Sulfur gallium zinc barium compound and sulfide gallium zinc barium nonlinear optical crystal and preparation method and use thereof

Abstract

The present invention relates to two sulfide gallium zinc barium compounds and sulfide gallium zinc barium nonlinear optical crystals and preparation methods and uses thereof. The chemical formula of the compounds and crystals are both Ba4ZnGa4Q 12 , where Q = S, Se, all belong to the orthorhombic system, space group I222, unit cell parameter #imgabs0##imgabs1#Z=2, volume #imgabs2#. Under 2090nm laser irradiation, the frequency doubling effect of this compound is about 1-1.3 times that of AgGaS2. The gallium zinc barium sulfide compound is synthesized by vacuum high temperature solid phase reaction method, and the gallium zinc barium sulfide nonlinear optical crystal is grown by high temperature solution method or Bridgman method (crucible descent method) for nonlinear optical frequency doubling devices.

Description

Technical Field

[0001] The present invention relates to two novel infrared nonlinear optical crystal materials, gallium zinc barium sulfide compounds, the general chemical formula of which is Ba 4 ZnGa 4 Q 12 , wherein Q=S, Se, and the preparation method of the nonlinear optical crystal and powder belongs to the field of optical technology and crystal material technology. Background Art

[0002] In recent years, the research on new nonlinear optical crystal materials with large mid- and far-infrared frequency doubling effect, wide transmission band, large optical damage threshold, and stable physical and chemical properties has gradually become a hot topic. The main nonlinear optical materials are: β-BaB 2 O 4 (BBO) crystal, LiB 3 O 5 (LBO) crystal, CsB 3 O 5 (CBO) crystal, CsLiB 6 O 10 (CLBO) crystal, KBe 2 BO 3 F 2 (KBBF) crystal, AgGaS 2 (AGS) crystal, AgGaSe 2 (AGSe) crystal and ZnGeP 2 (ZGP) crystals. Although the crystal growth technology of these materials has become increasingly mature, there are still obvious shortcomings: such as easy deliquesce of crystals, long growth cycle, serious layered growth habits, high price, low laser damage threshold and two-photon absorption. Therefore, finding new nonlinear optical crystal materials is still a very important and arduous task.

[0003] Chalcogenide crystals are important semiconductor materials and mid-infrared materials. Their performance has attracted widespread attention and is widely used in lighting, display, military security, laser medicine, etc. Due to their good comprehensive performance, they are conducive to obtaining strong nonlinear optical effects and are an ideal choice for new mid- and far-infrared nonlinear optical crystals. Summary of the invention

[0004] One of the objects of the present invention is to provide two gallium zinc barium chalcogenides.

[0005] The second object of the present invention is to provide a method for preparing two gallium zinc barium chalcogenides compounds.

[0006] The third object of the present invention is to provide two kinds of sulfide gallium zinc barium infrared nonlinear optical crystals.

[0007] The fourth object of the present invention is to provide two methods for preparing gallium zinc barium chalcogenide infrared nonlinear optical crystals.

[0008] The fifth object of the present invention is to provide two flux systems for growing barium gallium zinc sulfide infrared nonlinear optical crystals.

[0009] The sixth object of the present invention is to provide two applications of barium gallium zinc sulfide infrared nonlinear optical crystals.

[0010] One of the purposes of the present invention is achieved in that:

[0011] The present invention aims to provide two sulfide gallium zinc barium compounds, characterized in that the chemical formula of the compounds is Ba 4 ZnGa 4 Q 12 , where Q = S, Se, molecular weight 319.58-460.28, no symmetry center, belongs to the orthorhombic system, space group is I222, unit cell parameters are: 1) Ba 4 ZnGa 4 S 12 : Z = 2, unit cell volume 2) Ba 4 ZnGa 4 Se 12 : Z = 2, unit cell volume Under 2090nm laser irradiation, the powder frequency doubling ability of the crystal is about the same as that of commercial crystal AGS (AgGaS 2 ) is 1-1.3 times.

[0012] The second object of the present invention is achieved in this way:

[0013] The preparation method of the gallium zinc barium chalcogenide compound comprises the following steps:

[0014] (a) mixing a barium-containing compound, a zinc-containing compound, a gallium-containing compound and a sulfur (selenium)-containing compound to obtain the sulfide gallium zinc barium compound by a vacuum high temperature solid phase reaction method, wherein the molar ratio of the element barium in the barium-containing compound, the element zinc in the zinc-containing compound, the element gallium in the gallium-containing compound, and the element sulfur (selenium) in the sulfur (selenium)-containing compound is 3.75-4.25:0.3-1.2:3.75-4.25:10-16, mixing the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur (selenium)-containing compound raw materials uniformly, grinding them and putting them into a graphite crucible, then putting the graphite crucible into a closed reaction container, and heating the mixture under a vacuum degree of 10 -5 ~10 -1 After vacuuming and sealing under the condition of Pa:

[0015] The barium-containing compound includes at least one of a single substance of barium, barium sulfide (selenide), barium disulfide (selenide), and barium trisulfide (selenide);

[0016] The zinc-containing compound includes at least one of zinc element and zinc sulfide (selenide);

[0017] The gallium-containing compound comprises at least one of gallium, gallium sulfide (selenide), and gallium trisulfide (selenide);

[0018] The sulfur (selenium) element or sulfur (selenium)-containing compound includes at least one of sulfur (selenium) element, barium sulfide (selenide), barium disulfide (selenide), barium trisulfide (selenide), zinc sulfide (selenide), gallium sulfide (selenide), and gallium trisulfide (selenide).

