CN116902933A - Compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, preparation method and application - Google Patents
Compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, preparation method and application Download PDFInfo
- Publication number
- CN116902933A CN116902933A CN202310879311.9A CN202310879311A CN116902933A CN 116902933 A CN116902933 A CN 116902933A CN 202310879311 A CN202310879311 A CN 202310879311A CN 116902933 A CN116902933 A CN 116902933A
- Authority
- CN
- China
- Prior art keywords
- nonlinear optical
- temperature
- source material
- mercury
- quartz tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 210
- 230000003287 optical effect Effects 0.000 title claims abstract description 150
- -1 selenium phosphorus mercury Chemical compound 0.000 title claims abstract description 92
- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011669 selenium Substances 0.000 claims abstract description 250
- 238000000034 method Methods 0.000 claims abstract description 115
- 239000000126 substance Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 136
- 239000010453 quartz Substances 0.000 claims description 110
- 239000000463 material Substances 0.000 claims description 67
- 238000001816 cooling Methods 0.000 claims description 62
- 238000010438 heat treatment Methods 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 41
- 238000004806 packaging method and process Methods 0.000 claims description 39
- 238000000227 grinding Methods 0.000 claims description 38
- 229910052753 mercury Inorganic materials 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 30
- 238000007789 sealing Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 19
- 238000005360 mashing Methods 0.000 claims description 17
- 229910052711 selenium Inorganic materials 0.000 claims description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000005086 pumping Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000013467 fragmentation Methods 0.000 abstract description 2
- 238000006062 fragmentation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940100892 mercury compound Drugs 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/06—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using as solvent a component of the crystal composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Glass Compositions (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, a preparation method and application thereof, wherein the molecular formula of the compound is Hg 7 P 2 Se 12 Molecular weight is 1206.79, and molecular formula of the crystal is Hg 7 P 2 Se 12 The molecular weight is 1206.79, the symmetry center is not included, the three-inclined crystal system is adopted, and the space group isPThe unit cell parameters are: a= 12.573 (2) a, b= 14.523 (2) a, c= 16.247 (2)A, α= 77.509 (5) °, β= 75.191 (6) °, γ= 73.051 (5) °, z=5, volume 2711.1 (7) a 3 The crystal is prepared by a high-temperature melt method, a chemical vapor transport method, a fluxing agent method or a crucible descending method. The crystal has the advantages of high laser damage resistance, moderate nonlinear optical effect, wide light transmission wave band, high hardness, good mechanical property, difficult fragmentation and deliquescence, easy processing and storage and the like, and can be used for manufacturing infrared nonlinear optical devices.
Description
Technical Field
The invention belongs to the field of preparation of infrared nonlinear optical crystals, and in particular relates to a compound selenium phosphorus mercury (Hg) 7 P 2 Se 12 ) And a preparation method and application of the selenium phosphorus mercury infrared nonlinear optical crystal.
Background
The nonlinear optical crystal is a crystal material with nonlinear optical effects such as frequency multiplication, sum frequency, difference frequency, optical parametric amplification and the like. Only crystals without a centre of symmetry may have second order nonlinear optical effects. The second harmonic generator, upper and lower frequency converters, optical parametric oscillator and other nonlinear optical devices can be manufactured by utilizing the second-order nonlinear optical effect of the crystal. The laser generated by the laser can be subjected to frequency conversion through a nonlinear optical device to obtain more new laser sources, so that the development of a laser technology in a tunable wavelength range and the development of output power can be promoted.
Nonlinear optical crystal materials can be classified into three categories, namely ultraviolet nonlinear optical materials, visible and near infrared nonlinear optical materials, and mid-far infrared nonlinear optical materials, according to the application wave bands. Nonlinear optical crystal materials in the ultraviolet, visible and near infrared regions have been found to substantially meet practical application requirements, such as KTP (KTiOPO) which is the most practical for use in double frequency (532 nm) crystals 4 )、BBO(β-BaB 2 O 4 )、LBO(LiB 3 O 5 ) A crystal; in the deep ultraviolet crystal, KBBF (KBE) 2 BO 3 F 2 )、ABF(NH 4 B 4 O 6 F)、CBF(CsB 4 O 6 F) Alternatively. The nonlinear crystal in the mid-far infrared band is slow to develop; the mid-far infrared nonlinear optical material currently in commercial use is mainly a chalcopyrite structured semiconductor material, such as AgGaQ 2 (Q＝S，Se)、ZnGeP 2 Etc. However, these mid-far infrared nonlinear optical materials are mostly developedIn seventies, due to the existence of some intrinsic performance defects such as low laser damage threshold, two-photon absorption near 1 μm and the like, the application of the materials in the current high-power laser output field is greatly limited, the requirements of the current laser technology development cannot be completely met, and the development of novel mid-far infrared nonlinear optical crystal materials with balanced performance is needed.
Disclosure of Invention
The present invention aims to provide a compound of formula Hg 14 P 2 Se 12 Selenium phosphorus mercury compound.
Another object of the present invention is to provide Hg 14 P 2 Se 12 Selenium phosphorus mercury infrared nonlinear optical crystal.
It is a further object of the present invention to provide Hg 14 P 2 Se 12 A preparation method of selenium phosphorus mercury nonlinear optical crystal.
It is a further object of the present invention to provide Hg 14 P 2 Se 12 Use of selenium phosphorus mercury nonlinear optical crystal.
The molecular formula of the compound selenium phosphorus mercury is Hg 7 P 2 Se 12 The molecular weight is 1206.79, the crystal structure belongs to a triclinic system, the space group is P1, and the crystal structure is prepared by a high-temperature melt method.
The preparation method of the compound selenium phosphorus mercury comprises the following steps:
a. hg source materials are Hg and Hg according to the mol ratio Hg to P to Se=7:2:12 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 Mixing Se serving as a selenium source material uniformly to obtain a mixture;
b. grinding the mixture obtained in the step a to 100 meshes, filling the mixture into a quartz container, and pumping the mixture to 10 under vacuum condition - 3 Pa, performing fusion sealing;
c. and c, placing the sealed sample in the step b in a muffle furnace, heating to 450-550 ℃ at the speed of 10-40 ℃/h, keeping the temperature for 40-60h, then cooling to 300 ℃ at the speed of 10-20 ℃/h, taking out the sample after cooling, and mashing and grinding to obtain the powdered selenium phosphorus mercury pure sample.
