Химия дефектов - u124

21

kvx lh k jhklhf kh^_j`Zgby ijbf_kb jZkl_l b ijh\h^bfhklv JZkl\hj_gb_ `_ Zd p_ilhjghc ijbf_kb ih f_oZgbafm dhgljhebjm_fuo Zlhfguo ^_n_dlh\

Na2O ↔ 2 Na′Fe + O×O + V∙∙O

( → 2 FeO )

y\ey_lky g_[eZ]hijbylguf \ mkeh\byo ba[uldZ dbkehjh^Z ihkdhevdm \ZdZgkbb dbkehjh^Z Zggb]bebjmxl9∙∙O + 1/2 O2(g) ↔ O×O + 2 h∙.

>ey ijbf_kb-^hghjZ f_oZgbaf dhgljhebjm_fuo we_dljhgguo ^_n_dlh\ j_Z ebam_lky \ mkeh\byo ihgb`_ggh]h ^Z\e_gby iZjZ

Cr2O3 + 2 h∙ ↔ 2 Cr∙Fe + 2 O×O + 1/2 O2 (g)

( → 2 FeO )

<\_^_gb_ \ djbklZee ^\mo ihklhjhggbo ]_l_jh\Ze_glguo ijbf_k_c jZaebq gh]h agZdZ fh`_l ijb\_klb d wnn_dlm dhfi_gkZpbb aZjy^h\ dh]^Z djbklZee hdZ `_lky \ j_amevlZl_ e_]bjh\Zgby g_ijh\h^ysbf GZijbf_j h^gh\j_f_ggh_ e_]b jh\Zgb_ kmevnb^Z dZ^fby ^hghjghc b Zdp_ilhjghc ijbf_kyfb ijb\h^bl d lhfm qlh djbklZee ijbh[j_lZ_l k\hckl\Z baheylhjZ

Ga2S3 + Cu2S ↔ 2 Ga∙Cd + 2 Cu′Cd + 4 S×S

( → 4 CdS )

<hijhku

1.AZ\bkbl eb l_fi_jZlmjZ i_j_oh^Z³ijbf_kgZy ijh\h^bfhklv – kh[kl\_ggZy ijh \h^bfhklv´hl mjh\gy e_]bjh\Zgby djbklZeeZ dhgp_gljZpbb \\_^_gghc ijbf_ kb"

2.GZah\bl_ mkeh\by nhjfbjh\Zgby g_ij_ju\guo b h]jZgbq_gguo l\_j^uo jZk l\hjh\

3.< kemqZ_ dZdh]h f_oZgbafZ h[jZah\Zgby l\_j^h]h jZkl\hjZ fh`_l [ulv j_Zeb ah\ZgZ g_ij_ju\gZy jZkl\hjbfhklv"

22

4.DZd baf_gblky iehlghklv djbklZeeh\ ijb e_]bjh\Zgbb djbklZeeZ NaCl – oeh jb^hf fZ]gby djbklZeeZ ZrO2 – hdkb^hf dh[ZevlZ II djbklZeeZ Ga2O3 – hd kb^hf pbjdhgby IV) ?

5.Knhjfmebjmcl_ dZdmx ijbf_kv gZ^h \\_klb \ [bgZjguc djbklZee b ijb dZdbo mkeh\byo qlh[u jZamihjy^hq_gb_ ijhbahreh \ dZlbhgghc ih^j_r_ld_"\ Zgb hgghc ih^j_r_ld_"Hl\_l ijhbeexkljbjmcl_ ijbf_jZfb

AZ^Zqb b mijZ`g_gby

1.GZibrbl_ mjZ\g_gby hljZ`Zxsb_ \\_^_gb_ ijbf_kb \ fZljbpm ih f_ lh^m D:> b f_lh^m DW>

1		2		1	→	2
Z ZnO	→ Ga2O3;		^) As2O5			ZrO2;
[) Ga2O3	→	ZnO;	_)	ZrO2	→	As2O5;
\) CuCl	→	Cu2S;	`) Ag2S		→	AgCl;
]) Cu2S	→	CuCl;	a)	AgCl	→	Ag2S.

2.DZdh\ f_oZgbaf \oh`^_gby ijbf_kb \ kl_obhf_ljbq_kdbc djbklZee ^ey dhlh

jh]h D0= 10-30 D′s= 10-20 ijb ihklhygghc l_fi_jZlmj_"D0 – dhgklZglZ jZ\gh \_kby ijhp_kkZ we_dljhggh-^ujhqgh]h jZamihjy^hq_gby D′s – dhgklZglZ jZ\ gh\_kby ijhp_kkZ jZamihjy^hq_gby ih Rhlldb

3.<ZH bf__l djZkgmx ihehkm k\_q_gby k\yaZggmx k gZebqb_f \ZdZgkbc dbkehjh ^Z DZd baf_gblky bgl_gkb\ghklv k\_q_gby ijb e_]bjh\Zgbb <ZH hdkb^hf eb lby hdkb^hf Zexfbgby ijb m\_ebq_gbb ^Z\e_gby dbkehjh^Z"

4.Ijb hdbke_gbb gbd_ey h[jZam_lky nZaZ NiO bf_xsZy ijh\h^bfhklv j-lbiZ M\_ebqblky beb mf_gvrblky dhjjhaby NiO \ ijbkmlkl\bb Li2O? Cr2O3 ?

