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. . « A4 B6 , », 1995 . , , 90- .

1.
A4 B6 (. 1.1) (). (PbS, PbSe, PbTe) SnTe - 5 NaCl ( Oh - F m 3m ) [8]. [9, 10, 11], . . , , 0 K . NaCl ; 700 K 1- [12, 13, 14], <111> C3v - R3m . SnTe (<100 K), [15, 16]. SnSe, SnS, GeSe GeS 300 K 16 GeS (. . D2h - P nm a) [8], NaCl (. 1.1). , GeTe ( -GeTe) [8], [17] -GeTe 2 , . . D2h - P nnn. 800­880 K SnSe SnS 2- -- TlI 17 (. . D2h - C m cm , . . 1.1), GeSe NaCl. , , 18 60 SnTe PbTe GeS [ 18, 19], PbS PbSe , , 22 45 TlI [19]. (, , GeS). , 130­215 - CsCl [ 19]. , GeTe [20]. 1


A4 B6 . , : , , ­, [21]. SnTe, PbTe GeTe [11, 22] [9, 23, 24, 25] -- (TO-) - , , . Pb1-x Snx Te Sn1-x Gex Te [26, 27], [28], [29, 30], [28, 31], [32, 33] [34, 35, 36, 37] . Pb1-x Gex Te , . [38], Pb1-x Gex Te [31] [31, 39] Pb1-x Snx Te. Pb1-x Gex Te, , , Ge ­ . . . 1.1 A4 B6 , . . 1.2 () , , . . . 1.3 , , A4 B6 , Pb1-x Gex Te, .

2


1.1. A4 B6
1945 . . , , , , [21, 40]. . [ 40, 41, 42, 43]. [44], - , , . , TO-
2 TO

= 2 - 2 d , d 0

(1)

2 d 2 -- - d 0 , . 2 d d
2 dd

=

4e 2 ( µv0



+ 2) ·

Z 3

2

,

(2)

Z -- , -- , µ v0 -- [1]. , - (2 d > 2 ) d 0 , TO-. . , -- -- , . , , [ 45]. [46, 47, 48]. , ( ) , , . , . 3


TO- , . , , TO-, TO-, , , [47]. . [33, 49, 50], A4 B6 , . , Pb1-x Snx Te Pb1-x Gex Te [24, 51, 52] [31] ; , [53, 54]. [55] - GeTe [56]. [1], , , , . , «» [57] - , . , , Z , 2 d , d , Z Z i ( ). . NaCl CsCl, [58] , A 4 B6 - . (2), ( = 17­45) . , TO- , 45. A4 B6 , , , , 4


. [59, 60, 61, 62, 63], . [64, 65] , p (- s- ). , . . . p- [66], . . , , , . Z (. [33]). A4 B6 , Bi, . . [60, 61, 62, 63] A4 B6 V . p- , - A4 B6 , A B [60]. , A B. , . , ( PbS GeTe) «» A4 B6 . , (SnTe GeTe) «» , Bi, . , [61], [62], Z 0 [63]. [60] A4 B6 . , ( ) , 5


: , , . . - GeTe , . , A4 B6 . A 4 B6 [67, 68, 69, 70, 71]. AN B10-N , - , «» r r s p- A B:
A B A B r = rp - rp , r = (rp + rsA ) + (rp + rsB ).

(3)

r A B p- ( ), r sp- . . 1.2 AN B10-N , r - r [67]. , A4 B6 . , sp- (Bi, Sb, As). ( A B ) (PbS, PbSe, PbTe). sp GeS. GeTe SnTe , V , , . , , . [70] A4 B6 , . , Z [68, 69], [69] [71], [70]. GeTe SnTe [70] . , . A 4 B6 [ 72], 6


[73], [74]. [75] - [76]. A4 B6 [77].

