryst—l dire™tionD Ÿ IFR@PHA ™ryst—l growthD Ÿ QFI@VSA ™ryst—l pl—neD Ÿ IFR@PHA ™ryst—l sh—pingD Ÿ RFI@IIQA ™ryst—l stressD Ÿ QFI@VSA ™ryst—llogr—phyD Ÿ IFR@PHA guD Ÿ TFU@PQPA ™u˜—neD Ÿ TFP@IWPA ™u˜i™D Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ QFP@VWA gurieD Ÿ QFR@IHRA gurie pointD Ÿ QFR@IHRA ™urrentD Ÿ PFI@SIAD Ÿ PFQ@SVA g†hD Ÿ RFQ@IQHAD Ÿ RFR@IQRAD Ÿ SFP@ITWAD Ÿ SFQ@IURAD Ÿ TFI@IWIAD Ÿ TFP@IWPAD Ÿ TFQFP@PHPAD Ÿ TFRFI@PHVAD Ÿ TFRFP@PITAD Ÿ TFSFI@PPPAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSAD Ÿ TFT@PQHAD Ÿ TFU@PQPA gy™lo—dditionD Ÿ VFQ@PTIA gzo™hr—lskiD Ÿ QFI@VSAD Ÿ QFR@IHRAD Ÿ RFI@IIQA C gTHD Ÿ VFQ@PTIAD Ÿ VFS@PUUA gUHD Ÿ VFQ@PTIA ™—dmiumD Ÿ VFP@PSWA g—pPD Ÿ TFT@PQHA ™—l™iumD Ÿ PFS@TTAD Ÿ QFP@VWAD Ÿ TFT@PQHA ™—l™ium )uorideD Ÿ TFT@PQHA ™—r˜onD Ÿ QFP@VWA ™—r˜on monoxideD Ÿ QFP@VWA g—ro9s —™idD Ÿ RFI@IIQA ™—rrierD Ÿ PFI@SIAD Ÿ QFI@VSA ™—rrier densityD Ÿ QFI@VSA ™—rrier g—sD Ÿ TFU@PQPA ™—stD Ÿ QFQ@IHIA ™—thodeD Ÿ PFS@TTA ™—tionD Ÿ SFR@IVRA gfhD Ÿ SFR@IVRA gfiD Ÿ SFI@ITQA gdƒeD Ÿ VFP@PSWA ™ellsD Ÿ PFU@UVA ™er—mi™D Ÿ QFQ@IHIAD Ÿ QFR@IHRA ™er—mi™ pro™essingD Ÿ QFQ@IHIA ™h—l™ogenideD Ÿ TFP@IWPA ™h—l™opyriteD Ÿ IFR@PHAD Ÿ IFS@QVA ™h—m˜erD Ÿ RFW@ITHA ™h—nnelD Ÿ PFQ@SVA ™h—r™o—lD Ÿ QFP@VWA ™h—rgeD Ÿ IFP@WAD Ÿ PFP@SQAD Ÿ PFQ@SVA ™h—rge ™oe0™ientD Ÿ QFR@IHRA ™hemi™—lD Ÿ WFI@PVUA ™hemi™—l ˜—th depositionD Ÿ SFR@IVRA ™hemi™—l ˜e—m epit—xyD Ÿ SFI@ITQA ™hemi™—l v—por depositionD Ÿ RFR@IQRAD Ÿ SFP@ITWAD Ÿ SFQ@IURAD Ÿ TFI@IWIAD Ÿ TFP@IWPAD Ÿ TFQFP@PHPAD Ÿ TFRFI@PHVAD Ÿ TFRFP@PITAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSAD Ÿ TFT@PQHAD Ÿ TFU@PQPA ™hemi™—lly ™onverted gr—pheneD Ÿ VFR@PUPA ™hemie du™eD Ÿ VFI@PSWA ™hemisor˜D Ÿ SFP@ITWA ™hemistryD Ÿ @IA ™hir—lD Ÿ TFQFI@PHHA ™hlor—teD Ÿ RFI@IIQA ™hromiumD Ÿ QFP@VWA ™inn—˜—rD Ÿ IFR@PHA ™ir™uitD Ÿ RFV@ISQA ™itri™ —™idD Ÿ RFI@IIQA gl—usiusEgl—peyronD Ÿ TFP@IWPA ™le—ningD Ÿ RFI@IIQA ™lose p—™kedD Ÿ IFR@PHA gwyƒD Ÿ RFQ@IQHA gxE€€†D Ÿ PFS@TTA gyD Ÿ QFP@VWA D d—ngling ˜ondD Ÿ IFR@PHAD Ÿ IFS@QVA hgD Ÿ PFI@SIA de fois˜—udr—nD Ÿ QFI@VSA de™ompositionD Ÿ TFI@IWIAD Ÿ TFP@IWPAD Ÿ TFQFP@PHPA defe™tD Ÿ IFR@PHAD Ÿ SFI@ITQA degred—tionD Ÿ PFS@TTA delo™—liz—tionD Ÿ PFS@TTA depositionD Ÿ SFQ@IURAD Ÿ SFR@IVRAD Ÿ TFQFP@PHPAD Ÿ TFU@PQPA .

