Chng 4. Mt s tnh cht vt l quan trng ca vt liu v c GS.

Phm Vn Tng
Vt liu v c NXB i hc quc gia H Ni 2007. Tr 123 190. T kho: Tnh cht vt l ca vt liu v c, dn in, dn nhit, dn electron, pht quang, laze. Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

M c l c
Chng 4 MT S TNH CHT VT L QUAN TRNG CA VT LIU V C . 2 4.1 Nhm tnh cht in ................................................................................................... 2 4.1.1 Cht dn in ion, cht in li rn...................................................................... 2 4.1.2 Cht dn electron.............................................................................................. 22 4.1.3 Cc tnh cht in khc .................................................................................... 30 4.2 Nhm tnh cht t ..................................................................................................... 42 4.2.1 Phn l thuyt.................................................................................................... 43 4.2.2 V d mt s vt liu t, cu trc v tnh cht.................................................. 48 4.3 Cc tnh cht quang, vt liu pht quang v laze ..................................................... 57 4.3.1 S pht quang v cht pht quang.................................................................... 57 4.3.2 Laze .................................................................................................................. 63

Chng 4 MT S TNH CHT VT L QUAN TRNG CA VT LIU V C

C rt nhiu tnh cht vt l lin quan n vic s dng vt liu v c, trong chng ny ch gii thiu nhng nt c bn ca ba nhm tnh cht quan trng nht. l nhm tnh cht lin quan n kh nng dn in, lin quan n t tnh v lin quan n s pht quang.

4.1

Nhm tnh cht in

Da vo kh nng dn in ngi ta phn thnh: cht dn in, cht cch in v cht bn dn in. Da vo phn t mang in trong qu trnh dn in ngi ta phn thnh: cht dn in ion (i vi cht rn th gi l cht in li rn) v cht dn in electron. Ngoi ra da vo mi tng quan gia c v in cn c cht p in, mi tng quan gia nhit v in cn c cht ho in, hin tng nhit in, da vo kh nng phn cc ca cc t bo mng li cn c loi cht xenhet in.

4.1.1 Cht dn in ion, cht in li rn

Tnh dn in ca cc vt th rn c thc hin bng s dch chuyn electron hoc ion trong khong cch ln. Thng thng, ch mt trong cc phn t mang in chim u th, nhng cng c mt s vt liu v c th hin ng thi dn in ion v dn in electron. c trng cho kh nng dn in ca vt liu rn ngi ta dng khi nim dn in ring , tc l dn in ca mt th tch cht rn c tit din cng nh chiu di bng mt n v. dn in ring thng c biu din bng m1. cm1; m1.m1, CM.m1 (CM c l cimen c gi tr bng 1 m1). dn in ring ca mt vt bt k khng ph thuc vo bn cht cht mang in v c xc nh bng phng trnh. =

n e
i i i

(33)

ni l nng cht mang in tch loi i, ei v i l in tch v linh ng ca cht mang in tch . i vi electron v ion c in tch 1 th e = 1,6.1019C (in tch electron). Bng 31 gii thiu gi tr dn in ring ca mt s loi vt liu Thng thng, dn in ph thuc vo nhit , khi tng nhit th dn in tng (tr kim loi). Vi kim loi th ngc li, dn in c gi tr cc i khi nhit thp, c mt s kim loi gn khng tuyt i c tnh siu dn.

.
Bng 31 Gi tr dn in ring ca mt s loi vt liu Phn t dn in Ion Vt liu Tinh th ion Cht in li rn Cht in li mnh (lng) Kim loi Bn dn Cch in (m1. cm1) <1018104 103101 103101 10105 105102 <1012

Electron

Trong iu kin thng thng, a s cht rn c lin kt ion v lin kt cng ho tr (cc oxit, halogenua) th s dch chuyn ca cc ion l khng ng k. Cc ion thng c phn b ti cc nt xc nh ca mng li, s chuyn ch ca chng ch xy ra khi c mt khuyt tt trong mng tinh th. Ch nhit cao, khi m nng khuyt tt ln, cc ion c nng lng nhit ng k th mi o c gi tr ca dn in. V d dn in ca NaCl gn 800oC (ngha l gn nhit nng chy ca NaCl) bng 103 m1.cm1, cn nhit phng NaCl nguyn cht l cht cch in. Tuy nhin, c mt nhm cht rn, trong cc ion ca mt phn mng c th chuyn ng vi tc kh nhanh. l cht dn in ion, cht dn in siu ion. dn in ca cc vt liu ny l do tnh cht c bit ca cu trc tinh th ca chng, chnh l s c mt cc khe rnh trong mng li. Gi tr dn in ca vt liu ny cng tng ng vi dn in ca dung dch cc cht in li mnh. V d: dn in ca -Al2O3 25oC l do s dch chuyn ca ion Na+ v bng 103 m1.cm1. Hin nay ngi ta ch nhiu n vic nghin cu tnh cht ca cc cht in li rn, tm kim cc cht in li rn mi v m rng lnh vc s dng chng. Trc ht, chng ta kho st cc hp cht bc hai nh NaCl, AgCl. Tuy rng vic nghin cu tnh dn in ca cc tinh th ny thng c xt trong cc gio trnh vt l cht rn, nhng s hiu bit cc hin tng lin quan n n cng rt cn thit i vi lnh vc ho hc vt liu v c. 4.1.1.1 S khuch tn ion trong cc tinh th in hnh Xt vi v d c th: a. V d tinh th NaCl Thng thng cation linh ng hn anion. Gi s tinh th c cha mt nt trng Na+, di tc dng ca in trng, ion Na+ dch li l trng bn cnh, dng li v li l trng pha sau. Ion Na+ th hai dch n l trng mi iu ny cho ta thy hin tng dch chuyn l trng cation. Trong tinh th NaCl cng c l trng anion nhng linh ng ca chng b hn nhiu. Gi tr dn in ion ca tinh th NaCl l do s c mt ca l trng cation. S l trng cation li ph thuc vo nguyn cht ho hc v k thut ch ho nhit ca mu NaCl. C hai cch lm tng s l trng cation. Khi t nng tinh th s l trng cn bng nhit ng ca tinh th nguyn cht tng ln theo cp s lu tha (Nv = N.const.eH/2RT). Trong khi vic a tp cht l c ho tr khc cng lm pht sinh ra l trng. V d thm mt t MnCl2 to thnh dung dch rn Na1-2xMnxVxCl. Ngha l mi ion Mn2+ s lm xut hin mt l trng Na+. Loi l trng ny gi l l trng tp cht.

Cl Na Cl Na Cl

Na Cl Na Cl Na

Cl Na Cl

Na Cl
1

Cl
2

Na Cl Na Cl Na

Na Cl Na Cl

Na Cl

Cl

Na

Hnh 132 S dch chuyn l trng cation trong tinh th NaCl

nhit thp, nng l trng c ngun gc nhit cn rt b m ch yu l l trng tp cht. Do dn in tp cht l quyt nh. Khi nhit tng c th chuyn dn tp cht n dn ring. dn in ion ph thuc vo nhit theo phng trnh Arrenius. = A.e E/RT (34) E l nng lng hot ho, R l hng s kh, T l nhit tuyt i. Gi tr A bao gm nhiu hng s, trong c tn s dao ng ca cc ion linh ng. S ph thuc ca ln() vo 1/T l ng thng c h s gc l E/R. vng nhit thp th s l trng do nng tp cht quyt nh. ng vi mt nng tp cht c mt gi tr s l trng nht nh. Bi vy, trn hnh 133 vng dn tp cht c nhng ng song song ng vi tng nng tp cht. Trong khu vc ny ph thuc vo T l do s ph thuc ca linh ng cation vo nhit quyt nh. = o.eEdc/RT (35) Edc l nng lng hot ho ca s dch chuyn l trng cation.
lg
3 2 1

1/T
Hnh 133 S ph thuc dn ion ca NaCl vo nhit . Nhng ng song song trong khu vc tp cht ng vi tng nng khc nhau ca tp cht 1 - Tng lng tp cht; 2 - dn tp cht Edc; 3 - dn ring Edc + Eht/2

Cl
1

Na Na

Cl

Cl Na

2,82A

Cl

Hnh 134 Con ng dch chuyn ca ion Na+ trong tinh th NaCl

hiu c bn cht ca nng lng hot ho dch chuyn, chng ta hy kho st cc con ng c th cho php ion Na+ chuyn t nt mng sang l trng cnh . Hnh 134 biu din mt mnh ca cu trc tinh th NaCl (1/8 t bo) c cha mt l trng Na+. Mt trong ba ion Na+ c th nhy vo l trng . S nhy trc tip (theo ng chm chm) khng th xy ra c, v rng cc ion Cl (1) v (2) nu nh khng hon ton tip xc vi nhau th cng rt gn nhau, khng cho php Na+ lt qua c. Bi vy Na+ phi nhy qua v tr tm ca t din gm bn ion Cl (1,2,3,4). Mun th Na+ phi i qua hai ca s tam gic clo (1,2,3) v (1,2,4). Cn phi tnh ton kch thc cc ca s ny hnh dung c mc kh khn ca vic chuyn dch ion Na+. Thng s t bo mng NaCl l a = 5,64 di lin kt Na-Cl bng a/2 = 2,82 bn knh ion Na+ = 0,95, ca Cl l 1,85. di Na-Cl t cc bn knh c gi tr khong 2,82.
3

r'
1

30 o 2

Hnh 135 + Ca s tam gic m ion Na phi i qua trong tinh , th NaCl, r bn knh ca s, cc vng trn 1, 2, 3 l ion Cl c bn knh x/2

Trong cu trc gi ghm chc c nh NaCl th cc anion hoc tip xc vi nhau, hoc rt gn nhau. Cc ion 1, 2, 3 to thnh mt mnh ca lp xp kht v khong cch Cl(1) v
a 2 a 2 Cl(2) cng nh Cl(1) v Cl(3) bng: + = 3,99. Ngha l 0,3 ln hn 2rCl , 2 2 do cc ion Cl cnh nhau khng tip xc vi nhau.
1/ 2

Bn knh ca s r trong tam gic Cl(1), Cl(2), Cl(3) c th xc nh nh sau: cos(30o) = (rCl+r)=
x/2 1,995 = y rCl + r'

1,995 =2,30 cos 30 0

Nu rCl = 1,85 th r=0,45. Cng tng t nh vy c th xc nh bn knh r ca l trng ti tm lp phng. di ng cho khi lp phng bng (2rCl + 2r), ngha l:
a 2 a 2 a 2 2(rCl+r) = + + 2 2 2
1/ 2

= 4,88

T r= 0,59 Nh vy, s chuyn dch Na+ trong mng li NaCl rt kh khn. Ban u Na+ phi len qua mt l tam gic nh vi bn knh ca vng l 0,45, sau ri vo l trng t din c bn knh khi cu trng l 0,59. Thi gian Na+ lu li y rt ngn, t gi v tr Na+ phi len qua l tam gic th hai vi r= 0,45 ri mi ri vo l bt din. S tnh ton trn y ch l l tng v rng gn v tr l trng (khuyt tt) th no cng c sai lch v cu trc (ni rng ra) lm cho gi tr cc khong cch hi khc, nhng d sao s tnh ton cng cho thy vic chuyn dch Na+ phi vt qua mt hng ro nng lng hot ho ng k. Nh vy trong khu vc tp cht, dn ph thuc vo nng l trng, vo linh ng v c biu din bng h thc:
= n.e.o.eEht/2RT

(36)

nhit cao, trong khu vc dn in ring th nng l trng c ngun gc nhit vt nng l trng do tp cht. By gi Nv ph thuc vo nhit theo phng trnh Arrenius: Nv = N.const.eEht/2RT (37)

Phng trnh ny c dng ging phng trnh (24) trong Eht l nng lng hot ho ca s hnh thnh mt mol l trng cation, ngha l 1/2 nng lng cn thit hnh thnh mt mol khuyt tt Stki. linh ng ca l trng tnh theo phng trnh (35). Nh vy, v ton b dn in trong khu vc dn in ring tun theo phng trnh:
= N.const.e.o.eEdc/RT.o.eEht/2RT = A.e(Edc+Eht/2)/RT

(38) (39)

Hnh 133 biu din s ph thuc dn in ca tinh th NaCl cc mc nguyn cht khc nhau. Mt dy cc ng song song trong vng tp cht l dn ng vi tng nng tp cht nht nh, trong khi ch c mt ng duy nht ng vi khu vc dn ring. iu ny chng t dn ring khng ph thuc vo tp cht. Thc ra iu ch ng vi trng hp nng tp cht rt b (nh hn 1%), mc tp cht nh vy s khng nh hng n Edc l trng cation. lch ca s ph thuc dn in ring ln hn lch ca dn in tp cht. Xc nh hai gi tr lch cho php tnh c Edc v Eht. Nhng s liu thu c i vi tinh th NaCl (hnh 136) cho thy s ph thuc ca dn in vo nng tp cht nh trn s hnh 133 ch l l tng. Trong thc t c phn phc tp hn. Cc phn I v II ng vi cc vng dn ring v vng tp cht trong s n gin (hnh 133). ng chm chm l ng ngoi suy ca ng I v ng II cho thy s sai lch gia l thuyt v thc nghim. S xut hin phn I gn nhit nng chy (Tnc = 802oC) c th do hai nguyn nhn:

Nguyn nhn th nht do l trng anion tr nn linh ng hn nn thm mt phn gp vo . Nguyn nhn th hai l khi tng nng l trng nhit cao th tng tc bai-Hucken gia cc l trng cation v l trng anion cng th hin r rt. iu ny cng tng t nh tng tc gia cc ion trong dung dch. Lc pht sinh ra lc ht lm b tr mt phn nng lng to thnh l trng. Do s hnh thnh l trng tr nn d hn v nng ca n tng ln lm tng dn. Vn cn li cha r l i vi NaCl th nguyn nhn no l chnh.
Lg(m 1.cm 1.K) I'
1 2 3 4 5

I II III -1 1,4 1,6 1000/T (K )

1,2

Hnh 136 S ph thuc dn in ion trong tinh th NaCl nguyn cht

Phn III ( di 390oC) l sai lch m so vi ng l tng vng tp cht. iu ny lin quan ti s hnh thnh phc hp khuyt tt nh cp l trng cation-l trng anion hoc l trng cation v cation tp cht. Phc hp khuyt tt pht sinh khi tng tc gia cc khuyt tt n gin cnh nhau. Tng tc gia cc khuyt tt cnh nhau y khc vi tng tc bai-Hucken ni trn, lin quan n vic gi tnh trung ho in. cho l trng cation trong phc hp c th chuyn ng cn cung cp cho n mt nng lng phn li phc hp, do nng lng hot ho trn phn III ln hn Edc phn II.
Bng 32 dn in ca tinh th NaCl Qu trnh Dch chuyn ion Na+ (Edc) Dch chuyn ion Cl To cp Stki Phn li cp l trng Phn li cp l trng cation-ion Mn2+ Nng lng hot ho (eV) 0,65 0,85 0,90 1,10 2,18 2,38 Khong 1,3 0,27 0,50

Mc du dn ca tinh th NaCl c nhiu tc gi nghin cu nhiu phng th nghim khc nhau nhng cc gi tr thu c cng khng ph hp nhau. Gi tr Edc ca Na+ nm trong khong 0,65 0,85 eV (60 80 kJ/mol).

Ag Cl Ag Cl Ag

Cl Ag
1

Ag Cl

Cl Ag

Ag Cl Ag Cl Ag

Ag Cl Ag Ag Cl Ag (b) Cl

Cl

Cl Ag Cl 2 Ag Ag Cl Ag Ag Cl Ag Cl (a)

Ag

Hnh 137 Dch chuyn ion Ag+ gia cc nt

a) b) b.

bng cch chuyn trc tip gia cc nt (1), bng cch y Ag+ nm gia cc nt bnh thng ra gia cc nt (2). cc hng c th c ca vic y Ag+ vo v tr gia cc nt.

Tinh th AgCl

Vi clorua bc th khuyt tt in hnh l khuyt tt Frenken. Ngha l ion Ag+ xm nhp gia cc nt v cc l trng cation. Thc nghim chng t rng Ag+ gia cc nt (gi l Ag+ xm nhp) linh ng hn l trng Ag+. C hai kiu c ch dch chuyn Ag+ gia cc nt.

Dch chuyn trc tip qua cc nt (hnh 137a, 1). Dch chuyn gin tip bng cch y mt ion Ag+ ra khi nt ca n, ri ion Ag+ gia cc nt chim v tr nt (hnh 137a, 2).

Bng phng php dng ng v phng x Ag+ ri xc nh con ng dch chuyn ion bc nh du xc nh c ch gin tip hay cn gi l c ch y l ng. C ch l trng ca s dch chuyn ion Na+ trong tinh th NaCl v c ch y trong tinh th AgCl khc nhau. V c bn c hai u c cu trc kiu NaCl. Trong c ch l trng, ion Na+ dch chuyn t nh lp phng sang mt nh khc qua v tr gia cc nt l tm ca lp phng. Cn c ch y th Ag+ chuyn t v tr gia cc nt (tm ca lp phng) ti mt v tr gia cc nt khc (tm ca lp phng bn cnh) sau khi y mt ion Ag+ ra khi nh. nh hng ca tp cht cation, c ho tr khc nhau n dn in ca NaCl v AgCl l khc nhau. V d c mt Cd2+ trong trng hp NaCl s lm tng l trng cation, nhng trong trng hp AgCl v tch s nng Ag+ gia cc nt v nng l trng cation l khng i, nn tng l trng cation th s gim Ag+ gia cc nt, ngha l gim s phn t linh ng do s gim dn in (xem hnh 138).

Lg (m 1.cm 1.K)
+2

AgCl/Cd

1/T (K )
Hnh 138 S ph thuc dn in ca AgCl (c pha tp cht Cd2+) vo nhit

4.1.1.2 Cht in li rn

a s cc cht tinh th nh NaCl, MgO u c dn in ion thp v rng cc ion tuy c dao ng nhit nhng thng thng khng ri khi v tr nt mng. Trng hp ngoi l l mt s cht rn m trong mng li tinh th c mt hp phn cu trc (cation hoc anion) khng b gn cht vo nt mng li c th chuyn ng t do trong ton mng. Nhng cht nh vy c gi l cht dn in ion hay cht in li rn. Nh vy, cht in li rn chim v tr trung gian v cu trc cng nh v tnh cht gia mt bn l cht rn cu trc tinh th bnh thng, mt bn l cht in li lng. Trong cht rn c cu trc bnh thng cc ion b gn cht ti cc nt mng khng gian, cn cc cht in li lng th cc tiu phn hp phn khng c cu trc trt t gm cc ion chuyn ng linh ng.
Tng nng khuyt tt Cht trng thi tinh th bnh thng Chuyn pha Cht in li rn Cht in li lng

tC

10

x
546 o

C DTA

600 500 400 300 200 100

T
600

825

DTA
400 300

T
170

159

(a)
oC

200 100

(b)

856

x
577

(c)
Hnh 139 Gin nhit AgI (a), Ag2S (b), Li2SO4 (c)ng dn in k hiu x

nhit bin ho th hnh cc ion trong tinh th ca nhiu cht rn tr nn rt linh ng, do lm tng mnh dn in. Gin nhit ca AgI, Ag2S, Li2SO4 trn hnh 139 cho thy cc nhit bin ho th hnh (vi AgI l 159oC, vi Ag2S l 170oC, vi Li2SO4 l 577oC) ng dn in tng ln mt cch t ngt, t gi tr ti a cho ti nhit nng chy hon ton cng khng tng na. dn in ca cht in li rn c th tng ln do tng dn nng khuyt tt nhit cao. V d trn 600oC nng l trng anion ln n ni lm cho tinh th ZrO2 tr thnh cht dn anion O2 kh tt. Thc ra lc ny khng phi ZrO2 nguyn cht tuyt i m do s c mt ca tp cht c in tch khc vi Zr4+, l CaO, Y2O3, Sc2O3... V l thuyt cng nh thc nghim xc nh c rt nhiu cht in li rn c dn in t ti 0,1 10 1cm1. Gi tr ny ng vi trng thi khi phn ln cc ion trong tinh th ng thi chuyn ng. Nhiu tc gi ngh gi nhng cht nh vy l nhng cht dn in siu ion hay cht dn ion nhanh. Vic phn loi cc cht in li rn nh l cht trung gian gia cc tinh th ion thng thng v cht in li lng c khng nh bng s so snh S nng chy. Lc nng chy xy ra s mt trt t ng thi ca cation v anion. i vi cc cht mt in tch (hp cht A+B), v d NaCl c S nng chy bng 24 J/mol.K. Khi chuyn dng th hnh ca AgI 159oC c gi tr S bng 14,5 J/mol.K c th xem nh s gi nng chy ca phn mng cation Ag+, n khi nng chy AgI th xy ra s mt trt t ca phn mng I, do S nng chy tt nhin l b hn S nng chy ca cc cht mt in tch khc v ch bng 11,3 J/mol.K. Tng entropi bin ho th hnh v entropi nng chy gn bng entropi nng chy NaCl. iu ny cng thy c nhiu florua ca kim loi ha tr 2. V d PbF2, S nng chy ch bng 16,4 J/mol.K trong khi MgF2 hp cht ion in hnh c dn in thp th S nng chy bng 35 J/mol.K. Hnh nh khi un nng PbF2 ban u xy ra s mt trt t ca F ( trn 500oC ), gi tr entropi nng chy ch ng vi s mt trt t ca ion Pb2+. Hnh 140 trnh by dn in ring ca mt s cht in li rn di dng s ph thuc vo nhit theo phng trnh Arrenius.

