CN117602589A - Compound selenium gallium magnesium calcium and selenium gallium magnesium calcium infrared nonlinear optical crystal, preparation method and application - Google Patents
Compound selenium gallium magnesium calcium and selenium gallium magnesium calcium infrared nonlinear optical crystal, preparation method and application Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 258
- 239000011575 calcium Substances 0.000 title claims abstract description 175
- 239000013078 crystal Substances 0.000 title claims abstract description 157
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 129
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 124
- 230000003287 optical effect Effects 0.000 title claims abstract description 121
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 120
- FWLGASJILZBATH-UHFFFAOYSA-N gallium magnesium Chemical compound [Mg].[Ga] FWLGASJILZBATH-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 28
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 16
- 238000004891 communication Methods 0.000 claims abstract description 4
- 239000010453 quartz Substances 0.000 claims description 148
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 148
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 78
- 238000010438 heat treatment Methods 0.000 claims description 70
- 238000001816 cooling Methods 0.000 claims description 63
- 238000007789 sealing Methods 0.000 claims description 46
- 230000004927 fusion Effects 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 44
- 238000005086 pumping Methods 0.000 claims description 43
- 229910052786 argon Inorganic materials 0.000 claims description 39
- 239000011777 magnesium Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 22
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 13
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000005360 mashing Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 241000764238 Isis Species 0.000 claims 1
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000006757 chemical reactions by type Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
Abstract
The invention relates to a compound selenium gallium magnesium calcium and selenium gallium magnesium calcium infrared nonlinear optical crystal, a preparation method and application thereof, wherein the molecular formula of the compound is CaMg 6 Ga 6 Se 16 Molecular weight is 2065.89, its structure belongs to hexagonal system, and space group isPThe crystal is prepared by a high-temperature solid phase method, and the chemical formula of the crystal is CaMg 6 Ga 6 Se 16 Crystallizing in hexagonal system with space group ofP。CaMg 6 Ga 6 Se 16 The unit cell parameters of (2) area=b=17.5327(3) Å，c=7.7603(2) Å，V=2065.89(9) Å 3 . The size crystal can be obtained by adopting a high-temperature solid phase method and a crucible descending method. The crystal has the advantages of high 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, and can be used for manufacturing infrared nonlinear optical devices, including infrared band laser variable-frequency crystals, infrared lasers, infrared photoelectric devices, infrared communication devices or infrared laser guidance devices.
Description
Technical Field
The invention relates to a compound selenium gallium magnesium calcium and a preparation method and application of an infrared nonlinear optical crystal thereof, belonging to the field of infrared nonlinear optical crystals.
Background
The nonlinear optical material has important application value in the technical field of frequency conversion as a core device of an all-solid-state laser. Conventional oxy-nonlinear optical crystals, e.g. KBE 2 BO 3 F 2 (KBBF)、β-BaB 2 O 4 (β-BBO)、LiB 3 O 5 (LBO)、LiNbO 3 (LN)、KH 2 PO 4 (KDP) and KTiO (PO) 4 ) (KTP) has excellent optical properties and is widely used in the ultraviolet-visible-near infrared band, but due to their low nonlinear optical coefficient and narrow infrared cut-off edge, such crystalline materials are not suitable for use in the mid-and far-infrared band. AgGaS 2 (AGS)、AgGaSe 2 (AGSe) and ZnGeP 2 Commercial infrared nonlinear optical crystal materials such as (ZGP) generally have large nonlinear optical coefficients and wide infrared cut-off edges, however, due to intrinsic defects in these materials, such as narrow band gaps, low laser damage thresholds, I-type phase matching cannot be achieved, or strong two-photon absorption at 1 μm severely limits their application in the field of modern laser technology. Therefore, there is a need to develop and design novel infrared nonlinear optical crystal materials with wide band gap and large frequency doubling effects.
Disclosure of Invention
The invention aims to provide a catalyst having a chemical formula of CaMg 6 Ga 6 Se 16 Selenium gallium magnesium calcium and a preparation method thereof;
another object of the invention is to provide an infrared nonlinear optical crystal of selenium gallium magnesium calcium;
the invention further aims at providing a preparation method of the selenium-gallium-magnesium-calcium nonlinear optical crystal;
it is also an object of the present invention to provide the use of selenium gallium magnesium calcium nonlinear optical crystals.