QHP depth resolutionD Ÿ UFI@PQWA desorptionD Ÿ SFQ@IURAD Ÿ TFQFP@PHPA dete™tion limitD Ÿ UFI@PQWA devi™eD Ÿ RFQ@IQHA di—mondD Ÿ IFI@QAD Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ RFI@IIQA di˜or—neD Ÿ TFRFI@PHVA diele™tri™D Ÿ RFQ@IQHA diele™tri™ ™onst—ntD Ÿ TFRFI@PHVA di'erenti—l therm—l —n—lysisD Ÿ TFP@IWPA di'usionD Ÿ IFQ@ITAD Ÿ RFR@IQRAD Ÿ SFI@ITQAD Ÿ SFQ@IURA di'usion ˜—rrierD Ÿ TFU@PQPA di'usion ™oe0™ientD Ÿ IFQ@ITA diketon—teD Ÿ TFT@PQHA dinitrogenD Ÿ TFSFP@PPPA diodeD Ÿ PFR@TPA diphosphineD Ÿ TFQFI@PHHA dire™t ˜—nd g—pD Ÿ PFR@TPA dislo™—tionD Ÿ IFR@PHA dispersionD Ÿ QFQ@IHIA dop—ntD Ÿ RFR@IQRAD Ÿ SFI@ITQAD Ÿ SFQ@IURAD Ÿ TFRFI@PHVA doped semi™ondu™torD Ÿ IFP@WA dopingD Ÿ IFP@WAD Ÿ RFP@IPWA dr—inD Ÿ RFV@ISQA driveEinD Ÿ RFV@ISQA dryingD Ÿ QFQ@IHIA h„eD Ÿ TFP@IWPA environment—l he—lthD Ÿ WFI@PVUA epit—xi—lD Ÿ TFRFP@PITA epit—xyD Ÿ IFR@PHAD Ÿ SFI@ITQA et™hD Ÿ RFI@IIQAD Ÿ RFS@IQVAD Ÿ RFT@IRQAD Ÿ RFU@IRUAD Ÿ RFV@ISQA et™hingD Ÿ RFI@IIQA iuler9s theoremD Ÿ VFQ@PTIA ex™it—tionD Ÿ IFI@QA ex™itonD Ÿ PFS@TTA exposureD Ÿ RFS@IQVA eyeD Ÿ PFR@TPA INDEX F f—™eE™enteredD Ÿ IFR@PHA f—™etD Ÿ PFT@USA permi levelD Ÿ PFP@SQA pi„D Ÿ RFQ@IQHA (˜erD Ÿ QFR@IHRA pi™k9s pirst v—wD Ÿ IFQ@ITA (eld e'e™t tr—nsistorD Ÿ PFQ@SVAD Ÿ RFQ@IQHA (lmD Ÿ PFS@TTA (ringD Ÿ QFQ@IHIA )uidized ˜edD Ÿ QFP@VWA )uorideD Ÿ TFT@PQHA )uorineD Ÿ TFP@IWPA )uorosili™i™ —™idD Ÿ SFR@IVRA )uxD Ÿ TFI@IWIA frequen™yD Ÿ PFR@TPA pullereneD Ÿ VFQ@PTIA furn—™eD Ÿ QFP@VWA q—D Ÿ QFP@VWA q—esD Ÿ IFS@QVAD Ÿ PFR@TPAD Ÿ PFT@USAD Ÿ QFI@VSAD Ÿ RFI@IIQAD Ÿ SFI@ITQAD Ÿ SFP@ITWAD Ÿ TFQFP@PHPAD Ÿ TFSFP@PPPA q—es€D Ÿ PFR@TPA g—lli—D Ÿ QFI@VSA g—lliumD Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ PFR@TPAD Ÿ PFT@USAD Ÿ QFI@VSAD Ÿ QFP@VWAD Ÿ SFI@ITQAD Ÿ SFP@ITWAD Ÿ TFP@IWPAD Ÿ TFQFP@PHPA g—llium —rsenideD Ÿ PFR@TPAD Ÿ PFT@USAD Ÿ QFP@VWAD Ÿ RFI@IIQAD Ÿ SFI@ITQAD Ÿ SFP@ITWAD Ÿ TFQFP@PHPA g—rnetD Ÿ QFQ@IHIA g—sD Ÿ TFP@IWPA g—s ™onst—ntD Ÿ TFP@IWPA g—teD Ÿ PFP@SQAD Ÿ PFQ@SVAD Ÿ RFQ@IQHAD Ÿ RFV@ISQA qeD Ÿ IFS@QVA gel—tionD Ÿ QFQ@IHIA germ—iniumD Ÿ IFR@PHA germ—niumD Ÿ IFS@QVAD