11

lg (m 10 1 cm ) 1 2 3 4 5
ZrO2 CaF2 1

-AgI

H2SO4

RbAg4I5 NaAl2O3

NaZr2PSi2O12 AgCl 2

-AgI 3 4 1000/T(K)

Hnh 140 dn in ion ca mt s cht cin li rn

Di y chng ta kho st mt s cht in li rn quan trng.

a) -Al2O3
A C B A C B A C B A C B A C B A sp sp A B A C B A C A B C A B A C B A sp sp mt phn chiu gng

sp

sp

'' C C Hnh 141 Tnh lin tc ca cc lp Oxi trong cu trc v -Al2O3 +

Na

O2sp: bloc spinen

chng 1 gii thiu cu trc ca -Al2O3. y ni v cht in li rn ng vi cng thc Na2O.nAl2O3. Tinh th ca loi hp cht ny gm phn mng anion O2 c cu trc lp nh hnh 29, trong c bn lp O2 xp kht theo kiu spinen (gi l bloc sp) li n mt lp ch c 1/4 s ion O2, 3/4 s ion cn li l cc khong trng. Ion Al3+ c phn b c nh ti cc v tr t din gia hai lp O2 xp kht, ion Na+ nm lp c khong trng, do c th dch chuyn d dng di nh hng ca in trng.

12

-Al2O3 c hai dng th hnh v khc nhau th t sp xp cc lp (hnh 141). Dng cha hm lng kim ln (n = 5 7) cn dng b c n t 8 11. C hai dng u cha cc bloc tng t spinen MgAl2O4. Bloc spinen gm bn lp O2 xp kht lun phin theo th t ABCA c trng ca cu trc lp phng. Cc bloc sp tch bit nhau bng mt lp thiu oxi (gi l mt dn), ion Na+ c nh v trong mt . T bo mng lc phng c cc thng s a = 5,60; c = 22,5 (dng ) v a = 5,60, c = 33,8 (dng ), cc lp oxi trc giao vi trc c. T bo mng ca -Al2O3 c cha 2 bloc spinen, cn ca -Al2O3 c cha 3 bloc spinen.
m A m br B abr m A br A A C A A m B abr m br A C A m A
Na+ Na+ Na+ Na+

C A

m
(b)

(a)
A C

Na+

Hnh 142 Mt dn trong -Al2O3 a) O2- trong lp dn; b) Na+ chuyn dch trong lp dn

Cu trc spinen y c xem nh cu trc MgAl2O4 cha khuyt tt, trong spinen MgAl2O4 c t l ion Mg2+ v Al3+ l 1 : 2, trong khi spinen ca b v b" ch c Al3+ (nu khng k n cc ion l Li+, Mg2+), do cn bng in tch trong cc bloc spinen phi c cha cc l trng Al3+. Cu trc ca mt dn trong -Al2O3 l i tng nghin cu ca rt nhiu nh khoa hc, nhng cho n nay vn cn nhiu chi tit cha r. Hnh 142 biu din lp chc c ca oxi (k hiu A, B) nm ngay st di mt dn. Oxi gch sc l ca lp dn. Hnh v cho thy lp ny ch chim 1/4 v tr c oxi, c mi oxi C th c 3 v tr b trng, k hiu m. Trong -Al2O3 mt dn l phn x gng (xem hnh 141) do lp oxi gi ghm chc c pha di cng nh pha trn, ngha l trn lp dn C c mt lp oxi nm ng cc v tr AB nh lp di. Trong -Al2O3 mt dn khng phi l mt gng, lp oxi nm v hai pha lp dn lch v tr nhau. Ion Na+ trong -Al2O3 c th chim 3 v tr khc nhau:

V tr gia cc oxi (m). SFT6 V tr Biversa - Rosa (br). SFT6 V tr i Biversa - Rosa (abr).

Kt qu nghin cu cu trc cho thy Na+ ch yu v tr br v m, nhng cch chuyn dch no cng phi i qua abr. Trong v tr br cng nh m c kch thc ln, ion oxi c phi tr 6: (3 oxi lp di, 3 oxi lp trn). di lin kt Na-O trong v tr ny tng ln ( 2,4). V tr abr c kch thc b hn do hai oxi lp trn v lp di xp gn nhau. Khong cch Na-O ch = 2,3. Cc cation ho tr 1 khc nhau trong -Al2O3 u chim v tr br v m. Tr trng hp Ag+, Tl+ li chim v tr abr. iu ny l do xu hng to thnh lin kt cng ho tr vi c trng s phi tr thp.

13

C hai pha -Al2O3 v -Al2O3 u thuc hp cht bt hp thc c th tn ti trong mt khong thnh phn. Tuy nhin, c ch ca s pht sinh ra bt hp thc khc nhau. Thng thng ngi ta cho rng cu trc l tng ca -Al2O3 ng vi cng thc Na2O.11Al2O3 (hoc NaAl11O17). Tuy nhin, thc t -Al2O3 cha natri nhiu hn thnh phn . Ban u kt qu nghin cu cu trc -Al2O3 ca Biversa v Rosa cho thy mi t bo mng ca NaAl11O17 ch c mt ion Na+ trong mt dn nm v tr br. Sau kt qu nghin cu vi nhng mu c thnh phn gn Na2O.8Al2O3 li thy rng mi t bo c cha 11/3 ion Na+ phn b gia cc v tr br v m, tnh trung ho in lc ny t c do c b sung ion O2 chim mt s v tr m. Nh vy, so vi cu trc ca cc NaAl11O17 th -Al2O3 giu kim c cha ion Na+ xm nhp. Trong -Al2O3 c hp cht in hnh l Na2O.6,6Al2O3. Mi t bo c 1,2/3 ion Na+ nm trong mt dn. in tch ca ion Na+ b sung (2/3) khng c b tr bng cch xm nhp ion O2 vo mt dn m c l trng Al3+ trong bloc spinen. Vic m t c ch hnh thnh pha khng hp thc v cn phc tp hn na khi a thm Li2O, MgO vo. C hai oxit ny xm nhp vo bloc spinen v Li+, Mg2+ thay th v tr ca Al3+.
+ Tnh dn in v c ch tnh dn in.

Cht dn in rn c cu trc -Al2O3 thuc loi cht dn hai phng. Cc ion kim c kh nng chuyn ng dc theo mt dn nhng khng th i xuyn qua bloc spinen (xem hnh 142b).
lg (m-1 2 cm-1. 1 K) 0 1 2 3 4 5 6
2 4

Tl

K (0,36)
6 8

Na Ag (0,16) (0,30) (0,17) 10 12 1000/T(K)

Hnh 143 dn ca n tinh th -Al2O3 khi thay th bng cc cation khc nhau S liu trong ngoc l nng lng hot ho bng eV

dn ca -Al2O3 ln hn dn in ca -Al2O3 n 2 hoc 3 ln, nhng trc y vic iu ch -Al2O3 cha th tin hnh c, do cc s liu dn in ch kho st vi -Al2O3. Hnh 143 trnh by s ph thuc vo nhit ca dn in -Al2O3 khi thay th Na+ bng cation khc nhau. Gi tr cc i ca dn, v ng thi nng lng cc tiu ca s hot ho xc nh c Na+, Ag+ -Al2O3. Tng bn knh ion, dn km hn i, v rng cation ln K+, Tl+ kh lng dch chuyn d dng trong mt dn. Ion Na+ v Ag+ c kch thc thch hp, trong khi Li+-Al2O3 (trn hnh khng c) li c nng lng hot ho cao v dn b hn so vi Na+ -Al2O3 v Ag+ -Al2O3. iu ny c th do kch thc Li+ qu b, c kh nng phn cc ln nn khng thch hp nm trong hc c s phi tr cao, v bt buc phi nm p v mt trong cc lp oxi pha trn hoc pha di mt dn.

14

S ph thuc dn ca -Al2O3 vo nhit kh ph hp vi phng trnh Arrenius. Cho n tn 1000oC ng biu din vn thng v dn tng ln ti 107 ln. Trong khi dn in ca tinh th NaCl (hnh 136) ch trong khong nhit khng ln m ng biu din thay i hai, ba ln: l iu c bit ca cht in li rn. Mt iu c bit na ca cht in li rn l: khc vi cc cht dn ion nh NaCl, AgCl dn in ca cht in li rn c tnh cht lp li cao, ngha l mc du c iu ch bng phng php khc nhau cc phng th nghim khc nhau, gi tr dn in vn khng thay i ng k. iu ny chng t tnh dn in ca loi cht ny hu nh khng ph thuc vo s c mt ca nhiu tp cht. V d nng lng hot ha ca tnh dn Al2O3 thu c ca nhiu phng th nghim khc nhau u c tnh cht lp li v bng 0,16 0,01 eV. T kt qu kho st tnh dn in ca -Al2O3 cho thy khng th xem pha rn ny c trng thi cn bng ca khuyt tt, khng th p dng nh lut tc dng khi lng y. iu th nht l phng trnh xc lp nng khuyt tt Frenken, Stki ch p dng vi trng hp nng khuyt tt rt b (nh hn 0,1% v tr nt l khuyt tt), trong khi Al2O3 c mt lng ln (nu khng ni l tt c) ion Na+ linh ng. iu th hai l dn in ca -Al2O3 b nh hng khng ng k vi s c mt ca tp cht. Lng ion Na+ linh ng, ln n ni cn phi xem chng khng phi nh khuyt tt m nh nhng nt mng bnh thng ca cu trc. V d khi thm mt t MnCl2 vo n tinh th NaCl lm tng dn mt cch t ngt, nhng vi lng tp cht nh vy th nh hng khng ng k ti dn in ca -Al2O3. C ch tnh dn in ca -Al2O3 c th hnh dung qua hnh 144. Ion Na+ dch chuyn theo cc v tr br m abr br m. Nng lng hot ho ca tnh dn in bng 0,16 eV l tng hng ro nng lng m Na+ phi vt t v tr br ny ti v tr br bn cnh. Kt qu xc nh bng thc nghim cng nh t tnh ton cho thy tnh dn trong -Al2O3 theo c ch y ca cation gia cc nt. V d tinh th ban u ng vi cng thc NaAl11O17, ion Na+ chim cc v tr br, cn cc v tr m v v tr abr u b trng. Ion Na+ v tr br phi vt qua mt khe nh v tr m chui vo v tr abr ri t y li i qua v tr m ly ion Na+ v tr br bn cnh
m m br m br

m m m m m abr abr abr m m m br br br m m m m m m abr abr m m

Hnh 144 Con ng dn trong -Al2O3

Mt trong cc hng c nghin cu hin nay l tng dn ca gm -Al2O3. Trong hng c lu nhiu l tng hp -Al2O3 v thm mt lng nh Li2O v MgO vo tng dn. b) AgI v cc cht in li rn dn Ag+
+ AgI.

Cu trc: AgI c 3 dng th hnh theo nhit tng dn l , v . Trong -AgI c cu trc kiu blend ZnS (hnh 145). T bo mng gm phn mng anion kiu lp phng mt

15

tm ca I, trong khi lp phng c cha 4 cation Ag+ nm tm ca 4/8 lp phng nh. S phi tr l 4-4.

Hnh 145 T bo mng kiu blend O : I; : Ag+

-AgI c cu trc kiu vuazit (hnh 27). Phn mng anion gm cc ion I gi ghm chc c lc phng. Cation Ag+ nm cc hc t din. S phi tr l 4-4. -AgI c phn mng anion I kiu lp phng tm khi. Mi t bo mng c 12 hc t din, nhng ch c 4 cation Ag+. Cc ion I thc t khng linh ng, trong khi ion Ag+ c th dch chuyn t do t v tr hc t in ny n hc t din khc nh trong cht lng. Trng thi khng trt t ca Ag+ v kh nng chuyn ng nhanh ca n xc nh bn cht lin kt gia AgI. Cation Ag+ do c lp v ngoi cng l 4d nn c kh nng phn cc cao v hiu ng chn in tch ht nhn khng ln, cn I th d b phn cc. Nh vy gia it v bc c lin kt cng ho tr. Khi tham gia dn in, Ag+ chuyn ng t do t hc t din ny n hc t din khc qua v tr trung gian c phi tr tam gic ( v tr phi tr tam gic ny s phi tr ca bc ch l 3). Lin kt cng ho tr cc v tr trung gian ny c tc dng lm bn vng ho v lm gim nng lng ho ca dn.
+ RbAg4I5.
oC
600 500 400 300 200 100 0 5
8

1
6

1- RbI + lng 2 - RbI + Rb2AgI3 3 - Rb2AgI3 + AgI 4 - Rb2AgI3 + RbAg4I5 5 - Rb2AgI3 + lng 6 - AgI + lng 7 - Lng 8 - RbAg4I5 + lng 9 - RbAg4I5 + AgI

27o C 3

RbI

Rb2AgI3

RbAg4I5 % mol AgI

AgI

Hnh 146 Gin trng thi h RbIAgI

Cc nh lm n nh pha nhit cao ca -AgI l hng ch yu trong nghin cu ca cht dn ion AgI. thc hin hng ny ngi ta tin hnh thay th ion ca cc phn mng. Thnh tu ng k nht l thay th mt phn Ag+ bng Rb+ khi tng hp RbAg4I5. V mc dn ion th vt liu ny vt xa tt c cc cht in li rn tinh th khc. nhit phng (25oC) dn ca n l 0,25 m1cm1, nng lng hot ha dn l 0,07 eV, trong khi mc dn electron cc nh c th b qua 109 m1cm1. Hnh 146 l gin trng thi

16

ca h AgI-RbI cho thy to thnh hai hp cht nng chy khng tng hp l Rb2AgI3 v RbAg4I5. di 27oC hp cht RbAg4I5 phn hu theo phn ng:
RbAg 4 I5 AgI + Rb 2 AgI3

Tuy rng v ng hc, phn ng ny xy ra rt chm, nhng nu c mt m hoc hi it th c th xy ra vi tc rt nhanh. c th xc nh dn ca RbAg4I5 nhit phng th phi lm lnh rt thn trng trong kh quyn kh v khng c hi it. iu ch RbAg4I5, c th un trong chn khng mt hn hp RbIAgI theo t l mol 1 : 4 n nhit nng chy (500oC) ri lm lnh nhanh n nhit phng. Khi ngui lnh khi nng chy kt tinh to thnh vt th rn ng nht bao gm nhng tinh th nh khng hon chnh. Sau khi nhit khong 165oC trong 10 gi s to thnh nhng tinh th RbAg4I5 hon chnh. Cng c th khng cn a ln nhit nng chy bng cch thc hin phn ng trc tip gia cc pha rn AgI v RbI trong khong 100200oC. Phn ng c th xy ra vi tc ng k khi chun b hn hp ng th ca hai cht rn c phn tn tht cao v nn p sut cao. Cu trc RbAg4I5 khc vi cu trc ca AgI. Nhng trong RbAg4I5 cng c s phn b thng k cc ion Ag+ trong cc hc t din ca phn mng anion I . Cng nh trong cu trc ca -AgI, mng li tinh th ca RbAg4I5 c s hc t din rt nhiu so vi s cation Ag+. Ion Rb+ b gi cht cc hc bt din ca I. Khc vi ng s ph thuc dn vo nhit di dng ng thng theo phng trnh ca Arrenius, ng dn ca RbAg4I5 vo nhit l mt ng cong u n.
+ Cc cht in li rn khc dn xut ca AgI.

Cu trc khng trt t nh AgI c th n nh n nhit thp bng cch thay th cc cation c kch thc ln: NH + 4 , cation hu c. V d mt s loi hp cht c dn khong 1 1 o 0,02 n 0,2 m cm 25 C nh [(CH)3N]2Ag13I15, (C5H5NH)+Ag5I6 v NH4Ag4I5. Cng c th thay th mt phn I cho nhng pha c dn ion cao nh Ag3SI, Ag7I4PO4, Ag6I4WO4. c bit hp cht Ag6I4WO4 kh bn nhit v khng b nh hng ca m cng nh hi it. Mt hng l th l tng hp cc cht in li rn dng thu tinh bng cch ti nhanh n nhit phng cc hn hp nng chy gm AgI vi mt trong cc hn hp sau: Ag2SeO4, Ag3AsO4, Ag2Cr2O7.
c) Cht dn anion halogen

V d PbF2 c cu trc kiu florit nhit phng l tinh th ion in hnh c dn ion rt b, nhng trn 500oC c dn ion t ti 5 m1cm1. iu c bit ng quan tm l ng dn ph thuc vo nhit khng thay i t ngt do thay i cu trc tinh th nh trng hp AgI (hnh 139) m tng u t ti gi tr cc i 500oC, trn nhit tng khng ng k na, cn khi nng chy, thm ch dn cn hi gim (822oC). Tng t PbF2, hp cht SrCl2 c dn ion cao 700oC cho ti nhit nng chy (873oC). Cn CaF2 ch n nhit nng chy (1418oC) mi t dn ion ng k. C ch dn ion ca cc halogenua c cu trc florit hin nay cha r. y cn quan tm trong cu trc florit l khong trng ca tm t bo c bao quanh bng 6 ion Ca2+ v 8 ion F c kch thc kh ln, phi chng iu ny thun li cho s chuyn dch ion.

17

lg (m-1 cm-1) 1
2 3 4

Tnc

1
Hnh 147 dn ca PbF2

-1 1000/T(K )

d) Cht dn anion O2

ZrO2 nhit cao c dng th hnh lp phng kiu florit, dng ny c th tn ti bn nhit phng to dung dch rn vi CaO, Y2O3 v.v Oxit zirconi c bn ho nh vy nhit cao c tnh dn ion O2. C th iu ny do tch lu nhiu l trng O2 khi to dung dch rn vi ion dng thiu in tch. Thnh phn dung dch rn c th vit (CaxZr1-x)O2-x vi 0,1 < x < 0,2. Ngha l c a vo mt ion Ca2+ th lm xut hin mt l trng O2. dn ca ZrO2 khi bn ho bng 15% mol CaO, 1000oC l 5.102 m1cm1 v nng lng hot ho dn bng 1,3 eV. Vt liu ny nhit thp c dn ion rt b.
4.1.1.3 Vn nghin cu tm kim cc cht in li rn mi

C th tm tt cc iu kin c bn i vi cht in li rn l: 1. 2. 3. C nng ion linh ng cao (ngha l gi tr n trong phng trnh = n.e.m phi ln). C nhiu v tr cn trng cho ion linh ng. Nng lng ca v tr b chim v ca v tr cn b trng khng khc nhau lm, hng ro hot ha nh khi chuyn ion t v tr ny n v tr khc bn cnh. S c mt mt s ln v tr b trng c th l v ch nu nh ion vn chuyn khng th ri vo v nng lng hot ho cao. C mt cc knh, rnh m dch chuyn cc ion linh ng trong cu trc. Phn mng anion d b phn cc.

4. 5.

Trong -Al2O3 v ZrO2 bn vng ho, p ng 4 iu kin u cn trong cht dn Ag+ tho mn c 5 iu kin. Cc vt liu m tnh dn ion thp v cn thiu mt trong cc iu kin trn. V d nhiu silicat c cu trc khung nhng linh ng ca cation trong km v hng ro nng lng qu cao. Vic tm kim cht in li rn mi cho php pht hin c mt s hp cht c cu trc khung v linh ng cao ca cation. Mt trong cc hp cht kh l th l Na3Zr2PSi2O12 do cc tc gi Hong, Kafalac, Gudenaph tm ra v ngh gi l NASICON (t ting Anh Na+ Superionic Conductor). Cu trc khung ca NASICON gm cc bt din ZrO6 v cc t din (P,Si)O4 t hp vi nhau qua nh. Trong cu trc c mt h thng rnh to thnh li

18

khng gian, trong cc rnh c cha Na+ linh ng. dn Na+ ca NASICON cng tng ng vi -Al2O3. Zeolit c cu trc khung v cc hc trng vi ng knh ln cng c th lm cht in li rn. Tuy nhin thc t dn ion thp. Cc cation nm trong cu trc zeolit thng b hirat ho v d trao i nhng linh ng khng cao. Khi kh hirat ca zeolit c th lm cho cc rnh tr nn qu rng dn n vic cc cation np vo cc vch rnh, tng t nh Li+-Al2O3, do kch thc qu b ca Li+ nn chng nm p vo cc vch rnh lm cho dn ca Li+-Al2O3 b hn nhiu so vi dn ca -Al2O3. Nhu cu vt liu c dn Li+ kh ln do ngun in vi dng cc liti c sc in ng cao hn ngun in tng t nhng dng cc l Na+. Li2SO4 c nhit chuyn pha 572oC, dn Li+ ca pha nhit cao c gi tr khong 1 m1cm1 nhng nhit thp dn gim hn. Vic nghin cu thm tp cht lm n nh pha nhit cao cng ch h n 400oC. Li4SiO4, Li4GeO4 c dn Li+ trung bnh (khong 104 m1cm1) cu trc ca cc cht ny l cht nn thun li thm cc ph gia khc nhau. Cc hp cht ny gm cc t din ring l SiO4 v GeO4 to thnh cc mng li gm khong trng a din c mt chung, Li+ nm trong . C th tin hnh cc phn ng thay th. Li+ + Si4+ Si4+ 2Li+ P5+ Zn2+ (trong Li4SiO4) (trong Li4GeO4) Al3+ + Li+ (trong Li4SiO4)

S thay th nh vy c tc dng lm tng dn ion ca cht nn ln vi bc khong nhit khng cao lm (2030oC). Cht dn tt nht trong khong nhit trung bnh l Li14ZnGe4O16 (gi l LISICON) 300oC c = 101 m1cm1. Cht dn nhit phng th c Li3,5V0,5GeO0,5O4 c = 105 m1cm1. Mt pht hin bt thng khi nghin cu hn hp LiI v Al2O3. Trong hn hp ny khng c du hiu g chng t c phn ng ho hc nhng dn ca hn hp ng phn t gam cao hn vi bc so vi dn ca LiI nguyn cht (Al2O3 nguyn cht l cht cch in) v bng 105 m1. Nguyn nhn ca hin tng ny cha c gii thch nhng c th c lin quan n tnh dn b mt dc theo bin gii cc ht LiI v Al2O3.
lg (m-1 cm-1) 1
2 3 4
5 6 7 1000 500 300 100 25

Li Al2O3

Li2SO4 Li3,4Si0,4V0,6O4 Li4SiO4

0 1,0 Hnh 148 + dn ca vi cht dn Li

2,0

3,0

4,0

19

C nhiu cng trnh nghin cu tm kim cht dn proton. Hin bit c c hai cht l H3O+-Al2O3 v axit uranin photphat HUO2PO4.4H2O 25oC c dn 4.10 2 m1.cm1.
4.1.1.4 ng dng cht in li rn

1) Nguyn l lm vic ca pin in ho bng cht in li rn Trn c s cht in li rn c th ch to c cc loi pin in ho dng gii quyt cc nhim v khoa hc k thut khc nhau, chnh iu ny l nguyn nhn thc y vic nghin cu cc loi vt liu c dn ion. Hnh 149 trnh by s mt pin in ho lm bng cht in li rn. A1 v A2 l khng gian in cc c th l pha lng, pha rn, hoc pha kh vi bn cht ho hc ging nhau hoc khc nhau. V d A1 v A2 u l oxi nhng vi p sut ring phn khc nhau, hoc A1 l natri, A2 l lu hunh.