1.2.
1.2.1. A4 B6 , (SnTe, Pb1-x Snx Te) . 1.1 , - , Pb1-x Gex Te (, .) . [5, 78] , Ge Pb PbTe Ge, , . , , (). - () 60- [79] (. [80, 81] [82]). ( Li+ KCl) . , ( ), . , . [81]. . . , [81]. ( -- O N Si, N ) [83] , , . 7


[84]. , (, A1g F1u ), - . LiCl6 KCl , , Li KCl. [85, 86] . , , . , , , «» ( ) , , , « » -- . -- , , , ; , , 5 ( KTaO3 :Nb) 0.09 ( KTaO3 :Li). , . [ 87] , , - . , , , KCl:Li+ , KBr:Li+ RbCl:Ag+ [88, 89, 90]. , , [81]. , ( 1­1.5 ) [91]. . , , . , . Ge PbTe 1987 . [92] 8


(EXAFS) K- Ge L- Pb . , , Tc Ge ° <111>, 0.8 A. . , [93]. , Tc . (. . ), Tc Tc . , , . , [94], . [95] , . , [86, 96, 97, 98, 99, 100]. , , , ; , [93]. . : 1) , « » ( , , « » [99]) 2) , « » ( « » [ 99]). ( ) () . , « », . «» , , Tloc « » (. ) , . . , « ». «» , . , 9


«» [96, 97]. . [98, 99] . Tc «», , , , . , , , TO- . [95], , ( ) Tc , -- . ( Tc ), . , , [95, 100, 101]. , [95] , , . «», . «» . , , [95] , , , . [86], , , . - , . - (. [97]). KTaO3 :Li. , , , . , -, A4 B6 . [100, 101] , «» . . , . ; [102]. 10


1.2.2. , . , , . 1.2.1, , - , . 60- , , Tg , kTg - , [82, 103]. , , , Tg - ( 1/T ), Tg , . Tg ; , Tg , , . Tg - ; , , , . , OH- , Li+ . , - , T 0 . . , , - , [104] Hdd =
0

2

ij

1 (di dj ) - 3(nij dj )(nij dj ) , ri3 j

(4)

di dj -- , , nij = rij /rij -- rij , rij = |rij | -- i- j -. - , (V (r ) 1/r 3 ), , , . , , T = 0 , . () (). -

11


- [105, 106, 107]. , , , f (E ). , , . , f (E ), [105]. [108] , , . , Tg , 2/3. m , m = f (E ) · |P (E )|dE . (5) Tg m (T ) . , Tg 0 . . [82]. , , T = 0 . , , Tg , « », . , , , , Tg , , (. [109, 110]). , , . . , . (. . ) , . . - «» [ 110]. , , , ,

12


, , . , . 70- , KTaO3 , Na Li, [111]. [104]. , (4) . , , . - , «». «», [ 104], Rc = v/0 , v 0 TO- (2 (q) = 2 + v2 q2 ). . 1.1 0 , - A4 B6 2 , , 0 ° Rc ( 10 A). - [104] 1 Ki, (rij )di dj , (6) Hdd = j 2
i,j ,,

-- , Ki, (rij ) -- j - , r K (r ) = 1
0

+ (

4 2 e -r /Rc + + 2 3 r Rc 3V 1 1 1 1 +2 + - 3n n ) · 3 - e -r /Rc 3 2 r r r Rc 3r Rc -

(7) .

V -- , -- . (7) , K (r ) . , Rc rmin , , (4). , Rc > rmin , , , , (4).

13


, , . , , [ 112] . , , 3 xc · Rc 0.013 3 . xc · Rc 1/47 [113], , TO- 3 xc · Rc . [114] , , , , x < xc . [115] . , , ; - . , , , [116, 117] , . H =-
i,,

(ri )u (ri ),

(8)

-- , u -- - ri , . [116] ( , : u = q P P ) , , , (V (r ) 1/r 2 ), , . , 2/3. 14


[117] . , - + 2
2

>

G 3 nRc

Rc a

,

(9)

-- , n -- , a -- , G 1. . , . , ( Na KTaO3 ), [118]. Pb 1-x Gex Te ( , . 1.2.1, ), . . 1.3 Tc (x) Pb1-x Gex Te. Tc (x) = A(x - xc ) A = 1150 K, = 0.68 xc = 0.005 [119]. K1-x Lix TaO3 [120]. Tc (x) [121], - , ( ). Tc (x) x1/2 . , [122], x 1/3 , «» . , . Pb1-x Gex Te - [123]. ( Ge <111>). Tc (x) TO- . xc , (20 K), , 15


KCl:Li. , Ge Li. [82, 112, 124] , - 3 x · Rc < 0.1, . . , xc . , . [120] , [125], Tc (x) , V (r ) = V0 exp(-r /Rc )/r (. (7)). , , Rc T -1/2 , Tc (x) Tc (x) x2/3 Pb1-x Gex Te K1-x Lix TaO3 . [120] xc = 0.001 , (xc = 0.005), , , , . , . , Tc (x), , (. [126]). Tc , , , Tc . Tc ( ) (x - xc )1/2 . [127], Pb 1-x Gex Te «» . [128] , T1 , () ; - . T2 2- . , « » [85], [128] . , A4 B6 . , ( 16


), , , . PbTe, PbSe PbS , , Ge A4 B6 , , .

