Compound lead-silicon-oxygen-chlorine and lead-silicon-oxygen-chlorine nonlinear optical crystal as well as preparation method and application thereof

Abstract

The invention relates to a compound lead-silicon-oxygen-chlorine and a lead-silicon-oxygen-chlorine nonlinear optical crystal as well as a preparation method and application, the molecular formula of the compound is Pb9Si8O22Cl6, the molecular weight is 2654.22, the compound is synthesized by adopting a high-temperature solid-phase method, the molecular formula of the crystal is Pb9Si8O22Cl6, the molecular weight is 2654.22, the crystal belongs to a tetragonal system, the space group is Pm2, and the cell parameters of the crystal are as follows: a = 10.7034 (5), b = 10.7034 (5), c = 13.6949 (9), Z = 2 and V = 1568.93 (15) 3. The crystal is grown by adopting a Czochralski method or a Bridgman-Stockbarger method, the powder frequency-doubled effect of the crystal is about 2.5 times that of KDP (KH2PO4), and the lead-silicon-oxygen-chlorine nonlinear optical crystal obtained by the method has the advantages of stable physical and chemical properties, moderate mechanical hardness, difficulty in fragmentation, easiness in cutting, polishing processing and storage and the like; the crystal can be used as an ultraviolet nonlinear optical crystal to be applied to an all-solid-state laser.

Description

Technical Field

[0001] The invention relates to a lead silicon oxygen chlorine compound and a lead silicon oxygen chlorine nonlinear optical crystal as well as a preparation method and application thereof. Background Art

[0002] Ultraviolet nonlinear optical materials are key materials for solid-state lasers to generate ultraviolet coherent light. In order to obtain nonlinear optical materials with nonlinear optical properties, the commonly used method internationally is to introduce nonlinear optical functional elements that are easy to cause distortion into the structure. These elements mainly contain d 0 , d 10 The electronic structure of the transition metal cation polyhedron or the metal cation polyhedron containing lone electron pairs. At present, many excellent nonlinear optical crystals have been discovered, such as BBO (β-BBO), LBO (LiB3O5) crystal, CBO (CsB3O5) crystal, CLBO (CsLiB6O 10 ) crystals and KBBF (KBe2BO3F2) crystals. Although the crystal growth technology of these materials has become increasingly mature, there are still obvious shortcomings: such as easy deliquesce of crystals, long growth cycle, severe layered growth habits, etc. Therefore, the synthesis of new nonlinear optical crystal materials is still a very important and arduous task.

[0003] The present invention aims to provide a compound lead silicon oxide chlorine, the molecular formula of which is Pb9Si8O 22 Cl6, molecular weight 2654.22, was prepared by high temperature solid phase method.

[0004] Another object of the present invention is to provide a lead silicon oxygen chlorine nonlinear optical crystal, the molecular formula of which is Pb9Si8O 22 Cl6, molecular weight is 2654.22; the crystal belongs to the tetragonal system, and the space group is Its unit cell parameters are: α=90°, β=90°, γ=90°, Z=2,

[0005] Another object of the present invention is to provide a method for preparing lead silicon oxide chlorine nonlinear optical crystals, which is prepared by a pulling method or a crucible descent method.

[0006] Another object of the present invention is to provide the use of lead silicon oxide chlorine nonlinear optical crystal.

[0007] The compound lead silicon oxide chlorine described in the present invention has a molecular formula of Pb9Si8O 22 Cl6, molecular weight is 2654.22, the compound is synthesized by high temperature solid phase reaction method.

[0008] The preparation method of the compound lead silicon oxychloride adopts a high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0009] a. Weigh and mix the Pb-containing compound and the Si-containing compound in a molar ratio of 9:8, and transfer them into a ceramic crucible, wherein the Pb-containing compound is PbO, PbCO3, Pb(NO3)2, Pb(OH)2, PbSO4 or PbCl2; the Si-containing compound is SiO2, SiCl4, PbSi2O5 or PbSiO3;

[0010] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0011] A lead silicon oxygen chlorine nonlinear optical crystal, the molecular formula of the crystal is Pb9Si8O 22 Cl6, molecular weight is 2654.22, has no symmetry center, belongs to the tetragonal system, space group Unit cell parameters: α=90°, β=90°, γ=90°, Z=2,

[0012] The preparation method of the lead silicon oxygen chlorine nonlinear optical crystal adopts the pulling method or the crucible descent method:

[0013] The Czochralski method is used to prepare the lead silicon oxide chloride nonlinear optical crystal, and the specific operation is performed according to the following steps:

[0014] a. Weigh and mix the Pb-containing compound and the S-containing compound in a molar ratio of 9:8, transfer them into a ceramic crucible, place them in a muffle furnace, slowly heat them to 350°C, keep the temperature constant for 24 hours, then heat them to 580°C, keep the temperature constant for 24 hours, and naturally cool them to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder, wherein the Pb compound is PbO, PbCO3, Pb(NO3)2, Pb(OH)2, PbSO4 or PbCl2; the Si compound is SiO2, SiCl4, PbSi2O5 or PbSiO3;

[0015] b. Preparation of seed crystals: The polycrystalline powder obtained in step a is placed in a platinum crucible, and the platinum crucible is placed in a muffle furnace, and the temperature is raised to 600°C at a rate of 5-10°C / h to obtain a mixed melt, and the mixed melt is quickly cooled by 5-10°C, and the temperature is kept for 2-6 hours, and the cooling and keeping process is repeated until floating crystals appear on the melt page, and then the temperature is slowly cooled at a cooling rate of 0.5-10°C / d until the crystallization is completed, and then the temperature is cooled to room temperature at a cooling rate of 10-50°C / h, and Pb9Si8O is spontaneously crystallized. 22 Cl6 seed crystal;

[0016] Alternatively, the platinum wire fixed on the seed crystal rod is placed into the mixed melt, and the temperature is slowly reduced at a rate of 1-5°C / h until crystals appear on the platinum wire. The seed crystal rod is then rotated at a speed of 5-20r / min, and the temperature is slowly reduced at a rate of 0.1-10°C / d. When the seed crystal reaches the required size, it is lifted from the liquid surface and cooled to room temperature at a rate of 10-50°C / h to obtain Pb9Si8O 22 Cl6 seed crystal;

[0017] c. Pb9Si8O 22 Install the Cl6 seed crystal on the seed crystal rod, close the furnace door, set the temperature rise program to heat the melt; after it is completely melted, keep it for 4-6 hours and then pull the crystal to grow, and use the pulling method to grow Pb9Si8O in the induction furnace 22 Cl6 crystal, and the diameter of the crystal is 10mm; the rotation speed of the crystal grown by the Czochralski method is 2-15r / min, and the pulling speed is 0.1-1.5mm / h, to obtain a lead silicon oxygen chlorine nonlinear optical crystal;

[0018] The crucible descent method for preparing lead silicon oxygen chloride nonlinear optical crystals is specifically performed in the following steps:

[0019] a. Weigh and mix the Pb-containing compound and the Si-containing compound in a molar ratio of 9:8, transfer them into a ceramic crucible, place them in a muffle furnace, slowly heat them to 350°C, keep the temperature constant for 24 hours, then heat them to 580°C, keep the temperature constant for 24 hours, and naturally cool them to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder, wherein the Pb compound is PbO, PbCO3, Pb(NO3)2, Pb(OH)2, PbSO4 or PbCl2; the Si compound is SiO2, SiCl4, PbSi2O5 or PbSiO3;

[0020] b. Put the polycrystalline powder obtained in step a into a platinum crucible, put the platinum crucible into a muffle furnace, heat it to 600°C at a rate of 5-10°C / h to obtain a mixed melt, quickly cool the mixed melt by 5-10°C, keep it warm for 2-6h, repeat this cooling and keeping process until floating crystals appear on the melt page, then slowly cool it down at a cooling rate of 0.5-10°C / d until crystallization is completed, and then cool it down to room temperature at a cooling rate of 10-50°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal;

[0021] c. placing the seed crystal obtained in step b at the bottom of a quartz tube, a platinum crucible, a gold crucible, an iridium crucible or a ceramic crucible, and then placing the pure phase of the compound obtained in step a into the crucible, and then sealing the crucible;

[0022] d. Place the crucible in step c in a crucible descending furnace, heat it to 700-800°C at a rate of 5-10°C / h, keep it warm for 10-20h, adjust the position of the crucible so that the inoculation temperature is 600-650°C, and then lower the crucible at a rate of 1-10mm / d to keep the growth temperature unchanged. After the growth is completed, lower the growth furnace temperature to 30°C and take out the crucible to obtain Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0023] The lead silicon oxide chlorine nonlinear optical crystal is used in preparing multi-band frequency doubling devices or optical elements.

[0024] The lead silicon oxide chlorine nonlinear optical crystal is used in preparing 1064nm fundamental frequency light output by Nd:YAG laser for double, triple, quadruple or quintuple harmonic laser output.

