Table Of Content01 Qreuatnary Aylos Blased on IIV-I Siecmonucdrots
Na2S
850
800
ZnS·4Na2S 7 ZnO·4Na2O
p4
750
ZnS·3Na2S e3
p3 700
650
600 5
p2 530 6
e1 4 E 600E1 e
e2
3 650 2
p1
1
700
2ZnS·Na2S
750
800 900
850 1000
ZnS 20 40 60e4 80 ZnO
Mass.%
0 20 40 60 80 100
.21 ERUGIF aSZn(cid:150)N eth fo ecaursf suduiqiL . I.V ,volsaM mor(F .metsysraetnr yisauq OSZn(cid:150)
2
,.al(cid:29)te VINI TniI detisopDe , (cid:27) ).2791 .peD27-2564
n ogie7 Rs ithe en jotcprf oioaN S primary crtsayllin zoatifm rothe lud qiihapse
2
.)297t(cid:29)av e. 1l80oC ((cid:176)laMs101at 70C(cid:176)(cid:150)
01.1 RUMUFIAL(cid:150)RSE(cid:150)SUPSOPCCN(cid:150)TIZPO
ZnS(cid:150)K S(cid:150)Cu S . The hapse dagiram s it ontncsortcued. The CuZKSn uqaternary
2 2 2
acC (cid:176)rd tnsay5ll1izites tn the eo9trat gas lromet fmeIitpts mmi. d suecoon d nhyss i -
nal tsrtcuure twh ithe atltce iapratmeers a = 922 .3ad n c 9 .26m p= 3[1 a = 922 .3–
3 .0ad n c .0] 385 = a– 3 .1d nm 0pcau)(cataulolt aetMuBd ot(cid:29)hmel-y eidnleas. 1l200
cm• 8 g 7.3 3(cid:30) .996)a ad Gvnv 1mroeoil(cid:146)levaS (
CuZKSn as wtboaiend y busdln o(cid:31)atif oCu O + ZO n+ KOCH mitxure in the
2 2 3
Kf OoCcHs esxe% t05wh i) 1encas:Cestmehuocrriito/(sy 1y Z= n 9at 00C (cid:176)5– 0C (cid:176)
3
in tShe C .)au1ot(cid:29)a9t ea96, M. 2uBo0a alhml-ed Gvlnv 10mroeoil(cid:146)levaSw (o (cid:28)
2
11.1 RUMMUFULI(cid:150)IAU(cid:150)SSLSLAGCN(cid:150)TIZPO
nZS(cid:150)K S(cid:150)aG S .T eh aehspgdarai m si tontsnrotc ec.duT ehKZn Ga S uaq -
2 2 3 4 5 21
treanr y dupnomoc siroe mdfi nth si m,tesys hchiwtcraslyl iszei nt ehanol gaxeh
tsrtcuu ert hwit eht caetliapra trseem a 71 5 –1..a d9 0n=331 c 1 70.0 –=1m 1p.09
ysSemts Based on ZnS 11
(a 26 =. –03 078.0a dn (cid:29) (cid:176)3 (cid:176) –505.40i 0n. ehdbo mra)o lhr =07a tsdestngin1ucacl -
tea dlt yisned64. 43g • mc 3(cid:30) r ewhcS(cid:29)te( . a.)l399I n1 redro ot ceuordpKZn Ga S ,
4 5 21
ZGan S e d asvwloi snK rBi nal rom 9 ot:raii 1nuaq sasrlg-tz ,eauplom hchiwas w
2 4
ff oe hdtcwifst ae ush,rw aceny9Ad0 a o.1tftCeae h0trd(cid:176)ea ud mnuacv redueaen sdl
e vomer ot treaw toht hwitteaer d eregwuler iT eh .ylwolsw node dlooc elaspmt eha dn
ut. nehatheea dercdli
21.1 MURIA(cid:150)USSMUFREGLICM(cid:150)NUN(cid:150)TAISZPO
ZnS(cid:150)K S(cid:150)GeS . The hapse dagiram s it ontncsortcued. The K Zn Ge S uqater -
2 2 01 4 4 71
nary pmucood rons ifmed in tC t(cid:176)hts gma. slt encs oird Iymeny sct6rat nelt5us6ayl -
lizes in c ttsibrhe uctcuutre wh ithe atltce iapratmeer a 4 mp7 ., – cau0catlled .1 8= 9
cm• t2 y idnes1g 62. 3(cid:30) , ad ngerney 6 V p ag1e(ah.Pcli3k t(cid:29)ea. l. 20)04K Zn Ge S
01 4 4 71
as ytwsinhezsed fm roa mitx, u.K, 5 )r0e .Zf m5 )n 0olGm(e olm(om , 2.5 S )m(lom
2
ad nS 6 . ()mloTmhe tns ereagere wmeidx, seaeld in an aucatevd eislca itb, uead n
heated at 050C (cid:176)r of4(cid:29). sydaThs iaes d wwololy fblcooig nto rom otpmeerature at
twrn arbo-apnswrolleeyal vretto methawl h ieond vomreas wux (cid:28)cs esxC(cid:176)/Te. he 5h -
t renetcagnualr crtsayls t.hat aere avtiiinr ses