Ÿ QFR@IHRA gi˜˜siteD Ÿ QFQ@IHIA qyD Ÿ VFR@PUPA goldD Ÿ PFS@TTAD Ÿ QFP@VWA E ihˆD Ÿ UFI@PQWA e0™ien™yD Ÿ PFS@TTA e'usion ™ellD Ÿ SFI@ITQA ek—E—luminumD Ÿ QFI@VSA ele™tri™ (eldD Ÿ PFP@SQA ele™tri™ momentD Ÿ QFR@IHRA ele™trodeD Ÿ QFP@VWA ele™troless depositionD Ÿ SFR@IVRA ele™trolyteD Ÿ QFQ@IHIA ele™tronD Ÿ IFI@QAD Ÿ IFP@WAD Ÿ IFQ@ITAD Ÿ PFI@SIAD Ÿ PFS@TTAD Ÿ PFU@UVAD Ÿ QFI@VSAD Ÿ SFI@ITQA ele™tron —0nityD Ÿ PFS@TTA ele™tron mo˜ilityD Ÿ QFI@VSA ele™tron tr—nsportD Ÿ IFQ@ITA ele™troni™ m—teri—lsD Ÿ @IA elementD Ÿ IFR@PHA emissionD Ÿ PFS@TTAD Ÿ PFT@USA en™—psul—tionD Ÿ TFSFP@PPPA endohedr—l fullereneD Ÿ VFQ@PTIA energyD Ÿ IFI@QAD Ÿ PFR@TPA enth—lpyD Ÿ TFP@IWPA entropyD Ÿ TFP@IWPA G .

INDEX gr—pheneD Ÿ VFR@PUPA gr—phiteD Ÿ VFQ@PTIA gr—phite oxideD Ÿ VFR@PUPA green ˜odyD Ÿ QFQ@IHIA grindingD Ÿ RFI@IIQA qroup IPEITD Ÿ IFR@PHA qroup IQEISD Ÿ IFR@PHA qroup IRD Ÿ IFI@QA qroup ssE†sD Ÿ IFR@PHA qroup sssE†D Ÿ IFR@PHA qroup s†D Ÿ IFI@QA growthD Ÿ SFP@ITWA growth r—teD Ÿ SFQ@IURAD Ÿ TFQFP@PHPA interE—tomi™D Ÿ IFR@PHA inter™onne™tD Ÿ RFW@ITHA intern—l e0™ien™yD Ÿ PFS@TTA interstiti—lD Ÿ IFR@PHA intr—Epl—n—rD Ÿ IFR@PHA ion impl—nt—tionD IPW ioniz—tion potenti—lD Ÿ PFS@TTA ionsD Ÿ RFW@ITHA ironD Ÿ QFP@VWA isol—tionD Ÿ RFQ@IQHA isopreneD Ÿ RFU@IRUA isotherm—lD Ÿ TFP@IWPA s„yD Ÿ PFS@TTA QHQ H r—llEreroultD Ÿ QFQ@IHIA reD Ÿ UFI@PQWA heliumD Ÿ UFI@PQWA hemoglo˜inD Ÿ TFQFI@PHHA heterojun™tionD Ÿ PFS@TTA hex—gonD Ÿ IFR@PHA hex—gon—lD Ÿ IFR@PHA rpD Ÿ RFI@IIQA hf—™D Ÿ TFP@IWPA high pressureD Ÿ RFR@IQRA rs€D Ÿ QFR@IHRA rxyQD Ÿ RFI@IIQA holeD Ÿ IFI@QAD Ÿ IFP@WAD Ÿ PFP@SQAD Ÿ PFS@TTAD Ÿ SFI@ITQA holesD Ÿ IFQ@ITA hoppingD Ÿ VFS@PUUA hot isost—ti™ pressD Ÿ QFR@IHRA hydro)uori™ —™idD Ÿ RFI@IIQAD Ÿ SFR@IVRA hydrogenD Ÿ RFR@IQRAD Ÿ SFQ@IURAD Ÿ TFP@IWPAD Ÿ TFQFI@PHHAD Ÿ TFRFI@PHVA hydrogen peroxideD Ÿ RFI@IIQA hydrolysisD Ÿ SFR@IVRAD Ÿ TFRFP@PITA hydropho˜i™D Ÿ VFQ@PTIA hydrotherm—l synthesisD Ÿ QFR@IHRA hydroxideD Ÿ QFQ@IHIA sgD Ÿ RFV@ISQA idire™t ˜—nd g—pD Ÿ PFR@TPA im—geD Ÿ RFU@IRUA indi™esD Ÿ IFR@PHA indiumD Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ PFS@TTA indium tin oxideD Ÿ PFS@TTA inert g—sD Ÿ QFP@VWA inhi˜itorD Ÿ RFU@IRUA sn€D Ÿ IFS@QVA insul—tionD Ÿ TFRFI@PHVA insul—torD Ÿ PFQ@SVA integr—ted ™ir™uitD Ÿ RFT@IRQAD Ÿ RFV@ISQA J K L jun™tionD Ÿ PFQ@SVAD Ÿ PFU@UVA kineti™sD Ÿ TFP@IWPA unudsenD Ÿ SFI@ITQA veg†hD Ÿ SFQ@IURA l—ppingD Ÿ RFI@IIQA l—serD Ÿ PFT@USAD Ÿ RFT@IRQAD Ÿ SFP@ITWAD Ÿ SFQ@IURA l—tti™eD Ÿ IFR@PHAD Ÿ SFI@ITQA l—tti™e ™onst—ntD Ÿ IFS@QVAD Ÿ QFI@VSA l—tti™e p—r—meterD Ÿ IFR@PHAD Ÿ IFS@QVA le—dD Ÿ QFP@VWA le—d met—nio˜—teD Ÿ QFR@IHRA le—d zir™on—te tit—n—teD Ÿ QFR@IHRA vihD Ÿ PFR@TPAD Ÿ PFS@TTAD Ÿ QFI@VSA lensD Ÿ RFS@IQVA vewis ˜—seD Ÿ TFU@PQPA lifetimeD Ÿ IFQ@ITA lig—ndD Ÿ TFU@PQPA lightD Ÿ PFT@USAD Ÿ PFU@UVAD Ÿ RFS@IQVA light —mpli(™—tionD Ÿ PFT@USA light emitting diodeD Ÿ PFR@TPA light emitting diodesD Ÿ PFS@TTA liquidD Ÿ TFI@IWIA liquid ph—se depositionD Ÿ SFR@IVRA lithium nio˜—teD Ÿ QFR@IHRA lithogr—phyD Ÿ RFT@IRQA low pressureD Ÿ SFQ@IURA v€g†hD Ÿ TFRFI@PHVAD Ÿ TFRFP@PITAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSA v€hD Ÿ SFR@IVRA m—ng—neseD Ÿ QFP@VWA m—nuf—™turingD Ÿ WFI@PVUA m—skD Ÿ RFR@IQRAD Ÿ RFS@IQVAD Ÿ RFT@IRQA m—ss tr—nsportD Ÿ SFQ@IURA wfiD Ÿ SFI@ITQA I M m—gnesiumD Ÿ QFP@VWA .

QHR me—n free p—thD Ÿ IFI@QA me™h—ni™—l qu—lity f—™torD Ÿ QFR@IHRA me™h—nismD Ÿ TFQFP@PHPA wendeleevD Ÿ QFI@VSA mer™uryD Ÿ QFP@VWA mer™ury sul(deD Ÿ IFS@QVA wiƒpi„D Ÿ TFSFP@PPPA met—lD Ÿ PFQ@SVAD Ÿ RFV@ISQAD Ÿ TFU@PQPA met—l met—lliz—tionD Ÿ RFW@ITHA met—l org—ni™ ™hemi™—l v—por depositionD Ÿ TFP@IWPAD Ÿ TFT@PQHA met—l oxideD Ÿ TFRFP@PITA met—l oxide semi™ondu™torD Ÿ PFP@SQA met—liz—tionD Ÿ RFQ@IQHA met—lliz—tionD Ÿ TFU@PQPA mi™ro™ir™uitD Ÿ RFQ@IQHA willerD Ÿ IFR@PHA miner—lD Ÿ QFQ@IHIA minority ™—rrierD Ÿ IFQ@ITA mirrorD Ÿ PFS@TTAD Ÿ PFT@USA mixedEmet—l oxideD Ÿ QFQ@IHIA mo˜ilityD Ÿ IFP@WAD Ÿ QFI@VSA wyg†hD Ÿ SFP@ITWAD Ÿ SFQ@IURAD Ÿ TFP@IWPAD Ÿ TFQFP@PHPAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSAD Ÿ TFT@PQHA mole™ul—r ˜e—m epit—xyD Ÿ SFI@ITQA mole™ul—r weightD Ÿ QFR@IHRA mole™uleD Ÿ TFI@IWIA moly˜denumD Ÿ QFP@VWA momentumD