Title The Structural and Electronic Properties of Amorphous Ge andits Alloys( Dissertation_全文 )
Author(s) Tamura, Kozaburo
Citation 京都大学
Issue Date 1973-11-24
URL https://doi.org/10.14989/doctor.k1407
Right
Type Thesis or Dissertation
Textversion author
Kyoto University
彪三f・惨r鍍σt
TheStz・UGt{xra工andE=Lc試c七ronla"c
of'Amorph◎lxsGea蕊dit.・sA工1轟ys
●一 ■L一富」 」學噛艦■t』■■陣一 闇■幽幽融 口岬 ■一 寧凶馳岬■■■曜
AThesis
Presentedちothe・Fa(}ultyOfSCience
-K
y。 七b、Unive㍗si七y
by
KQzaburo.Tamura
lg73
吻 輯 一
Properties
額182幽 『
Preface
Thestructureandelectr)n二cproperties。fa涌 。r'・phousG∋ロarequitedifferentfromthGs20f↓iquidGe,Whichisdense・ly
Packed,hastheoctahed'tallolcalenvironmentsratheヱ 。tlan
tetrahedralandexhibitsametalユicbehavior.
Ther£oreitisinterestingtoinvestigatethephysicaX
propertiesofamorphousGeby・apPlyingpressur'n一
工tiεfound七hatthesemiconductorto鵬etaltransi七ion
occursatpressure◎f60kbarinamorphousGe。Thetransitj。)n
pressureischangedbyadditionofSn.Theatomicarrange!P
ofamorphousGe。SnalloysareteprahedralwitharanOo鵬nea
estneighbourenvironment.
Effectofpressureoncm・)rphouS・Ge-Nia=Lloyswasstudied。
Semiconductortorletaltransl・ ごion◎ccursintheconce論tratiつ 姑
rangebelow30at.i'Niatalmostthesamepressureasin
amorphousGe.AmorphQusGe一 潤ialloyswitho・'cr3Ca七 。%Ni
concentrationshowmしta1ユicpr◎perties.
X-rayscattere童 三tensitycurvesf'oreamorphousG⇔ ・・Nialloys
inthecgncentrationrangeove1-;30at.%Nishowqu≦te,}imユ1ゑr
patternwiththoseforユiquid・
TheinvestigationsofthesystematiovariationG.atαnic
andelectronicstvuctureofsuchamQrphQu昌g.IXQyswithg◎nce夏V・"
rat二 〇nanda工sotheextentofthesimilarityofphysicalp炉o卿
pertiesintheseamorphou/s,ハ110yswitht//`()sein上iquidst3ちe
areinteresting●
Thevalencebandspectr.pa◎famorpbcusGe_』i,Gく.,/i・ean(孟
Ge-A凹alloysareipves亀 嵐gatedbymeans◎fX。rayphot◎-gZoctこ こ》n
一1一
emission.The8hapeandpositi(・nofthepeakin七hespecCrum
associatedwithd-statechangewithconcentrati◎ra・
Thisthesi8containst。hreeつartsa5follow3
Parti O●
Part'エ エ:
Part皿:
Nonmetalto]M【etalTransitioninAmorphous
GeandGe_SnAlioysunderHighPressure
EffectofPressureontheEiectronie
Pr・opertiesofAmorphousGe-NiAlle"s
X-rayPhotoen{issionSpec㌻raofValenceBan(ス δ
inAゴnorp}。ow3Ge-Ni,Ge塵Feand,Gg一 ムuAXユ ♪y3
一2一
Parti
Non-MetaltoMeta1TranεitioninA㎞orph」mu
C..andGe-SnAlloy3underHighPressure
一3一
§lI】n七roduction
Therehasbeenmanyexperimen七alandtheOre七iCaliムves七iga.・
ti。n。(ユ)。nth。pr。P。r七i。s。f、 、,。rph。u。G。becau8ei七i・ 七h・
most七ypicaユexamp■eofamorphoussemicOnduc七 〇rs・Thes七ruc七utre
ofamorphousGehasbeeninvestiga七edbyX-rayandelectron
diffrac七i。n。xp。rim。n七 。.(2・・4)Theradia・di。tribu七i。nfun。 七i。n
deducedfrom七hediffrac七ionda七ashow8tha七theatomsin七he
amorpho,asGearesurroしmded「byatetrahedronof◎thera七 〇ms
wi七hanaverageseparationsim5ユar七 〇 七ha七intheorystaユILine
G・.S・v・ra・m。d・X。(5kη)f・rth・structur・ 。f。rP。rph。u・G・
havebeenproposedonthebasisoftheseresul七8.①hemier◎-
scopics七ructuures,forexampユe,theexis七enceOfvacancies,
voidsanddangUngbcndse七c.havgbeens七udiedbymeansofthe
m。asur。m。n七 。 。fth。d。n。ity,(8・9)。m。11ang、escatt。ring.。f
。lec七r。ndiffra。 七i。n(10)andESR.(li》H。w。v。r七h。d。finit。
pictureforthes七ruc七ureofa血orphou8Geseemstobeunknown
a七presen七.工tshouldbea=Lson.oticedthat七hestructur'aland
e]-ectronicprS)pertiesofamorphousGearequitedifferentfrom
七hoseof=LiquidGewhichisdenselypackedwiththeoc七ahedraユ
ユocalenviron皿entsratherthante七rahedraユandexhibi七sametaユ1ic
b。havi。r.(12)Mhi。i。in。 。ntra。 七 七。th。fa。 七tha七 七heam。rpheuS
me七aユandaユ ユoysproducedby8evera■methodsbehavelike七he
corr 、espondingliquid3七atein七he8tructuralandelectronic
(ユ3)properties・
Thepic七ure。fc。nducti。nmechanisminam。rph・ 鴨semiconduct◎r
ha8becomec=Learerbyvariousexperimen七aユand七heore七ica].effort8。
ThecOnductionprocesscon七ainsintrkisicandextrinsicconduc-
tionsoverthewho工etemperaturerange.A七highte血peratじ エethe
一4一
intrinsiceonduc七ioni8dominantandi七appearswithalarge
a。tiva七i。n。n。rgy.A。Stuk。(i4)hase即ha。izedf。rm。 ・・y。m。rph。uq
8entconduc七 〇rs七heplo七 〇fZogari七hmicconduc七ivityagains七
reciproeal七emperatur'egivesagoods七raightユineaS8ameas
forcrystaLiinesemic。nduc七 〇r.A七lowtempera七ureitheextrinsic
conductionbecomesdominan七 。Extrinsicconduc七ioniscausedby
七hehoppingof七heユocaユizedeiec七ronsinthebaねdtailorin
七hevicini七yoftheFermilevel.Alargenumberofas-depositedグfiユms8howaαr写1awdependenceoftheconductivityuptoroom
(15)七emperatureandevenabove,assuggestedby斑ot七 。Thisseems
七〇suggesttha七thehopPingin七heユ ◎caユizeds七a七egnear七he
Fermilevelisdominan七.Fur七hermorethetunnelingexperimen七s
。upP。rtth±ssi七ua七i。n.(16)・fh。PPing。 。ndu。 七i。n。rph。n。n
assi8ted七u㎜e=Lingce-nduGtionreallyexiststwhichi8、meof七he
mos七impor七an七featutreinamorphou8semiconduc七 〇r,iti8inter-
es七ingtoinvestiga七6七heeffec七 〇fpressureonthiscenductien
てユ7)mechanism・Theh。PPihgmvbU.itycanbeexpヱessedas1'Oi ,iows;
/・(・=(eYpka'・ip/k7♪eptEdk(7e-2c「d フ伽r・ 吻i・anav・rag・ 。pti・ ・1ph。n。nfr・qu・n・y,φi・d・c,。n・tant,
Edis七hehopPingac七ivationenergy70ζgive8もherateoよfa=L工 鱒off
。fth・ エ。・alizedwav・f㎜ ・七i。n・?anddi・ 漉av・r朗 ・int・rat・nt・
separation.Thereforeiti8七 〇beexpectedtha七therrゆbility
inereasesveryTapidlywi七hdecreasinεdW血esst.hewavefuncti。ns
εrespread・ou七 ●
Since七hedensi七y,s七ructureandelectronicpropertiesof
amorphousGearequitedifferentfrom七ho8eofユiquidGe,i七is
エntere8七ingt。inve8七iga¢ethephy8icaユproperties。fam。rph。us
一5一
Gebycompression.Theinves七iga七iononthechangeofmobili七y
gaporhoPPingconductionprocesswi七hpressureisals(1,importan七 ・
Themeasuremen七 〇fresis七ivi七yasafunc七ionofpressureup七 〇
28kbarha。beenr,p。r七 。dbyCamph。n8en。ta・.(ユ8)f。r七h。vari。u8
amorphou8Gepreparedby七heeユec七rolytic,evaporationandspat一
七eringme七hod,andforthoseannealeda七153ρC.
工nthispaperwereporttheeffeo七 〇fpressureonthe
eユec七ricaLresis七anceofa皿 。rph◎u8GeandGe-Snaユ ユoy8underhigh
pressureuptoX30kbar・
一6一
§2ExperimentaユProcedure
2-lPrepara七ionofSampユes
Amorphou8Geandi七saユloyfi=L皿swerepreparedbyevapora-
tionont◎themicasu"bs七ra七eskep七a七 〇rbelowroOmtempera七Lxre
㎜d。rvacu。mb。tt。rth。n10-6七 。rr.τh。vacuumwa。k。p七bヒ1。w
-6 七〇rrdし λringeVapora七ion.ユ ~2xlO
Thesamplewasevapora七edfrom七he「baske七 〇f七hetungs七en
filamen七withO.3mminadiame七erwhichwasoutgassedcarefully
undervacuum.MhedistancebetweenthetungstenfiLamentandthe
subs七ratewasabou七IO・cm.Theratesofdeposi七ionwereabou七
〇
500A/minand七heevapora七ions廓ereperfoでmedabouteveryone
minuteat=LOminu七esユntervaユsinordertoprevent悲la.eheating
upofthesubstra七eduetO七heradiationfrem七h@filamen七as
P◎ssible●
ThesmaユlpeユletsofGeorGe-Snmixtuure・withabou七2m皿in
adiame七erweredropPedonebyonein七 〇 七hebaskG㌻oftungsten
fi=Lamen七 七hro㎎htheguideofstainles8tubeundervacuumvand
thenevapora七ed.工 七isweUkn(twn七hattwOcQnst工tuents,Geand
Snarecompe七elysolublein七heユiquid8七a七ebu七dSsso=Lublein
thesolid6七a七einaLmostthewhoieconcentrationrange.Therefore
theGe-Snaユloysmeユ 七edinaevacua七edquartztubewererapidly
quenchedi.n七 〇wa七erinorder七 〇 〇b七ain七hehomogeneousailoypellets●.
Themicasubs七ratesshavedandcu七frommicasheetswereof20pm
ormerethicknessandユanlsquare.ThefilmsofAgandAuwith
5000£ 七hicknessdeposi七edon七hemica8ubstra七ewereusedasthe
e=Lectrodeswhichwerekep七 〇.lmmapar七fro皿eacho七her.,The
samPユewa8dePosi七edon七hesubstra㌻e七hro㎎hthemaskwi七ha8エi七
〇fO.ユminwid七hwhichwasputonthe8ub8trate.⑦hethickness
一7r
of8amplesusedforthepresentmeasuremen、 七wereusualユy∴L《 ノ2ト ム血 ●
ロThedimensionsofsampleson七he£ 臣icasubstratesareshownin
Fig。 ユschematiCally.