The rofmagls-sig nn ogriein ths iternary tm seyss iwn ohsin giuF3 r.e (1Ikmaoa
aa.md Jnad7)za96ki 1
GeS2
K2S 20 40 60 80 ZnS
R.UE GI3F1 The orglafssm-ig ngron eiin the ZnS(cid:150)K S(cid:150)GeS uqtaeirsnary tsmey. s(Frm o
2 2
, ]apaJaines[eIJn amam. dd nka. Mozaa, kTi, okInyTooMsIn. tnSJt. ncdhUi. ivl. uy s. tr , )9(91,
).796, 1126
21 Qreuatnary Aylos Blased on IIV-I Siecmonucdrots
31.1 RUNFIML(cid:150)TUUSIA(cid:150)SSCN(cid:150)TIZPO
ZnS(cid:150)K S(cid:150)nSS . The hapse dgairam s it ontncsortcued. K nZSn S , K Zn nS S ,
2 2 2 3 8 6 4 5 71
Kad n Zn nS S tm hef o(cid:31)Trt she tm. seysthirouqs atin erfmead n apmurcooe dnrs y
01 4 4 71
crtsayllizes in o twyromlpoh pomd. nsocati(cid:31)i (cid:29) K- nZSn S crtsayllizes in the tri -
2 3 8
licnc itsrtcuure twh ithe atltce iapratmeers a = 6 .6537, – 51.0 b = 96 .9976, – 1.0
,(cid:29)3.0– 9 c.1351= , (cid:176)30.0(cid:29)– (cid:176) 0.459= ad n, (cid:176)30.0(cid:31)– (cid:176) 6.419= caucatlled ; (cid:176)30.0– (cid:176) (cid:28)67.511=
cm• 1 g 1ty i.dnes3 3(cid:30) . ; ad ngerney Vp ag20 3.e (cid:31) K- nZSn S crtsayllizes in tc he ibuc
2 3 8
aprataltctmee er ithe tstrwh itcuure g 1 33.3aty idnescaucatlled 2., 0– 6 2.131= • cm 3(cid:30) ,
. KVad ngerney 5 p age2.5 nZSn S C (cid:176)ts a ltat d mens 5ro4iy aglss4fm s ihacratcer -
2 3 8
.)aV (Frd a2d Kna1natd5 ezis 2i01izy tf 2e.gp oernahe ed by g
K Zn nS S crsytallizes in the tetraognal structure wtih the lattice param -
6 4 5 71
eters a = .4257 31– 0.07 and c = 27 927.– 0.05 pm (Manos et(cid:29)al. 2005)
[ a = .6 9731– 0.2 and c = 89.05 – 0.2 pm (Kanatzidis et(cid:29)al. a99,17 ,] )benergy
ga(cid:27)pVV 2 2[(9.8.47M eaenos et(cid:29)al. 20,] a05)nd calculated dentsiy 29.77 g • cm 3(cid:30)
(Kanatzidis et(cid:29)a.)l.a9 9,1b7
K Zn nS S ts lmegncory tneluat 20C (cid:176)8ad ncrtsayllizes in the c ibuctsrtcuure
01 4 4 71
apatlttctre he aiwh itmeer ag 280.t9 y icaudnecsatlmlpe, d 3 .0– 9923 .1= • cm 3(cid:30) ad n,
V (ahPclit(cid:29)ak e.. 20, 2l02 e).30034(cid:150)1.gp 3ernaey g
(cid:29) K- nZSn S s i rofmed thgh uro the w ols lcooig n) Cm(cid:176)/in1~(f o a t lme
2 3 8
K OC 0n + S f + Zm 7n + Sr0oC to rom t(cid:176)pmoeer. atu)are (Frd a2d Kna1natdzis 2i0
2 3
, erveater wwoHhcneuqig nf othe asme t lmeeld to aromus ohpy aglssK nZSn S ,
2 3 8
ehiapgl-sse ncrttsmeae aiytpt lsonlabtto lilg inzmees ts iw anopn lenuobaelhih g cwni
(cid:31) K- nZSn S . y alssGK nZSn S s wohsa agls stn ortaieinsd 2w0Cat 2(cid:176), y ololb~fa
2 3 8 2 3 8
hasertiglsep c-, snrtpsta.yC(cid:176)iC alg at 4(cid:176)l86n8d meln9in at 3zoati
KZn, mn, SA itxf oure heatteib, d slueca ia iun aum cvseuadaer ens ld wS ad n, S
2
(cid:27)4) 0C(cid:176)/(to h400C (cid:176)r of92(cid:150)96(cid:29)h, ad ntn heeld cootC o (cid:176)2at 5a rate f Co(cid:176)/4h(cid:150)C(cid:176)/h 6
hte wicrtto h-wstsbiaoyaolls f ileoKn y Zn nS S (K, aaMbanats o,ndzis it(cid:29)9e97a. l1
6 4 5 71
t(cid:29)ea. l. 20)50The pt rcoudt usmbe ahesd wtwh iasegsd dedl iytmehrofmamde iad n
drted wi.h aie acntoetd enher
K Zn nS S rofms y bren aotcif oZn ad nn Stwh iK S ux (cid:28)in K:nSZ:n S :S=