1.3. A4 B6
, , A 4 B6 , . -- , . Pb1-x Gex Te -- A4 B6 , Ge. Pb1-x Gex Te . [129], (Tc ) (. 1.3). , Pb1-x Gex Te 2- . [130, 131, 132] . Pb1-x Gex Te . q = 0 , [25, 133, 134] Pb1-x Gex Te. F1u ; Tc A1 E , . TO- [38, 135], Pb1-x Gex Te. , , . ( <100>) Pb1-x Gex Te

17


Tc [133]. , . [129] [133] , Pb1-x Gex Te . Pb1-x Gex Te, [136], Tc , , , [133]. , [127] Tc 18 K, Ge . Ge Pb1-x Gex Te, , (EXAFS) K- Ge [92]. , Ge ° 0.7­0.8 A <111> , . Tc , Pb-Te. Pb1-x Gex Te [137, 138, 139] [140] ; - [139] [141, 142]. A4 B6 p­n-. , . 1.3.1. , , A4 B6 , , Tc . , A4 B6 , , , . (T ) SnTe [52, 143]. , 18


(T ), . Pb1-x Snx Te [31, 144] Pb1-x Gex Te [31, 39] (. 1.4). , , , Tc , , r - , . [143] TO-, Tc - . SnTe [143] , , 10 . [145] , = 2.1 , 12- , TO-, , , . . , [146] A4 B6 . , , - TO- Tc . , TO-, TA- . SnTe , = 5 . Pb1-x Snx Te [147], Pb1-x Gex Te (20­48 ) [31]. TO- [148] . , -- . , . , , TO-. A4 B6 , L- , ( ) , . 19


Hint (k , k) = g1 (q · n)(Pq · n), (10)

g1 -- , Pq -- - , k , k -- , q = k - k, n -- k0 . , , Hint (r) = g2 · P 2 (r), (11)

g2 -- . [149], [145] : 1) , TO-, ; 2) A4 B6 - . [150], A4 B6 , [146]. [148, 150] . . , , (q, T ) q kF . , . , T = Tc , :
(1)

m kTc n

-2/3

,

(2)

m (kTc )2 n-1 ,

(12)

m -- , k -- , n -- . Tc Pb1-x Gex Te . [151]. [149, 150, 151] , [98, 99] (. . 1.2). 20


( , Tc |T - Tc |-1/2 ). T = Tc Nd 4 n
-4/3

,

(13)

Nd -- , -- . . [152] (T ) -- , Pb1-x Gex Te Pb1-x Snx Te. p-Pb0.99 Ge0.01 Te 15­22 K ( Tc = 37 K) , (. 1.5,). ( ) -- Ge, . , , . [153]. , p-Pb0.99 Ge0.01 Te (Tc = 35 K) [31], . [154] (T ) p-Pb0.985 Ge0.015 Te, Tc 48 K . (T ) (. 1.5,): , , , . , ( Tc ) Tc 0, -- , . --, , , . , . [154] , , T 0. , [119], , . . . . [155] . 21


(T ) p-Pb0.9 Ge0.1 Te [156] , Tc - . Pb1-x Gex Te, , Tc Tc , ( , ) . , . (T /Tc 10%) . (T ) Pb1-x Gex Te n- p- [119]. . , Ge (Tc > 50 K) . Tc (19­27 K) , . x = 0.008­0.01 10 K, x = 0.006 (Tc < 0) 20 K . -- , x = 0.006 4 K . , . , Pb1-x Gex Te Tc - [ 152], T < Tc . Pb1-x Gex Te Ge, , [157]. , [158]. Tc , . (T ) Pb0.994 Ge0.006 Te (Tc < 0) [119]. , , Tc (T ) . (T ) Pb0.96 Ge0.04 Te, . [159], 22