[0019] The vacuum high temperature solid phase reaction method can be used to prepare the gallium zinc barium sulfide compound according to the following chemical reaction formula:

[0020] 1) 4Ba+Zn+4Ga+12Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0021] 2) 4BaQ+Zn+4Ga+8Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0022] 3) 4Ba+ZnQ+4Ga+11S→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0023] 4)4Ba+Zn+4GaQ+8Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0024] 5) 4Ba+Zn+2Ga 2 Q 3 +6Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0025] 6) 4BaQ+ZnQ+4Ga+7Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0026] 7) 4BaQ+Zn+4GaQ+4Q→Ba 4 ZnGa4 Q 12 , where Q = S, Se

[0027] 8) 4BaQ+Zn+2Ga 2 Q 3 +2Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0028] 9) 4BaQ+ZnQ+4GaQ+3Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0029] 10) 4BaQ+ZnQ+2Ga 2 Q 3 +1Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0030] (b) placing the sealed reaction container in a muffle furnace, heating it to 600-900° C. in stages, keeping the temperature for 30-100 hours, and cooling it to room temperature to obtain a gallium zinc barium sulfide compound.

[0031] In step (a), the corresponding raw materials are weighed in an airtight container with water and oxygen contents of 0.01 to 0.2 ppm, respectively, and the airtight container is a glove box filled with argon.

[0032] In step (b), the staged heating is to increase the temperature from room temperature to 400-600°C at a rate of 10-50°C / h, keep the temperature for 30-100 hours, then increase the temperature to 600-900°C at a rate of 5-40°C / h, and keep the temperature for 30-100 hours; the slow cooling is to cool down to room temperature at a rate of 1-10°C / h.

[0033] The reaction container is generally a quartz glass tube or other reaction containers available in the prior art, so as to facilitate melting and sealing.

[0034] The third object of the present invention is achieved in this way:

[0035] The present invention aims to provide two novel chalcogenide gallium zinc barium infrared nonlinear optical crystals, characterized in that the chemical formula of the crystal is Ba 4 ZnGa 4 Q 12 , where Q = S, Se, molecular weight 319.58-460.28, no symmetry center, belongs to the orthorhombic system, space group I222, unit cell parameters are: 1) Ba 4 ZnGa4 S 12 : Z = 2, unit cell volume 2) Ba 4 ZnGa 4 Se 12 : Z = 2, unit cell volume Under 2090nm laser irradiation, the powder frequency doubling ability of the crystal is about the same as that of commercial crystal AGS (AgGaS 2 ). Therefore, the infrared nonlinear optical crystal of gallium zinc barium sulfide has potential application value in the infrared region.

[0036] The fourth object of the present invention is achieved in this way:

[0037] The preparation method of barium zinc gallium chalcogenide infrared nonlinear optical crystal comprises the following steps:

[0038] (a) The single-phase polycrystalline powder of the gallium zinc barium sulfide compound obtained in claims 1 to 3 or the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur-containing compound are mixed and then subjected to a vacuum high-temperature solid-phase reaction method to obtain the gallium zinc barium sulfide infrared nonlinear optical crystal, wherein the molar ratio of the element barium in the barium-containing compound, the element zinc in the zinc-containing compound, the element gallium in the gallium-containing compound, and the element sulfur (selenium) in the sulfur (selenium)-containing compound is 3.75-4.25:0.3-1.2:3.75-4.25:10-16, the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur (selenium)-containing compound are mixed uniformly, ground and then put into a graphite crucible, and then the graphite crucible is placed in a reaction vessel and heated to 10°C. -5 ~10 -1 After vacuuming and sealing under the condition of Pa:

[0039] The barium-containing compound includes at least one of a single substance of barium, barium sulfide (selenide), barium disulfide (selenide), and barium trisulfide (selenide);

[0040] The zinc-containing compound includes at least one of zinc element and zinc sulfide (selenide);

[0041] The gallium-containing compound comprises at least one of gallium, gallium sulfide (selenide), and gallium trisulfide (selenide);

[0042] The sulfur (selenium) element or sulfur (selenium)-containing compound includes at least one of sulfur (selenium) element, barium sulfide (selenide), barium disulfide (selenide), barium trisulfide (selenide), zinc sulfide (selenide), gallium monosulfide (selenide), and gallium trisulfide (selenide).