01 4 4 71 2 2
2 1ro atiat :050C 3(cid:176)r o:f60(cid:29)1h twh i:the t x1enlcooig nto rom otpmeerature C(cid:176)at /5h
(ahPclik t(cid:29)ea. l20, 30. 20)04The cs esxeux (cid:28)(K S ) as wed vomretwh iH eOMto
2 x
eal vrehte wih-wsiolleyc ibuccrtsay, lshh cwiare y omderlateair e tlsabr of(a w ef
) aed nned to brtoee sd usder inyernda.het atrpesom
41.1 RUMUFIL(cid:150)RE(cid:150)DUPICSNBOP(cid:150)IUCZR
nZS(cid:150)bR S(cid:150)Cu SbRCutncsoTZrSnhe tcuet do. ns idgairahapm se The . uqaterna ry
2 2 2
acrt0C d (cid:176)nsa97yat ltls lititmetzen es he ot rroIagtm. setifmeyn d hss ipmucoos id n -
aptatlsrtrctnaae ithe l ttmecuwerh is ure a ad n8 .593= c[m p.5 9531= a 2 .0– 0 .963=
ad n c .5 = 013– 14 .0m p(auot aMuBohml-elt(cid:29)ea. ] l)12a0d n0caucatlled ty idnes
cm• 34 g .4 3(cid:30) .996)a ad Gvnv 1mroeoil(cid:146)levaS (
bRCuZSn a s tbwoaieny d usdlbf n o(cid:31)atCoiu O + ZO n+ bR OC mitxure in the
2 2 2 3
bRf ocs esxe% t05wh i) 1encasesCt:mehoucrriito/(sy y 1Z= n OC 9at 0 0C (cid:176)5– 0C (cid:176)
2 3
in tShe C .996)a ad Gvnv 1mroeoil(cid:146)levaSw (o (cid:28)
2
ysSemts Based on ZnS 31
51.1 RUMMUFULI(cid:150)IU(cid:150)DLSICNLB(cid:150)AIUGZR
nZS(cid:150)bR S(cid:150)aG S . The hapse dagiram s it ontncsortcued. The ZnbR Ga S uqa -
2 2 3 4 5 21
ternary pmucood ns irofmed in ths itmse, yshh cwicrtsayllizes in the naoagl xhe
tsrtcuure twh ithe atltce iapratmeers a 0 1– 2 = 2.3.340a1d n c .0 5 1– 4= 6 .109m p
(a 1 0= 28 a.d n138– .0 (cid:29) (cid:176) 3– 30.400.9(cid:176) in 0= 7bhemoordh1ral ) tseatsd ingncaucl -
atled ty idn5 es87.3g • cm 3(cid:30) er whcS(t(cid:29)ea. l. )3991Ths ipmucood nas wtboaiend if
ZGna S as wt epkin r BbRat a tpmeerature e vabo0C (cid:176)51f ots itilg nmeipt onr of
2 4
.ylwolwy a1 dn sd tenaold dn cheoo
61.1 RUNFILM(cid:150)TUUSI(cid:150)DICNB(cid:150)IUZR
nZS(cid:150)bR S(cid:150)nSS . The hapse dagiram s it ontncsortcued. The bR nZSn S uqater -
2 2 2 2 6
nary pmucood ns irofmed in thts im. seyt sIcrtsayllizes in the lonicomnc i tsrtcuure
twh ithe atltce iapratmeers a 3 .= – 7862., 0 b 6 .= 5– 34, 14.0 c = .285 7– 2 .0mp,
ad n (cid:31) (cid:176) 2= 1.31– 1(cid:176) 02.0at 3 81K; gerney p ag0.0 3; Vead ncaucatlled ty idnes
cm• 9 g 6.53 3(cid:30) .)ba, (Ka997natdzt(cid:29)ais ei. 1l
The ren aotcif on, SZn, bR , Sad nS at 400C (cid:176)r of4(cid:29)s ydapn uoa lcooig nrate f o
2
C(cid:176)/4h awrdoenfd h-rbofsiroe acgrtnsayf bls Ro nZSn S . ) (Kbaa,natdz99is i7t(cid:29)ea. l1
2 2 6
The pt rcoudt usmbe ahesd wtwh iasegsd dedl iytmehrofmamde iad ndred itwh i
.ae acntoetd enher
71.1 RCNUM(cid:150)IUFZIL(cid:150)RSEE(cid:150)CUPSOPC
ZnS(cid:150)Cs S(cid:150)Cu S . The hapse dagiram s it ontncsortcued. The sCCuZSn uqater -
2 2 2
nary pmucood ns irofmed in ths itm. seyst Its lmeat C (cid:176)589ad ncrtsayllizes in the
ttenaoragl tsrtcuure twh ithe atltce iapratmeers a = 2 .140ad n c = 42 .081m pad n
caucatlled ty idnes8 7.4g • cm 3(cid:30) a ve (cid:146)levaaSd n(Gv mrooil. 996)1sCCuZSn as w
2
tboaiend y busdln o(cid:31)atf ioCu O + ZO n+ sC OC mitxure in the encasesrhy ciitos -
2 2 3
