Abhishek Singh MatE 297, SJSU Spring 2006

Magnetic Nano Particles -Fabrication, Analysis and Application
Introduction Since the beginning of this century, 2000, science and engineering has seen a rapid increase in interest for ateria!s at the nano"sca!e# $n fact, statistica! data fro %u& 'esearch, $nc# sho(s that (or!d(ide spending on research and de)e!op ent of nano" techno!ogy is in e&cess of *+ bi!!ion ,-.# /he United States go)ern ent a!one is spending o)er *- bi!!ion annua!!y ,-.# 0ano" ateria!s ha)e attracted such a strong interest because of the physica!, e!ectronic, and agnetic properties resu!ting fro their 1uantu si2e ,2.# /he potentia! for nano"techno!ogy is i ense!y di)erse (ith potentia! app!ications in the fie!ds of e!ectronics, bio edica! de)ices, energy app!ications, i!itary uses, and (aste anage ent ,2.# 0ano" ateria!s cou!d be uti!i2ed to design nano"transistors, to de)e!op and de!i)er edicines for !oca!!y treating diseases and ai! ents (ithin the body, and for the creation ne( age (eapons and ar or for i!itary app!ications ,3.# U!ti ate!y, nano" techno!ogy has the potentia! to offer ne(, ine&pensi)e, and ore efficient ateria!s for a greater range of app!ications than achie)ab!e by bu!k ateria!s today# 4ithin the fie!d of nano" ateria!s under (or!d(ide research is the subset of agnetic nano" ateria!s# /his paper (i!! discuss the botto "up synthesis of agnetic nano"partic!es )ia ther a! deco position of eta!"carbony! co p!e&es, describe so e of the ethods used to characteri2e agnetic partic!es, and discuss current research for app!ication of these partic!es# Synthesis /here are any techni1ues for the synthesis of agnetic nano"partic!es inc!uding5 icro"e u!sion, reduction of eta!"sa!ts, gas"phase reduction of eta! co p!e&es, ther o!ysis of eta!"po!y er co p!e&es, and ther a! deco position of eta!"carbony! co p!e&es# $n this paper, the ther a! deco position of eta!"carbony! (i!! be discussed because it is a techni1ue (hich has successfu!!y been uti!i2ed to synthesi2e agnetic nano"partic!es# Meta!"carbony! co p!e&es are a co ercia!!y a)ai!ab!e product and ha)e been used in the past for preparation of coba!t and iron based cata!ysts, aking the readi!y app!icab!e for usage in synthesis of agnetic nano"partic!es ,2.# $n this synthesis techni1ue, the funda enta! goa! is to produce ato s in so!ution, (hich 1uick!y and spontaneous!y for u!ate into nano"partic!es# Mean(hi!e, contro!!ing their si2e and shape by uti!i2ing a surfactant, (hich (i!! strong!y adsorb onto the surface of the nano"partic!es, pro)ides a stabi!i2ing cap !ayer and si u!taneous!y ser)es as a hindrance for the binding of ore ato s onto the nano"partic!e, hence pre)enting further gro(th ,6.# /he eta!"carbony! pre"cursor ser)es to pro)ide the eta! ato s, the coordinating organic so!)ent pro)ides a ediu for disso!ution, and the surfactant ser)es to contro! gro(th and orpho!ogy# A eta!"carbony! co p!e& is in7ected into an organic coordinating i&ture at e!e)ated te peratures, (hich !eads to the breakdo(n of the eta!"carbony! co p!e& into encapsu!ated eta! nano"partic!es (ith !i1uid and gaseous


