ii SRINCPUS OF PHUSICALSHEMISTRY corsa andor (uch 2s ata, he alee and VB.) i fl of less wile te es) oy put Only 2 Sal aon: of ery ses © allow oe Soin he combusn ny cone ng He wey el ah fs een ver cy lel Tie moves of ston win i CB. cnt elt ‘chndiction: In somte-metallic conductors, the''V.B. and dhe C.B. actually ayerlap resulting i @ parily. Any ec member ie VB. nC, Well we Ee Inasts tn sr, th VB. al nd he Ei er) aT i a 4 Re nev Jone exergy pn ne sa 1 Wek dow. eb ent sen ven a et) Mp omeraes or ane ery he ees Hl a sn cage a an tr - Senlondcors. We tl de vie lara secur wh eikutson in gn mprty as wen Sed Te bx nen ini Semcon ae aa ag Tuan tas seracofsc, he VD fal nde CB. emg 0) Coe ewe be yo an hove, 0 sol a ese cn jon Sony ese sal sont of dr dt) ioe, Le, only Reig Oe materi a taal catio, Te deal entiy Serer Wi ee in egress moe ad tor eons ae tered wh nr in enprann ‘Renae tere of ye tere second Tos gomnn 6-007 eV) a bate cnt Tas adboe eV), Avan leon jomps om tev ote Cy iene blind hla ‘ie tn pail chapel sd sean deen Conjunto beeen arp at VB, Sih le was ving Contcon an car ie By te sea eetons movsg wie CB. oY Pee nr moving in eV a A icotee trom emer ster | py 4 Tenses ded nat we cotavy nz isco base | ‘Sigs Was tment ay ee ces ad ls ct 1 ase seam weet the egerue dependence of lee : ceeeevgr, fora mle catct,#emiseitr ada perm shown in i 36. sa ersten nich havnt ney ie ete es ean en, malic condutr i anes wit ei ont ht aes wit boca expemare, 1 olegtecor wba h an deal cot) a TR Snthsuing copes and superar 2 bsane al bas 20 eesti trosuce bel 1 cen perature calle ciel z eae TAME se ae : ‘Bail Comat and are Gaps or ‘The conductivity of a semiconductor follows the ee Gemn At pendence with actyayion a Ge core mice | ‘pe Ee Tass, # 1g = oh expC Balk) dy Ci ( BY2KD age Epa o WAlGeS tor de eteniensd oF Group IV" eeeeiee =e ‘THE SOLO STATE * 1201 Extrine Semiconductors 1Lis posse to inerease the charge carts if sons wit more Aeros tan, parent leméat canbe intoiced by the process know as doping. Esuemely lw coneearaon fh dopa bot ‘oe atom per 10? atoms of the host material) are needed. Pate silica (Si) and germanium (Ge) can be rade mote coniutng icone mane by adn dopant impres which ca ge crc Sor Ge are fit de exteney pore by z0Nereiig. Then some arene (As) ams wih fe Valence clecons areal te Ge cosa An exeely small mer of Ge aon ae randomly replaced by AS toms. Only fou of he ive ute leon on eae AS atom are equi form Bonds in he age. The fit elton on As atom i aot bonded. At tw temperatures, the ith slo i Iodine on he AS son. However, a normal temperatures, sone of these fi eestons on As ae excited othe conucon band where they act as charge cares, This probes what known xine conduction. Se the clrent is cared by exces cleo, this is Kowa AS miype Semicoaduction. The mzgune of seniconsciy in an enn senzondocr ar greet Wan Ut In anise pre semiconductor Ifthe donor Assos are fr apart fom one another, thei electrons ae leas andthe donor tnd will be earrw (Fig. 37a) The filed dopant bid! is near Gus below) e enpty conduction ‘acd of he tie Alterttvely, a exysal of pu’ Si or Ge is doped wit atoms ofan element which bas three valence electrons per atom, such a gal- lium (Ga) or ‘nda (a). Bac galt sto tas tree outer eles to fom thee bonds inthe lace, these electrons casos form four bonds in the late 1 complete the covalent Structure. One bod i incomplete and the ste whic renin unecopied bcase ofthe mising letra is called a postive hole. More for rally, 2 dogs ams forma. very eacea empty ceptor band that es above te fll silicon valence tanf (Fig. 37). Ai T=0 K, the acceptor bad i empy but ai T > 0 K, it can amcagtthemally ecies eecwons fom the Si valence band. Tis forms new positive toes ine Si valence band. Te holes appear 10 move in & dcecton opposite fo the motion ‘of deco. The postive nets “hop trough the band. ince the charge carirs