[0043] The vacuum high temperature solid phase reaction method can be used to prepare the barium gallium zinc sulfide infrared nonlinear optical crystal according to the following chemical reaction formula:

[0044] 1)4Ba+Zn+4Ga+12Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0045] 2)4BaQ+Zn+4Ga+8Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0046] 3)4Ba+ZnQ+4Ga+11Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0047] 4)4Ba+Zn+4GaQ+8Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0048] 5)4Ba+Zn+2Ga 2 Q 3 +6Q→No 4 ZnGa 4 Q 12 ,in Q=S,If

[0049] 6)4BaQ+ZnQ+4Ga+7Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0050] 7)4BaQ+Zn+4GaQ+4Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0051] 8)4BaQ+Zn+2Ga 2 Q 3 +2Q→No 4 ZnGa 4 Q 12 ,in Q=S,If

[0052] 9)4BaQ+ZnQ+4GaQ+3Q→Ba 4 ZnGa 4 Q 12 ,in Q=S,If

[0053] 10)4BaQ+ZnQ+2Ga 2 Q3 +1Q→Ba 4 ZnGa 4 Q 12 , where Q = S, Se

[0054] (b) placing the sealed reaction container in a muffle furnace, heating it to 600-900° C. in stages, keeping the temperature for 30-120 hours, and cooling it to room temperature to obtain a gallium zinc barium sulfide compound.

[0055] In step (a), the corresponding raw materials are weighed in an airtight container with water and oxygen contents of 0.01 to 0.2 ppm, respectively, and the airtight container is a glove box filled with argon.

[0056] In step (b), the staged heating is from room temperature to 400-500°C at a rate of 10-50°C / h, and kept warm for 30-120 hours, and then the temperature is raised to 600-900°C at a rate of 5-40°C / h, and kept warm for 30-120 hours; the slow cooling is cooling to room temperature at a rate of 1-10°C / h.

[0057] The reaction container is generally a quartz glass tube or other reaction containers available in the prior art, so as to facilitate melting and sealing.

[0058] The fifth purpose of the present invention is achieved in this way:

[0059] The invention provides a barium gallium zinc chalcogenide infrared nonlinear optical crystal, the chemical formula of which is Ba 4 ZnGa 4 Q 12 , wherein Q = S, Se; the preparation process comprises: uniformly mixing the raw materials containing barium compounds, zinc compounds, gallium compounds and sulfur (selenium) compounds, grinding them and putting them into a muffle furnace, heating them in stages and keeping them warm for a long time, and finally slowly cooling them to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0060] The flux preparation method of the barium zinc gallium sulfide infrared nonlinear optical crystal provided by the present invention adopts a vacuum high-temperature solid phase reaction method or a Bridgman method (crucible descent method) to grow the barium zinc gallium sulfide infrared nonlinear optical crystal, and the specific operation is carried out according to the following steps:

[0061] a. Prepare the barium gallium zinc sulfide infrared nonlinear optical crystal by vacuum high temperature solid phase reaction method.

[0062] 1) In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.01-0.1 ppm, the single-phase polycrystalline powder of the gallium zinc barium compound obtained according to any one of claims 1 to 3 or a mixture of the single-phase polycrystalline powder of the gallium zinc barium compound obtained according to any one of claims 1 to 3 and a flux is placed in a clean graphite crucible (wherein the molar ratio of the single-phase polycrystalline powder of the gallium zinc barium compound to the flux is 1:0.1-30), and then placed in a sealed reaction container, and the sealed reaction container containing the raw materials is placed in a vacuum degree of 10 -5 -10 -3 Pa and then sealed after vacuuming;

[0063] Alternatively, a mixture of the barium-containing compound, the zinc-containing compound, the gallium-containing compound, and the sulfur (selenium)-containing compound in a molar ratio of 3.75-4.25:0.3-1.8:3.75-4.25:3-16 or a mixture of the barium-containing compound, the zinc-containing compound, the gallium-containing compound, the sulfur (selenium)-containing compound and the flux is directly placed in a clean graphite crucible (wherein the molar ratio of the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur or selenium-containing compound to the flux is 3.75-4.25:0.3-1.2:3.75-4.25:10-16:0.1-30), and then placed in a sealed reaction container, and the sealed reaction container containing the raw materials is placed in a vacuum degree of 10 -5 -10 -3 Pa and then melted and sealed.

[0064] 2) Place the sealed reaction vessel in step 1) into a muffle furnace, heat the temperature from room temperature to 400-600°C at a rate of 10-50°C / h, keep warm for 30-120 hours, then heat the temperature to 600-900°C at a rate of 5-40°C / h, and keep warm for 30-120 hours;

[0065] 3) Cooling down to room temperature at a rate of 1-8°C / h to prepare a barium gallium zinc sulfide infrared nonlinear optical crystal.

