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