5.H[gZjm`_gh qlh jZajmr_gb_ ZrO2 ijb gZ]j_\Zgbb gZ \ha^mo_ ihl_jy dbkehjh ^Z m\_ebqb\Z_lky \ ijbkmlkl\bb P2O5 H[tykgbl_ wlh y\e_gb_

6.DZd h[tykgblv lhl nZdl qlh jZajmr_gb_ Fe2O3 ijb gZ]j_\Zgbb gZ \ha^mo_ aZ f_^ey_lky ijb aZ]jyag_gbb bkoh^gh]h hdkb^Z ^bhdkb^hf lblZgZ"

7.Kdhjhklv l\_j^hnZaghc j_Zdpbb ZnO + CuSO4 → ZnSO4 + CuO mf_gvrZ_lky ijb e_]bjh\Zgbb bkoh^gh]h ZnO hdkb^hf ojhfZ III). H[tykgbl_ wlhl nZdl

23

mqblu\Zy qlh ZnO - fZl_jbZe n-lbiZ Z iehlghklv _]h ih\ur_gZ ih kjZ\g_ gbx kh kl_obhf_ljbq_kdbf khklZ\hf

8.DZd baf_gblky kdhjhklv l\_j^hnZaghc j_Zdpbb )H &X&O2 → Cu + FeCl2 ijb e_]bjh\Zgbb&X&O2 kmevnb^hf f_^b II)?

9.PbCl2 - nZaZ k jZamihjy^hq_gb_f ih Nj_gd_ex \ dZlbhgghc ih^j_r_ld_ DZd baf_gblky bgl_gkb\ghklv ijhp_kkh\ ^bnnmabb ijb e_]bjh\Zgbb wlhc nZau kmevnb^hf k\bgpZ"

10.H[jZah\Zgb_ ribg_eb MgAl2O4 b^_l iml_f h^ghklhjhgg_c ^bnnmabb bhgh\ Mg2+ b _′ < dZdhf kemqZ_ [m^_l gZ[ex^Zlvky [he__ bgl_gkb\guc jhkl kehy ijh^mdlZ _keb ribg_ev bf__l kl_obhf_ljbq_kdbc khklZ\ beb _keb kehc MgAl2O4 ihemq_g jZkl\hj_gb_f B2O3 \ kl_obhf_ljbq_kdhc ribg_eb \ hdbkeb l_evghc Zlfhkn_j_"

EBL?J:LMJ:

1.L_jfh^bgZfbdZ b fZl_jbZeh\_^_gb_ ihemijh\h^gbdh\ Ih^ j_^ < F =eZah\Z

F F_lZeemj]by k

2.Gh\bdh\ B B Jhabg D F DjbklZeeh]jZnby b ^_n_dlu djbklZeebq_kdhc j_ r_ldb F F_lZeemj]by k

3.Nbklmev < NbabdZ b obfby l\_j^h]h l_eZ < -o l F F_lZeemj]by

4.=hgqZjh\ ? = K_f_gh\Z = < M]Zc Y : Obfby ihemijh\h^gbdh\ Mq_[ ihk

<hjhg_` Ba^-\h <hjhg_` mg-lZ k

5.<_kl : Obfby l\_j^h]h l_eZ L_hjby b ijbeh`_gby < -o l F Fbj

KhklZ\bl_eb

K_f_gh\Z =ZebgZ <eZ^bfbjh\gZ

Kmrdh\Z LZlvygZ IZ\eh\gZ

J_^Zdlhj Dmag_ph\Z A ?

24

IJBEH@?GB?