[0066] The flux mainly includes self-fluxing agents, such as S(Se), Ba, BaS(BaSe), BaS 2 (BaSe 2 ), BaS 3 (BaSe 3 ), Zn, ZnS(ZnSe), Ga, GaS(GaSe), Ga 2 S 3 (Ga 2 Se 3), the composite flux includes Ba-S(Se), Ba-ZnS(ZnSe), Ba-GaS(GaSe), Ba-Ga 2 S 3 (Ga 2 Se 3 )、BaS(BaSe)-S(Se)、BaS 2 (BaSe 2 )-S(Se), BaS 3 (BaSe 3 )-S(Se), Zn-S(Se), Zn-Ga, Zn-GaS(GaSe), Zn-Ga 2 S 3 (Ga 2 Se 3 ), ZnS(ZnSe)-S(Se), ZnS(ZnSe)-Ga, ZnS(ZnSe)-GaS(GaSe), ZnS(ZnSe)-Ga 2 S 3 (Ga 2 Se 3 ), Ga-S(Se), Ga-GaS(GaSe), Ga-Ga 2 S 3 (Ga 2 Se 3 )、GaS(GaSe)-S(Se)、Ga 2 S 3 (Ga 2 Se 3 )-S(Se) or more.

[0067] The molar ratio of Ba to S (Se) in the composite flux Ba-S (Se) system is 2-5:1-10; the molar ratio of Ba to ZnS (ZnSe) in the Ba-ZnS (ZnSe) system is 1-4:1-10; the molar ratio of Ba to GaS (GaSe) in the Ba-GaS (GaSe) system is 2-5:1-6; 2 S 3 (Ga 2 Se 3 ) system with Ba and Ga 2 S 3 (Ga 2 Se 3 ) molar ratio is 2-5:1-4; the molar ratio of BaS(BaSe) to S(Se) in the BaS(BaSe)-S(Se) system is 2-7:1-6; BaS 2 (BaSe 2 )-S(Se) system 2(BaSe 2 ) and S(Se) in a molar ratio of 2-7:1-4; BaS 3 (BaSe 3 )-S(Se) system 3 (BaSe 3 ) to S(Se) is 2-7:1-3; the molar ratio of ZnS(ZnSe) to S(Se) in the ZnS(ZnSe)-S(Se) system is 2-7:1-10; the molar ratio of ZnS to Ga in the Zn-Ga system is 0.5-7:1-6; the molar ratio of Zn to GaS(GaSe) in the Zn-GaS(GaSe) system is 0.5-7:1-4; 2 S 3 (Ga 2 Se 3 ) system with ZnS (ZnSe) and Ga 2 S 3 (Ga 2 Se 3 ) molar ratio is 0.5-7:1-3; the molar ratio of Ga to S(Se) in the Ga-S(Se) system is 2-5:1-10; the molar ratio of Ga to GaS(GaSe) in the Ga-GaS(GaSe) system is 2-5:1-6; 2 S 3 (Ga 2 Se 3 ) system Ga and Ga 2 S 3 (Ga 2 Se 3 ) molar ratio is 2-5:1-4; the molar ratio of GaS(GaSe) to S(Se) in the GaS(GaSe)-S(Se) system is 2-5:1-4:1-10; Ga 2 S 3 (Ga 2 Se 3 )-S(Se) system 2 S 3 (Ga 2 Se 3 ) and S(Se) in a molar ratio of 2-5:1-10.

[0068] b. Use the Bridgman method (crucible descent method) to prepare barium zinc gallium sulfide infrared nonlinear optical crystals.

[0069] 1) In an airtight container which is a glove box filled with inert gas argon and has a water content and an oxygen content of 0.01-0.1 ppm, the single-phase polycrystalline powder of the sulfide gallium zinc barium compound obtained according to any one of claims 1 to 3 or a mixture of the single-phase polycrystalline powder of the sulfide gallium zinc barium compound obtained according to any one of claims 1 to 3 and a flux (wherein the molar ratio of the single-phase polycrystalline powder of the sulfide gallium zinc barium compound to the flux is 1:0.1-30) is heated to melt to obtain a mixed melt, and then the temperature is lowered or the mixture is grown at a constant temperature to prepare a sulfide gallium zinc barium infrared nonlinear optical crystal;

[0070] Alternatively, a mixture of the barium element in the barium-containing compound, the zinc element in the zinc-containing compound, the gallium element in the gallium-containing compound, and the sulfur (selenium) element in the sulfur (selenium)-containing compound in a molar ratio of 3.75-4.25:0.3-1.2:3.75-4.25:10-16 is directly prepared, or a mixture of the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur (selenium)-containing compound or a mixture of the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur (selenium)-containing compound and a flux is directly heated to melt to obtain a mixed solution (wherein the molar ratio of the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur or selenium-containing compound to the flux is 3.75-4.25:0.3-1.2:3.75-4.25:10-16:0.1-30), and then the mixture is cooled or grown at a constant temperature to prepare a chalcogen gallium zinc barium infrared nonlinear optical crystal.