Ÿ PFR@TPA mono™lini™D Ÿ IFR@PHA monol—yerD Ÿ SFI@ITQA monosil—neD Ÿ QFP@VWA morphologyD Ÿ QFR@IHRAD Ÿ UFP@PRUA wyƒD Ÿ PFP@SQAD Ÿ PFQ@SVAD Ÿ RFV@ISQA wyƒpi„D Ÿ PFQ@SVAD Ÿ RFQ@IQHAD Ÿ RFR@IQRA mulliteD Ÿ TFRFP@PITA w‡x„D Ÿ VFQ@PTIA INDEX neg—tive resistD Ÿ RFU@IRUA xrQD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSA ni™kelD Ÿ QFP@VWA nio˜iumD Ÿ UFI@PQWA nitreneD Ÿ RFU@IRUA nitri™ —™idD Ÿ RFI@IIQA nitrideD Ÿ IFS@QVAD Ÿ RFS@IQVAD Ÿ RFV@ISQAD Ÿ TFSFI@PPPA nitrogenD Ÿ RFI@IIQAD Ÿ RFU@IRUAD Ÿ TFP@IWPAD Ÿ TFRFI@PHVAD Ÿ TFSFI@PPPA nitrous oxideD Ÿ TFRFI@PHVA nonE™entrosymmetri™D Ÿ QFR@IHRA novol—k resinsD Ÿ RFU@IRUA npnD Ÿ PFI@SIAD Ÿ RFP@IPWA O o™t—hedr—lD Ÿ IFR@PHA yhgfD Ÿ VFR@PUPA ohmD Ÿ IFP@WA ole(nD Ÿ TFU@PQPA org—nosili™onD Ÿ TFSFP@PPPA orient—tionD Ÿ IFR@PHA orthorhom˜i™D Ÿ IFR@PHA oxid—tionD Ÿ PFS@TTAD Ÿ RFR@IQRAD Ÿ RFV@ISQAD Ÿ TFRFP@PITAD Ÿ VFQ@PTIA oxideD Ÿ PFP@SQAD Ÿ PFQ@SVAD Ÿ RFS@IQVAD Ÿ RFV@ISQAD Ÿ SFR@IVRA oxygenD Ÿ PFS@TTAD Ÿ QFP@VWAD Ÿ RFR@IQRAD Ÿ RFV@ISQAD Ÿ TFRFI@PHVAD Ÿ TFRFP@PITA pEn jun™tionD Ÿ IFQ@ITA pEtypeD Ÿ PFI@SIAD Ÿ PFP@SQAD Ÿ PFQ@SVAD Ÿ PFU@UVAD Ÿ RFI@IIQAD Ÿ SFI@ITQAD Ÿ UFI@PQWA p—™k—gingD Ÿ RFQ@IQHA €eg†hD Ÿ SFQ@IURA p—ssiv—tionD Ÿ RFQ@IQHAD Ÿ TFSFP@PPPA p—tternD Ÿ RFT@IRQAD Ÿ RFU@IRUAD Ÿ RFV@ISQAD Ÿ RFW@ITHA €—uliD Ÿ IFI@QA €ig†hD Ÿ SFQ@IURAD Ÿ TFRFI@PHVAD Ÿ TFRFP@PITAD Ÿ TFSFI@PPPAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSA perovskiteD Ÿ QFQ@IHIA ph—seD Ÿ PFT@USA ph—se di—gr—mD Ÿ TFRFP@PITA phosphideD Ÿ IFR@PHAD Ÿ IFS@QVAD Ÿ TFQFI@PHHA phosphineD Ÿ TFQFI@PHHAD Ÿ TFRFI@PHVAD Ÿ TFU@PQPA phosphorousD Ÿ QFP@VWA phosphorous —™idD Ÿ TFQFI@PHHA phosphorusD Ÿ QFI@VSAD Ÿ TFQFI@PHHA photolithogr—phyD Ÿ RFS@IQVAD Ÿ RFT@IRQAD Ÿ RFU@IRUA photolumines™e™eD Ÿ PFS@TTA P N nEtypeD Ÿ PFI@SIAD Ÿ PFP@SQAD Ÿ PFQ@SVAD Ÿ PFU@UVAD Ÿ RFI@IIQAD Ÿ SFI@ITQA xPD Ÿ TFSFI@PPPA xPyD Ÿ TFSFP@PPPA n—no™—rD Ÿ VFS@PUUA n—no™ryst—lD Ÿ VFP@PSWA n—nom—teri—lsD Ÿ VFQ@PTIA n—nop—rti™leD Ÿ VFI@PSWAD Ÿ VFP@PSWA n—nosheetD Ÿ VFR@PUPA n—notu˜eD Ÿ VFQ@PTIA n—tive oxideD Ÿ QFI@VSA x˜D Ÿ UFI@PQWA neg—tiveD Ÿ RFS@IQVA .