sf Ccs oesxt% e0) wh 5i1tmeCour:/y (Zn = 1 OC at 900C i0(cid:176)C – 5(cid:176)n tShe C .wo (cid:28)
2 3 2
81.1 RUMUCFYNM(cid:150)LII(cid:150)BTUUREZSTI(cid:150)SEC
ZnS(cid:150)Cs SYb(cid:150) S . The phase daigram is ont contsructed. The YbSCsZn quater -
2 2 3 3
crttsahe yt liIln izes tm. seysthis iron fmed s inapmucoord ny tsrtcrouc uibtmre orhoh
twh itathe ltce apiratmeers a , 50.3 – 04.59 = 3 b 2.6 – , 0a.d n725 = 1 c 1 0.0 – 04.4 = 1
g 924 .4ty idnescaucatlled ad n; acef) 010(r ofV e1 62.p aggerney K; 2 – 3 51at(cid:29)m(cid:29)p • cm 3(cid:30)
YbSZsCn. a2(0lt(cid:29). e)ll tMhec0i4 ytsaitns imhezsg ewhe usn d itxsCf uore S , ZS, n,
3 2 3
a. ITd sanCs he e heasatwlepmd to 900C (cid:176)in 8(cid:29)4t hpe, at kths itpmeeratur o96(cid:29)h, re f
aeld to rd com topnmooe.8(cid:29)he4rature in 1
91.1 CNM(cid:150)IURZI(cid:150)USEMCUFREGLIM(cid:150)UNAS
ZnS(cid:150)Cs S(cid:150)GeS sCThe tncsortcued. t ons idagiram hapse The . ZGne S uqaternar y
2 2 2 3 8
pmucood ns irofmed in ths itm. seyt sIcrtsayllizes in the lonicomnc itsrtcuure twh i
tatlhe tcape iratmeers a 0, .24.260– 4 7= b, 09.0– 1 0.8961= cm0p8 , .0– 1 23.261=
41 Qreuatnary Aylos Blased on IIV-I Siecmonucdrots
ad n (cid:31) ; (cid:176) cau0(cid:176)cat– lle067d .t50048 y i6.dnes.g 3 = 97 • cm 3(cid:30) ; aV d ngerney 2 p a3.ge3
(roMrs it(cid:29)e. ao ). l31Ttbo2a0in sC ZGne S , a mitxure f osC , SZn, G, ead nS in
2 3 8 2
the papprroatie rs oatas iwadded to a fused islca itbue de iinse a (cid:31)l-nveentld giroogl
auTcat. xevattahe ds (cid:28)b, ebwn uheoe mese-aeeld(cid:31)aaat , y tihert d watna nelsk n egd
tmehan eenga(cid:150)(cid:28)yxme oto tsart the r. enaotcit Ias wtn heheated roe my tgslnroutnil
m2(cid:29)tibael oics oto Tan d . ownwttluid owa g qar toahe ii~ns aif boenwue olofgl d la l
20a0iCm(cid:176)/r at a rf ~atie o.n
0.21 RUMUFLN(cid:150)UIMSUCN(cid:150)RIE(cid:150)PLZOPAC
nZS(cid:150)CuAlS haptsertwlh ie ns otiuitTldnchsaopago. se srit ohe nlrd as toiciuSem d.
2
tstZrat % aS nhe tncuuenaroare ltt.fmeimrg 0we elhid nomi0 tn i1the 86ernf ao(cid:150)vl -
perature f o0010C (cid:176)e (uhoDnoa. d n)erts4iat TdBhe 971atltce iapratmeers f old osi
ns otuilosicnrease p uto % 1 Cu.lAomSl ad ntn hedecre. ase% t A3 C3u.lAomSl ,
2 2
crttshat atym stetsltetytnarroolsirihe hagl in ttn cfmezus iews d h ius ire hapse w ena
tathe ltcae piratmeers a 2 a.d n33 = 5 c m.9 p20.4 = 1
ccrdoAig nto the data f oibbnos R, a)d nt2he 97kMsiy v1kosatltce (iapratmeers
e hacgnlieny alrtwhiin the ty ienegomo. hnogrieThe yharcpcotlei(cid:150)hapsertle itrans -
rofmn oatitaes % kalce . pZSnat xQy uiatpaproemr5 l.atl6eomnary hapses ere t won
uod inn ttfm.sehys si
t Ias widcatneid Galal() o rd992t1hat t is ie lbipssoto predt cithe ae uvlat hh cwi
the yharcpcotle ihapse in ths itm seysdpapsiears ( x ) ad n T ( x ) r ovibhear ofthe
c c
Zn Cu)A(l S s yaollr ofhh cwia yharcpcotlei(cid:150)hapsertllei-ie kddroersiig ntrains -
2 x (cid:30)1 x 2
e terroxt.vssin fmmn eootatitxutnieisiln woh eitnalod siol si
1.21 RUMUFCNLI(cid:150)(cid:150)RIEU(cid:150)LPSZOPLACG