The molecular formula of the compound selenium gallium magnesium calcium is CaMg 6 Ga 6 Se 16 Molecular weight is 2065.89, its structure belongs to hexagonal system, and space group is
The preparation method of the compound selenium gallium magnesium calcium comprises the following steps:
a. according to chemical formula CaMg 6 Ga 6 Se 16 The molar ratio of Ca to Mg to Ga to Se=1:6:6:16 is that raw materials are weighed and mixed uniformly under the argon condition; the mixture was then filled into quartz containers and evacuated to 10 a under vacuum -3 Pa, performing fusion sealing; wherein the Ca raw material is Ca or CaSe; the Mg raw material is Mg or MgSe; the Ga material is Ga or Ga 2 Se 3 The selenium raw material is Se simple substance;
b. c, placing the sealed sample in the step a in a muffle furnace, heating to 900-950 ℃ at a speed of 10-40 ℃/h, and keeping the temperature for 25-35h; and then cooling to room temperature at the speed of 10-20 ℃/h, taking out, putting into a mortar, and mashing and grinding to obtain the powdered compound selenium gallium magnesium calcium.
An infrared nonlinear optical crystal of selenium gallium magnesium calcium has a chemical formula of CaMg 6 Ga 6 Se 16 Belonging to hexagonal system, the space group isThe unit cell parameters are->
The preparation method of the selenium-gallium-magnesium-calcium infrared nonlinear optical crystal adopts a high-temperature solid-phase method and a crucible descending method:
the high-temperature solid phase method for growing the selenium gallium magnesium calcium infrared nonlinear optical crystal comprises the following steps of:
a. according to chemical formula CaMg 6 Ga 6 Se 16 The molar ratio of Ca to Mg to Ga to Se=1:6:6:16, and uniformly mixing; filling into a quartz tube, and pumping the quartz tube to 10 by a vacuum pump -3 Performing fusion sealing after Pa vacuum degree, wherein the Ca source material is Ca or CaSe; mg source
The material is Mg or MgSe; the Ga source material is Ga or Ga 2 Se 3 The Se source material is Se simple substance;
b. c, placing the quartz tube in the step a into a muffle furnace with program temperature control, heating to 900-950 ℃ at a heating rate of 10-20 ℃/h, preserving heat for 25-35h, and cooling to room temperature at a cooling rate of 4-6 ℃/h to obtain selenium-gallium-magnesium-calcium infrared nonlinear optical crystal;
the crucible descent method for growing selenium gallium magnesium calcium infrared nonlinear optical crystal comprises the following steps:
a. according to chemical formula CaMg 6 Ga 6 Se 16 The molar ratio of Ca to Mg to Ga to Se=1:6:6:16, and uniformly mixing; filling into a quartz tube, and pumping the quartz tube to 10 by a vacuum pump -3 Performing fusion sealing after Pa vacuum degree, wherein the Ca source material is Ca or CaSe; mg source
The material is Mg or MgSe; the Ga source material is Ga or Ga 2 Se 3 The Se source material is Se simple substance;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 950-1000 ℃ at a heating rate of 20-30 ℃/h, and preserving heat for 40-50h;
c. c, vertically descending the quartz tube in the step b at a speed of 0.1-0.2mm/h, growing the crystal in the descending process of the crucible descending furnace for 10-40 days, continuously annealing the crystal in the crucible descending furnace after the growth is finished, and cooling to room temperature at a cooling rate of 20-40 ℃/h to obtain the selenium-gallium-magnesium-calcium infrared nonlinear optical crystal;
or placing the quartz tube in the step b into a crucible descending furnace, and cooling the furnace temperature from 950-1000 ℃ to room temperature at a cooling rate of 1-2 ℃/h to obtain the selenium-gallium-magnesium-calcium infrared nonlinear optical crystal.
The selenium gallium magnesium calcium infrared nonlinear optical crystal is used for preparing an infrared all-solid-state laser, an infrared laser guidance radar, laser medical treatment or medium-long distance laser communication.
The invention relates to a preparation method and application of a compound selenium gallium magnesium calcium and an infrared nonlinear optical crystal thereof, taking selenium gallium magnesium calcium as an example, wherein the selenium gallium magnesium calcium crystal is prepared according to the following chemical reaction formula:
(1)Ca+6Mg+6Ga+16Se＝CaMg 6 Ga 6 Se 16 ；
(2)CaSe+6Mg+6Ga+15Se＝CaMg 6 Ga 6 Se 16 ；
(3)Ca+6MgSe+6Ga+10Se＝CaMg 6 Ga 6 Se 16 ；
(4)Ca+6Mg+3Ga 2 Se 3 +7Se＝CaMg 6 Ga 6 Se 16 ；
(5)CaSe+6MgSe+6Ga+9Se＝CaMg 6 Ga 6 Se 16 ；
(6)CaSe+6Mg+3Ga 2 Se 3 +6Se＝CaMg 6 Ga 6 Se 16 ；
(7)Ca+6MgSe+3Ga 2 Se 3 +Se＝CaMg 6 Ga 6 Se 16 ；
(8)CaSe+6MgSe+3Ga 2 Se 3 ＝CaMg 6 Ga 6 Se 16 。
the invention relates to a preparation method and application of a compound selenium gallium magnesium calcium and an infrared nonlinear optical crystal thereof, and the size of the compound selenium gallium magnesium calcium and the infrared nonlinear optical crystal is more than 2.90 multiplied by 0.90 multiplied by 0.10mm can be obtained by adopting a high-temperature solid-phase method or a crucible descending method 3 A selenium gallium magnesium calcium infrared nonlinear optical crystal; the large-size crucible is used, and the growing period is prolonged, so that the selenium-gallium-magnesium-calcium infrared nonlinear optical crystal with a correspondingly large size can be obtained.