[0025] The lead silicon oxide chlorine nonlinear optical crystal is used in preparing a frequency doubling generator, an up or down frequency converter or a bright oscillator.

[0026] The preparation method of the lead-silicon-oxygen-chlorine nonlinear optical crystal of the present invention, wherein the container in the method is a ceramic crucible, a platinum crucible or a gold crucible, and before using the container, the container must be cleaned with acid, then rinsed with deionized water, and dried. The resistance furnace used is a muffle furnace and a tubular furnace.

[0027] The lead silicon oxide chlorine nonlinear optical crystal obtained by the method of the present invention can obtain a corresponding large-sized nonlinear optical crystal lead silicon oxide chlorine by using a large-sized container and extending the growth period of the crystal.

[0028] The lead silicon oxygen chlorine compound of the present invention has the molecular formula Pb9Si8O 22 Cl6, using high temperature solid phase method to prepare lead silicon oxygen chlorine compound according to the following chemical reaction formula:

[0029] 6PbO+3PbCl2+8SiO2→Pb9Si8O 22 Cl6;

[0030] 2PbO+3PbCl2+4PbSi2O5→Pb9Si8O 22 Cl6;

[0031] 6PbCO3+3PbCl2+8SiO2→Pb9Si8O 22 Cl6+6CO2↑;

[0032] 8PbCO3+PbCl2+7SiO2+SiCl4→Pb9Si8O 22 Cl6+8CO2↑;

[0033] 2PbCO3+3PbCl2+4PbSi2O5→Pb9Si8O 22 Cl6+2CO2↑;

[0034] 6Pb(NO3)2+3PbCl2+8SiO2→Pb9Si8O 22 Cl6+12NO2↑;

[0035] 8Pb(NO3)2+PbCl2+7SiO2+SiCl4→Pb9Si8O 22 Cl6+6NO3↑;

[0036] 6PbSiO3+3PbCl2+2SiO2→Pb9Si8O 22 Cl6;

[0037] 6Pb(OH)2+3PbCl2+8SiO2→Pb9Si8O 22 Cl6+6H2O↑;

[0038] 6PbSO4+3PbCl2+8SiO2→Pb9Si8O 22 Cl6+6SO3↑.

[0039] The crystal obtained by the present invention has the advantages of wide light transmission band, high hardness, good mechanical properties, not easy to break and deliquesce, easy to process and store, etc. The nonlinear optical device made of the series of compound calcium halide borate nonlinear optical crystals obtained by the method of the present invention uses Nd:YAG Q-switched laser as light source at room temperature, incident infrared light with a wavelength of 1064nm, and output green laser with a wavelength of 532nm, and the laser intensity is equivalent to 2.5 times that of KDP (KH2PO4). BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1is the powder X-ray diffraction pattern of the present invention;

[0041] Figure 2 The Pb9Si8O 22 Cl6 crystal structure diagram;

[0042] Figure 3 The working principle diagram of the nonlinear optical device made by the present invention includes (1) a laser, (2) a full focusing lens, and (3) a Pb9Si8O 22 Cl6 is a nonlinear optical crystal, (4) is a beam splitter, and (5) is a filter. DETAILED DESCRIPTION

[0043] The present invention is described in detail below with reference to the accompanying drawings and embodiments:

[0044] Example 1

[0045] According to the reaction formula: 6PbO+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O from Cl6 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0046] a. Weigh and mix PbO, PbCl2 and SiO2 in a molar ratio of 6:3:8, and transfer them into a ceramic crucible;

[0047] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0048] Example 2

[0049] According to the reaction formula: 2PbO+3PbCl2+4PbSi2O5→Pb9Si8O 22 Cl6, preparation of Pb9Si8O 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0050] a. Weigh and mix PbO, PbCl2 and PbSi2O5 in a molar ratio of 2:3:4, and transfer them into a ceramic crucible;

[0051] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0052] Example 3

[0053] According to the reaction formula: 6PbCO3+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6CO2↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0054] a. Weigh and mix PbCO3, PbCl2 and SiO2 in a molar ratio of 6:3:8, and transfer them into a ceramic crucible;

[0055] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0056] Example 4

[0057] According to the reaction formula: 8PbCO3+PbCl2+7SiO2+SiCl4→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+8CO2↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0058] a. Weigh and mix PbCO3, PbCl2, SiO2 and SiCl4 in a molar ratio of 8:1:7:1, and transfer them into a ceramic crucible;