nZS(cid:150)aCGuS . The hapse dagiram s it ontncsortcued. The CGuaS ternary mco -
2 2
puod ncrtsayllizes in the yharcpcotleit-ype tsrtcuure ( a = 34 5ad n c = 7 04, 1)mp
hh cwis isoed lcto the hapsertleit-ype tsrtcuure (Hahn t(cid:29)ea. . l)559T1he tsrtcuure
ismroialT. fmhnapon atosterrhe tatutilsciie frtly liioatslid ttecs uosihe uncrsoeree s v
in ths itm seysp u% to C4Gu0 aS.lom ad nthe atltce iapratmeer lieny alrdecreases
2
fm ro4 .450m pr ofZS nto 0 .345m pr ofthe ld osin, otuilostncoainig n40 % .lom
CGuaS e lppA. )(8591The yharcpcotlei(cid:150)hapsertle itrorafmn oatnsitaes kalce pat
2
xy ipapromlate% 3 3.lZoS nmr ofthe tos ignanenalig nat 80. 0C(cid:176)The ibtluy ilosf o
CGuaS . C(cid:176)Qiun at% 5erZat S nna9s 7ireu.qa3 .ly ol mhap3seres to e uot d onw3nf
2
ae uvlptrethe do t cie lbipssos it tih) at 9G9a2liaadlcat1n(s eiwo d rdt Itm. setiyhsn s i
at hh cwtiyhe harcpcotle hiapse in thtm seds iypapssiears ( x ) ad n T ( x r or ov) fibhea
c c
Ztnhe )CGua( S yharcpcotleia (cid:150)hh hapcsweritldlerdoetrisr oi-ie rkaifg nns yaol l -
2 x (cid:30)1 x 2
e terroxt.vssin fmmn eootatitxutniiesiln woh eitnalod siiol sis
masTf oln aohe Ctf dadl Guaiout ioSmn i cnreatses hahe rdas enstd nhermatsl a -
2
ibtly if oZS n(Do t(cid:29)e. )lad . nos iotlS9ui92los1in hh cwi3 .% 5af 3 .d on0.lZom1S n
are alcerepd y bCGuaS gbien to depmcsoe oat tpmeeratures hgher ithan btoh d ne
2
bmmee.rs
Ttof he erts te biogotm hansewys iisend fm roZS nad nCGuaS in the H S atom -
2 2
e icglrtn. Ssay))ls (ZSn859e 1lheprppe Asat 90r o1(cid:29)h (0C (cid:176)f CGuaS( ) at x 3 50. = 0
(cid:30)1 x 2 x
ysSemts Based on ZnS 51
ad n3 01.ere 0wwgn roy bmheccail par ovtrapnsrot ig usnodiie nas the trapnsrot
t neag(Do t(cid:29)e. )a. Tl992he 1hace gre nzoas wt epkat 0C (cid:176)58ad nthe wgtroh e nzoat
. T0C(cid:176)he tr1apnsro8at pros cacs weserk.er 1 wort feud oi
2.21 RUMUFCNLI(cid:150)R(cid:150)IE(cid:150)UDPNSZOPIC
nZS(cid:150)CuInS . tus nooiCunld osins otuilosare rofmed ebtn eewbtoh tsosirtcuural
2
CauZd S Innf Sno) cibucanaod agl nx(omdhens ocati(cid:31)i (aP) aray. slt(cid:29)4eu.k g(iu1F re
2
tf trohe n e taoetnaoguirnCagl luTo. lsId osihe Sn)2030 txdfnos em dm neros ocati(cid:31)i
2
% .lom00 1to 1 4fm rZoS nf oomdn ocati(cid:31)ic ibucthe f othhat wie lZ, Sn% .lom9 2to 0
a) d nTt2. bZoahe S9n7itncenours e1sd (cid:31)lribabnos kMsmed (tniy d Rdvf he atkooa s
ee wtubhmaoSt(cid:29)e) a8. l97her1e w(t ias wuod nfthat ZS nad nCuISn rofm a ld osi
2
n otuilosseres itwh ia arbod mibtlsciiy ip agat rom otpmeeratu. reThe asme turs esl
e vbhaen etboaiend in rohcSr t(cid:29)ea. l20) 5(0ad nrohcSr gaagaer ner n. d 2n0)5(0WW
t(cid:29)ea. l20) 5(0tboaiend roe macucrate ironfmn oatit abuothe ohatp-se wd le(cid:31)in ths i
tmse, yshere wc ibucad nttenaoragl meid xcrtsayls xtc. osiet Ias wwn ohsthat ths i
d le(cid:31)ers vcoat rom otpmeerature the naotl iipmcsoore ag0 n1.0(cid:26) x (cid:26) 1 4.0r ofthe
)2(Z sSnyaoll CuI(Sn ) ais dcatnweit d I. 4at, .d dnghese atdeuaiiuFa d n 1lrie re cn
x 2 (cid:30)1 x
hapsye harcpcotle tihe hh cwiat ae uvlthe predt cito e lbipssos it ithat ) 992Ga1lal(o dr