An infrared nonlinear optical crystal of selenium phosphorus mercury has a molecular formula of Hg 7 P 2 Se 12 The molecular weight is 1206.79, the symmetry center is not included, the three-inclined crystal system is adopted, the space group is P1, and the unit cell parameter is α＝77.509(5)°，β＝75.191(6)°，γ＝73.051(5)°，Z＝5。
The preparation method of the selenium phosphorus mercury infrared nonlinear optical crystal adopts a high-temperature melt method, a chemical vapor transmission method, a fluxing agent method or a crucible descending method to carry out crystal growth:
the method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. uniformly mixing Hg source material, P source material and simple substance Se according to the mol ratio Hg to P to Se=7:2:12, grinding to 100 meshes, loading into a quartz tube, vacuumizing to 10 -3 Pa, sealing, placing into a muffle furnace, heating to 450-550deg.C at a rate of 10-40deg.C/h, maintaining the temperature for 60-100h, cooling to 300 deg.C at 10-20deg.C/h, taking out sample, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound, wherein the Hg source material is Hg, hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. putting the compound powder into a quartz tube, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 450-500 deg.C, keeping constant temperature for 24-72 hr, slowly cooling to room temperature at 1-5deg.C/hr, closing the muffle furnace, cooling the quartz tube, and cutting to obtain black Hg 14 P 2 Se 12 An infrared nonlinear optical crystal;
the chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. directly mixing Hg source material, P source material and simple substance Se according to the mol ratio Hg to P to Se=7 to 2 to 12, loading into a quartz tube, vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, and placing in a tube-type growth furnace, wherein the Hg source material is Hg or Hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. chemical vapor transport in a tube furnace, hg by a horizontal or vertical gradient temperature field 7 P 2 Se 12 Heating to 450-550 ℃ at 25 ℃/h for 8-20 days, slowly cooling to room temperature at 1-5 ℃/h after the growth is finished, closing the tubular growth furnace, cutting after the quartz tube is cooled, and obtaining black Hg at the low temperature end 7 P 2 Se 12 An infrared nonlinear optical crystal;
the method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
a. uniformly mixing Hg source material, P source material and Se source material according to a molar ratio of 6.5-8:2:12-14, placing into a clean graphite crucible, placing the graphite crucible into a quartz tube, and pumping the quartz tube to 10 by using a vacuum pump -3 Pa, then carrying out melting sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 450-550 ℃ at a speed of 10-40 ℃/h, keeping the temperature for 60-100h, cooling to 300 ℃ at a speed of 10-20 ℃/h, taking out the sample, and mashing and grinding to obtain Hg 7 P 2 Se 12 In powder form, wherein the Hg source material is Hg, hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. mixing the selenium phosphorus mercury powder obtained in the step a with fluxing agent Se, hgSe or Hg according to the mass ratio of 1:0.5-4.5 2 Cl 2 Mixing, placing into a quartz tube with diameter of 35mm and length of 20cm, and pumping the quartz tube to 10 by vacuum pump -3 Pa, performing fusion sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 430-480 ℃, and maintainingMaintaining the constant temperature for 30-68h, and cooling to room temperature at a cooling rate of 2-9deg.C/h to obtain black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal;
the method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. uniformly mixing Hg source material, P source material and Se source material according to a molar ratio of 6.5-8:2:12-14, placing into a clean graphite crucible, placing the graphite crucible into a quartz tube, and pumping the quartz tube to 10 by using a vacuum pump -3 Pa, then carrying out melting sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 450-550 ℃ at a speed of 10-40 ℃/h, keeping the temperature for 60-100h, cooling to 300 ℃ at a speed of 10-20 ℃/h, taking out a sample, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 Then the mixture is put into a quartz tube and vacuumized to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, heating to 480-560 ℃ at 5-20 ℃/h, and keeping the temperature for 60-100h until the raw materials are melted;
or mixing Hg source material, P source material and Se source material at a molar ratio of 6.5-8:2:12-14, placing into a clean graphite crucible, placing the graphite crucible into a quartz tube, and pumping the quartz tube to 10 by vacuum pump -3 Pa, then carrying out melting sealing, putting the quartz tube into a crucible descending furnace with a programmed temperature, heating to 450-550 ℃ at a speed of 10-40 ℃/h, and keeping the temperature for 60-100h until the raw materials are melted, wherein the Hg source materials are Hg and Hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at the speed of 0.1-3mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 Growing the crystal for 20-40 days, after the crystal growth is finished, keeping the crystal in a crucible descending furnace for annealing, and cooling to room temperature at a speed of 40-60 ℃/h to obtain black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
The selenium phosphorus mercury infrared nonlinear optical crystal is used for preparing an infrared band laser variable frequency crystal, an infrared laser, an infrared electro-optical device, an infrared communication device or an infrared laser guidance device.
The compound selenium phosphorus mercury Hg of the invention 14 P 2 Se 12 The preparation method comprises the following steps:
(1)7Hg+2P+12Se＝Hg 7 P 2 Se 12 ；
(2)7Hg+P 2 Se 5 +7Se＝Hg 7 P 2 Se 12 ；
(3)7HgSe+P 2 Se 5 ＝Hg 7 P 2 Se 12 ；
(4)7HgSe+2P+5Se＝Hg 7 P 2 Se 12 ；
(5)21Hg 2 Cl 2 +12P+72Se＝6Hg 7 P 2 Se 12 +14PCl 3
(6)21HgI+6P+36Se＝3Hg 7 P 2 Se 12 +7PI 3 。
the preparation method of the selenium phosphorus mercury infrared nonlinear optical crystal can obtain Hg with the size of centimeter level 7 P 2 Se 12 A nonlinear optical crystal; the large-size crucible is used, and the growing period is prolonged, so that Hg with correspondingly large size can be obtained 7 P 2 Se 12 Nonlinear optical crystal.
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 application of the selenium phosphorus mercury infrared nonlinear optical crystal in the technical field of laser comprises the application of preparing an infrared band laser variable frequency crystal, an infrared laser, an infrared electro-optical device, an infrared communication device or an infrared laser guidance device.
The selenium phosphorus mercury infrared nonlinear optical crystal has the advantages of low synthesis temperature, transparency, no inclusion, low cost, easiness in obtaining larger-size crystals and the like; hg obtained 7 P 2 Se 12 The infrared nonlinear optical crystal and the device have the advantages of laser damage resistance, moderate nonlinear optical effect, light-transmitting wave Duan Kuan, high hardness, good mechanical property, difficult fragmentation and deliquescence, easy processing and storage and the like; the Hg is 7 P 2 Se 12 The nonlinear optical crystal can be used for manufacturing an infrared nonlinear optical device.
Drawings
FIG. 1 is a schematic diagram of the structure of a selenium phosphorus mercury crystal according to the present invention;
FIG. 2 is a graph showing the comparison of the X-ray diffraction patterns of polycrystalline powder before and after melting of selenium phosphorus mercury crystals according to the present invention with theoretical values;
FIG. 3 is a schematic diagram of the operation of an optical device according to the present invention, wherein 1 is a laser, 2 is a convex lens, and 3 is Hg after crystal post-treatment and optical processing 7 P 2 Se 12 Nonlinear optical crystal, 4 is prism, 5 is 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
According to the reaction formula 7hg+2p+12se=hg 7 P 2 Se 12 Preparation of Compound Hg 7 P 2 Se 12 ：
Mixing 1.404 g Hg,0.062 g P and 0.948 g Se, grinding to 100 mesh, loading into quartz tube, and vacuumizing to 10 -3 Pa, melting and packaging, placing into a muffle furnace, heating to 500 ℃ at a speed of 25 ℃/h, keeping the temperature for 48h, cooling to 200 ℃ at 10 ℃/h, closing the muffle furnace, taking out a sample after cooling, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound.