A1

cht in li rn

A2

Hnh 149 Pin in ho bng cht in li rn

S (E)

Sc in ng (S) pht sinh ra trong pin c tnh theo phng trnh Nest: E = Eo + RT ln [oxi ho]
nF [kh]

(40)

Ti mi bin gii in cc cht in li thit lp mt th oxi ho - kh. V d trn ant c qu trnh oxi ho M = M+ + e. ng vi th oxi ho kh:
+ E1 = E o M / M+ RT [M + ] ln F [M]

o trong E M / M + l th oxi ho kh tiu chun ca phn ng , [M+] v [M] l nng

cc tiu phn, F l hng s Faraay (96500 C). Ion M+ pht sinh ra ant chuyn ng qua cht in li rn sang phn ng vi anion X bn catt l sn phm ca phn ng X + e = X ng vi th oxi ho kh:
+ E2 = Eo X / X RT [X] ln _ F [X ]

Tng i s E1 v E2 l sc in ng (S) ca mch, lin quan n gi tr th ng p G ca phn ng xy ra trong pin X + M MX theo h thc: G = nEF (41)

20

Pin in ho vi cht in li rn c th p dng nghin cu nhit ng hc xc nh gi tr G ca nhiu phn ng trong pha rn. V d pin Ag(r)AgI(r)Ag2S(r), Slng, C(r) c s dng xc nh gi tr G ca phn ng xy ra trong pin 2Ag + S Ag2S. V Ag v S u trng thi tiu chun nn G o Ag S = 2EF.
2

Bng thc nghim xc nh c s ph thuc ca sc in ng (S) vo nhit ta c th tnh c entropi, entanpi ca phn ng. 2) Ch to cc ngun in Trn c s cht in li rn c th ch to ra cc ngun in. Trong cc pin s dng cht in li rn quan trng i vi k thut c l l pin S Na trong s dng cht in li rn l Na+-Al2O3. y l loi acquy c in dung ring ln (tnh theo n v khi lng) v c cng sut cao. Acquy lu hunh natri u tin c dng cho xe in v h thng cn bng cng sut cc nh my in, hin nay nhiu nc tin hnh ci tin hon thin loi acquy ny. y l loi acquy kh n gin, c th m t nh trn hnh 150. Cht in li rn -Al2O3 ngn cch natri lng (ant) v lu hunh lng (catt). Cht in li rn c lm thnh mt ng rng bt kn mt u, pha trong cha natri lng, pha ngoi l lu hunh lng (c th t ngc li). V lu hunh lng l cht c lin kt cng ho tr khng dn in nn catt c ch to bng pht graphit tm lu hunh. V ngoi ca acquy lm bng thp khng r ng vai tr cc gp. Khi phng in trong pin xy ra phn ng: 2Na + xS Na2Sx
natri cht cch in Al2 O3 cht in li rn Al2 O3 lu hunh (trng thi tch in) hoc sunfua natri (tch in)

Hnh 150 Pin lu hunh natri vi cht in li rn -Al2O3

Phn ng: 2Na + 5S Na2S5 (2,08 V) giai on u phng in x c gi tr bng 5, ng vi cng thc sunfua giu lu hunh nht Na2S5. Theo qu trnh phng in gi tr x gim. Hnh 151 l gin trng thi ca h Na S. Pin ny vn hnh 300 350oC. Gin cho thy l ngng nhit thp nht gi trng thi lng ca sn phm phng in (cc hp cht sunfua natri) trong mt khong thnh phn kh rng. Trong qu trnh phng in gi tr x 3 (ng vi 60% S, 40% Na) th c kh nng bt u xut hin tinh th Na2S2, nu phng in tip s lm khi catt ho rn dn. in p cc i khi lm vic 300oC t 2,08 V. Khi phng in t gi tr x = 3 in p gim n 1,8 V. Gi tr l thuyt v in dung ca acquy ny t 750 W.gi/kg nhng trn thc t ch t c 100 200 W.gi/kg.

21

C
+

500

Na2S lng

lng
Na2S5 + lng

400

Na2S
300

Na2S2

Na S Na2S2 + 2 4 lng + lng

hai pha lng

200

Na2S2
+

Na2S5

lng

100

Na2S4

Na2S5 + S
60 80 90

Na Na2S2

Na2S4

Na2S5

Hnh 151 Gin trng thi h Na S

Cc loi pin lm bng cht in li rn khc c u vit l to c ngun in vi kch thc rt b. Cc ngun in ny c s dng cung cp cho ng h in t v mt s thit b cho mc ch qun s. Trong s cc h in ho lm vic tt i vi mc ch ny thng s dng hai loi pin sau: AgRbAg4I5I2 LiLiII2
E khng kh
O
2-

(0,65 V) (2,80 V)
1/2O2 + 2e O2ZrO2 (CaO) O
2-

1/2O2 + 2e

P' O

P'' O2 (khng kh)

(a)

P' O

P'' O

(b)

cht in li rn cc in cc xp 2e Hnh 152 Pin nng oxi vi cht in ly rn bng ioxit zirconi n nh
2e

Thng ngi ta s dng cc phc ca it nh (CH3)4NI hoc phc c cha anion poliiotit v phc chuyn dch in tch (poli-2-vinyl pyriin) thay th it. Pin LiI2 rt thun tin s dng trong cardiosti-mulator 37oC, mt dng 110 microampe/cm2, nng lng ring t 0,8 W.gi/cm3 c th s dng trn 10 nm. 3) Cc cm bin v pin nng oxi Pin in ho vi cht in li rn c th s dng o p sut ring phn ca kh hoc nng kh tan trong cc cht lng. Hnh 152 trnh by s mt pin nng bng cht in li rn l ZrO2 (CaO). Thit b gm mt ng bt kn di, trong ng c kh bit p sut ring phn oxi (v d khng kh). Bn ngoi v ng c ph bng kim loi xp dng lm in cc v c th cho oxi khuch

22

tn ra vo. Hnh 152b l s dch chuyn ion oxi qua cht in li rn v cc phn ng in cc xy ra khi PO2 < PO2. S ca pin lin quan n thng s p sut ca oxi.
'' RT PO 2 E= ln ' 4F PO 2

(42)

V rng ZrO2 n nh bng CaO c dn ion tt ch nhit cao nn loi pin ny c kh nng lm vic trong khong nhit 500 1000oC, lc c th o c p sut ring phn ca oxi ti 1016 atm. Cht in li rn trn c s ThO2 n nh c th o c p sut ring phn ca oxi b hn na. Pin nng oxi cng tng t nh loi u d ZrO2 (CaO) c nhiu ng dng rng ri, c bit trong phn tch kh thi, o lng s hp th oxi khi th, nghin cu nhng cn bng kh v oxit kim loi (CO/CO2, H2/H2O) v o hot ca oxi ho tan trong kim loi nng chy.
4) Pin nhin liu

Oxit zirconi n nh lm di dng hnh ng hoc dng a c s dng trong cu to pin nhin liu lm vic nhit cao. Trong c mt khng gian in cc cha oxi hoc khng kh, cn khng gian in cc kia cha kh chy, v d H2 hoc CO. Bn ngoi cht in li rn y cng ph cc in cc kim loi xp. Trn b mt cc in cc xy ra cc phn ng: H2 + 1/2O2 H2O hoc CO +1/2O2 CO2 u vit ca pin nhin liu l khng bao gi c s phn cc ho in cc v c th cung cp mt dng cao (0,5 A/cm2), nng lng ring cao (0,5 W/cm2). Tuy nhin, khi s dng cc pin nhin liu cn quan st ch hm nng chm chp n nhit lm vic. V cu trc ang i hi phi gii quyt nhiu vn . Qu trnh xy ra trong pin nhin liu l thun nghch: thay i hng ca dng li c th phn hy hi nc thnh oxi v hiro. S in phn nhit cao nh th c th s dng tch tr in nng di dng ho hc. Trong nhng trng hp khc c th s dng phn ng loi ny y oxi ra khi CO2 s dng trong cc con tu v tr hoc ui oxi ra khi kim loi lng

4.1.2 Cht dn electron

Cc vt liu dn in vi cht mang in tch l electron gm kim loi, cht bn dn (nu tnh n dn rt b ca cht in mi th c th xp c cht in mi vo loi ny). Nhng phn sau s thy khi gii thch c ch dn in ca cht bn dn ngi ta phn thnh cht bn dn loi n (dn electron) v bn dn loi p (dn l trng dng). Cht bn dn loi n th khng phi bn ci na v cht mang in y l electron, cn cht bn dn loi p v thc cht cng do s dch chuyn electron theo chiu ngc li. Do y chng ta xp vo loi vt liu dn electron. Trong bng 31 chng ta thy, da vo dn in ngi ta quy c gi cht dn in kim loi l cht c dn cao ( = 102 106 m1cm1), cht in mi (hay cn gi l cht cch in) l cht c dn rt b (<1012 m1cm1 ), cht bn dn c gi tr dn trung gian (khong 105 102 m1cm1). im khc nhau c bn trong c ch dn in ca loi vt liu ny l s ph thuc ca dn in vo nhit . Cht bn dn cng nh cht in mi c dn in tng khi tng

23

nhit , trong khi kim loi th dn in gim khi tng nhit . V rng dn in c xc nh theo h thc (33) = n.e.. Do s ph thuc ca dn in vo nhit c quyt nh bi s ph thuc ca ba thng s n, e, , vo nhit . Vi tt c cc cht dn electron th e l gi tr khng i v khng ph thuc vo T. Do ch cn xt n s ph thuc vo T ca n v . Ni chung, khi tng nhit th linh ng ca cht mang in gim v tng cng va chm gia electron vi phonon (do s tn x electron trong h nt giao ng ca mng li tinh th). Bi vy, s khc nhau gia kim loi v cht bn dn ch yu lin quan n s ph thuc n vo nhit . Kim loi c nng cht dn in rt ln v khng thay i khi thay i nhit T. i lng duy nht lm thay i ch l . V gim khi tng nhit nn ca kim loi gim khi tng nhit . Vi cht bn dn v cht in mi th khi tng nhit n tng rt nhanh theo cp s lu tha, do tuy c hi gim nhng vn tng nhanh. Vi ngha ny cht in mi c th xem nh l trng hp gii hn, v rng nhit thp gi tr n rt b. nhit cao n tng ln lm cho dn in ca mt s cht in mi c th t gi tr dn in ca cht bn dn, ngc li nhit thp mt s cht bn dn c th tr thnh cht in mi. Trong phn ny chng ta kho st cc cht bn dn.
4.1.2.1 Thuyt vng nng lng ca vt liu rn

Theo phng php obitan phn t chng ta c th hnh dung s to thnh cc vng nng lng trong mng li tinh th nh sau: cc nguyn t ring l (khi chng xa nhau nh trong pha kh) th electron chim cc mc nng lng hon ton xc nh. S chnh lch gia hai mc nng lng E1 v E2 ng vi mt bc x c tn s xc nh trong vch quang ph E2 E1 = h (trong h l hng s Plank, l tn s bc x). Khi cc nguyn t dch li gn nhau nh trong mng li tinh th th cc obitan nguyn t s b phn tch ra. V d t hp 2 obitan nguyn t 1s to thnh hai obitan phn t lk v plk vi nng lng khc nhau l Elk < Es < Eplk. Nu t hp n nguyn t s to thnh N mc nng lng khc nhau ca N obitan phn t. V d vi 1 cm3 kim loi th gi tr N t ti khong 1022 n 1023 nguyn t. Do N mc nng lng ny to thnh mt vng nng lng lin tc. S sai khc ca cc mc nng lng trong vng ny ch khong 1022 eV. Theo nguyn l Paoli th mi obitan phn t cng nh obitan nguyn t ch c ti a hai electron. Do s electron cc i trong cc vng nng lng to thnh khi t hp cc obitan nguyn t s, p, d, f s l 2N (vng s), 6N (vng p), 10N (vng d), 14N (vng f). Vng nng lng c lp y cc electron, gi l vng ho tr, cc electron y gi vai tr lin kt trong mng li tinh th. Vng nng lng cn trng (cao hn vng ho tr) gi l vng dn. Nu trong vng ny c mt electron th chnh nhng electron ny s l cht mang in tch trong qu trnh dn in. Ty thuc vo cu trc nguyn t v mc i xng ca tinh th m vng ho tr v vng dn c th xen ph nhau (hnh 154), hoc khng xen ph nhau (hnh 155). Trong trng hp khng xen ph nhau th vng ho tr v vng dn cch nhau mt khong nng lng gi l vng cm Eg. Ty theo gi tr vng cm ngi ta phn ra thnh cc cht cch in (Eg > 3eV), cht bn dn (Eg < 3eV). Cht dn in kim loi th khng c vng cm (Eg = 0).

24

Mc nng lng E

16

S nguyn t
Hnh 153 S hnh thnh vng nng lng khi cc nguyn t dch li gn nhau trong mng li tinh th

V d hnh 154 trnh by s cu trc vng nng lng ca kim loi natri. Trn hnh v cho thy rng ca cc vng nng lng ph thuc vo khong cch gia cc nguyn t natri trong mng li tinh th. khong cch ro (gi tr o c bng thc nghim), cc obitan 3s v 3p ca cc nguyn t cnh nhau trong tinh th xen ph vo nhau to thnh mt vng nng lng lin tc kh rng. khong cch cc obitan 1s, 2s, 2p ca cc nguyn t cnh nhau khng xen ph vo nhau m vn nh v cc mc nng lng hon ton xc nh thuc v tng nguyn t ring r. iu ny c ngha rng trong tinh th natri, electron 3s c chuyn ng trong vng nng lng lin tc (vng xen ph 3s v 3p) trong ton b tinh th. Cn cc electron 1s, 2s, 2p th nh v hon ton ph thuc v tng nguyn t ti cc nt mng. Nu nh tng tng khi nn tinh th natri vi mt p lc ln cho khong cch gia cc nguyn t dch gn li n v tr r th cc obitan 2s v 2p s xen ph vi nhau to thnh vng nng lng lin tc (vng 2s v 2p) v lc cc electron ny khng nh v na m c th chuyn ng trong khp mng li, ngha l tham gia vo lin kt, nhng khong cch gi thit cc electron 1s vn nh v mc hon ton xc nh thuc v tng nguyn t ring bit. Gi thit ny cng c th t ra i vi vic nn cc n cht khc. V d t s tnh ton cho thy khi nn vi p lc 106 atm c th to thnh hiro kim loi.
nng lng

3p 3s 2p 2s 1s r' ro

Hnh154 nh hng ca khong cch gia cc nguyn t ln v tr cc mc nng lng v vng nng lng trong tinh th natri kim loi

Cu trc vng nng lng ca cc nguyn t thuc phn nhm chnh nhm IV trong bng h thng tun hon c m t theo cch khc. Trong khi natri kim loi c mng li lp

25

phng tm khi (s phi tr l 8) th C, Si, Ge, Sn (xm) c mng li tinh th kiu kim cng, mi nguyn t u nm v tr tm ca t din ngha l c bao quanh bi 4 nguyn t khc. 3N OA 3p Min c m N OA 3s 2N obitan phn lin kt cn trng
Eg

2N obitan lin kt bo ho electron

Hnh 155 M hnh vng nng lng trong tinh th silic

V d Si c cu hnh electron ca lp v ngoi cng l 3s2 3p2. Bn electron ny u nm trn obitan nguyn t lai ho sp3. Khi cc nguyn t Si gn li nhau trong mng li tinh th th mt obitan nguyn t lai ho sp3 ca nguyn t ny t hp vi obitan nguyn t lai ho sp3 ca nguyn t bn cnh to thnh hai obitan phn t: obitan lin kt (c nng lng thp hn nng lng ca obitan nguyn t lai ha sp3) v obtan phn lin kt * (c nng lng cao hn nng lng ca obitan nguyn t lai ho sp3). Hai vng nng lng: vng gm cc obitan lin kt (vng ho tr) v vng gm cc obitan phn lin kt (vng dn) cch nhau mt khong nng lng (gi l vng cm). i vi tinh th Si th vng ho tr c lp y electron, vng dn cn trng. rng ca vng cm c gi tr 1,1 eV.
e- eevng dn e-

vng cm
+ + + +

vng ho tr
Hnh 156 Hng chuyn dch ca cht mang in trong bn dn

Bng 33 rng vng cm ca cc nguyn t nhm IV Nguyn t Kiu mng SPT li Cacbon (C) Kim cng Silic (Si) Kim cng Gecmani (Ge) Kim cng Thic xm (Sn) Kim cng Thic trng (Sn) T phng Ch (Pb) Lp phng mt tm

4 4 4 4 6 12

rng vng cm (eV) 6,0 1,1 0,7 0,1 0 0

c tnh Cch in Bn dn Bn dn Bn dn Kim loi Kim loi

Di tc dng kch thch bn ngoi (nhit , nh sng,) electron vng ho tr c th nhn c nng lng nhy sang vng dn. Khi nm trong in trng, electron trong vng dn chuyn ng v in cc dng, cn vng ho tr im c mt electron nhy sang vng dn s tr thnh l trng dng. Do tc dng ca in trng ngoi, electron ca

26

nt mng bn cnh v pha cc m nhy sang l trng dng. Do dng in chuyn dch trong vng ho tr c th dng nh cc l trng dng chuyn dch v pha in cc m (hnh 156).
4.1.2.2 Cc loi cht bn dn

Cht bn dn c th phn thnh hai loi:

a) Cht bn dn l nguyn t nguyn cht nh Si, Ge, thic xm. Cc cht bn dn loi ny c s electron trong vng dn hon ton xc nh bi rng ca vng cm v nhit . Nu gi nE l lng tng i electron c nng lng E, nng lng Fermi-Dirac ta c:
nE = 1 E Ef +I e kT
_

(43)

Khi EEf >> kT th hm phn b Fermi-Dirac tr thnh hm b Boltzmann n gin hn:

n E = e( EEf ) / kT

(44)

Vi cht bn dn l nguyn t nguyn cht th s electron trong vng dn bng s l trng dng trong vng ho tr, mc Fermi nm gia vng cm. Nng lng cn thit chuyn electron vo vng dn ch bng Eg/2, v lng electron chuyn vo vng dn s l:

n = A.e

E g / 2 kT

2mkT 2 2 h

3/ 2

.e E / 2kT

(45)

y m l khi lng electron, h l hng s Plank. Di tc dng ca in trng ngoi electron trong vng dn chuyn v dng cc, l trng dng trong vng dn i v m cc. Gi tr dn ring theo electron() t l vi nng cht mang dng v linh ng ca chng.

= e.(ne + ph)

(46)

y e l in tch electron, n l lng electron chuyn ng trong 1cm3, p l lng l trng dng, e, h l linh ng ca electron v ca l trng dng (vi cht bn dn l nguyn t nguyn cht th n = p). linh ng ca cht mang dng ch lin quan n s phn b cc loi khuyt tt trong mng tinh th.
b) Cht bn dn tp cht l cht bn dn trn nhng c a thm tp cht vo ( d hiu chng ta gi l cht bn dn do a tp cht vo). Chng ta kho st cc vng nng lng thay i ra sao khi a tp cht vo Si nguyn cht. V d a mt lng rt t Ga vo tinh th Si to thnh dung dch rn thay th. V rng Ga ch c 3 electron ho tr, do trong t din GaSi4 ch c 3 lin kt cng ho tr bnh thng, cn mt lin kt GaSi gi l lin kt thiu electron. Theo thuyt vng nng lng th lin kt mt electron ng vi mc nng lng khng nm trong vng ho tr ca silic, m to thnh mt mc nng lng ring bit hi cao hn mc nng lng cao nht ca vng ho tr (ngha l nm ngay st pha trn ca vng ho tr). Mc nng lng ny gi l mc nhn cch vng ho tr khong 0,1 eV. Do , ch vi s kch thch nhit rt b l electron t vng ho tr s nhy vo li l trng dng trong vng ho tr. Nu nng Ga t hn th mc nhn phn tn v e y khng tham gia vo phn gp ca dn in. Di nh hng ca in trng ngoi, l

27

trng dng trong vng ho tr i v pha cc m. Nh vy, thm tp cht Ga vo th Si tr thnh cht bn dn loi p.
(a) Si
X O

Si
O X

(b) Si
X O
X O

Si
O X thiu mt electron X O

(c) Si
X O

Si
O X mt electron d X O

Si
X O

Ga
X O

As
X O

Si
1,1eV

Si

Si

Si
e

Si

Si

vng dn e
0,1eV

vng dn
0,1eV

vng dn e e e vng ho tr

mc cho

e mc nhn

vng ho tr

vng ho tr

Hnh 157 Tnh dn in ca Si nguyn cht

(a) Si nguyn cht; (b) Si c tp cht Ga - l cht bn dn loi p; (c) Si c tp cht As - l cht bn dn loi n. Nu tp cht thuc nhm V, v d As vo Si th As cng thay th mt v tr ca Si trong t din. By gi trong t din AsSi4 c mt electron d nguyn t As. Electron d ny c mc nng lng xc nh nm trong vng cm ngay st pha di vng dn v cch vng dn mt khong bng 0,1 eV. Mc nng lng ny gi l mc nng lng cho v ch cn kch thch nhit khng ln l electron mc ny s nhy vo vng dn v tham gia dn in, to thnh cht dn loi n. Chng ta c th phn bit cht bn dn nguyn cht v cht bn dn a tp cht vo nh sau:

dn in ca cht bn dn tp cht ( nhit phng) cao hn dn in ca cht bn dn nguyn cht. V d 25oC Si nguyn cht c dn in khong 102 m1cm1, khi thm tp cht vo dn in tng ln vi bc. dn in ca cht bn dn tp cht c th xc nh chnh xc bng nng tp cht a vo. iu ny c s dng khi tng hp cc vt liu xc nh. Cn dn ca cht bn dn nguyn cht th ph thuc vo nhit v tp cht ngu nhin.