in ths itm seysdpapsiears ( x ) ad n T ( x ) r ovibhear ofthe Zn )CuI(n S s yaollr of
c c 2 x (cid:30)1 x 2
hh cwia yharcpcotlei(cid:150)hapsertllei-ie kddroersiig ntn ortaiinse twh ivitxtnesereminal
roxt.ssin fmn eootatuiillod sosi
t, °C
1200
1000
800
600
CuInS2 20 40 60 80 ZnS
FIGURE .14 Phase diagram of the ZnS(cid:150)CuInS system. (From Parasyu. kVe,t (cid:29)O.al.,
2
oCmpd s.yollA .J ,.al(cid:29)te .G ,rgeanW ;0230 ,75 ,)2(cid:150)1(843 , htwoGrrCst y ..J ).0250 ,653 ,3(cid:150))(3482 ,
61 Qreuatnary Aylos Blased on IIV-I Siecmonucdrots
. al(cid:29)tero rhcS( reul s(cid:146)adrgeV wollof sraetpaerm ecttail eth ,snogier esahpe-lgins ethI n
e sahp w ueet trhftizo ecnednpee dnottiarnecno cT e.h)052 r0egna Wrdo arnhcS ,0520
.)8791 .al(cid:29)te eewathubmoS(a letiy nrmifor notiaivedam lls sah sraetpaer mecttail
ccrdoAig nto the data f oaPrthØ t(cid:29)e, )a. l9961the (CuZn ISn uqaternary mco -
2 4
tyhapseprtle e tisrf otcuc uibrue ccrttsahe yt liIln izes tm. seysthis iron fmed s ipuod n
twh ithe atltce iapratmeer a .5 – .5 0 mp7, = t ub45ths ipmucood ncan be e nof othe
.nsotiipmn csoootuillod sosi
Zne aslpmder woP )CuI(n S the f otrlesn d-aotatcosie ipray epere brewd s yaol l
2 x (cid:30)1 x 2
ts nmeeleat 0C (cid:176)59ad nanenaeld twh ilcooig nrates ebtn eewC(cid:176)/2h ad nC(cid:176)/24h in
trohhe tcSnein otr re rt(cid:29)aiee igpm(acsdooer n. l2ro, w0hagcSer n5or . 020aP)d 5n0W
es aslpmtwh i4 .0< x < 0 .ere 1wao lspraepred y bthe direnaotcl ifrezieg ntmeohd
rohcSr (t(cid:29)ea. l. 20)50The s yaere neolgwilozmeohd at 900C (cid:176)r of240(cid:29)h r oat 680C (cid:176)
ty 6the0an heat d n0C(cid:176), h 05a0(cid:29)r onere fenaweld ty he[20a) 5. 0lt(cid:29)eager n(Wh 20(cid:29)1r of
to min 5(cid:29)1fm ro0C 3(cid:176)310C(cid:176)(cid:150)13at ; )2030a. (laPt(cid:29)eratayer swuk d lcoin hecnd euqere w
TCu. he Z]n)8971a. lt(cid:29)eee wtubhmaoS(tnoh m1 ISn tbtoaahe y s iwbpmeuncood d n
2 4
.6)0at 0C9(cid:176)t9(cid:150)m6ns meetl8imhe 0he(ef tca1xcaPofiaheu0C l at(cid:176)m r. roirlg e t(cid:29)enthØ
uen ,XRD ,)ATD( sisylaan larmeht laitnereffid hguohtr detagitsevni saw metsys sThi -
X DE htiw MTEHR dan ,noitaidar nortohrcnys gnisu noitcarffid ,noitcarffid redwop nort
.)5002 .la(cid:29)te rengaW ,5002 rengaW dan rrohcS ,5002 .la(cid:29)te rrohcS ,3002 .la(cid:29)te kuysaarP(
3.21 RUNFOL(cid:150)CUCINS(cid:150)REIL(cid:150)PISZOPC
ZnS(cid:150)Cu S(cid:150)iSS Tdhtapn. csoagse ihe t rornas itcueTm Cd. uhe SiZSn uqater nary
2 2 2 4
er h(cid:228)cSf(C (cid:176)5– C (cid:176)321gti1ns conat rly rtoment eluIfmetimt. ss pemid ucn ood hynss i
ad nthe sciN7) 971accrdoig n[to the data f oao Yt(cid:29)ea. l, 7)891(t idepmcsooes at
crtatssapatd alrnyrot] 0tCc(cid:176)c rle ttatcihe iulbwithe h miumoirhon h1zre es – 20C (cid:176)6 -
teers , 10.0– a4 7.347= ad n, b10.0– 1 60.40= Atn ekiad nus mso(Rm p1 0.0c– 94 .316=
[) 1120 a 4, 47= b a, d n936= c; 7)971d loah Wcd nhiceSl(m p3 16= a 4, 07= b 6= 4, 0
ad n c; 7)961a. t(cid:29)lethe (scim Np608 = a , .5347= b a6d , n.936= cer h(cid:228)cSf(m p.5 316=