2-2Apparatus
FOrmeasuremen七80felectriCa=LresiS七anCeathighpres8ure
upto130kbar,pressurewasapPliedatroom七empera七urebyan
。PP。 。i七。anvi、typ。apPara七u。d。v。 、。P。dbyBaL。hanandDri。kam。r.119)
usinganexternalhydrauユicpress.Apyrophy=LZitepel=Letofthe・
apPropria七esizeandshapeWi七hO.33mminacenterthicknes8
and5.00mmindiameterw'asusedforpres8uuremedium.ムf七er
pre-・compressionthecen七er.fla七areaof七hepyrophyユli七epeユle七
wa、r。m。v。dwi七hadri、i。nd七h。nth。pyr。phyi、it。rin錨 藩 継eユ
The8chemeaticdiagramofthecenterassemb=Lyareshown
inFig.2,inorder七 〇makecユearthesitua七iOnofsa皿plegeometry●
Theelec七ricaユcon七actsweremadethroughthethincOpPersheets
COnneCti・ngbetweentheCementedtUngStenCarbi .deianViXSandthe
electrodesoffiユmonthemicasub8trate..
2-5Caユibra七ionandMeasurementofRe8istance
Theele6七ricaLresistancewasmeasturedbydetec七i尊gthe
change80fpo七entiaLacressthesamp=Lecausedbyasma=Lユcons七ant
directcun7rent・Thevoltageandcurren七probeswere80=Ldβred七 〇.
theou七sideofs七eeユjacke七softhe七woanvils.Pressしcreswere
deteiminedbyth・fixedp・in七s・fBi(エ ー工工),Bi(エV-V)andPb(エ ーII)
transi七ion8a七25.4,77andl30kbar.工t8houldbenoticed七ha・ 七the
pressuresgeneratedinAgClmediumaresensitivelyaffectedby
t ,hegeometricaLarrangement8foraエ1七hepartsofhighpressunre
一8一
ce11.Theerrorofcalibra七ionswasa「boし しt=LO◎1● 「PGdecide
thepressuremorepreciselywemeasured七heparalleiresistance
of七hesampleandBifilmwi七habout=L'トLmthieknessdepo8i七ed
jus七 〇n七hefilmofthesampユe.A七ypica■examplefor七he
measuremen七issh。wninFig.3.エnthepreSen七experiments,the
8harp七ransi七ionfromn◎n-me七altome七alofsampユestookplace
a七pressurebetweenthetwofixedcaLibrationpoin七sofBi。
Thereforei七wa8po8sibletodecidethe七ransi七ionpres8urewithin
theerroroflのPt2ツ 』.Thecopper-cons七antanther血ocoupiewas
inser七edintonearthesamplethroughthehoユeof七he8idejaCket
tomea8ure七hetempera七ureofthe8ampleO
一9一
§5Resし 〔LtsandDi8cussion
3一 ユPureGe
Fig.4showstheeユec七ricalresis七anceversuspressしure・curves、
ofamorphousandpolycry8七aLlineGe.Thepolycry8七aユiineGewas
obtainedbyanneaユing七heamorphousfi■ma七5000Cundervacuum
f・ ・anhqur,工 七wa・en・ur・df。rth・filmann・al・da七50。 。Ct。
show七hecrys七ai=Line=LinesindexedasadiamondtypeStructure
from七heX-raydiffrac七ionmeasuremen七.
Onincreasin呂pressure,七he・eleetricaLresistanceofthe
polyerystaユlinefilmgraduallyincreasesup七 〇about50kbar
andthendecreases.工 七suddeniydropsa七pressureofIOOkbarwhゴch
isnearly七hesameast七 〔eprevi(クusda七aforもrys七al.ZineGeobserved
byMin。muraandDri。karm・r・(2・)。nth。 。th。rhandth。pres8ure
dependenceoftheresis七ancein七heamorphousGeisverydiffe7ent
from七hecrys七a=LMneGe.Theresi∈ …七ivityofamorphou8Geis
estimat・d七 ・b・3xユ02n・ ・ma七a七 皿。。pneri・press、 、r。.エt。lightly
increasesup七 ◎about10kbarandrapidlydeereasesbyafactor
。f6~7-Th・nti七dr。P・sharplyd・wn七 ・ab。u七2xL。2pa-,ma七
60kbarand七heseconddropdownto2~3xユOpSI。cmapPearsat
aboutIOOkbarwhichcorrespondsto七hatobservedforthepoly謄
crystaLlinefilms● 工七isno七iced七hatthereSistancechaxges
verylittlewithpressureintherangeofpre8surebetween60and
ユOOkbar.
Thepressuredependenceoftheresistanceintheamorphou8
Gewa8preci8elymea8uredinthe=Lowpres8ureregionbyusing
Cu-B・P「essu「ebomb・Fig・5・h。w・theresuユP,f・rth・pressur・
dependenceoftheresistanceinamorphousGeu、P七 〇 ユOkbar,where
thevaLueofresi8tanceisnormaユizedbytha七a七atmospheric
一10一
pressur。.P。 。landBr。 。k。(21)hav。m。a。ur。dthech。ng。 。f七he
resis七anceofcrysta=LlineGewithpressureup七 〇30kbar.Their
resul七isalsoshowninFig.5.工 七isnoticed七hatthepresstxre
dlnR,
.foras-deposi七edamorphousGei8deriva七iveofresistancedp
-2-'.4
.Ox10smaller七hanthatforcrystal"neGe.kbarwhichismuch
(18),Recent=LyCamphausene七al.夙averepor・tedmeasurementsof
resistanceasafunctionofpressureup七 〇28kbarforamorphous
Gepreparedbythethree'differentme七hodsandalsoanneaieda七
=L550C.Ourdataforamorphous ,Gei8ingoodagreementwi七htheir resuユ 七 〇funanneaユedspu七 七eredGe.'Theyhaveshown・that
thevaria七ionofresistancewithpressurefoT七heanneaユed
amQrphoussamp=Leisverydifferen七fromtha七fortheunannea=Led
amorphoussamples.ThelogarithmiCresistanceversuspressure
curvesofannealedamorphoussamp=LesgiveagOOds七raight=LineS
dlnRandthei「p「e3su「e'de「iva七iv・ ⑪a「ealm。 ・七thesarP・astha七
〇fcrys七alユineGe・Anotherimpor七an七
aspec七is七ha七 七hepressurecoefficien七sof七heOp七icalgap,which
essen七iallygivestheelec七rica=Lgapoftheintrinsicconduction,
arepositiveandaユmost七hesameforannealedandunannealed
amorphoussamplesinspi七eofthefact七hat七hepressurecoefficient8
0fresistancearequitedifferenteachother.Thereforei七i8not
unreasona「bleassump七ionthattheex七rinsic.conductionispre願
d。minantforthe七ranspor七mechani8皿inas-dep。sitedam。rph。us
Gecomparedtotha七incrys七aユ ユineGe. .●Thetemperatし αredependeneeofresis七anceinamorphousGe
unde「p「e8su「eandthepre8s・n・edependence。factivati・nenergy
一11一
areshowninFig.6andFig.7'respec七iveiy・Theac七iva七ion
energyinFig.7deducedfrom七hederivative◎flogari七hmic
resis七anceversusreciproealof七empera七urenearroomtempera七ure
doesno七represen七theintrinsicactiva七iOnenergy.工 七mus七be
thought七ha七 七heextrinsiceonduc七ionprocessiss七 且ldominant
inthis七empera七ureregion,whiehhasbeen8七udiedbymany
inves七iga七 〇rsa七a七mosphericpres8ure.①heamoTphousGeexhibits
semicondue七ingbehaviourup七 〇60kbar.1七i昌considered七hat
Gesampleshowsme七aユliobehaviour叫nder七hepressunre「be七ween60
andlOOkbar,sincethere8is七ancegradual■ydecreaseswi七h
fa=LZingtempera七uureand.thesampユ.ebecomessupercondue七 〇rnear
5・K.(22)Thesamp、 。und。rpre8sur。 。v。r100kbari。m,七al・i。and
thetempera七urecoefficien七 〇fre8i8tanceissm .allbutposi七iveas
showninFig.8.
For七heGesamp=Leunderpressurebetween60andユOOkbar,
七hesharplinescorresponding七 〇crystallines七ructurecOu=Ldnot
bede七ectedinX-raydiffraetionpattern.Bu七thedetermina七ion
of七hedefini七es七ruc七urea七highpressurdhasno七ye七been
。uccessfu・.Th。recentw。rk(23)。fam。rph。u。Siund。rhighpre8。ure
hasreveaユedtha七semiconduc七 〇rtometal七ransi七iOnOCcursa七 七he
presgureofIOOkbarwhichi8muchlowerthan七hatobservedfor
crystallineSi,assameasinthecaseofamorphOusGe.On
decreasingpressuretheresis七ancereeovers七 〇 七hesameva=Lue
beforecompression, .and七heaspec七 〇ftheresis七ance-pressure
curveisreproduciblebyrepea七ing七heapPlica七ionandreleaseof ロthesampleinl
pressure・Af七erreleasingpressure〈 ㌻h・me℃ 証licphaserec。v・rs
tosemiconduc七 〇r,however,theX-raydiffractionMeasu)7emen七show8
tha七thesampユehasanam・rph。usstruc七vUre.Thisevidenceenc。urages
一12一
ustobelievetha七 七heGesampleunderpressurebetween60and
X-ray
lOOkb・ ・isam・rph・u・ ・Th・^pa七 七ern・fthesampiereleasedback
fr。mth。pressureも ・ユ・w七hefirs七 七ransi七i。np・in七 七。atm・spheric
pressurehasbeenjus七 七hesameas七ha七 〇famorphousGeatnorma■
pressure.However七hesamp=Lesreユeasedbackfrom七hepressure
between60and=LOOkbarwerecry8七a■1ized.X-raydiffrac七ion
linesofthesamplereleasedfrom七hepressureofabou七80kbar
couldbeindexedfortha七 〇fthesamediamondstructureas
crystaユlineGe,whi■e七hesamplereleasedfrom七hepressure
(24) ,a『bove=LOOkbarshowsthe七e七ragonal8七ruc七ure.BundyandKasper
havefoしmd七ha七 七he七e七ragonalGeconsistedoflinkagesofrather
dis七 〇rted七e七rahedraeanbeformedwhencrys七allineGewi七hdiarnond
s七ruc七ureiscompressedoverlOOkbarandthenreleasedback七 〇
atmosphericpressしure.ThesampleunderpressureoverIOOkbar
mayhav。 β一・Sn.七ypes七ructur。(25)。inceth。tran。i七i。npressure
coincidesto七hatofcrystaLiineGeandalsothestructureof
七hesamplereleasedfromover100k「bari8七hesameas七hatof
crystailineGe.
Fig.4!may。 ㎎gesttha七Sam・rph。u。'n。n-m。taLt。`an。rph。u。'
me七 ε江 七ransi七ionoceursa七thepres8ureof60kbar『byapPユ ‡cation
ofpressureforamorphousGeand七he七ransi七iona七XOOkbar,accom-
pani・dby七h・resi・ 七ancedr。pbyafa・ 七。r・f2・di.Q-}i・du・t。th・
crys七a■=Liza七ientoβ 一Sn七ypestructure.Furtherworkby七he
presen七author8revea■8tha七 七he七ransitionpressureOfamorphou8
G・ann・al・da七2gO,3。Oand4。O。Ci・thesam・a・that。fa・ 。d・p。 ・i七・
amorphou8Ge.