28

lg(n)
3 2 1

lg() (a)
3 2

(b)
1

T1

Hnh 158 S ph thuc vo nhit ca nng cht mang in (a) v dn (b) trong cc cht bn dn 1 - Vng dn tp cht; 2 - Vng bo ho; 3 - Vng dn ca cht nguyn cht

dn ca vt liu bn dn phi km nhy vi s thay i nhit (vng 2). cho vng bo ho 2 tht rng phi dng hai phng php: 1) Chn vt liu c vng cm rng. 2) a vo cht bn dn nhng tp cht to ra vng nhn (hoc vng cho) nm gn mp vng ho tr (hoc vng dn). Trong hai trng hp ny vng 1 chuyn v pha nhit thp, cn vng 3 chuyn v pha nhit cao.
4.1.2.3 Nguyn tc tng hp gm bn dn

Ngoi cc loi bn dn trn y cn c th k thm mt s loi vt liu bn dn khc nh:

Hp cht gia nguyn t nhm III v nhm V (gi l hp cht AIIIBV) (v d GaAs, InSb); hp cht gia nguyn t nhm II v nhm VI (gi l hp cht AIIBVI) (v d CdTe, ZnS, ZnTe). Gm oxit v gm hp cht gia cc oxit.

Ni chung tnh bn dn ca cc cht rn v c c quyt nh bi cc khuyt tt trong mng tinh th do a tp cht vo, hoc bi s sai khc vi thnh phn hp thc do to thnh cc nt mng trng trong mng... Phng php tng hp gm bn dn c da trn c s iu chnh cc khuyt tt ca mng li tinh th. iu ch cc vt liu ny c th s dng cc oxit kim loi chuyn tip t Sc n Ni. l cc nguyn t c phn mc 3d cha c lp y. Trong c th k n Cr2O3, MnO, Fe2O3, CoO, NiO v cc hp cht gia cc oxit nh ZnFe2O4, MgCr2O4, LaMnO3 iu ch gm bn dn c th s dng 3 phng php l phng php iu chnh ho tr, phng php iu ch hp cht bt hp thc, phng php pha long. + Phng php iu chnh ho tr l a cc ion l vo mng tinh th ca oxit kim loi c ho tr thay i. Cc loi gm bn dn iu ch theo phng php ny da vo hp cht cc h NiOLi2O, NiOCr2O3, Li2OZnO.

29

Ni2+ O2 Ni2+ O2 Ni2+ Ni2+ O2 Ni2+ O2 Ni2+ Ni2+ O2 Ni2+ O2 Ni2+ 22+ 2 2+ 2 2 2+ 2 3+ 2 2 2+ 2 3+ 2 O Ni O Ni O O Ni O Ni O O Ni O Ni O 2+ 2 2+ 2 2+ 2+ 2 2 2+ 2+ 2 + 2 2+ O Ni Ni O Ni O Ni Ni O Ni O Li O Ni 2 2+ 22+ 2 2 3+ 2 2+ 2 2 2+ 2 2+ 2 Ni O Ni O Ni O Ni O O Ni O Ni O O O ( a) (b) (c) Hnh 159 Mng li niken oxit: hon chnh (a); tha oxi (b); thm tp cht Li+ (c )

V d i t oxit niken (NiO) tinh khit l cht rn mu xanh nht v l cht cch in. Mu ca n l do s dch chuyn d d trong Ni2+ v tr phi tr bt din. Khi oxi ho nh NiO trong khng kh, v d 1000oC th niken oxit tr thnh mu en v dn in tng ln 2+ 3+ ng k. Sn phm oxi ho c th biu din theo cng thc: Ni1 3x Ni 2x Vx O (hnh 159b). Khi oxi ho th oxi t pha kh i ti b mt tinh th, mt phn Ni2+ khuch tn t trong ln b mt cn bng in tch d v c s xut hin ng thi vi l trng cng vi ion Ni2+ bin thnh Ni3+. Oxit niken en dn in l do electron i t Ni2+ ti Ni3+: Ni2+ Ni3++ e Ni3+ Ni2+ + p S dch chuyn electron nh vy c th xem nh s dch chuyn ca Ni3+, do niken oxit l cht bn dn loi p. Tnh dn in ca niken oxit c c ch nhy. V s trao i electron trong h Ni2+/Ni3+ l do qu trnh kch ng nhit, nn s trao i ph thuc vo nhit . Theo quan im ca thuyt vng nng lng c th gii thch rng cc obitan d ca niken xen ph yu vo nhau, do hnh thnh mt vng nng lng d tng i hp. Tuy nhin, cht bn dn niken oxit thng khng c s dng v rng kh iu chnh tnh bn dn in. Tnh dn in ca n va ph thuc vo nhit li va ph thuc vo p sut ring phn ca kh quyn oxi ho NiO. trnh iu ny c th a vo y mt tp cht iu chnh ho tr, v d a ion Li+ vo v tr ca ion Ni2+ n nh v tr Ni3+ khc (hnh 159c). Oxit liti tham gia to dung dch rn vi oxit niken cho thnh phn ng vi cng thc 3+ +2 +3 Li x Ni1 (v do dn) ch ph 2x Ni x O . Trong dung dch rn nh vy, nng ca Ni + thuc vo nng tp cht Li m khng ph thuc vo p sut ring phn ca oxi na. 25oC dn thay i rt mnh khi thay i thnh phn. Khi x = 0 c dn vo khong 1010 1 cm1, khi x = 0,1 dn t 0,1 1cm1 (hnh 160) . Theo phng php ny c th iu ch c nhiu cht bn dn. V d: (Sr1-xLax) (Ti1-xFex)O3 Zn(TixFe2-2xFex)O4 Tix(Fe2-2xFex)O3 (SbxSn1-2xSnx)O2 (cu trc kiu perpskit) (cu trc spinen) (cu trc hematit) (cu trc rutin)

+ Theo phng php iu ch hp cht bt hp thc, ngi ta p mt mu bt oxit kim loi ri nung trong mi trng oxi ho hoc mi trng kh. Ph bin nht l nung trong kh quyn ca kim loi . V d mu TiO2 nung trong hi Ti, mu ZnO nung trong hi Zn, mu FeO nung trong hi Fe

30

2+ 3+ Thnh phn ca vt liu bn dn thu c khc vi hp thc. V d Fe1 3x Fe 2x y l l trng. Gi tr ca x = 0,1.

x)O.

dn 10 ring m-1cm-1 1
10-1 10-2
-3 10 35

9,05% 2,4%
0,1 %Li2O

0,01 %Li2O
30 25 20

1/T

Hnh 160 S ph thuc ca dn niken oxit vo lng tp cht + Li Ni2+ O2 Ni2+ O2 O2 Ni3+ O2 Ni2+ 2+ O2 O2 Ni 2 2+ 2 Ni O Al3+ O Hnh 161 a Al2O3 vo NiO

dn in ca loi bn dn ny l do s c mt ca l trng. + Ni dung ca phng php pha long l trn ln cht dn in, cht bn dn vi cht khng dn in to thnh dung dch rn. V d cht bn dn hnh 159c, by gi thay th mt v tr Li+ v mt v tr Ni2+ bng ion Al3+ s lm xut hin thm mt l trng (hnh 161).

4.1.3 Cc tnh cht in khc

4.1.3.1 Hin tng nhit in v pin nhit in

Khi cho hai kim loi (hoc hp kim) khc nhau tip xc vi nhau th ti ch tip xc xut hin mt sc in ng E. Sc in ng ny ph thuc vo bn cht ca kim loi v vo nhit ca ch tip xc. S d c sc in ng ch tip xc l v mi kim loi (hoc hp kim) c mt nng electron ho tr bnh qun khc nhau. Bn c nng electron cao c th chuyn electron v bn c nng electron thp. Nhng kh nng chuyn electron nh vy cn ph thuc vo nhit ch tip xc.
V d: Ta cho ba si dy A, B, C hn tip xc vi nhau nh hnh 162. Gi s nhit T1 v T2 khc nhau th trong mch kn CABC s pht sinh ra mt dng in lm quay in k D. Sc in ng pht sinh ra trong mch CABC l E = VAB + VBC + VCA.

31

T2 T1 A B T2
Hnh 162 S mch nhit in

C D C

Mt khc theo Pencher th sc in ng pht sinh ra mt mi hn ca hai si dy AB l: VAB = VB VA +

kT n 0 A ln n 0B e

(47)

y k l hng s Boltzmann, e l in tch electron, T l nhit ti ni tip xc hai si dy, n0A v n0B l nng electron bnh qun ca mi si dy. Vy trong mch kn CABC ta c: VAB = VB VA + kT1/e.ln.(n0A/n0B) VCA = VA VC + kT2/e.ln.(n0C/n0A) VBC = VC VB + kT2/e.ln.(n0B/n0C) E = VAB + VCA + VBC =
kT1 n 0 A kT2 + ln e e n 0B
n 0B

ln

n 0C n + ln 0 B n 0A n 0C

kT n E = kT1 ln n 0 A + 2 ln 0 B
e

n 0A

E=

n k1 (T1 T2 )ln 0A e n 0B

(48)

Ngha l sc in ng ca mch CABC ch ph thuc vo bn cht ca hai kim loi A v B, hiu s gia T1 v T2. i vi mt cp dy nht nh, khi gi nhit T2 c nh th sc in ng nhit E pht sinh ra trong mch ch ph thuc vo nhit T1. l nguyn tc ca vic s dng pin nhit in o nhit . Thng thng nhit T2 c gi 0oC (hn hp nc v nc ). Yu cu i vi mt cp nhit in l: Sc in ng nhit ln v thay i tuyn tnh theo nhit T1; Bn i vi mi trng oxi ho kh, khng b n mn (c bit nhit cao). nh gi sc in ng nhit ca cc kim loi v hp kim, ngi ta thng xc nh gi tr E ca pin nhit in c mt dy l kim loi hoc hp kim mun o, cn mt dy l platin nguyn cht, nhit T2 gi 0oC cn nhit T1 gi 100oC. Nu k hiu kim loi so snh l S, ta c:
T2 T 2 ET T1 ( A / B ) = E T1 ( A / S ) E T ( S / B )
2 1

(49)

Ta c th da vo h thc tnh sc in ng nhit ca mt pin nhit in bt k khi nhit T2 l 0oC cn nhit T1 l 100oC.

32

V d tnh sc in ng nhit ca pin cromen alumen trong iu kin T2 l 100oC, T1 l 0oC. Ecromen alumen = Ecromen Pt Ealumen Pt = + 2,95 (1,2) = 4,15 (mV). Sc in ng nhit ca Cu-constantan cng trong iu kin nh trn l: ECu-constantan = ECu Pt Econstantan - Pt = + 0,75 (3,4) = 4,15 (mV). Theo quy c (c bit thun li khi lp rp cc pin nhit in) th tn gi ca mt cp nhit in cn gi theo th t in cc dng trc, in cc m sau. V d, cn gi cp nhit in cromen alumen, cp nhit in ng constantan, cp platin (ri) platin
Bng 34 Sc in ng nhit ca kim loi v hp kim trong cp nhit in vi Pt nhit T2 o bng 0 C Sc in ng Gii hn trn ca T (oC) Kim loi hoc hp kim nhit 100oC (mV) Gi lu o nhanh Antimoan (Sb) +4,86 550 Cromen (89%Ni; 9,8%Cr; 1%Fe; 0,2%Mn) +2,95 1000 1250 Nicrom (80%Ni, 20%Cr) +2,00 1000 1100 St (Fe) +1,80 600 800 Molipen (Mo) +1,31 2000 2500 Vng (Au) +0,80 Volfram (W) +0,79 2000 2500 ng (Cu) +0,75 350 500 Bc (Ag) +0,72 600 700 Platin (Roi) (90%Pt, 10%Rh) +0,62 1300 1600 Platin (Pt) +0,00 1300 1600 Alumen (94%Ni; 0,5% Fe; 2% Al; 2,5%Mn; 1%Si) 1000 1250 1,20 Vng Palai (60%Au; 40%Pd) 1100 1200 1,47 Niken (Ni) 1000 1100 1,52 1300 1200 Vng Platin Palai (60% Au, 30%Pd; 10%Pt) 1,91 Bc Palai (30%Ag, 70%Pd) 1100 1200 2,47 1200 1100 Vng Palai (40% Au, 60%Pd) 2,78 Au Ag Pd (10%Au, 30%Ag, 60% Pd) 1200 1300 3,11 Constantan (60%Cu, 40%Ni) 600 800 3,40 Copen (56%Cu, 44%Ni) 600 800 4,00 Bitmut (Bi) 200 7,34

Mun xc nh sc in ng nhit ca pin nhit in nhit bt k ti T1 th phi bit s ph thuc gi tr E theo nhit . S ph thuc ca E theo nhit T1 thng c biu din di dng bng trong cc ti liu chuyn v phn tch nhit. Trong bng 35 cho bit gi tr sc in ng nhit ca mt s pin nhit in ph bin trong cc phng th nghim mt vi gi tr nhit T1 trong iu kin nhit T2 c gi 0oC. Nu nhit T2 khng gi c 0oC (v d nhit phng chng hn) th cn hiu chnh li gi tr E theo h thc: E (T1/0oC)= ET1/T + ET/0oC T1 l nhit u mi hn AB hnh 160, t l nhit T1 khi o. ng dng ca pin nhit in ch yu xc nh nhit , ngoi ra cn lp rp nhiu thit b nghin cu khoa hc khc nhau trong cc thit b phn tch nhit. Khi ghp ni tip n cp nhit in s thu c mt acquy c sc in ng nhit ln gp n ln sc in ng nhit ca mt cp. Nhng ngun acquy nh vy c s dng khai thc nng lng mt tri, cn trong thin vn th dng o nhit cc ngi sao

33

Bng 35 Sc in ng nhit ca mt s cp nhit in (n v l milivn) ph thuc vo nhit T1 (khi gi T2 o 0 C) Nhit T1(oC) 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 Pt+10/Rh v Pt 0,00 0,64 1,44 2,31 3,25 4,22 5,22 6,26 7,33 8,43 9,57 10,74 11,92 13,12 14,31 15,50 17,84 Cromen alumen 0,00 4,10 8,13 12,21 16.39 20,64 24,90 29,14 33,31 37,36 41,31 45,14 48,85 52,41 53,81 St constantan 0,00 5,40 10,90 16,56 22,07 27,58 33,27 39,30 45,72 52,29 58,22 Cromen copen 0,00 6,95 14,65 22,90 31,48 40,15 49,60 57,75 66,40 St copen 0,00 5,75 5,75 18,10 24,55 30,90 37,40 44,10 51,15 ng constantan 0,00 4,16 4,16 14,13 20,04 26,19 -

4.1.3.2 Cht in mi

Danh t cht in mi (dielectric material) do Faraay ln u tin a ra ch cc cht khng dn in. Trong thc t th d nhiu hoc t, cht no cng c dn in. Do cht gi l in mi cng c gi tr dn tuy rt b (khong nh hn 1012 m1cm1). Tuy nhin, trong cht in mi th qu trnh chuyn dch cc in tch v s mt mt nng lng lin quan n qu trnh ny chim u th so hn vi qu trnh dn. C th xem mt cch gn ng l trong cht in mi hu nh khng c cc in tch t do c th b in trng ngoi chuyn dch i mt khong cch ln. Cht in mi c cu to t cc nguyn t hoc phn t trung ho in, hoc t cc ion dng v ion m (tinh th ion) c gn cht cc v tr cn bng trong mng tinh th. Di tc dng ca in trng ngoi, cc in tch trong cht in mi b ri lon trong phm vi phn t, nguyn t, hoc t bo mng. Khi khng c in trng th lng cc in ca mt th tch nguyn t bt k trong cht in mi u c gi tr bng khng. Khi c mt in trng th cc in tch c du khc nhau chuyn dch theo hng chuyn ngc nhau lm cho mmen in ca th tch nguyn t s khc khng v lc cht in mi b phn cc. Tnh cht ca cht in mi c xc nh bng mt loi t in phng (hnh 163). Nu gia hai bn in cc l chn khng th in dung Co ca t l: Co = eo.A/d (50) eo l thm in mi ca chn khng bng 8,854.1012 F/m, A l din tch ca bn in cc, d l khong cch gia hai bn in cc. in dung ca t in nh vy ch ph thuc vo kch thc hnh hc. Nu t mt in p V gia hai bn in cc th t in s tch lu c mt in tch. Qo = Co.V (51)

34

bn cc dng
++++++++++++++++

cht in mi
+++++++++++++++

bn cc m
Hnh 163 T in phng

By gi ta t cht in mi vo gia hai bn in cc v vn gi mt in p bng V nh vy th in tch t in tch lu c s tng ln Q1, cn in dung tng ln n gi tr C1. Ngi ta gi thm in mi ca cht in mi l v c xc nh bng t l:

= C1/Co

(52)

ph thuc vo phn cc, hoc s dch chuyn in tch trong cht in mi. Vi khng kh = 1, vi a s cc cht rn lin kt ion c t 5 10, cn i vi cht xenhet in (v d BaTiO3) = 103 104.
phn cc ca cht in mi l h s lin quan n mmen lng cc P v in trng cc b E. P = .E phn cc bao gm nhiu hp phn (53) (54)

= e+ i + d + s

e l phn cc electron do s chuyn dch cc m my in t i vi ht nhn nguyn t. Tt c cc cht u c kiu phn cc ny. i l phn cc ion, c trng cho kh nng dch chuyn tng i ca cation v anion i vi v tr cn bng ti cc nt ca mng li tinh th. d l phn cc lng cc (cn gi l phn cc tch thot) c trng cho cc phn t phn cc (v d HCl, H2O). Khi khng c in trng ngoi th cc phn t phn cc c phn b mt cch hn lon, n ch tham gia vo chuyn ng nhit v c nng lng t l thun vi nhit (kT). Khi nm trong mt in trng th cc lng cc c mt nh hng u tin dc theo hng ca in trng ngoi, cht in mi b phn cc. d ph thuc rt mnh vo nhit ( nhit thp c th xem nh cc lng cc b ng cng li). s l hp phn in tch th tch c trng cho cc vt liu khng c tnh cht in mi tt, v n c kh nng dch chuyn cc cht mang in tch trong mt khong cch tng i ln. V d tinh th NaCl, Na+ c th dch chuyn theo l trng dng hng n cc m lm xut hin lp in kp gia bin gii tinh th NaCl v bn in cc (thc ra loi cht rn ny phi xp vo cht in li rn ng hn l xp vo cht in mi). thm in mi ca cc cht ny gi l thm in mi biu kin v c gi tr khong 106 107. Nh vy gi tr ny khng c trng i vi cht in mi. Gi tr phn cc gim dn theo th t s > d > i > e.

35

Gi tr v thm in mi c th xc nh bng thc nghim bng cch o in dung, o microvon v o tnh cht quang hc trong mt khong kh rng ca tn s ca dng xoay chiu (hnh 164). Khi tn s thp (103 hz) c th c mt c 4 hp phn trong , tn s sng v tuyn (106 hz) th hp phn trong s in tch th tch khng kp to thnh trong a s vt liu dn ion, do khng c nh hng n gi tr tch thot. Trong dy sng ngn (109 hz) c th dng s nh hng ca cc lng cc vnh cu, v rng lng cc khng theo kp s thay i ca in trng ngoi. Thi gian tch thot i vi s phn cc ion (i) bin mt cc tn s ln hn vng ph hng ngoi (1012 hz). Tip tc tng tn s ln na th ch cn hp phn e o c trong vng cc tm. Khi t mt in p xoay chiu vo cht in mi th xy ra s mt mt nng lng lin quan n cc qu trnh phn cc. S mt mt nng lng trong cht in mi c biu din bng h thc: W = V2.G.C.tg (55) G = 2/f, f l tn s ca in p xoay chiu, C l in dung ca mu nghin cu, V l phn hiu dng ca in p, tg l t s gia dng thc hin (active) trong cht in mi v dng h khng (reactive), thng gi l tang ca gc tn tht ca cht in mi. Trong k thut ngi ta khng dng gi tr tuyt i ca s mt mt nng lng m dng gi tr tang ca gc tn tht (tg).
thm in mi ' 106
105 104 10 3 102 10 1

e + i + d + s e + i + d o ' '
10 3 106 10 9

e + i e
1012

Hnh 164 Hin tng phn cc trong cht in mi

tn s f

i vi cht in mi ng nht thuc loi phn cc electron (e) v phn cc ion (i) th tg thay i t l nghch vi tn s ca in p v tng khi tng nhit . Cc loi s cch in, in p dng c tn s 50 hz 20oC, tg nm trong khong 0,0025 0,035. Vi cc loi cht in mi tt th tg c th t ti 105. Mt i lng quan trng na ca cht in mi l in p nh thng. Ta c th hiu mt cch gn ng khi nim in p nh thng l vi mt dy xc nh ca cht in mi, khi t gia mt in p bng bao nhiu s xy ra hin tng phng in. VEt = UEt/h (56) VEt l tr s trung bnh ca in p nh thng (kV/mm hoc kV/cm); UEt l in p nh thng (kV), h l dy ca cht in mi im b nh thng (mm hoc cm).