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 discloses application of a selenium-gallium-magnesium-calcium infrared nonlinear optical crystal in the technical field of laser, which comprises application in 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 gallium magnesium calcium infrared nonlinear optical crystal optical device has wide band gap (2.71 eV), high laser damage threshold (9.1 xAGS) and strong nonlinear optical effect (1.5 xAGS).
The compound selenium gallium magnesium calcium and selenium gallium magnesium calcium infrared nonlinear optical crystal also comprises isomorphic selenium gallium magnesium strontium and selenium gallium magnesium barium.
Drawings
FIG. 1 is a CaMg of the invention 6 Ga 6 Se 16 A crystal structure diagram of (2);
FIG. 2 is a CaMg of the present invention 6 Ga 6 Se 16 Is a graph of experimental band gap;
FIG. 3 is a CaMg of the invention 6 Ga 6 Se 16 And a plot of the frequency multiplication strength of AGS versus the powder particle size;
FIG. 4 is a CaMg of the present invention 6 Ga 6 Se 16 The crystal working principle diagram is that 1 is a laser, 2 is a convex lens, 3 is a selenium gallium magnesium calcium crystal, 4 is a prism, and 5 is a filter; the laser beam emitted by the laser 1 is emitted into the selenium-gallium-magnesium-calcium monocrystal 3 through the convex lens 2, and the generated emitted laser beam passes through the prism 4 and the filter 5, so that the required laser beam is obtained.
Detailed Description
The invention will be described in detail with reference to the drawings and examples.
Example 1
The chemical formula ca+6mg+6ga+16se=camg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing Ca, mg, ga and Se simple substances according to the proportion of the reaction formula under the argon condition, uniformly mixing, filling into a quartz container, and pumping to 10 under the vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 900 ℃ at the speed of 10 ℃/h, keeping the temperature for 35h, cooling to room temperature at the speed of 20 ℃/h, taking out, and putting into a mortar for triturating to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 2
In the chemical reaction formula case+6mg+6ga+15se=camg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing simple substances of CaSe, mg, ga and Se according to the proportion of the reaction formula, uniformly mixing, filling into a quartz container, and pumping to 10 under vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 910 ℃ at the speed of 20 ℃/h, keeping the temperature for 32h, cooling to room temperature at the speed of 18 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 3
Chemical formula ca+6mgse+6ga+10se=camg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing Ca, mgSe, ga and Se simple substances according to the proportion of the reaction formula under the argon condition, uniformly mixing, filling into a quartz container, and pumping to 10 under the vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 920 ℃ at a speed of 30 ℃/h, keeping the temperature for 30h, cooling to room temperature at a speed of 16 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 4
In the form of chemical reaction Ca+6Mg+3Ga 2 Se 3 +7Se＝CaMg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing Ca, mg and Ga according to the proportion of the reaction formula under the argon condition 2 Se 3 Mixing Se simple substances uniformly, filling into a quartz container, and pumping to 10 under vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 930 ℃ at a speed of 40 ℃/h, keeping the temperature for 28h, cooling to room temperature at a speed of 14 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 5
With chemical reaction case+6mgse+6ga+9se=camg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing simple substances of CaSe, mgSe, ga and Se according to the proportion of the reaction formula, uniformly mixing, filling into a quartz container, and pumping to 10 under vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 940 ℃ at a speed of 40 ℃/h, keeping the temperature for 26 hours, cooling to room temperature at a speed of 12 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 6
In the chemical reaction type CaSe+6Mg+3Ga 2 Se 3 +6Se＝CaMg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing CaSe, mg and Ga according to the reaction formula proportion under the argon condition 2 Se 3 Mixing Se simple substances uniformly, filling into a quartz container, and pumping to 10 under vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 950 ℃ at a speed of 40 ℃/h, keeping the temperature for 26 hours, cooling to room temperature at a speed of 10 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 7
By chemical reaction Ca+6MgSe+3Ga 2 Se 3 +Se＝CaMg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing Ca, mgSe and Ga according to the proportion of the reaction formula under the argon condition 2 Se 3 Mixing Se simple substances uniformly, filling into a quartz container, and pumping to 10 under vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 920 ℃ at a speed of 30 ℃/h, keeping the temperature for 30h, cooling to room temperature at a speed of 12 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 8
In the chemical reaction type CaSe+6MgSe+3Ga 2 Se 3 ＝CaMg 6 Ga 6 Se 16 Preparation of the compound:
a. weighing CaSe, mgSe and Ga under the argon gas according to the proportion of the reaction formula 2 Se 3 Mixing Se simple substances uniformly, filling into a quartz container, and pumping to 10 under vacuum condition -3 Pa, performing fusion sealing;
b. and c, placing the sealed sample in the step a in a muffle furnace, heating to 900 ℃ at a speed of 20 ℃/h, keeping the temperature for 33h, cooling to room temperature at a speed of 16 ℃/h, taking out, and putting into a mortar for mashing and grinding to obtain the powdery selenium gallium magnesium calcium pure sample.