, 30 K, 0.4 20 /. . , -, , ( x, Tc = 120 K), -, , ( 7 ), . (T ), S- - Pb0.92 Ge0.08 Te [160]. , (T ) Pb1-x Gex Te -- . , , , . , , : , . 1.3.2. A4 B6 , (. . 1.1), , . 60- , 2- Eg , 1- Eg [161]. , A4 B6 . , , L- [3]. (., , [162]) L- T - L-. Pb1-x Gex Te [140], [163] [163, 164] , Tc ( ) Pb1-x Gex Te PbTe, Tc , . . 23


, T -. [165] k · p- A 4 B6 , . Tc D3d C3v T - Cs L-. , , , ( ) . , « » « ». T - ; T - 3- ( ) , . L- . E (k) ( ) ( ) A4 B6 [139]. -- [139], [141, 142] [142] Pb1-x Gex Te . C3v . . T - L- . , T - L-, E x = 0.015 4.2 K 4­8 5­10 [139]. [142] pPb1-x Gex Te x < 0.034 E , 18 . , . , , . , , , , . , . Eg . Pb1-x Gex Te Eg [137, 166] p­n- 24


[137, 167]. , x , , Tc (. 1.6), . . Tc dEg /dT . Eg (T ), , [161]. Eg (x, T ) Pb1-x Gex Te [25, 135, 138, 139, 168, 169] [170], , . . Tc Eg , [138], , . Pb1-x Gex Te [25, 135, 138, 168] . , (T ) Pb1-x Gex Te SnTe , ( ) , [25, 168] SnTe (12.5 ). [138] Pb1-x Gex Te x > 0.09 (n 3 · 1017 -3 ) , Tc L- T -. , L- T - , , [139, 170]. , Tc , . [ 171] A 4 B6 , - . TO- . Eg , , Eg : - , Eg , TO-, . [172] L- T - , [171, 173], , k = 0 , [173] 25


( k ). , [ 172], [171] L- T -. k = 0 , , . . - . [170], Pb1-x Gex Te , k · p. , . n- , BaF2 , = 5­6.3 ( ) = 70­163 ( ). , C3v - T -, . T - ( ) . L- , , T -. , L- T - (10 ) Pb0.99 Ge0.01 Te. 1.3.3. , 0 (T ) , , ( ). , ( ­), [ 21]. , . 1.2, . , ( Tc ) 0 , , -: 0 = C /(Tc - T ), C -- -. d(1/ 0 )/dT Tc 2. 105 K 103 K ­. A4 B6 ( ) 26


, 0 , . A4 B6 p­n-, , - -. p­n- , ( p- n-) [ 174]. , p-, n- . , A4 B6 : , Pb1-x Snx Te x > 0.25 p- . , p­n- , Eg . , 0 , . - P (E ) Tc p­n- . p­n-, , 0 . . p­n-, Pb1-x Gex Te x = 0.03, 0.045 0.06, [130]. C (T ) , , [129], , [129] . p­n- U , . [175] [130] P (E ). , E (P ) = c1 P + c3 P 3 + c5 P 5 , p­n T U . c5 , c3 , , Pb1-x Gex Te . C (T ) C (U ) . . [131] p­n- , . 27


p­n-. E = 2P + 2P 3 , -- -. , (T - Tc ), . , C (U ) p­n-. Tc p­n- , C -4/3 Vb - U , . . , p­n- . U C (T ) . [21]. . C (T ) C (U ) [130, 176]. [177, 178] , Tc p­n- Pb1-x Gex Te C -4/3 Vb - U . [179] p­n- Pb1-x Gex Te x = 0.02­0.06 . 0 1/C 2 (U ). 1/ 0 (T ) Tc 2, . , Tc p­n- , . C (T ) C (U ) p­n- Pb1-x Gex Te x = 0.027­0.06, [178] , ( = 3 · 10-11 .-. .), - (C = 6 · 105 K), Ps ( 1 /2 ). 10 K. , x 0 0.06 C , . [180], , , p­n-. E 4P . , p­n- , ( ) . [178] , C Ps : C = 3.1 · 104 K, Ps = 4.5 /2 . , 28


p­n- , p­n-, . p­n- , p­n- - . [155] p­n- Pb1-x Gex Te x < 0.02. C (T ) , . , , ( ), C (T ) 30 K. C (T ) p­n-. p­n- <100>, C (T ) , <111>, . , -- . [155] , - . - 0 p ­n-, . C (T ) [130, 179], . 0 , -. 0 (TO , LO ) -. Pb1-x Gex Te 0 [38, 132, 181]. [132] 0 , - x < 0.05 p- : 0 , , , . , , TO-. [181] A 4 B6 , 0 , . [182], PbTe TO (T ) Tcext , . 29