36

nh thng l mt hin tng kh phc tp. i vi cht in mi kh th in p nh thng l in p ion ho kh. Tt nhin gi tr lin quan vi nng lng lin kt ca cc obitan ho tr ca cc cht kh . V d i vi khng kh p sut kh quyn trong trng ng nht th VEt = 30 kV/cm. C ch s nh thng ca cht in mi lng (v d vi cc loi du bin th) ph thuc vo sch v mc loi ht kh c trong cht in mi. Khi trong cht lng cha hp cht dn in tt th gia cc cc trc khi b nh thng c mt cu ni bng cc tp cht . Dng in qua cht lng c tng dn lm tng s to nhit v nhit cht in mi quanh vng cu ni tng dn n im si. Lc ny to ra mt rnh kh v bt u phng in. in p nh thng cc cht in mi lng cha c sch v cha ui ht kh c gi tr nm trong khong 1 10 kV/cm. Khi lm sch tht cn thn th gi tr ny c th t ti 1000 kV/cm. S nh thng cc cht lng nguyn cht l do cc electron p ln cc phn t cht lng lm ion ho n. Nh vy, c ch s nh thng ca cht lng nguyn cht cng tng t nh c ch s nh thng ca cht kh. in p nh thng ca cht in mi rn cao hn nhiu in p nh thng ca cht in mi kh cng nh cht in mi lng. C mt s cht in mi rn c VEt t ti 10.000 kV/cm. Vi cht in mi rn c th phn thnh hai dng nh thng: nh thng v nhit v nh thng v in. nh thng v nhit c th gii thch nh sau: Khi tng cng ca dng i qua cht in mi th lng nhit sinh ra tng ln. Mt khc, nhit tng li lm tng dn in ca n v nh vy li lm tng cng dng v do lm tng nhit trong lng cht in mi. Cui cng trong cht in mi t ti nhit lm phn hu nhit cht rn. bn in ca cht in mi rn khi b nh thng v nhit c gi tr khong 10 100 kV/cm. nh thng v nhit ph thuc vo thi gian chu tc dng ca nhit v in p. Khi hai gi tr tng ln th gi tr in p nh thng v nhit gim xung. nh thng v in l do qu trnh tng s lng electron trong cht in mi di nh hng ca in trng mnh. Cc qu trnh ny gm: s ion ho do va p electron ln nguyn t hoc ion trong mng li, s t pht x electron t catt. nh thng v in khng ph thuc vo thi gian tc dng ca in p v nhit . Tnh ng nht ca vt liu hnh dng ca in trng v.v cng c nh hng n in p nh thng ca cht in mi rn. Khi dy ca mu th tng s lm gim tnh ng nht ca mu.
4.1.3.3 Cht xenhet in

Cng nh cht in mi, di tc dng ca in trng ngoi cht xenhet in b phn cc, nhng khc vi cht in mi hai im l:
Cht xenhet in c thm in mi rt cao. Khi ngt in trng ngoi trong vt liu xenhet in vn cn gi li tnh phn cc.

Khi tng in p bn ngoi (V) vi cht in mi thng thng th tc phn cc cm ng tng mt cch u n v do in tch cm ng cng tng u n theo h thc Q = C.V. Vi cht xenhet in th khng phi n gin nh vy. Mi quan h gia phn cc cm ng P vi in p V c hin tng tr, ngha l ng biu din s ph thuc gia P v V khi tng V khng lp li nh khi gim V. Cht xenhet in c c trng bng s c mt phn cc bo ho Ps khi tng in p (v d 23oC vi BaTiO3 c Ps = 0,26 C/cm2), v phn cc tn d Pr (ngha l phn cc vn cn li sau khi ngt in trng ngoi). gim phn cc n gi tr 0 th cn phi t mt in trng ngoi ngc chiu vi in trng ban u (gi l trng khng t). Bng 36 gii thiu mt s cht xenhet. Tt c cc cht u c cc cu trc m trong c mt cation (v d Ti4+ trong BaTiO3) c th chuyn dch (khong 0,1 ) trong vng phi tr anion ca mnh, chnh s chuyn dch lm pht sinh ra

37

lng cc v do thm in mi ca cht xenhet in c gi tr ln. T bo mng li ca perpkit (hnh 36 v 37) cho thy ion Ti4+ nm trong v tr bt din TiO6. T kch thc Ti4+ v O2 cho ta bit c Ti4+ c th dch chuyn t do trong mt gii hn no ca bt din TiO6. Hnh 38 cho thy trn 120oC t bo mng ca BaTiO3 thuc h lp phng bn vng khng c mmen lng cc ring, v tt c cc in tch u c phn b mt cch i xng. Do trn 120oC BaTiO3 ch l mt cht in mi thng thng, tuy rng c thm in mi cao.
P (C/m2) PS Pr Ec

V(v/m)

Hnh 165 Vng in tr ca cht xenhet in in hnh

ng chm chm i qua gc to biu din c tnh ca cht in mi thng thng

Bng 36 Nhit Curie ca mt s vt liu xenhet in Cht xenhet in Nhit Curie (Tc, oC) Barititanat BaTiO3 Mui xenhet KNaC4H4O6.4H2O Kali niobat KNbO3 Kaliihirophotphat KH2PO4 Ch titanat PbTiO3 Liti niobat LiNbO3 Bimut titanat Bi4Ti3O12 Galini molipat Gd2(MoO4)3 Zirconat titanat ch (PZT) Pb(ZrxTi1-x)O3 120 T 18 n +24 434 150 490 1210 675 159 Ph thuc vo gi tr x

Di 120oC mng tinh th BaTiO3 b sai lch, bt din TiO6 mt tnh i xng (xem hnh 38), ion Ti4+ b x dch trong bt din theo mt hng xc nh no (dch gn v mt O2 hoc gia hai ion O2, hoc gia ba ion O2). Nu s dch chuyn xy ra trong tt c cc bt din TiO6 th trong vt liu pht sinh ra phn cc t nhin. Trong cht xenhet in BaTiO3, mi mt bt din TiO6 b phn cc di nh hng ca in trng ngoi dn ti s nh hng cng bc ca tt c cc lng cc. Sau khi xp t tt c cc lng cc theo mt hng nht nh th vt liu t trng thi bo ho Ps. T gi tr Ps o c trong thc nghim ngi ta xc nh c khong cch m ion Ti4+ ri khi tm bt din TiO6 hng v mt trong cc ion oxi l 0,1 , gi tr ny kh ph hp vi kt qu xc nh c bng phng php ghi gin nhiu x tia X. Nu so vi di lin kt Ti O trong bt din (1,95 ) th khong chuyn dch cng b hn. Hnh 166 cho bit s nh hng ca cc lng cc, y mi mi tn ng vi mt bt din bin dng TiO6. Trong cc xenhet in tng t BaTiO3 c cu trc men do cc lng cc TiO6 cnh nhau t sp t mt cch song song vi nhau (hnh 167). Kch thc ca cc men khc nhau thng t ti (theo mt ct ngang) hng chc n hng trm angstron. Trong gii hn

38

ca mt men, cc lng cc phn cc theo mt hng tinh th. phn cc ca mt mu xenhet in bng tng vect ca phn cc cc men.
Hnh 166 S biu din s nh hng ca cc lng cc trong: cht xenhet in (a), cht antixenhet in (b), cht xenheti in (c) (a) (b) (c)

x Khi t vo in trng s lm thay i phn cc ring ca mu xenhet in, nguyn nhn ca s thay i c th l cc qu trnh sau:

Thay i hng phn cc ca men. iu ny xy ra nu tt c cc lng cc TiO6 trong gii hn kho st u thay i hng ca mnh, v d tt c cc lng cc trong men 2 thay i hng song song vi lng cc ca men 1 (xem hnh 167). Lm tng s phn cc trong gii hn ca mi men, iu ny c th xy ra nu trc khi t in trng th cc lng cc c s nh hng khng trt t. Chuyn ng ca cc thnh men lm cho kch thc ca cc men nh hng dc theo trng tng ln do gim cc men c hng khng thun li. V d trn hnh 167 men 1 c th tng ln khi chuyn dch mt bc sang phi, thc hin s chuyn ng th cc lng cc trn bin gii men 2 phi chp nhn s nh hng theo mi tn chm chm.

Hnh 167 Cc men xenhet in b ngn cch bi thnh men

Trng thi xenhet in thng thy khi nhit thp, v rng s chuyn ng nhit tng ln khi tng nhit s ph v cu trc men c trng thch hp ca s chuyn dch cc bt din cnh nhau do ph v cu trc men. Nhit m bt u xy ra s ph v gi l im Curie (Tc). Trn Tc th vt liu tr thnh paraelectric (ngha l khng xenhet in na), thm in mi ca n vn c gi tr cao nh trc (hnh 168), nhng phn cc tn d khi khng c trng ngoi th khng thy na. Trn nhit Tc i lng tun theo nh lut Curie Weiss.

= C/(T q )

( 57)

39

C l hng s Curie, q l nhit Curie Weiss. Thng thng Tc v q trng nhau hoc ch khc nhau vi . S chuyn t trng thi xenhet in sang trng thi paraelectric Tc l mt v d s chuyn pha trt t thnh khng trt t (v d trong ng thau) khng xy ra s chuyn dch khuch tn ion trong mt khong cch ln. Di nhit Tc tnh trt t c thc hin bng cch sai lch u tin hoc lch mt cch phi hp vi nhau ca cc a din, ngha l mt s chuyn pha di ch. pha paraelectric nhit cao s sai lch v s lch cc a din nu c xy ra th cng ch mang tnh cch ngu nhin. iu kin cn thit ca s phn cc t pht v tnh cht xenhet in trong tinh th l tinh th phi thuc nhm khng gian khng c tm i xng. Pha paraelectric bn trn Tc thng l i xng tm cn tnh trt t xy ra khi lm lnh li gim i xng n nhm khng gian khng c i xng tm na.
10000 8000 6000 4000 2000 40 80 120 160

'

Tc

Hnh 168 Gin cho bit thm in mi ca gm BaTiO3 ph thuc nhit

Hin nay bit n hng trm vt liu xenhet in trong c mt nhm kh ln l hp cht oxit c cu trc perpkit bin dng (khng phi dng lp phng). Nhng hp cht c cha cc cation c b tr thun li trong phi tr bt din bin dng Ti, Ni, Ta. Tnh khng ng u ca cc lin kt trong cc bt din bin dng l nguyn nhn pht sinh ra s phn cc v mmen lng cc. Khng phi tt c cc perpkit u l xenhet in. V d khc vi BaTiO3 v PbTiO3, canxititanat khng c tnh xenhet in, hnh nh lin quan n s khc nhau v kch thc ca cation ho tr 2. Bn knh ln ca ion Ba2+ cng nh Pb2+ c nh hng lm gin n t bo mng li so vi ion Ca2+, iu ny lm ko di lin kt Ti O trong BaTiO3 (cng nh trong PbTiO3) v lm chuyn dch mnh Ti4+ trong bt din TiO6. Trong thnh phn ca cc oxit khc nhau c tnh xenhet in c cha cation m lin kt gia cation vi oxi khng ng u v c cp electron t do trn lp v ngoi cng. iu ny c th xy ra vi cation ca nguyn t p nng c hai n v ho tr thp hn ho tr gii hn ca nhm nh Sn2+, Pb2+, Bi3+... Cc oxit xenhet in c s dng lm cc t in c thm in mi ln, c bit gn nhit Tc (hnh 168). Bi vy, trong iu ch vt liu ang theo ui mt mc ch tng , ngha l to ra vt liu c Tc gn vi nhit phng. c bit, nhit Curie ca BaTiO3 (120oC, hnh 168) c th gim i ng k v khong nhit chuyn cng c m rng ra khi thay th mt phn Ba2+ hoc Ti4+ bng cc cation khc: thay th Ba2+ bng Sr2+ gy ra hin tng co t bo mng li li v gim Tc, thay th Ti4+ (hot ng) bng cation in tch 4 khc (khng hot ng), c bit Zr4+, Sn4+ cng gim mnh Tc. Trong cc cht antixenhet in cng c s phn cc t pht v bn cht ging nh s phn cc ca cht xenhet in. Cc lng cc c th ca cht antixenhet in c sp xp

40

trt t vi nhau sao cho mi mt lng cc nm gia hai lng cc i song song hai bn (hnh 166b). Kt qu phn cc t pht ca vt liu bng khng. Trn im Curie antixenhet in, vt liu tr nn paraelectric bnh thng. Ch zirconat PbZrO3 (233oC), natri niobat NaNbO3 (638oC), amoni ihirophotphat NH4H2PO4 (125oC) l v d cc cht antixenhet in (s trong ngoc l im Curie). Tnh cht in ca antixenhet in v xenhet in rt khc nhau. V rng trong trng thi antixenhet in, s phn cc t pht khng c nn khng thy c vng t tr trong in trng xoay chiu, tuy rng i vi cc cht cng c thm in cao gn im Tc (vi PbZrO3 c 100 200oC v 3000 230oC). i khi s sp xp trt t i song ca cc lng cc trong cht antixenhet in v song song trong vt liu xenhet in c bn rt gn nhau. Trong nhng trng hp nh vy th mt s thay i nh ca iu kin bn ngoi c th dn ti s chuyn pha. V d, di tc dng ca in trng ngoi PbZrO3 c th chuyn t trng thi antixenhet sang trng thi xenhet in. in trng gy nn s chuyn ph thuc vo nhit . Tng ng vi trng hp c s bin ho phn cc nh c m t trong hnh 169. in trng thp khng c t tr v rng PbZrO3 trong iu kin l cht antixenhet in, cn khi in trng mnh hn (c hai pha) PbZrO3 tr thnh trng thi xenhet v pht sinh vng t tr. Ngi ta cn bit c c mt dng khc ca hin tng phn cc na, l cu trc antixenhet ch pht sinh ra trong mt hng no . Cu trc men ca dng nh vy c ch trn hnh 166c, s phn cc ring bng khng theo hng x, nh trong cht antixenhet, nhng theo hng Z li khng bng khng. V d cht Bi4Ti3O12, monohirat ca tactrat liti v amoni (nhng cht nh vy gi l cht xenhetielectric).
E(kV/cm)
P

(a)
30 20 10

(b)

xenhet antixenhet in paraelectric oC

E

220

225

230

235

Hnh 169 S ph thuc gia nhit chuyn trng thi antixenhet-xenhet trong PbZrO3 vo in trng (a) v tnh phn cc trong qu trnh chuyn (b)

4.1.3.4 Cht ha in (pyroelectric)

Cc tinh th ho in cng c ngun gc vi cht xenhet in ngha l chng u khng c tm i xng v c s phn cc t pht. Tuy nhin, khc vi cht xenhet in ch hng Ps khng c th thay i bng in trng bn ngoi. phn cc ca cht ho in ph thuc vo nhit .

PS = .T

(58)

l h s ho in. S pht sinh ra phn cc ho in c gii thch nh sau, khi un nng s lm gin mng li tinh th do lm thay i di ca lng cc. V d tinh th ho in nh km oxit ZnO c cu trc vuazit. Hp cht ny gm cc lp ion O2 gi ghm

41

chc c lc phng v cc ion Zn2+ chim mt kiu hc t din, v d T+. Tt c cc t din ZnO46 u nh hng theo mt hng v v rng mi t din l mt lng cc, nn v ton b tinh th phn cc. Trn cc mt i din ca tinh th ZnO theo ch s 001 ch c th c mt loi ion O2 hoc Zn2+. Tuy nhin, trn b mt ca tinh th thng hp th cc phn t ca tp cht nn che ph mt in tch. Do hiu ng ho in ca tinh th thng khng pht hin c khi nghin cu nhit thng m ch pht hin khi un nng.
400 300 200 100 1 0,2 2

C
3

PbZrO3

0,4

0,6

0,8 PbTiO3

Hnh 170 Gin pha h PZT 1- Pha antixenhet; 2- Pha mt thoi (xenhet in ); 3- Perpkit lp phng (paraelectric); 4- Pha t phng (xenhet in ).

4.1.3.5 Cht p in (piezoelectric)

Trong tinh th ca cht p in, s phn cc v in tch cc mt i din pht sinh khi t ln mt ng sut c hc. Cng nh cc cht xenhet in v cht ho in, tinh th ca cht p in phi thuc h khng c tm i xng. S xut hin hiu ng p in ngoi vic ph thuc vo cu trc tinh th cn ph thuc vo hng ca ng lc t vo. V d vi tinh th thch anh, hiu ng p in ch xut hin di p lc ca lc nn vung gc v song song vi trc i xng bc hai. S ph thuc gia phn cc (P) v ng lc () theo h thc: P = d d l h s p in. Rt nhiu tinh th m trong cu trc c cha cc mnh t din (v d ZnO, ZnS) u c tnh p in. V rng khi t mt ng sut trt ln th lm sai lch t din. PZT l mt trong cc nhm cht in p quan trng nht. l dung dch rn gia zircronat v titanat ch (PbZrO3, PbTiO3). Trn gin hnh 170 cho thy cc khu vc ca thnh phn pha rn c tnh cht xenhet in v tnh cht antixenhet in. Tnh cht p in tt nht ng vi thnh phn cu t ng phn t gam. Cc tnh cht xenhet, p in, ho in u c chung mt nguyn nhn l s pht sinh cc vng phn cc trong tinh th, do gia cc vt liu ny phi c tnh cht chung. Tt c cc vt liu u thuc v nhm cht in mi, do trc ht l nh hng ca in trng ln tnh cht in ca chng. Cc cht p in thuc vo phn nhm cht in mi m khi t ng sut c hc ln th pht sinh ra in tch, cn khi nm trong in trng th n li sinh ra ng sut c hc. Cc cht ho in to thnh phn nhm vi cht p in, trong cc vt liu c s phn cc t pht, v c mmen lng cc tng cng. Mt s cht ho in cng c tnh cht xenhet c th l hng phn cc t pht, trong c th quay ngc tr li di tc dng in trng ngoi. Do theo nh ngha th cc vt liu xenhet in cng l vt liu p (59)

42

in v vt liu ho in, nhng ni ngc li th cha chc, ngha l khng phi tt c cc cht p in c tnh cht ho in.
X1

X1

X2

X3

X1

+ +

X2

X3

X1

Hnh 171 S pht sinh lng cc khi nn tinh th thch anh theo hng vung gc v song song vi trc i xng bc hai

4.2

Nhm tnh cht t

Ngoi tnh nghch t c trng cho tt c cc hp cht v c, c mt s cht rn v c c tnh cht c bit, lin quan n s c mt nhng electron cha ghp i. Cc electron cha ghp i nh v trn cc cation kim loi. Bi vy nhng tnh cht t s ni n trong phn ny c trng ch yu i vi cc kim loi chuyn tip, cc lantanoit v rng cc hp cht phn ln c cc electron d v f cha ghp i. C th phn loi cc vt liu t nh sau:
Vt liu thun t l vt liu m trong spin ca cc electron cha ghp i c th nh hng mt cch ngu nhin. Vt liu st t l vt liu m tt c cc spin ca cc electron cha ghp i c nh hng song song vi nhau, do c mmen t ln. Vt liu phn st t khi spin ca cc electron c thn cc v tr i song song v lng cc spin theo hai chiu ngc nhau bng nhau do mmen t tng cng bng khng. Loi vt liu ny cn gi l vt liu antiferomagnhetic. Khi lng spin theo hai chiu ngc nhau khng bng nhau th mmen t tng cng khc khng v gi l vt liu ferimagnhetic.

Nh vy l c mt mi tng quan gia tnh cht t v tnh cht in, c bit l tnh cht xenhet in. S khc nhau duy nht ch ch cc vt liu t khng c mt in tch t duy nht (n cc, monopole) tng t nh in tch in ngha l in tch ca ion, ca electron. Vt liu t trn c s oxit, v d ferrit (MgFe2O4), hin nay c s dng rng ri sn xut cc li bin th, cc thit b ghi t, gi cc thng tin. L thuyt v t kh phc tp, trong s dng nhiu danh t, k hiu, n v o rt d nhm ln nhau. Tnh trng cn rc ri hn na do trong thc t s dng c hai phng php nh gi mmen t ca cc ion c electron

43

c thn (hai phng trnh ny c khi cn mu thun vi nhau). Trong phn ny ch trnh by mt s kin thc ti thiu cn thit c kh nng hnh dung cc kiu vt liu t khc nhau v gii thch mi lin h vi cu trc tinh th.

4.2.1 Phn l thuyt

4.2.1.1 Cht trong t trng

Nu t mt cht trong t trng c cng H th mt ng sc trong mu (gi l cm ng t) bng tng s cng t trng H v mt phn gp no ca chnh mu na. B = H + 4I I l cng t ho ca mt n v th tch mu.
Bng 37 cm t ca cc cht khc nhau Cht Nghch t Thun t St t Phn st t Gi tr x in hnh 1.106 0 102 2 10 106 0 102 Bin thin x khi tng T khng gim gim tng Ph thuc vo cng t trng Khng Khng Ph thuc Ph thuc

(60)

t thm P v cm t c xc nh theo h thc sau:

P = B/H = I + 4 x; x = I/H cm t mol c xc nh theo h thc:

(61)

= x F/d
F l khi lng mol ca mu, d l t trng.