QHT siverD Ÿ QFP@VWA slidingD Ÿ VFS@PUUA slim rodD Ÿ QFP@VWA slurryD Ÿ QFQ@IHIA ƒm—lleyD Ÿ VFQ@PTIA ƒnD Ÿ IFS@QVA sodiumD Ÿ QFQ@IHIA sodium hydroxideD Ÿ RFI@IIQA solEgelD Ÿ QFQ@IHIAD Ÿ QFR@IHRA sol—rD Ÿ PFU@UVA solidD Ÿ TFI@IWIA solid solutionD Ÿ IFS@QVA solid st—teD Ÿ IFR@PHA solventD Ÿ QFQ@IHIAD Ÿ RFU@IRUA sour™eD Ÿ RFV@ISQA spe™trumD Ÿ UFI@PQWA spinE™o—tD Ÿ RFU@IRUA sputteringD Ÿ RFW@ITHA ste—dy st—teD Ÿ IFQ@ITA ste—mD Ÿ RFR@IQRA step ™over—geD Ÿ TFRFI@PHVAD Ÿ TFU@PQPA stepperD Ÿ RFS@IQVA stimul—ted emissionD Ÿ PFT@USA ƒ„wD Ÿ VFS@PUUA stoi™hiometri™D Ÿ IFS@QVA stoi™hiometri™ r—tioD Ÿ UFI@PQWA stru™tureD Ÿ IFR@PHAD Ÿ UFP@PRUA su˜lim—tionD Ÿ TFP@IWPA su˜limeD Ÿ QFP@VWAD Ÿ TFP@IWPA su˜stitutionD Ÿ IFR@PHA su˜str—teD Ÿ SFI@ITQAD Ÿ SFQ@IURA sul(deD Ÿ IFR@PHAD Ÿ IFS@QVA sulfurD Ÿ IFS@QVAD Ÿ VFP@PSWA sunD Ÿ PFU@UVA super—™idD Ÿ TFQFI@PHHA super™ondu™torD Ÿ SFP@ITWA supers—tur—tionD Ÿ SFR@IVRA surf—™eD Ÿ IFR@PHAD Ÿ PFP@SQAD Ÿ PFT@USAD Ÿ RFI@IIQAD Ÿ SFI@ITQAD Ÿ SFQ@IURAD Ÿ SFR@IVRAD Ÿ TFU@PQPAD Ÿ UFP@PRUAD Ÿ VFS@PUUA surf—™e —™ousti™ w—veD Ÿ QFR@IHRA ƒ‡x„D Ÿ VFQ@PTIA synthesisD Ÿ QFP@VWAD Ÿ VFI@PSWA INDEX „qeD Ÿ TFP@IWPA therm—lD Ÿ RFR@IQRA thermogr—vimetri™ —n—lysisD Ÿ TFP@IWPA thin (lmD Ÿ RFQ@IQHAD Ÿ SFI@ITQAD Ÿ SFP@ITWAD Ÿ SFQ@IURAD Ÿ SFR@IVRAD Ÿ TFRFI@PHVAD Ÿ TFSFI@PPPAD Ÿ TFU@PQPAD Ÿ UFI@PQWA thresholdD Ÿ PFP@SQA tinD Ÿ IFR@PHA tit—niumD Ÿ QFP@VWA tolueneD Ÿ RFU@IRUA topEdownD Ÿ VFI@PSWA top—zD Ÿ QFQ@IHIA toxi™D Ÿ TFQFI@PHHA toxi™ityD Ÿ TFI@IWIA tr—ns—min—tionD Ÿ TFSFI@PPPAD Ÿ TFSFP@PPPAD Ÿ TFSFQ@PPSA tr—nsdu™erD Ÿ QFR@IHRA tr—nsistorD Ÿ PFI@SIAD Ÿ PFQ@SVA tr—nsportD Ÿ TFI@IWIA tri™lini™D Ÿ IFR@PHA trimethylg—lliumD Ÿ SFP@ITWA U …rpD Ÿ QFR@IHRA …vƒsD Ÿ RFV@ISQA ultr— high frequen™yD Ÿ QFR@IHRA ultr—high v—™uumD Ÿ SFI@ITQA um˜rell—D Ÿ TFQFI@PHHA unit ™ellD Ÿ IFR@PHA …€ƒD Ÿ SFP@ITWA …†D Ÿ RFT@IRQA v—™—n™iesD Ÿ IFR@PHA v—™uumD Ÿ RFW@ITHAD Ÿ TFP@IWPA v—l—n™e ˜—ndD Ÿ IFP@WA v—len™eD Ÿ IFI@QA v—len™e ˜—ndD Ÿ RFR@IQRA v—n der ‡——lD Ÿ SFP@ITWA v—n—diumD Ÿ QFP@VWA v—por pressureD Ÿ QFP@VWAD Ÿ SFI@ITQAD Ÿ SFQ@IURAD Ÿ TFI@IWIAD Ÿ TFP@IWPA †erg—rd9s l—wD Ÿ IFR@PHA †erti™—l ƒ™—nning snterferometryD Ÿ UFP@PRUA †qpD Ÿ VFQ@PTIA vis™ousEsuspensionEspinningD Ÿ QFR@IHRA †vƒsD Ÿ RFQ@IQHAD Ÿ RFV@ISQAD Ÿ TFU@PQPA voltD Ÿ PFQ@SVA volt—geD Ÿ PFI@SIAD Ÿ PFP@SQAD Ÿ PFQ@SVA †ƒsD Ÿ UFP@PRUA †ƒƒ€D Ÿ QFR@IHRA Ÿ RFS@IQVAD Ÿ RFV@ISQAD Ÿ RFW@ITHA V T t—ndem —™™eler—torD Ÿ UFI@PQWA t—rgetD Ÿ RFW@ITHA „iwD Ÿ VFQ@PTIAD Ÿ VFR@PUPAD Ÿ VFS@PUUA „iyƒD Ÿ TFRFI@PHVA tern—ryD Ÿ IFS@QVAD Ÿ QFQ@IHIA tetr—gon—lD Ÿ IFR@PHAD Ÿ IFS@QVA tetr—hedr—lD Ÿ IFR@PHA tf—™D Ÿ TFP@IWPA W w—ferD Ÿ IFS@QVAD Ÿ RFI@IIQAD Ÿ RFR@IQRAD .