Example 2
According to the reaction type 7Hg+P 2 Se 5 +7Se＝Hg 7 P 2 Se 12 Preparation of Compound Hg 7 P 2 Se 12 ：
1.404 g Hg,0.455 g P 2 Se 5 Mixing with 0.553 g Se uniformly, grinding to 100 mesh, loading into quartz tube, vacuumizing to 10 -3 Pa, melting and packaging, placing into a muffle furnace, heating to 480 ℃ at a speed of 25 ℃/h, keeping the temperature for 48h, cooling to 200 ℃ at 10 ℃/h, closing the muffle furnace, taking out a sample after cooling, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound.
Example 3
According to the reaction type 7HgSe+P 2 Se 5 ＝Hg 7 P 2 Se 12 Preparation of Compound Hg 7 P 2 Se 12 ：
3.206 g of HgSe and 0.455 g of P 2 Se 5 Mixing, grinding to 100 mesh, loading into quartz tube, and vacuumizing to 10 -3 Pa, melting and packaging, placing into a muffle furnace, heating to 520 ℃ at a speed of 15 ℃/h, keeping the temperature for 60h, cooling to 200 ℃ at 15 ℃/h, closing the muffle furnace, taking out a sample after cooling, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound.
Example 4
According to the reaction type 7hgse+2p+5se=hg 7 P 2 Se 12 Preparation of Compound Hg 7 P 2 Se 12 ：
Uniformly mixing 1.404 g of HgSe,0.062 g of P and 0.395 g of Se, grinding to 100 meshes, loading into a quartz tube, and vacuumizing to 10 -3 Pa, melting and packaging, placing into a muffle furnace, heating to 550 ℃ at a speed of 25 ℃/h, keeping the temperature for 48h, cooling to 200 ℃ at 10 ℃/h, closing the muffle furnace, taking out a sample after cooling, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound.
Example 5
According to the reaction type 21Hg 2 Cl 2 +12P+72Se＝6Hg 7 P 2 Se 12 +14PCl 3 Preparation of Compound Hg 7 P 2 Se 12 ：
9.889 g Hg 2 Cl 2 Mixing 0.372 g P and 5.692 g Se uniformly, grinding to 100 mesh, loading into quartz tube, vacuumizing to 10 -3 Pa, melting and packaging, placing into a muffle furnace, heating to 450 ℃ at a speed of 40 ℃/h, keeping the temperature for 48h, cooling to 200 ℃ at 10 ℃/h, closing the muffle furnace, taking out a sample after cooling, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound.
Example 6
According to the reaction formula 21hgi+6p+36se=3 Hg 7 P 2 Se 12 +7PI 3 Preparation of Compound Hg 7 P 2 Se 12 ：
Mixing 9.548 g of HgI,0.186 g of P and 2.846 g of Se uniformly, grinding to 100 meshes, loading into a quartz tube, and vacuumizing to 10 -3 Pa, melting and packaging, placing into a muffle furnace, heating to 500 ℃ at a speed of 20 ℃/h, keeping the temperature for 36h, cooling to 200 ℃ at 10 ℃/h, closing the muffle furnace, taking out a sample after cooling, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound.
Example 7
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
the powder obtained in example 1 was placed in a quartz tube having a diameter of 25mm by 240mm and evacuated to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 520 deg.C, keeping constant temperature for 60h, slowly cooling to room temperature at a speed of 1 deg.C/h, closing the muffle furnace, cooling the quartz tube, and cutting to obtain black Hg with a diameter of 3×2mm 14 P 2 Se 12 An infrared nonlinear optical crystal.
Example 8
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
the compound powder obtained in example 2 was chargedIn a quartz glass tube with phi 25mm multiplied by 240mm, vacuumizing to 10 - 3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 500 ℃, and keeping the temperature for 55h; slowly reducing the temperature to 200 ℃ at the speed of 3 ℃/h, closing the muffle furnace, and cutting after the quartz tube is cooled to obtain phi 3 multiplied by 3mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 9
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
the compound obtained in example 3 was placed in a quartz glass tube having a diameter of 25mm by 240mm and evacuated to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 480 ℃, and keeping constant temperature for 36h; slowly reducing the temperature to 200 ℃ at the speed of 2.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain phi 2 multiplied by 2mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 10
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
the compound obtained in example 4 was placed in a quartz glass tube having a diameter of 25mm by 240mm and evacuated to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 520 ℃, and keeping constant temperature for 40h; slowly reducing the temperature to 200 ℃ at the speed of 5 ℃/h, closing the muffle furnace, and cutting after the quartz tube is cooled to obtain phi 3 multiplied by 2mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 11
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
the compound obtained in example 5 was placed in a quartz glass tube having a diameter of 25mm by 240mm, and evacuated to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 450 ℃, and keeping the temperature for 70h; slowly reducing the temperature to 200 ℃ at the speed of 3.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain phi 5 multiplied by 3mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 12
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
the compound obtained in example 6 was placed in a quartz glass tube having a diameter of 25mm by 240mm, and evacuated to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 500 ℃, and keeping the temperature for 24 hours; slowly reducing the temperature to 200 ℃ at the speed of 4.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain black Hg with the diameter of phi 6 multiplied by 2mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 13
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. according to the reaction formula 7hg+2p+12se=hg 7 P 2 Se 12 Directly mixing 1.404 g Hg,0.062 g P and 0.948 g Se (i.e. Hg: P: se=0.0070 mol:0.002mol:0.012 mol), grinding to 100 mesh, placing into quartz glass tube with phi 25mm x 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 520 ℃, and keeping the temperature for 60h;
b. slowly reducing the temperature to 200 ℃ at the speed of 2.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain phi 3 multiplied by 2mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 14
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. according to the reaction type 7Hg+P 2 Se 5 +7Se＝Hg 7 P 2 Se 12 Directly 1.404 g Hg,0.455 g P 2 Se 5 And 0.553 g Se (i.e., hg: P) 2 Se 5 Se=0.0070mol:0.001 mol:0.007mol), uniformly mixing, grinding to 100 mesh, placing into quartz glass tube with diameter of 25mm×240mm, and vacuumizing to 10 -3 Pa, sealing with oxyhydrogen flamePlacing the mixture in a muffle furnace, slowly heating to 500 ℃, and keeping the temperature for 60 hours;
b. slowly reducing the temperature to 200 ℃ at the speed of 3 ℃/h, closing the muffle furnace, and cutting after the quartz tube is cooled to obtain phi 3 multiplied by 3mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 15
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. according to the reaction type 7HgSe+P 2 Se 5 ＝Hg 7 P 2 Se 12 3.206 g of HgSe and 0.455 g of P are directly added 2 Se 5 (i.e. HgSe: P 2 Se 5 =0.0070mol:0.001mol), uniformly mixing, grinding to 100 mesh, placing into quartz glass tube with phi 25mm×240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 480 ℃, and keeping the temperature for 60h;
b. slowly reducing the temperature to 200 ℃ at the speed of 2.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain phi 2 multiplied by 2mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 16
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. according to the reaction type 7hgse+2p+5se=hg 7 P 2 Se 12 Directly mixing 1.404 g of HgSe,0.062 g of P and 0.395 g of Se (i.e. HgSe: P: se=0.0070 mol:0.002mol:0.005 mol), grinding to 100 mesh, placing into a quartz glass tube with phi 25mm by 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 520 ℃, and keeping the temperature for 60h;
b. slowly reducing the temperature to 200 ℃ at the speed of 2.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain phi 3 multiplied by 2mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 17
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. according to the reaction type 21Hg 2 Cl 2 +12P+72Se＝6Hg 7 P 2 Se 12 +14PCl 3 9.889 g Hg was directly added 2 Cl 2 0.372 g of P, and 5.692 g of Se (i.e., hg 2 Cl 2 P: se=0.021 mol:0.012mol:0.072 mol), uniformly mixing, grinding to 100 mesh, placing into quartz glass tube with diameter of 25mm x 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 480 ℃, and keeping the temperature for 60h;
b. slowly reducing the temperature to 200 ℃ at the speed of 3.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain phi 5 multiplied by 3mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 18