(62)

Cc vt liu t khc nhau l do s khc nhau ca cc gi tr P, , x v cc i lng ph thuc vo nhit nh th no. Cht nghch t c c trng bng gi tr m, b ca , x v P < I. Cht thun t th cc i lng dng (P > I, v x dng). Nu t trong t trng th s ng sc i qua cht thun t ln hn so vi s ng sc i qua chn khng, nhng s ng sc i qua cht nghch t th c phn gim i (hnh 172). Do cht thun t b t trng ht, cn cht nghch t b t trng y nh.

(a) H

(a) H

nghch t

nghch t

Hnh 172 Cht thun t v cht nghch t trong t trng

Cht st t c c trng bng gi tr v x ln, cn P >> I v do b t trng ht rt mnh. cht phn st t P > I cn v x cng c cc gi tr dng v gn vi cht thun t.
4.2.1.2 nh hng ca nhit . nh lut Curie Weiss

44

-1

nh lut Curie -Weiss nh lut Curie

lch = C -1 T (K )

Hnh 173 1 S ph thuc = f(T) theo nh lut Curie v Curie Weiss

cm t ca vt liu t khc nhau, khc nhau v s ph thuc vo nhit v ngay c gi tr cu chng. Nhiu cht thun t tun theo nh lut n gin ca Curie (c bit khu vc nhit cao) ngha l cm t t l nghch vi nhit .

= C/T

(63)

C l hng s Curie. Tuy nhin ph hp tt hn vi cc d kin thc nghim l nh lut Curie Weiss.

= C/(T+q)
1

(64)

q l hng s Weiss. Hnh 174 gii thiu hai kiu ph thuc ca cm t theo nhit = f(T). Vi cht st t v cht phn st t th s ph thuc vo nhit ca khng tun theo nh lut Curie v nh lut Curie Weiss (hnh 174). nhit thp, cht st t c cm t rt ln, khi tng nhit th gim mnh (hnh 174b). Trn nhit Curie (Tc) th mt tnh st t v bin thnh cht thun t v li tun theo nh lut Curie Weiss. cm t ca cht phn st t tng khi tng nhit (hnh 174c). Nhit m cm t c gi tr cc i gi l nhit neli TN. Trn TN vt liu tr thnh thun t. (a) Thun t x
Tc Thun t (b) St t
(c) Phn st t Thun t

TN

Hnh 174 th biu din s ph thuc ca cm t vo nhit : (a) cht thun t; (b) cht st t; (c) cht phn st t

i lng ca cc vt liu khc nhau v s ph thuc ca n vo nhit c gii thch nh sau: cm t ca cht thun t c gi tr dng l do trong cht thun t c cc electron c thn ng thi spin ca chng c khuynh hng xp xp theo hng ca t trng. Trong vt liu st t, spin ca cc electron c sp xp song song v c tng tc t hp cc spin ca nhng ion cnh nhau trong mng li tinh th. Gi tr ln l do s sp xp song song ca spin trong cht ngay c khi nhit thp v t trng mnh. Trong cc cht phn st t, cc spin electron c sp xp i song song v b tr ln nhau. Do loi vt liu ny c

45

th c gi tr khng ln. Gi tr cn li lin quan n s mt trt t trong vic phn b spin. Vt liu no th khi tng nhit cng lm tng s chuyn ng ca cc ion v electron. Do iu ng nhin l khi tng nhit th khuynh hng ch yu l tng s mt trt t ca cu trc. Trong cc vt liu thun t th nng lng nhit ca electron v ca ion c kh nng b tr mt phn tnh trt t pht sinh ra di tc dng ca t trng ngoi. Thc t ngay t khi mt t trng ngoi th s nh hng ca cc spin electron li tr nn mt trt t. Do khi tng nhit th cm t ca cht thun t gim theo nh lut Curie v Curie Weiss. Vt liu st t v phn st t th khi tng nhit s lm tng tnh mt trt t ca s phn b sn c trt t ca cc spin song song v i song song. Vi cht st t th iu ny c tc dng lm gim khi tng nhit. Vi cht phn st t th vic gim mc trt t i song song li lm tng . Thng thng, c trng cho tnh t ca vt liu ngi ta dng gi tr mmen t m, v rng thng s ny lin quan trc tip vi s electron c thn. S ph thuc gia v l:
= N.2.2/3kT = 2,83 .T

(65) (66)

N l s avgar, b manheton Bohr, k l hng s Boltzmann v

cm t, mmen t ca mt cht c xc nh bng php cn t. Mu c t gia cc cc ca in t ri cn khi lng mu tu thuc vo cng ca t trng. Electron c thn trong cc cht thun t b t trng ht nn khi lng tng ln khi ngt nam chm in. Ngoi suy gi tr thu c ca cm t v cn tnh n cc yu t khc nhau, c bit l tnh nghch t ca mu v gi ng mu.
4.2.1.3 Tnh ton i lng mmen t

Hai nguyn nhn c bn pht sinh ra mmen t l spin ca electron v chuyn ng obitan ca electron. Phn gp ln nht cho mmen t tng cng l spin ca electron. C th m t mt cch th thin electron nh l mt in tch im m v t quay xung quanh trc ca n. Gi tr mmen spin trong mu theo cch m t nh vy bng 1,73 manheton Bohr (B) Trong : 1B = eh/4mc (67) y e l in tch electron, h l hng s Planck, m l khi lng electron, c l tc nh sng. tnh mmen spin ca mt electron th s dng cng thc:
s = g s(s + 1) (68)

y s = 1/2 l s lng t spin, g 2,00 tha s Lander, thay cc gi tr vo ta c s =1,73B. Vi nguyn t hoc ion c s electron c thn ln hn 1 th mmen spin tng cng bng:

46

S = g S(S + 1)

(69)

y S l tng s s lng t spin ca cc electron c thn. Nh i vi ion st cao spin Fe3+ c 5 electron c thn S = 5/2 cn = 5,92. Bng 38 gii thiu gi tr s ca mt s ion. Trong mt s cht, s chuyn ng ca electron quanh ht nhn cng dn ti s pht sinh mmen obitan, a mt phn gp vo mmen tng cng. i vi nhng cht nh vy, mmen tng cng bng:
S+L =
4S(S + 1) + L( L + 1)

(70)

L l s lng t obitan ca electron. Cc phng trnh (67) v (69) s dng tnh mmen t ca cc nguyn t cng nh cc ion c lp. i vi cht rn th phng trnh (69) khng s dng c, v rng cc mmen obitan b trit tiu hon ton hoc mt phn. iu ny l do in trng ca cc nguyn t xung quanh (hoc ion xung quanh) hn ch s chuyn ng obitan ca electron. Cc s liu thc nghim thu c v mmen t ca cc ion trn bng 38 v trong cn a thm nhng gi tr tnh ton theo phng trnh (69) v (70). a s trng hp gi tr thc nghim gn bng hoc c phn no hi ln hn gi tr tnh ton khi xut pht ch c mmen spin.
Bng 38 Gi tr thc nghim v l thuyt mmen t ca cc ion ca kim loi chuyn tip Ion S electron c thn S (tnh c) s+L (tnh c) thc nghim V4+ 1 1,73 3,00 ~1,8 V3+ 2 2,83 4,47 ~2,8 Cr3+ 3 3,87 5,20 ~3,8 Mn2+ 5 (trng thi cao spin) 5,92 5,92 ~5,9 Fe3+ 5 (trng thi cao spin) 5,92 5,92 ~5,9 Fe2+ 4 (trng thi cao spin) 4,90 5,48 5,1 5,5 Co3+ 4 (trng thi cao spin) 4,90 5,48 ~5,4 Co2+ 3 (trng thi cao spin) 3,87 5,20 4,1 5,2 Ni2+ 2 2,83 4,47 2,8 4,0 Cu2+ 1 1,73 3,00 1,7 2,2

Cc phng trnh va trnh by tnh mmen t da trn c s ca c hc lng t. Vic kho st mt cch chi tit ca phng php ny rt kh khn v b my tnh ton kh phc tp. S ph hp gia tnh ton v thc nghim ni chung l khng tt (xem bng 38). Thng thng, cc nh chuyn mn nghin cu v s dng cc cht st t cng nh phn st t dng mt phng php khc n gin hn nhiu tnh ton mmen t. Trong khun kh ca phng php ny ngi ta chp nhn rng mmen t ca mt electron cha ghp i bng 1mB. Nh vy th mmen t ca ion c n electron c thn bng nB. V d c hai ion cao spin Mn2+ v Fe3+ u c mmen t bng 5B. H thc chnh xc hn tnh ton mmen t c dng:
= gS

(71)

y g = 2 cn S = n/2 l trng thi spin ca electron. Gi tr mmen t s tnh theo phng php phn no thp hn gi tr thc nghim trong bng 38, du sao phng php ny cng c ch tnh . cho phng trnh (71) ph hp tt vi thc nghim phi thay i gi tr g, xem n nh mt thng s iu chnh. Phng trnh (71) ch tnh mmen t spin. Nu chp nhn rng g c

47

th ln hn 2 th iu ny ng vi vic a vo s b chnh c mt mmen obitan. V d vi Ni2+ ngi ta chp nhn l g = 2,2 2,3.
4.2.1.4 C ch trt t st t v phn st t tng tc trao i

Trong cc cht thun t, mmen t ca cc ion ring r c cha electron c thn, nh hng mt cch ngu nhin. Trt t ho chng ch xy ra di tc dng ca t trng ngoi. Nng lng tng tc gia t trng v lng cc c th tnh ton d dng. Trong phn ny khng nu chi tit ca vic tnh ton, nhng v ton b c th ni rng i lng nng lng ln hn nng lng nhit ca ion hoc ca lng cc v bng kT. Trong cc cht st t v phn st t th trt t nh hng ca mmen t xy ra mt cch t nhin. Bi vy, trt t cn phi c trng bng mt nng lng dng no ca s tng tc gia cc spin cnh nhau c sp xp song song hoc i song song. S ghp i ca cc spin hoc tng tc tp th ca chng c bn cht c hc lng t. Hin tng xy ra c th hnh dung mt cch nh tnh, tuy nhin bc tranh r rng v dt im ca st t, v d nh st, coban cho n nay vn cha bit c. Tng tc ca cc spin xy ra trong cht phn st t gi l tng tc trao i. Qu trnh i vi niken oxit c trnh by trn s hnh 175. Ion Ni2+ c 8 electron d. Nu Ni2+ nm v tr bt din ca cc ion oxi th 2 trong 8 electron c phn b trong cc obitan eg (dz2 v dx2 y2). Nhng obitan nh hng song song vi trc ca t bo mng do chng nh theo hng ca cc ion oxi bn cnh. Nhng electron c thn ca obitan eg ca Ni2+ c th tng tc vi cc obitan p ca ion O2. Kt qu ca tng tc lm pht sinh ra mt trng thi kch ng lm chuyn electron t obitan eg ca Ni2+ ln obitan p ca ion oxi. Trn mi obitan p ca O2 c 2 electron ghp i i song song. Do trong trng hp nu ion Ni2+ v O2 nm gn nhau n ni tng tc electron c th xy ra th trong ton b tinh th s to thnh mt mch cc electron tng tc. Kt qu spin ca tt c cc ion Ni2+ bn cnh b ion O2 tch ra v nh hng i song song.
o b ita n p z o b ita n d 2 z

Ni2

O2

Ni

2+

Hnh 175 Tng tc spin ca cc electron d ca Ni qua obitan p ca ion oxi lm pht sinh tnh phn st t

4.2.1.5 Mt s khc nim khc

Vt liu st t c cu trc min tng t nh cu trc min ca cht xenhet in (cu trc men). Trong mi men nh vy tt c spin nh hng song song. Tuy nhin, mc du trong vt liu v ton b l bo ho t nhng cc men khc nhau vn c nh hng khc nhau. Di tc dng ca t trng ngoi, trong cc cht st t xy ra hin tng tng t nh hin tng trong cht xenhet in nm trong in trng. ng cong ph thuc t ho M hoc cm ng t B vo cng t trng H cng c vng t tr (ging nh vng t tr trong cht xenhet in hnh 165). Khi gi tr cng t ln s t bo ho t, lc

48

spin ca tt c men nh hng song song vi nhau. S t ho v kh t ca vt liu trong t trng theo hng ngc nhau th xy ra s tn nng lng, thng thng thot ra di dng nhit. Gi tr nng lng t mt mt trong mt chu k (t ho - kh t) t l vi din tch ca vng t tr. l gi tr tn tht t trong vng t tr. i vi mt s lnh vc dng vt liu st t th yu cu cn thit l tn tht t trong vng t tr phi rt nh. iu c ngha l din tch vng t tr cng b cng tt. Vt liu c lc khng t Hc nh gi l vt liu t mm. Lc khng t l cng ca t trng ngc chiu cn thit t vo kh t hon ton trong vt liu . Vt liu t mm c c trng bng t thm thp, do nn vng t tr hp v din tch b. Vt liu t cng c c trng bng lc khng t cao t ho cn li Mr ln. Vt liu t cng rt kh kh t bi vy c s dng lm nam chm vnh cu. Trong tinh th vt liu st t, mmen t hp thnh c phn b dc theo mt s hng u tin. V d st hng song song vi cc trc ca t bo lp phng. Nhng trc nh vy gi l trc d t ho (hnh 176a). Nhiu vt liu t c tnh t gio, ngha l c th bin dng khi t ho. V d Ni v Co b co li theo hng t ho v gin ra theo hng trc giao. Trong t trng yu th st c c tnh ngc li, cn trong t trng mnh th dng ca st cng thay i nh Ni v Co. Mc thay i ny khng ln lm. H s t gio c xc nh bng t l s = L/Lo. Ni chung, s thay i kch thc di tc dng ca t trng cng ch tng ng vi s thay i kch thc khi un nng mu vi .

4.2.2 V d mt s vt liu t, cu trc v tnh cht

4.2.2.1 Kim loi v hp kim

Nm kim loi chuyn tip Cr, Mn, Fe, Co, Ni v a s cc lantanit u c tnh st t v phn st t. Rt nhiu hp kim v hp cht gia kim loi cng c c trng bng mt mc trt t t no . Hnh 176 gii thiu cc cht st t Fe, Co, Ni.
a c
60 o

Co, TC = 1404 K Ni, TC = 631 K -Fe, Tc = 1043 K Hnh 176 Trt t st t trong cu trc Fe (lp phng tm khi),Ni (lp phng tm mt) v Co (chc c lc phng)

Spin trong Fe nh hng theo hng 100 song song vi mt cnh ca t bo mng. Spin trong Ni nh hng theo hng 111 ngha l song song vi ng cho khi ca lp phng. Spin ca Co nh hng song song vi trc c ca t bo mng. Nhng v d ny chng t s tn ti tnh st t khng lin quan g n cu trc ca tinh th. Cr v Mn nhit thp l cht phn st t. Nhit Neli TN ca Mn v Cr bng 95 K v 313 K. Mng li tinh th ca mangan rt phc tp cn ca Cr th c mng li lp phng khi tm nh Fe. Trong mng li Cr cc spin nh hng i song song vi mt

49

trong cc trc ca t bo mng. Mt s c trng ca vt liu st t c trnh by trn hnh 177. Hnh a cho bit s ph thuc cm t (hoc mmen t) theo nhit . Trn trc tung t gi tr ca t ho bo ho ca st ng vi gi tr cc i ( 0 K), trc honh t t l nhit thc vi nhit Curie (gi l nhit quy i). Bi vy im Curie nhit qui i bng n v (T/TC = 1). S dng ta ny cho php so snh vt liu c nhit Curie khc nhau v mmen t khc nhau. Hnh a cho thy t tnh ca st v niken rt ging nhau, cc gi tr T/TC thp t ho bo ho ca kim loi khng thay i v bt u gim rt nhanh khi T gn ti TC. Trn nhit Curie th Fe, Ni, Co u l thun t. Gn nhit TC ng biu din khng tuyt tnh na. S sai lch lin quan n vic tn ti gn ca trt t spin. Trt t xa c trong trng thi st t (di TC) b bin mt, cn trt t gn vn gi c mt phn no trn TC. Bi vy nhit (hng s Weiss) hi khc TC.
t ho bo ho
0,8 0,6 0,4 0,2 0,2 0,4 0,6 0,8 1,0 T/Tc

-1

Cp (J/mol)

(a) Ni, Fe

8.10 6.10 4.10 2.10

4

(b)
60

(c) Fe
40 20

Ni
Tc
400 600 800

T(oC)

200 400 600 800 1000 T (K)

Hnh 177 Mt s tnh cht ca vt liu st t

a) S ph thuc ca t ho bo ho i vi t ho bo ho 0 K vo nhit quy i; b) S ph thuc gia gi tr nghch o cm t vo nhit (gn TC c sai lch vi s ph thuc tuyn tnh); c) Nhit dung ca Fe nh l mt hm i vi nhit . Vic chuyn t trng thi st t sang trng thi thun t nhit TC c m t bng nhng thng s nh l mt s chuyn pha loi hai bt k (hoc chuyn pha dng ). l mt v d ca s chuyn pha t trt t thnh khng trt t. Trng thi trt t tuyt i ch tn ti 0 K. bt k nhit no th cng xy ra qu trnh mt trt t, nhit cng tng th s mt trt t cng tng. S ph thuc ca nhit dung vo nhit i qua cc i TC (hnh 177c). Cc lantanit cng c mt cu trc t trt t do s c mt ca electron c thn 4f (tr nguyn t 4f0 l La v 4f14 l Yb v Lu). nhit thp hn nhit phng th a s cc lantanit u l phn st t. C mt s lantanit (ch yu cui dy) c th l st t hay phn st t tu thuc vo nhit . Khi gim nhit th cc nguyn t ny c bin ho sau: Thun t Phn st t St t Bng 39 gii thiu TC v TN ca mt s nguyn t.
Bng 39. Nhit TN (bin ho phn st t) v TC (bin ho st t) ca cc lantanit Nguyn t Ce Pr Nd Sm Eu Gd TN (K) 12,5 25,0 19,0 14,8 90 TC (K)

293

50

Tb Dy Ho Er Tm

229 179 131 84 56

222 85 20 20 25

4.2.2.2 Oxit ca kim loi chuyn tip

S thay i tnh cht t ca cc oxit ny cng lin quan n s thay i tnh cht in ni trong phn trc. Ba oxit thuc chu k 4 ca nhm ny l TiO, VO, CrO l cc cht nghch t. Trong cc electron d khng nh v tng ion M2+ ring bit m chuyn dch trong ton mng li, chng lp mt phn vng t2g. Hnh nh mmen t ca cc electron khng nh v khng tng tc vi nhau. Do cc cht ny nghch t v c dn in cao. Oxit ca cc nguyn t chuyn tip (MnO, FeO, CoO, NiO) nhit cao th thun t, cn nhit thp c c trng bng cu trc t c trt t, cc electron d nh v ti cc ion M2+ ring bit. Chnh s nh v ca cc electron c thn l nguyn nhn ca tnh t v khng c tnh dn. Cc oxit MnO, FeO, CoO, NiO nhit thp th phn st t, nhit cao th thun t. Nhit TN ca cc oxit l MnO - 153oC, FeO - 75oC, CoO - 2oC, NiO + 250oC. Cu trc tinh th ca tt c cc oxit trng thi phn st t cng nh trng thi thun t u ging nhau. nhit cao chng c cu trc kiu NaCl. C th tng tng v m t cu trc ny theo nhiu phng khc nhau. y tin nht l xem cu trc tinh th theo mt trong bn hng 1 1 1, ngha l song song vi ng cho ca t bo lp phng mt tm. V d cu trc tinh th NiO gm cc ion Ni2+ v O2 lun phin. Di 250oC cu trc tinh th chu s bin i thnh mt thoi sai lch, dc theo trc bc ba song song vi hng 1 1 1 mng li hi b co li. Trong MnO cng c th xy ra s co tng t nh vy. Ngc li, trong cu trc FeO dc theo trc ny c phn b gin ra. i xng ca cu trc gim, v rng tt c cc trc bc bn v ba trong s cc trc bc ba tr thnh khng i xng na. Ch cn mt yu t i xng l trc bc ba. Mc sai lch ca mng li lp phng khng ln lm do trn gin nhiu x tia X cha chc thy c. Nguyn nhn ca s sai lch mt thoi ca mng tinh th NiO lin quan n s trt t ho phn st t ca ion Ni2+. Trong gii hn ca mt lp cation, spin ca tt c cc ion Ni2+ nh hng song song vi nhau nhng i song song vi spin cc ion Ni2+ ca lp bn cnh (hnh 178). Siu cu trc t nh vy ch c nghin cu bng phng php th ntron. Lc s khuch tn ntron s xy ra trn ht nhn nguyn t cng nh trn cc electron c thn. Kiu khuch tn trn ht nhn cho ta bc tranh nhiu x tng t nh bc tranh nhiu x ca tia X. Cng ca cc pic trn gin ntron v trn gin tia X hi khc nhau. Cu trc phn st t (kiu khuch tn th hai) th hin di dng cc vch ph trn gin ntron ca mu bt. C th c hai nguyn nhn lm xut hin cc vch ny l: a) Tng tc tp th ca cc electron c thn c th dn ti xut hin siu cu trc.