they uti!i2ed o!eic acid and triocty!phosphine o&ide 9/.Abhishek Singh MatE 297. dich!oroben2ene is organic coordinating so!)ent (hich ser)es to pro)ide a ediu for disso!ution of the coba!t octacarbony!# .>. of ?untes et a!# in their e&peri enta! (ork a!so used coba!t octacarbony! as a precursor and disso!)ed it in dich!oroben2ene# =o(e)er. nuc!eation spontaneous!y occurs and the i&ture of tripheny!phosphine and o!eic acid are used as surfactants (hich ser)e to stabi!i2e the nuc!eated nano"partic!es# /he (ork of 8ang et a!# yie!ded spherica! coba!t nano"partic!es (hich are 6"+ n in a)erage si2e as sho(n in Aigure .<+< (as in7ected into an organic coordinating i&ture ade up of dich!oroben2ene 9:6=6:!2<.6. o!eic acid 9:-+=36.# Aigure 2 disp!ays trans ission e!ectron icroscope 9/EM< resu!ts of ?untes et a!# Aigure 25 Asse b!ies of 6 & 7> n hcp":o 0ano"rods 9Ear C -00 n < .2<.# 2 .>.6.nce disso!)ed. rather than e p!oying a i&ture of o!eic acid and tripheny!phosphine as a surfactant. SJSU Spring 2006 by"products# $n the e&peri enta! (ork of 8ang et a!# coba!t octacarbony! 9:o29:.. ?untes et a!# produced rod shaped coba!t nano"partic!es ranging in si2e fro 6&2> n to 6&7> n in !ength by (idth .# Aigure -5 /EM $ age of 2"B Super!attice of :o 0ano"partic!es and =istogra A)erage Si2e C 7#2 D 0#>n . and tripheny!phosphine 9:-+=->?< at a te perature of 220 @:# $n this e&a p!e.?.<# Ey changing the surfactant.

a!!o(ing one to identify crysta! p!anes# Aurther ore. can be ca!cu!ated.6. re nant agneti2ation. and K is the ang!e of diffraction# nλ = d sin θ E1uation - /he output fro G'B ana!ysis yie!ds a p!ot.# $n this paper &"ray diffraction 9G'B< and trans ission e!ectron icroscopy (i!! be discussed for geo etric characteri2ation and super conducting 1uantu interference de)ice 9SHU$B< agneto etry for agnetic characteri2ation# X-ray Diffraction (XRD) $n G'B. SJSU Spring 2006 Characterization: Geo etric and Magnetic $n order to proper!y characteri2e agnetic nano"partic!es and grasp an understanding of their properties5 geo etric and agnetic infor ation is of essence . (hich is in the range of the repeat distance in ost crysta!!ine so!id ateria!s . uti!i2ed G'B in order to e)a!uate peak broadening (ith si2e decrease and their resu!ts are sho(n in Aigure 3# 3 . in this case G"rays. shape. (hereas the critica! agnetic para eters are5 agnetic o ents. diffraction occurs (hen a sa p!e is irradiated (ith e!ectro agnetic radiation.7. J is the (a)e!ength.6. bond !engths. d. as sho(n in Aigure 3# Aro this one can deter ine the crysta!!ographic p!anes that are being diffracted and since the (a)e!ength and diffraction ang!e is kno(n.# Feo etric para eters inc!ude5 si2e. and crysta! structure. (hich is sho(n in E1uation -.6.# Biffraction occurs based on EraggIs !a(.# Each e!e ent has a uni1ue absorption spectru so uti!i2ing G"ray diffraction and absorption e!e enta! identification is obtained as (e!! as the repeat distance# Sche)chenko et a!. d is the repeat distance.# /he (a)e!engths of G"rays are angstro s in agnitude. (hich can be uti!i2ed to create a ap of the crysta! structure# A!ternati)e!y.7. co position. a co!!ection of standards can be uti!i2ed to co pare the peaks in the diffractogra (ith !iterature )a!ues. coerci)ity.Abhishek Singh MatE 297. (hich sho(s intensity )ersus diffraction ang!e. the e1uip ent can be configured to ha)e a detector to easure G"ray absorption# /his detector has been uti!i2ed in the (ork of =or es et a! . and b!ocking te perature . and there is interaction (ith a structure (here the repeat distance is on the sa e order as the (a)e!ength of the e!ectro agnetic radiation . (here n is an integer. using EraggIs !a( the repeat distance. saturation agneti2ation.