QHV ATTRIBUTIONS Attributions golle™tionX Chemistry of Electronic Materials idited ˜yX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentG™olIHUIWGIFTG vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4€ref—™e to the ghemistry of ile™troni™ w—teri—ls4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSSPVGIFIG €—geX I gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4sntrodu™tion to ƒemi™ondu™tors4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQTRUGIFQG €—gesX QEV gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG f—sed onX sntrodu™tion to ƒemi™ondu™tors fyX fill ‡ilson …‚vX httpXGG™nxForgG™ontentGmIHHIGPFIQG woduleX 4hoped ƒemi™ondu™tors4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQUHQGIFPG €—gesX WEIT gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG f—sed onX hoped ƒemi™ondu™tors fyX fill ‡ilson …‚vX httpXGG™nxForgG™ontentGmIHHPGPFISG woduleX 4hi'usion4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQUQHGIFPG €—gesX ITEPH gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG f—sed onX hi'usion fyX fill ‡ilson …‚vX httpXGG™nxForgG™ontentGmIHIHGPFIRG woduleX 4gryst—l ƒtru™ture4 fyX endrew ‚F f—rronD g—riss— ƒmith …‚vX httpXGG™nxForgG™ontentGmITWPUGIFIHG €—gesX PHEQU gopyrightX endrew ‚F f—rronD g—riss— ƒmith vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGPFHG .

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QIH woduleX 4v—ser4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQVHPGIFIG €—gesX USEUU gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG f—sed onX veƒi‚ fyX fill ‡ilson …‚vX httpXGG™nxForgG™ontentGmIHIPGPFITG woduleX 4ƒol—r gells4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQVHQGIFRG €—gesX UVEVQ gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG f—sed onX ƒol—r gells fyX fill ‡ilson …‚vX httpXGG™nxForgG™ontentGmIHIQGPFIQG woduleX 4€roperties of q—llium ersenide4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPWUHGIFUG €—gesX VSEVW gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ƒynthesis —nd €uri(™—tion of fulk ƒemi™ondu™tors4 fyX g—riss— ƒmithD endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPQWQTGIFTG €—gesX VWEIHI gopyrightX g—riss— ƒmithD endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGPFHG woduleX 4ger—mi™ €ro™essing of elumin—4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPQUTGIFSG €—gesX IHIEIHR gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4€iezoele™tri™ w—teri—ls ƒynthesis4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSRRIGIFPG €—gesX IHREIII gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4porm—tion of ƒili™on —nd q—llium ersenide ‡—fers4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmITTPUGIFQG €—gesX IIQEIPW gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGPFHG ATTRIBUTIONS .