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. according to the reaction formula 21hgi+6p+36se=3 Hg 7 P 2 Se 12 +7PI 3 Directly mixing 9.548 g of HgI,0.186 g of P and 2.846 g of Se (i.e. HgI: P: se=0.021 mol:0.006mol:0.036 mol), grinding to 100 mesh, loading into a quartz glass tube with phi 25mm x 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 500 ℃, and keeping the temperature for 60 hours;
b. Slowly reducing the temperature to 200 ℃ at the speed of 3.5 ℃/h, closing the muffle furnace, and cutting the quartz tube after the quartz tube is cooled to obtain black Hg with the diameter of phi 6 multiplied by 2mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 19
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
chemical vapor transport of the compound obtained in example 1 in a tube furnace and Hg by a horizontal gradient temperature field 7 P 2 Se 12 The crystals are grown and the crystal is grown,raising the temperature to 550 ℃ at 25 ℃/h, and slowly reducing the temperature to 200 ℃ at a speed of 1 ℃/h after the growth is finished for 10 days, closing the tubular growth furnace, and cutting after the quartz tube is cooled to obtain phi 2 multiplied by 1mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 20
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
chemical vapor transport of the compound obtained in example 2 in a tube furnace and Hg by a vertical gradient temperature field 7 P 2 Se 12 Heating to 450 ℃ at 25 ℃/h for 8 days, slowly cooling to room temperature at a rate of 2 ℃/h after the growth is finished, closing the tubular growth furnace, cooling the quartz tube, and cutting to obtain black Hg with phi 2 multiplied by 2mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 21
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
chemical vapor transport of the compound obtained in example 3 in a tube furnace and Hg by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the temperature is increased to 520 ℃ at 25 ℃/h, the growth period is 10 days, the temperature is slowly reduced to room temperature at the speed of 3 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled, thus obtaining black Hg with the diameter of phi 2.5 multiplied by 1.5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 22
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
chemical vapor transport of the compound obtained in example 4 in a tube furnace and Hg by a horizontal gradient temperature field 7 P 2 Se 12 Growing the crystal, heating to 530 ℃ at 25 ℃/h, and growing for 15 days, and after the growth is finished, obtaining the crystalSlowly cooling to room temperature at a rate of 4 ℃/h, closing the tubular growth furnace, cooling the quartz tube, and cutting to obtain black Hg with the diameter of phi 3 multiplied by 1mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 23
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
Chemical vapor transport of the compound obtained in example 5 in a tube furnace and Hg by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the temperature is increased to 500 ℃ at 25 ℃/h, the growth period is 18 days, the temperature is slowly reduced to room temperature at the speed of 5 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled, thus obtaining black Hg with the diameter of phi 8 multiplied by 5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 24
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
chemical vapor transport of the compound obtained in example 6 in a tube furnace and Hg by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the temperature is increased to 490 ℃ at 25 ℃/h, the growth period is 20 days, the temperature is slowly reduced to room temperature at the speed of 3.5 ℃/h after the growth is finished, the muffle furnace is closed, and the quartz tube is cut after being cooled, thus obtaining the black Hg with the diameter of phi 4 multiplied by 4mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 25
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. according to the reaction formula 7hg+2p+12se=hg 7 P 2 Se 12 1.404 g Hg,0.062 g P and 0.948 g Se (i.e. Hg: P: se=0.0070 mol:0.002mol:0.012 mol) were mixed homogeneously, placed in a quartz glass tube having a diameter of 25mm by 240mm, and evacuated to 10 mm -3 Pa, packaging with oxyhydrogen flame, and placing in a tubular growth furnace;
b. chemical vapor transport is carried out in a tube type growth furnace at the temperature of 25 ℃/h to 550 ℃, and Hg is carried out by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the growth period is 10 days, the temperature is slowly reduced to 200 ℃ at the speed of 1 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled to obtain phi 2 multiplied by 1mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 26
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. according to the reaction type 7Hg+P 2 Se 5 +7Se＝Hg 7 P 2 Se 12 Directly 1.404 g Hg,0.455 g P 2 Se 5 And 0.553 g Se (i.e., hg: P) 2 Se 5 Se=0.0070mol:0.001 mol:0.007mol), and after uniform mixing, placing into quartz glass tube with diameter of 25mm by 240mm, and vacuumizing to 10% -3 Pa, packaging with oxyhydrogen flame, and placing in a tubular growth furnace;
b. chemical vapor transport is carried out in a tube type growth furnace at a temperature of 25 ℃ per hour to 530 ℃, and Hg is carried out by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the growth period is 10 days, the temperature is slowly reduced to 600 ℃ at the speed of 1 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled to obtain phi 2 multiplied by 2mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 27
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. according to the reaction type 7HgSe+P 2 Se 5 ＝Hg 7 P 2 Se 12 3.206 g of HgSe and 0.455 g of P are directly added 2 Se 5 (i.e. HgSe: P 2 Se 5 =0.0070mol:0.001mol), and after uniform mixing, filling into a quartz glass tube of Φ25mm×240mm, and evacuating to 10 -3 Pa, packaging with oxyhydrogen flame, and placing in a tubular growth furnace;
b. raising the temperature to 520 ℃ at 25 ℃/h, carrying out chemical vapor transmission in a tube type growth furnace, and carrying out Hg by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the growth period is 10 days, the temperature is slowly reduced to 200 ℃ at the speed of 1 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled to obtain black Hg with the diameter of phi 2.5 multiplied by 1.5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 28
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. according to the reaction type 7hgse+2p+5se=hg 7 P 2 Se 12 Directly mixing 1.404 g of HgSe,0.062 g of P and 0.395 g of Se (i.e. HgSe: P: se=0.0070 mol:0.002mol:0.005 mol), placing into a quartz glass tube with phi 25mm x 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, and placing in a tubular growth furnace;
b. chemical vapor transport is carried out in a tube type growth furnace at a temperature of 25 ℃ per hour to 530 ℃, and Hg is carried out by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the growth period is 10 days, the temperature is slowly reduced to 200 ℃ at the speed of 1 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled to obtain phi 3 multiplied by 1mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 29
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. according to the reaction type 21Hg 2 Cl 2 +12P+72Se＝6Hg 7 P 2 Se 12 +14PCl 3 9.889 g Hg was directly added 2 Cl 2 0.372 g of P, and 5.692 g of Se (i.e., hg 2 Cl 2 P: se=0.021 mol:0.012mol:0.072 mol), mixing, placing into quartz glass tube with diameter of 25mm x 240mm, and vacuumizing to 10% -3 Pa, packaging with oxyhydrogen flame,placing in a tube-type growth furnace;
b. raising the temperature to 500 ℃ at 25 ℃/h, carrying out chemical vapor transmission in a tubular growth furnace, and carrying out Hg by a horizontal gradient temperature field 7 P 2 Se 12 The crystal grows, the growth period is 10 days, the temperature is slowly reduced to 200 ℃ at the speed of 1 ℃/h after the growth is finished, the tube type growth furnace is closed, and the quartz tube is cut after being cooled to obtain black Hg with the diameter of phi 8 multiplied by 5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 30
The chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. according to the reaction formula 21hgi+6p+36se=3 Hg 7 P 2 Se 12 +7PI 3 Directly mixing 9.548 g of HgI,0.186 g of P and 2.846 g of Se (i.e. HgI: P: se=0.021 mol:0.006mol:0.036 mol), placing into a quartz glass tube with phi 25mm by 240mm, and vacuumizing to 10% -3 Pa, packaging with oxyhydrogen flame, and placing in a muffle furnace;