[0071] 2) placing the crucible containing the mixture prepared in step 1) into a crystal growth furnace, slowly lowering the crucible, and passing the crucible through a heating furnace with a certain temperature gradient, controlling the furnace temperature to be slightly higher than the melting point of the material; selecting a suitable heating zone, when the crucible passes through the heating zone, the material in the crucible is melted, and when the crucible continues to descend, the temperature at the bottom of the crucible first drops below the melting point and begins to crystallize, and the crystal continues to grow as the crucible descends, thereby preparing a sulfide gallium zinc barium infrared nonlinear optical crystal.

[0072] The flux mainly includes self-fluxing agents, such as S(Se), Ba, BaS(BaSe), BaS 2 (BaSe 2 ), BaS 3 (BaSe 3 ), Zn, ZnS(ZnSe), Ga, GaS(GaSe), Ga 2 S 3 (Ga 2 Se 3 ), the composite flux includes Ba-S(Se), Ba-ZnS(ZnSe), Ba-GaS(GaSe), Ba-Ga 2 S 3 (Ga 2 Se3 )、BaS(BaSe)-S(Se)、BaS 2 (BaSe 2 )-S(Se), BaS 3 (BaSe 3 )-S(Se), Zn-S(Se), Zn-Ga, Zn-GaS(GaSe), Zn-Ga 2 S 3 (Ga 2 Se 3 ), ZnS(ZnSe)-S(Se), ZnS(ZnSe)-Ga, ZnS(ZnSe)-GaS(GaSe), ZnS(ZnSe)-Ga 2 S 3 (Ga 2 Se 3 ), Ga-S(Se), Ga-GaS(GaSe), Ga-Ga 2 S 3 (Ga 2 Se 3 )、GaS(GaSe)-S(Se)、Ga 2 S 3 (Ga 2 Se 3 )-S(Se) or more.

[0073] The molar ratio of Ba to S (Se) in the composite flux Ba-S (Se) system is 2-5:1-10; the molar ratio of Ba to ZnS (ZnSe) in the Ba-ZnS (ZnSe) system is 1-4:1-10; the molar ratio of Ba to GaS (GaSe) in the Ba-GaS (GaSe) system is 2-5:1-6; 2 S 3 (Ga 2 Se 3 ) system with Ba and Ga 2 S 3 (Ga 2 Se 3 ) molar ratio is 2-5:1-4; the molar ratio of BaS(BaSe) to S(Se) in the BaS(BaSe)-S(Se) system is 2-7:1-6; BaS 2 (BaSe 2 )-S(Se) system 2 (BaSe 2 ) and S(Se) in a molar ratio of 2-7:1-4; BaS 3 (BaSe 3 )-S(Se) system 3 (BaSe3 ) to S(Se) is 2-7:1-3; the molar ratio of ZnS(ZnSe) to S(Se) in the ZnS(ZnSe)-S(Se) system is 2-7:1-10; the molar ratio of ZnS to Ga in the Zn-Ga system is 0.5-7:1-6; the molar ratio of Zn to GaS(GaSe) in the Zn-GaS(GaSe) system is 0.5-7:1-4; 2 S 3 (Ga 2 Se 3 ) system with ZnS (ZnSe) and Ga 2 S 3 (Ga 2 Se 3 ) molar ratio is 0.5-7:1-3; the molar ratio of Ga to S(Se) in the Ga-S(Se) system is 2-5:1-10; the molar ratio of Ga to GaS(GaSe) in the Ga-GaS(GaSe) system is 2-5:1-6; 2 S 3 (Ga 2 Se 3 ) system Ga and Ga 2 S 3 (Ga 2 Se 3 ) molar ratio is 2-5:1-4; the molar ratio of GaS(GaSe) to S(Se) in the GaS(GaSe)-S(Se) system is 2-5:1-4:1-10; Ga 2 S 3 (Ga 2 Se 3 )-S(Se) system 2 S 3 (Ga 2 Se 3 ) and S(Se) in a molar ratio of 2-5:1-10.

[0074] The sixth object of the present invention is achieved in this way:

[0075] The aforementioned barium gallium zinc sulfide infrared nonlinear optical crystal is suitable for use in mid- and far-infrared band laser frequency doubling crystals, infrared communication devices, and infrared laser guidance devices. It can also be used to prepare frequency doubling generators, up or down frequency converters, or optical parametric oscillators. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 is the compound Ba prepared by the present invention 4 ZnGa 4 Q 12 , where Q = S, theoretical X-ray spectrum of Se crystal.