; 7)971, 4971the sciNad n a, 1.0– 6 .347= bad n, 1.0– 8 .936= ao c(Ym p2 .0– 7 .316=
Aatn ed us nkimso96(4 R.3[97 .pxer3eateis catud n ocniatnmeil; aldnesil ]7)891a. t(cid:29)le
g 94 .3ad n] )1120 • cm 3(cid:30) p aggerney ad n; ylepresevtci, E [V e25 .3= E V e2 .0– 0.4 3=
g g
.7)97d 1loh acd WhinceSl] (7)89t(cid:29)aao e. 1l(Y
o Ttboain Cu SiZSn , tmehocriitc osirs oatif othe tns meeleere wheated uder n
2 4
a uaum cv0to 010C (cid:176)in 2(cid:29)1h, d lheat ths itpmeeratu8(cid:29)r6e r oh, f1ad ntn heeld cooat
ben ee vcrhatsaye iglls snts I. )1120Atn ekiad ntus pmemersoat(rom uRore Ct(cid:176)o /.5h 7
y br o) 1praep1hrgeva tah-pimAd 2eitus 0erd mn enatkisot(lystd-us satinoRsie hesre
the rohtinzoal grt adnefirezieg n(atMushta it(cid:29)ea. l20) my 5he0r occabpiar ol tvrans -
prot ig usnI as the trapnsrot t neagthe (sciN, t(cid:29)eer h(cid:228)cSaf7. l96ad n, 14the sci9N71
2
.7)89t(cid:29)aao e. 1l, Y797d 1loh acd WhinceSl
4.21 CNR(cid:150)RIE(cid:150)UPMZOPUFRECGLIM(cid:150)UNAS
ZnS(cid:150)Cu GeS . hPase dagiram f oths itm seyss iwn ohsin giuFre .5 1 (aPraysuk
2 3
t(cid:29)ea. l. 20)50The pertetic ciipt ons i% at . Z3 Sn.4loTmhe thermal eftcs ef0C (cid:176)at 18
that d ucolcrod prnesoto the hapse tn ortaiinsf oCu ZGneS fm rottenaoragl to
2 4
ysSemts Based on ZnS 71
t, °C
1086
1000 1030
969
800
810
4
S
e
G
600 n
Z
2
u
C
400
Cu2GeS3 20 40 60 80 ZnS
RUE GIF.51 Phase daigram f othe ZnS(cid:150)Cu GeS tsmey. s(Frm oaP. raysuk, Vet(cid:29).Oa, .l
2 3
. AllJoys Compd. ), 20.5, 805)2(cid:150)1(97, 3
cordoitpt ioaeu9nC Te(cid:176)senattreb96c coets d. ihe rse vt orronc ierte cbtumorhuowhre
tCf uhe otre ay igenengomToh. Zhe S% n.loma6 d n ZGneS nas lid ator siw d nhe ro
2 4
.%ibtluy iils tn tesotss lp.ms inenhhe caoolon 2 m
There s ie noiternmedatie uqaternary hapse Cu ZGneS in ttm thsets lys ihat sme
2 4
ginconry tnelu20C (cid:176)at 1C (cid:176)0681(1atMu[shta it(cid:29)ea. lC 0(cid:176); 720)501– 1C (cid:176)5er h(cid:228)cSf(
ad nthe sciN, 7)971depmcsooes at 20C (cid:176)6– 0C (cid:176)1ao (Yt(cid:29)ea, . l]7)89a1d ncrtsayl -
lizes in the ttenaoragl tsrtcuure twh ithe atltce iapratmeers a = 7 21.345– 0.009
ad n c = 90 .0501– 02 .0m p[ a = 1 .345ad n c = . 09412 m per h(cid:228)cSf(ad nthe sciN
; 7)971 a = 9 2.45ad n c = 7 .0841m p(aDs t(cid:29)ea. l] )3120ad ncaucatlled ty idnes
0.1 – 0002 g 653.4 • cm 3(cid:30) (aPraysut(cid:29)ak e.. 20l)50
dnu s Toahpnicm oo ectazsllci alset uirr ttchcrynbiusmi w e eoceththhtitraorltoh
sreteaamrp a , 63 .–.00 5 =7 b ,d 4an6 .–.0 7 =64 c) 789 (cid:29) ot.aeal1 92m .–pY(.081 =6
[a ,0 5=7 b = ,86 4dan c ;)7 79d lhoc1 diane 8hlWc mSp1 (=6 a , 7 4=7 b , =5d an64
;)7691 .al(cid:29)te ehcstci(N mp 216 = a ,4.057 = b dan ,4.764 = e hcstiN dan re(cid:228)fhccS( 5.816 =
nerimepxe dan noitalucalc ;])0891 regnisnualG dan neuG ,9791 .al(cid:29)te neuG ,7791 ,4791 -
7g 3. d54an3. s4eitisn teald • mc 3(cid:30) 4g 3.4 )[779 d1lo dhWanciehlcS ( • mc 3(cid:30) (cid:29). tanleeuG (
pag ygrene dan ;ylevitcepser ,])0891 regnisnualG dan neuG ,9791 E. la(cid:29)te ijusT( Ve 2.2 =
g