一13一
3-2AmorphousGe-Snalloy8
(22)wehavereportedthepressvLre工n七hepreviouspaper
dependencesof七heresis七ancesinamorphousGe-Niaユloys・The
sharpnessofthetransi七ionfromnon-me七al七 〇me七aユ
of
changeswi七hadditionANitoGeandit「become8dali,tho㎎hthe
七ransitionpressuredoesno七changesomuch.Thechangein七he
charac七erofcovalen七bondingwi七haddi七ionofSntoGemaygive
aILargeeffec七 〇n七heoP七icalgapand工ocaユiza七ionofthecarrier8
wi七henergiesneartheFernilevelinam。rph。usGe・Theref。re
i七isin七eres七ing七 〇explorewhetherthe七ransi七ionpressure
changesorno七byaddi七ionofSn・
Inrecentyearsthes七udieshavebeenrepor七edanamorphous
G。-Sna、 、。y。byaf。wau七h。r。.S.Sa七 。et証..(26)hav。m。a。ur。d
七hetempera七uredependenceofthedcconduc七ivi七yand七hefrequency
dependence・f七heac。 ・nduc七ivi七ya七r。 ・血temperatureinGe-Sn
alloyfiユms.Theyhavetried七 〇interpret七heresuユ 七sonthe
basisofpseudo-gapmodel.Thes七ructu]7alandoP七icaユpropertie8
havebeens七udiedinde七ai=Lsontheseaユ ユoysystemswithSncon-
centrati。n・,25,and5・a七.gl.byR.」.[D。 曲 。taL.(27)Acc。rd-
ingtoTemkinetaユ.theminimumopticalgapdecreaseswith
inereasingSnconten七.
Fig.gshowstheintensi七ypa七 七ernsofX-raydiffrac七i◎n
withou七anycorrec七ionfora【norphousGe-SnaLIOys.Thevaria七iOn
of七hediffrac七ionpa七 七ernswithincreasingSnconcen七rationi8
(22)qui七edifferentfro皿 七hoseofamorphousGe-Nialloys.{The
a七〇micarrangementisfound七 〇be七e七rahedralwithaxandom
nearestneighbourenvironmen七 ●Temkinetaユ.haves七udiedthe
一14一
s七ructuraユproper七iesofamorphousGe-Snaユ=Loysinmoredetails・ ●Theradia=Ldis七ributionfunc七ionshowstha七 七hemeansepara七ion
betweenGea七 〇mssligh七lyincreaseswithSnconcentration●
Fig.10shows七hepressuredependenee80fresis七ancesin
Ge-Sna=L=Loysin七herangeofconcen七ra七ioniessthanユOa七.『toSn.
Theresistivi七ydoesnotchangesomuchwithSn60ncen七ra七ionat
a七mospheriepressureanda七room七empera七ure.1七c◎uユdbeseen
七hatthesharptransi七ionsfr◎mnon-metal七 〇me七a=Lexistin
七heseconcentra七ionrangeandchangθ ・Ni七hadditionofSn・The
resistancesdecreasewithincreasingpressurenearlyinthesame
wayas七ha七 〇fpureamorphousGeandthe七ransi七ionpressure
increaseswi七hincreasingSncon七ent.The,ehangeof七hetransition
pressし ロrewi七hincreasingSnconten七waspreciselyde七erminedbyu8i.ng
themethodmen七ionedin§2anditi8showninFig.=Ll.Recent=Ly 、ithasbeenfound七hat七hetransitiOnpressure'changesremarkabユy
by七headdi七ionofSi七 〇Geandi七 土ncreasesby20kbarbythe
additionofIOa七.『toSicon七en七.工 七wi=L=Lbepublished=La七erinde七aiユ
ThemeasurementsofX-raydiffrac七ionザHa=L=Lcoefficien七,
七hermopower,oP七icalproper七iesetc.atvarioustempera七uresunder
highpressurewilibehe=Lpfu■forunders七anding七henatureof
n。n-me七altometa].tran8iti。ninam。rph。usGeandGe-Sn母 ユ。ys・
一 工5一
《ユ)
(2》
(3}
(4》
(5}
(6)
(7)
《8》
(9)
(ユO)
(11)
(12)
(13)
(14}
(エ5)
(16}
(17}
(18}
(19}
(20}
《21)
References
See,forexample
N.F.MottandE.A.Davis;ElectronicProcessin
Non。CrystallineMaterials,Oxford(1971)
D・Adler;AmorphousSemicondt}ctorCRCPressL◎hdon(馬971》
H.RichterandO.F置rst;Z.Naturforsch盤L(ユ951)38
H.Ri,ht。randG.Br。itling;・Z.Naturf。rschユ3・(1958》998
器二呈δS?蜘k3含 呈dW・Pau';J● ・N。n鱒C「ysta11'neSo1'qs
T.B.LightandC.N。J.Wagner;」.App1。Cryst.⊥(1968}199
機1テ 甥c'andR・Mana'1a;」'N。n-C「ysta'HneS。"ds主
D.E.Polk;J.Non-CrystallineSolids5(ユ97ユ 》365 A.H.Clark;Phys.Rev.154(1967}750
T.B.Light;Phys.Rev●Letters葦 …(ユ969)ggg
S.C.MossandJ.F.Graczyk;Phys.Rev.Letters」 篁 《1969》1167
M.H.BrodskyandR.S.Title;Phys.Rev.Letters毫}(1969》581
S.P.Isherwood,B.R.OrtonandR.Manaila3」.Non齢CrysValユine
solids8-lo(1972)691
A.K.Sinha;Phys.Rev●(B)ユ(ユ970}454i
J.Stuke;」 。Non-CrystallineSolidS」 』(=L970)ユ
E●A.DavisandN.F.Mott;Phi1.]Mag.22(ユ970》903
J●W・OsmunandH.Friやzsche;ApPl.Phys●Letters工6(1970)87
N●F.Mott;Phi1.Mag.19(1969)835
謡8望 齢s?呈 う731Aら塁うC。nne'1andW・Pau1;」 ・N。n-C「ysta".‡ne
A● .S。BalchanandH●G●Drickarner;Rev●sci.Instrum.32(1961}308
S●MinomuraandH・G●Drickamer;」.Phys.Chem●Solids23(1962)
45ユ ー
W.Pau工andH.Brooks;Phys.Rev.94(1954}ll28 一
憎16一
(22)
(23)
(24)
(25}
(26)
(27》
K●Tamura,J.Fukushima,H.Endo,S.Minomura,O.Shimomuraand
K.Asaumi;Proc.of2nd工nternationalConferenceof七he
PropertiesofLiquidMeta1,Tokyo,1972《TaylorandFrancis},P295
S.Minomura;PrivateCo㎜unication
F●P.BundyandJ.S.Kasper;Sciencel39(1963》 ・340
」●C.Jamieson;Science139(ユ963}762
S・Sato,N●YamaguchiandH●gzaki;」 ●Phy8・Soc●Japan33(1972》
1497-
R・J・Temkin,G・A・N・ConnellandW・Pa叫lSolidS七a七eCo㎜uaica- 、・
tionsユ1(1972》159ユ
一 ↓7一
Fig.1.
Fig.2.
Fig.3.
Fig.4.
Fig.5.
Fig.6。,
Fig.7.
班g88.
Figureσaptions
Dimension80fsampledepo8itedonthemicasubs七ra七e
usedformeasuremen七 〇fe=Lec七r・icaLresis七a').cea七high
pressure■
Cen七erassemblyofhighpresSし じrece工L.
A七ypicaユexampiefor七hemeasuremen七 〇fparaユlel
resis七anceofsampleandBiffユm9.Transitionpressure
ofsamp=Leゴsdecidedpreeiselywithrespect七 〇 七he七wo
fixedpointscfBi.
Electricalresis七anceversuspressuregurvesfor
amorphousandpolycrys七aLlineGefilms.Polycrys七aユ 。
ユinefilmβisob七aineqbyannea工 ㎞ga夏10rphou$f工 ↓皿a七
5000C.
Thenormalizedresistanceしversuspres8urefoヱramorロ
phousandcrystal.LineGe.Theresuユ 七 〇fcrys七aユline
G。i。tak。nfr。m七h。databyPaalandBr。 。k。.(21)
Tempera七 しロPedependenceofresis七anceofamorphousGe
・nearroom七empera七urea七pressureof30,45and60kbar●
Pressuredependenceofac七ivationenergydeducedfrom
thederiva七iveoflogresis七anceversusreciprocaL
of七empera七uresh◎wninF工9.6.
Resistanceversustempera七urecurvenearroomtemper-
atureatPresSure◎f1ユOkbar.
一18一
Fig.9.
Fig.=LO.
Fig.11.
tVhein七en8itypa七 七emof:': -raydiftr・ac七ionfor
amorphousGe-Snalloys.
Resis七anc、eversuspressure・clユrvesof●amorphousGe-Sn
alloys.
Tran・i七i。npressur・ 。fam。rph。u・G・-Snali。y・wi七h
respectto七heSneontent'.田ransiti◎npressureis
determinedbythemethodshownin,Fig.3.
一19一
Fig1
/L-一 ・・1mm
一旙 系「
→
ノ~0 .1mm
τ
τ/'/''ノ ノ
"
~1mm
一∠
Sαmp【eMicαsubstrαte
(~1淋mthick)(・-20pamthick)
Etectr。de.。fAg&Au
(~5000Athick)
Fig2
ノ!.「
趣..,、.ノ奨 麟 絃,/詣 ・
ぐ 羅 蟻 こ・,、,乙 拶ノ
ぐ聴,ノ ε灘 囎sten
1~・一り鐙1{;'・
鳶}_/一 辮hとlll㌘disk、 .'レ、.-Sqmptefilm
≡h・Micαsheet&ム
1\憧 藝'驚 \_llr鑛1臨lm'・タミ・
/津 ・・い.._ .、_/"Cuelectrode\ \ こ ・・1-・ ク'
鶴.写 、 、一 ノ ㍉
〆講 ゴ 》:㍉,/薦1帆 ・"'・ 鷲 ・;Si;.譲 ジ ぞ 邑}
'ド も'・,
1ド.ビ'
Fig3
40
(
鉦よO)
囚OZ《トの回Uり田匡
30
20
1C
L◎wBi
↓ 一
ト
iGe-5at%Sn,HighBi
↓ ↓
11020304050
0ZLPRSSURE(kg/cmユ)
-22一
1.0
0.5
60 70
(
7σ1
♂1
501
6
.げ
20
で
りロ
コ
ε
£◎
)ω
りZ
〈
ト◎り
国uらU.配
10.
噌霊も
置鑑
∩)
齢∩V
!
Fig4
℃005tαd㎏α
\
e
、、
n
、・;
!
