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CN116288725B - Compound sulfur-phosphorus-mercury-zinc and sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal and preparation method and application thereof - Google Patents

Compound sulfur-phosphorus-mercury-zinc and sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal and preparation method and application thereof Download PDF

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CN116288725B
CN116288725B CN202310230594.4A CN202310230594A CN116288725B CN 116288725 B CN116288725 B CN 116288725B CN 202310230594 A CN202310230594 A CN 202310230594A CN 116288725 B CN116288725 B CN 116288725B
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CN116288725A (en
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潘世烈
李俊杰
王宏善
王霖安
楚羽
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
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Abstract

本发明涉及一种化合物硫磷汞锌和硫磷汞锌红外非线性光学晶体及制备方法和应用，该化合物的化学式为Zn2HgP2S8，分子量为649.79 g/mol，采用高温固相法合成；该晶体的化学式Zn2HgP2S8，分子量为649.79 g/mol，不具有对称中心，结晶于正交晶系，空间群为Aea2，晶胞参数为：a＝16.2706(12)Å，b＝7.9266(7)Å，c＝9.0620(7)Å，Z＝4。采用高温熔体自发结晶法、化学气相传输法、助熔剂法和坩埚下降法制备所述红外非线性光学晶体。本发明获得的硫磷汞锌红外非线性光学晶体可用于制作红外非线性光学器件，为光学、激光光刻和通讯领域提供一种重要的用途。

The invention relates to a compound of sulfur-phosphorus-mercury-zinc and a sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal and a preparation method and application thereof. The compound has a chemical formula of Zn 2 HgP 2 S 8 and a molecular weight of 649.79 g/mol, and is synthesized by a high-temperature solid phase method. The crystal has a chemical formula of Zn 2 HgP 2 S 8 and a molecular weight of 649.79 g/mol, has no symmetry center, crystallizes in an orthorhombic system, has a space group of Aea 2, and has unit cell parameters of a=16.2706(12)Å, b=7.9266(7)Å, c=9.0620(7)Å, and Z=4. The infrared nonlinear optical crystal is prepared by a high-temperature melt spontaneous crystallization method, a chemical vapor transport method, a flux method, and a crucible descent method. The sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal obtained by the invention can be used to make infrared nonlinear optical devices, providing an important application in the fields of optics, laser lithography, and communications.

Description

Compound mercury zinc thiophosphate and mercury zinc thiophosphate infrared nonlinear optical crystal, and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of infrared nonlinear optical crystals, and particularly relates to a compound of zinc thiphos-mercury and zinc thiphos-mercury infrared nonlinear optical crystal, a preparation method and application thereof.
Background
Nonlinear optical materials play an important role in modern laser science and technology, and crystals with nonlinear optical effects such as frequency multiplication, sum frequency, difference frequency, parametric amplification and the like are called nonlinear optical crystals. The nonlinear optical effect of the crystal can be used for manufacturing nonlinear optical devices such as a second harmonic generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator and the like. The laser generated by the laser can be subjected to frequency conversion through a nonlinear optical device, so that laser with more useful wavelengths is obtained, and the method has important application in the fields of expanding the frequency of the laser, ultrashort/ultrastrong laser pulse, optical communication, generating entangled photons and the like. According to the operating band, the nonlinear optical crystal can be divided into four bands, deep ultraviolet (DUV, <200 nm), ultraviolet (UV, 200-400 nm), visible/near infrared (vis-NIR, 0.4-3 μm), and mid/far infrared (M-F-IR, including 3-5 and 8-13 μm atmospheric transparent windows), respectively.