51

Hnh 178. Cu trc phn st t ca MnO, FeO, NiO biu din t bo mng gi lp phng (khng v v tr ca ion oxi)

b) Ntron khuch tn trn cc electron c thn, trong khi tia X khng b khuch tn. Hnh 179 gii thiu gin nhiu x ntron ca MnO ghi trn v di nhit TN v gin nhiu x tia X ca mu bt MnO nhit phng.
Cng Nhiu x ntron 80K o a=8,85A
111* 311* 400 331* 511* 440 622

222

(a)

Nhiu x ntron 293K o a=4,43A

111 311 200 220

(b)

200

th rngen 293K o a=4,43A

20

111

220 311 40 60

(c)

80

Hnh 179. Gin nhiu x ntron v gin nhiu x tia X mu bt MnO ( = 1,542 )cc vch u c ch s Mille i vi t bo lp phng

So snh hai bc tranh nhiu x thu c trn TN (b v c) cho thy v tr cc vch tng t nhau nhng rt khc nhau cng . Cu trc kiu NaCl th cc gi tr hkl phi chn hoc l. Do 4 vch u tin trn hai gin nhiu x c cc ch s 111, 200, 220, 311 nhng trn gin nhiu ntron cc vch 200, 220 li c cng rt b. iu ny l do khuch tn ntron trn ion Mn2+ v O2 ngc nhau v du, t khc nhau v i lng. Bc tranh hon ton khc khi quan st gin nhiu x tia X, cc vch 200 v 220 c cng cao v rng tia X b khuch tn bng cc ion Mn2+ v O2 lan truyn cng pha. So snh cc hnh 179a v 179b cho thy di nhit TN trn gin nhiu x xut hin cc vch b sung (c nh du sao). Cc vch b sung l ca pha siu cu trc phn st t. Nh ni trn, i xng thc ca pha phn st t l mt thoi nhng mt cch gn ng c th xem nh lp phng vi thng s mng gp i. 80 K (<TN) a = 8,85 cn 293 K (>TN) a = 4,43 (hnh 178). Th tch ca cc t bo nguyn t t l vi nhau nh 8 : 1. Cc vch ph trn gin nhiu x

52

ntron ca pha phn st t c th ghi cc k hiu nh trn hnh 179a. Tt c cc gi tr hkl u l.

4.2.2.3 Spinen

V cu trc ca spinen c trnh by chng 2. Trong phn ny ch quan tm n phng din t tnh do s bn n cc spinen c cng thc MFe2O4. y M l cation ho tr 2 (Fe2+, Ni2+, Cu2+, Mg2+ ). Cc ferit thng thng l spinen o hon ton hoc o mt phn. V rng ion Fe3+ c 5 electron theo thuyt trng tinh th th khng thch hp vi v tr bt din. iu l th l cu trc t ca ferit c th l st t hoc cng c th l phn st t. iu ny do cc ion nm trong v tr t din c spin t nh hng i song song vi cc spin t ca cc ion nm trong v tr bt din (xem hnh 180). Trong hnh 180 khng v cc ion O2. Vic tnh ton mmen t ca cc spinen khc nhau c s dng h thc (71). V d tnh mmen t ca ZnFe2O4 nhit thp nht c cu trc spin o. [Fe3+]Te[Zn 2+, Fe3+]OcO4 V rng mt na s ion Fe3+ nm trong v tr t din, cn mt na khc th nm v tr bt din, spin ca chng i song song nn mmen tng cng ca ion Fe3+ bng khng, ion Zn2+ c mmen t bng khng. Vy y l cht phn st t. Kt qu thc nghim khng nh iu l ng (TN = 9,5K).
V tr 8a (t din) V tr 16d (bt din)

z y x

Hnh 180. Cu trc t ca spinen st t v spinen phn st t V tr 8a (t din), v tr 16d (bt din)

Vi ferit magie MgFe2O4 cng thu c kt qu nh vy. Tuy nhin thc t y l cht st t, ngha l c mt gi tr mmen t no . C th gii thch hin tng ny theo hai cch. Th nht l c th ferit c cu trc mt phn trn ln, trong mt phn ln Fe3+ nm trong hc bt din, cn mt phn nh Fe3+ nm trong hc t din. Nh vy, cc spin i song song ch b tr nhau c mt phn thi. Th hai c th l mmen t hiu dng ca ion Fe3+ cc v tr khc nhau khng ging nhau. Kt qu nghin cu thc nghim khng nh quan im th nht. nhit cao MgFe2O4 dn dn c cu trc spinen thun. Mc o ca spinen nhit phng ph thuc rt mnh vo ch ho nhit ban u. Quan trng nht l tc ngui lnh. Nh trong cc mu ti nhanh th mc o ca spinen s nh v mmen t ca nhng cht nh vy cao hn nhng mu lm ngui lnh chm n nhit phng. Ferit mangan l spinen trn ln, mc o ca n khong 20%. V rng c hai ion Mn2+ v Fe3+ u c cu hnh electron d5 nn mmen t chung khng ph thuc vo mc o v cch ch ho nhit. C th ch i rng MnFe2O4 l cht st t v mmen t chung ca n bng 5B. Thc nghim cng chng t iu .

53

ngha to ln nht v s phn b cation vo cc hc khc nhau c th ly v d ferit c thnh phn M1-xZnxFe2O4, y M l Mg, Ni, Co, Fe, Mn. Khi x = 0 th c cu trc spinen o, ngha l [Fe3+]Te[Fe3+,M2+]OcO4. Nu spinen o hon ton th c th tnh c mmen t ca cc ferit khc nhau c cc gi tr l: M = Mg, = 0; M = Ni, = 2; M = Co, = 3; M = Fe, = 4; M = Mn, = 5. Cc gi tr tm c bng thc nghim c phn no cao hn (hnh 181). Ferit km nguyn cht (x = 1) nhit phng c cu trc spinen thun. Tuy nhin spin ca ion Fe3+ nm trong hc bt din, nh hng mt cch ngu nhin v hon ton khng c trt t dc theo mt hng no c. Bi vy ZnFe2O4 thun t t ho bo ho bng khng. Khi hnh thnh spinen hn hp bng cch thay th mt phn Zn2+ vo v tr M2+ s xy ra s chuyn dn dn t cu trc spinen o ti cu trc spinen thun. Vic a ion Zn2+ vo hc t din li dn ti s y Fe3+ t hc t din vo hc bt din ngha l 3+ 2+ 3+ [Fe1-x Zn 2+ x ]Te [M1-x Fe1+x ]O c O 4 . Nu dung dch rn vn cn phn st t (MFe2O4 khi x = 0) th mmen t phi tng tuyn tnh theo x v khi x = 1 (ZnFe2O4) phi bng 10B. Tuy nhin rt lu trc khi t thnh phn x = 1 tng tc phn st t ca spin cc ion v tr t din v bt din b ph v v i lng t ho bt u gim. cc gi tr nh ca x i lng t ho bo ho thu c t thc nghim cn tng dn ph hp vi gi thit phn st t. Khi x = 0,4 0,5, s ph thuc t ho bo ho vo thnh phn dung dch rn i qua cc i.
t ho bo ho B
10 9 8 7 6 5 4 3 2 1

M1 -xZnxFe2O4 Mn Fe Co Ni

Mg
0,2 0,4 0,6 0,8 1,0

Hnh 181. S ph thuc mc t ho bo ho vo thnh phn dung dch rn

3+ 2+ 3+ [Fe1-x Zn 2+ x ]Te [M1-x Fe1+x ]O c O 4

T tnh ca cc ferit v s bin i ca chng c xc nh khng nhng ch bng gi tr ca mmen t ca chng m cn bng nhiu thng s khc. Trong c t ho bo ho Mbh, hng s t gio s, t thm P, hng s bt i xng tinh th hc v t K1. Tu theo mc ch thc t ngi ta c th chn cc ferit c nhng tnh cht thch hp. S thay i cc thng s t c th t c bng cch to thnh cc ferit hn hp dung dch ca hai hay nhiu ferit nguyn cht. V d, khi thay th ion Mn2+ bng ion Fe2+ trong MnFe2O4 c th to 2+ 3+ thnh dung dch rn Mn1-x Fe 2+ x Fe 2 O 4 vi thng s bt ng hng t bng khng. Thng s ny c trng cho s d dng ti nh hng mmen t ca cht trong t trng ngoi. S gim tnh cht bt ng hng t lm tng thm t l mt iu rt quan trng i vi ng dng thc t.
4.2.2.4 Granat

54

Mt s granat l vt liu t quan trng. Cng thc chung granat c th biu din di dng A3B2X3O12. A l ion c bn knh ln ( 1 ) v s phi tr 8. Trong tinh th granat th ion A nm trong tm lp phng bin dng. B v X l cc ion c kch thc b chim cc v tr t din v bt din tng ng. Trong granat c tnh cht t quan trng nht l: A = Y hoc l t him (Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), B v X l Fe3+. Mt trong s cc i din quan trng nht ca granat l granat ytri Y3Fe5O12. C th c cc t hp A B X khc na, v d:

55

A Grossula Uvarvit Pirp Andradit Ca3 Ca3 Mg3 Ca3 Ca3 Ca3 Na2Ca NaCa2

B Cr2 Al2 Al2 Fe2 CaZr Te2 Ti2 Zn2

X Si3 Si3 Si3 Si3 Ge3 Zn3 Ge3 V3

O O12 O12 O12 O12 O12 O12 O12 O12

Granat st ytri v tt c cc granat nguyn t t him u c nhit Curie t 548 n 578 K. nh gi mmen t ca cc granat cn phi tnh mmen t ca c ba kiu ion nm trong cc hc lp phng bin dng (s phi tr 8 k hiu 24c), hc t din (k hiu 24d) v bt din (k hiu 16a). Hnh nh spin ca cc ion nm trong cc nt 24d nh hng i song song vi spin ca nhng ion cc nt 24c v 16a. Mmen t ca cc ion Fe3+ chim hai v tr khc nhau thng b tr cho nhau, do c mt n v cng thc M3Fe5O12 ch cn mmen t ca mt ion Fe3+ cha bo ho. V rng ion Y3+ c cu hnh electron l d0 nn mmen t ca Y3+ bng khng. Vy mmen t ca granat st ytri phi bng 5B, thc nghim chng t iu ny. Mmen t ca granat t him c th tnh theo cng thc (3M 5)B. y M l mmen t ca ion v tr 24c. Ion Gd3+ c 7 electron f do Gd = 7B.Vy mmen t tng cng ca granat st gaoli phi bng 16B. Gi tr ny kh ph hp vi gi tr thc nghim. Vi ion Lu3+ (cu hnh f14) c Lu = 0. Do mmen t tng cng bng 5B, ph hp vi thc nghim. Mmen obitan ca cc ion t Tb n Yb c l khng b nn hon ton, bi vy gi tr M phn no cao hn gi tr tnh theo cng thc (69) l cng thc ch tnh n mmen t ca spin. Hnh 182 so snh cc gi tr thc nghim v tnh ton. Cc gi tr thc nghim u nm gia hai ng l thuyt, iu chng t rng mmen obitan ch b nn mt phn thi.

B
25 20 15 10 5 0 -5
Hnh 182. Mmen t granat t him 0 K 1- Tnh theo phng trnh (70); 2- Tnh theo phng trnh (69); 3- Gi tr thc nghim

1
Tb Cd Dy Ho

3
Er Tm Yb Lu

Mmen t ca granat t him ph thuc vo nhit c dng c bit. Mmen t granat t him 0 K gim khi tng nhit v nhit b tr th bng 0. Sau li tng nhng c du ngc li. n nhit Curie li gim n 0 (hnh 183). Nguyn nhn ca s ph thuc l do spin ca cc ion trong phn mng t him b mt trt t nhanh hn spin ca cc ion trong phn mng st.

56

Cc cation trong thnh phn granat d dng thay i bng nhng cation khc v do thay i mt cch h thng tnh cht t ca loi vt liu ny. V d ion ca nguyn t ho tr 3 c bn knh ln nm v tr 24c c th thay th mt phn bng cc ion Ca2+ v m bo tnh trung ho in th mt phn ion Fe3+ v tr t din li b thay th bng V5+, cng thc ca loi granat nh vy c th vit di dng:
3+ 3+ 3+ 5+ [Y3-2x Ca 2+ 2x ]Fe 2 [Fe3-x Vx ]O12

4.2.2.5 Imenhit v perpkit

Imenhit l tn gi ca mt nhm cht c cng thc ABO3, trong A l Fe, Co, Ni, Cd, Mg; B l Ti, Rh, Mn. Chng c cu trc tng t Cr2O3, hematit -Fe2O3 v corun -Al2O3. Imenhit c mng li mt thoi (a = 5,538, = 54o41) nhng tin nht xem n nh mng lc phng c kch thc ln (a = 5,048, c =14,026). C th tng tng mt cch n gin cu trc tinh th gm phn mng gi ghm chc c lc phng ca ion O2, cation chim 2/3 v tr bt din. Cu trc tinh th ca imenhit cng c th hnh dung l dn xut ca mng li NiAs trong 1/3 v tr bt din trng.
Mmen t B
18 16 14 12 10 8 6 4 2 100 -2

Dy3Fe5O12

nhit b tr nhit Curi

200 300 400 500 600

T (K)

Hnh 183. S t ho t nhin ca granat st-dydim ph thuc vo nhit

Cu trc perpkit trnh by kh k trong chng 2. Mt s oxit c cha Fe3+, Mn3+,4+ c cu trc perpkit l nhng cht st t. V d hn hp La3+Mn3+O3 v A2+Mn3+,4+O3 to thnh dung dch rn thay th bc hai.
3+ 3+ 4+ [La1-x A 2+ x ] [Mn1-x Mn x ]O 3

Trong ion c kch thc ln La3+ v A2+ nm v tr c s phi tr 12 cn ion Mn3+,4+ nm hc bt din. A2+ c th l Ca2+, Sr2+, Ba2+, Cd2+, Pb2+. Kt qu nghin cu chi tit cc h ny cho thy gin trng thi ca chng, tnh cht t c trng tinh th ca chng rt phc tp.
4.2.2.6 Magnhetplmbit

l khong vt c cng thc PbFe12O19. Hp cht cng c cu trc nh vy nhng trong ch b thay th bng bari BaFe12O19 c tn gi l hexaferit bari l mt cu t quan trng ca nam chm vnh cu. Cu trc ca magnhetplmbit cng ging nh cu trc ca Al2O3 (cng thc NaAl11O17 xem hnh 29, 141, 142). Hnh 141 cho thy -Al2O3 c cu trc gm cc lp oxi gi ghm chc c. Mi chu k c 5 lp. C mi lp c 4 oxi trong t bo mng, nhng n lp th nm th ch c mt ion oxi; do mi mt tng c (4 4) + 1 = 17 ion oxi. Trong -Al2O3 th ion Na+ c phn b cc v tr trong ca lp th nm. Cn trong

57

magnhetplmbit th lp th nm ch c 3 ion oxi (ngha l ch cn thiu 1 ion), v tr cn trng c ion kch thc ln Pb2+ hoc Ba2+ chim. Do mt tng ca magnhetplmbit c (4 4) + 3 = 19 ion v mt ion Ba2+ (hoc Pb2+). Hexaferit bari c cu trc t rt phc tp, v rng ion Fe3+ chim 5 v tr khc nhau trong tinh th. Tuy nhin mmen t tng cng ca BaFe12O19 bao gm mmen t ca 8 ion Fe3+ nh hng cng chiu v mmen t ca 4 ion Fe3+ nh hng theo chiu ngc li. Do mmen t tng cng bng 20B.

4.3

Cc tnh cht quang, vt liu pht quang v laze

4.3.1 S pht quang v cht pht quang

4.3.1.1 nh ngha v nhn xt m u Pht quang l tn gi chung ca hin tng pht ra nh sng ca cht sau khi hp th nng lng bn ngoi. C nhiu ngun bc x kch thch khc nhau. Nh quang pht quang l s pht quang do tc dng ca phtn nh sng. in pht quang l pht quang do tc dng ca nng lng in, cn pht quang tia m cc l dng tia m cc hoc chm electron c nng lng ln gy ra s pht quang, nu s pht sng ch ko di c 108 giy sau khi ngng kch thch th gi l s pht hunh quang. Nh vy, s pht hunh quang dng li hn ngay sau khi ly ngun kch thch. Nu sau khi ly ngun kch thch m s pht sng cn ko di tip tc (hng giy, hng pht, hng gi) th gi l hin tng pht ln quang.

Vt liu pht quang c cha hai thnh phn chnh: cht tinh th ng vai tr nn (v d ZnS, CaWO4, Zn2SiO4), cht hot ho thm vo tinh th nn mt lng rt t (v d cation Mn2+, Sn2+, Eu2+) i khi cn c thm mt lng cht ph gia th hai gi l cht ph gia tng nhy. C ch ca s pht bc x nh sng ca cht pht quang v c c trnh by trong hnh 184. Ni chung nng lng ca cht pht ra b hn nng lng ca tia kch hot, ngha l s pht sng ca cht rn thng thng chuyn dch v pha sng di so vi tia kch hot. Trong cc n hunh quang (lnh vc quan trng nht trong vic s dng cht pht quang v c) th bc x kch hot l nh sng cc tm (ngun bc x thu ngn).
S kch H hot H H H H H H H H H H H A H H (a) H H H H H H H pht tia H H H
S kch H hot H H H H H H H H H H H H truyn nng lng H S A H H H H H (b) H H H H pht tia

58

Hnh 184. C ch s pht quang a) Mng tinh th nn l H, a thm cht hot ho A vo b) Mng tinh th nn l H, a thm cht hot ho A v cht tng nhy S.

Hnh 185 gii thiu s mt bng n hunh quang: gm mt ng thu tinh bn trong ph cht hunh quang. Trong ng c lp y hi thu ngn v argon. Khi phng in qua bng n cc electron va p vo nguyn t Hg trng thi kch ng, cc electron chuyn sang mc nng lng cao hn. Khi chuyn tr li trng thi c bn chng s gii phng ra cc tia cc tm c di sng 2540 v 1850. Cc tia ny va p ln lp cht hunh quang ph mt bn trong ng lm pht nh sng trng.
ng thu tinh
-

ph cht hunh quang

1850

Hg

2540

nh sng trng
Hnh 185. S n hunh quang

Hnh 186 l quang ph bc x ca cc cht hunh quang trn c s nn ZnS c hot ho bng cc cht khc nhau. Mi cht hot ho ng vi mt quang ph c trng lm cho nn tinh th ZnS c mt nh sng nht nh. Trong qu trnh pht quang, cc ion cht hot ho u trng thi kch ng.
c ng bc x Co Mn Ag
xanh da tri l cy
4000 5000

vng
6000

Hnh 186. Quang ph hunh quang ca cht pht quang trn nn ZnS c cha cc cht hot ho khc nhau, khi bc x bng nh sng cc tm Ion Ag+ Sb3+ Eu
2+

di bc sng ()

Trng thi c bn 4d10 4d105s2 4f7

Trng thi kch thch 4d95p1 4d105s15p1 4f65d1

Cht nn dng iu ch tinh th pht ln quang gm hai nhm:

59

Cht in mi c trng bng kiu lin kt ion. V d Cd2B2O5, Zn2SiO4, apatit 3Ca3(PO4)2.Ca(Cl,F)2, khi a cht hot ho vo tinh th nn ny s pht sinh ra mt dy mc nng lng gin on. V tr ca cc mc nng lng c bin i bng s bao quanh tng khu vc ca mng tinh th cht nn. m t tnh cht pht quang trong cc hp cht ion ny ngi ta dng to hnh th (configuration). Cc sunfua bn dn vi lin kt cng ho tr, v d ZnS. Trong cu trc vng ch yu c bin ho bng cch thm cc mc nng lng nh v do a thm ion kch hot vo.

4.3.1.2 Mu to hnh th (configuration coordinate)

Biu din th s ph thuc th nng ca trng thi c bn v trng thi kch thch ca electron tm cht pht quang vo to tng qut (thng l khong cch gia cc nguyn t). Hnh 187 trnh by s ph thuc ca trng thi c bn. ng cong th nng cho php nh gi nh tnh s thay i th nng ph thuc khong cch gia cc nguyn t. ng cong i qua cc tiu ng vi i lng cn bng no ca di lin kt re. Trong trng thi c bn ca electron ch c th c nhng trng thi dao ng gin on khc nhau ca ion ng vi cc mc nng lng V0, V1 ng cong th nng trn hnh 187 tng ng vi mi trng thi electron ca tm pht quang.
Th nng

re

V2 V1 V0

Khong cch cc nguyn t

Hnh 187. S thay i th nng ca trng thi c bn ca tm pht quang ph thuc vo khong cch gia cc nguyn t trong tinh th ion

Hnh 188 m t v tr in hnh cc ng cong th nng ca trng thi c bn v ca trng thi kch. S dng hnh 188 gii thch mt s nt c bit ca cht pht quang. Trc ht, qu trnh kch thch l chuyn tm hot ng t mc nng lng A ca trng thi c bn ln mt trong cc mc dao ng cao hn. V d mc B ca trng thi kch thch. Sau trong qu trnh tch thot (relaxation) nhanh trng thi kch thch s chuyn v mc nng lng thp C v xy ra s tch ly mt phn nng lng. Nng lng mt i di dng nhit. Cui cng tm hot ng quay v trng thi c bn ca mnh (ln mc A, hoc mc D) v pht ra nh sng. V rng nng lng kch hot chuyn t A n B cao hn nng lng pht ra khi chuyn t C n D, nn bc x pht ra c c trng bng sng di hn so vi bc x kch hot. Hnh 188 c th gii thch hin tng tt nhit xy ra khi mt nhit cao no th s pht sng ca cht pht quang gim i r rt.

60

Hnh 188 cho thy im E ng cong th nng ca trng thi c bn v ng cong th nng ca trng thi kch thch giao nhau. Nh vy, im ny ion trng thi kch thch c th chuyn v trng thi c bn cng mc nng lng. Nh vy im E l im di chuyn c bit. Nu ion chuyn vo trng thi kch thch c nng lng v t im E th n c th ri ln mt trong nhng mc dao ng ca trng thi c bn. Nu iu ny xy ra th tt c nng lng tch ra c thot ra di dng nng lng dao ng v khng c s pht sng. Bi vy nng lng ng vi im E c gi l nng lng ti hn. Mc ti hn nh vy ca nng lng c th t c bng cch un nng v rng khi nng lng nhit ca ion tng ln v kh nng chuyn ln mc dao ng cao hn.