ー
;
ー
ー
ー
-
ー
-
-
ー
:
ー
ー
ー
;
;
ー
ー
ー
-ー
、
n
\
A
、、、軸隔陶鋤鴨駒馳輌鱒一一一一一一一一
eGus始巾OmA
㍉、
軸嚇一●軸
50100
PRESSURE(Kbqr)一23一
150
Fig5
0◎
日-
6
5
4
R(P)3R(0)
2
10グ
crystαltineGe
P◎u!&Br◎oksぐ54)
αmorph◎usGe
Presentwork一 一■ 一 一一 ■■ 脚 引一 鱒
一 ■■●
1020PRESSURE(kbαr)
Fig6
lo6
18
(∈
40
)国OZ
〈↑の
一の
ω㏄
御30Kbαr
御45Kbar
..の60Kbar
4013.0 3.23.43.6
1・3/T(・Kf)
3.8
一25一
Fig7
36
(
>
o
)
2
>O匡山Z山
j
Z9
↑《≧
↑Oく
、 、、 、
0.0050
PRESSURE(Kbar)
100
コ
.6
5
4
3
●
●
●
(∈
£O
)田OZくトの目の国㏄
。
2
1
0。0
.110κbar
ロ300.310320330
TEMPERATURE(OK)
一27一
Fig8
Fig9
(
cn・◇rジ
● 卿ロo●
あ』翌
紳δ
負δ
■
●
翰
)
〉踊
卜a螂 ・・1
ζノ》
1鑑
漏
を一
二:z
》一剛
Ge-25a土%Sn
Ge凸15at.O/oSn
Ge-10ε 吐以。Sn
翼
Ge-5at%Sn
PureGe
1 2 3
K(=4π
4
sinθ)
56-28一
入
(
∈
=o
)
山OZく↑uり一〇山に
♂1Fig10
・601
501
401
げー
201
10
1
司01
一つζ→く『)く \×
\\
\,
\x
OAmOrphousGe
△Ge-5αtg1。Sn
×Ge-10atgノ 。Sn
、×\ 〉鰍
'"Xs\x一
0 50
PRESSURE
-29一
100
(Kbαr)
150
Fig11
70
(』ゆ幽遮
)M…㏄⊃uり
uりω配乱
z60
嚢畿の
z《疋縢己s-50
0
Ge
5
qtρ1。Sn
10
一30一
Part 11
EffectofPressureontheElectronic
ofAmorphousGe-NiAlloys
Properties
一'31一
5.工.工ntroduction
TheX・-raydiffracセionpatterns《Madere七al196!7)fromthe
amorphousmetalsanda1工oysproducedbyevaporationonセoacold'
substratearenearlythesameasthoseobservedinaliquid
state.Thereare,howeveユ ㍉ ユargedifferencesinthestructure
andelectrica工proper'ヒiesbetweenam◎rphousandliquidGe.
TheamorphousGebehaves工ikeasemiconductor,whi工eliquidGe
likeme七a1.Theradialdis七ributionfunctionofamorphousGe
deducedfrornX-raymeasurernentshowsthatthefirstandsecond
peaksdono● ヒapPeara七thepositioncorrespondingtothe工iquid
state・Thesec。ndpeakisrelativelyhighandthec。 。rdinati。n
nurnbera七thenearestneighbourisabout4(RichterandBreitユing
19戸8》Thedensi'ヒyof'arnorphousGeisapproximately4.8gr/cm,
much工owerthanthatinaliquidphase.
エnthispaper,wereportmeasurementsofX-raydiffraction,●density,andX-rayphotoelectronspectrafortheamorphousphase
ofGe-Niaユ ユoys.Wereportalsothevariationofelectrical
resistancewithpressureuptoユ00Kbaratroomtemperature£or
amorphousGe-Niaエ エoysintheconcentrationrangeto30at亀
Ni,whichbec。mesmetaエ ユicapPr。ximatelya七60Xbar.
一・32一
§2●Experirnentaユs
Am。rph。usthinfilms。fab。ut1Mrnthicknessareprepared
-6b
ycondensationinユOtorrfromthemixturesoffinepowders
ofGeandNi,xapidlyquenchedfrorntheirmelt,ontemi.caor
glasssUbstratesatroorntemperature,andatエiquidN2ternper-
aturefor'ヒhemaximumconcentrationof60a七 審Ni.
PressureareapPユiedarヒ=oomternperaturebyanoPPosed-
anvi工 七ypeapparatusdeveユopedbyBalchanandDrickarner(ユ96ユ 》
PressuresaredeterminedbythefixedpointofBi(ユ ー2)and
Bi(3-5),transitions・Thedensityisderヒer】 【ninedfromtheweight
USingndCrObalanCeandthethiCkneSSUSi明interEerOmeter。
一 ・33一
§3●Results
X-rayscatteredintensitycurvesエ(K)。fam。rPh。usGe-Ni
aii。ySaresh。wninFig.ユ.エntensityofthe・firstpeakbecomes
weakerandtheposi七io耳ofthesecondpeakshif七sremarkably
七〇alOWerValUeOfKWithinCreaSingCOnCentratiOnOfNi・
エ七isnoticedthat工(K)curveiゴ ・arnorphousGe顧40at審Nialloy
showsquiteasirniiarpa・ ヒtemwithユiquidGe-42a七9Niaエ エoy・
Fig.2ashowsthepressuredependenceoftheresistanceofarnor・ ・
phousGe-Nia1工oys.工ntheserrticonductingamorphousGe・-Ni
aZloy,七hetrans‡tionstometa1工icstatesoccuratpressure
around60Kbar,assameasthecritica工pressureobservedin
pureamorphous、Ge.Nediscontinuousjumpintheresistancein
themetallicarn6ごphousGe-Nia:loysovとr30at亀Niisobserved
underpressure.Theconcentrationdependenceofresistivity
ofarnorphousGe髄Nialloysatatmosphericpressureand60Kbar
isshowninFig.2b.TheresistivityofamorphousGedecreases
withincreasingconcentrationofNiandmetaiZicconductivity
withtheconcen七rationover30at$Nib
X-ray(AltW》ph。 七。electr。nspectr。Scρpyissh。wninFig・3
asafunctionofNi-concentration.Thevaユencebandofarnorphous
Gehasthesinglebroadrnaxirnuminthedis'ヒributionandtheband
srヒructureofamorphousGeisremarkablyalteredontheaddition
ofNi.Apronouncedpeakduetothedelectrondensityofstate
ofNiapPearsanごintensityofthispeakbecomesstrongerwith
Ni.concentration・Thepositionofthepeakc◎rrespondingto
thedelectrondensityofstateofpureNishiftstowardXower
一34一
energysidebyalユoying.ThedspectruminarnorphousGe-Ni
a1エ 。ysa=eessentiallyunchangedwi七hNic。ncentra七i。ninthe
range・ofconcentrationlessthan30a七 亀Ni,butitshifts
graduaZlywithNic。ntentinエargecgncentrati。n。fNi・The
densityofstateatFerrnienergyincreaseswirヒhNiconcentra`ヒion・
TheFerrnienergyisdete=mined,withaAusample,astheposi-
tionwherethe6sbandisdowntoha工fi'ヒsheigh七.Fig.4shows
themeasureddensityofamorphousGe-Nialloysatroomtemper-
aturerヒhedensi七yofamorphousGeis4.8gr/cmandthedensi-
tiesofamorphousGe-Niaユ エoysincreaserapidlywithNicon-
centrationandapproachtothevalueofthesupercooZed工iquid
Ge-Nia工10ydowntb=oomtemperatureintheconcentrationrange
over30at審Ni,deducedf=omdataforpureliquidGeandNi'assuming'thattw。c。nstituentsaresimplymixedeach。ther・
一35一
§.4.DiscussionandConclusion
Despiternuchpu肌ishedliteratureonセhestructure。fam。r-
ph。usGe,itisn。tfu1エyunderst。 。da七present・Theelectr。nic
propertiesofa皿o=phousGedependsprincipaユ1yonthelocalen-
vironrnentsoftheconstituentatorns,i.e。,onthefirs七coordi-
nationmユrUber.Thehomopolarbindingforcep=eventstheforrna-
tionofacユosepackedmetallicstructure.A・furtherincrease
。faveragec。 。dina七i。nnumberisachievedbyai1。ying.τhe
alloysareprobabユysignificantlymoredisorderedthanthepure
amorphousGe.He=eisacompositiona工disorder(Economoue七a1●
1970)inadditiontotheユac150flong=angetransla七ionalorder.
エnorder七 〇sa七isfythelocalvalencerequirements,theconnec-
tivityofrヒhenetworkmus・ ヒ ℃hangerandornユy,and工ocaldisorder'
iSCOnseqUentlyinCreaSed.
エtisreasonabietoconsiderthepo .ssibilitythatthe
additionofNimaybreakthecovalentbondofamo】rPhousGeand ロthenthecoordinationnumberincreases.Themeasurrnentsof七he
X-raydiffractionanddensi七yexhibitsthatthestructuresof
amorphousGe-NialloysintherangeofNiconcentrationover
30atgissimiユarwith七hatintheエiquida1↓oyandtheybecorae
metallic・Thissuggeststha七insucha1エoys七hecovaユen七may
compユetelydisappear.工nsuchmeta1ユicregionwithdense
packing,4vaユenceelectronsperatomofGegointoconduction
bandand4selectronsofNiwouユdbecomenon一 工ocalizedstate.
Theρonduc七ionbandinGe-Nialloymaybebuiltupwitha魎mixingofvaユenceeユect=onsofGeandNi.工 七shouldberemarked
一36一
七ha七theshiftofthepeakduetothedelectrondensityofsta七e
ofNiasseeninFig.3reflectsthechangeofFermiユeveユby
コaユ10ying(40,50&60at亀 》 工nthesmaエ エconcentrationrange
ofNi,wheretheshif七 〇fpeakinpho‡ 二〇emissionspectraisvery
smal工withNiconcentrarヒion,asshowninFig.3,the4selectrens
ofNiaddedtoamo=phousGea=eextremeiyユocalizedbecauseof
alargenumberofspatia1=ando㎜essand七hedeeppotentialof
Ni.Thereforethereisonユyave=y工imitedsharingofeユectrons
betweenGeandNi.TheadditionofNiincreasestheconcentra一
七ionofb=okenbondsandtheaverageseparationbetweenGeatoms
isreduced.Finallyitseemsevidenセtha七 「ヒhepressureinduced
metaliics七ateofamorphousGe鵬Nia1工oyshasacriticaldensity
whichisequivalenttothatof工iquidstate.
一37'一
References
Baユchan,A.S.,andD=idくarner,H.G.,Rev●Sci.工nsrヒr.32,(196i),-
308.
Economou,E.N.,Kirkpatrick,S.,Cohen,M.H.,andEggarter,T.P-
Phys.Rev.Letterso互(ユ970),520.
GUntherodt,H.σ.andBusch,G.,Privatecommunication.
Mader,S.,Nowick,A.S.,andWidrn年roH.tAgtaMetallurgica,ユ 三
(ユ967),2030
Richter,H.oan(#Bre;tling,G.,Z.NaturEorsh.,ユ3a(1958》,998。
FigureCap七ions
Fig.工
Fig.2a
Fig.2b
Fig.3
Fig。4
X-rayscatteredintensitycurveofarnorphousand工iquid
Ge-Niaユ10ys.
ThepressuredependenceoftheresisセanceofamorphOus
Ge-Nialloysatroomtemperature.
Theconcentrationdependenceofresistivityofamorphous
Ge-Nialloysatatmosphericp=essure(●)andabove60Kbar
(0)Dashedlineshowsthatof1工quidsta七emeasuredby
G㎞therodt&Busch(ユ97ユ)
Xロ 「ayph。t。electr。n・pec七=af。ran。rph。u・Ge-Nialユ 。y・ ・
ThedensitiesatarnoxphousGeoNia1工oysa七roomtemper-
a七ure.