<Z`g_crb_ dhgklZglu b _^bgbpu wg_j]bb

IhklhyggZy :\h]Z^jh NA = 6,02 ×10 23 fhev-1

IhklhyggZy ;hevpfZgZ k = 1,38 ×10-23 >` × D-1 = 8,62 ×10-5 w<×D-1

IhklhyggZy IeZgdZ h = 6,62 ×10-34 >` ×k We_f_glZjguc we_dljbq_kdbc aZjy^ e = 1,60 ×10 –19 De :lhfgZy _^bgbpZ fZkku Z _ f ×10-27 d] FZkkZ ihdhy we_dljhgZ m0=9,11 ×10-31 d] Kdhjhklv k\_lZ \ \Zdmmf_ c = 3 ×108 f × k-1

FheyjgZy ]Zah\Zy ihklhyggZy R >` × fhev-1 × D-1

>` ×1018 w<

w< ×10-19 >`

LZ[ebpZ

OZjZdl_jbklbdZ f_`^hmaebc \ j_r_ldZo jZaebqgh]h lbiZ

Lbi j_r_l	Qbkeh	imklhl \	Dhwnn	Hlghkbl_evguc jZa
db	we_f_gl yq_cd_		dhfiZdl	f_j f_`^hmaebc
			ghklb
	HdlZw^j	L_ljZw^j		HdlZw^j L_ljZw^j
=PD D	4	8	0,74	0,41	0,225
=_dk D	4	8	0,74	0,41	0,225
HPD D	6	12	0,68	0,154	0,291
:efZa D	-	8	0,364	-	1,000

- jZaf_ju f_`^hmaebc ^Zgu gZ hkgh\Zgbb fh^_eb `_kldbo rZjh\

25

LZ[ebpZ

WglZeviby b wgljhiby h[jZah\Zgby \ZdZgkbc

\ djbklZeeZo ijhkluo \_s_kl\

DjbklZee	Lbi j_r_l	TF, K	HV, w<	SV / k
	db
Al	=PD	934	0,67	0,7
Ag	=PD	1235	1,13	1,5
Au	=PD	1338	0,95	0,7
Cu	=PD	1357	1,28	2,4
α-Fe	HPD	1808	1,4
K	HPD	337	0,39
Li	HPD	454	0,40
Mo	HPD	2890	3,2
Na	HPD	371	0,39
Nb	HPD	2741	2,6
Ni	=PD	1726	1,6
Pb	=PD	601	0,59
Pt	=PD	2045	1,51
W	HPD	3680	3,6	2
Zn	]_dk	693	0,53
C ZefZa	ZefZa	~3820	4,16
C ]jZnbl	]_dk		3,3
Ge	ZefZa	1211	2,10	7,5
Si	ZefZa	1683	2,32	8,0
Te	]_dk	723	0,8

26

						LZ[ebpZ
WglZeviby h[jZah\Zgby \ w< ^_n_dlh\ Rhlldb HS b Nj_gd_ey \
dZlbhgghc		HF b Zgbhgghc H′F ih^j_r_ldZo bhgguo djbklZeeh\
DjbklZee		Lbi j_	LF D	GS	HF	H′F
		r_ldb
NaF		=PD	1253	2,49	3,53	3,39
NaCl		=PD	1077	2,26	2,88	4,60
NaBr		=PD	1028	2,11	2,56	4,84
NaI		=PD	924	1,77	2,00	5,14
KF		=PD	1153	1,92	4,27	2,57
KCl		=PD	1049	2,20	3,46	3,73
KBr		=PD	1003	2,13	3,16	4,17
KI		=PD	1046	2,00	2,73	4,26
AgCl		=PD	728	1,98	-	-
AgBr		=PD	707	-	-	-
AgI		=_dk	825	-	0,6-0,8	-
CuCl		=PD	695	2,27	1,05	-
CaF2		=PD	1633	7,0-8,6	6,0	2,6-2,7
SrF2		=PD	1463	6,9-8,1	-	2,2-2,4
BaF2		=PD	1553	6,3-6,9	-	1,6-2,0
MgO		=PD	3073	4-9	-	-
CaO		=PD	2845	5,5-8	-	-
SrO		=PD	1703	5-7	-	-
CeO2		=PD	2223	2,0	4,2	20
ThO2		=PD	>3073	1,9	5,2	16
UO2		=PD	2449	~7	~10	~9

27

LZ[ebpZ

WglZeviby h[jZah\Zgby \ w< \ZdZgkbc b Zglbkljmdlmjguo ^_n_dlh\ \ ZefZahih^h[guo ihemijh\h^gbdh\uo kh_^bg_gbyo

DjbklZee	TF, K	H (VA)	H (VB)	H (AB)	H (BA)
GaP	1740	2,98	2,64	0,38	0,68
GaAs	1511	2,59	2,59	0,35	0,35
GaSb	985	2,03	2,56	0,08	0,32
InP	1343	3,04	2,17	0,42	0,89
InAs	1216	2,61	2,07	0,33	0,57
InSb	798	2,12	2,12	0,27	0,27
ZnO	>2073	5,41	3,00	5,98	5,43
ZnS	2123	3,47	3,13	1,45	1,74
ZnSe	1710	3,09	3,09	1,25	1,25
ZnTe	1512	2,54	3,60	0,96	0,78
CdS	2023	3,56	2,69	1,48	1,86
CdSe	>1623	3,18	2,65	1,25	1,42
CdTe	1248	2,75	2,75	0,94	0,94