The nonlinear optical crystal materials in the visible light region and the ultraviolet light region can basically meet the requirements of practical application, and the practical crystal mainly comprises KTP (KTiOPO 4)、BBO(β-BaB2O4)、LBO(LiB3O5) crystal and KBBF(KBe2BO3F2)、ABF(NH4B4O6F)、CBF(CsB4O6F) which is practical in the deep ultraviolet crystal can be selected. Currently, several kinds of crystals realizing commercialization in the infrared region are AgGaS 2(AGS),AgGaSe2(AGSe)、ZnGeP2 (ZGP), which have excellent performance in the infrared band, including large frequency multiplication coefficient, wider mid-infrared transmission range and the like. However, with the rapid development of lasers in various industries, commercial materials find some of their intrinsic problems in applications, such as low laser damage threshold and low AGSe thermal conductivity of AGS crystals, and the ZGP crystals generate two-photon absorption around 1 μm of the most commonly used Nd: YAG output, which causes that they cannot meet the increasingly developed application requirements in various fields, and development of novel infrared nonlinear optical crystal materials with balanced large frequency multiplication and high damage threshold is needed.
Disclosure of Invention
The invention aims to provide a compound of zinc thimerosal, which has a chemical formula of Zn 2HgP2S8 and a molecular weight of 649.79g/mol and is synthesized by a high-temperature solid-phase method.
The invention further aims at providing a far infrared nonlinear optical crystal in the zinc mercuric sulfate, wherein the chemical formula of the crystal is Zn 2HgP2S8, the molecular weight of the crystal is 649.79g/mol, the crystal belongs to an orthorhombic system, the space group is Aea2, and the unit cell parameters are as follows: α=β=γ=90°,Z=4。
The invention further aims at providing a preparation method of the Zn 2HgP2S8 infrared nonlinear optical crystal.
It is also an object of the present invention to provide the use of Zn 2HgP2S8 infrared nonlinear optical crystals.
The chemical formula of the compound of the invention is Zn 2HgP2S8, the molecular weight is 649.79g/mol, and the compound is prepared by a high-temperature solid phase method.
The preparation method of the compound of the sulfur, phosphorus, mercury and zinc adopts a high-temperature solid phase method, and comprises the following specific operation steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the mol ratio of 1.8-2.5:1:2:7.5-8.5, putting the mixture into a clean graphite crucible, putting the graphite crucible into a quartz tube, and carrying out fusion sealing after the quartz tube is pumped to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. And C, placing the quartz tube sealed in the step a into a muffle furnace with a programmed temperature, heating to 600-630 ℃ at a rate of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at a rate of 3-5 ℃ per hour to obtain the compound thimerosal zinc.
The chemical formula of the sulfur phosphorus mercury zinc infrared nonlinear optical crystal is Zn 2HgP2S8, the molecular weight is 649.79g/mol, the crystal is an orthorhombic system, the crystal belongs to a non-heart space group, aea2, and the unit cell parameters are as follows: α=β=γ=90°,Z=4。
the preparation method of the sulfur phosphorus mercury zinc infrared nonlinear optical crystal adopts a high-temperature melt spontaneous crystallization method, a chemical vapor transmission method, a fluxing agent method or a crucible descending method to grow the crystal;
the crystal is grown by the high-temperature melt spontaneous crystallization method, and the specific operation is carried out according to the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. C, filling the compound sulfur phosphorus mercury zinc polycrystal powder obtained in the step a into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, and then carrying out fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, raising the temperature to 600-630 ℃ at the temperature raising rate of 20-35 ℃ per hour, carrying out constant temperature reaction for 26-98 hours, and then cooling to room temperature at the temperature lowering rate of 2-8 ℃ per hour, so that the Zn 2HgP2S8 infrared nonlinear optical crystal is obtained through spontaneous crystallization;
The chemical vapor transport method for growing Zn 2HgP2S8 nonlinear optical crystal comprises the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. C, filling the compound sulfur phosphorus mercury zinc powder obtained in the step a into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, and then carrying out fusion sealing, putting the sealed quartz tube into a tubular furnace growing device, slowly heating to 650-680 ℃, reacting at the constant temperature for 30-95h, slowly cooling to the room temperature at the temperature of 3-8 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field, and obtaining Zn 2HgP2S8 infrared nonlinear optical crystals in the growth period of 12-45 days;
the method for growing Zn 2HgP2S8 nonlinear optical crystal by using the fluxing agent method comprises the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. Mixing the compound sulfur phosphorus mercury zinc powder obtained in the step a with a fluxing agent ZnCl 2 according to the mass ratio of 1:0.5-4.50, filling the mixture into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 610-650 ℃, keeping the constant temperature for 30-68h, and then cooling to room temperature at a cooling rate of 2-9 ℃ per hour to obtain a light green transparent Zn 2HgP2S8 infrared nonlinear optical crystal;
the crystal growth method by the crucible descent method comprises the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. Putting the compound sulfur phosphorus mercury zinc obtained in the step a into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, carrying out fusion sealing, putting the sealed quartz tube into a Bridgman furnace with the temperature controlled by a program, slowly heating to 650-700 ℃ at the heating rate of 15-30 ℃ per hour, preserving heat for 30-50 hours, carrying out vertical crucible descent at the speed of 0.3-0.8mm per hour after the raw materials are completely melted, carrying out crystal growth in the descending process of the Bridgman furnace, carrying out continuous annealing at the speed of 10-25 ℃ per hour after the growth is finished until the temperature is reduced to the room temperature, and obtaining the Zn 2HgP2S8 infrared nonlinear optical crystal.