一38一
(2
モ
コ
〉」o差
n」o
)
〉↑一ωZ山卜≡
1
''
''
1
1ノ
'
2
liquidGe-42at.el.Ni
amorphOus
Ge-50at.%Ni
Ge-40at.910Ni
Ge-30Gt.%Ni
Ge-20at.%Ni
Ge-10at.%Ni
amorphousGe
345
K(払 π興)A"i
-39一
6
Fig1
Fig.2
lo7
♂1
501
410
(∈
`o)
30
20
1
1
山
りZ
<↑の
一の山α
10
1.
鴨ン』×、欧
×'狭
\\
\へ
X
2騨O
ヨ0
払Q
(E
Y
ε`o
)
〉=
≧
↑の一のUに
♂
◆
◆
◇
O
×
●
ム
ロ
1-_g./一 十 一一
◇ 十
o
Ge
204060
αt●01』Ni-r9夢
PUreAmσnOt℃us'Ge
Gc軸5αt。1。Nl
10Gt。1。Ni
20at。 ノ。Ni
30at。 ノ。Ni
亀
鞠
ー
し
∩
)
コ一(
》1
50100
PRESSURE(Kb(ユr)-40一
150
ZO一のの一ΣU
ZO¢トOU」山6
↑0工氏
〉<αー×
LO
>↑一のZ山↑Z
一
Fig.3
Amorphous
Gc-『60Qtg1。Ni
Gc-50qt%Ni
へ な ●●㌔
㌔
G¢-40Qt?ノ 。Ni
つ●♂噛●冒隔軸●
Gc-
G¢-20Gt?,。Ni
、.●りψA
G¢-10at?1。Ni
ゾ 宛 、・岬.
AmorphousGe
'be欄b軸 鵬
●
酒●
ん照窓赫楓↓煽蹄
♂
●
甥ノ●
φ
ノW〆強
鱒,~
.W
、句.」....∵
.、曳
》
.、脚(
♂●。
ら'
"
〆鴨
●
、
.
.
●●
●
●、ノ
ノ○
ノ
.ノ
●
'●
いノ幅}
・部駕轡"吻
(ハ。●、
}
、
●●・..
、
.
の●寸~函
、へ、
榔}
●
●
●
・ ●
偽
.炉.〆 、蜘 も鱒
q隔●●一
・・㌔ 脚 朝ρ
●,iiN・ ●
●
「いiee
㍉ ♂㍉ 職り●鴨・・肉 ●
'ψ
、 』』一 、5 .k●
●
㍉鱒軸隔》 貞晩"
.●一
、 』ρρ●●・・一鞠 一ρ㍉一A
}㌦ ♂P・..一♂ 鵬"■.
fE
o
一100 一5.O
ENERGY
一4i一
(eV)
0.0
Fig.4
10◎
《C
E)8・o
?
占)6P
ヒ
罵z4ρω0
2D
OD6
'
"う弓O一一'',
、 隔 、ロ軸●
,"
1
'
ノ
'
1!
'
6
/1"ノ
/1
'/ノ'
"/チ9
'汐'
Ge
20 4060
αt.%
80 窟◎0
閥1
一42一
Part ill
X-rayPhotoemissionSpectraofValenceBands
inAmorphou3Ge●Ni,Ge鱒FeandGe鱒AuAlloys
r43一
§ユIn七roduc七ion
Mos七rnetalsarefreetodissolveinoneano七herwhenthey
areユiquid,and七hea七 。micandeユectr。nics七ruc七uure。fnumber
・fdifferentaZユ 。ysys七 ・mshavebeeninves七igatedaSafuncti。n
。fc。ncentra七i。nin七heユiquidstate.H・wevertherearevbry
fewsys七emswhichshowacomple七eraぬgeofso=Lutioninbo七h
theliquidand七hesolidphase.ForNi-Gesystem,七he七wo
cons七i七uen七sareoh工ysligh七 工ysoiubleinaNirichphasein
so=Lidsta七eandfor皿so-ca=Lledelec七roncompoし しndswhichexis七
a・Ni3G・with七hes七ruct・re。fCu3Autyp・andNiG・wi七hth・
struc七ureof1航P七ype.ForF6-Ge,theso■ubi=Li七yofFe血Ge
isverylowanditisalsoimpossi'b=Le七 〇makecrystaユXineaユ コ.oys
・fGeandAuinawh・lec・ncentra七i・nrange・H。weve;七heNi-Ge・
Fe-GeandAu-Gesystemsarecomp=Le七e=Lymiscib=Lewheniiquid.
Theprecisemeastxrementsfor七hephysica工propertiesofthese
alloysareno七easy,since七heirmel七ingtemperatvUresarecon-
siderablyhigh.
1七hasbeenshown七ha七theamorphousalloysofGe-Ni,Fe
andAuwi七hvariousconcen七ra七ionscanbeeasilyProducedby
evapora七ionon七 〇asubs七ra七e.TheXロr .ayore=Lectrondiffraction
(1)patternsof七hesea=LloysshowhighLydiffusediffrac七ionrings.
TheX-rayscatteredintensi七ycurves工(k)foramorphousGe-Ni
alloystn七heconeentrati。nrangeover50a七.%Nish。wsintlar
pa七 七erns「 宙ith七hoseforliquid,七ho㎎htheTearelargedifferencesコin七hestruc七tnraLande=Lectricalproper七iesbe七weenamorphous
andLiquidG。.(2)(3)Recent・yStrit。h。 遡d魎haver。p。rt。d
tha七theamorphoUsGe-nobleme七aユaユioyso「b七ain6dbycondensa七ion
becomesuperconduc七ingintherangeofconcen七ra七ionbetween25
一44一
and8。a七.%Auandσu.(4)Thes・ ・p・r・。ndu・ 七ivi七y。f七hesephasesi・
be=Lievedtobedue七 〇Geforcedin七 〇ame七al=Liciiquid-1ike
struc七urewithahighercoordinationnumber七han七ha七 〇fthe
semiconduc七ingdiamonds七rue七ure.Thereforei七isinteres七ing'
七〇s七udy七hesys七ema七icvaria七ionofa七 〇micandeユec七r6nic
structqreofsuchamorphousaユloyswi七hconcen七ra七i◎nandalso
七heex七entofthesimiユari七yofphysicaユproper七iesin七hese
amorphousalユoyswi七hthoseinユiquids七ate.
Bu。h。 七a、.(5)hav。m。a。ur。d七hee・ec七ri。al.resi。 七ivi七y,
magneticsuscep七ibiコ.i七yandHa=Llcoefficien七 〇fユiquidGe-Fe,
-c。,-Niand-cual1。ys.Thecbncentra七i。nrangewhichsh。ws七he
nega七ive七empera七urecoefficien七sfor七heresis七ivi七yofGe
aユ ユoysirlcreasesfromCutoFeaユ ユoys.Fromtheexperimen七aユ
da七afor七heconcen七ra七ion、dependenceoftheelec七ronicproper一
七iesof七hesea=Lloys,theyhavesugges七edthefol=Lowingschematic
densityofs七a七esofd-e=Lec七ronsfordifferen七concentrationof
Fe-Gealloys.ForpureiiquidFe,thedensi七yofs七atesis
splitin七 〇 七wopeaksand七heFermienergyliesonthelowenergy
sideof七hehighenergypeak.Ona=Lioyingwi七hGe,thesplit-
tingisreduced,七hemidd=Leof七he3d-bandandFermienergy
movein七 〇thepbsi七ionsof七hevir七ualbounds七a七efor■iquid
Gerichaユloys.①herefore,thedensi七yofsta七esat七heFermi
energyincreasesforFerichalloysanddecreasebeyondacertain
c。neen七ra七i。n,f。rwhich七heFermienergym。'vesthr。ughthe
second,bu七reducedpeak.Thereforei七isinteres七ing七 〇 〇b七ain
theinformationconcerni㎎ 七hedensi七yofs七atesforthesealloys .
Recentlymanyinves七igatorshavecarriedoutthemeastnre-
m・n七f。rth・d・n・ity。estates。fNi,C。,F・,Au,andCu・ 七・.by
一45∴
(6)(7)(8)usingX-rayph。tg・lec七r。n・pectr。sc。py(XPS)techniqu・ ・
Theyhaveshown七ha七XPScaninprincipleprovideara七her
direc七de七erm、ina七ionof七hedensi七yofs七a七esnear七heFermi
leveiasweilasverypreciseinforma七iononcore・eZec七r◎nbind-
ingenergies.Sincethekineticenergyof七hepho七 〇e血t七ed
elec七ronisverylargecqnparedwi七h七hebandwidthand七he
energyユossesdue七 〇 七hescattergdeユec七r。nsphotoexcited・inside
thesamplearedistribu七edoveralargerange,theuseofXPS
七echniqueensvtresthepred。minan七lybalkpatureof七hetransi-・
tion,asma■lcon七ribu七ionofineiasticaユlyscat七erede=Lec七ron8,
andn。ar、y。n。rgy-ind。p。nd。n七escap。d。p七h.Ba。randBu。h(9)
haves七udiedbyusingXPStec㎞iquethedensi七yofsta七esof
Aコ.whichiswel=Lknownasoneofnearlyfreee].ec七ronmetals
andfoし しrld七hes七rikingsimi■ari七yof'theva=Lencebandspec七rしun
wi七hcompu七eddensi七yofs七a七es.Thiss七udyofALde皿ons七ra七es
七hatXPSisasa七isfac七 〇ry七echniquefors七udying七hedensi七y
ofs七a七esandthedifferentprocessesinvolvedintheXPShave
aweakinfユUence。ntheshape。fbandspectrunwhichiscユ 。seエy
related七 〇thedensityofs七ates.
工nthepresen七paperX-rayphotoelectronemisSionstudiesOf
amorphousalloysbe七weenGeandM,FeandAuarereported
X-rayphotoelectronemissionspectrahavebeenobtainedwhich
con七aininforma七ionabou七thepositionandshapeOfd-bandsas
weUasabou七thepositionofcoreユeveユs.
一46一
§2Experimen七a」LProeedure
SpectraweremeasuLredonaKEC-X200elec七ronspectrometer
u・ing七hechara・ 七・ri・ti・A・k・ ・L,2X-ray(Z・486K・V>radia七i。n・
Thekine七icenergyofpho七 〇emit七edeユrec七ronswasanalyzedina
hemisphericaleユectros七a七icanalyzerandtheenergyseZected
by七hespectrome七erwasvaTiedins七epofO。 ユeV・Thecoun七s
a七eachenergywereaccumula七ed.Theto七alins七rumentalresOiu一
七ionincユudingtn'eX-rayiinewid七hisslight=Ly「be七 七erthanユ.OeV.
Toprepareamorphousspecimens,the皿ix七ur'esofGeandNi,
GeandFe,andGeandAuwithvariousconcentrations,rapid=Ly
quenchedfrom七heirmd=L七s,were'evaporatedon七 〇cleans七aゴ 典],ess
s七eelplatea七roomtemperaturefromthe七ungs七enfilamentin
thesamp=Leprepara七ionchamber.The七ungs七enfilamen七andGe
alloyswerecarefuL=Lyoutgassed.Thebackgroundpressurewas
ini七iaLlylxユ 〇-5㎜Hgandi七r。se七 〇2xiO-5mmHgduring
七heevapora七ion.Thesanp=Lewascarefullyevapora七edstepby
s七epforaveryshor七period七 〇preven七 七hecrys七al=Liza七ionof
thecondensedsampledue七 〇theradiationfromt㎜gs七enfilamen七.
