Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.chem.msu.ru/rus/events/mendel-xiv/objects/plachinda.pdf Äàòà èçìåíåíèÿ: Tue May 25 12:26:29 2004 Äàòà èíäåêñèðîâàíèÿ: Sat Dec 22 17:59:57 2007 Êîäèðîâêà: ISO8859-5

..


- M2IIB5O9HAL

: ... .. .-.. ..

- 2003 .


..................................................................................................................................... 3 1. ........................................................................................................ 3 1.1. ....................................................... 3 1.2. - .......................................................................................... 6 1.2.1. . ........................................................ 7 1.2.2. ................................ 8 1.2.3. .................................................. 9 1.2.4. . ............................................................... 9 1.2.5. . ........................ 10 1.3. dijk . ................................................................................................................ 11 2. ................................................................................. 15 2.1. 2.2. 2.3. 2.4. 2.5. 2.6. 2.7. 3. 4. 5. 6. ................................................................................... ............................................................................. ....................................................... .............. ............................. .......................................................................... .................... 15 16 16 16 16 19 19

. ............................................................................................. 20 ...................................................................................... 20 .............................................................................................................................. 23 ............................................................................................................ 23

. ............................................................... 24

2



, , - (), - - . () - , . , . , , , .. . (XeCl ArF & KrF)[1]. . , . . , . , . . Pb2B5O9Br , . , . , . - , , ; ; ; , .

1.
1.1.

, () , , " ". 3


. [2] 1961 . = 694,3 (. 1). . , (.. = 347,15 ).

P, E P = 0 ( (1) E + ( 2 ) E 2 + (3) E 3 + ( 3) E 3 + ....) (1.1) (i) , , Pi = 0 i(1) E j (1.2) j . , .. , (2 n)=0. .. , , . ( ) P = an sin(n t + n ) (1.3)
, . P(2)
2 2 n (1.4) 2 E - 2 E = Å 0 2 P ( 2 ) t c t , . , , . , . . , , , r2, .. . ( 1.7) (1.4), ur r ur 2 ur 2 u (2 ) 2 E = Å 0 E + Å 0 2 E + Å 0 2 P (1.5) t t t Z 2

4


: Ei1(z,t) = Re[E1i(z) exp i(1t-k1z)], (1.6) Ek2(z,t) = Re[E2k(z) exp i(2t-k2z)], (1.6)b Ej3(z,t) = Re[E3j(z) exp i(3t-k3z)], (1.6) , (1.5) . (1.6)) 1.5 , 12Å0=k12,

. , 1 = 2 => 3 = 2 1. , (1) , .. dE1i/dz Ë 0. 3, 3=0 dE3 j Å = -i 0 dijk E1i E1k exp(ikz ) (1.7) dz = 1 = 1/2 3, k = k3(j) - k1(i) - k1(k), k1(i) - 1, i. E3j(0) = 0, .. , l, (1.7)

=3. P2 ,

S - . 1Ë3Ë0n2 .

, 1. , [P()]2. 2. dijk, [(2)]2 3. l2 `sin2(x)/x2'-, l , , , . 4. k=0. , .. . k(2)=2k(), , . (2) ijk(1, 2, 3) . (2) , , , 27 . , dijk=1/2(2)ijk.
5


Px d11 Py = d 21 P d z 31

d12 d d
22 32

d13 d d
23 33

d14 d d
24 34

d15 d d
25 35

Ex2 2 Ey d16 2 Ez d 26 2 Ez Ex d36 2E E xz 2 E y Ex





, .. 18 . dij=0. 32 21 . (P1 - ), 18 . , [3], , , i,j,k , 18 10[4].
1.2. -

, 1. 2. 3. (walkoff angle) 4. , 5. 6. 7. 8. . 1975 , , . , KH2PO4 (KDP), (5)-(8), . , - . , (1), (2) (9) LiNbO3 KNbO3 . KTiOPO4 (KTP), , KDP LiNbO3 , KTP , . , . , , KB5O8*4H2O (KB5)[5]. -BaB2O4 (BBO)[6], , : LiB3O5 (LBO) [7], Ke2BO3F2 (KBBF) [8], Sr2Be2BO7 (SBBO) [9] , : , d33 = 64*10-9 esu LiNbO3 [10], 1, , . , 6


, Pb2B5O9Br, ( 1800 . SiO2 ) [11]. , - , ?Ë (B3O6)3-, (B3O7)5- (BO3)3-, .. , . [12], . , 1, , . . . , , [13] -[14] - [15,16], [17,18,19,20 . ]. .

1.2.1. . Pb2B5O9Br, , , (M3B7O13X) (M2B5O9X, M = , X = ). , , 1
1. .

() Cr, Co Mg,Cr,Mn,Fe,Co,Ni,Cu,Zn, Cd Cr,Mn,Fe,Co,Ni,Cu, Cd Cr,Mn,Fe,Co,Ni,Cu, Cd

F Cl Br I

() Ca,Sr,Ba,Eu,Pb Ca,Sr, Eu,Pb Cl Br

2

NdAl3(BO3) [21]


4

[BO3]3-
3

d11 (-5.81) d d d d d
11 13 32 21 22

Ca4GdO(BO3) [22] BiB3O6[23]

[BO3]3-
3-

Ba3(B3O6)2[24]

LiB3O5[25]

[B3O6] 2 [BO3]3- 1 [BO4]5- (1) [B3O6]3- 3 [BO3]3-, 6- B-O [B3O7]3- 2 [BO3]3- 1 [BO4]5-, 6- B-O

(-10.46); d (-0.37); d (-0.73); d (5.95); d15 (0.72); d23

(-1.03); 31 (-2.15); 33 (-0.22) (0.43); (-6.74)
12 22 32

d11 d31 d33 d31 d32 d33

(-0.07); d (-0.12); d (-0.12) (-2.22); (2.06); (-0.43)

(4.45); (-0.12);

7


K(B5O6(OH)4]. [B5O10]5- 4 2H2O[26] [BO3]3- 1 [BO4]5- 6 B-O Ca2B5O9Cl[27] [B5O12]9- 2 [BO3]3- 3 [BO4]5-, 6- B-O Eu2B5O9Br[28] [B5O13]11- 2 [BO3]3- 3 [BO4]5-, 6- B-O

d d d d d d

31 32 33 31 32 33

(-0.12); (0.02); (-1.03) (0.96); (0.74); (-0.03)

d31 (0.05); d32 (0.04); d33 (-0.38)

1.2.2. ( Ca2B5O9ClÇ(H2O), 59, BO4 BO3[29]. , , , , , (.2)

. 2 Pb2B5O9Br

8


713, BO4 3. , , , , . , ( 3), .
3 ( )

N 1 5 6 7 Ca2B5O9Cl Ca2B5O9Br Sr1.94Eu0.06B5O9Cl Sr1.94Eu0.06B5O9Br

. a(Õ) Pnnm Pnn2 P41212 Pnnm P41212 Pnnm Pnn2 Pnn2 Pmm2 Pnn2 11.2600 11.397 11.35 11.50
1

b(Õ) 11.13 11.256 11.35 11.38 11.58 11.574 11.301 11.382 11.320 11.431

c(Õ) 6.30 6.293 6.50 6.48 6.69 6.700 6.504 6.484 6.536 6.5399

Reference [34] [27] [34] [34] [34] [30] [28] [28] [27] [11]

1

9 Ba1.94Eu0.06B5O9Cl 10 Ba2B5O9C1 11 Eu2B5O9Cl 12 Eu2B5O9Br 13 Pb2B5O9Cl 14 Pb2B5O9Br

11.58 11.716 11.364 11.503 11.320 11.524

1.2.3. ( Aa) (YAG:Nd3+ -) . (I2=10-12 . SiO2) Ba2B5O9Cl*0.5H2O [30]. , [ 31]. Pb2B5O9Br Pb(1) Pb(2). , Pb-O Pb(1), Pb(2) , Pb(2) c Br- `' , "" . - , , , , . 1.2.4. . . [32,33] , Pb2B5O9Br, . , Na+, , , , [20].

9


[34] ( 1000À) . 1.2.5. . (M3B7O13X) - . , . , , : 5MeO+7B2O3+MeX2=2Me3B7O13X. , , ( ), MeO()+2HX()=MeX2+H2O. . 7B2O3 () +MeX2 () + . 5MeX2 () + 5H2O ()
. . HBO3 H3BO3 (BOX)3?

2Me3B7O13X () + 10HX()

5MeX2 () +5H2O ()

5MeO () +10HX ()

[35] . , 30 150, 3 .3 . B2O3, (.3). B2O3 1100

.3

10


200 B2O3. , . 2*H2O H3BO3, . . HX/H2O . , , B2O3. , . B2O3 , . : 900 5./20.
1.3. dijk .

d , . , , , [14,15]. , g=Eh+iC (1.4.1), Eg Eg2=gg*=Eh2+C2 (2). [36] . 2 2 (0)=1+ [(h p ) 2 / Eg ](1 - B + 1 B 2 ) = 1 + (h p ) 2 A /( Eh + C 2 ) (1.4.3), B=Eg/4Ef, A= 1 - B + 1 B 2 , 3 3
Ne 2 Ef - , p - p = . m , . . [40,37] [1(0)-1]-1=+(Z)2. 2 Eg C 2 2 (1.4.3) , = , .. , , ( Z ) = 2 ( h p ) 2 A Eh

(1.4.2) |Z-Z|, . , C , , Z Z C ( - ) (1.4.4). (1.4.4) r r , , , , . -. 4k k s = ( f a0 ) ,
kf - , kf3=32N. C (1.4.4) Z Z C = 1 be 2 ( - )e - ks R (1.4.5) , R = 1 (r + r ) , b 2 r r 4 0 . 0.14 0.7 1 4 . , , , , (1.4.5) (1.4.4) . a[40]

11


Eh r - s (1.4.6), r . C () Si (1=5.7 12.0 ) , s=2.48. , , - . (2), , , . q, , . dv [38] m = eE = eE0 e - i t , m - , edt , `- , , & v = ieE m , r ` r = v, r = eE m 2 , , , e 2 E e 2 0 P = er = 0 (1.4.7). 2 , , = m m 2
2 && [39] Z + 0 Z + vZ 2 = (eEz cos t ) m (1.4.8)

, (1.4.9) , cos(2t), 1 ve 2 Ez2 cos 2 t (1.4.9) , ( <<0) z (2 ) =- 26 2 m 0 , 1 ve3 2 Pz (2 ) = ez (2 ) = zzz Ez cos 2 t , zzz = - (1.4.10), 6 2 m 2 0 (1.4.9). z . , z >>Ez. Ez . e z z=0 z0= 2 , m 0 (0`) z -( ) 2 z + 2 z + 2 z z = 0
0 0 0 2 ( 0 ) = + 2 z0 = + 2 e z m 0 . 2 2 0 2 0

= e 2 0 m 02 ,
, z zz = (1.4.10) ,
zzz

=

1 zz . 4 z 0

-2ve3 z 0 , 6 m 2 0

(1.4.3) (1.4.7) , ( h p ) 2 2 Ne 2 ) DA = (h ) 2 f (1.4.11), f- , = 2 , ( h p ) = ( p m Eg . () (1.4.11). , (1.4.11)

12


, , =(nref2-1), nref - . , , P = 0 = qr (1.4.12) , - , . , q , , , (1.4.12) - , q . r Eh(Eh) (), Á. (1.4.11) , = -



E

b 2 g

[ ( Eh ) 2 + (C ) 2 ] (1.4.13).

(1.4.13) , Í(r+r)= r0, d=r+r=0, p=const . C (1.4.5) r C C = r = - 1 be - ks r0 ( Z + Z ) 2 e 2 , , rr r0=Í(r+r)=Íd 4 0 r r

r=r (1.4.12) C = -be
C = -

- k s r0

( Z + Z )

b e

2

qd

2

,

Z + Z r Z + Z 0 b , (C ) 2 = 2C C , = -2 C C qd Z - Z r0 Z - Z Z + Z 0 b2 f (1.4.14). - b (C ) 2 = 4 2 Z - Z i dq Eg (1.4.3) Eh (1.4.6) , r r. (1.4.6) Eh , , ( C). , , Eh (1.4.6) , dijk Eh r r , . , r r. , Eh r r Eh (r-r)2. , (1.4.6) , , , , . Eh, (Eh) - (1.4.6) ( Eh 2 ) (r - rc ) 2 s (1.4.15), rc - . , .. . , . (1.4.15) - . r , .. , , . , [11,12] rc r0 0.35. Eh2 (Eh2) (Eh2) , , .. ( h ) av = 1 2 ( h ) + ( h ) , (1.4.11) (1.4.2) ,
13


E

-2 h

=

1

2

( E

-2 h

) +(

, ( Eh-2 )

(1.4.16). (1.4.16) (1.4.15) ( r - r ) 2 s + ( r - rc ) 2 s - ( r - r0 ) 2 s + ( r - r0 ) 2 s , Eh-2 = ( Eh 2 )0 c (1.4.17), 2( r0 - rc ) 2 s E
-2 h 2 s -1

)

( Eh-2 )0 - , rr r0. , Eh2,
2 2 Eh = - s( Eh ) 0

( r - rc ) 2 s -1 + ( r - rc ) ( r0 - rc ) 2 s
3

r , =
2

r - r r + r



r E 2 , E = -4 s (2 s - 1) 0 h b (1.4.18). dq r0 - rc (1.4.18) (1.4.14) (1.4.13) , 2 2 Z + Z 4 2 Z + Z 2 r r = fi + s (2 s - 1) 0 f c 0 b , zzz = fi + s (2 s - 1) 0 f c b . Z -Z dq Z -Z dq r0 - rc r0 - rc zzz dijk. Å Å Å d ijk = F Å d ijk = Gijk N bÅ zzz , zzzÅ-
2 h

Å

Å, FÅ - Å , N bÅ -
Å , Gijk =
1 n b



iÅ ( ) Å ( ) kÅ ( ) - Å j

, Å, Å ; , dijk (.. ). -

d ijk =
.


Å

Å F

2 ZÅ + ZÅ Å r Å Å Å 0 ( bÅ ) 2 Å f + s (2 s - 1) Å f ÅÅ GN Å r - rÅ Z - Z Å dq

0 i c ijk

Å
b

(1.4.19)



0

c

- , . , . .. , . , , , . , [15] . [40], , , . , ? Ë (bond subformula), A-B AaBbCcDdGg... N ( B - A) a N ( A - B ) b A B (1.4.20), A,B,C,D,G... N CA N CB , , N(B-A) - B .. A, NCA- .. A. (20) 14


N ( B - A)a AB N CA

N ( A - B ) bN N ( B - A ) aN

CA CB

,

n=

N ( A - B)bN N ( B - A)aN

CA CB

(1.4.20`)

A B. (1.4.19)

d ijk =


Å

Å F

Z Å + nZ Å Z - nZ


Å


Å

2 Å r Å Å Å 0 ( bÅ ) 2 Å Å f + s (2s - 1) Å Å f Å Å G N (1.4.19`) r -r dq
0 i c ijk b 0 c

2.
2.1. 2.1.1.

, - - FR-552 "Enraf Nonius Delft" () STOE STADI/P CuKl-. , , . . . 100 10 . -2, Á0.002 .. Powder-2, - WinXpow. PCPDF. 2.1.2. ( ) ( , Nd-, = 1.064 , 10 , 25 /) , . 0.532 " " -77. - 3 . , 0.1-0.3 % (.. ), . . ..-.. .. ( . .. ). 2.1.3. () DELTA SERIES TGA7 PERKIN-ELMER - . 10 /. , . . +0.5À, +0.01 . () 1000 . .

15


2.2.

B2O3, H3BO3, , , , PbBr2 PbCl2 ( ). [41] 2.2.1. . B2O3 MB4O7, =Ca,Sr,Ba,Pb. : B2O3 ( ), , , , "" 10-4., --62 400oC 56 2.2.2. . 300oC (10-1-10-3 Hg .) 2.2.3. CdBr2 CdCl2. . . , 2.2.2.
2.3.

PCPDF. ( )
2.4. .

, , M2B5O9Br (M=Ca,Sr,Ba,Cd,Pb X=Cl,Br,I) 3. , 1-7 . 8-11,14 , , , , . , , Cd2+ . , , , , [35] , . , Ba2B5O9Br 20- BaBr2. . . [35] 800. , , .
2.5.

. . " "[42]. .. , , , . , . Pb2B5O9Br, d ( 7.5). 16


50 . 4 , . , 4 , -, , ?Ë, -, - - .
4 (I/I
(SiO2)

) ,

(I/I(SiO2)) 30 Sr2B5O9Br 6 Sr2B5O9Cl 800 Pb2B5O9Br 200 Pb2B5O9Cl , , , , , ( ). , - Pb2B5O9Br. , (750 56.) ( 8 ), 2 /2. (T) (. 4) - , .. . ( 7.6). 727, . . ( 7.7), . , -, , , , 727. : , , , .
. 4 Pb 2B5O9Br



17


1 2 3 4 5 6 7 8 1 1 1 1 1 1 1 1 1 1 2 2
1 2

2 2 2 2 2 2 2 2 PbBr2*1PbO*3PbB4O7 PbBr2*1PbO*3PbB4O7 PbBr2*1PbO*3PbB4O7 PbCl2*1PbO*3PbB4O7 SrBr2*1SrO*3SrB4O7 SrCl2*1SrO*3SrB4O7 BaBr2*1BaCO3*3BaB4O7 BaBr2*1BaCO3*3BaB4O7

. . . . . . . . . . . . . . . . . . . . .

T1 t1 T2 t2 T3 t3 T4 .... 1 . . 0->24h-> 450->2h->650->3->400 750 . . 0->24h->760->4h->760->48h->600->12h->25 . . 450 90 450 17 0->2h->450->2h->600->24h 750 0->2h->450->2h->600->24h 750 0->2h->450->2h->600->24h 750 710 2 0->2h->450->2h->600->24h 750 . . . . 5 450 5 600 2 600 3 450 0->5.5h->400-> 4h->400->9.5h->900->8.6h 0->2h->200->2h->400->4h->400->10h->100 0->2h->200->2h->400->4h->400->10h->100 0->5.5h->400-> 4h->400->9.5h->900->8.6h 0->2h->450->2h->600->24h 750 710 2 710 2 5 450 5 600 2 600 3 450 450 90 17 0->2h->450->2h->600->24h 750 0->12->600->72->600->48->300 0->2->400->56->700->56

2 . +BaB2O4
.

9 0 1 2 3 4 5 6 7 8 9 0 1

2BaBr2*1BaCO3*3BaB4O7 3BaCO3*1BaBr2*5H3BO3 3BaCO3*1BaBr2*5H3BO3 3BaCO3*1BaCl2*5H3BO3 3CaCO3*1CaCl2*5H3BO3 1CdBr2*3CdO*5B2O3 1CdBr2*3CdO*5B2O3 1CdCl2*3CdO*5B2O3 1CdCl2*3CdO*5B2O3 2PbCl2*2PbO*3PbB4O7 2PbI2*2PbO*3PbB4O7 1PbI2*3PbO*10H3BO3 2PbI2*2PbO*3PbB4O7

" " " BaB2O4+X +X +X + Pb2SiO4

3



18


2.6.

, , . , d . , -. Pb2B5O9X (X = Cl, Br) - "" () (). , , . , , . 3 PbO, PbBr2 ( PbCl2) B2O3, 33, , 0,5 . , , 10-20. 680 710. . . 0.5 3 . (. ) . , , .
2.7.

, [37] , [20] , OH . . .. ( 7.3-7.4) SPECORD UVVIS , , (3200 -1), :, , , . , , , , . , ,


, ( Pb2B5O9Br - 1800 . . SiO2 , Pb2B5O9Cl - 680 . . SiO2 ).

3. .
. (. 1.7) Pb2B5O9Br. [43]: Pb2B5O9Br=2/9Pb(1)O(1)9/4+ 2/9Pb(1)O(2)9/3 +2/9Pb(1)O(3)9/4 +2/9Pb(1)O(5)9/3 +2/9Pb(1)O(6)9/4 +2/9Pb(1)O(7)9/4 +2/9Pb(1)O(9)9/4 +2/9Pb(1)Br(1)9/2 +2/9Pb(1)Br(2)9/2 +2/9Pb(2)O(1)9/4 +2/9Pb(2)O(1)9/4 2/9Pb(2)O(1)9/4 +2/9Pb(2)O(3)9/4 +2/9Pb(2)O(4)9/3 +2/9Pb(2)O(6)9/4 +2/9Pb(2)O(7)9/4 +2/9Pb(2)O(8)9/3 +2/9Pb(2)Br(1)9/2 +2/9Pb(2)Br(2)9/2 +B(1)O(1)+ B(1)O(5)4/3+ B(1)O(6)+ B(1)O(7)+ B(2)O(3)+ B(2)O(2)4/3+ B(2)O(7)+ B(2)O(4)4/3+ B(3)O(1)+ B(3)O(3)+ B(3)O(9)+ B(3)O(8)4/3+ B(4)O(4)+ B(4)O(4)+ B(4)O(8)3/4+ B(5)O(2)+ B(5)O(5)+ B(5)O(9)3/4 , n -1 [44] = ii , - i- , i -



i

i- . 2Pb2B5O9Br=3PbO+5B2O3+PbBr2, , n=1.782 , , , 1.7. , d 7.5 (dÅ Õ; EhÅ, CÅ ev; qÅ e; 3xxÅ pm/V) Pb2B5O9Br 311=2.32*10-1pm/V, 322=6.74*10-1pm/V, 333=-9.01*10-1pm/V. Eu2B5O9X (X = Cl, Br) 311=3.00*10-1pm/V, 322=5.66*10-1pm/V, 333=-6.54*10-1pm/V () 311=2.79*10-1pm/V, 322=5.30*10-1pm/V, 333=-6.56*10-1pm/V (), , .

7. .
- . . , , , Cd2+ (1,24 = 8) , Ca2+ (1.26 = 8)[1], .. , , , . (FL) , 20


? Ë, [40]. , "RA/RB - FL" ( RA - , RB - ) ( [45] RA, RB FL) , (. 5) , ?Ë , - ?Ë. , RA FL ?Ë ? Ë (, Na+Pb+Ln). .

7,0

6,5

Pb2+ Sr2+

Eu2+


6,0

Ca2+

Ri()/Ri(B)

5,5

Cd2+

5,0


Mn2+ Zn2+ Cu2+

4,5

4,0

Ni2+ Mn2+ Co2+ Fe2+
0,25 0,30 0,35 0,40 0,45

Mg2+

3,5 0,20


. 5 "RA/RB - FL".

, , ?Ë , . =4, - = 9. , - 3d 9 , . , . ?Ë , Pb2B5O9Br - - - [11-18], . Pb2B5O9Cl - . , . Pb2B5O9Cl, 21


(). OH . , Pb2B5O9Cl, . , . , , , Sr, Ca Ba - , . , Pb2B5O9Br , dijk, . , -, dijk , , , , ?3, Eu2B5O9X (X = Cl, Br), [28]. .
6 . M2B5O9X (M = Eu, X = Cl, Br; M = Pb, XC =Br) d311.
d(311) for bonds
6,00E+01 4,00E+01 d( 311) 2,00E+01 0,00E+00 - 2,00E+01 - 4,00E+01 N bond 0 5 10 15 20 25 30 35 40 Eu- Br Eu- Cl Pb- Br

6 d311. , (.6) dijk 31-34, (4)- (5)-, .. , . . , , 3 , Gijk dijk . , , . .