Example 9
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
the chemical formula ca+6mg+6ga+16se=camg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. weighing 0.043g of Ca, 0.156g of Mg, 0.448g of Ga and 1.353g of Se according to the molar ratio of 1:6:6:16 under argon, uniformly mixing, putting into a quartz tube with the length of 24cm and the diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with a programmed temperature, heating to 900 ℃ at a heating rate of 10 ℃/h, preserving heat for 35h, and cooling to room temperature at a cooling rate of 4 ℃/h to obtain the quartz tube with a size of 2.90 multiplied by 1.10 multiplied by 0.20mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 10
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
in the chemical reaction formula case+6mg+6ga+15se=camg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. 0.127g of CaSe, 0.156g of Mg, and the like are weighed according to the mol ratio of 1:6:6:15 under argon,Mixing 0.448g Ga and 1.268g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 910 ℃ at a heating rate of 12 ℃/h, preserving heat for 33h, and cooling to room temperature at a cooling rate of 4.5 ℃/h to obtain the quartz tube with the size of 2.92 multiplied by 1.08 multiplied by 0.19mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 11
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
chemical formula ca+6mgse+6ga+10se=camg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. weighing 0.043g of Ca, 0.664g of MgSe, 0.448g of Ga and 0.846g of Se according to a molar ratio of 1:6:6:10 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 920 ℃ at a heating rate of 14 ℃/h, preserving heat for 32h, and cooling to room temperature at a cooling rate of 5 ℃/h to obtain the quartz tube with the size of 2.94 multiplied by 1.06 multiplied by 0.18mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 12
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
in the form of chemical reaction Ca+6Mg+3Ga 2 Se 3 +7Se＝CaMg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. 0.043g Ca, 0.156g Mg, 1.209g Ga are weighed out under argon according to a molar ratio of 1:6:3:7 2 Se 3 Mixing with 0.592g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. will step by stepPutting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 930 ℃ at a heating rate of 16 ℃/h, preserving heat for 30h, and cooling to room temperature at a cooling rate of 5.5 ℃/h to obtain the quartz tube with the size of 2.96 multiplied by 1.04 multiplied by 0.17mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 13
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
with chemical reaction case+6mgse+6ga+9se=camg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. weighing 0.127g of CaSe, 0.664g of MgSe, 0.448g of Ga and 0.761g of Se according to a molar ratio of 1:6:6:9 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with a programmed temperature, heating to 940 ℃ at a heating rate of 18 ℃/h, preserving heat for 28h, and cooling to room temperature at a cooling rate of 6 ℃/h to obtain the quartz tube with a size of 2.98X1.02X10.16 mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 14
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
in the chemical reaction type CaSe+6Mg+3Ga 2 Se 3 +6Se＝CaMg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. 0.127g of CaSe, 0.156g of Mg and 1.209g of Ga are weighed according to a molar ratio of 1:6:3:6 under argon 2 Se 3 Mixing with 0.507g Se, loading into quartz tube with length of 24cm and diameter of 12mm, and vacuum pumping to 10 - 3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 950 ℃ at a heating rate of 20 ℃/h, preserving heat for 26h, and cooling to room temperature at a cooling rate of 5 ℃/h to obtain the quartz tube with the size of 3.00 multiplied by 0.98 multiplied by 0.14mm 3 Selenium gallium magnesium calcium infrared non-elementA linear optical crystal.