TO (T ) , Tcext . 0 ( ), Tcext , ( Pb, Te, ). Tcext , PbTe [183]. , A4 B6 , Pb0.56 Sn0.44 Te 2.5 [184], 6­8 K. 0 Pb1-x Snx Te , [30]; Pb1-x Gex Te [123]. 0 Pb1-x Gex Te(Ga) [185] Pb1-x Snx Te(In) [186]. 0 A4 B6 , III . , , Pb1-x Gex Te(Ga) 10 [187]. , , Pb1-x Gex Te, Pb1-x Snx Te Sn1-x Gex Te. Pb1-x Gex Se . 3, . Pb1-x Gex Te1-y Sey (x > 0.25) [188, 189]. (. [190]). , - .


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1-x

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44


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14. .., .., .. Pb1-x Gex Se. -- . . XI . . . (, 1987), . 2, . 83. 15. .., .. Pb1-x Gex Te1-y Sy (Ge, S). -- . . XI . . . (, 1987), . 2, . 20. 16. .., .. Pb1-x Gex Te1-y Sy , (Ge, S). -- . , . ., 1987, . 51, . 10, . 1683­1687. 17. .., .. A 4 B6 . -- , 1987, . 46, . 11, . 425­427. 18. .., .. A4 B6 . -- , 1988, . 30, . 2, . 531­535. 19. .., .. PbGeTeSe, PbSe­GeTe. -- . ., ., 1988, . 29, . 6, . 100­103. 20. .., .., .. . -- . . XI . . . . (, 1988), . 2, . 30­31. 21. Vavilov V.S., Lebedev A.I., Sluchinskaya I.A. The electrical and optical properties of semiconducting dipolar glasses. -- Proc. 19th Int. Conf. Phys. Semicond. (Warszawa, 1988), p. 1689­1692. 22. .. 5 C3v . -- . ., ., 1989, . 30, . 6, . 68­71. 23. .., .., .. Pb1-x Snx Te1-y Sey . -- . ., ., 1989, . 30, . 5, . 83­85. 24. .., .. Pb1-x Snx Te1-y Sey . -- . . XII . . . (--, 1989), . 1, . 48. 25. .., .. Pb1-x Snx Te1-y Sey . -- , 1990, . 32, . 6, . 1780­1784. 26. .., .. Pb1-x Snx Te1-y Sey Pb1-x Snx Te1-y Sy . -- , 1992, . 34, . 5, . 1491­1495. 27. .., .. Pb1-x Snx Te1-y Sy . -- . . XIII . . (, 1992), . 2, . 83. 28. .., .., .. PbTe1-x Sx . -- , 1993, . 35, . 1, . 169­172. 29. .., .. PbTe1-x Sx Pb1-x Gex Te. -- , 46


1993, . 35, . 3, . 629­635. 30. Lebedev A.I., Sluchinskaya I.A. Unusual phase transitions in Pb1-x Snx Te1-y Sey and Pb1-x Snx Te1-y Sy crystals induced by Sn off-center ions. -- Ferroelectrics, 1993, v. 143, p. 91­98. 31. Lebedev A.I., Sluchinskaya I.A. Ferroelectric phase transitions in IV-VI semiconductors associated with off-center ions. -- 8th Int. Meeting on Ferroelectricity (Gaithersburg, USA, 1993), Abstract P3-190. Abstracts book, p. 332. 32. Lebedev A.I., Sluchinskaya I.A. Glass-like behavior of electrical properties of quaternary solid solutions of IV-VI semiconductors with off-center ions near Curie temperature. -- MRS Fall 1993 Meeting (Boston, USA, 1993), Abstract P8-15. Abstracts book, p. 123. 33. Lebedev A.I., Sluchinskaya I.A. Low-temperature phase transitions in some quaternary solid solutions of IV-VI semiconductors. -- J. Alloys and Compounds, 1994, v. 203, N 1­2, p. 51­54. , , , : http://scon155.phys.msu.su/rus/impur_r.html

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