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QIP woduleX 4epplying wet—lliz—tion ˜y ƒputtering4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQVHHGIFQG €—gesX ITHEITP gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG f—sed onX sntrodu™tion to wyƒpi„s fyX fill ‡ilson …‚vX httpXGG™nxForgG™ontentGmIHPHGPFIPG woduleX 4wole™ul—r fe—m ipit—xy4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSUIPGIFPG €—gesX ITQEITV gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4etomi™ v—yer heposition4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSUQUGIFPG €—gesX ITWEIUQ gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ghemi™—l †—por heposition4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSRWSGIFPG €—gesX IUREIVR gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4viquid €h—se heposition4 fyX iliz—˜eth ‡hitsittD endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPWUURGIFIG €—gesX IVREIVW gopyrightX iliz—˜eth ‡hitsittD endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ƒele™ting — wole™ul—r €re™ursor for ghemi™—l †—por heposition4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPUVRTGIFIG €—gesX IWIEIWP gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG ATTRIBUTIONS woduleX 4hetermin—tion of ƒu˜lim—tion inth—lpy —nd †—por €ressure for snorg—ni™ —nd wet—lEyrg—ni™ gompounds ˜y „hermogr—vimetri™ en—lysis4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQTRWGIFPG €—gesX IWPEPHH gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG .

ATTRIBUTIONS woduleX 4€hosphine —nd ersine4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmQQHRQGIFQG €—gesX PHHEPHP gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4we™h—nism of the wet—l yrg—ni™ ghemi™—l †—por heposition of q—llium ersenide4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSTIRGIFTG €—gesX PHPEPHV gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ghemi™—l †—por heposition of ƒili™— „hin pilms4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPRVWUGIFRG €—gesX PHVEPIT gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ghemi™—l †—por heposition of elumin—4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPRWIVGIFSG €—gesX PITEPPI gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4sntrodu™tion to xitride ghemi™—l †—por heposition4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPTIIUGIFIG €—geX PPP gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ghemi™—l †—por heposition of ƒili™on xitride —nd yxynitride4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPTIPHGIFIG €—gesX PPPEPPS gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ghemi™—l †—por heposition of eluminum xitride4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPTIQPGIFIG €—gesX PPSEPQH gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4wet—l yrg—ni™ ghemi™—l †—por heposition of g—l™ium pluoride4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPTIITGIFQG €—gesX PQHEPQP gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG QIQ .

QIR woduleX 4€re™ursors for ghemi™—l †—por heposition of gopper4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPSRPVGIFRG €—gesX PQPEPQV gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4‚utherford f—™ks™—ttering of „hin pilms4 fyX evishek ƒ—h—D endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPRIIGIFQG €—gesX PQWEPRU gopyrightX evishek ƒ—h—D endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG ATTRIBUTIONS woduleX 4„he eppli™—tion of †ƒs @†erti™—l ƒ™—nning snterferometryA to the ƒtudy of gryst—l ƒurf—™e €roE ™esses4 fyX snn— uurg—nsk—y—D endre—s vuttgeD endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPQPTGIFRG €—gesX PRUEPSV gopyrightX snn— uurg—nsk—y—D endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4sntrodu™tion to x—nop—rti™le ƒynthesis4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPQUPGIFPG €—geX PSW gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4ƒemi™ondu™tor x—nop—rti™les4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPQURGIFRG €—gesX PSWEPTI gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4g—r˜on x—nom—teri—ls4 fyX endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPSVHGIFRG €—gesX PTIEPUP gopyrightX endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4qr—phene4 fyX ghristopher iF r—miltonD endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPWIVUGIFQG €—gesX PUPEPUT gopyrightX ghristopher iF r—miltonD endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG .

ATTRIBUTIONS woduleX 4‚olling wole™ules on ƒurf—™es …nder ƒ„w sm—ging4 fyX €innE„song ghi—ngD endrew ‚F f—rron …‚vX httpXGG™nxForgG™ontentGmPPWTSGIFQG €—gesX PUUEPVT gopyrightX €innE„song ghi—ngD endrew ‚F f—rron vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGQFHG woduleX 4„he invironment—l smp—™t of the w—nuf—™turing of ƒemin™ondu™tors4 fyX t—son roldenD ghristopher uelty …‚vX httpXGG™nxForgG™ontentGmIRSHQGIFQG €—gesX PVUEPWW gopyrightX t—son roldenD ghristopher uelty vi™enseX httpXGG™re—tive™ommonsForgGli™ensesG˜yGPFHG QIS .

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