an e!ectron bea . SJSU Spring 2006 Aigure 3# Si2e"dependent G'B ?attern of :o?t3 0ano"crysta!s . (hich capture trans itted e!ectrons and dark"fie!d detectors that capture back"scattered e!ectrons. is trans itted through a thin sa p!e of nano"partic!es .6. an i age is generated# Bepending on the configuration and capabi!ities of the /EM.+.# 6 . a!!o(ing ade1uate i age capture of nano"partic!es .# Using bright"fie!d detectors. ho(e)er.# Aigure 6 disp!ays a /EM i age of go!d nano"partic!es (ith si2es !ess than 20 nano" eters# Aigure 6# /EM $ age of 0ano"partic!es of Fo!d . a trans ission e!ectron icroscope is a better too! for e&traction of si2e and shape data because it yie!ds rea! i ages fro (hich easure ents can be ade# $n a trans ission e!ectron icroscope.Abhishek Singh MatE 297.# Transmission Electron Microscopy (TEM) $t is possib!e to uti!i2e an G'B e1uipped (ith G"ray absorption detector to e&tract partic!e si2e and shape data. reso!ution of 2 Angstro s can be achie)ed. focused by e!ectro agnetic !enses.+.-3.

nano" e!ectronics. data storage.# 8ang et a!#.>.# Applications in !"# Magnetic nano"partic!e app!ications are being in)estigated in u!tip!e discip!ines fro bio edica! sensors.Abhishek Singh MatE 297. etc# /(o app!ications.# /he f!o( of e!ectrons across the thin insu!ating !ayer is kno(n as the Josephson current and is e&tre e!y sensiti)e to agnetic fie!ds . are5 deto&ification of conta inated personne! for the i!itary and drug de!i)ery and treat ent# :urrent techni1ues in both of these fie!ds are )ery !i ited and ini a!!y robust and nano"techno!ogy has the potentia! to enhance the capabi!ities in both fie!ds i ense!y# Deto!ification of "ontaminated #ersonnel $ Military Eioche ica! (arfare is steadi!y beco ing a greater threat (or!d(ide# $n the case of a conf!ict (here a so!dier is e&posed to to&ins there are )ery fe( options for sur)i)a!# :urrent edica! deto&ification treat ent ethods a)ai!ab!e are dia!ysis and b!ood > . as sho(n in Aigure ># Aigure >5 =ysteresis %oop of ?o(der of :o 0ano"partic!es at 2>0 L and -0 L . drug de!i)ery. in their e&peri enta! (ork. (hich are being hea)i!y in)estigated by se)era! research groups. agnetic resonance i aging.9. uti!i2ed a SHU$B to capture hysteresis beha)ior of different!y prepared coba!t nano"partic!e sa p!es at t(o different te peratures. (hich is e&tre e!y )a!uab!e for agnetic nano"partic!e ana!ysis# /he SHU$B is ade up of t(o Josephson 7unctions# A Josephson 7unction is ade up of t(o superconductors (hich are separated by a thin insu!ating !ayer.9.# A SHU$B easures agnetic signa!s on the order of -0"9 /es!a and !ess .9. (hich a!!o(s e!ectrons to cross through . SJSU Spring 2006 Superconducting Quantum Interference Device Magnetometry (SQ ID) A superconducting 1uantu interference de)ice 9SHU$B< is used to easure )ery (eak agnetic signa!s.