[0059] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0060] Example 5

[0061] According to the reaction formula: 2PbCO3+3PbCl2+4PbSi2O5→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+2CO2↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0062] a. PbCO3, PbCl2 and PbSi2O5 were weighed and mixed evenly in a molar ratio of 2:3:4, and then transferred into a ceramic crucible;

[0063] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0064] Example 6

[0065] According to the reaction formula: 6Pb(NO3)2+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+12NO2↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0066] a. Weigh and mix Pb(NO3), PbCl2 and Si2O5 in a molar ratio of 6:3:8, and transfer them into a ceramic crucible;

[0067] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0068] Example 7

[0069] According to the reaction formula: 8Pb(NO3)2+PbCl2+7SiO2+SiCl4→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6NO3↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0070] a. Pb(NO3)2, PbCl2, SiO2 and SiCl4 were weighed and mixed evenly in a molar ratio of 8:1:7:1, and then transferred into a ceramic crucible;

[0071] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0072] Example 8

[0073] According to the reaction formula: 6PbSiO3+3PbCl2+2SiO2→Pb9Si8O 22 Preparation of Pb9Si8O from Cl6 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0074] a. Weigh and mix PbSiO3, PbCl2 and SiO2 in a molar ratio of 6:3:2, and transfer them into a ceramic crucible;

[0075] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0076] Example 9

[0077] According to the reaction formula: 6Pb(OH)2+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6H2O↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0078] a. Weigh and mix Pb(OH)2, PbCl2 and SiO2 in a molar ratio of 6:3:8, and transfer them into a ceramic crucible;

[0079] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0080] Example 10

[0081] According to the reaction formula: 6PbSO4+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6SO3↑ 22 The polycrystalline powder of Cl6 compound is prepared by high temperature solid phase method, and the specific operation is carried out according to the following steps:

[0082] a. Weigh and mix PbSO4, PbCl2 and SiO2 in a molar ratio of 6:3:8, and transfer them into a ceramic crucible;

[0083] b. Place the ceramic crucible in step a in a muffle furnace, slowly heat it to 350°C, keep it at this temperature for 24 hours, then heat it to 580°C, keep it at this temperature for 24 hours, and then naturally cool it to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder.

[0084] Embodiment 11

[0085] According to the reaction formula: 6PbO+3PbCl2+8SiO2→Pb9Si8O 22Preparation of Pb9Si8O from Cl6 22 Cl6 nonlinear optical crystal is pulled by the Czochralski method. The specific operation is carried out in the following steps:

[0086] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 1 was placed in a platinum crucible, and the platinum crucible was placed in a muffle furnace. The temperature was raised to 620°C at a rate of 10°C / h to obtain a mixed melt. The mixed melt was quickly cooled by 6°C and kept warm for 12 hours. The cooling and keeping process was repeated until floating crystals appeared on the melt surface. The temperature was then slowly cooled at a rate of 7°C / d until crystallization was completed. The temperature was then cooled to room temperature at a rate of 20°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal;

[0087] The Pb9Si8O obtained in Example 1 22 The Cl6 polycrystalline powder was placed in a crucible, and the platinum crucible was placed in a pulling furnace. 22 Install the Cl6 seed crystal on the seed crystal rod, close the furnace door, and set the heating program to heat up the melt;

[0088] After being completely melted, the crystal was kept for 4-6 hours, and then the crystal was grown at a rate of 3 r / min and a pulling speed of 0.5 mm / h to obtain a Φ12 mm×14 mm×2 mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0089] Example 12

[0090] According to the reaction formula: 2PbO+3PbCl2+4PbSi2O5→Pb9Si8O 22 Cl6, preparation of Pb9Si8O 22 Cl6 nonlinear optical crystal is pulled by the Czochralski method. The specific operation is carried out in the following steps:

[0091] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 2 was placed in a platinum crucible, and the platinum crucible was placed in a muffle furnace, and the temperature was raised to 650°C at a rate of 5°C / h to obtain a mixed melt. The mixed melt was quickly cooled by 5°C and kept warm for 12 hours. This cooling and keeping process was repeated until floating crystals appeared on the melt surface, and then the temperature was slowly lowered to a temperature of 5°C / d until the crystallization was completed, and then the temperature was lowered to room temperature at a rate of 10°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal;

[0092] The Pb9Si8O obtained in Example 2 22 The Cl6 polycrystalline powder was placed in a crucible, and the platinum crucible was placed in a pulling furnace.22 Install the Cl6 seed crystal on the seed crystal rod, close the furnace door, and set the heating program to heat up the melt;

[0093] After being completely melted, it is kept for 4-6 hours, and then the crystal is grown at a rate of 3r / min and a pulling speed of 0.4mm / h to obtain Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0094] Embodiment 13

[0095] According to the reaction formula: 6PbCO3+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6CO2↑ 22 Cl6 nonlinear optical crystal is pulled by the Czochralski method. The specific operation is carried out in the following steps:

[0096] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 3 was placed in a platinum crucible, and the platinum crucible was placed in a muffle furnace. The temperature was raised to 620°C at a rate of 7°C / h to obtain a mixed melt. The mixed melt was quickly cooled by 6°C and kept warm for 10 hours. The cooling and keeping process was repeated until floating crystals appeared on the melt surface. The temperature was then slowly cooled at a rate of 20°C / d until crystallization was completed. The temperature was then cooled to room temperature at a rate of 10°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal;

[0097] The Pb9Si8O obtained in Example 3 22 The Cl6 polycrystalline powder was placed in a crucible, and the platinum crucible was placed in a pulling furnace. 22 Install the Cl6 seed crystal on the seed crystal rod, close the furnace door, and set the heating program to heat up the melt;

[0098] After being completely melted, the crystal was kept for 4-6 hours, and then the crystal was grown at a rate of 5 r / min and a pulling speed of 0.3 mm / h to obtain a Φ12 mm×10 mm×2 mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0099] Embodiment 14

[0100] According to the reaction formula: 8PbCO3+PbCl2+7SiO2+SiCl4→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+8CO2↑ 22 Cl6 nonlinear optical crystal is pulled by the Czochralski method. The specific operation is carried out in the following steps:

[0101] Preparation of Pb9Si8O 22Cl6 seed crystal: The polycrystalline powder obtained in Example 4 was placed in a platinum crucible, and the platinum crucible was placed in a muffle furnace. The temperature was raised to 750°C at a rate of 9°C / h to obtain a mixed melt. The mixed melt was quickly cooled by 10°C and kept warm for 10 hours. This cooling and keeping process was repeated until floating crystals appeared on the melt surface. The temperature was then slowly lowered to a temperature of 2°C / d until crystallization was completed. The temperature was then lowered to room temperature at a rate of 15°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal;

[0102] The Pb9Si8O obtained in Example 4 22 The Cl6 polycrystalline powder was placed in a crucible, and the platinum crucible was placed in a pulling furnace. 22 Install the Cl6 seed crystal on the seed crystal rod, close the furnace door, and set the heating program to heat up the melt;

[0103] After being completely melted, the crystal was kept for 4-6 hours, and then the crystal was grown at a rate of 4 r / min and a pulling speed of 0.3 mm / h to obtain a Φ10 mm×8 mm×1 mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0104] Embodiment 15

[0105] According to the reaction formula: 2PbCO3+3PbCl2+4PbSi2O5→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+2CO2↑ 22 Cl6 nonlinear optical crystal is pulled by the Czochralski method. The specific operation is carried out in the following steps:

[0106] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 5 was placed in a platinum crucible, and the platinum crucible was placed in a muffle furnace, and the temperature was raised to 750°C at a rate of 10°C / h to obtain a mixed melt, and the mixed melt was quickly cooled by 10°C and kept warm for 12 hours. This cooling and keeping process was repeated until floating crystals appeared on the melt surface, and then the temperature was slowly cooled at a rate of 4°C / d until the crystallization was completed, and then the temperature was cooled to room temperature at a rate of 20°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal;

[0107] The Pb9Si8O obtained in Example 5 22 The Cl6 polycrystalline powder was placed in a crucible, and the platinum crucible was placed in a pulling furnace. 22 Install the Cl6 seed crystal on the seed crystal rod, close the furnace door, and set the heating program to heat up the melt;

[0108] After being completely melted, the crystal was kept for 4-6 hours, and then the crystal was grown at a rate of 6 r / min and a pulling speed of 0.2 mm / h to obtain a Φ8 mm × 6 mm × 2 mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0109] Example 16

[0110] According to the reaction formula: 6Pb(NO3)2+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+12NO2↑ 22 Cl6 nonlinear optical crystal, using the crucible descent method, the specific operation is carried out according to the following steps:

[0111] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 6 was placed in a ceramic crucible, and the ceramic crucible was placed in a muffle furnace, and the temperature was raised to 750°C at a rate of 10°C / h, kept at this temperature for 1 day, and then slowly cooled to room temperature at a rate of 5°C / d to obtain Pb9Si8O 22 Cl6 seed crystal;

[0112] The obtained Pb9Si8O 22 The Cl6 seed crystal was placed at the bottom of the platinum crucible, and the Pb9Si8O 22 The Cl6 compound polycrystalline powder is placed in a platinum crucible, and the platinum crucible is sealed;

[0113] The platinum crucible was placed in a crucible descending furnace and heated to 850°C at a rate of 5°C / h. The temperature was kept at this temperature for 24 hours. The crucible position was adjusted to keep the inoculation temperature at 750°C. The crucible was then lowered at a rate of 2mm / h. At the same time, the growth temperature was kept constant. After the growth was completed, the growth furnace temperature was lowered to 30°C. The crucible was taken out to obtain a Φ16mm×12mm×2mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0114] Embodiment 17

[0115] According to the reaction formula: 8Pb(NO3)2+PbCl2+7SiO2+SiCl4→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6NO3↑ 22 Cl6 nonlinear optical crystal, using the crucible descent method, the specific operation is carried out according to the following steps:

[0116] Preparation of Pb9Si8O 22Cl6 seed crystal: The polycrystalline powder obtained in Example 7 was placed in a ceramic crucible, and the ceramic crucible was placed in a muffle furnace, and the temperature was raised to 800°C at a rate of 5°C / h, kept at this temperature for one day, and then slowly cooled to room temperature at a rate of 10°C / d to obtain Pb9Si8O 22 Cl6 seed crystal;

[0117] The obtained Pb9Si8O 22 The Cl6 seed crystal was placed at the bottom of the gold crucible, and the Pb9Si8O 22 The Cl6 compound polycrystalline powder is placed in a gold crucible, and the gold crucible is sealed;

[0118] The gold crucibles were placed in a crucible descending furnace and heated to 900°C at a rate of 10°C / h. The temperature was kept at this temperature for 24 hours. The crucible position was adjusted to keep the inoculation temperature at 850°C. The crucible was then lowered at a rate of 1mm / h. At the same time, the growth temperature was kept constant. After the growth was completed, the growth furnace temperature was lowered to 30°C. The crucible was taken out to obtain a Φ12mm×12mm×2mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0119] Embodiment 18

[0120] According to the reaction formula: 6PbSiO3+3PbCl2+2SiO2→Pb9Si8O 22 Preparation of Pb9Si8O from Cl6 22 Cl6 nonlinear optical crystal, using the crucible descent method, the specific operation is carried out according to the following steps:

[0121] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 8 was placed in a ceramic crucible, and the ceramic crucible was placed in a muffle furnace, and the temperature was raised to 700°C at a rate of 5°C / h, kept at this temperature for 1 day, and then slowly cooled to room temperature at a rate of 8°C / d to obtain Pb9Si8O 22 Cl6 seed crystal;

[0122] The obtained Pb9Si8O 22 The Cl6 seed crystal was placed at the bottom of the platinum crucible, and the Pb9Si8O 22 The Cl6 compound polycrystalline powder is placed in a platinum crucible, and the platinum crucible is sealed;

[0123] The platinum crucible was placed in a crucible descending furnace and heated to 900°C at a rate of 10°C / h. The temperature was kept at this temperature for 24 hours. The crucible position was adjusted to keep the inoculation temperature at 650°C. The crucible was then lowered at a rate of 5mm / h. At the same time, the growth temperature was kept constant. After the growth was completed, the growth furnace temperature was lowered to 30°C. The crucible was taken out to obtain a Φ14mm×12mm×2mm Pb9Si8O22 Cl6 nonlinear optical crystal.

[0124] Embodiment 19

[0125] According to the reaction formula: 6Pb(OH)2+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6H2O↑ 22 Cl6 nonlinear optical crystal, using the crucible descent method, the specific operation is carried out according to the following steps:

[0126] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 9 was placed in a ceramic crucible, and the ceramic crucible was placed in a muffle furnace, and the temperature was raised to 800°C at a rate of 5°C / h, kept at this temperature for 1 day, and then slowly cooled to room temperature at a rate of 10°C / d to obtain Pb9Si8O 22 Cl6 seed crystal;

[0127] The obtained Pb9Si8O 22 The Cl6 seed crystal was placed at the bottom of the platinum crucible, and the Pb9Si8O 22 The Cl6 compound polycrystalline powder is placed in a gold crucible, and the gold crucible is sealed;

[0128] The gold crucibles were placed in a crucible descending furnace and heated to 800°C at a rate of 10°C / h. The temperature was kept at this temperature for 24 hours. The crucible position was adjusted to keep the inoculation temperature at 650°C. The crucible was then lowered at a rate of 5mm / h. At the same time, the growth temperature was kept constant. After the growth was completed, the growth furnace temperature was lowered to 30°C. The crucible was taken out to obtain a Φ10mm×16mm×2mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0129] Embodiment 20

[0130] According to the reaction formula: 6PbSO4+3PbCl2+8SiO2→Pb9Si8O 22 Preparation of Pb9Si8O by Cl6+6SO3↑ 22 Cl6 nonlinear optical crystal, using the crucible descent method, the specific operation is carried out according to the following steps:

[0131] Preparation of Pb9Si8O 22 Cl6 seed crystal: The polycrystalline powder obtained in Example 10 was placed in a ceramic crucible, and the ceramic crucible was placed in a muffle furnace, and the temperature was raised to 650°C at a rate of 5°C / h, kept at this temperature for 1 day, and then slowly cooled to room temperature at a rate of 8°C / d to obtain Pb9Si8O 22 Cl6 seed crystal;

[0132] The obtained Pb9Si8O22 The Cl6 seed crystal was placed at the bottom of the platinum crucible, and the Pb9Si8O 22 The Cl6 compound polycrystalline powder is placed in a gold crucible, and the gold crucible is sealed;

[0133] The gold crucibles were placed in a crucible descending furnace and heated to 700°C at a rate of 8°C / h. The temperature was kept at this temperature for 24 hours. The crucible position was adjusted to keep the inoculation temperature at 550°C. The crucible was then lowered at a rate of 4mm / h. At the same time, the growth temperature was kept constant. After the growth was completed, the growth furnace temperature was lowered to 30°C. The crucible was taken out to obtain a Φ10mm×8mm×2mm Pb9Si8O 22 Cl6 nonlinear optical crystal.

[0134] Embodiment 21

[0135] Any of the Pb9Si8O obtained in Examples 11-20 22 Cl6 nonlinear optical crystal is processed according to the matching direction. Figure 3 As shown in the figure, it is placed at position 3. At room temperature, a Q-switched Nd:YAG laser is used as the light source. 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 Pb9Si8O 22 Cl6 single crystal 3 produces green doubled frequency light with a wavelength of 532nm, and the output intensity is 2.5 times that of KDP under the same conditions. The output light beam 4 contains infrared light with a wavelength of 1064nm and green light of 532nm, which is filtered out by filter 5 to obtain green laser with a wavelength of 532nm.

Claims

1. A compound lead silicon oxygen chlorine, characterized in that The molecular formula of this compound is Pb9Si8O 22 Cl6, molecular weight is 2654.22, the compound is synthesized by high temperature solid phase reaction method.

2. A method for preparing the compound lead silicon oxychloride as claimed in claim 1, characterized in that The high temperature solid phase method is used for preparation, and the specific operation is carried out according to the following steps: a. Weigh and mix PbO and PbCl2 in a molar ratio of 4:5, and put them into a dry quartz glass tube. Use a vacuum pump to evacuate the glass tube and flame seal it; b. Place the quartz glass tube in step a in a muffle furnace, slowly heat it to 610 °C, keep it constant for 24 h, and then cool it to room temperature at a rate of 1 °C / h. Finally, the glass tube is corroded during the experiment to obtain Pb9Si8O 22 Cl6 compounds.

3. A lead silicon oxygen chlorine nonlinear optical crystal, characterized in that The molecular formula of the crystal is Pb9Si8O 22 Cl6, molecular weight is 2654.22, has no symmetry center, belongs to the tetragonal system, space group P 4 (——) m 2(No. 115), unit cell parameters: a =10.7034(5) Å, b = 10.7034(5) Å, c = 13.6949(9) Å, α = 90°, β = 90°, γ = 90°, Z= 2, V=1568.93(15) Å 3 .

4. The method for preparing the lead silicon oxygen chlorine nonlinear optical crystal according to claim 3, characterized in that Prepared by Czochralski method or crucible descent method: The Czochralski method is used to prepare the lead silicon oxide chloride nonlinear optical crystal, and the specific operation is performed according to the following steps: a. Weigh the Pb-containing compound and the Si-containing compound in a molar ratio of 9:8 and put them into a mortar, mix them evenly and grind them carefully, transfer them into a ceramic crucible, place them in a muffle furnace, slowly heat them up to 350 °C, keep the temperature constant for 24 h, then heat them up to 580 °C, keep the temperature constant for 24 h, and naturally cool them down to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder, wherein the Pb compound is PbO, PbCO3, Pb(NO3)2, Pb(OH)2, PbSO4 or PbCl2; the Si compound is SiO2, SiCl4, PbSi2O5 or PbSiO3; b. Preparation of seed crystals: the polycrystalline powder obtained in step a is placed in a platinum crucible, the platinum crucible is placed in a muffle furnace, and the temperature is raised to 600°C at a rate of 5-10°C / h to obtain a mixed melt, the mixed melt is rapidly cooled by 5-10°C, and the temperature is kept for 2-6 hours, and the cooling and keeping process is repeated until floating crystals appear on the melt page, and then the temperature is slowly cooled at a rate of 0.5-10°C / d until the crystallization is completed, and then the temperature is cooled to room temperature at a rate of 10-50°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal; Alternatively, a platinum wire fixed on a seed crystal rod is placed into the mixed melt, and the temperature is slowly lowered at a rate of 1-5 °C / h until crystals appear on the platinum wire. The seed crystal rod is then rotated at a speed of 5-20 r / min, and the temperature is slowly lowered at a rate of 0.1-10 °C / d. When the seed crystal reaches the required size, it is lifted from the liquid surface and cooled to room temperature at a rate of 10-50 °C / h to obtain Pb9Si8O 22 Cl6 seed crystal; c. Pb9Si8O 22 Cl6 seed crystal is installed on the seed crystal rod, the furnace door is closed, and the heating program is set to heat up the melt; after it is completely melted, the crystal is pulled and grown after keeping the temperature for 4-6 hours, and Pb9Si8O is grown by the pulling method in the induction furnace. 22 Cl6 crystal, and the diameter of the crystal is 10 mm; the rotation speed of the crystal grown by the Czochralski method is 2-15 r / min, and the pulling speed is 0.1-1.5 mm / h, to obtain a lead silicon oxygen chlorine nonlinear optical crystal; The crucible descent method for preparing lead silicon oxygen chlorine nonlinear optical crystals is specifically performed in the following steps: a. Weigh the Pb-containing compound and the Si-containing compound in a molar ratio of 9:8, put them into a mortar, mix them evenly and grind them carefully, transfer them into a ceramic crucible, place them in a muffle furnace, slowly heat them up to 350 °C, keep the temperature constant for 24 h, then heat them up to 580 °C, keep the temperature constant for 24 h, and naturally cool them down to room temperature to obtain the compound Pb9Si8O 22 Cl6 polycrystalline powder, wherein the Pb compound is PbO, PbCO3, Pb(NO3)2, Pb(OH)2, PbSO4 or PbCl2; the Si compound is SiO2, SiCl4, PbSi2O5 or PbSiO3; b. Put the polycrystalline powder obtained in step a into a platinum crucible, put the platinum crucible into a muffle furnace, heat it to 600°C at a rate of 5-10°C / h to obtain a mixed melt, quickly cool the mixed melt by 5-10°C, keep it warm for 2-6 hours, repeat this cooling and keeping process until floating crystals appear on the melt page, then slowly cool it down at a cooling rate of 0.5-10°C / d until crystallization is completed, and then cool it down to room temperature at a cooling rate of 10-50°C / h to spontaneously crystallize and obtain Pb9Si8O 22 Cl6 seed crystal; c. placing the seed crystal obtained in step b at the bottom of a quartz tube, a platinum crucible, a gold crucible, an iridium crucible or a ceramic crucible, and then placing the pure phase of the compound obtained in step a into the crucible, and then sealing the crucible; d. Place the crucible in step c in a crucible descending furnace, heat it to 700-800°C at a rate of 5-10°C / h, keep it warm for 10-20 hours, adjust the position of the crucible so that the inoculation temperature is 600-650°C, and then lower the crucible at a rate of 1-10 mm / d to keep the growth temperature unchanged. After the growth is completed, lower the growth furnace temperature to 30°C and take out the crucible to obtain Pb9Si8O 22 Cl6 nonlinear optical crystal.

5. Use of the lead silicon oxide chlorine nonlinear optical crystal as claimed in claim 3 in preparing multi-band frequency doubling devices or optical elements.

6. Use of the lead silicon oxide chlorine nonlinear optical crystal as claimed in claim 3 in preparing a harmonic laser output of 1064nm fundamental frequency light output by a Nd:YAG laser for double, triple, quadruple or quintuple frequency.

7. Use of the lead silicon oxide chloride nonlinear optical crystal as claimed in claim 3 in the preparation of a frequency doubling generator, an up or down frequency converter or a bright oscillator.

Images