b. slowly heating to 490 deg.C, chemical gas phase transmission in tubular growth furnace, hg by horizontal gradient temperature field 7 P 2 Se 12 The crystal grows for 15 days, after the growth is finished, the temperature is slowly reduced to 200 ℃ at the speed of 3.5 ℃/h, the muffle furnace is closed, and after the quartz tube is cooled, the quartz tube is cut to obtain phi 4 multiplied by 4mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 31
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. grinding 5 g of pure selenium phosphorus mercury powder of the compound obtained in the example 1 uniformly, placing into a crucible, placing into a quartz glass tube with phi 25mm multiplied by 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 530 ℃ to melt the raw materials;
b. After the raw materials are completely melted, the crucible is lowered down vertically at a speed of 1mm/hAnd (3) lowering, during which selenium, phosphorus and mercury crystal growth is carried out, wherein the growth period is 15 days, after the crystal growth is finished, the crystal is left in a crucible lowering furnace for annealing, and the temperature is lowered to room temperature at the speed of 43 ℃ per hour, so that black Hg with the particle diameter of phi 3.9 multiplied by 3.3mm is obtained 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 32
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. grinding 5 g of pure selenium phosphorus mercury powder of the compound obtained in the example 2 uniformly, placing into a crucible, placing into a quartz glass tube with phi 25mm multiplied by 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 518 ℃ to melt the raw materials;
b. after the raw materials are completely melted, vertically descending a crucible descending furnace at a speed of 1mm/h, growing selenium, phosphorus and mercury crystals in the descending process for 15 days, after the growth of the crystals is finished, keeping the crystals in the crucible descending furnace for annealing, and cooling to room temperature at a speed of 46 ℃/h to obtain black Hg with the grain diameter of phi 3.3 multiplied by 2.5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 33
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. grinding 5 g of pure selenium phosphorus mercury powder of the compound obtained in the example 3 uniformly, placing into a crucible, placing into a quartz glass tube with phi 25mm multiplied by 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 525 ℃ to melt the raw materials;
b. after the raw materials are completely melted, vertically descending a crucible descending furnace at a speed of 1mm/h, growing selenium, phosphorus and mercury crystals in the descending process for 15 days, after the growth of the crystals is finished, keeping the crystals in the crucible descending furnace for annealing, and cooling to room temperature at a speed of 50 ℃ per hour to obtain black Hg with the grain diameter of phi 4.1 multiplied by 2.1mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 34
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. grinding 5 g of pure selenium phosphorus mercury powder of the compound obtained in the example 4 uniformly, placing into a crucible, placing into a quartz glass tube with phi 25mm multiplied by 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 515 ℃ to melt the raw materials;
b. After the raw materials are completely melted, vertically descending a crucible descending furnace at a speed of 1mm/h, growing selenium, phosphorus and mercury crystals in the descending process for 15 days, after the growth of the crystals is finished, keeping the crystals in the crucible descending furnace for annealing, and cooling to room temperature at a speed of 40 ℃/h to obtain black Hg with the grain diameter of phi 3.6X2.8 mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 35
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. grinding 5 g of pure selenium phosphorus mercury powder of the compound obtained in the example 5 uniformly, placing into a crucible, placing into a quartz glass tube with phi 25mm multiplied by 240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 520 ℃ to melt the raw materials;
b. after the raw materials are completely melted, vertically descending a crucible descending furnace at a speed of 1mm/h, growing selenium, phosphorus and mercury crystals in the descending process for 15 days, after the growth of the crystals is finished, keeping the crystals in the crucible descending furnace for annealing, and cooling to room temperature at a speed of 55 ℃/h to obtain black Hg with the grain diameter of phi 3.2 multiplied by 1.9mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 36
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. 5 g of pure selenium phosphorus mercury powder of the compound obtained in example 6 are groundGrinding, placing into crucible, placing into quartz glass tube with diameter of 25mm×240mm, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 535 ℃ to melt the raw materials;
b. after the raw materials are completely melted, vertically descending a crucible descending furnace at a speed of 1mm/h, growing selenium, phosphorus and mercury crystals in the descending process for 15 days, after the growth of the crystals is finished, keeping the crystals in the crucible descending furnace for annealing, and cooling to room temperature at a speed of 60 ℃ per hour to obtain black Hg with the grain diameter of phi 3.5 multiplied by 2.1mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 37
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. according to the reaction formula 7hg+2p+12se=hg 7 P 2 Se 12 1.404 g Hg,0.062 g P and 0.948 g Se (i.e. Hg: P: se=0.0070 mol:0.002mol:0.012 mol) are directly mixed, placed in a crucible, placed in a quartz glass tube having a diameter of 25mm by 240mm, and evacuated to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, and slowly raising the temperature to 550 ℃ to melt the raw materials;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at a speed of 1mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 After the crystal growth is finished, the crystal is left in a crucible descending furnace for annealing, and is cooled to room temperature at the speed of 50 ℃/h, thus obtaining black Hg with the speed of phi 2 multiplied by 2mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 38
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. according to the reaction type 7Hg+P 2 Se 5 +7Se＝Hg 7 P 2 Se 12 Directly 1.404 g Hg,0.455 g P 2 Se 5 And 0.553 g Se (i.e., hg: P) 2 Se 5 :Se＝0.007mol:0.001mol 0.007 mol), mixing uniformly, placing into quartz glass tube with phi 25mm x 240mm, placing into muffle furnace with program temperature control, heating to 450 deg.C at 10 deg.C/h, keeping temperature for 60 hr, cooling to 300 deg.C at 10 deg.C/h, taking out sample, mashing and grinding to obtain Hg 7 P 2 Se 12 Powder, filling into quartz tube, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, heating to 480 ℃ at 5 ℃/h, and keeping the temperature for 60 hours until the raw materials are melted;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at the speed of 0.1mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 After the crystal growth is finished, the crystal is left in a crucible descending furnace for annealing, and cooled to room temperature at the speed of 40 ℃/h, thus obtaining black Hg with the grain diameter of phi 2.5 multiplied by 2mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 39
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. according to the reaction type 7HgSe+P 2 Se 5 ＝Hg 7 P 2 Se 12 3.206 g of HgSe and 0.455 g of P are directly added 2 Se 5 (i.e. HgSe: P 2 Se 5 =0.007mol:0.001mol), and after uniform mixing, put into a clean graphite crucible, put the graphite crucible into a quartz tube of Φ25mm×240mm, and pump the quartz tube to 10 using a vacuum pump -3 Pa, then carrying out fusion sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 450 ℃ at a speed of 10 ℃/h, keeping the temperature for 80 hours until the raw materials are melted,
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at the speed of 0.5mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 After the crystal growth is finished, the crystal is left in a crucible descending furnace for annealing, and cooled to room temperature at the speed of 45 ℃/h, thus obtaining black Hg with the speed of phi 2 multiplied by 1mm 7 P 2 Se 12 Infrared nonlinear lightAnd (5) learning to obtain crystals.