The sulfur phosphorus mercury zinc infrared nonlinear optical crystal is used for preparing infrared band laser variable frequency crystals, infrared electro-optical devices, infrared communication devices or infrared laser guidance devices.
The Zn 2HgP2S8 compound of the invention can be prepared according to the following chemical reaction formula:
(1)2Zn+Hg+2P+8S=Zn2HgP2S8;
(2)2ZnS+Hg+2P+5S=Zn2HgP2S8;
(3) 2Zn+Hg+P2S5+3S＝Zn2HgP2S8;
(4) 2ZnS+HgS+P2S5＝Zn2HgP2S8。
According to the preparation method of the sulfur phosphorus mercury zinc infrared nonlinear optical crystal, zn 2HgP2S8 infrared nonlinear optical crystals with the size of centimeter level can be obtained, and Zn 2HgP2S8 infrared nonlinear optical crystals with the corresponding larger size can be obtained by using a large-size crucible and prolonging the growing period.
According to crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the required angle, thickness and section size, and the light-passing surface of the crystal is polished, so that the crystal can be used as a nonlinear optical device.
The invention further provides a nonlinear optical device. The nonlinear optical device comprises the Zn 2HgP2S8 nonlinear optical crystal. The Zn 2HgP2S8 nonlinear optical crystal can be used to prepare a nonlinear optical device comprising means for passing at least one beam of incident electromagnetic radiation through at least one piece of Zn 2HgP2S8 nonlinear optical crystal to produce at least one beam of output radiation having a frequency different from the incident electromagnetic radiation.
The Zn 2HgP2S8 nonlinear optical crystal prepared by the method is easy to grow and transparent without wrapping in the growth process, has the advantages of high growth speed, low cost, easiness in obtaining larger-size crystals and the like, the obtained Zn 2HgP2S8 nonlinear optical crystal and device have the advantages of large nonlinear optical effect, light-transmitting wave Duan Kuan, high hardness, good mechanical property, difficulty in fragmentation and deliquescence, easiness in processing and storage and the like, and the Zn 2HgP2S8 nonlinear optical crystal can be used for manufacturing infrared nonlinear optical devices.
Drawings
Fig. 1 is a schematic structural diagram of the present invention, in which Zn, hg and P are four coordinated with S atoms in a crystal structure, ZHPS has a typical three-dimensional (3D) defect diamond-like structure, in which three tetrahedrons composed of Zn 2HgS8 layers and pseudo layers of PS 4 are arranged in parallel along the c direction, and the two layers are connected to each other by sharing S atoms.
FIG. 2 is a schematic view of the SHG effect of the present invention, zn 2HgP2S8 exhibits a medium size NLO response in the 180-214 220 μm particle size range, approximately 1.1 times that of the baseline AgGaS 2.