[ )0102 ;E)7891 .la(cid:29)te oaY( Ve 2.0 – 40.2 = .])779E1 dloW dan hcielhcS( Ve 1.2 =
g g
The tsrtcuures f oo twyromlpohps f oCu ZGneS e vhaben etdeermiend y b
2 4
. T6)8he 9o(cid:31)oMde rt f si1aotd m nhed Ws il(a eht(cid:31)tetenaioryragol mlpoh ptwh ithe
atltce iapratmeers a = 7 25ad n c 4 5= 0m. p1The sed ncoyromlpoh phas a odupse -
bhemoordhral tsrtcuure ad ncan be descrbeid in terms f oty lrpipre imvtliicl etwh i
ronaogtl aes ohx a 66 = 3, 0 b , ad n55 = 6 c m.2 p5 = 7
esueacBt ehg yrene enetbewttree -seika dntasntetn-yip etsrtcuu ser simasl, l
tbo htsrtcuu serac ntxsiocei nize t dssyeehn sflaspomCu ZGneS . dgrioccn Aotte h
2 4
81 Qreuatnary Aylos Blased on IIV-I Siecmonucdrots
ahctreracized si dupnomocth si fotsrtcuu erttrete-syeip ke ,snotauilcacl selrpp-iicn(cid:31)trs
ybt ehan olttegratsrtcuu ert hwit eht caetliapra rtseem a 4. 62=a dn5 c 3.084 m =p1
[a 8a d.n53 =5 naeCd hn V( 3ec4 p2a.g yrg]ea nden)0b1(cid:29) t an.e20eChl m (1p0.64 =1
,)vdin raR3aa dn120tasntetn-yip etsrtcuu er siahctreracize d aosl ybt ehanol ttegra
tsrtcuu ert hwit eht caetliapra trseem a = 82.35a dn c 1. =4 mp071[ a 3. =33ad 5n
. )3120vdin raRaa dn neCh( Ve 412. pagg yrenea dn ])0b120c a.l(cid:29)te neCh( mp 1.4071 =
dgrioccnA ott eh notauilcacl fo neCh ,(cid:29)te)0bw ua.e rdl1tetv-rzeidi20ytly( pspeof o
t treceseiikbmroohrtoht(srtcuu ert hwit eht caetliapra trseem a =,4.457 b , 9. =156
a dn c =6 )2.2m6pa dn ctiasbmnr totoenhsrrtoithcuu er(t hwit eht caetliapratrs eem
a ,3.057 = ba d,n7.456 = cC urof txsie duloc )mp 62.26 = ZGneS .dupnomoc
2 4
uC SeGnZ gIni ssnuoit careorpa alcvmie hy edtehctab nibsa ow r t o pseastahtnr
2 4 2
,n euG7 7d 9hlco 1i da,en4hlcWS r7ee9 h, c(cid:228)fdsht an1echiS (cid:29)cNt7tstne e6i.9(gNala1
a (cid:29)) rtat.io5v0ea2uhl0is t,aM789 (cid:29) ot.aea1l ,Y089 re1gnisnua nld eanG,uG979(cid:29) t.ea1l
. )3102 .al(cid:29)te saD ,5020 .al(cid:29)te tauhista(M dothem gnizeefr tnediagr talnorzioh ro alcreitv
etam tagrsnit eth :noitcaer ettas-dlios yb dezisethnys saw dnuopmoc sthi fo redwop eTh -
uC ,SnZ salri SeG dan ,S SeG dan SnZ fo tnuoam ssecxe %51 thiw demxi erew i jus(T
2 2 2
d etaetr-ta e dhoanuca enivb etuluauo rpzdantiqemal essa ewtuemr.Txih)01 0.2(cid:29)tale
(cid:29)0 .r hoCuC(cid:176)10(cid:150)fC5(cid:176)06 5ta5 SeGnZ e turarepmet- w sCa de(cid:176) zei0ottwha5sle6 thnys
2 4
.dn(cid:31)ermoc ton saw esahp eturarepmet-hghi etyp-etwur iztA .etyp ettannis fo esahp
atgetesd ivinas wtm seytsaah4d un0dns ierh 0e r5at ena0wC (cid:176)e0(cid:29)ig ld ns yaTolhe l
At, Xh, aERgM (d Sh DTuranoPDraysut(cid:29)ak e.. 20l)50
ZnS(cid:150)Cu S(cid:150)GeS . The tosihermal sen otcif oths itm seysat 400C (cid:176)s iwn ohsin
2 2
6 g(.aiuFPre ray1suk t(cid:29)ea. . l20Tere s )a5he 0wyanolenaleld at 400C (cid:176)udrig 0n50(cid:29). h
atgetesAd ti, Xhva, aERT.s igMtd Sh DTum wrnnosehDys si
GeS
2
Cu GeS
2 3
Cu4GeS4 Cu2ZnGeS4
Cu GeS
8 6
Cu S 20 40 60 80 ZnS
2
6.1 ERUGIF S(cid:150)nZuC eth fo noitces ralmethosI S(cid:150)SeG . V.O y,uksaarP mor(F .C0(cid:176)40 ta metsys
2 2
,.al(cid:29)te dpmo.C syollA .J ).5020 ,58 ,)2(cid:150)1(793 ,