are now the postive holes, shs type of conduction is krowa as p-tpe conduction. tn principle, any ofthe Group V elements (sch a8 P, As, b, Bi) can ‘ve ued o make n-type semiconductors bt, because oft ow meting point AS is most sommonly Used, Silay, any of the Group II element och ss B, Al, Gas Tn) en be wed to make p-1ype Saks ne nd Un) i oot cma wd Bt fs omg pa. A loeb of deao impurity can produce a dramatic change i he Conduct of a semiondco. For example, part ofa donor impurity per 1 parts of germanism increases ls conductivity By a fecor of 10 ‘The combination of m and p-ype semi-condoctors (known as m-p junction), fads intresting ‘plications ia the manufacture of transistors. This device can coodut electric cient mote easily ‘in one patter direction tha i the eevere direction sod, therefore, canbe vedas a rectifier fot Fg 37, Thebans of aang Sei) = pe mane1202 PRINCPLES OF PHYSICAL CHEMISTRY ‘hanging alternating current into direct eurent. The device is schematically represented in Fig. 38. Fig 38, Secor aig a ii, ‘The material on the left side of each junction is n-type conductor obained by doping germanium with say, arsenic. The mins signs represent exta electrons, The material on the ight side ofthe junction is p-type conductor obtained by doping germanium with, say, indium. The posi signs fepresent ‘postve hoes’ arising from the deficiency of electrons at the indium impurity cetres. ‘When an external voltage is applied in such a way as to cause mation of electoas(n-eateat) from, left to right and motion of positive holes (p-currem) from right fo let (Fig. 35a), cunt is readily conducted. If dretion of voltage is reversed so that there is separation of elecuons and positive lols as showin Fig. 35(), sete is cancellation of m and p-currents and beac the conduction sop. ‘Ths, the n-p junction permits the current fom an outside soure t flow in one direstion only. ductivity Superconductor superconducton is of wo ype, vic, low temperate saperccdctvity (L18C) sd igh eagera sopercontutviy (TSC). An Wel secon b Spd tae 2eto oF very ile eleteal resistance, Low Temperature Superconductivity (LTSC). LTSC was first discovered in 1911 by the Dutch physicist H- Kameringh-Onnes who was awarded the 1913 Papies Noval rze for Ms cotbaions to low temperature physics which eto the production of ligud bela. He fous tat dow w 415, K, the resstance of mercury decreased with decrease in temperature a8 is the case wih most tetas, However, a eical temperate Tz=415 K, the resistance fell sharply clase to 20, Tus, aor below the critical emperatre, iequry became a superconductor. At ver lw temperatures, ‘any mets, alloys and certain compounds become superconductors, the ertcal emperanes for superonductiviy jing between 01 K and 10 K. Since &superconducor bas almost zero resistance, iceanedryaneectscuret witout lasing energy and, in principle, the cent can fw fr eve. Superondacor alo exhibit what is called Meisner effet: sates aa superconductor doe not allow the mignetc field to pass through it. In other words, it behaves like a perfecly diamagnetic substance. The Meisser effect gives ese to leittion; levitation oceuts when objects. fot in, This can be achieved by the mutual repulsion between a Permaneat magnel and a superconductor. A supercondtor is diamagnetic because it expel all internal apneic Selds arising fom unpired ‘ezeres, The key io understanding LTSC was provided bythe etebraed BCS theory proposed in 1957 by he Ameen physi J. Barden, [Cooper and J. Scheer who were vated the 1972 ysis Nobel Prize. The ceaal ole inthe BCS theory of LISC i played by the Cooper par. LCovper expand tow two elettons could inert in supércondrorfoming Bound sare déspte eit couotbic puson. The Cooper pai of lecttnt eon aout of the idee, le i ectoes vit the mi Ot the sop ir UE. Tae ce Way Pesta ag aso athe ae eae ey Gpices yards Ic; The-delnaton