[0077] Figure 2 For the present invention 4 ZnGa 4 Q 12 , where Q = S, the working principle diagram of the nonlinear optical device made of Se crystal, where 1 is the laser, 2 is the emitted light beam, and 3 is the Ba 4 ZnGa 4 Q 12 , where Q=S, Se crystal, 4 is the output light beam, and 5 is the filter. DETAILED DESCRIPTION

[0078] The present invention is described in detail below with reference to the accompanying drawings and implementation examples, but is not limited to the described embodiments.

[0079] Example 1

[0080] Preparation of polycrystalline powder of gallium zinc barium sulfide compound by vacuum high temperature solid phase reaction:

[0081] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials Ba: Zn: Ga: S (Se) were weighed in a molar ratio of 3-5: 0.2-1.8: 3-5: 10-20. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10 hours, then raise the temperature to 700°C at a rate of 30°C / h, keep it warm for 100 hours, and then cool it to room temperature at a rate of 7.5°C / h to obtain polycrystalline powder of sulfide gallium zinc barium compound.

[0082] Preparation of Barium Gallium Zinc Sulfur Infrared Nonlinear Optical Crystals by Vacuum High Temperature Solid Phase Reaction:

[0083] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.01 ppm respectively, the starting materials Ba: Zn: Ga: S (Se) were weighed in a molar ratio of 1-3: 1-10: 0.1-5: 4-20. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10h, then raise the temperature to 1000°C at a rate of 30°C / h, keep it warm for 100h, and then cool it to room temperature at a rate of 5°C / h to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0084] Example 2

[0085] The polycrystalline powder of gallium zinc barium chalcogenide compound is prepared by high temperature solid phase reaction;

[0086] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials Ba: ZnS (ZnSe): Ga: S (Se) were weighed in a molar ratio of 3-5: 0.2-1.8: 3-5: 8-18. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10h, then raise the temperature to 850°C at a rate of 30°C / h, keep it warm for 100h, and then cool it to room temperature at a rate of 5.5°C / h to obtain the main phase sulfide gallium zinc barium compound polycrystalline powder.

[0087] The infrared nonlinear optical crystal of barium zinc gallium sulfide was prepared by high temperature solid phase reaction;

[0088] In a glove box filled with inert gas argon and containing water and oxygen contents of 0.05 ppm respectively, the starting materials Ba: ZnS (ZnSe): Ga: S (Se) were weighed in a molar ratio of 1-3: 1-10: 0.1-5: 4-12. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10h, then raise the temperature to 950°C at a rate of 30°C / h, keep it warm for 100h, and then cool it to room temperature at a rate of 5°C / h to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0089] Example 3

[0090] The polycrystalline powder of gallium zinc barium chalcogenide compound is prepared by high temperature solid phase reaction;

[0091] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials, i.e., BaS(BaSe):Zn:Ga:S(Se), were weighed in a molar ratio of 3-5:2-8:0.2-1.8:4-12. The raw materials were mixed evenly and ground carefully in a mortar. Then, the raw materials were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 20°C / h, keep it warm for 20h, then raise the temperature to 750°C at a rate of 40°C / h, keep it warm for 80h, and then cool it to room temperature at a rate of 8°C / h to obtain the main phase sulfide gallium zinc barium compound polycrystalline powder.

[0092] The infrared nonlinear optical crystal of barium zinc gallium sulfide was prepared by high temperature solid phase reaction;

[0093] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials, i.e., BaS(BaSe):Zn:Ga:S(Se), were weighed in a molar ratio of 1-3:2-10:1-3:4-12. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 20°C / h, keep it warm for 20h, then raise the temperature to 990°C at a rate of 40°C / h, keep it warm for 100h, and then cool it to room temperature at a rate of 5°C / h to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0094] Example 4

[0095] The polycrystalline powder of gallium zinc barium chalcogenide compound is prepared by high temperature solid phase reaction;

[0096] The starting materials, namely Ba: Zn: Ga, were weighed in a glove box filled with inert argon gas and having a water content and an oxygen content of 0.05 ppm respectively. 2 S 3 (Ga 2 Se 3 The molar ratio of S(Se) to S(Se) is 3-5:0.2-1.8:1-3:4-15. The raw materials are mixed evenly and ground carefully in a mortar. Then, the raw materials are put into a clean graphite crucible. The graphite crucible is put into a quartz tube of φ13×200mm and the quartz tube is evacuated to 10 -2Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 25°C / h, keep it warm for 20h, then raise the temperature to 700°C at a rate of 20°C / h, keep it warm for 50h, and then cool it to room temperature at a rate of 5°C / h. The main phase obtained is polycrystalline powder of sulfide gallium zinc barium compound.