Example 40
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. according to the reaction type 7hgse+2p+5se=hg 7 P 2 Se 12 Directly mixing 1.404 g of HgSe,0.062 g of P, and 0.395 g of Se (i.e., hgSe: P: se=0.0070 mol:0.002mol:0.005 mol), placing into a clean graphite crucible, charging the graphite crucible into a quartz tube having a diameter of 25mm by 240mm, and pumping the quartz tube to 10 by using a vacuum pump -3 Pa, then carrying out melting sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 550 ℃ at a speed of 40 ℃/h, keeping the temperature for 100h, cooling to 300 ℃ at a speed of 20 ℃/h, taking out a sample after cooling, and mashing and grinding to obtain Hg 7 P 2 Se 12 Powder, filling into quartz tube, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, heating to 560 ℃ at 20 ℃/h, and keeping the temperature for 100h until the raw materials are melted;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at the speed of 2mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 After the crystal growth is finished, the crystal is left in a crucible descending furnace for annealing, and cooled to room temperature at the speed of 45 ℃/h, thus obtaining black Hg with the speed of phi 2 multiplied by 1mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 41
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. according to the reaction type 21Hg 2 Cl 2 +12P+72Se＝6Hg 7 P 2 Se 12 +14PCl 3 9.889 g Hg was directly added 2 Cl 2 0.372 g of P, and 5.692 g of Se (i.e., hg 2 Cl 2 P: se=0.021 mol:0.012mol:0.072 mol), mixing uniformly, placing into a clean graphite crucible, loading the graphite crucible into a quartz tube having a diameter of 25mm by 240mm, and using a vacuum pump to discharge the quartz The pipe is drawn to 10 -3 Pa, then carrying out fusion sealing, putting the quartz tube into a muffle furnace with a temperature controlled by a program, heating to 500 ℃ at a speed of 25 ℃/h, and keeping the temperature for 80 hours until the raw materials are melted;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at a speed of 3mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 After the crystal growth is finished, the crystal is left in a crucible descending furnace for annealing, and cooled to room temperature at the speed of 55 ℃/h, thus obtaining black Hg with the grain diameter of phi 5 multiplied by 5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 42
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. according to the reaction formula 21hgi+6p+36se=3 Hg 7 P 2 Se 12 +7PI 3 Directly mixing 9.548 g of HgI,0.186 g of P, and 2.846 g of Se (i.e., hgI: P: se=0.021 mol:0.006mol:0.036 mol), placing into a clean graphite crucible, charging the graphite crucible into a quartz tube of Φ25mm×240mm, and pumping the quartz tube to 10 using a vacuum pump -3 Pa, then carrying out melting sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 550 ℃ at a speed of 35 ℃/h, keeping the temperature for 90 hours, cooling to 300 ℃ at a speed of 20 ℃/h, taking out a sample after cooling, and mashing and grinding to obtain Hg 7 P 2 Se 12 Powder, filling into quartz tube, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, heating to 560 ℃ at 5 ℃/h, and keeping the temperature for 90 hours until the raw materials are melted;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at the speed of 2mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 After the crystal growth is finished, the crystal is left in a crucible descending furnace for annealing, and is cooled to room temperature at the speed of 50 ℃/h, thus obtaining black Hg with the speed of phi 4 multiplied by 2mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 43
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
5 g of the compound obtained in example 1 are pure phase and 2.5 g of Hg as fluxing agent in a mass ratio of 1:0.5 2 Cl 2 Mixing, placing into a quartz tube with diameter of 35mm and length of 200mm, and pumping the quartz tube to 10 by vacuum pump -3 Pa, performing fusion sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 430 ℃, keeping the constant temperature for 30 hours, and cooling to room temperature at a cooling rate of 2 ℃/h to obtain phi 5 multiplied by 3mm black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 44
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
5 g of the compound obtained in example 2 was mixed with 5 g of Se as a flux at a mass ratio of 1:1, and the mixture was placed in a quartz glass tube having a diameter of 35 mm. Times.200 mm, and the quartz tube was evacuated to 10℃by a vacuum pump -3 Pa, performing melt sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 450 ℃, keeping the constant temperature for 50 hours, and cooling to room temperature at a cooling rate of 5 ℃/h to obtain black Hg with the particle diameter of phi 10 multiplied by 5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 45
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
5 g of the compound obtained in example 3 was mixed with 10 g of HgSe as a flux in a mass ratio of 1:2, and put into a quartz tube having a diameter of 35mm X200 mm, and the quartz tube was evacuated to 10 using a vacuum pump -3 Pa, performing fusion sealing, putting the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 480 ℃, keeping the constant temperature for 68 hours, and cooling to room temperature at a cooling rate of 9 ℃/h to obtain black Hg with the diameter of phi 6.5 multiplied by 6mm 7 P 2 Se 12 An infrared nonlinear optical crystal;
example 46
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
the compound obtained in example 4 was mixed with 1.2 g of selenium phosphorus mercury powder and 3.6 g of fluxing agent Hg in a mass ratio of 1:3 2 Cl 2 Mixing, filling into quartz tube with diameter of 35mm×200mm, and pumping the quartz tube to 10 deg.f by vacuum pump -3 Pa, performing melt sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 460 ℃, keeping the constant temperature for 48 hours, and cooling to room temperature at a cooling rate of 5 ℃/h to obtain black Hg with the particle diameter of phi 6.7X6.4 mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 47
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
the compound obtained in example 5 was mixed with 1.0 g of selenium phosphorus mercury powder and 4.0 g of fluxing agent Hg in a mass ratio of 1:4 2 Cl 2 Mixing, filling into quartz tube with diameter of 35mm×200mm, and pumping the quartz tube to 10 deg.f by vacuum pump -3 Pa, performing melt sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 470 ℃, keeping the constant temperature for 55h, and cooling to room temperature at a cooling rate of 7 ℃/h to obtain black Hg with the particle diameter of phi 7.0 multiplied by 6.8mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 48
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
1.2 g of selenium phosphorus mercury powder of the compound obtained in example 6 and 5.4 g of fluxing agent Se are mixed according to the mass ratio of 1:4.5, and are filled into a quartz tube with the diameter of 35mm multiplied by 200mm, and the quartz tube is pumped to 10 by using a vacuum pump -3 Pa, performing melt sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 480 ℃, keeping the constant temperature for 30 hours, and cooling to room temperature at a cooling rate of 9 ℃/h to obtain black Hg with the particle diameter of phi 7.3 multiplied by 7.5mm 7 P 2 Se 12 An infrared nonlinear optical crystal.