--.-2. functiona! organic capping !ayers. a portion of the fie!d is absorbed by the ferro agnet.nce at the affected region.# Drug Delivery and Efficacy Brug de!i)ery and effecti)e app!ication of drugs (ithin the body is another hea)i!y in)estigated app!ication for agnetic nano"partic!es# 'esearchers are particu!ar!y in)estigating ferro agnetic nano"partic!es (ith respect to treat ent of )arious cancers# /he goa! is to ha)e edicines functiona!!y bind to agnetic nano"partic!es and uti!i2e a agnetic gradient to guide the nano"partic!e to the affected region# . this re nant agneti2ation has to be o)erco e .# /his effecti)e!y yie!ds an energy !oss in the for of heat (hich is proportiona! to the area (ithin the hysteresis !oop . by uti!i2ing a agnetic fie!d gradient. and coba!t ferro agnetic nano"partic!es# /he ne&t phase of research is identifying pre"do inant to&ins. then agnetic nano"partic!es can be sent into the b!oodstrea of a conta inated person# /hen . ca!!ed the re nant agneti2ation# 4hen a re)erse fie!d is app!ied. nicke!. can be uti!i2ed.-0.# =ysteresis is depicted in Aigure 3 and is characteristic of ferro agnetic ateria!s# =ysteresis occurs in ferro agnets because (hen an e&terna! fie!d is app!ied and re o)ed.# 'esearchers are uti!i2ing this ther a! energy for !oca!i2ed heating (ithin the body# .# :urrent research has sho(n success in this tag and drag approach using go!d coated iron.nce the edicine has been guided 6 . (hich (i!! functiona!!y bind to the to&ins (ithin the body.-0. to&ins can be e&tracted fro the body# $n research this ethodo!ogy has been !abe!ed tag and drag and is depicted in Aigure 6# Aigure 65 /ag and Brag Beto&ification of :onta inated ?ersonne! )ia Magnetic 0ano" partic!es . and bio"co patibi!ity . SJSU Spring 2006 purification. the hysteretic beha)ior of ferro agnetic partic!es is uti!i2ed to pro)ide ther a! acti)ation .Abhishek Singh MatE 297. both of (hich ha)e !o( rates of success and take e&tensi)e periods of ti e to undergo# Magnetic nano"partic!es are being in)estigated for their capabi!ity to bind (ith to&ins (ithin the body# /he )arious synthesis techni1ues inc!uding the ther a! deco position of eta!"carbony! co p!e&es ha)e sho(n that agnetic nano"partic!es are stabi!i2ed by an organic surfactant (hich acts as a capping !ayer# $f a che ica!!y acti)e capping !ayer.-2.

SJSU Spring 2006 )ia a agnetic gradient to a desired !ocation. current and future research is geared to(ards si2e distribution contro!# Aor ost app!ications it is critica! to ha)e a specific si2e as (e!! as )ery tight distribution# :urrent research is pushing to synthesi2e super"!attices of agnetic nano"partic!es (hich sho( si2e distribution of !ess than >M# Aor the app!ications discussed in this paper. the agnetic fie!d is )aried to create hysteresis# /his in effect causes !oca!i2ed heating that he!ps in the acti)ation and co p!etion of a che ica! reaction bet(een the app!ied edicine and the ad)erse!y affected area# :urrent research is atte pting to de)e!op agnetic nano"partic!es (ith !arge agnetic o ents and resistance to physica! breakdo(n (ithin the body# Future !esearch and #e$elop ent Aor agnetic nano"partic!es. future research is being geared to(ards disco)ering bioco patib!e capping !ayers# /his is essentia! in order to uti!i2e agnetic nano" partic!es in vivo# Su ary :urrent research has sho(n that synthesis of agnetic nano"partic!es is achie)ab!e# /he app!ications for agnetic nano"partic!es are )ery di)erse# $n order to ake use of the potentia! of agnetic nano"partic!es. research is being geared to find functiona! surfactants (hich ser)e to eet app!ication re1uire ents# Eioco patibi!ity in the case of drug de!i)er and deto&ification app!ications and conducti)ity in the case of e!ectronic app!ications are e&a p!es of such# As research e)o!)es and so!utions to current !i itations are reso!)ed. the integration of agnetic nano"partic!es into e)eryday use beco es a c!earer rea!ity# 7 .Abhishek Singh MatE 297. (ork in synthesis refine ent is necessary. to contro! geo etric and agnetic properties# Aro an app!ication aspect.