[0097] The infrared nonlinear optical crystal of barium zinc gallium sulfide was prepared by high temperature solid phase reaction;

[0098] The starting materials, namely Ba: Zn: Ga, were weighed in a glove box filled with inert argon gas and having a water content and an oxygen content of 0.05 ppm respectively. 2 S 3 (Ga 2 Se 3 The molar ratio of S(Se) to S(Se) is 1-3:1-10:0.1-5:5-15. The raw materials are mixed evenly and ground carefully in a mortar. Then, the raw materials are put into a clean graphite crucible. The graphite crucible is put into a quartz tube of φ13×200mm and the quartz tube is evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 25°C / h, keep it warm for 20h, then raise the temperature to 970°C at a rate of 20°C / h, keep it warm for 70h, and then cool it to room temperature at a rate of 3°C / h to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0099] Example 5

[0100] The polycrystalline powder of gallium zinc barium chalcogenide compound is prepared by high temperature solid phase reaction;

[0101] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials, i.e., BaS (BaSe): ZnS (ZnSe): Ga: S (Se), were weighed in a molar ratio of 3-5: 0.1-1.8: 3-5: 5-15. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10 hours, then raise the temperature to 720°C at a rate of 30°C / h, keep it warm for 50 hours, and then cool it to room temperature at a rate of 4°C / h to obtain a polycrystalline powder with sulfide gallium zinc barium compound as the main phase.

[0102] The infrared nonlinear optical crystal of barium zinc gallium sulfide was prepared by high temperature solid phase reaction;

[0103] In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.05 ppm respectively, the starting materials, namely BaS (BaSe): ZnS (ZnSe): Ga: S (Se), were weighed in a molar ratio of 1-3: 2-10: 0.1-1.8: 1-10. The raw materials were mixed evenly and ground carefully in a mortar. Then, they were placed in a clean graphite crucible. The graphite crucible was placed in a quartz tube of φ13×200 mm, and the quartz tube was evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10h, then raise the temperature to 1000°C at a rate of 30°C / h, keep it warm for 100h, and then cool it to room temperature at a rate of 2°C / h to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0104] Example 6

[0105] The polycrystalline powder of gallium zinc barium chalcogenide compound is prepared by high temperature solid phase reaction;

[0106] The starting materials, namely BaS(BaSe):Zn:Ga, were weighed in a glove box filled with inert argon gas and having a water content and an oxygen content of 0.05 ppm respectively. 2 S 3 (Ga 2 Se 3 The molar ratio of S(Se) to S(Se) is 3.5:0.1-1.8:1-3:1-10. The raw materials are mixed evenly and ground carefully in a mortar. Then, the raw materials are put into a clean graphite crucible. The graphite crucible is put into a quartz tube of φ13×200mm and the quartz tube is evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10h, then raise the temperature to 730°C at a rate of 30°C / h, keep it warm for 30h, and then cool it to room temperature at a rate of 6°C / h to obtain polycrystalline powder of sulfide gallium zinc barium compound.

[0107] The infrared nonlinear optical crystal of barium zinc gallium sulfide was prepared by high temperature solid phase reaction;

[0108] The starting materials, namely BaS(BaSe):Zn:Ga, were weighed in a glove box filled with inert argon gas and having a water content and an oxygen content of 0.05 ppm respectively. 2 S 3 (Ga 2 Se 3The molar ratio of S(Se) to S(Se) is 1-3:2-10:0.1-2:3-15. The raw materials are mixed evenly and ground carefully in a mortar. Then, the raw materials are put into a clean graphite crucible. The graphite crucible is put into a quartz tube of φ13×200mm and the quartz tube is evacuated to 10 -2 Pa and melt-seal it, put the sealed quartz tube into a pit muffle furnace, raise the temperature to 400°C at a rate of 30°C / h, keep it warm for 10h, then raise the temperature to 1000°C at a rate of 30°C / h, keep it warm for 50h, and then cool it to room temperature at a rate of 3.5°C / h to obtain sulfide gallium zinc barium infrared nonlinear optical crystal.

[0109] Embodiment 7:

[0110] Any Ba obtained in Examples 1-6 4 ZnGa 4 Q 12 , where Q = S, Se crystal is processed into a frequency doubling device with a size of 5mm×5mm×6mm according to the matching direction, and the attached Figure 2 As shown in the figure, it is placed at the position 3, and the infrared beam 2 with a wavelength of 2090nm is emitted by the laser 1 and enters Ba 4 ZnGa 4 Q 12 Single crystal 3, where Q=S, Se single crystal 3, produces doubled frequency light with a wavelength of 1045nm, and the output intensity is 1-1.3 times that of AGS under the same conditions. The output light beam 4 contains infrared light with a wavelength of 2090nm and doubled frequency light of 1045nm, which is filtered out by filter 5 to obtain laser with a wavelength of 1045nm.