Example 49
Hg of any one of examples 7 to 43 was used 7 P 2 Se 12 An infrared nonlinear optical crystal is arranged at the position with the reference number of 3 of the device shown in figure 3, and at room temperature, a Q-switched Ho, tm, cr, YAG laser is used as a light source, infrared light with the incident wavelength of 2090nm is output, frequency multiplication light with the wavelength of 1045nm is used, and Hg is used 7 P 2 Se 12 The laser intensity of the crystal output is equal to AgGaS under the same condition 2 The output intensity is equivalent.
Example 50
Hg of any one of examples 7 to 43 was used 7 P 2 Se 12 An infrared nonlinear optical crystal, as shown in FIG. 3, is arranged at position 3, where 1 is a laser, 2 is a convex lens, hg 7 P 2 Se 12 An infrared nonlinear optical crystal, wherein 4 is a prism and 5 is a filter; the laser beam emitted by the laser 1 is emitted into Hg through the convex lens 2 7 P 2 Se 12 The crystal 3, the generated outgoing laser beam passes through the prism 4 and the filter 5, thereby obtaining a desired laser beam.
Hg using the present invention 7 P 2 Se 12 The device made of the infrared nonlinear optical crystal can be a frequency multiplication generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator and an optical parametric amplifier.
The above embodiments are only for illustrating the technical scheme of the present invention and are not limiting. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that the present invention may be modified or substituted without departing from the spirit and scope of the invention.
Claims (5)
1. A compound selenium phosphorus mercury is characterized in that the molecular formula of the compound is Hg 7 P 2 Se 12 The molecular weight is 1206.79, the crystal structure is a triclinic system, and the space group isP1, adopting a high-temperature melt method.
2. The method for preparing the compound selenium phosphorus mercury according to claim 1, which is characterized by comprising the following steps:
a. hg source materials are Hg and Hg according to the mol ratio Hg to P to Se=7:2:12 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 Mixing Se serving as a selenium source material uniformly to obtain a mixture;
b. grinding the mixture obtained in the step a to 100 meshes, filling the mixture into a quartz container, and pumping the mixture to 10 under vacuum condition -3 Pa, performing fusion sealing;
c. and c, placing the sealed sample in the step b in a muffle furnace, heating to 450-550 ℃ at the speed of 10-40 ℃/h, keeping the temperature for 40-60h, then cooling to 300 ℃ at the speed of 10-20 ℃/h, taking out the sample after cooling, and mashing and grinding to 100 meshes to obtain the powdery selenium-phosphorus-mercury pure sample.
3. An infrared nonlinear optical crystal of selenium phosphorus mercury is characterized in that the molecular formula of the crystal is Hg 7 P 2 Se 12 The molecular weight is 1206.79, the symmetry center is not provided, the compound belongs to a triclinic system, and the space group isPThe unit cell parameters are a= 12.573 (2) a, b= 14.523 (2) a, c= 16.247 (2) a, α= 77.509 (5) °, β= 75.191 (6) °, γ= 73.051 (5) °, z=5.
4. The method for preparing selenium phosphorus mercury infrared nonlinear optical crystal according to claim 3, wherein the crystal growth is carried out by a high-temperature melt method, a chemical vapor transport method, a fluxing agent method or a crucible descending method:
the method for growing selenium phosphorus mercury infrared nonlinear optical crystal by the high-temperature melt method comprises the following steps:
a. uniformly mixing Hg source material, P source material and simple substance Se according to the mol ratio Hg to P to Se=7:2:12, grinding to 100 meshes, loading into a quartz tube, vacuumizing to 10 -3 Pa, sealing, placing into a muffle furnace, heating to 450-550deg.C at a rate of 10-40deg.C/h, maintaining the temperature at 60-100 h, cooling to 300 deg.C at 10-20deg.C/h, taking out sample, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 A compound, wherein the Hg source material is Hg, hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. putting the compound powder into a quartz tube, and vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a muffle furnace, slowly heating to 450-500 deg.C, maintaining the temperature at 24-72 h, slowly cooling to room temperature at 1-5 deg.C/h, closing the muffle furnace, cooling the quartz tube, and cutting to obtain black Hg 14 P 2 Se 12 An infrared nonlinear optical crystal;
the chemical vapor transport method for growing selenium phosphorus mercury infrared nonlinear optical crystal comprises the following steps:
a. directly mixing Hg source material, P source material and simple substance Se according to the mol ratio Hg to P to Se=7 to 2 to 12, loading into a quartz tube, vacuumizing to 10 -3 Pa, packaging with oxyhydrogen flame, and placing in a tube-type growth furnace, wherein the Hg source material is Hg or Hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. chemical vapor transport in a tube furnace, hg by a horizontal or vertical gradient temperature field 7 P 2 Se 12 Heating to 450-550 ℃ at 25 ℃/h for 8-20 days, slowly cooling to room temperature at 1-5 ℃/h after the growth is finished, closing the tubular growth furnace, cutting after the quartz tube is cooled, and obtaining black Hg at the low temperature end 7 P 2 Se 12 An infrared nonlinear optical crystal;
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the fluxing agent method comprises the following steps:
a. uniformly mixing Hg source material, P source material and Se source material according to a molar ratio of 6.5-8:2:12-14, placing into a clean graphite crucible, placing the graphite crucible into a quartz tube, and pumping the quartz tube to 10 by using a vacuum pump -3 Pa, then carrying out fusion sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 450-550 ℃ at a speed of 10-40 ℃/h, and keeping constantCooling to 300 deg.C at 10-20deg.C/hr for 60-100 hr, taking out sample after cooling, and mashing and grinding to obtain Hg 7 P 2 Se 12 In powder form, wherein the Hg source material is Hg, hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. mixing the selenium phosphorus mercury powder obtained in the step a with fluxing agent Se, hgSe or Hg according to the mass ratio of 1:0.5-4.5 2 Cl 2 Mixing, placing into a quartz tube with diameter of 35 mm and length of 20 cm, and pumping the quartz tube to 10 by vacuum pump -3 Pa, performing fusion sealing, placing the sealed quartz tube into a muffle furnace with a programmed temperature control, heating to 430-480 ℃, keeping the constant temperature for 30-68h, and cooling to room temperature at a cooling rate of 2-9 ℃/h to obtain black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal;