61

Hnh 188. S thay i th nng ca trng thi c bn v trng thi kch thch ca tm cht cht pht quang ph thuc vo khong cch gia cc nguyn t

iu trnh by trn y gii thch hin tng tt nhit kiu chuyn tc l mt trong cc v d ca s chuyn khng bc x. Trong nhng qu trnh chuyn nh vy ion kch thch mt nng lng d ca mnh bng cch truyn nng lng dao ng ra xung quanh trong mng li ca tinh th nn. trng hp ny, ion kch thch c th quay li mc nng lng thp m khng pht ra bc x in (ngha l nh sng).
chuyn nng lng th nng Kch thch bc x

Trng thi c bn ca cht tng nhy

Trng thi c bn ca cht hot ho

Hnh 189. Chuyn nng lng khng bc x trong cht hunh quang c cha cht tng nhy

Mt kiu khc ca s chuyn khng bc x lin quan n trng hp cht pht quang cha cht tng nhy gi l s chuyn nng lng khng bc x (hnh 189). S chuyn nng lng khng bc x c thc hin nu: + Mc nng lng ca cht hot ho v cht tng nhy trng thi kch thch gn nhau. + Ion cht hot ho v cht tng nhy chim v tr gn nhau trong mng li tinh th nn. Trong trng hp nh vy, di tc dng ca chiu sng kch thch, trc ht chuyn tt c cc ion ca cht tng nhy ln trng thi kch thch. Sau mi xy ra s chuyn nng lng ln ion ca cht hot ho bn cnh. Lc ny qu trnh chuyn khng xy ra s mt nng lng (hoc ch mt mt phn nng lng khng ng k), cn ion ca cht tng nhy li chuyn v trng thi c bn. Cui cng cc ion hot ho chuyn sang trng thi c bn v pht ra nh sng. S chuyn khng bc x nng lng l c s ca tc dng nhim c do mt s tp cht. C ch ca tc dng nhim c l vic chuyn nng lng t cht tng nhy hoc cht hot ho sang nguyn t tp cht. Lc ny nng lng khuch tn trong mng li tinh th ca cht nn chuyn thnh nng lng dao ng. Khi iu ch cc tinh th ln quang cn phi loi

62

ht cc ion c khuynh hng gy ra s chuyn khng bc x v trng thi c bn (v d Co2+, Fe2+, Ni2+).
4.3.1.3 Mt s vt liu pht ln quang

Hin nay nghin cu thc nghim rt nhiu h kiu nn-cht hot ho vi mc ch xc nh cc c tnh ch yu ca chng nh l nhng cht pht ln quang. Trong c nhiu h t ra c trin vng s dng thc t. Tuy nhin, cc tin b trong vic to ra nhiu vt liu pht quang mi u lin quan n vic gii thch mt cch l thuyt mi quan h gia cu trc tinh th v v tr mc nng lng ca cc ion tp cht. Di y a ra vi v d ca vic s dng cht pht quang. Trong cc bng n hunh quang s dng rng ri cht pht quang trn nn apatit vi cc ph gia l ion Mn2+ v Sb3+. Fluoapatit c cng thc Ca5(PO4)3F, a thm Sb3+ th s pht ra mu vng da cam, ng thi a c hai ion Mn2+ v Sb3+ s cho mt ph pht x kh rng ca vt liu pht quang bao gm ton vng pht nh sng trng. Thay th mt phn F trong fluoapatit bng ion Cl c th thay i s phn b di sng ca ph bc x. Hiu ng ny c gii thch nh sau: thay th Cl vo v tr F lm thay i v tr mc nng lng ca cc ion hot ho v do lm thay i di sng bc x. Nh vy, s thay i thnh phn ho hc ca cht pht sng l mt bin php c hiu qu t mu mong mun khi chiu sng.
Bng 40. Mt s cht pht quang s dng trong n hunh quang Cht pht quang Hot ho Mu Villemit Zn2SiO4 Mn 2+ Xanh da tri Y2O3 Eu3+ iopzit CaMg(SiO3)2 Ti Xanh Vollastnit CaSiO3 Pb, Mn Xanh (Sr,Zn)3(PO4)2 Sn Da cam Fluoapatit Ca5(PO4)3(F,Cl) Sn, Mn Trng

Ion hot ho l Eu3+ c gi tr quan trng nht. Khi a n vo cht pht quang s cho nh sng mu , iu ny c s dng cho mn nh v tuyn mu. Trong cht pht quang YVO4:Eu3+, nhm [VO4]3 hp th nng lng tia m cc trong ng pht electron, ion Eu3+ l mit (cc pht) pht nng lng. Vic chuyn in tch t nhm VO43 cho Eu3+ hnh nh l qu trnh khng pht x xy ra theo c ch trao i qua ion O2. S pht sinh trt t phn st t ca cc ion Ni2+ trong NiO cng gii thch bng c ch ca s tng tc trao i nh vy. S chuyn nng lng trong cc cht pht quang theo c ch trao i c bit c hiu qu nu lin kt ho hc kim loi oxi kim loi dc theo mt ng. Chnh trong trng lc mi t c s xen ph cc i cc obitan nguyn t. Trong cht pht quang YVO4:Eu3+ gc gia cc lin kt vanai oxi ropi bng 170o, do vic chuyn nng lng c thc hin mt cch nhanh chng. Khi dng cht hot ho l ion Eu3+ th v nguyn tc c th thc hin s chuyn nng lng ln cc mc f khc nhau. Nhng s chuyn khc nhau nh vy c th quan st c v rng mu ca cc cht pht quang ph thuc vo cu trc ca tinh th nn, c bit l vo v tr i xng m ion Eu3+ chim. Nu Eu3+ nm tm i xng (v d khi hot ho cc tinh th NaLuO2 v Ba2GdNbO6 bng Eu3+) th xc sut ln nht l kiu chuyn 5D07F1. Kt qu cht pht quang ny pht ra nh sng mu da cam. Nu Eu3+ khng nm tm i xng (nh trng hp NaGdO2-Eu3+) th xc sut ln nht l kiu chuyn 5D07F2 v nh sng l mu . Nh vy cu trc tinh th nn c gi tr bc nht i vi mu ca cht pht quang.

63

chun b lm mn hnh ca cc v tuyn mu ngi ta s dng cc cht pht quang m cc c ba mu: (thng thng l YVO4-Eu3+) Xanh (ZnS:Ag+) Da tri (ZnS:Cu+).

chun b lm mn hnh ca v tuyn en trng, s dng hn hp xanh (ZnS Ag+) v vng ((Zn, Cd)S:Ag+) lm cht pht m cc.
4.3.1.4 Cht pht quang phn tch tr
(a) Giai on kch thch th hai Giai on kch thch th nht
Kch thch (b)

Pht quang

Pht quang

Hnh 190. S ca qu trnh xy ra trong cht pht quang phn tch tr (a) v trong cht pht quang thng (b)

Trng thi c bn

Trng thi c bn

Cht pht quang phn tch tr l mt loi cht pht sng gn y ang c lu nhiu. Nt khc bit ca loi cht ny l n pht ra mt dng photon c nng lng ln (bc sng ngn) hn nng lng kch thch ban u. ng dng ca cht pht quang phn tch tr l cho php bin i bc x hng ngoi thnh bc x in t c nng lng ln hn (thnh nh sng thy c). D nhin y nh lut bo ton nng lng vn khng b vi phm. y qu trnh kch thch xy ra hai hoc nhiu giai on. Hin nay nghin cu kh k cc cht pht quang phn tch tr trn c s YF3, NaLa(WO4)2 v -NaYF4 vi cht tng nhy l Yb3+, cht hot ho l Er3+. Khi chiu nh sng vo cc cht pht quang bng nh sng hng ngoi th n pht quang mu xanh da tri. Trong thc hin chuyn 2 phtn b Yb3+ hp th trong qu trnh chiu sng vt liu bng tia hng ngoi ln ion Er3+ bn cnh. Sau hai giai on kch thch cht hot ho bt u pht ra sng in t trong vng thy c.

4.3.2 Laze
Laze rn lm vic da trn c s s dng cc cht pht quang phi tho mn mt s i hi c bit. Tn gi laze c rt ra t cc ch u tin ca Ligh Amplification by Stimulated Emission of Radiction (c ngha l khuch i nh sng bng bc x do kch thch ca s pht x). Qu trnh kch thch bao gm s chuyn cc tm hot ho sang trng thi kch thch (gi l qu trnh bm np), c th lu li trng thi ny mt thi gian kh lu. Trng thi c c trng bng phn ln cc tm hot ng u b kch thch c gi l trng thi kch o. Trong laze s pht mt photon nh sng bng mt tm hot ng s kch thch s pht sng bng nhiu tm hot ng khc, v tt c cc sng in t pht ra u cng pha. Do pht sinh ra mt chm rt mnh hoc mt xung bc x kt hp. Nm 1960 Meiman ln u tin ch to ra laze rubi. Hin nay lnh vc ny tr thnh mt mn khoa hc k thut c lp lin quan n vic s dng laze trong nhiu lnh vc khc

64

nhau nh: chp nh, gii phu, cc phng tin lin lc, o lng chnh xc Ngi ta ch to thnh cng rt nhiu kiu laze, c th phn tch thnh 3 kiu: laze kh, laze trn cc thuc mu s dng sng di v laze rn. y ch ni n laze rn.
4.3.2.1 Laze rubi

Laze rubi l my pht lng t quang hc u tin. n nay trn na th k qua ri m vn ang c s dng rng ri. Quan trng nht ca laze rubi l n tinh th Al2O3 c cha khong 0,05% khi lng Cr3+. Ion Cr3+ thay th Al3+ trong cc bt din bin dng ca tinh th corun lm cho corun c mu hng (t Cr3+) hoc xanh da tri (nhiu Cr3+). Hnh 191 biu din v tr mc nng lng ca ion Cr3+ trong rubi. Vic bm np laze c thc hin nh ngun nh sng mnh, v d bng n xenon. Khi electron d ca Cr3+ c th chuyn t trng thi c bn 4A2 sang trng thi cao hn 4F2, 4F1. Sau xy ra s chuyn khng bc x n mc 2E. Thi gian lu electron li trng thi kch thch 2E kh lu khong 5.103 giy. iu c ngha l kp to nn mt trng thi kch o. Bc x laze pht ra khi chuyn electron t trng thi kch thch 2E v trng thi c bn. S chuyn ny kch thch ng thi nhiu ion v bc x in t pht ra cng truyn theo mt pha.
Nng lng 103 cm-1
30
4

F1 F2

Chuyn khng bc x

20

2 10

hp th
4

E bc x lade 6934

A2

Hnh 191. Mc nng lng ca Cr3+ v bc x laze trong tinh th rubi

Hnh 192 biu din s thit b laze rubi. Phn chnh ca thit b ny l mt thi rubi di vi centimet, ng knh 1 2 cm. Thi rubi c bao quanh bng cc bng n pht xung. Mt u thi rubi c t gng phn chiu cc xung i vo ng rubi. u kia thi rubi t mt thit b c bit gi l chuyn mch Q. Ci chuyn mch Q ny c pht ra tia lade, hoc phn chiu tr li to mt chu k mi. Chuyn mch Q c th l mt gng quay. Cu trc nh vy cho php t c bc x c cng ti u, v rng cc xung nh sng pht ra c phn x t gng trc ra sau qua thi rubi lm tng cng ln.

Hnh 192. S thit b o laze rubi

4.3.2.2 Laze neodim

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Nng lng103 cm-1

20 4

F3/2 hp th 8800 bc x laz e 10600

4

10

I11/2

I9/2

Hnh 193. Mc nng lng ca ion Nd3+ trong laze neodim

Cht pht quang s dng ch yu trong laze ny thng lm bng thu tinh hoc granat nhm-ytri: Y3Al5O12. Tm hot ng trong vt liu ny l Nd3+. Hnh 193 c ch v tr cc mc nng lng v s chuyn nng lng khi laze lm vic. Bc x kch thch l mt bng n mnh. Khi hp th nng lng c th chuyn tip ln mt vi mc sau thc hin s chuyn khng bc x v mc kch thch 4F3/2, t 4F3/2 nhy v trng thi 4I11/2 km theo s pht tia laze c bc sng 10600 (vi thu tinh neodim) hoc 10640 (vi Y3Al5O12; Nd3+), thi gian lu li 4F3/2 kh ln v ph thuc vo nng Nd3+.
Cu hi v bi tp 1. Cc tp cht sau y: a) KCl; b) NaBr; c) CaCl2; d) AgCl; e) Na2O c nh hng n dn in ca tinh th NaCl khng? Nu c th nh hng nh th no? 2. Cng cu hi nh trn nu nh hng ca cc tp cht sau y n dn in ca tinh th AgCl? a) AgBr; b) ZnCl2; c) Ag2O. 3. Da vo gin trng thi hnh 151 gii thch ti sao ch lm vic v kh nng lm vic ca acquy lu hunh natri 200oC v 300oC li khc nhau? 4. Cu hnh in t ca canxi l 1s2 2s2 2p6 3s2 3p6 4s2. Gii thch ti sao canxi li c tnh dn in kim loi. 5. V m hnh vng nng lng ca silic (Si) vi rng vng cm l 1,1 eV. Nguyn t no c th a vo Si c vt liu bn dn loi p? V m hnh nng lng ca vt liu thu c khi mc nhn phn b cao hn mc ho tr l 0,01 eV. 6. Tinh th no ca cc cht sau y c tnh p in: NaCl, CaF2, CsCl, ZnS, NiAs, TiO2. Gii thch. 7. Nguyn tc s dng cn t xc nh vt liu thun t, st t, phn st t. 8. Gii thch t tnh ca cc spinen sau y:

a) b) c)

ZnFe2O4 phn st t; MgFe2O4 st t v mmen t tng khi tng nhit ; MnFe2O4 st t v mmen t khng ph thuc vo nhit .

9. Tnh dn in ca CaTiO3 v PbTiO3 thuc vo nhit khc nhau nh th no. 10. Thnh phn ch yu ca vt liu pht quang v chc nng ca tng hp phn . 11. Ti sao cht pht quang tch tr li c th pht ra nh sng c di bc sng ngn hn di bc sng ca bc x kch hot? iu ny c mu thun vi nh lut bo ton nng lng khng?

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12. Yu cu chung ca cc vt liu rn s dng trong laze.

67

Ph lc Mt s gi tr c trng ca kim loi

Tn Antimoan Bc Bari Berili Caimi Canxi Ch Coban Crm ixprozi ng Ecbi Galini Gali Gecmani Hafni Honmi Ini Irii Kali Km K hiu Sb Ag Ba Be Cd Ca Pb Co Cr Dy Cu Er Gd Ga Ge Hf Ho In Ir K Zn Tnc 630 961 710 1280 321 850 327 1492 1900 1500 1083 1525 1320 30 958 2000 1500 156 2443 63 419 RA 1,61 1,44 2,24 1,12 1,52 1,97 1,75 1,25 2,885 1,77 1,28 1,75 1,79 1,53 1,39 1,59 1,76 1,67 1,36 2,35 1,37 moxh 3,5 1 (2) 2 2 2 2 2,4 2,3 3,6 3 (4) 1,2 3 3 (1) 3 (2) 4 4 3 (1) 3 3,4 (6) 1 2 2,07(2) 2,70(8) 2,76(6) 3,00(12) 1,57(3) 1,67(4) 2,19(4) 2,35(6) 2,40(6) 2,47(8) 2,34(4) Pb2+ 4+ 2,18(6) Pb 2,052,14(6) 1,932,01(6) 2,02(6)Cr3+ 6+ 1,70(4)Cr 2,31(6) 1,86(2) 1,972,66(6) 2,29 (6) 2,44(7) 1,87(4) 2,00(6) 1,79(4) 1,94(6) 2,11(6) 2,23(8) 2,30(6) 2,42(8) 2,18(6) 2,32(8) 2,13(6) 2,03(6) 2,78(6) 3,00(12) 2,00(4) 2,15(12) dM-O T bo mng li rob 4,5067 o 57 6 lfmt4,0875 lfkt5,019 clf2,2856 3,5832 clf2,9788 5,6167 lfmt5,582 lfmt4,9502 clf2,507 4,069 lftk2,8846 clf3,5923 5,6545 lftm3,6147 clf3,559 5,592 clf3,6315 5,777 octhob 4,52 7,661 4,526 blend 5,6575 clf3,1946 5,0511 clf3,5761 5,6174 tetr3,2512 4,9467 lfmt3,8389 lfkt 5,32 clf2,6649 4,9468 d (g/cm3) 6,62 10,05 3,5 1,83 8,65 1,55 11,4 8,90 7,19 8,54 8,96 9,05 7,89 5,91 5,32 13,1 8,08 7,31 22,5 0,86 7,14

68

Lantan Liti Lutexi Magi Mangan Molipen Natri Neoim Niken Niobi Nhm rpi Osmi Palai Platin Poloni Prazeoim Rni Roi Rubii Ruteni St Samari Scani Selen Sronti

La Li Lu Mg Mn Mo Na Nd Ni Nb Al Eu Os Pd Pt Po Pr Re Rh Rb Ru Fe Sm Sc Se Sr

920 180 1700 650 1250 2620 98 1024 1453 2420 660 900 2700 1552 1769 254 935 3170 1960 39 2400 1539 1052 1400 217 770

1,88 1,55 1,72 1,60 1,37 1,40 1,91 1,82 1,25 1,47 1,43 2,06 1,35 1,37 1,39 1,76 1,82 1,37 1,34 2,54 1,34 1,26 1,80 1,64 1,40 2,15

3 1 3 2 2,3,4,7 (3,4,5) 6 1 3 (4) 2 (3) (4) 5 3 2,3 4 (6) 8 2 (4) 4 (6) 2,4 3 (4) 3,4.5.7 3 (4,6) 1 4 (6) 8 2,3 (4,6) (2) 3 3 (2) 4,6 2

2,46(6) 2,68(10) 1,99(4) 2,14(6) 2,25(6) 2,37(8) 1,89(4) 2,12(6) 2,10(6) 1,66(4) 1,82(4) 2,00(6) 2,39(4) 2,72(9) 2,40(4) 2,52(8) 2,10(6) 1,98(6) 2,04(6) 2,06(7) 1,79(4) 1,93(6) 2,35(6) 2,43(7) 2,03(6) 2,04(4) 2,02(6) 2,03(6) 2,50(8) 2,41(6) 2,39(8) 2,03(6) 1,97(6) 2,07(6) 2,02(6) 2,89(6) 3,13(12) 2,08(6) 2,02(6) 2,18(6) 1,86(4) 2,36(6) 2,49(8) 2,13(6) 2,27(8) 1,69(4) 2,56(6)

ABAC3,770 12,131 lfkt3,5092 clf3,5050 5,5486 clf3,2094 5,2105 lfkt 8,914 lfkt3,1469 lfkt4,2906 ABAC3,6582 11,802 lfmt3,524 lfkt3,006 lfmt4,0495 lfkt4,578 clf2,7353 4,3191 lfmt3,8907 lfmt3,9239 cub 3,345 ABAC3,6702 11,828 clf2,760 4,458 lfmt3,8044 lfmt 5,70 clf2,7058 4,2816 lfkt2,8664 rob 8,996 23o13 clf3,3080 5,2653 ABAC4,3655 4,9590 lfmt6,0849

6,17 0,53 9,84 1,74 7,43 10,0 0,97 7,0 8,90 8,40 2,70 5,26 22,6 12,0 21,4 (9,2) 6,77 21,0 12,4 1,53 12,2 7,86 7,54 3,0 4,79 2,6

69

2,84(12) Tantan Tali Thic Thu ngn Tecnexi Terbi Thori Titan Tuli Ta Tl Sn Hg Tc Tb Th Ti Tm 3000 304 232 -39 2700 1450 1700 1680 1600 1,47 1,71 1,56 1,55 1,35 1,77 1,82 1,47 1,74 (3,4) 5 1 (3) 2,4 1,2 (3)4(5,6)7 3,4 3,4 (2) 4 (2) 3 2,07(6) 2,04(6) 2,90(6) 3,16(12) 2,62(8) 2,09(6) 2,37(3) 2,09(2) 2,04(6) 2,32(6) 2,28(8) 2,40(6) 2,49(9) 2,26(6) 2,01(6) 2,27(6) 2,39(8) 2,45(9) 1,88(4) 2,1 (4) 2,19(6) 1,76(4) 1,81(4) 1,98(6) 2,26(6) 2,38(9) 2,29(6) 2,50(9) 2,12(6) 2,24(8) lfkt3,3026 clf3,4566 5,5248 tetr5,8315 3,1814 rob 3,005 70o32 clf2,735 4,388 clf3,599 5,696 lfkt5,0843 clf2,9506 4,6788 clf 3,5372 5,5619 octhob2,854 5,869 4,955 lfmt 4,0783 lfkt 3,028 lfkt 3,1650 lfmt 5,481 clf 3,6451 5,7305 clf 3,2312 5,1477 16,6 11,85 7,3 13,6 11,5 8,28 11,7 4,51 9,33

Urani Vng Vanai Vonfram Ytecbi Ytri Ziriconi

U Au V W Yb Y Zr

1133 1063 1920 3380 824 1500 1850

1,56 1,44 1,35 1,41 1,94 1,82 1,60

(3) 4(5) 6 (1), (3) 2-5 (4) 2,3 3 4

19,07 19,3 6,1 19,3 6,98 4,47 6,49

K hiu trong bng:

RA: l bn knh nguyn t () moxh: l mc oxi ho chnh (s ghi trong ngoc l mc oxi ho khng bn). Tnc: l nhit nng chy (oC) dM-O: l di lin kt trong mng li tinh th oxit () (s ghi trong ngoc l s phi tr ca kim loi trong mng tinh th ). T bo mng li c ghi hng s mng (): lfmt (lp phng mt tm a); lfkt (lp phng khi tm a); cdlf (chc c lc phng a, c); octhob (trc thoi a, b, c); rob (mt thoi a, ); tetr (t phng a, c); blend (tng t ZnS, a); ABAC (lc phng a, c); ABAB (lc phng a, c). d (g/cm3): t trng.