Example 15
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
by chemical reaction Ca+6MgSe+3Ga 2 Se 3 +Se＝CaMg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. 0.043g of Ca, 0.664g of MgSe and 1.209g of Ga are weighed according to the molar ratio of 1:6:3:1 under argon 2 Se 3 Mixing with 0.085g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump -3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with temperature controlled by a program, heating to 940 ℃ at a heating rate of 14 ℃/h, preserving heat for 25h, and then cooling to room temperature at a cooling rate of 4.5 ℃/h to obtain the quartz tube with the size of 3.04 multiplied by 0.94 multiplied by 0.12mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 16
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by high-temperature solid phase method:
in the chemical reaction type CaSe+6MgSe+3Ga 2 Se 3 ＝CaMg 6 Ga 6 Se 16 Preparing selenium gallium magnesium calcium infrared nonlinear optical crystal:
a. 0.127g of CaSe, 0.664g of MgSe and 1.209g of Ga are weighed out under argon in a molar ratio of 1:6:3 2 Se 3 Mixing, placing into quartz tube with length of 24cm and diameter of 12mm, and vacuum pumping to 10 -3 Performing fusion sealing after Pa vacuum degree;
b. putting the quartz tube in the step a into a muffle furnace with program temperature control, heating to 930 ℃ at a heating rate of 10 ℃/h, preserving heat for 30h, and cooling to room temperature at a cooling rate of 4 ℃/h to obtain the quartz tube with the size of 3.10 multiplied by 0.90 multiplied by 0.10mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 17
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.156g of Mg, 0.448g of Ga and 1.353g of Se according to the molar ratio of 1:6:6:16 under argon, uniformly mixing, putting into a quartz tube with the length of 24cm and the diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 950 ℃ at a heating rate of 20 ℃/h, and preserving heat for 50h;
c. the quartz tube in the step b is vertically lowered at the speed of 0.10mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 10 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is reduced to room temperature at the cooling speed of 40 ℃ per hour, so that the crystal with the length of 3.10X0.90X0.20 mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 18
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.156g of Mg, 0.448g of Ga and 1.353g of Se according to the molar ratio of 1:6:6:16 under argon, uniformly mixing, putting into a quartz tube with the length of 24cm and the diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 950 ℃ at a heating rate of 20 ℃/h, and preserving heat for 50h;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 950 ℃ to room temperature according to the cooling rate of 1.0 ℃/h, thus obtaining 3.09 multiplied by 1.10 multiplied by 0.10mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 19
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe, 0.156g of Mg, 0.448g of Ga and 1.268g of Se according to a molar ratio of 1:6:6:15 under argon, uniformly mixing, and filling into a container with a length of 24cm and a diameter of 24cmThe quartz tube was pumped to 10 by a vacuum pump into a quartz tube of 12mm - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 955 ℃ at a heating rate of 22 ℃/h, and preserving the heat for 49 hours;
c. the quartz tube in the step b is vertically lowered at the speed of 0.12mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 15 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is reduced to the room temperature at the cooling speed of 35 ℃ per hour, so that the crystal with the length of 3.08X1.09 multiplied by 0.11mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 20
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe, 0.156g of Mg, 0.448g of Ga and 1.268g of Se according to a molar ratio of 1:6:6:15 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 955 ℃ at a heating rate of 22 ℃/h, and preserving the heat for 49 hours;
c. the quartz tube in the step b was placed in a crucible lowering furnace, and the furnace temperature was lowered from 955℃to room temperature at a lowering rate of 1.0℃per hour, yielding 3.07X 1.08X 0.12mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 21
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.664g of MgSe, 0.448g of Ga and 0.846g of Se according to a molar ratio of 1:6:6:10 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 960 ℃ at a heating rate of 24 ℃/h, and preserving the heat for 48 hours;
c. the quartz tube in the step b is vertically lowered at the speed of 0.14mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 20 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to the room temperature at the cooling speed of 30 ℃/h, so that 2.06 multiplied by 1.07 multiplied by 0.13mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 22
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.664g of MgSe, 0.448g of Ga and 0.846g of Se according to a molar ratio of 1:6:6:10 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 960 ℃ at a heating rate of 24 ℃/h, and preserving the heat for 48 hours;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 960 ℃ to room temperature according to the cooling rate of 2.0 ℃/h, thus obtaining 3.05X1.06X0.14 mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 23
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.043g Ca, 0.156g Mg, 1.209g Ga are weighed out under argon according to a molar ratio of 1:6:3:7 2 Se 3 Mixing with 0.592g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 965 ℃ at a heating rate of 26 ℃/h, and preserving heat for 47h;
c. in step bThe quartz tube of (2) is vertically lowered at a speed of 0.16mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 25 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to room temperature at a cooling speed of 25 ℃ per hour, so as to obtain 3.04 multiplied by 1.05 multiplied by 0.15mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 24
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.043g Ca, 0.156g Mg, 1.209g Ga are weighed out under argon according to a molar ratio of 1:6:3:7 2 Se 3 Mixing with 0.592g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 965 ℃ at a heating rate of 26 ℃/h, and preserving heat for 47h;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 965 ℃ to room temperature according to the cooling rate of 1.5 ℃/h, thus obtaining 3.03X1.04×0.16mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 25
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe, 0.664g of MgSe, 0.448g of Ga and 0.761g of Se according to a molar ratio of 1:6:6:9 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 970 ℃ at a heating rate of 28 ℃/h, and preserving the heat for 46h;
c. vertically descending the quartz tube in the step b at a speed of 0.18mm/h, growing the crystal in the descending process of the crucible descending furnace for 30 days, and after the growth is finished, adding the crystalContinuously annealing the body in a crucible descending furnace, and cooling to room temperature at a cooling rate of 23 ℃ per hour to obtain 3.02X1.03X10.17 mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 26
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe, 0.664g of MgSe, 0.448g of Ga and 0.761g of Se according to a molar ratio of 1:6:6:9 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 970 ℃ at a heating rate of 28 ℃/h, and preserving the heat for 46h;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 970 ℃ to room temperature according to the cooling rate of 2.0 ℃/h, thus obtaining 3.01X1.02X0.18 mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 27
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.127g of CaSe, 0.156g of Mg and 1.209g of Ga are weighed according to a molar ratio of 1:6:3:6 under argon 2 Se 3 Mixing with 0.507g Se, loading into quartz tube with length of 24cm and diameter of 12mm, and vacuum pumping to 10 - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 975 ℃ at a heating rate of 30 ℃/h, and preserving heat for 45h;
c. the quartz tube in the step b is vertically lowered at a speed of 0.20mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 35 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is reduced to room temperature at a cooling speed of 20 ℃/h, so that 3.00 multiplied by 1.01 multiplied by 0.19mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear lightAnd (5) learning to obtain crystals.