The method for growing selenium phosphorus mercury infrared nonlinear optical crystal by using the crucible descent method comprises the following steps of:
a. uniformly mixing Hg source material, P source material and Se source material according to a molar ratio of 6.5-8:2:12-14, placing into a clean graphite crucible, placing the graphite crucible into a quartz tube, and pumping the quartz tube to 10 by using a vacuum pump -3 Pa, then carrying out melting sealing, putting the quartz tube into a muffle furnace with a programmed temperature, heating to 450-550 ℃ at a speed of 10-40 ℃/h, keeping the temperature at 60-100 h, cooling to 300 ℃ at 10-20 ℃/h, taking out the sample, and mashing and grinding to obtain powdery Hg 7 P 2 Se 12 Then the mixture is put into a quartz tube and vacuumized to 10 -3 Pa, packaging with oxyhydrogen flame, placing in a crucible descending furnace, heating to 480-560 ℃ at 5-20 ℃/h, and keeping the temperature at 60-100 h until the raw materials are melted;
or mixing Hg source material, P source material and Se source material at a molar ratio of 6.5-8:2:12-14, placing into a clean graphite crucible, placing the graphite crucible into a quartz tube, and pumping the quartz tube to 10 by vacuum pump -3 Pa, then melting and sealing, and placing the quartz tube into a crucible descending furnace with programmed temperature, heating to 450-550 ℃ at a speed of 10-40 ℃/h, and keeping the temperature at 60-100 DEG C h, melting the raw materials, wherein the Hg source materials are Hg and Hg 2 Cl 2 、HgI 2 Or HgSe; the P source material is P or P 2 Se 5 The selenium source material is Se;
b. after the raw materials are completely melted, the crucible descending furnace is vertically descended at the speed of 0.1-3 mm/h, and Hg is carried out in the descending process 7 P 2 Se 12 Growing the crystal for 20-40 days, after the crystal growth is finished, keeping the crystal in a crucible descending furnace for annealing, and cooling to room temperature at a speed of 40-60 ℃/h to obtain black Hg 7 P 2 Se 12 An infrared nonlinear optical crystal.
5. Use of the selenium phosphorus mercury infrared nonlinear optical crystal of claim 3 in the preparation of an infrared band laser variable frequency crystal, an infrared laser, an infrared electro-optic device, an infrared communication device or an infrared laser guidance device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310879311.9A CN116902933A (en) | 2023-07-18 | 2023-07-18 | Compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310879311.9A CN116902933A (en) | 2023-07-18 | 2023-07-18 | Compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116902933A true CN116902933A (en) | 2023-10-20 |
Family
ID=88362512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310879311.9A Pending CN116902933A (en) | 2023-07-18 | 2023-07-18 | Compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116902933A (en) |
-
2023
- 2023-07-18 CN CN202310879311.9A patent/CN116902933A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018184312A1 (en) | Compound cesium fluoroborate, non-linear optical crystal of cesium fluoroborate, preparation method therefor and use thereof | |
| CN113174640B (en) | Sulfur germanium magnesium lithium middle and far infrared nonlinear optical crystal, preparation method and application | |
| CN111334858B (en) | Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application | |
| CN116240633A (en) | Compound orthorhombic selenium gallium barium and orthorhombic selenium gallium barium nonlinear optical crystal, preparation method and application thereof | |
| CN114411260A (en) | Compound selenium indium sodium, nonlinear optical crystal thereof, preparation method and application thereof | |
| CN103290480B (en) | Li 2in 2siS 6compound, Li 2in 2siS 6non-linear optic crystal and method for making and purposes | |
| CN113060711B (en) | Compound cadmium sulfur phosphorus, mercury sulfur phosphorus and mercury infrared nonlinear optical crystal, and preparation method and application thereof | |
| WO2020015367A1 (en) | Nonlinear optical crystal, preparation method therefor and use thereof | |
| CN110921676A (en) | Compound lead fluoroborate, lead fluoroborate nonlinear optical crystal, preparation method and application | |
| CN103060917B (en) | BaGa 2siS 6compound, BaGa 2siS 6non-linear optic crystal and method for making and purposes | |
| CN114057207A (en) | Compound sodium octaborate decafluoride, sodium octaborate decafluoride nonlinear optical crystal, preparation method and application | |
| CN114134575B (en) | Chalcopyrite type compound containing alkaline earth metal defects, infrared nonlinear optical crystal, preparation method and application | |
| CN117602589A (en) | Compound selenium gallium magnesium calcium and selenium gallium magnesium calcium infrared nonlinear optical crystal, preparation method and application | |
| CN116902933A (en) | Compound selenium phosphorus mercury and selenium phosphorus mercury infrared nonlinear optical crystal, preparation method and application | |
| CN103290479B (en) | Li 2in 2siSe 6compound, Li 2in 2siSe 6non-linear optic crystal and method for making and purposes | |
| CN114457427A (en) | Selenium gallium lithium middle and far infrared nonlinear optical crystal and preparation method and application thereof | |
| CN105543971B (en) | A kind of AgZnPS4Nonlinear optical crystal and preparation method thereof and device for non-linear optical | |
| CN103030146B (en) | BaGa2SiSe6 compound, BaGa2SiSe6 nonlinear optical crystal and preparation method and application | |
| CN111139524B (en) | Potassium fluoborate, potassium fluoborate nonlinear optical crystal, preparation method and application | |
| CN114672880A (en) | Compound rubidium fluoroborophosphate and rubidium fluoroborophosphate nonlinear optical crystal, and preparation method and application thereof | |
| CN116240634A (en) | Compound monoclinic phase selenium gallium barium and monoclinic phase selenium gallium barium nonlinear optical crystal, preparation method and application thereof | |
| CN109137070B (en) | Zn3P2S8Preparation method and application of nonlinear optical crystal | |
| CN114074944B (en) | Compound rubidium boron phosphorus oxygen and rubidium boron phosphorus oxygen nonlinear optical crystal, preparation method and application | |
| CN109656079B (en) | Application of BaHgSnS4 nonlinear optical crystal | |
| CN112919485B (en) | Compound potassium borate nitrate, potassium borate nitrate nonlinear optical crystal, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |