CN103590107B - Boronic acid compound caesium zinc and boric acid caesium zinc non-linear optic crystal and Preparation method and use - Google Patents

Abstract

The invention relates to a compound cesium zinc borate and a cesium zinc borate nonlinear optical crystal, a preparation method and an application thereof. The chemical formula of the cesium zinc borate compound is Cs ₃ Zn ₆ B ₉ O ₂₁ , the molecular weight is 1224.24, and the compound cesium zinc borate is a nonlinear optical crystal. The chemical formula of the crystal is Cs ₃ Zn ₆ B ₉ O ₂₁ , the molecular weight is 1224.24, it belongs to the orthorhombic crystal system, the space group Cmc2 ₁ , and the unit cell parameters are , its powder frequency doubling effect reaches 3 times that of KDP (KH ₂ PO ₄ ), the compound cesium zinc borate is synthesized by solid state reaction method; the cesium zinc borate nonlinear optical crystal is grown by high temperature melt method, the cesium zinc borate nonlinear optical Crystals have high mechanical hardness, are easy to cut, polish and store, and are widely used in the preparation of nonlinear optical devices such as frequency multiplier generators, up-frequency converters, down-frequency converters, or optical parametric oscillators.

Description

Compound cesium zinc borate and cesium zinc borate nonlinear optical crystal, preparation method and use

technical field

The invention relates to a compound cesium zinc borate and a cesium zinc borate nonlinear optical crystal with a chemical formula of Cs ₃ Zn ₆ B ₉ O ₂₁ , a preparation method of the crystal and a nonlinear optical device made of the crystal.

Background technique

Nonlinear optical crystal materials are one of the important optoelectronic information functional materials and the important material basis of optoelectronic technology, especially laser technology. They have broad application prospects and huge potential in information, energy, industrial manufacturing, medicine, scientific research, military and other fields Value. The developed countries in the world have put the research on new nonlinear optical crystal materials in a priority position, and included them in the research plans of each country as an important strategic measure.

Due to its large band gap, low two-photon absorption probability, and high laser damage threshold, borate crystals are conducive to obtaining strong nonlinear optical effects, and are ideal for new ultraviolet nonlinear optical crystals. The introduction of transition metal cations such as d ⁰ and d ¹⁰ into borate can further increase the frequency doubling effect. Therefore, the synthesis of transition metal borates will be an effective means to design UV nonlinear optical materials with large frequency-doubling effect.

Contents of the invention

The object of the present invention is to provide a cesium zinc borate compound and a cesium zinc borate nonlinear optical crystal, both of which have the chemical formula Cs ₃ Zn ₆ B ₉ O ₂₁ .

Another object of the present invention is to provide a preparation method for synthesizing compounds by a solid-state reaction method and growing a cesium zinc borate nonlinear optical crystal by a high-temperature melt method.

Another object of the present invention is to provide the use of a cesium zinc borate nonlinear optical device, which is used to prepare a frequency multiplication generator, an up or down frequency converter or an optical parametric oscillator.

A cesium zinc borate compound described in the present invention has a chemical formula of Cs ₃ Zn ₆ B ₉ O ₂₁ and a molecular weight of 1224.24. The compound is synthesized by a solid phase reaction method.

A compound cesium zinc borate nonlinear optical crystal, the chemical formula of the crystal is Cs ₃ Zn ₆ B ₉ O ₂₁ , the molecular weight is 1224.24, it has no center of symmetry, it belongs to the orthorhombic crystal system, the space group Cmc2 ₁ , and the unit cell parameters are Z=4, Its powder frequency doubling effect is three times that of KDP (KH ₂ PO ₄ ).

The preparation method of the cesium zinc borate nonlinear optical crystal adopts the solid phase reaction method to synthesize the compound and the high-temperature melt method to grow the cesium zinc borate nonlinear optical crystal, and the specific operation is carried out according to the following steps:

a. Uniformly mix cesium zinc borate single-phase polycrystalline powder with flux, heat it to a temperature of 650-1000°C at a rate of temperature rise of 1-30°C/h, and keep the temperature constant for 5-80 hours to obtain a mixed melt, Then lower the temperature to a temperature of 500-800°C, wherein the molar ratio of cesium zinc borate single-phase polycrystalline powder to flux is 1:1-6;

Or directly mix cesium-containing compound, zinc-containing compound, boric acid and flux evenly, heat it to a temperature of 650-1000°C at a heating rate of 1-30°C/h, and keep the temperature for 5-80 hours to obtain a mixed melt, Then cool down to a temperature of 500-800° C., wherein the molar ratio of cesium-containing compound, zinc-containing compound, boric acid and flux is 1-2: 2-4: 3-6: 1-18;

b. Preparation of cesium zinc borate seed crystals: Slowly lower the mixed melt obtained in step a to room temperature at a rate of 3-10° C./h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

c. Put the crucible containing the mixed melt obtained in step a into the crystal growth furnace, fix the seed crystal obtained in step b on the seed crystal rod, lower the seed crystal from the top of the crystal growth furnace, and preheat the seed crystal For 5-60 minutes, the seed crystal is brought down to contact with the liquid surface of the mixed melt or in the mixed melt for remelting, keep the temperature for 5-60 minutes, and drop to the saturation temperature at a rate of 1-60°C/h;

d. Slowly lower the temperature at a rate of 0.1-5°C/day, and rotate the seed rod at a speed of 0-60rpm to grow the crystal. After the single crystal grows to the required size, lift the crystal from the surface of the mixed melt, and The temperature is lowered to room temperature at a rate of 1-80°C/h, and then the crystal is taken out from the furnace to obtain the cesium zinc borate nonlinear optical crystal.

The cesium-containing compound in cesium zinc borate described in step a is Cs ₂ O, CsF, CsCl, Cs ₂ CO ₃ , CsNO ₃ , CsOH, Cs ₂ C ₂ O ₄ ·H ₂ O or Cs ₂ C ₂ H ₃ O ₂ , the zinc-containing compound is ZnO, Zn(NO ₃ ) ₂ , ZnCO ₃ , ZnC ₂ H ₃ O ₂ , Zn(OH) ₂ or ZnCl ₂ and the boron-containing compound is H ₃ BO ₃ or B ₂ O ₃ .

The flux described in step a is Cs ₂ OB ₂ O ₃ , Cs ₂ O-PbO, CsF-B ₂ O ₃ , CsF-PbO, B ₂ O ₃ -PbO or B ₂ O ₃ -PbO-Cs ₂ O.

The molar ratio of Cs ₂ O to B ₂ O ₃ in the flux Cs ₂ OB ₂ O ₃ system is 1-3:2-5; the molar ratio of Cs ₂ O to PbO in the Cs ₂ O-PbO system is 1-3:3 -8; the molar ratio of CsF to B ₂ O ₃ in the CsF-B ₂ O ₃ system is 1-6:2-5; the molar ratio of CsF to PbO in the CsF-PbO system is 1-6:3-8; B ₂ The molar ratio of B ₂ O ₃ to PbO in the O ₃ -PbO system is 2-5:3-8; the molar ratio of B ₂ O ₃ , Cs ₂ O to PbO in the B ₂ O ₃ -PbO-Cs ₂ O system is 2- 5:1-6:3-8.

The use of the cesium zinc borate nonlinear optical crystal, the cesium zinc borate nonlinear optical crystal is used to prepare a frequency doubling generator, an up-frequency converter, a down-frequency converter or an optical parametric oscillator.

The cesium zinc borate compound provided by the invention has a chemical formula of Cs ₃ Zn ₆ B ₉ O ₂₁ , which is prepared by a solid phase reaction method according to the following chemical reaction formula:

(1) 3Cs ₂ CO ₃ +12ZnO+18H ₃ BO ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +3CO ₂ ↑+27H ₂ O↑

(2)6CsNO ₃ +12ZnO+18H ₃ BO ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6NO ₂ ↑+27H ₂ O↑+3O ₂ ↑

(3) 6CsHCO ₃ +12ZnO+18H ₃ BO ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6CO ₂ ↑+27H ₂ O↑

(4)3Cs ₂ CO ₃ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +3CO ₂ ↑

(5) 6CsNO ₃ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6NO ₂ ↑+3O ₂ ↑

(6)6CsHCO ₃ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6CO ₂ ↑+3H ₂ O↑

(7)3Cs ₂ C ₂ O ₄ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +2CO ₂ ↑+4CO↑

(8) 6CsCl+12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +3Cl ₂ ↑

The obtained crystal has the advantages of relatively wide light transmission band, high hardness, good mechanical properties, not easy to break and deliquescence, easy to process and store, and the like. The nonlinear optical device made of the compound cesium zinc borate nonlinear optical crystal obtained by the method of the present invention, at room temperature, uses Nd:YAG Q-switched laser as light source, the incident wavelength is 1064nm infrared light, and the output wavelength is 532nm Green laser, the laser intensity is equivalent to 3 times of KDP (KH ₂ PO ₄ ).

Description of drawings

Fig. 1 is an x-ray diffraction pattern of Cs ₃ Zn ₆ B ₉ O ₂₁ powder of the present invention.

Fig. 2 is the working principle diagram of the nonlinear optical device made of Cs ₃ Zn ₆ B ₉ O ₂₁ crystal of the present invention, wherein 1 is a laser, 2 is an emitting light beam, 3 is a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal, and 4 is an output beam, 5 is a filter.

detailed description

The present invention is described in detail below in conjunction with accompanying drawing and embodiment:

Example 1:

According to the reaction formula: 3Cs ₂ CO ₃ +12ZnO+18H ₃ BO ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +3CO ₂ ↑+27H ₂ O↑ to synthesize Cs ₃ Zn ₆ B ₉ O ₂₁ compound:

Weigh Cs ₂ CO ₃ , ZnO, H ₃ BO ₃ at a molar ratio of 1:4:6 and put them into a mortar, mix and grind carefully, then put them into a corundum crucible with an opening of Φ100mm×100mm, and put them into a muffle furnace In the middle, slowly heat up to 300°C, keep the temperature for 24 hours, cool to room temperature, take it out and put it into the muffle furnace after the second grinding, then raise the temperature to 750°C, keep the temperature for 24 hours, cool to room temperature, take it out and grind it for the third time Then put it into a muffle furnace, and then keep the temperature at 750°C for 48 hours, take out the cesium zinc borate compound single-phase polycrystalline powder obtained by grinding, and carry out X-ray analysis on the product. The obtained X-ray spectrum is consistent with cesium zinc borate Cs ₃ The X-ray spectra obtained from the Zn ₆ B ₉ O ₂₁ single crystal structure are consistent;

The obtained cesium zinc borate Cs ₃ Zn ₆ B ₉ O ₂₁ compound single-phase polycrystalline powder and flux CsF-H ₃ BO ₃ are molar ratio Cs ₃ Zn ₆ B ₉ O ₂₁ : CsF-B ₂ O ₃ =1: 3. The molar ratio of CsF to B ₂ O ₃ is 3:5, mix them, put them into a Φ80mm×80mm open platinum crucible, heat it up to 750°C at a heating rate of 30°C/h, and keep the temperature at 15°C. hours, to obtain a mixed melt, and then lower the temperature to 650 ° C;

Slowly cool down to room temperature at a rate of 0.5°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Crystal growth in the compound melt: fix the obtained Cs ₃ Zn ₆ B ₉ O ₂₁ seed crystal on the seed rod and lower the seed crystal from the top of the crystal growth furnace, first preheat the seed crystal on the surface of the mixed melt for 10 minutes, Immerse in the liquid surface, make the seed crystal remelt in the mixed melt, keep the temperature for 30 minutes, and quickly cool down to the saturation temperature of 650°C;

Then lower the temperature at a rate of 2°C/day, and rotate the seed rod at a speed of 10 rpm. After the crystal growth is completed, the crystal is removed from the liquid surface, and the temperature is lowered to room temperature at a rate of 10°C/hour, and a size of 56 mm can be obtained. Cs ₃ Zn ₆ B ₉ O ₂₁ crystal × 40 mm × 30 mm.

The raw material cesium carbonate in the reaction formula can be replaced by cesium oxide or cesium nitrate or cesium oxalate or cesium hydroxide or cesium bicarbonate, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, boric acid Can be replaced by boron oxide.

Example 2:

According to the reaction formula: 6CsNO ₃ +12ZnO+18H ₃ BO ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6NO ₂ ↑+27H ₂ O↑+3O ₂ ↑ to synthesize Cs ₃ Zn ₆ B ₉ O ₂₁ compound:

Weigh CsNO ₃ , ZnO, H ₃ BO ₃ raw materials directly in a molar ratio of 1:2:3, and mix the weighed raw materials with flux Cs ₂ OB ₂ O ₃ in a molar ratio of 1:4, wherein Cs _{2 The molar ratio of O to B2O3 is 3 :} 5, put it into a Φ80mm×80mm open platinum crucible, raise the temperature to 800°C, keep the temperature for 60 hours to obtain a mixed melt, and cool down to a temperature of 650°C;

Slowly cool down to room temperature at a rate of 1.5°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained Cs ₃ Zn ₆ B ₉ O ₂₁ seed crystal on the seed crystal rod and lower the seed crystal from the top of the crystal growth furnace. Remelt in the mixed melt, keep the temperature for 30 minutes, and quickly cool down to the saturation temperature of 600°C;

Slowly lower the temperature at a rate of 1°C/day without rotating the seed rod. After the crystal grows to the required size, lift the crystal from the surface of the melt and lower it to room temperature at a rate of 20°C/h, then remove the crystal from the Take it out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 36mm×22mm×15mm.

The raw material cesium nitrate in the reaction formula can be replaced by cesium oxide or cesium carbonate or cesium oxalate or cesium hydroxide or cesium bicarbonate, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, boric acid Can be replaced by boron oxide.

Example 3:

According to the reaction formula: 6CsHCO ₃ +12ZnO+18H ₃ BO ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6CO ₂ ↑+27H ₂ O↑ to synthesize Cs2(HCO ₃ ) ₂ compound:

Cs2(HCO ₃ ) ₂ , ZnO, H ₃ BO ₃ are weighed directly as raw materials in a molar ratio of 1:2:3, and the weighed raw materials are mixed with flux CsF-PbO in a molar ratio of 1:3, wherein The molar ratio of CsF to PbO is 3:1, put it into an open platinum crucible of Φ80mm×80mm, raise the temperature to 780°C, keep the temperature at constant temperature for 60 hours to obtain a mixed melt, and then lower the temperature to 620°C;

Slowly cool down to room temperature at a rate of 3.5°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained Cs ₃ Zn ₆ B ₉ O ₂₁ seed crystal on the seed crystal rod and lower the seed crystal from the top of the crystal growth furnace. Remelt in the mixed melt, keep the temperature for 30 minutes, and quickly cool down to the saturation temperature of 615°C;

Slowly lower the temperature at a rate of 3°C/day, rotate the seed crucible at a speed of 5 rpm, lift the crystal from the surface of the melt after the crystal grows to the desired size, and lower it to room temperature at a rate of 1°C/h, then The crystal is taken out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 25mm×24mm×10mm.

The raw material cesium bicarbonate in the reaction formula can be replaced by cesium carbonate or cesium nitrate or cesium oxalate or cesium hydroxide or cesium oxide, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, boric acid Can be replaced by boron oxide.

Example 4:

According to the reaction formula: 3Cs ₂ CO ₃ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +3CO ₂ ↑Synthesis of Cs ₃ Zn ₆ B ₉ O ₂₁ compound:

Weigh Cs ₂ CO ₃ , ZnO, B ₂ O ₃ raw materials directly in a molar ratio of 1:4:3, and mix the weighed raw materials with flux B ₂ O ₃ -PbO in a molar ratio of 1:3, wherein The molar ratio of B ₂ O ₃ to PbO is 5:1, put it into a Φ80mm×80mm open platinum crucible, raise the temperature to 750°C, keep the temperature at a constant temperature for 80 hours to obtain a mixed melt, and then lower it to a temperature of 615°C;

Slowly cool down to room temperature at a rate of 5°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained Cs ₃ Zn ₆ B ₉ O ₂₁ seed crystal on the seed crystal rod and lower the seed crystal from the top of the crystal growth furnace. Remelt in the mixed melt, keep the temperature for 5 minutes, and quickly cool down to the saturation temperature of 600°C;

Then slowly lower the temperature at a rate of 3°C/day, and rotate the seed rod at a speed of 15 rpm. After the crystal grows to the desired size, remove the crystal body from the surface of the melt and drop it to room temperature at a rate of 15°C/h, and then The crystal is taken out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 35mm×25mm×20mm.

The raw material cesium oxide in the reaction formula can be replaced by cesium carbonate or cesium nitrate or cesium oxalate or cesium hydroxide or cesium bicarbonate, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, the oxide Boron can be replaced by boric acid.

Example 5

According to the reaction formula: 6CsNO ₃ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6NO ₂ ↑+3O ₂ ↑ to synthesize Cs ₃ Zn ₆ B ₉ O ₂₁ compound;

Weigh CsNO ₃ , ZnO, B ₂ O ₃ raw materials directly in a molar ratio of 2:4:3, and mix the weighed raw materials with flux CsF-PbO in a molar ratio of 1:2, wherein the molar ratio of CsF to PbO Put it into an open platinum crucible of Φ80mm×80mm at a ratio of 5:1, raise the temperature to 760°C, keep the temperature at a constant temperature for 80 hours to obtain a mixed melt, and then lower the temperature to 650°C;

Slowly cool down to room temperature at a rate of 10°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained seed crystal on the seed rod and lower the seed crystal from the top of the crystal growth furnace, first preheat the seed crystal on the surface of the mixed melt for 25 minutes, and partially immerse it under the liquid surface, so that the seed crystal can be refluxed in the mixed melt. Melt, keep the temperature for 25 minutes, and quickly cool down to the saturation temperature of 615°C;

Then lower the temperature at a rate of 5°C/day, and rotate the seed rod at a speed of 30rpm. After the crystal grows to the desired size, lift the crystal from the surface of the melt, and lower it to room temperature at a rate of 35°C/h, and then The crystal is taken out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 22mm×32mm×20mm.

The raw material cesium nitrate in the reaction formula can be replaced by cesium bicarbonate or cesium carbonate or cesium oxalate or cesium hydroxide or cesium oxide, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, oxidation Boron can be replaced by boric acid.

Example 6

According to the reaction formula: 6CsHCO ₃ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +6CO ₂ ↑+3H ₂ O↑ to synthesize Cs ₃ Zn ₆ B ₉ O ₂₁ compound:

Weigh CsHCO ₃ , ZnO, B ₂ O ₃ raw materials directly in a molar ratio of 2:4:3, and mix the weighed raw materials with flux CsF-PbO in a molar ratio of 1:3, wherein the molar ratio of CsF to PbO 5:1, put it into an open platinum crucible of Φ80mm×80mm, raise the temperature to 800°C, keep the temperature for 5 hours to obtain a mixed melt, and then lower the temperature to 620°C;

Slowly cool down to room temperature at a rate of 4.0°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained Cs ₃ Zn ₆ B ₉ O ₂₁ seed crystal on the seed crystal rod and lower the seed crystal from the top of the crystal growth furnace. Remelt in the mixed melt, keep the temperature for 25 minutes, and quickly cool down to the saturation temperature of 605°C;

Then lower the temperature at a rate of 3°C/day, and rotate the seed rod at a speed of 50rpm. After the crystal grows to the required size, the crystal body is separated from the surface of the melt, and the temperature is lowered to room temperature at a rate of 70°C/h, and then the The crystal is taken out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 22mm×21mm×16mm.

The raw material cesium bicarbonate in the reaction formula can be replaced by cesium carbonate or cesium hydroxide or cesium oxalate or cesium nitrate or cesium oxide, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, oxidation Boron can be replaced by boric acid;

Example 7

According to the reaction formula: 3Cs ₂ C ₂ O ₄ +12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +2CO ₂ ↑+4CO↑ to synthesize Cs ₃ Zn ₆ B ₉ O ₂₁ compound:

Put Cs ₂ C ₂ O ₄ , ZnO, B ₂ O ₃ into a mortar at a molar ratio of 1:4:3, mix and grind carefully, then put it into a corundum crucible with an opening of Φ100mm×100mm, and press it tightly. Put it into the muffle furnace, slowly raise the temperature to 500°C, and keep the temperature constant for 4 hours. After cooling, take out the crucible. At this time, the sample is relatively loose. Then take out the sample and grind it evenly, then put it in the crucible, and keep it in the muffle furnace at temperature 750°C and constant temperature for 48 hours, take it out, put it into a mortar, mash and grind it to get Cs ₃ Zn ₆ B ₉ O ₂₁ compound, X-ray analysis of the product, the obtained X-ray spectrum is consistent with that of cesium zinc borate Cs ₃ The X-ray spectra obtained from the Zn ₆ B ₉ O ₂₁ single crystal structure are consistent;

Mix the synthesized Cs ₃ Zn ₆ B ₉ O ₂₁ compound with the flux Cs ₂ O-PbO in a molar ratio of 1:3, wherein the molar ratio of Cs ₂ O to PbO is 5:1, and put it into the opening of Φ80mm×80mm In a platinum crucible, heat up to a temperature of 900°C, hold the temperature for 50 hours to obtain a mixed melt, and then lower it to a temperature of 750°C;

Slowly cool down to room temperature at a rate of 4.0°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained Cs ₃ Zn ₆ B ₉ O ₂₁ seed crystal on the seed crystal rod and lower the seed crystal from the top of the crystal growth furnace. Remelt in the mixed melt, keep the temperature for 25 minutes, and cool down to the saturation temperature of 715°C;

Then lower the temperature at a rate of 2°C/day, and rotate the seed rod at a speed of 28rpm. After the crystal grows to the desired size, the crystal body is separated from the surface of the melt, and the temperature is lowered to room temperature at a rate of 25°C/h, and then the The crystal is taken out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 30mm×22mm×15mm.

The raw material cesium oxalate in the reaction formula can be replaced by cesium carbonate or cesium hydroxide or cesium bicarbonate or cesium nitrate or cesium oxide, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, oxidation Boron can be replaced by boric acid;

Example 8

According to the reaction formula: 6CsCl+12ZnO+9B ₂ O ₃ →2Cs ₃ Zn ₆ B ₉ O ₂₁ +3Cl ₂ ↑synthesis of Cs ₃ Zn ₆ B ₉ O ₂₁ compound:

Put CsCl, ZnO, B ₂ O ₃ in a molar ratio of 2:4:3 into a mortar, and mix the weighed raw materials with flux H ₃ BO ₃ -Cs ₂ O-PbO in a molar ratio of 1:1 , wherein the molar ratio of B ₂ O ₃ , Cs ₂ O and PbO is 6:3:4, put it into a Φ80mm×80mm open platinum crucible, raise the temperature to 760°C, and keep the temperature for 80 hours to obtain a mixed melt, then drop to Temperature 650°C;

Slowly cool down to room temperature at a rate of 10°C/h, and spontaneously crystallize to obtain cesium zinc borate seed crystals;

Fix the obtained seed crystal on the seed rod and lower the seed crystal from the top of the crystal growth furnace, first preheat the seed crystal on the surface of the mixed melt for 25 minutes, and partially immerse it under the liquid surface, so that the seed crystal can be refluxed in the mixed melt. Melt, keep the temperature for 25 minutes, and quickly cool down to the saturation temperature of 615°C;

Then lower the temperature at a rate of 5°C/day, and rotate the seed rod at a speed of 30rpm. After the crystal grows to the desired size, lift the crystal from the surface of the melt, and lower it to room temperature at a rate of 35°C/h, and then The crystal is taken out from the furnace to obtain a Cs ₃ Zn ₆ B ₉ O ₂₁ crystal with a size of 22mm×32mm×20mm.

The raw material cesium chloride in the reaction formula can be replaced by cesium carbonate or cesium hydroxide or cesium oxalate or cesium nitrate or cesium oxide, zinc oxide can be replaced by zinc carbonate or zinc nitrate or zinc oxalate or zinc hydroxide or zinc chloride, the oxidation Boron can be replaced by boric acid;

Example 9

Process any Cs ₃ Zn ₆ B ₉ O ₂₁ crystal obtained in Examples 1-8 into a frequency doubling device with a size of 5 mm × 5 mm × 6 mm according to the matching direction, place it at position 3 as shown in Figure 2, and place it at room temperature Next, a Q-switched Nd:YAG laser is used as the light source, and the incident wavelength is 1064nm. The infrared beam 2 with a wavelength of 1064nm emitted by the Q-switched Nd:YAG laser 1 is injected into the Cs ₃ Zn ₆ B ₉ O ₂₁ single crystal 3, and the infrared beam with a wavelength of 532nm is generated. The output intensity of the green frequency-doubled light is 5 times that of KDP under the same conditions. The outgoing beam 4 contains infrared light with a wavelength of 1064nm and green light with a wavelength of 532nm, which is filtered by the filter 5 to obtain a green laser with a wavelength of 532nm.

Claims (7)

1. a boronic acid compound caesium zinc, is characterized in that the chemical formula of this compound is Cs ₃zn ₆b ₉o ₂₁, molecular weight 1224.24, adopts solid reaction process synthetic compound.

2. a boronic acid compound caesium zinc non-linear optic crystal, is characterized in that the chemical formula of this crystal is Cs ₃zn ₆b ₉o ₂₁, molecular weight 1224.24, does not have symmetry centre, belongs to rhombic system, spacer Cmc2 ₁, unit cell parameters is z=4,

3. a preparation method for boronic acid compound caesium zinc non-linear optic crystal according to claim 2, it is characterized in that adopting solid reaction process synthetic compound and high temperature solution method growth boric acid caesium zinc non-linear optic crystal, concrete operations follow these steps to carry out:

A, boric acid caesium zn cpds single-phase polycrystalline powder to be mixed with fusing assistant, temperature 650-1000 DEG C is heated to the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 DEG C again, obtain mixed molten liquid, the mol ratio of its mesoboric acid caesium zn cpds single-phase polycrystalline powder and fusing assistant is 1: 1-10;

Or directly will mix with fusing assistant containing Cesium compound, zinc compound and boric acid, temperature 650-1000 DEG C is heated to the temperature rise rate of temperature 1-30 DEG C/h, constant temperature 5-80 hour, obtain mixed molten liquid, be cooled to temperature 500-800 DEG C again, obtain mixed molten liquid, the mol ratio wherein containing Cesium compound, zinc compound and boric acid and fusing assistant is 3: 6: 9: 1-10;

B, prepare boric acid caesium zinc seed crystal: the mixed molten liquid obtained by step a is slowly down to room temperature with the speed of temperature 0.5-10 DEG C/h, spontaneous crystallization obtains boric acid caesium zinc seed crystal;

C, the crucible filling the mixed molten liquid that step a obtains is inserted in crystal growing furnace, the seed crystal obtained by step b is fixed on seed rod, seed crystal from crystal growing furnace top, first preheating seed crystal 5-60 minute, seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid, constant temperature 5-60 minute, is down to temperature of saturation with the speed of temperature 1-60 DEG C/h;

D, again with the speed slow cooling of temperature 0.1-5 DEG C/day, the growth of crystal is carried out with 0-60rpm rotating speed rotary seed crystal rod, arrive after required yardstick until single crystal growing, by crystal lift-off mixed molten liquid surface, and be down to room temperature with temperature 1-80 DEG C/h speed, then crystal is taken out from burner hearth, boric acid caesium zinc non-linear optic crystal can be obtained.

4. method according to claim 3, to is characterized in that described in step a containing Cesium compound being Cs ₂o, CsF, CsCl, Cs ₂cO ₃, CsNO ₃, CsOH, Cs ₂c ₂o ₄h ₂o or Cs ₂c ₂h ₃o ₂, zinc compound is ZnO, Zn (NO ₃) ₂, ZnCO ₃, ZnC ₂h ₃o ₂, Zn (OH) ₂or ZnCl ₂.

5. method according to claim 4, is characterized in that fusing assistant described in step a is Cs ₂o-B ₂o ₃, Cs ₂o-PbO, CsF-B ₂o ₃, CsF-PbO, B ₂o ₃-PbO or B ₂o ₃-PbO-Cs ₂o.

6. method according to claim 5, is characterized in that fusing assistant Cs ₂o-B ₂o ₃cs in system ₂o and B ₂o ₃mol ratio be 1-3: 2-5; Cs ₂cs in O-PbO system ₂o and PbO mol ratio is 1-3: 3-6; CsF-B ₂o ₃csF and B in system ₂o ₃mol ratio be 1-6: 2-5; In CsF-PbO system, CsF and PbO mol ratio is 1-6: 3-6; B ₂o ₃b in-PbO system ₂o ₃be 2-5: 1-3 with PbO mol ratio; B ₂o ₃-PbO-Cs ₂b in O system ₂o ₃, Cs ₂o and PbO mol ratio is 2-5: 1-6: 3-8.

7. a purposes for boric acid caesium zinc non-linear optic crystal according to claim 2, is characterized in that, this boric acid caesium zinc non-linear optic crystal is for the preparation of doubly frequency generator, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.