Example 28
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.127g of CaSe, 0.156g of Mg and 1.209g of Ga are weighed according to a molar ratio of 1:6:3:6 under argon 2 Se 3 Mixing with 0.507g Se, loading into quartz tube with length of 24cm and diameter of 12mm, and vacuum pumping to 10 - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 975 ℃ at a heating rate of 30 ℃/h, and preserving heat for 45h;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 975 ℃ to room temperature according to the cooling rate of 1.5 ℃/h, thus obtaining 2.99X1.00×0.20mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 29
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.043g of Ca, 0.664g of MgSe and 1.209g of Ga are weighed according to the molar ratio of 1:6:3:1 under argon 2 Se 3 Mixing with 0.085g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump -3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 980 ℃ at a heating rate of 26 ℃/h, and preserving the temperature for 44h;
c. the quartz tube in the step b is vertically lowered at a speed of 0.12mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 40 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to the room temperature at a cooling speed of 35 ℃ per hour, so that 2.98X0.99X0.19 mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 30
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.043g of Ca, 0.664g of MgSe and 1.209g of Ga are weighed according to the molar ratio of 1:6:3:1 under argon 2 Se 3 Mixing with 0.085g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump -3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 980 ℃ at a heating rate of 26 ℃/h, and preserving the temperature for 44h;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 980 ℃ to room temperature according to the cooling rate of 2.0 ℃/h, thus obtaining 2.97X0.98X0.18 mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 31
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.127g of CaSe, 0.664g of MgSe and 1.209g of Ga are weighed out under argon in a molar ratio of 1:6:3 2 Se 3 Mixing, placing into quartz tube with length of 24cm and diameter of 12mm, and vacuum pumping to 10 -3 Performing fusion sealing after Pa vacuum degree;
b. b, placing the quartz tube in the step b into a crucible descending furnace with a temperature controlled by a program, heating to 985 ℃ at a heating rate of 22 ℃/h, and preserving heat for 43h;
c. the quartz tube in the step b is vertically lowered at a speed of 0.18mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 20 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to the room temperature at a cooling speed of 23 ℃ per hour, so that 2.96 multiplied by 0.97 multiplied by 0.17mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 32
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe and 0 according to a molar ratio of 1:6:3 under argon664g of MgSe and 1.209g of Ga 2 Se 3 Mixing, placing into quartz tube with length of 24cm and diameter of 12mm, and vacuum pumping to 10 -3 Performing fusion sealing after Pa vacuum degree;
b. b, placing the quartz tube in the step b into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 985 ℃ at a heating rate of 22 ℃/h, and preserving the temperature for 43h;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 985 ℃ to room temperature according to the cooling rate of 1.5 ℃/h, thus obtaining 2.95 multiplied by 0.96 multiplied by 0.16mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 33
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.156g of Mg, 0.448g of Ga and 1.353g of Se according to the molar ratio of 1:6:6:16 under argon, uniformly mixing, putting into a quartz tube with the length of 24cm and the diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 990 ℃ at a heating rate of 28 ℃/h, and preserving the heat for 42h;
c. the quartz tube in the step b is vertically lowered at a speed of 0.20mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 10 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is reduced to room temperature at a cooling speed of 40 ℃ per hour, so that 2.94 multiplied by 0.95 multiplied by 0.15mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 34
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.156g of Mg, 0.448g of Ga and 1.353g of Se according to the molar ratio of 1:6:6:16 under argon, uniformly mixing, putting into a quartz tube with the length of 24cm and the diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Melting after Pa vacuum degreeFusing and sealing;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 990 ℃ at a heating rate of 28 ℃/h, and preserving the heat for 42h;
c. the quartz tube in the step b was placed in a crucible lowering furnace, and the furnace temperature was lowered from 990℃to room temperature at a lowering rate of 2.0℃per hour, yielding 2.93X 0.94X 0.14mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 35
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe, 0.156g of Mg, 0.448g of Ga and 1.268g of Se according to a molar ratio of 1:6:6:15 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 995 ℃ at a heating rate of 24 ℃/h, and preserving heat for 41h;