The七 〇七alevaporationtimewasoneminu七e.Mhedis七ancebe七ween
thesu「bs七ra七ean,d七ungstenfilamen七w孕sabou七=LOcm.「Dhe
thieknessofamorphousfiユmsob七ainedbyevapora七ionwasabou.七
500A.Thefilmswere七hendirectly七ransferredto七heanalyzer'.
Onrecordingthespectra,七hevacuumofpho七 〇emissionchamber
-7Wasmaintaineda七IO ㎜Hg.
エnspi七eof七hiscarefulpreparati。ntO(ls)andC(ls)were
presen七inthespectra.Theintensityra七iosofthecontaminant
O(ユs)t。Ge(3d),Ni(2P),Fe(2P),andAtz(4f)lineswereverysman
一47一
andnoincreaseof七hein七ensityratiowasobservedduuringthe
measuremen七s.Therewasnochangeof七heshapeinthecorelevel
signalsdueto七heoxideformationinNi,FeandAua七 。msnear
七hesurface.AUrunswere皿adeunderthec。nditi。nwhichO(ls)
ユinehadnegligib■eintensi七yand七hecOreユeveエshavenarrOw
andstab=Lewid七hs.
Since七heevapora七ionratesof七hecons七i七uenta七 〇msin
a].loys皿igh七bedifferen七,七herecouユdbesomeambiguitiesfor
七hedeterminationsofaUoyconcen七ra七ionsof七hesample.工 七
wasseen七ha七 七heintensi七iesof七hei.nnercoreユeveユsinthe
Ni,FeandAuchangedaユ 」nos七=LinearZywith七hecorresponding
concen七ra七ion●
一48一
§3Experimen七alResul七s
Theionicstruc七uresofGe-Ni,Ge』FeandGe-Auaエ ユoy
fiユmsusedfor七hepresen七measuremen七sareamorphous,excep七
pureNi,FeandAu.ForpLnreNi,.FeandAuspecimensi七is
impossible七 〇 〇1)tain七heamorphouss七a七esbycondensationa七
r。 。m七 。mp。ra七uure.エn七h,pr。vi。u。pap。r(ユ)w。r。p。r七 。dthe
X-・raysca七teredin七ensi七ycしurvesofamorphousGe-Niaユloys● ,
=【tiswellknown七hat七hereare■argedifferencesin七he
struc七uralande=Lee七ronicproper七i・esbe七weenamorphousand
liquidGe.AmorphousGebehavesエike・asemiconduc七 〇r,whiエe
■iquidGelikeme七al.HoweverX-raypa七 七ernsofamorphous
Ge-Nial=Loysremaヱ 「kab=Lychangewi七hincreasingconcen七ra七ion
ofNi,andbecomesimi=Larto七hoseinliquidalloysin七he
range。fNiconcen七ra七ion。ver30a七.%,wheretransi七i。nfr。 皿
Semiconduc七ingtOme七allics七a七eoCcurs.
Fig.=Lshowstheexperimen七alvaユencebandspec七rafroエn
amorphousGe-Nialloyswithou七anycorrec七ion。Togetthe
"true"densi七y。fs七a七es,c。rrec七i・nshave七 。be・apPZied七 。
七heda七a.The七ransi七ionprobabiユitiesareafunctionof七he
en・rgy。ftheini七ials七a七e,varyingby・ab。ut10%。verthe
widthof七hed-bandinNi.工 七isa七preSen七impossibleto
correc七forthiseffec七.TheFermienergywasde七ermined,with
at6inユayerofAuevapora七eda七 七heposi七ionwherethe6s-band
isdown七 〇haユfi七sheigh七.Thespec七rumofthevaユenceband
ロ◎fNiformsanarrowbandasaresul七 〇f七hecomparative].y
iocalizedna七ureofthed-wavefunc七ionandappearsasasing=Le
P・akwithmaximumint・n・ityat-1・OeVb・1・wEFandahalfwidth
oftheorderof2.7eV.Themaximumdensityofsta七escanbe
一49一
s。mewha七cユoser七 〇 七heFermiZeveユas3c。nsequenceof七he
to七aエinstrumen七aZbroadening.Themainpeakassocia七edwith
Nid-s七atesinthedensityofs七atesofamorphousGe-Niaユloys
showsaremarkabユeshif七 七〇 二Lowerenergieswithrespect七 〇
七heFermiユeveユEFwi七haddi七ionofGe七 〇,Ni.工nhighconcen_
七ra七ionregionover70・a七.%Ge,whereaユ ■oysshowse=nic◎nduct・ 一
~
ingproperty,七hechangeofposi七ionofpeakisre二La七iveユy
smaユ ユwi七hincreasingconcentrationofGea曵ditisdifficu↓ 七
七〇determineprecisely七hepositionsof七hepeakssincethe
peaks皿ergein七 〇broadvalencebandofGe.ThehaZf・wid七hof
themainpeakbecomesnarr◎werwi七hincreasingconcen七ration
ofGe,七hough七hereareconsiderableatnbigui七iesfortheestirna-
ti。nof七hehalf・ ・wid七hbqcause。fahighba6kgr。undatユow
energyreg■onO
Therawda七aforthevaユencebandregionsofamorphous
Ge-FeaユloysareshowninFig.2.Thespec七rumof七hevaユenee
'bandinFeisbroadenedtowards=Lowerenergiesbecauseof七he
highc。ntribu七i。n。fs皿aユenergyユossesandn。preciseエ 。c帥i。n
ofthe・bo七 七〇mofthebandispossibZein七hiscase.Thespec七rum
shows・amainpeakwithmaximuma七 一ユ.2eV.Themainpeakin
七hedensi七yofsta七esassociatedwi七hFed-s七atesshifts七 〇wards
lOWerenergieSrela七iVe七 〇Ewithaddi七ionofGe七 〇Fe.TheF
charlgeofposi七ionsof七he皿ainpeaksin七hespectraofamorphous
Ge-Feaユ ユoysiscompara七iveiysm臼 ユ.lin七heGerichrangeofロc℃ncen七ra七ionnearユyassameasinthecase。fam。rphousGe-Ni
a=L=Loys・Thehalf・widthofmainpeakdecreaseswith'i.ncreasingof
Geeonten七 ●
Fig・3sh。wsthevaユencebandspectrafr。man。rph。usGe-Au
一50一
alloys.Thepho七 〇elec七riccrosssρc七ionofAu.isextremeZyhigh
compared七 〇 七heo七herme七aユs.Thepeaksorigina七edfrom七he
d-sta七e◎fAusitesapPearin七hespec七rumwhenonユy2a七 ・%Au
isaddedtoGe.Thein七ensi七iesof七hespec七rashowninFig.3
arenormalizedfor七heheigh七softhemaximumpeaks七 〇be七he
samefortheal=Lofspec七ra.Thehalfwid七hof七hed-bandof
pureAuisapProxima七ely5.4eVandthe七woseparatedpealcsとre
ユoca七edat-3.2eVand・-6.OeV-Mhecon七ributionofsca七 七ered
e工ec七rons七 〇thespeetrしunisverysmallandhasanegligible
influenceon七hebandshape.Theposi七ionof七hepea}【which
ユieatlowerenergysidedoesno七changeonalloyingwithGe,
りwhi=Letha七a七higherenergysiderema∫kabユyshif七s七 〇wardslower
energieSrela七iVe七 。EF・
Fig.4,5and6showtheposi七ionsofpeakswi七hrespec七
七・EFinG・3d3/2・ ・ree■ectr・ngPectra。btain・dfr。m七h・
measure皿en七forGe-Ni,FeandAuaエ ユ.oys.Thepositionswi七h
respect七 。EFarealm。s七independent。fthec。ncentrati。n。e
aLLOyswithin七heexperimen七alerrOrs.
Thep。 ・iti。n・ 。fNi2P3/2c。 「・ ユ・v・1w抽 「espec七 七。EFin
Ge-NiaエLoysareplo七teda8afunctionofconcentrationinFig.7.
Th・p。 ・itionofNi2P3/2c。 「・1・v・lwith「espec七t・EF・hift・
tolowerenergieswithincreasingGe.AsshowninFig.8,0niy
・man・hif七 ・ 。fF・2P3/2・ 。「・ ユev・ ユar・ 。bS・ 「v・df。 「G・-F・an。y・ ・
Fig・9shows七hec。ncen七 「ati。ndependencesofAu4f7/2and4f5/2
c・rseユevelswi七hrespeet七 ・ ㍉inGe-Auall。ys・Thechange。f
Au4f7/2c。 「eleveli・quitesimila「 七。 七hat。fAu4fS/2・Th・
P。 ・i七i。nsofAu4f5/2and4f7/2co「 ・X・v・lsa「 ・f・undt・und・rg。
considerablechangeswithGeconcentration,・andthepositions
8hift七 〇lowerenergieswiththeadditionofGe,asinthecase
-51一
52
alioys.Ge-Niof
§4Discussien
Thephysicalproper七iesof七he七ransi七ionmetaユaZloys
(IO)on七hebasisofarigidbandwerefirs七discussedbyMo七七
model.ThismodeXassしunes七ha七 七heparen七meta=Lsandaユ ユoys
of七hemhave七hesamedistribu七ionofenergys七ates,and七hese
s七3七esarefiUed七 〇aleve=LapPrepriate七 〇theelectron一 七〇-atom
ra七ioof七hesys七em.Cu-Nialloywhichhas・longbeenconsidered
theprototypea1=Loywhosemagne七icprop琴rtiesareexpXainedby
七herigidbandmodel.However七herecen七measuremen七sofX-ray
ph。 七。e・ect。 。_issi。nbyHufn・r・ta・.(ll)ha。d・ 一 七ra七 ・d
七hatrigidbandmodelisqui七einapPropria七eforal二LCu-Nia=Lloy8。
工nalloysofCu-Ni,Cud-s七a七esareloca七edin七heenergyregion
associa七edwi七hCud-s七a七esinpureCuandsimilarlyNid-s七a七es
areユoca七edin七heenergyregionassOcia七edwithNid-s七a七esin
pureNi.Thedensity。fs七ates。fCu-Nial1。ysb㎝'bemadeup
呵bysuperimposing七hoseofNiandCu..The]refore七hereisindeed
onユyaverylimi七edsbaring。feユectr。nsby七hetw。c。nstituents・
ThedensityofstatesofCu-Nia1■oysa七theFermiユeveldeduced
from七heirda七aisingoodagreementwiththeore七icaユpredic七ions
(12)basedon七hecoheren七po七en七ia=Lapproxima七ion.
[D。k。kuraandKanam。ri(i3)hav。discu。sedtheeユectr。ni。
struc七uureofimpunrityato血sofnon一 七ransi七ionelementsin七ran-
sitionme七alL(AIinNiandPd,etc.)on七hebasisofabini七io
。a・ 。虹ati。nwithth。use。fpseud。-Greenianm。 七h。d.(14)n,he
噛
valenceorbi七aユsofsandpsymme七riesof七heimpuri七ya七 〇皿may
co皿binewi七h七hestpanddorbitalsofsuurroundinghOst.atoms
七〇formbondingandε 滋七ibounding皿olecu■arorbi七aユs.Accordingto
theircaユ ・ula七i。ntthed・nsi七y・fstatesf。r七hesgrp。rbitaL・
一53一
ofAユasimpurity'inNishowsgenera]ユyahumpbeloworin七he
⊥owerhaLfof七he・d-bands;i七isfol■owed七henbyadipwhich
isbroadfor七hes-・orbi七alex七endinginthewholerangeof
the.d-bands.F。rthep-。rbi七aLs,theb。tt。mOft4edipis
si七ua七edaround七he七 〇pof七hed-bands.
Thevaria七ionsofthepositionsofmainpeaksass。cia七ed
withthed・-sta七esofNiandFewi七heoncen七rationarep=Lo七 ・七ed
inFig.■0.Themainpeaksassocia七edwi七hd-s七ates。fNi 、andFeinthedensi七yofs七a七es。famorph。uSGe-NiandGe-Fe
alloysshowtheremarkableshif七 七〇lowerenergieswi七hr6spec七
totheFermileve■wi七haddi七ionofGe七 〇NiandFe。ノThevalenceorbi七alsofGemayco坦binewi七hthes,p,and
dorbi七alsofsurroundingNia七 〇ms七 〇formbondingandan七ibond-・
ingorbitals.AsaresuLt,七hedensi七yofstatesofGeinNi
mayhaveahumpwith'highdensi七ydis七ribu七ionof`electronsnear
phebot七 〇mofthed-bandofNitoformbondings七ate.Therefore
theshif七 〇fmainpeak七 〇lowerenergieswi七haddi七ienofGeas
showninFig6ユOmaysugges七tha七 七hevalenceorbi七alsofGe
combinewi七hthed-orbitalofNi七 〇formbondingorbitaLs,and
this「bondings七atesex七endwi七hinereasingGeconten七,even七uaユ ユy
七〇 七ha七'ofvalenceorbitalsofGe.工 七isinteres七ingthatinthe
hig上}cohcen七rati・onregionover70a七 ・%Ge,whereaユloyssh◎w
semiconduc七ingproper七y,thechangeofposi七ionofpeakis
rela七iveユysrnaコ.lwi七hincreasingconeen七ra七ionOfGe.
Thesa買1eexpla且ationfor七heshif七 〇fmainpeakabove
mentionedmay「beaユsoappropria七e㌻othecaseofGg-Fealloys.
Thepositionsofmainpeaksofd鱒s七a七esofAuaresituated
in七helowenergies,muchlowerthanthoseofNiandFe.工nthe
一54一
pho七 。electr。nemissi◎nspec七ra◎fAu-GeaLl。ys七hemidd■eof
mainpeakassocia七edwi七hd-sta七esofムu皿oves七 〇wardslower
energiesreferred七 〇Ef・ 工七isno七iced七ha七 七he皿ainpeaks
don。 七con七inuouslymergein七 〇theva].encebands七ruc七ureof
Gewithdecreasingconcentra七ionofAuincon七ras七 七〇『thecases
6fNi-GeandFe-Geallgys・ ・
Thesp].it七,ingof七hepeakass6cia七edwi七hthed-band・of
加observedforAu-Gealユoysisbelieved七 〇beaspinorbi七
effec七.Fig.=L2shows七hevaria七ionofthesepara七ionbe七w .een
twopeakswi七hGeconcen七ration.Thesepara七ionbe七weenpeaks
degreaseswi七hincreasingGe60nten七inthea工Loys・Mhisevidence
maybeattribu七ed七 〇themixingofthed-orbi七al幽inAuwiththe
s,P-orbitals・in.Ge.
MheapPar・ntvaria七i。n。fNi2P3/2・F・2P3/2・and"pr。bab・y
。fAu3f5/2qnd4f7/2c。 「・ エ・v・1・with・Ll。yingmaybea七 七「ibu七ed
t。 七hech・nge。fF・ 「miユ ・v・1・inceNi2P3/2andF・2P5/2・ 。「e
⊥evelsユ 』Leinconsiderabiylowerehergieswi七hrespect七 〇Fer血i
energy・Thus,asshowninFig.12,i七isreasonab=Leassumption
七hattheFermilevelsofGe_Ni,Ge曹FeandGe-Aushifttowards
tohigherenergieswi七htheaddi七ionofGe七 〇Ni,FeandAu.
1七isnoticed七ha七 七hechangeof七heFermileve■inGe-Fewi七h
Geconcen七ra七i◎nisqui七esmallco皿paredtoo七heraユ ⊥oys.Fig.
i5・how・tha七the3d5/2co「 ・1・v・1・ 。fG・inGe-Ni・G・-F・and
Ge-Aual⊥ 。ysareshif七edt。wardsユ 。werenergiesbythesame
ad五〇untseorrespondingtoahigherihgoftheFermiユeve=L.There-.
fore,theelee七ronbindingenergiesofc6reユeve=Lsof(}einNi,
FeandAuarehighercomparedtotha七inpureGeanddecrease
wi七hinereasingofGeconcen七ra七ion.
一55一
Th・fa・ 七 七ha七theelec七r・nbinding・n・ 「gy。f3d5/2c。 「e
leve=L◎fGeinNiishighercomparedwi七h七ha七inpuyeGeas
showninFig.ユ3s㎎geststhe七ransferofchargefromGeatoms
t。Nia七 〇ms七 〇formthebondingbetweenGeandNi.Thecharge
flowdue七 〇thebondingbetweenGeandNideereaseswi七hinど
ereasingGeconcen七ration.
Th。m。a、ur。m。n七 。f七h。Mδssbau。ri。 。m。r。hif七f。rAual・ 。y。(15)
indica七es七hatthereisarathersubstan七ialfユowofs4ike
elec七ron・chargeoh七 。Ausi七es。nail。ying,c。nsisten七withthe
view'tha七AuisreXative=Lyelec七ronegative・Thiseviden(}eis
entirelyconsis七en七wi七h七hebehavioturobservedforGe鱒Aua=Lloys
in七hepresen七work.
in
Ourspectraf・r七hepuream。rphOusGeisパxce1↓en七agreemen七
wi七hth。recen七res、 、・t。 。b七ain。d・byエ,y。 七a・.(16)Th。d。n。i七y
ofstatesof七hevalencebandofamorphousGeextendsエ5eV
b・i・wEF・ み・p。in七 ・d。utbyL・y・ 七a・ ・ 七hegr・ssvaria七i・n。f
in七 ・n・i㌣f。r七h・a皿 ・rph。u・G・wi七hrespect七q・nbrgyi・ ・i血lar
七。 七与ec「y・taXlin・G・m・a・mP・dby七h・m・Th・p・ 昨n・ar㍉arised
fromp-likebonding、orbi七alremainsessen七ialユy七heshapeof
crystaUineGearid。 七her七w。s一 ユikepeakssitua七edin⊥ 。wer
energiessideobservedincrystalmergein七 〇asinglebroad
peakofintermediateenergyin七heam。rphouss七a七e.
Finaily,thepho七 。eユectronemissi。nspectra。b七ainedfr。m ロへthepresen七experimen七ist。beheエpfuZf。r。btai叫ng七hekn。wエedge
of・thedensi七yofs七a七es㎞liquidalloys.
1七maybeconsideredtha七 七hespectrafr。 皿 七hevalencebands
foramorphousGe-Ni,Ge-FeandGe-Aua=Lユ.oysin七heme七aユ .lic
regi。naresimiユar七 〇 七h。se'f。rユiquidstates.
一56一
References
(1)
'(2)
13)
(4)
(5)
(6)
(7)
(8)
(9)
(IO)
(u)
(エ2)
K.Tamura,」.Fukushima,H.Endo,S.Minomuura,O.Shimomura,
ε山dK.Asaumi;Proc.of2nd工n七erna七ionaユ.ConferenceQf
七hePropertiesof工 、iquidMetals,Tokyo,1972,p.30=L(Tay=Lor
landFrancis).
G.A.N.ConnelandW.Paul,'J.Non-crys七aユ ユ㎞eSo工id'8-10
(,72)2×5
A.H.Clark,Phys.Rev.ユ54(曾67)750
B.S七ritzherandH.Wuhユ,Proc.ofIL2七hLowTemperatし ロρe
PhysicsConference,Kyo七 〇,197ユ,P.339
G.Bush,H-」.Gun七herodt,H.U.Kunzi,H.A.Meier,A。 七en
BoSchandA.Zimmerma㎜ ・;Proe。of2nd工n七erna七iona工Conference ●ofthePro'per七iesof=LiquidMe七a=Ls.{Dokyo,1972,P●263,
P.277(TaylorandFrancis)
C。S.Fadley.andD.ム.Shirley;?hys.ReV.Le七ters茎 』(168)
980
M。F.Sorokina,O.工.Kユjus㎞ikov,S.A.Ne㎜onov,・V.A.
MrapeznikovandV.G。Zyryanov;PhysicaScripta4('7=L)=Lg5 営Y.Baer,P.F.Heden,J.Hedman,M.Kユasson,C.Nordling
andK.Siegba㎞;PhysicaScr・iptal(,70)55
Y.BaerandG.Bush;Phys.Lett6rs30(t73)280
N.F.Plo七 七,Adv.inPhys.・ ユE(t64)325
S。Hufner,G.K.Wer七hei血,R.Z,.CohenandJ.H.Wernick;
Phys.Rev.Let七ers28(曾72)488 -G.M.S七 〇cks,R.W.Williams,andJ.S.Fauユ ㎞er,Phys.Rev.
工je七ters2至 」(t7L)253andPhys.Rev.昼L(171)4390D
一57一
(13)
(■4)
(15)
(16)
1(.TerakuraandJ.Kanamori,Prog.Theor.Phys.AL6(曾7工)ユOO7
J.Kan㎝ 。ri,K.虫erakura,andK;Yamada,Pr。9』h・ 。r.Phys.
4ユ、e69)ユ426andProg.Theor.Phys.SupP=L.No.46(170>221
R.[i.Cohen,Y.Yafe七a捻dK.W。Wes七,Phys.Rev.互 乏(警71L)ご
2872
L・Ley,S・Kowaユczyk,R・Po=Llak・a尊dD・A・Shi4ey;Phys・Rev・
Let七ers箆(172)ユ088
一58一
Fig.1
Fig.2
Fig.3
Fig.4
Fig.5
Fig.6
Fig.7
Fig.8
Fig.9
Fig.ユO
Fig.=LL
FigureCap七ions
XPSvalencebandspec七raforamorphousGe-Nialloys.
TheFermienergywasde七ermined,withaAusampie,as
thepositionwherethe6sbandisdown七 〇haユfi七s
heigh七.
XPSvalencebandspee七rafo工rε 皿orphousGe脚Feaユloys.
XPSvaユence・bandspec七rafora瓜orphousGe-Aua1■oys.
P。 ・i七i。n。fG・3d3/2・ 。「eelect「 。nlqv・ ユwith「espect
七・Efinam。rph。us・Gq-Nia1エ 。ys・
P。 ・i七i。n・fG・5d3/2c。 「eelec七 「。ni・v・Zwi七 与 「espec七
七・Efinam。rph・usGe-FeaU。ys・
P・si七i。n。fG・5dS/2・ 。「eeユect「 。n1・v・ ユwith「espect
七。Efinam。rph。u・Ge-AUalユ 。ys・t
Chang・wi七hal・ 。ying・fNi ・2P3/2・ ユ・v・iwi七hrespect
toEfinGe-Niε ユユoys●
Changewi七hall。y血9。fthep。 ・i七i。n。fF・2P3/21・v・1
withrespeet七 ・EfinGe-Feall。ys・
Changeswi七hal1。ying。fth・p。 ・i七i。n・ ρfAu4f5/2・nd
4f7/21・v・ ユ・wi七hrespec七t。EfinG・-Aual・L。y・ ・
Positionofthepeakassociatedwi七hd-・sta七esreferred
t。Efin七heXPSvalence-bandspectra。#am。rph。us
Ge-NiandGe-Fe・a).loys 、.
Shift。fFermLユeveユina皿 。rph。usGe-M,Fe,加ali。ys.
一59一
Fi9.12
Fig.i5
Coneen七ra七iondependenceof七hespli七 七ingof七he
valencebandinGe一 加alユ 。ys'.
Changewithaユloyingofelec七ronbindingenergiesof
c。reエevgエs。fGe .inNi・FeandAu・
一60一
ZO一のO一Σ国
ZOにトO国」甲
O」b工巳
〉<αー×
」O
>ト一のZ国トZ
一
●●・
●8●
・.
■
● ●
げ
・■●
●
ロ
リ ・
8鯛Pの ● ・
・ ・ゆ 8
'ご ● ・㌧1
甘 ●'●.
'8●
PURENi・ 幅".●
・'
●8-■・ノ舶の ・●b● ■● ● ●
り ♂●o働凝
。.、 ・'ノ ㌧..● ●
●
りD'●
●■慶 ●
.漣'●ゆ
be-8剛M♂}諮 ● ノノ∵'1
噺ノ ノ1くd● ● ●
・ ●鞠[
'● ● 、 ● ●ロゆ
の',も ●
G¢ 口600tツ ●Ni●."●,=● ● ・
幽 い^吋!∴ ∴=Ge'饗iノ ノ路
.1㍗魂』 噛Pノ'∫ 、
・ ・
G¢'4。 αt?'・Niノ:=・.
墜ジ 惑・ ● ●●
コ コ ワ
:::課~》押!!\ 喬ゾ'蟻 も頓 ψ 、 ・胴
'噸 』。嗣 ψへ働擢 、A囎織吠w論 認
kー
ρ?IE
●
●
・●
●
「
.
●
●●●
●
、
,馬
9
口・
・
●●
.、腕
・、
●
●
=● ●軸
・ 内ゆ」♂Wh》e脚 偽
、 ㌔饅●㍉
馬触 砂マ、
、、
ち馬}㌔
ノリ
、『一 ~絶」の●
つ
、鱒
>hvi,,《 》9
、」ゐ~ い 」
軸《 》 ㌔ド・《 へ
一1QO 一5.O
ENERGY(¢V)
-61一
OD
Fig1
Z9
のの一Σ山
ZOに↑O巴
山6
↑O工巳
〉<にー×
LO
〉↑一のZ山↑≡
Fig.2じ
「
●ー
.
、
℃
、
ノ
●
●
・
●
●
●
●
●
●
●
●
・
●
・
.
●・
●、
●
●
、㌔
●・
■
靹
●・・.
、犠
噌●
・.●
、
●
、㌧
○●
●●
歴.'
.γ
!瀞
へ.
,/ぷ
●
●
●
○
●
●
ψ運伊"戸oo
¢FERUP
薄
調
●●
〃♂、
.㌔却
●
,
轄".σ
●o●}
.轟♂、・●
●
㌔細.〆
〆♂
●
●
9
●
Fノ!
ノ
,輪}'誠冒ノ
CFOツしα08口CG
(納い
1
●
●
●
●
,
ノ.
豆
陀O/OtGO6一¢G
●
●・%
.嘱・
㍗
赫ん
●●
!罰㌦●も馬細ρ'
●
拶♂ぜ}
ー-
●
・
●●
●
●
o●
漣・酬
、
.
.
●編
施・.
●
漕●
●
み●
み●、酒
●㌔
".
"の
(.'
陀ん㌍α05一¢G
●
●
●
●
○!駐●
●●
㌦メψ琳貞
嶋
●●
●
、
。.
顎メ、.
♂
'{。
.ψ{、
●'
陀んゼαO,4一@G
♂鯉の
欄●●1
・、
●
●
.・
.
●
・.
●
●
・
・
.
.
、
㌧卸鵡
(●
儲V㌦型騨
ず¢押
F
曳
%
"
α
ノ
20
~
@
{軸
●
●へ"一漕楴蝉!遡
eFOツtQO1一¢G
●・
.
・
●
●
、
.
.
・・
獅ノノ
凶G
一
s
内
。u
凶ゆ
げmA
評〆●・「
㌔"、蝸横轟」"
c
らの
迦●㌦
の.
●、
価
・働。.A.
v●
fE
一150 一1()O
ENERGY -62一
一5.0
(¢V)
O.O
3∩
卜
O
.●
%
.
.
・.
●
(,
・●
●●
●。.・・
噌
o
●
●・、
.
(
●●
・o
●
u
♂'
、
〃
、●もも
o、・ ●●.貞 一 轟♂軸
剛畝'凶躍
・●
㌧ ㌔ 》一 。ハ!い
●
、襯隅 《)'、
O
呂
.
㌔
ノ
ω・
艶一
■
.●
●●
●●
●■
●●●●■●
'釦マ
、・'、
● ●
'~∴㌧■
写1瑞蹟~~ ●'
2atgl』Au
,貞
、● ●
瀞 ぜ幾w●撃
..轟 ∵●
●●o■
緊口 、
の
"●
磁・.
も●
■ ●●
.・ ・●●
●●●,
●
●
'り■
●
,
●
レ
'●●
P
●
1
・
●
.
●
●
,
6
.●
●●
、
か
、●●
●●
幽
、
..
・'
.●・
.
●
●
●
●
●●
.」,i
l・
・
・
●●
・
.
●
●
・
●
馬.
■
●、.
●
●
.
・
D
♂
,
6
0
6
.・.
●
●
ハ●・o● ●
,・
㍉〆●
!.●,
● ㍉●
Au
凡~♂㌦幽{の
●㌔へ昭)〆
●●
'
'
●
陰Pure
9
●
■脚・
.o
●
●
o
.●
%㌦
●●
○
●
●
●8
.
.躍
Ge・-80atg1。Au
・
●
,
●
●
o
●●
●
・
●●
・
●
(撃尭
・
・
・
●
、、へ、〆
曜
●
●
●
●
・
●・
u 、、.
、㌔
国
。・.
●
●
●
・・
.
●
●・
篤、'「」
、.、
・.騨
Ge-60αtρ ノoAu・.!
'.
♂● ●"~~㌦ ノ φ〆 」
・ 嘔
;.
Ge-30atgノ 。Auノ ・
、、 〆 ・~!執
『 、 、繍 ・.・●.ぜ …
●●
●
●
●●6
■
畢●
●●●●
●
、
鴨'.・
●
・.D㌔・
o
●
㎡
・♂
Ge-10Qtgノ 。Au
Ge一
、
.
●.
ぜ,
ノ
●鵠蜘.
転・・
・●噸
}
。
㌦
.
り●・
●'寡
■,
・
・・●,
・∴
●
・●
舶
■喝
●
,'脚 ・
Am。rρh。usGe、 営
・'へ㌣ が
》 ㍗
●
●
●
'
■
●
・
・
E
O.0一5 .0・・10 .O5.01 鱒
)¢V
(GYER
NE
Z9
のの一Σ田
ZO匡トO山」田6
ト○工氏
〉〈匡ー×
」O
〉↑一のZ山↑≡
Fig4
0
(U
OO
Q)
2
(∠
一
一
(〉Φ)」山〉山」
Qoつ
ZOに↑O山」山
山にOO
一31.0
Ge3d3/2
一一一「露 一蜂 殊
●1
0
N
50
qt.%Ge
鵬
Ge
Fig5
(""'28P
も
と
睾
H-29.o
D30一
ZOにトO山」山
山匡OO
一31.0
Ge3d3/2
⊥舜t
O
角
50
at.9/。Ge
00
e
l
G
65
99
的㎝
eg。研D
O9
曜
o
重←重も…重」…
z/spεeo
0●tε一一
∩○刀m
m「mO,「刀O
Z
ひ σo
σ6乙'-K
話
ス
襲σ8乙一)
9's]
7Fig
、
2P3/2
,N
ρ
墨
、
、φ、、
,
、、
、、
、、
853.0
髄Ge
50qt%Ge
一854.0
855.0
(〉①
)」山〉山」
ZO径トO田」山
山αOO
一856.0
O
M
一
Fig8
(-707.O
も
と
望巴 一70ao
90司η
ZO㏄トQ国」山
田にOO
一710.O
Fe2P3/2
唖+け 一
e
O
F50
qt%Ge
切
Ge
68
Fig,9
(-86.0>①
」国〉山」
Z
O配」-O山」山
ωαOQ
一87.O
嘲88.0
一89.0
oAu4f7ン12→
噂一一 △Au4f5i/2
泰
、
蚤
・、
」㌣
季
番
Y
-
T李
季
率
・、
、、
T冷Y
J八丁
、
、
、
、
、杢、、
、
室\
鱒
一83.0
pt84.O
一85()
一86D
U
O
A
50
αt創。Ge
∞
e
-・G
3ζ○
ー ω● ○
POSr「IONOFPEAK(eV)
ー N● ○
⊥ ● O
㎜ 喋 8
㎝ 0
9 撃 ○ ①
○
○Φ
○
OO
聯
Z T O の
「 Φ - ○ の
コ の 一 〇
「 δ =
(eV)
N 。 O
LEVEL
ド o
FERMI
SH{FT・
OF・
○ ● ○
ビ d
、
、
、 ・ 、
o ;
-ー ○ Φ
● 3 ー ○ の
尋 〉 午 ○ Φ
. ・ 謎
φ 、 ヘ ト
、
マ 、
禍 い い ~ Ψ 幽 、
〉「z
⊂Φ
一.o
㎝ O
9 撃 ○ ①
刈 ド
δ ○
○ の
Fig12
(
も)
のとく山巳
Z山田≧〆ト田
3.0
2.O
ゆー ZO}↑〈¢く住山O
O.00
/堂
王'
''
''
浸'
運ノ
'!
''
'
Ge
50
qt.%Au
100
Au
一72一
Fig.13
2.0
(
〉
Φ
)
壌.0
Qof
「
Ge3d3/2
Ni-Ge
-一 ・一一一Fe-Ge
-一 一 一一Au-Ge
、、
、、
、、
、、
、、
、、 ●、 ●一 ・一 ・一 _こ \、 ●一
1っOI
oM齢
50
qt。 ノ。Ge
100
Ge
Acknowledgement
Theauthorwould 、1卑ketoacknowledgethecontiuing
gUidanceandencouragemen七 、ofProfessorsH.Ende,T.Haseda,
S,Mino㎜raands.工kedag工npreparingthispresentation,the
authorhadmanydiscussionswithhiscolieagues,Mr.」.Fu㎞shima,
Mr.O.ShimomuraandMr.K.Asaumi.Theircontributionstothis
presentationh{≒vebeenverygreatandItakepieasureinacknowユ ー
edgingtheimportantpartplayedbythem.Theauthorwasfavored
tohavetheassistanceofDr.1(.Kishiwhocontributedhisexperi-
mentalski1工andsuggestioninthe・experiment、rbfX-rayphoto-
electronemission●TheauthorthankstoProfessorsM.Tanaka,
M・WatabeandDr.F.Yonezawa,Pr◎fessorJ・Kanamoriand
Dr.K.Terakuraformanyheユpfuldiscussions.Thanksaredueto
胚r→T.Ohtani,Mr.Ode,Dr.H.Okashitaandalsomycolleaguesinour
laboratory一 工n'theend工wou工dlike㌻oexpressmyt・hanksto
Miss.M.Okamotoandmywife.占
一74一