Fig. 3 is a schematic diagram of an exemplary nonlinear optical device according to the present invention, wherein 1 is a laser, 2 is a convex lens, 3 is a Zn 2HgP2S8 nonlinear optical crystal after crystal post-treatment and optical processing, 4 is a prism, and 5 is a filter.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving the same or similar purpose, unless expressly stated otherwise. Each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise. The description is only intended to aid in the understanding of the invention and should not be taken as limiting the invention in any way.
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1
The compound Zn 2HgP2S8 is prepared by a high-temperature solid phase method through a chemical reaction formula 2Zn+Hg+2P+8S=Zn 2HgP2S8,, and the specific operation is carried out according to the following steps:
Weighing 0.101g of Zn, 0.154g of Hg, 0.048g P and 0.197g S according to a molar ratio of 2:1:2:8 under vacuum, uniformly mixing, putting into a clean graphite crucible, putting the graphite crucible into a quartz tube with a length of 24cm and a diameter of 12mm, pumping the quartz tube to a vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing melt sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 630 ℃ at a rate of 20 ℃ per hour, and preserving heat for 35 hours to obtain the polycrystalline powder of the compound Zn 2HgP2S8.
Example 2
The compound Zn 2HgP2S8 is prepared by a high-temperature solid phase method according to a chemical reaction formula 2ZnS+Hg+2P+6S=Zn 2HgP2S8, and the specific operation is carried out according to the following steps:
Weighing 0.195g ZnS, 0.201g Hg, 0.062g P and 0.192g S according to a molar ratio of 2:1:2:6 under the condition of inert atmosphere, uniformly mixing, putting into a clean graphite crucible, putting the graphite crucible into a quartz tube with a length of 24cm and a diameter of 12mm, pumping the quartz tube to a vacuum degree of 10 -3-10-5 Pa by using a vacuum pump, carrying out fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 650 ℃ at a speed of 18 ℃ per hour, and preserving heat for 32 hours to obtain polycrystalline powder of the compound Zn 2HgP2S8.
Example 3
The compound Zn 2HgP2S8 is prepared by a high-temperature solid phase method according to the chemical reaction formula 2Zn+Hg+P2S5+3S=Zn 2HgP2S8, and the specific operation is carried out according to the following steps:
weighing 0.121g of Zn, 0.185g of Hg, 0.205g P 2S5 and 0.089g S according to a molar ratio of 2:1:1:3 under vacuum, uniformly mixing, putting into a clean graphite crucible, putting the graphite crucible into a quartz tube with the length of 24cm and the diameter of 12mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, carrying out melt sealing, putting the sealed quartz tube into a muffle furnace with the temperature controlled by a program, heating to 640 ℃ at the speed of 19 ℃ per hour, and preserving heat for 28 hours to obtain the polycrystalline powder of the compound Zn 2HgP2S8.
Example 4
The compound Zn 2HgP2S8 is prepared by a chemical reaction formula 2ZnS+HgS+P 2S5＝Zn2HgP2S8 and a high-temperature solid phase method, and the specific operation is carried out according to the following steps:
Weighing 0.180g ZnS, 0.215g HgS and 0.205g P 2S5 according to a molar ratio of 2:1:1 under the condition of inert atmosphere, uniformly mixing, putting into a clean graphite crucible, putting the graphite crucible into a quartz tube with a length of 24cm and a diameter of 12mm, pumping the quartz tube to a vacuum degree of 10 -3-10-5 Pa by using a vacuum pump, then carrying out melt sealing, putting the sealed quartz tube into a muffle furnace with a programmed temperature, heating to 670 ℃ at a rate of 24 ℃ per hour, and preserving heat for 35 hours to obtain the polycrystalline powder of the compound Zn 2HgP2S8.
Example 5
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a high-temperature melt spontaneous crystallization method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 1 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 600 ℃ at the rate of 20 ℃ per hour, preserving heat for 50 hours, and then cooling to room temperature at the cooling rate of 4 ℃ per hour to obtain the zinc mercury zinc sulfur phosphorus infrared nonlinear optical crystal with the size of 0.25 multiplied by 4.08 multiplied by 6.15mm 3.