22


8.


Ç Pb2B5O9Cl, Pb2B5O9Br, Sr2B5O9Cl, Sr2B5O9Br. Pb2B5O9Br. Ç Pb2B5O9X (X = Cl, Br) . . . . B-O . dijk M2B5O9X

Ç

9.
: .. .. .. ..

23


.
[1]Takatomo Sasaki, Yusuke Mori, Masashi Yoshimura, Yoke Khin Yap, Tomosumi Kamimura, Recent development of nonlinear optical borate crystals: key materials for generation of visible and UV light Materials Science and Engineering, 30 (2000) 1-54 [2] P.A. Franklin, A.E. Hill, C.W. Peters and G. Weinreich, Phys. Rev. Lett. 7 (1961) 118 [3] D. A. Kleiman, Phys. Rev. 126, 1977 (1962) [4] Non linear optics lecture notes 2001 Prof. W. Ubachs laser centre Vrije Universiteit Amsterdam department of physics and astronomy (. ) [5] C.F. Dewey Jr., W.R. Cook Jr., R.T. Hodgson, J.J. Wynne, Appl. Phys. Lett. 26 (1975) 714. [6] C. Chen, B. Wu, A. Jiang, G. You, Sci. Sin. B7 (1984) 598. [7] R. Komatsu, T. Sugawara, K. Sassa, N. Sarukura, Z. Liu, S. Izumida, Y. Segawa, S. Uda, T. Fukuda, K. Yamanouchi, Appl. Phys. Lett. 70 (1997) 3492; S. Uda, R. Komatsu, T. Sugawara, N. Sarukura, T. Fukuda, T. Sasaki, in: T. Sasaki (Ed.), Proceedings of the International Symposium on Laser and Nonlinear Optical Materials, Singapore, 3-5 November 1997, Oxford Grap. Print, Singapore, 1997, p. 320. [8] L. Mei, Y. Wang, C. Chen, B. Wu, J. Appl. Phys. 74 (1993) 7014. [9] C. Chen, Y. Wang, B. Wu, K. Wu, W. Zeng, L. Yu, Nature (London) 322 (1995) 373. [10] .. // . , ., "", 1975 ., 223 . [11] .. , .. , .. , .. . Pb2[B5O9]Br . // . 2002, 47, 6,

1013-1017
[12] C. Chen, Development of new nonlinear optical crystals in the borate series, in: Laser Science and Technical International Handbook, Vol. 15, Harwood, New York, 1993 [13] J. C. Phillips. Ionicity of the chemical bondin crystals. Rev. Mod. Phys., 42:317-356, 1970. [14] J. A. Van Vechten. Quantum dielectric theory of electronegativity in covalent systems. I. Electronic dielectric constant. Phys. Rev., 182:891-905, 1969. [15] B. F. Levine. Bond-charge calculation of nonlinear optical susceptibilities for various structures. Phys. Rev., B7:2600-2626, 1973. [16] B. F. Levine. Bond susceptibilities and ionicities in complex crystal structures. J. Chem. Phys., 59:1463-1486, 1973. [17] S. Zhang, Chin. J. Chem. Phys. 47, 109 (1991). [18] D. Xue and S. Zhang, J. Phys.: Condens. Matter 8, 1949 (1996). [19] D. Xue, S. Zhang, J. Phys. Condens. Matter 9 (1997) 7515 [20] D. Xue and S. Zhang, Appl. Phys. Lett. 68, 57 (1999). [21] D. Xue andS. Zhang. Calculation of the nonlinear optical coe.cient of NdAl3(BO3)4 crystal. J.

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24


[25] D. Xue andS . Zhang. Nonlinear optical properties of (B3O7)5- and(B3O6)3- groups. Appl. Phys., A65:451-456, 1997. [26] D. Xue andS . Zhang. The origin of nonlinearities in K[B5O6(OH)4] Ç 2H2O crystal. Phys. Stat. Sol (b), 200:351- 358, 1997. [27] MM. D. J. Lloyd, A. Levasseur, and C. Fouassier. Crystal structure for the bromoborate (Ca2B5O9Br).

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[28] K. Machida, G. Adachi, Y. Moriwaki, and J. Shikawa. The crystal structure and luminescence properties of europium (ii) haloborates. Bull. Chem. Soc. Jpn., 54:1048-1051, 1981. [29] .. , .. , .. . - OD- . . 45. 11. (2000) [30] Ferro O., Merlino S., Vinogradova S.A. et al. //J. Alloys and Compounds. 200. V.305.P.63. [31] Corker D.L., Glazer A.M. //Acta Cryst B. 1996 V.52 P.260 [32] Ghos S., Wan C. //Am. Mineral. 1979. V.64. P. 187. [33] Wan C., Ghos S. //Am. Mineral. 1983. V.68. P. 604. [34] T.E.Peters, J. Baglio //J. Inorg. Nucl. Chem., 32, 1089 (1970) [35] H. Schmid. Die Syntese von Boraziten mit Hilfe chemischer Transportreaktionen //J. Chem. Solids (1965) Vol.26, pp. 973-988 [36] D. Penn, Phys Rev. 128, 2093 (1962) [37] H.Nara, J. Phys. Soc. Japan 20, 778 (1965) [38] .. . .. VIII ( ), . ?Ë 2001 IX ?78 [39] B. F. Levine. Electrodynamical bond-charge calculation of nonlinear optical susceptibilities Phys. Rev. Letters vol. 22, 15 (1969) [40] I. D. Brown. Chemical and steric constraints in inorganic solids. Acta Cryst., B48:553-572, 1992. [41] . , .: . .,1956, .224 [42] .. . [43] Pauling L. //J. Sam Chem. Soc. 49, 765-790 (1927) [44] Pinnov D.A. Guide lines for selection of acustooptic materials Journal of quantum electronics, 1970, V. 6 N4 p.223=238 [45]R.D.Shannon. Acta Cryst. 1976. A32, p.751-767

25


7.
7.1. Pb2B5O9Br

0,8 0,7



0,6 0,5 0,4 0,3 0,2 0,1 200 400 600 800 1000 1200

()

7.2.
2000 1800 1600 1400 1200 1000 800 600 400 200 0 100

50



15-20

5

26


7.3. Pb2B5O9Br, . ,

100



80

60

40

20

0 4000 3000 2000 1000 0

k, [cm ]

-1

7.4. Pb2B5O9Cl, . ,

80 70 60 50 40 30 20 10 0 -10 4000 3000 2000 1000 0



k, [cm ]

-1

27


7.5.
d
2 2 2 2 2 2 3 2 2 2 2 2 2 2 2 3 3 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 .6 .5 .6 .5 3. .8 .9 .1 .9 .7 .9 .8 .6 .5 .6 .8 .0 .0 .4 .5 1. .4 .4 .5 .4 .4 .4 .5 .4 .4 .3 .3 .4 .3 .3 .3
Å

Pb2B5O9Br
E
Å h

CÅ
35.9534 33.2945 34.9544 31.4082 24.1513 31.3369 27.8106 45.5022 53.7591 33.1185 26.6544 24.5941 35.8851 39.0625 30.2267 30.522 46.9873 47.4468 17.2593 16.6866 15.4614 15.5621 17.6652 14.863 16.4188 19.9392 16.0758 15.1693 19.7355 16.2067 9.2938 9.6275 8.681 9.6049 10.1072 8.4122

f

c

Å



Å

q

Å

G311Å
-2.50E-04 0.0162 -2.68E-03 -0.0393 0.0731 0.0158 7.52E-03 0.2074 -0.252 0.1479 -0.1841 0.0397 0.2944 -0.3416 -0.1982 0.1563 -5.35E-03 8.70E-04 0.0506 -1.55E-03 -0.1402 -0.2886 -2.41E-03 5.07E-04 -0.2104 -0.3009 -0.0731 0.0231 -0.0917 -0.0848 -0.1875 -0.2976 0.1119 -0.0878 0.0866 -1.85E-03



Å 311

G322Å
-0.2112 0.2353 -0.3793 -0.1356 0.2216 0.1389 0.0776 5.42E-03 -7.82E-03 0.0211 -4.63E-03 0.0184 1.33E-06 -0.0203 -0.0458 0.0483 -0.3664 0.0774 4.06E-03 -0.2132 -0.0376 -0.0963 -0.0804 0.0374 -0.1355 -0.0224 -0.2996 4.60E-03 -9.70E-05 -0.2531 -1.21E-04 -0.0528 0.0288 -0.259 0.116 -0.1794



Å 322

G333Å
-0.011 0.5847 -0.236 -0.7224 0.0363 3.99E-03 0.8693 0.0113 -0.0225 5.29E-03 -7.56E-03 0.9114 0.4985 -0.3272 -0.599 9.88E-03 -0.1162 4.89E-04 0.9168 -0.0116 -6.24E-03 -0.1956 -5.80E-04 0.9425 -0.074 -0.0535 -0.1187 0.9582 -7.94E-04 -0.0658 -7.41E-03 -0.3627 0.7797 -0.3733 0.6743 -6.64E-03



Å 333

455 105 774 729 122 038 467 228 189 393 987 465 477 531 145 349 827 707 138 312 492 873 902 208 489 057 639 059 127 581 751 022 211 533 201 921

1 1 1 1 1 1 1 1 1 1 1 2 1 1 1

3.5596 4.0534 3.4552 3.814 2.3606 3.0819 2.7245 2.3593 2.7892 3.2649 2.6088 2.9684 3.5524 3.8876 3.6652 2.9987 2.4359 2.4597 6.8383 3.8155 4.7327 4.8486 4.7778 4.0494 5.8442 17.078 5.4434 4.3981 6.8684 15.596 8.0355 0.6456 16.622 8.7648 9.9592 7.4954

9.71E-03 0.0146 9.68E-03 0.0145 9.46E-03 9.58E-03 9.51E-03 2.68E-03 2.68E-03 9.62E-03 9.49E-03 0.0144 9.70E-03 9.81E-03 0.0145 9.56E-03 2.68E-03 2.68E-03 0.4877 0.4067 0.4759 0.4765 0.4117 0.4719 0.4822 0.4232 0.4799 0.4739 0.4221 0.4808 0.7902 0.8214 0.7857 0.7924 0.7959 0.8122

0.0946 0.2177 0.0969 0.2286 0.1354 0.1066 0.1187 0.0287 0.0247 0.1016 0.1235 0.2829 0.0948 0.0882 0.2362 0.1092 0.0278 0.0276 3.0341 3.6542 3.2965 3.2804 3.5045 3.3961 3.1506 3.2072 3.2011 3.3443 3.2313 3.1816 6.4987 4.9992 6.9001 6.3125 6.0335 5.6491

1.5722 1.8227 1.5689 1.8064 1.5157 1.5551 1.5383 1.9169 1.9244 1.5623 1.5318 1.7299 1.572 1.5815 1.7953 1.5515 1.9185 1.9189 0.4799 0.5115 0.4477 0.4496 0.5302 0.4365 0.4652 0.5711 0.459 0.4423 0.5676 0.4613 0.232 0.2711 0.2126 0.2417 0.2572 0.232

-2.25E-09 6.17E-07 -1.00E-07 -1.63E-06 4.73E-06 6.87E-07 3.91E-07 4.29E-07 -4.11E-07 5.96E-06 -2.55E-06 2.38E-06 1.06E-05 -1.10E-05 -8.68E-06 7.08E-06 -1.05E-08 1.69E-09 3.71E-03 -1.27E-04 -0.0142 -0.0288 -1.69E-04 1.44E-05 -0.0179 -0.0147 -1.66E-03 2.47E-03 -4.64E-03 -1.88E-03 0.1003 0.3497 -0.2794 0.1745 -0.0385 2.90E-03

-1.90E-06 8.97E-06 -1.42E-05 -5.62E-06 1.44E-05 6.05E-06 4.04E-06 1.12E-08 -1.28E-08 8.48E-07 -6.43E-08 1.10E-06 4.79E-11 -6.51E-07 -2.01E-06 2.19E-06 -7.23E-07 1.51E-07 2.98E-04 -0.0175 -3.82E-03 -9.60E-03 -5.64E-03 1.06E-03 -0.0116 -1.10E-03 -6.80E-03 4.93E-04 -4.90E-06 -5.61E-03 6.49E-05 0.062 -0.072 0.515 -0.0515 0.281

-9.89E-08 2.23E-05 -8.81E-06 -2.99E-05 2.35E-06 1.74E-07 4.52E-05 2.33E-08 -3.67E-08 2.13E-07 -1.05E-07 5.47E-05 1.80E-05 -1.05E-05 -2.63E-05 4.47E-07 -2.29E-07 9.52E-10 0.0672 -9.53E-04 -6.34E-04 -0.0195 -4.07E-05 0.0267 -6.31E-03 -2.62E-03 -2.69E-03 0.1027 -4.01E-05 -1.46E-03 3.97E-03 0.4261 -1.9468 0.7424 -0.2995 0.0104

28


7.6. Pb2B5O9Br
104.0
1.500

160.0
102.0

140.0
100.0
1.000

120.0
100.0

776. 9C el

98.0
96.0
94.0
92.0

0.500

80.0
60.0
612. 7Cel
8. 9%

0.000

DTG mg/min

DTA uV

40.0

90.0
88.0
86.0
84.0

-0.500

20.0
0.0
727. 4Cel
772. 0C el

-1.000

-20.0
-1.500

-40.0

82.0
80.0
21. 1%

-60.0
-2.000

-80.0
-100.0

78.0
76.0
74.0

-2.500

0.0

100.0

200.0

300.0

400.0 Temp Cel

500.0

600.0

700.0

800.0

7.7. Pb2B5O9Br

29

TG %