Praseodymium ion doped scandium terbium aluminum lutetium garnet magneto-optical crystal and preparation method and application thereof

Abstract

The invention provides a praseodymium ion doped scandium terbium aluminum lutetium garnet magneto-optical crystal as well as a preparation method and application thereof, and relates to the field of magneto-optical crystal materials. The chemical formula of the praseodymium ion doped scandium terbium aluminum lutetium garnet magneto-optical crystal is Tb3 (1-y) Pr3ySc2 (1-x) Lu2xAl3O12, x is equal to 0.1 to 0.2, and y is equal to 0.05 to 0.1. The praseodymium ion doped scandium terbium aluminum lutetium garnet magneto-optical crystal can realize large-size and non-cracking growth, has a large Verdet constant, has good processability and heat-conducting property, has a crystal light transmission range of 400-1600 nm, can be used as a core crystal material of a visible-near infrared band magneto-optical device, and has a wide application prospect. And particularly, the crystal material is an ideal crystal material of an isolator in a high-power laser, and has great economic and social value potential.

Description

Technical Field

[0001] The invention relates to the field of magneto-optical crystal materials, and in particular to a praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal and a preparation method and application thereof. Background Art

[0002] Magneto-optical crystals are an important optical functional crystal material based on magneto-optical effect, which are widely used in magneto-optical switches, magneto-optical modulators, magneto-optical isolators, current sensors, optical fiber communications and other fields. 3+ Crystal materials, such as TGG (Tb 3 Ga 5 O 12 ), TSAG(Tb 3 Sc 2 Al 3 O 12 ) crystals. Among them, TGG crystals are prone to serious problems such as gallium oxide volatilization and spiral growth during the growth process, resulting in serious component deviation, resulting in poor crystal quality and difficulty in growing. 3+ After the addition of ions, although the crystal becomes a homogeneous melt, the thermal stress is extremely large and segregation occurs during the growth process, and cracking is very likely to occur, which seriously affects the size and quality of the crystal. 3+ To partially replace Sc in TSAG 3+ , get TSLAG(Tb 3 Sc 2(1-x) Lu 2x Al 3 O 12 ) crystal, no longer has a tendency to crack, but the crystal Verdet constant is lower than that of TSAG crystal. Summary of the invention

[0003] In order to solve the above problems, the present invention provides a praseodymium ion doped scandium terbium aluminum lutetium garnet magneto-optical crystal and its preparation method and application, which can obtain a new magneto-optical crystal with both no cracking and high magneto-optical performance.

[0004] In order to achieve the above object, the present invention provides the following technical solutions:

[0005] The present invention provides a praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal. The chemical formula of the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal is Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 , where x=0.1~0.2, y=0.05~0.1.

[0006] The present invention provides a method for preparing the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal described in the above technical solution, comprising the following steps:

[0007] 1) Pr 2 O 3 , Tb 4 O 7 Sc 2 O 3 、Al 2 O 3 、Lu 2 O 3 According to the chemical formula Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 Weigh the mass and mix to obtain a mixture, wherein x=0.1-0.2, y=0.05-0.1;

[0008] 2) calcining the mixed material obtained in step 1) to obtain a calcined material;

[0009] 3) melting the calcined material obtained in step 2), and growing crystals by a Czochralski method to obtain crystals;

[0010] 4) Cooling the crystal obtained in step 3) to 25-30° C. to obtain a praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal.

[0011] Preferably, the calcination conditions in step 2) include: a temperature of 1250 to 1350° C. and a time of 10 to 12 hours.

[0012] Preferably, the melting temperature in step 3) is 60 to 100° C. higher than the melting point, and the temperature is kept for 6 to 20 hours.

[0013] Preferably, the conditions of the pulling method include: a pulling speed of 0.8 to 1.5 mm / h and a rotation speed of 10 to 16 rpm.

[0014] Preferably, the cooling rate in step 4) is 10-20°C / h.

