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..

Er,Yb:RAl3(BO3)4 ( R = Y,Gd)

:

.. .. .-. ... .. ,

:

:

.

2016

:
.....................................................................................3 1: .............5
1.1 - .................5 1.2 RAl3(BO4)3.............................................8 1.3 RAl3(BO4)3 ....................12 1.3.1 -. ..............12 1.3.2 RAl3(BO4)3...............................15 1.3.3 ............16

2: ................................17
2.2 ............................................17 2.4 ........................................................18 2.5 ........................................................18 2.6 - ...............................................................19

3 ............................................20
3.1 RAl3(BO3)4...............................................20 3.2 ......................................................24 3.3 - ..............................................................27 3.4 ...................................................28

.............................................................30

2

, , , . , , . RAl3(BO3)4, R - , CaMg3(CO3)4 (Ballman A., 1962). . , , . . . -, , . Er3+ Yb3+ 1.5 , . (1.4 1.6 ) , , . , Er - , ( .., 2008). , (Nd,Y)Al3(BO3)4 (Amano Sh., 1989). Cr:NdAl3(BO3)4 (Hattendorf H.-D., 1978). NdAl3(BO3)4 , .. , , YAl3(BO3)4 Cr Yb:YAB
3+

Yb3+ - 333
3

(Wang G., 1995). -
3

, , InGaAs (Dekker P., 2001). , - 2-3 , , 130 (Lecoq P., 2006). «» ( ) (Della Ventura G., 1993), . , , (Callegari A., 2000). , , . , . - , . . - , . : 1) 2) GdAl3(BO3)4, YAl3(BO3)4, - . ...

4

1 - ( )
1.1. -
BO3 . BO3 BO4 , , . , . BO3 BO4 , , , (. 1). N = N/N ( N N -- ), . (N/N) ( N 1) n = n/n, n n -- 3- 4- . -, -, - . , . , . , 3-, (5). -- ( .., 1978), - : + 2
-

.

, BnOm, «» . , 2 3 + 22- = 2 4- 5
5

«» 2 4- «» 5 . , 2, , N/N. , « », . , , ( «» ). N < 1 , , , ( .., 2007).

6

. 1. « » ( ) ( .., 2007): I -- : -- (3-), -- (BO4-); II.1 -- -- - : -- 2 -- 3 -- (n); II.2 -- : -- (2 + 1), -- (2 + 2), -- (4 + 1); III -- : -- (3) + (2 + 1), -- (4 + 1) + (2 + 2), -- (2 + 2) + (2 + 1) + 1

7

1.2. RAl3(BO3)

4

, RAl3(BO3)4 (.. R32). (. 2) R . (1) , - . 31 , . (32) «» , , 2 « ». ( .., 1981). R , . RAl- (.. C2/c C2) ( .., 1988). 2-3 .

8

. 2. RAl3(BO3)4 a) R32 ) XY ( .., 1988) ,

. , NdAB ( 870° 1150°) . (870 - 900°) -. , .. -, ( .., 1980). . GdAB , 850 900 1050 - 1060° ( .., 1981), , . - 1060°, - ( ). , ( 20 . % Nd Gd )
9

GdAB . YAl3(BO3)4 ( .., 1981), NdAB ( .., 1980) GdAB ( .., 1981). 1. 1. . . YAl3(BO3)4 R32 NdAl3(BO3)4 C2/c GdAl3(BO3)4 C2 RAl3(BO3)4 a,е b,е c,е 9.295(3) 7.243(2) 7.262(3) 9.365(3) 11.138(7) 103.41(4) 7.227(3) 9.315(3) 16.184(4) 90.37(4)

Rhkl % 3.7 5.0 5.2

N . 450 3641 5063

(Beregi E., 2012) GdAB, Tb Eu. . C2/, R32. , . (1080) (. 3), (1060) . 2. 2. Tb,Eu:GdAB (Beregi E., 2012) Eu0.02Tb0.12Gd0.86Al3(BO3)4 a=7.227(1), b=9.315(1), c=21.688(3), =95.90(2) a=7.214(1), b=9.313(2), c=21.634(4), =96.04(3) a=7.227(1), b=9.315(1), c=21.686(3), =95.89(2)
10

. C2/c

V(е3) 1452.3(3)

Z 8

V/Z е3) 181.5

Eu0.02Tb0.12Gd0.86Al3(BO3)4 ( ) Eu0.18Tb0.19Gd0.63Al3(BO3)4

C2/c

1445.4(5)

8

180.6

C2/c

1452.2(3)

8

181.5

Eu0.02Tb0.12Gd Eu0.19Tb0.19Gd Tb
0.18

0.86 0.62

Al3(BO3)4 Al3(BO3)4

Gd0.82Al3(BO3)4

a=9.294(2), c=7.251(2) a=9.293(2), c=7.252(2) a=9.299(2), c=7.253(1)

R32 R32 R32

542.5(2) 542.2(2) 543.3(1)

3 3 3

180.8 180.7 180.1

. 3. GdAB:Tb,Eu (Beregi E., 2012)

11

1.3. RAl3(BO4)3
1.3.1 -. - , -, , -, , , . , ( ) ( ) . , : BaO-B2O3, PbO-B2O3, PbF2-B2O3, Bi2O3-B2O3, - PbO-PbF2-B2O3 Bi2O3-PbO-B2O3. , , .

, , , . . , 23 , . PbO Pb - 1.5 , 23- 3-4 . , , . , , 1978). - , . , . - , , , . , , ,
12

.

, (..

( . ., 1978). K2/3, - , ( .., 2007). , K 2Mo3O10. (Jing Li,2007), , : K2CO3 + 3MoO3 K2Mo3O10 + CO2 K2Mo3O10 K2MoO4 + 2MoO3 K2Mo3O10 K2MoO4 3 K2MoO4*10H2O H2MoO4 500 . , ( .., 2008). , RAl3(BO3)4, , , -. , RAl- , . (Al5BO9), .. R2O3-Al2O3-B2O3-K2O-o3 Al2O3. -, B2O3 R2O3. - ( .., 2008). Rl- 1150-900. R2O3-Al2O3-B2O3-K2O-MoO3 RAl3(BO3)4-(K2Mo3O10-Y2O3-B2O3). RAl3(BO3)4 20 17 .% (. 4). 10 .% , , , 2.5-5.0 .%. , , KR(MoO4). 20%- - (. 4). ,
13

: RAl3(BO3)4 RBO3, RAl3(BO3)4 Al18B4O33. . B2O3 R2O3. - , RBO3. RAl3(BO3)4 17 .%, (. 4). KR(MoO4)2. , - . .

. 4. , 20 17 .% YAB YAl3(BO3)4--(K2Mo3O10Y2O3B2O3) K2Mo3O10Y2O3B2O3 YAB 1150--900°: () -- 20 .% YAB () - -- 17 .% YAB.

14

1.3.2. RAl3(BO3)4 RAl3(BO3)4 - 1962 (Ballman A.A. 1962). - - : . . , , , , (. 5). : 2-3 , , 2 -3 (Zili Cao, 2013).

.

5.

,

YAl3(BO3)4,

(Zili Cao,2013). , . , -.

15

, . . , . . - -. . . . , . , . .

1.3.3. . , , - . . . (Majchrowski A., 2005) YAB:Cr YAB:Cr
3+ 3+

. , 2.2 , .

16

2 2.1
YAl3(BO3)4, GdAl3(BO3)4 : Y2O3, Gd2O3, Er2O3, Yb2O3, Al2O3, H3BO3. -1.4-40 2.5. 1370 (. 6). .

. 6: .

17

2.2
, . . Pt 10 . , (. 7). , . , (. 8). 100% .

. 7. :

18

. 8.

19

2.3
- 1 (CoK -, Fe-, 0,05, 2 .) d(hkl) I(hkl) . . : · · · · ( d(hkl) I(hkl)) · . : · (, , ) · · - ; · · ( )

20

2.4 -
, . «» , , , , . , , : , . , , , , .
3 , , , 3 - .

. , . .. 10
-6

10-3 . -

( ) . . ( , , ) , , , . , .

21

3 3.1 RAl3(BO3)
4

: Er, Yb ( Y). :
Y0.98Yb
0.02

Al3(BO3)4, Y0.86Yb

0.11

Er

0.02

Al3(BO3)4, Y0.81Yb

0.11

Er

0.08

Al3(BO3)4, Y0.85Yb

0.11

Er

0.04

Al3(BO3)4,

GdAl3(BO3)4, YAl3(BO3)4 (. 9)

, , , , . 3: YAl3(BO3)4 GdAl3(BO3)4.

2209

Y0.98Yb0.02Al3(BO3) +100%- 3BO3
4

1250 3.

-

2210

Y0.86Yb0.11Er0.02Al3( BO3)4 +100%- 3BO3 Y0.81Yb0.11Er0.08Al3(B O3)4 +100%- 3BO3 Y0.85Yb0.11Er0.04Al3(B O3)4 +100%- 3BO3

1250 , 3

: BO3. 4 .

2215

1250 3

2216

1250 3

22

2231

GdAl3(BO3)4 +100%- 3BO3

1275 3

.

2232

YAl3(BO3)4 +100%- 3BO3

1350 3

. 9: YAl3(BO3)4 GdAl3(BO3)4

23

3.2
YAl3(BO3)4 GdAl3(BO3)4 "" YAl3(BO3)4 GdAl3(BO3)4 (. 10 11). 2 : ) ) , . 2209 (. 12). 2210, 2215, 2216 (. 13). 2231 (. 14) , "" GdAl3(BO3)4.

STOE Powder Diffraction System

09-Mar-2011
(Range 1)

1400

1200

1000

Absolute Intensity

800

600

400

200

0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

2Theta

. 10: "" YAl3(BO3)4

24

- NA PR2087.mid; - 28.05.2012 17:08:14; - Co;

2 400

2 200

2 000

1 800

( / )

1 600

1 400

1 200

1 000

800

600

400

200

0

. = 8; . = 80; = 0.02; . = 1; = 16 ; . . = 3053;

. 11: "" GdAl3(BO3)4

. 12: 2209. : .

25

.13 2216.

. 14: 2231: ,

26

3.3 -
2216 BO3 1380, 1240 -1 ~700 -1, BO4 ~1090, 1030 -1. (. 15).

B

0,6

0,4

B
0,2 0,0 3500 3000 2500 2000 1500 1000 500

A

.15: 2231. .

27

3.4
2209 . . 2210, 2215, 2216 , . 2231 GdAl3(BO3)4: , GdAl3(BO3)4. , 100% , , , , GdAl3(BO3)4. , . , , , . GdAl3(BO3)4 , , . GdAl3(BO3)4 - .

28

1.
2. Y0.86Yb
0.11

Y0.81Yb

0.11

:
0.11

Y0.98Yb

0.02

Al3(BO3)4,

Er
4

0.02

Al3(BO3)4,

Er

0.08

Al3(BO3)4,

Y0.85Yb

Er

0.04

Al3(BO3)4,

GdAl3(BO3)4,

YAl3(BO3)

3. 4. ,

29

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Eng. 1989. V. 17. P. 48.
2. Ballman A.A. A new series of synthetik borates isostructural with the arbonate mineral

huntite. // Amer. Mineral. 1962. V. 47. P. 1380 3. Beregi E., SajС I., Lengyel K. et al. Polytypic modifications in heavily Tb and Eu doped gadolinium aluminum borate crystals // J. Cryst. Growth. 2012. V. 351. P. 72.
4. Callegary A., Caucia F., Mazzi F. et. al. The crystal structure of peprossiite-(Ce), an anhydrous

REE and Al mica-like borate with squarepyramidal coordination for Al // Amer. Mineral. 2000. V.85. P.586.
5. Dekker P., Dawes J.M., Piper J.A. et al. Continuous wave and Q-switched diode-pumped

neodymium, lutetium: yttrium aluminium borate lasers // Opt. Commun. 2001. V. 195. P. 431.
6. Della Ventura G., Parodi G.C., Mottana A., Chaussidon M. Peprossiite-(Ce), a new mineral

from Campagnano (Italy): the first anhydrous rare-earth-element borate // European Journal of Mineralogy. 1993. V. 5. P. 53.
7. Hattendorf H.-D., Huber G., Danielmeyer H.G.J. Efficient cross pumping of Nd
3+

by Cr3+ in

Nd(Al,Cr)3(BO3)4 // Phys. C: Solid State Phys. 1978. V. 11. P. 2399. 8. Jing Li, Qiang Li, Jiyang Wang et al. Growth, thermal and optical properties of Yb:GdYAl3(BO3)4 crystal // Optical Materials. 2007. V. 29. P. 1741. 9. Majchrowski A., Ebothe J., Fuks-Janczarek I. et al. Two-photon absorption in YAB:Cr nanocrystallites // Optical Materials. 2005. V. 27. P. 675. 10. P. Lecoq, A. Annenkov, A. Gektin, M. Korzhik, C. Pedrini. Inorganic Scintillators for Detector Systems // Spinger. 2006. P. 251.
11. Wang G., Gallagher H.G., Han T.P.J. et al. Optical and electron spin resonance spectroscopy
3+

of Ti3+-doped yttrium and gadolinium aluminoborates // J. Cryst. Growth. 1995. V.153. P. 169. 12. Zili Cao, Xuesong Yu, Yinchao Yue, Zhanggui Hu. Synthesis and growth mechanism of tubular YAl3(BO3)4 crystals in millimeter diameter // J. Cryst. Growth. 2013. V. 362. P. 111.
13. .., .., ., ..

YAl3(BO3)4 // . . 1981. . 22, . 196. 14. .., .., .., .. - // . 1988. . 33. . 1287. 15. .., .., .., .. TR-Al- GdAl3(BO3)4 // . 1981. . 261. . 361.
30

16. .., .., .. . Nd,Al- NdAl3(BO3)4 // . 1980. . 255. . 854. 17. .. // . 1978. .4. .5. 18. .. - // . 2008. . 53. . 546. 19. .. - // . 2008. . 53. . 546. 20. .. // . 2007. 12. . 53. 21. .., .., . . (Er,Yb):YAl3(BO3)4 // . 2008. . 53. . 194. 22. . . . .: . 1978. 267 .

31