c. the quartz tube in the step b is vertically lowered at a speed of 0.18mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 15 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to the room temperature at a cooling speed of 35 ℃ per hour, so that 2.92 multiplied by 0.93 multiplied by 0.13mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 36
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.127g of CaSe, 0.156g of Mg, 0.448g of Ga and 1.268g of Se according to a molar ratio of 1:6:6:15 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible lowering furnace with a temperature controlled by a program, raising the temperature to 990 ℃ at a heating rate of 24 ℃/h, and preserving the temperature for 41h;
c. placing the quartz tube in the step c in a crucible lowering furnace, and cooling the furnace temperature from 995 ℃ to room temperature at a cooling rate of 1.5 ℃/h to obtain 2.91 multiplied by 0.92 multiplied by 0.12mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 37
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.664g of MgSe, 0.448g of Ga and 0.846g of Se according to a molar ratio of 1:6:6:10 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 1000 ℃ at a heating rate of 20 ℃/h, and preserving heat for 40h;
c. the quartz tube in the step b is vertically lowered at the speed of 0.16mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 20 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to the room temperature at the cooling speed of 30 ℃ per hour, so that 2.90 multiplied by 0.91 multiplied by 0.11mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 38
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. weighing 0.043g of Ca, 0.664g of MgSe, 0.448g of Ga and 0.846g of Se according to a molar ratio of 1:6:6:10 under argon, uniformly mixing, putting into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by a vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 1000 ℃ at a heating rate of 20 ℃/h, and preserving heat for 40h;
c. placing the quartz tube in the step b into a crucible descending furnace, and cooling the furnace temperature from 1000 ℃ to room temperature according to the cooling rate of 1.0 ℃/h to obtain 2.91 multiplied by 0.90 multiplied by 0.10mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 39
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.043g Ca, 0.156g Mg, 1.209g Ga are weighed out under argon according to a molar ratio of 1:6:3:7 2 Se 3 Mixing with 0.592g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 960 ℃ at a heating rate of 22 ℃/h, and preserving heat for 45 hours;
c. the quartz tube in the step b is vertically lowered at the speed of 0.14mm/h, the crystal grows in the descending process of the crucible descending furnace, the growth period is 25 days, after the growth is finished, the crystal is continuously annealed in the crucible descending furnace, and the temperature is lowered to the room temperature at the cooling speed of 25 ℃ per hour, so that 2.92 multiplied by 0.91 multiplied by 0.12mm is obtained 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 40
Growing selenium gallium magnesium calcium infrared nonlinear optical crystal by a crucible descent method, wherein the specific operation is carried out according to the following steps:
a. 0.043g Ca, 0.156g Mg, 1.209g Ga are weighed out under argon according to a molar ratio of 1:6:3:7 2 Se 3 Mixing with 0.592g Se, placing into a quartz tube with a length of 24cm and a diameter of 12mm, and pumping the quartz tube to 10 by vacuum pump - 3 Performing fusion sealing after Pa vacuum degree;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 960 ℃ at a heating rate of 22 ℃/h, and preserving heat for 45 hours;
c. the quartz tube in the step b is placed in a crucible descending furnace, and the furnace temperature is reduced from 960 ℃ to room temperature according to the cooling rate of 1.5 ℃/h, thus obtaining 2.93 multiplied by 0.92 multiplied by 0.14mm 3 Selenium gallium magnesium calcium infrared nonlinear optical crystal.
Example 41
The selenium gallium magnesium calcium infrared nonlinear optical crystal obtained in any one of examples 9-40 was placed at the position 3 as shown in fig. 4, and Q Ho was adjusted at room temperature: tm: cr: as a light source, 2090nm output of the YAG laser was observed, and 1045nm double frequency light output was observed, with an output intensity 1.5 times that of AGS of the same condition (fig. 3).
Example 42
Any one of the CaMg obtained in examples 9 to 40 6 Ga 6 Se 16 An infrared nonlinear optical crystal, as shown in FIG. 4, is arranged at the position 3, wherein 1 is a laser, 2 is a convex lens, and 3 is CaMg 6 Ga 6 Se 16 An infrared nonlinear optical crystal, wherein 4 is a prism and 5 is a filter; laser beam emitted by the laser 1 is emitted into CaMg through the convex lens 2 6 Ga 6 Se 16 The crystal 3, the generated outgoing laser beam passes through the prism 4 and the filter 5, thereby obtaining a desired laser beam.