[0015] Preferably, in step 1) Pr 2 O 3 , Tb 4 O 7 Sc 2 O 3 、Al 2 O 3 、Lu 2 O 3The purity is 99.999%.

[0016] The present invention also provides the application of the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal described in the above technical solution in magneto-optical switches, magneto-optical modulators, magneto-optical isolators, current sensors or optical fiber communications.

[0017] The beneficial effects of the present invention are:

[0018] The praseodymium ion doped scandium terbium aluminum lutetium garnet magneto-optical crystal Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 ,x=0.1~0.2,y=0.0,5~0.1, is a new type of magneto-optical crystal material, belonging to the cubic crystal system, the crystal can achieve large size, crack-free growth, and has a large Verdet constant, at the same time, the crystal has good processing performance and thermal conductivity, the crystal light transmission range is 400~1600nm, can be used as the core crystal material of visible-near infrared band magneto-optical devices, especially the ideal crystal material of isolators in high-power lasers, with great economic and social value potential. The preparation method is highly operable and conducive to large-scale mass production. DETAILED DESCRIPTION

[0019] The present invention provides a praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal. The chemical formula of the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal is Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 , where x=0.1~0.2, y=0.05~0.1.

[0020] The present invention provides a method for preparing the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal described in the above technical solution, comprising the following steps:

[0021] 1) Pr 2 O 3 , Tb 4 O 7 Sc 2 O 3 、Al 2 O 3 、Lu 2 O 3 According to the chemical formula Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al3 O 12 Weigh the mass and mix to obtain a mixture, wherein x=0.1-0.2, y=0.05-0.1;

[0022] 2) calcining the mixed material obtained in step 1) to obtain a calcined material;

[0023] 3) melting the calcined material obtained in step 2), and growing crystals by a Czochralski method to obtain crystals;

[0024] 4) Cooling the crystal obtained in step 3) to 25-30° C. to obtain a praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal.

[0025] The present invention converts Pr 2 O 3 , Tb 4 O 7 Sc 2 O 3 、Al 2 O 3 、Lu 2 O 3 According to the chemical formula Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 Weigh the mass and mix to obtain a mixture, wherein x=0.1-0.2, y=0.05-0.1. In the present invention, the Pr 2 O 3 , Tb 4 O 7 Sc 2 O 3 、Al 2 O 3 、Lu 2 O 3 The purity is preferably 99.999%.

[0026] The present invention calcines the obtained mixed material to obtain a calcined material. In the present invention, the calcination conditions preferably include: a temperature of 1250 to 1350° C. and a time of 10 to 12 hours. The present invention preferably presses the mixed material into blocks and places them in a crucible for calcination. The present invention does not specifically limit the conditions such as the size of the pressed blocks, and those skilled in the art can operate according to conventional procedures.

[0027] The present invention melts the obtained calcined material and uses the Czochralski method to grow crystals to obtain crystals. In the present invention, the melting temperature is preferably 60 to 100° C. higher than the melting point and the temperature is kept for 6 to 20 hours. In the present invention, the conditions of the Czochralski method preferably include: a pulling speed of 0.8 to 1.5 mm / h and a rotation speed of 10 to 16 rpm.

[0028] The present invention cools the obtained crystal to 20-30° C. to obtain the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal. In the present invention, the cooling rate is preferably 10-20° C. / h.

[0029] The present invention also provides the application of the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal described in the above technical solution in magneto-optical switches, magneto-optical modulators, magneto-optical isolators, current sensors or optical fiber communications.

[0030] In order to further illustrate the present invention, the present invention is described in detail below in conjunction with embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0031] Example 1

[0032] Pr 2 O 3 (99.999%), Tb 4 O 7 (99.999%), Sc 2 O 3 (99.999%), Al 2 O 3 (99.999%), Lu 2 O 3 (99.999%) raw materials according to the chemical formula Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 Calculate the mass required for each raw material and weigh it accurately, where x=0.1, y=0.1. Then put the prepared raw materials into a mixer to mix them evenly, and press the mixed sample into blocks and place them in a crucible. Then place the sample in a muffle furnace for calcination. The sintering temperature is 1350°C and the sintering time is 10 hours to obtain a sintered material. Place the obtained sintered material in a pulling furnace, raise the temperature to 60°C above the melting point, melt it completely, and keep the temperature constant for 8 hours, then slowly drop the temperature to the crystallization point for crystal growth, the pulling speed is 1.0mm / h, and the rotation speed is 15rpm. When the growth process is over, the crystal is pulled out of the melt and cooled to room temperature at an annealing rate of 20°C / h, and then the crystal Tb is taken out 2.7 Pr 0.3 Sc1.8 Lu 0.2 Al 3 O 12 .

[0033] Example 2

[0034] Pr 2 O 3 (99.999%), Tb 4 O 7 (99.999%), Sc 2 O 3 (99.999%), Al 2 O 3 (99.999%), Lu 2 O 3 (99.999%) raw materials according to the chemical formula Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al 3 O 12 Calculate the mass required for each raw material and weigh it accurately, where x=0.2, y=0.05. Then put the prepared raw materials into a mixer to mix them evenly, and press the mixed sample into blocks and place them in a crucible. Then place the sample in a muffle furnace for calcination. The sintering temperature is 1250°C and the sintering time is 12 hours to obtain a sintered material. Place the obtained sintered material in a pulling furnace, raise the temperature to 80°C above the melting point, melt it completely, and keep the temperature constant for 10 hours, then slowly drop the temperature to the crystallization point for crystal growth, the pulling speed is 1.2mm / h, and the rotation speed is 16rpm. When the growth process is over, the crystal is pulled out of the melt and cooled to room temperature at an annealing rate of 15°C / h, and then the crystal Tb is taken out 2.85 Pr 0.15 Sc 1.6 Lu 0.4 Al 3 O 12 .

[0035] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal, characterized in that: The chemical formula of the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal is Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al3O 12 , where x=0.1~0.2, y=0.05~0.

1.

2. A method for preparing the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal according to claim 1, characterized in that: The following steps are involved: 1) Pr2O3, Tb4O7, Sc2O3, Al2O3, Lu2O3 according to the chemical formula Tb 3(1-y) Pr 3y Sc 2(1-x) Lu 2x Al3O 12 Weigh the mass and mix to obtain a mixture, wherein x=0.1-0.2, y=0.05-0.1; 2) calcining the mixed material obtained in step 1) to obtain a calcined material; 3) melting the calcined material obtained in step 2), and growing crystals by a Czochralski method to obtain crystals; 4) Cooling the crystal obtained in step 3) to 25-30° C. to obtain a praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal.

3. The preparation method according to claim 2, characterized in that: The calcination conditions in step 2) include: a temperature of 1250 to 1350° C. and a time of 10 to 12 hours.

4. The preparation method according to claim 2, characterized in that: The melting temperature in step 3) is 60 to 100° C. higher than the melting point, and the temperature is kept for 6 to 20 hours.

5. The preparation method according to claim 2, characterized in that: The conditions of the pulling method in step 3) include: a pulling speed of 0.8 to 1.5 mm / h and a rotation speed of 10 to 16 rpm.

6. The preparation method according to claim 2, characterized in that: The cooling rate in step 4) is 10-20°C / h.

7. The preparation method according to claim 2, characterized in that: In the step 1), the purity of Pr2O3, Tb4O7, Sc2O3, Al2O3 and Lu2O3 is 99.999%.

8. Use of the praseodymium ion-doped scandium terbium aluminum lutetium garnet magneto-optical crystal according to claim 1 in the preparation of magneto-optical switches, magneto-optical modulators, magneto-optical isolators, current sensors or optical fiber communications.