Example 6
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a high-temperature melt spontaneous crystallization method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 2 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 615 ℃ at the speed of 22 ℃ per hour, preserving heat for 45 hours, and then cooling to room temperature at the cooling speed of 6 ℃ per hour to obtain the zinc mercury zinc sulfur phosphorus infrared nonlinear optical crystal with the size of 0.39X3.98X6.10 mm 3.
Example 7
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a high-temperature melt spontaneous crystallization method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 3 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 625 ℃ at the speed of 26 ℃ per hour, preserving heat for 60 hours, and then cooling to room temperature at the cooling speed of 7 ℃ per hour to obtain the zinc mercury zinc sulfur phosphorus infrared nonlinear optical crystal with the size of 0.22 multiplied by 4.20 multiplied by 6.36mm 3.
Example 8
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a high-temperature melt spontaneous crystallization method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 4 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a programmed temperature, heating to 630 ℃ at the rate of 32 ℃ per hour, preserving heat for 55 hours, and then cooling to room temperature at the cooling rate of 5 ℃ per hour to obtain the zinc mercury zinc sulfur phosphorus infrared nonlinear optical crystal with the size of 0.18 multiplied by 4.56 multiplied by 6.08mm 3.
Example 9
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a chemical vapor transmission method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in the example 1 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, then carrying out fusion sealing, putting the sealed quartz tube into a tube furnace growth device with a program temperature control, slowly heating to 655 ℃, keeping the temperature for 58 hours, slowly cooling to the room temperature at the rate of 3.5 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field during the process, and cutting after the quartz tube is completely cooled, thus obtaining the sulfur-phosphorus-mercury-zinc nonlinear optical crystals with the size of 0.98X3.58X5.08 mm 3.
Example 10
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a chemical vapor transmission method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in the example 2 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, then carrying out fusion sealing, putting the sealed quartz tube into a tube furnace growth device with a program temperature control, slowly heating to 650 ℃, keeping the temperature for 68 hours, slowly cooling to room temperature at the rate of 5 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field during the process, and cutting after the quartz tube is completely cooled, thus obtaining the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystals with the size of 1.32X4.38X6.51 mm 3.
Example 11
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a chemical vapor transmission method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in the embodiment 3 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, then carrying out fusion sealing, putting the sealed quartz tube into a tube furnace growth device with a program temperature control, slowly heating to 663 ℃ and keeping the temperature for 70 hours, slowly cooling to the room temperature at the rate of 3 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field during the process, and cutting after the quartz tube is completely cooled, thus obtaining the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystals with the size of 0.82 multiplied by 4.62 multiplied by 6.08mm 3.
Example 12
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a chemical vapor transmission method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in the example 4 into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, then carrying out fusion sealing, putting the sealed quartz tube into a tube furnace growth device with a program temperature control, slowly heating to 678 ℃, keeping the temperature for 70 hours, slowly cooling to the room temperature at the rate of 6 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field during the process, and cutting after the quartz tube is completely cooled, thereby obtaining the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystals with the size of 1.92 multiplied by 3.93 multiplied by 6.58mm 3.
Example 13
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a fluxing agent growth method, and the specific operation is carried out according to the following steps:
The method comprises the steps of preparing the compound Zn 2HgP2S8 polycrystal powder obtained in the embodiment 1 and a fluxing agent ZnCl 2 according to the mass ratio of 1:3, filling the mixture into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a programmed temperature, slowly heating to 618 ℃, carrying out constant-temperature reaction for 65h, slowly cooling to room temperature at the rate of 6 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field during the reaction, and cutting after the quartz tube is completely cooled, thereby obtaining the sulfur-phosphorus-mercury-zinc nonlinear optical crystals with the size of 0.82 multiplied by 4.46 multiplied by 6.33mm 3.