CaMg Using the invention 6 Ga 6 Se 16 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.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution 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 gallium magnesium calcium is characterized in that the molecular formula of the compound is CaMg 6 Ga 6 Se 16 Molecular weight is 2065.89, its structure belongs to hexagonal system, and space group isIs prepared by a high-temperature solid phase method.
2. The method for preparing the compound selenium gallium magnesium calcium according to claim 1, which is characterized by comprising the following steps:
a. according to chemical formula CaMg 6 Ga 6 Se 16 The molar ratio of Ca to Mg to Ga to Se=1:6:6:16 is that raw materials are weighed and mixed uniformly under the argon condition; the mixture was then filled into quartz containers and evacuated to 10 a under vacuum -3 Pa, performing fusion sealing; wherein the Ca raw material is Ca or CaSe; the Mg raw material is Mg or MgSe; the Ga material is Ga or Ga 2 Se 3 The selenium raw material is Se simple substance;
b. c, placing the sealed sample in the step a in a muffle furnace, heating to 900-950 ℃ at a speed of 10-40 ℃/h, and keeping the temperature for 25-35h; and then cooling to room temperature at the speed of 10-20 ℃/h, taking out, putting into a mortar, and mashing and grinding to obtain the powdered compound selenium gallium magnesium calcium.
3. An infrared nonlinear optical crystal of selenium gallium magnesium calcium is characterized in that the chemical formula of the crystal is CaMg 6 Ga 6 Se 16 Belonging to hexagonal system, the space group isThe unit cell parameters are->
4. The method for preparing selenium gallium magnesium calcium infrared nonlinear optical crystal according to claim 3, wherein a high-temperature solid phase method and a crucible descending method are adopted:
the high-temperature solid phase method for growing the selenium gallium magnesium calcium infrared nonlinear optical crystal comprises the following steps of:
a. according to chemical formula CaMg 6 Ga 6 Se 16 The molar ratio of Ca to Mg to Ga to Se=1:6:6:16, and uniformly mixing; filling into a quartz tube, and pumping the quartz tube to 10 by a vacuum pump -3 Degree of vacuum PaThen carrying out melt sealing, wherein the Ca source material is Ca or CaSe; the Mg source material is Mg or MgSe; the Ga source material is Ga or Ga 2 Se 3 The Se source material is Se simple substance;
b. c, placing the quartz tube in the step a into a muffle furnace with program temperature control, heating to 900-950 ℃ at a heating rate of 10-20 ℃/h, preserving heat for 25-35h, and cooling to room temperature at a cooling rate of 4-6 ℃/h to obtain selenium-gallium-magnesium-calcium infrared nonlinear optical crystal;
the crucible descent method for growing selenium gallium magnesium calcium infrared nonlinear optical crystal comprises the following steps:
a. according to chemical formula CaMg 6 Ga 6 Se 16 The molar ratio of Ca to Mg to Ga to Se=1:6:6:16, and uniformly mixing; filling into a quartz tube, and pumping the quartz tube to 10 by a vacuum pump -3 Performing fusion sealing after Pa vacuum degree, wherein the Ca source material is Ca or CaSe; the Mg source material is Mg or MgSe; the Ga source material is Ga or Ga 2 Se 3 The Se source material is Se simple substance;
b. c, placing the quartz tube in the step a into a crucible descending furnace with a temperature controlled by a program, heating to 950-1000 ℃ at a heating rate of 20-30 ℃/h, and preserving heat for 40-50h;
c. c, vertically descending the quartz tube in the step b at a speed of 0.1-0.2mm/h, growing the crystal in the descending process of the crucible descending furnace for 10-40 days, continuously annealing the crystal in the crucible descending furnace after the growth is finished, and cooling to room temperature at a cooling rate of 20-40 ℃/h to obtain the selenium-gallium-magnesium-calcium infrared nonlinear optical crystal;
or placing the quartz tube in the step b into a crucible descending furnace, and cooling the furnace temperature from 950-1000 ℃ to room temperature at a cooling rate of 1-2 ℃/h to obtain the selenium-gallium-magnesium-calcium infrared nonlinear optical crystal.
5. Use of the selenium gallium magnesium calcium infrared nonlinear optical crystal according to claim 3 in the preparation of an infrared all-solid-state laser, an infrared laser guidance radar, laser medical treatment or medium-to-long distance laser communication.
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| CN116145260A (en) * | 2021-11-19 | 2023-05-23 | 天津理工大学 | Series alkaline earth metal magnesium-based chalcogen (seleno) compound and nonlinear optical crystal thereof, and preparation method and application thereof |
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| CN116145260A (en) * | 2021-11-19 | 2023-05-23 | 天津理工大学 | Series alkaline earth metal magnesium-based chalcogen (seleno) compound and nonlinear optical crystal thereof, and preparation method and application thereof |
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