pioduces-a ion of increased posite cle rant Sse ae nh ed ein ns by Be ee ip ot te pe ratcon fb sionger ‘hen’ the repulsion between he-eletrons, the ie} coupled together into a. Cooper pl. wth the defomed. lice a8 the THE SOUD STATE 1203 A Cooper por umiergoes ess scanering than an individual electron as it travels through the Inte becuse the distri cased by one eletton can attract back the other electron should tbe Scatered out of is pat in olision. Since the Cooper paris stable against sca, Ht ean cary charge freely trough the solid thereby lving rise 10 superconduction. The BCS tigy, which is mathematical tur de force, shows that the two electrons of the Cooper pair must be raoving in opposite dietons and thir corclaions may persist over lengths as darge as 10m. The binding energy of the Cooper par is of she order of 10 eV. That is why supercondctviy is low temperature phenomenon. When hv >> binding energy, strong absorption occurs as the Cooper pais ‘break down, The binding every a OK, Ey(), is given by FAO = 353 AT, 38) Eq. 48 shows good agreement withthe observed values of E, and T,. At T > OK, ony afew of. ‘he Coope girs break down. The eesulting individual electron inerat with the reaning Cooper pairs and reduce E Fly, at To Ey disappears; there are no more Cooper pits and te material eases to bea sueteondutr. 1K may be mentioned tat since the electrons ina! Cooper pair have opposite sins, the pai has resultant zero spin, Ths, the eleetzon pis in a superconductor ae bosons (unlike indvidaal eletons with spin which ave fermions) and any number of them can exist inthe ee quantum sae at the same te. Also, te current ina superconductor involves the entre sytem of Cooper pis wing as & vt We may meation here tat the American physicist John Bardeen (1908-1991) was the only piysicst wo win rwo Nobel Prizes in physics. He had shared the fist Nobel Prize in 1956 with ‘Walter Brattain (1902-1987) and Wiliam Stockley (1910-1989) for ther rescarches on semiconductors and their discovery of the wansisor effect. High Temperature Superconductvty (HSC). Bessie ofthe véry low temerares at which sos teri become saperonditng which implies tat Tis very low, LTSC has nt found ‘widespread wse. The highest valu of 7, inown ant 1986 as about 29K. In tat er, Bede {nd A Muller (who were working for TBM in Zrith, Switariind) dicoveted supra cy 2 ‘ite onde Bu-La-Cu-O sytem, which had 27, of about 35K: Bedageané Maller wee swarded ‘the 1987 Paysics Nobel Prize for the discovery of HTSC. Another high 7- superconductor YBa;CusO;__ 1 (£204) Was discovered in 1987 by Chinese-American physicists, Wa, Ch” {nd ic covores, the 7. big 93K. Thi temperate i sips beaue (—GraEOy it allows lig airogen (bling point 77K) tobe used as cola eater than the more expensive figs eum, Tis spereonuston, ese ytum-artum- | _COYOs cuptte, iste 1-2-3 ysem because ofthe rato of e metals peel. The { —GiBa, ‘o-stchomety appear to be notsary for HTC. I appetr tht copper is ——-e* 2] recescay for supereoaiety de efor to riplaee i by oer cemeat hae not tore fu ‘This cuprates the peroaie structure. This comprises of thee cubic prove uns tacked ne on topo the oer ging a longed (stragonal tcl The upper aa the ler cbes have a Ba¥* ion atthe body-cétied postion and the smaller ‘Cu? og ‘at cach comer. Fhe middle cube is similar but has a Y3* ion at the body centre. A gerovdbte sfotce bar We formla ABO, and the solctlomecy of tis compound would be ‘amiCwby. Since te formate acre found jr YBAC\O; here i evident mative oxygen ‘deficiency {bout 25% of oxygen sites in the crystal are vacant. Tee LISC of mets and alloys tas beet explained by the BCS theory. Howeve, tere is ot resent no saat theory of HFS. Nevers, te flowing feats ay bebo in mind 1. Many warm sueeondutors consi coppe which is know to exist in ire oxiaton sts, (+0, (I and (S40 Alo Cu forms many teragonally stored comple.