Example 14
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a fluxing agent growth method, and the specific operation is carried out according to the following steps:
The compound Zn 2HgP2S8 polycrystal powder obtained in the example 2 and a fluxing agent ZnCl 2 are mixed according to the mass ratio of 1:3.5, then the mixed material is filled into a quartz tube with the length of 20cm and the diameter of 35mm, the quartz tube is pumped to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump for fusion sealing, the sealed quartz tube is put into a muffle furnace with the temperature controlled by a program, the temperature is slowly increased to 632 ℃, the constant temperature is reacted for 45 hours, the temperature is slowly reduced to the room temperature at the speed of 4 ℃ per hour, the vapor phase transmission growth of Zn 2HgP2S8 nonlinear optical crystals is carried out through a horizontal gradient temperature field during the reaction, and the quartz tube is cut after the quartz tube is completely cooled, so that the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal with the size of 0.98 multiplied by 4.13 multiplied by 6.27mm 3 is obtained.
Example 15
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a fluxing agent growth method, and the specific operation is carried out according to the following steps:
The compound Zn 2HgP2S8 polycrystal powder obtained in the example 3 and a fluxing agent ZnCl 2 are mixed according to the mass ratio of 1:4, then the mixed material is filled into a quartz tube with the length of 20cm and the diameter of 35mm, the quartz tube is pumped to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump for fusion sealing, the sealed quartz tube is put into a muffle furnace with the temperature controlled by a program, slowly heated to 643 ℃ for constant temperature reaction for 55 hours, slowly cooled to room temperature at the speed of 6.5 ℃ per hour, the vapor phase transmission growth of Zn 2HgP2S8 nonlinear optical crystals is carried out through a horizontal gradient temperature field during the constant temperature reaction, and the quartz tube is cut after being completely cooled, so that the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystals with the size of 0.61 multiplied by 4.33 multiplied by 6.65mm 3 are obtained.
Example 16
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by adopting a fluxing agent growth method, and the specific operation is carried out according to the following steps:
the compound Zn 2HgP2S8 polycrystal powder obtained in the example 4 and a fluxing agent ZnCl 2 are mixed according to the mass ratio of 1:4.5, then the mixed material is filled into a quartz tube with the length of 20cm and the diameter of 35mm, the quartz tube is pumped to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump and then is subjected to fusion sealing, the sealed quartz tube is put into a muffle furnace with the temperature controlled by a program, the temperature is slowly increased to 650 ℃, the constant temperature is reacted for 45 hours, the temperature is slowly reduced to the room temperature at the speed of 5.5 ℃ per hour, the vapor phase transmission growth of Zn 2HgP2S8 nonlinear optical crystal is carried out through a horizontal gradient temperature field during the reaction, and the quartz tube is cut after the quartz tube is completely cooled, so that the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal with the size of 0.63 multiplied by 4.89 multiplied by 6.97mm 3 is obtained.
Example 17
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by a crucible descent method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 1 into a quartz tube with the length of 24cm and the diameter of 12mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, carrying out melt sealing, putting the sealed quartz tube into a Bridgman furnace with the temperature controlled by a program, heating to 650 ℃ at the speed of 15 ℃ and then preserving heat for 35 hours, then descending the quartz tube at the speed of 0.35mm/h in a vertical crucible, growing the crystal in the descending process of the Bridgman furnace, wherein the growth period is 16 days, and continuously annealing at the speed of 20 ℃/h until the temperature is reduced to the room temperature after the growth is finished, thus obtaining the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal with the size of 0.39X4.42X6.28 mm 3.
Example 18
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by a crucible descent method, and the specific operation is carried out according to the following steps:
Putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 2 into a quartz tube with the length of 24cm and the diameter of 12mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, carrying out melt sealing, putting the sealed quartz tube into a Bridgman furnace with the temperature controlled by a program, heating to 665 ℃ at the speed of 20 ℃ per hour, preserving heat for 45 hours, then descending at the speed of 0.5 mm/hour by a vertical crucible, growing the crystal in the descending process of the Bridgman furnace, wherein the growth period is 20 days, and continuously annealing at the speed of 18 ℃ per hour until the temperature is reduced to room temperature after the growth is finished, thus obtaining the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal with the size of 0.60 multiplied by 4.98 multiplied by 6.58mm 3.
Example 19
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by a crucible descent method, and the specific operation is carried out according to the following steps:
putting the compound Zn 2HgP2S8 polycrystal powder obtained in example 3 into a quartz tube with the length of 24cm and the diameter of 12mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, carrying out melt sealing, putting the sealed quartz tube into a Bridgman furnace with the temperature controlled by a program, heating to 670 ℃ at the speed of 25 ℃ for 48 hours, then descending the quartz tube at the speed of 0.6mm/h in a vertical crucible, growing the crystal in the descending process of the Bridgman furnace, wherein the growth period is 25 days, and continuously annealing at the speed of 22 ℃/h until the temperature is reduced to the room temperature after the growth is finished, thus obtaining the sulfur-phosphorus-mercury-zinc infrared nonlinear optical crystal with the size of 0.15X4.03X6.22 mm 3.
Example 20
The Zn 2HgP2S8 infrared nonlinear optical crystal is prepared by a crucible descent method, and the specific operation is carried out according to the following steps:
The compound Zn 2HgP2S8 polycrystal powder obtained in example 4 was put into a quartz tube having a length of 24cm and a diameter of 12mm, the quartz tube was evacuated to a vacuum degree of 10 -3-10-5 Pa by a vacuum pump and then subjected to melt sealing, the sealed quartz tube was then put into a Bridgman furnace with a programmed temperature control, and heated to 675 ℃ at a rate of 30 ℃ per hour, and then kept warm for 50 hours, and then was lowered at a rate of 0.7mm per hour in a vertical crucible, and the crystal was grown in the Bridgman furnace with a growth cycle of 30 days, and after the growth was completed, continuous annealing was performed at a rate of 25 ℃ per hour until the temperature was lowered to room temperature, to obtain a zinc-mercury-sulfur infrared nonlinear optical crystal having a size of 0.66×4.32×6.55mm 3.
Example 21
Through tests, the Zn 2HgP2S8 infrared nonlinear optical crystal prepared in the examples 5-20 belongs to an orthorhombic system, the space group is Aea2, the nonlinear optical crystal does not have a symmetrical center, and the unit cell parameters are as follows: α=β=γ =90°, z=4. The crystal has good frequency doubling effect, and the light transmission range is 0.3-17 μm, and FIG. 1 is a schematic diagram of Zn 2HgP2S8 nonlinear optical crystal structure;
the Zn 2HgP2S8 crystals obtained in examples 5-20 were not easily broken, were not easily deliquesced, and were easily cut, polished and stored. Placing the Zn 2HgP2S8 crystal obtained in the examples 5-20 at the position with the device number of 3 shown in the figure 3, taking a Q-switched Ho, tm, cr, YAG laser as a light source, inputting infrared light with the wavelength of 2090nm, outputting frequency multiplication light with the wavelength of 1045nm, and using the Zn 2HgP2S8 crystal to output laser with the intensity 1.1 times that of AgGaS 2 under the same condition;
Fig. 3 is a schematic diagram of an exemplary nonlinear optical device made of the Zn 2HgP2S8 nonlinear optical crystal according to the present invention, in which 1 is a laser, 2 is a convex lens, 3 is a Zn 2HgP2S8 nonlinear optical crystal after crystal post-treatment and optical processing, 4 is a prism, 5 is a filter, and a laser beam emitted from the laser 1 is injected into Zn 2HgP2S8 monocrystal 3 through the convex lens 2, and the resulting emitted laser beam passes through the prism 4 and the filter 5, thereby obtaining a desired laser beam.
The device manufactured by using the Zn 2HgP2S8 nonlinear optical crystal is a frequency multiplication generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator, an optical parametric amplifier and the like.

Claims (3)

1. The sulfur phosphorus mercury zinc infrared nonlinear optical crystal is characterized by having a chemical formula of Zn 2HgP2S8, a molecular weight of 649.79 g/mol, being an orthorhombic system, belonging to a non-cardiac space group, aea2, and unit cell parameters of a= 16.2706 (12) a, b= 7.9266 (7) a, c= 9.0620 (7) a, a=beta=gamma=90 DEG, and Z=4.
2. The method for preparing the sulfur phosphorus mercury zinc infrared nonlinear optical crystal according to claim 1, which is characterized in that the method adopts a high-temperature melt spontaneous crystallization method, a chemical vapor transport method, a fluxing agent method or a crucible descending method to grow the crystal;
the crystal is grown by the high-temperature melt spontaneous crystallization method, and the specific operation is carried out according to the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. C, filling the compound sulfur phosphorus mercury zinc polycrystal powder obtained in the step a into a quartz tube with the length of 20cm and the diameter of 35 mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by using a vacuum pump, and then carrying out fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, raising the temperature to 600-630 ℃ at the temperature raising rate of 20-35 ℃ per hour, carrying out constant temperature reaction at 26-98 h, and then cooling to room temperature at the temperature lowering rate of 2-8 ℃ per hour to enable the quartz tube to spontaneously crystallize to obtain Zn 2HgP2S8 infrared nonlinear optical crystals;
The chemical vapor transport method for growing Zn 2HgP2S8 nonlinear optical crystal comprises the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. C, filling the compound sulfur phosphorus mercury zinc powder obtained in the step a into a quartz tube with the length of 20cm and the diameter of 35mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, and then carrying out fusion sealing, putting the sealed quartz tube into a tubular furnace growing device, slowly heating to 650-680 ℃, carrying out constant-temperature reaction for 30-95 h, slowly cooling to room temperature at 3-8 ℃ per hour, carrying out vapor transmission growth of Zn 2HgP2S8 nonlinear optical crystals by a horizontal gradient temperature field, and obtaining Zn 2HgP2S8 infrared nonlinear optical crystals in a growth period of 12-45 days;
the method for growing Zn 2HgP2S8 nonlinear optical crystal by using the fluxing agent method comprises the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. Mixing the compound sulfur phosphorus mercury zinc powder obtained in the step a with a fluxing agent ZnCl 2 according to the mass ratio of 1:0.5-4.50, filling the mixture into a quartz tube with the length of 20 cm and the diameter of 35 mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a program temperature control, heating to 610-650 ℃, keeping the constant temperature of 30-68 h, and then cooling to room temperature at a cooling rate of 2-9 ℃ per hour to obtain a light green transparent Zn 2HgP2S8 infrared nonlinear optical crystal;
the crystal growth method by the crucible descent method comprises the following steps:
a. Uniformly mixing a Zn source material, an Hg source material, a P source material and simple substance S according to the molar ratio of 1.8-2.5:1:2:7.5-8.5, placing the mixture into a clean graphite crucible, placing the graphite crucible into a quartz tube, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing fusion sealing, placing the quartz tube into a muffle furnace with a program temperature control, heating to 600-630 ℃ at the speed of 15-18 ℃ per hour, performing solid phase reaction, and cooling to room temperature at the speed of 3-5 ℃ per hour to obtain a compound of sulfur phosphorus mercury zinc, wherein the Zn source material is Zn, znCl 2, znS or ZnI 2, the Hg source material is Hg, hg 2Cl2 or HgS, and the P source material is P or P 2S5;
b. putting the compound sulfur phosphorus mercury zinc obtained in the step a into a quartz tube with the length of 20 cm and the diameter of 35 mm, pumping the quartz tube to the vacuum degree of 10 -3-10-5 Pa by a vacuum pump, performing melt sealing, putting the sealed quartz tube into a Bridgman furnace with the temperature controlled by a program, slowly heating to 650-700 ℃ at the heating rate of 15-30 ℃ per hour, preserving heat for 30-50 hours, performing vertical crucible descent at the speed of 0.3-0.8mm per hour after the raw materials are completely melted, performing crystal growth in the descending process of the Bridgman furnace, continuously annealing at the speed of 10-25 ℃ per hour after the growth is finished until the temperature is reduced to room temperature, and obtaining the Zn 2HgP2S8 infrared nonlinear optical crystal.
3. The use of a zinc mercuric sulfide infrared nonlinear optical crystal according to claim 1 in the preparation of an infrared band laser variable frequency crystal, an infrared electro-optic device, an infrared communication device or an infrared laser guidance device.
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