Claims

1. Two sulfide gallium zinc barium compounds, characterized in that The chemical formula of this compound is Ba4ZnGa4Q 12 , where Q = S, Se, molecular weight 319.58-460.28, belongs to the orthorhombic system, space group I222, unit cell parameters are: 1) α=β=γ=90°,Z=2,unit cell volume 2) α=β=γ=90°,Z=2,unit cell volume 2. The method for preparing the gallium zinc barium chalcogenide compound according to claim 1, characterized in that The method is carried out in the following steps: a barium-containing compound, a zinc-containing compound, a gallium-containing compound and a sulfur (selenium)-containing compound are mixed and a vacuum high-temperature solid phase reaction method is used to prepare the compound sulfide gallium zinc barium compound, wherein the molar ratio of the element barium in the barium-containing compound, the element zinc in the zinc-containing compound, the element gallium in the gallium-containing compound, and the element sulfur (selenium) in the sulfur (selenium)-containing compound is 3.75-4.25:0.3-1.2:3.75-4.25:10-16. The barium-containing compound includes at least one of a single substance of barium, barium sulfide (selenide), barium disulfide (selenide) or barium trisulfide (selenide); The zinc-containing compound is at least one of zinc element or zinc sulfide (selenide); The gallium-containing compound includes at least one of gallium, gallium monosulfide (selenide) or gallium trisulfide (selenide); The sulfur (selenium) element or sulfur (selenium)-containing compound includes at least one of sulfur (selenium) element, barium sulfide (selenide), barium disulfide (selenide), barium trisulfide (selenide), zinc sulfide (selenide), gallium monosulfide (selenide), and gallium trisulfide (selenide).

3. The method for preparing a gallium zinc barium sulfide compound according to claim 2, characterized in that: It is prepared by vacuum high temperature solid phase reaction method, and the specific operation steps are as follows: a. In an airtight container filled with inert gas argon and having a water content and an oxygen content of 0.01-0.1 ppm, a barium compound (barium element), a zinc compound (zinc element), a gallium compound (gallium element), a sulfur (selenium) element or a sulfur (selenium) compound is mixed evenly in a ratio of 3.75-4.25:0.3-1.2:3.75-4.25:10-16. After grinding, put it into a clean graphite crucible, put it into a sealed reaction container, and place the sealed reaction container with the raw materials under a vacuum degree of 10 -5 -10 -3 Pa and then sealed after vacuuming; b. The sealed reaction vessel in step a is placed in a muffle furnace, heated from room temperature to 400-500°C at a rate of 10-50°C / h, kept warm for 30-100 hours, and then heated to 600-800°C at a rate of 5-40°C / h, and kept warm for 30-100 hours; c. Cool down to room temperature at a rate of 1-10°C / h, take out the sample, put it into a mortar, crush and grind it, and obtain the compound Ba4ZnGa4Q 12 The polycrystalline powder, wherein Q = S, Se, is subjected to X-ray analysis of the obtained polycrystalline powder of gallium zinc barium sulfide compound, and the obtained X-ray diffraction spectrum is consistent with the Ba4ZnGa4Q 12 , where Q = S, which is consistent with the theoretical X-ray spectrum of Se.

4. Two types of chalcogenide gallium zinc barium nonlinear optical crystals, characterized in that: The general chemical formula of the crystal is Ba4ZnGa4Q 12 , where Q = S, Se, molecular weight 319.58-460.28, no symmetry center, belongs to the orthorhombic system, space group I222, unit cell parameters are: 1) α=β=γ=90°,Z=2,unit cell volume 2) α=β=γ=90°,Z=2,unit cell volume 5. The method for preparing the barium gallium zinc chalcogenide nonlinear optical crystal according to claim 4, characterized in that: The crystal is grown by vacuum high temperature solid phase reaction method or Bridgman method (crucible descent method) to form gallium zinc barium sulfide nonlinear optical crystal.

6. The method according to claim 5, characterized in that The specific operation of vacuum high temperature solid phase reaction method is carried out according to the following steps: a. In a glove box filled with inert gas argon and having a water content and an oxygen content of 0.01-0.1 ppm, the single-phase polycrystalline powder of the gallium zinc barium compound obtained according to any one of claims 1 to 3 or a mixture of the single-phase polycrystalline powder of the gallium zinc barium compound obtained according to any one of claims 1 to 3 and a flux is placed in a clean graphite crucible, and then placed in a sealed reaction vessel. The sealed reaction vessel containing the raw materials is placed in a vacuum degree of 10 -5 -10 -3 Pa and then sealed after vacuuming; Alternatively, a mixture of the barium element in the barium-containing compound, the zinc element in the zinc-containing compound, the gallium element in the gallium-containing compound, and the sulfur (selenium) element in the sulfur (selenium)-containing compound in a molar ratio of 3.75-4.25:0.3-1.2:3.75-4.25:10-16 or a mixture of the barium-containing compound, the zinc-containing compound, the gallium-containing compound, the sulfur (selenium)-containing compound and the flux is directly placed in a clean graphite crucible, and then placed in a sealed reaction container. The sealed reaction container containing the raw materials is placed in a vacuum degree of 10 -5 -10 -3 Pa, and then melt and seal. b. The sealed reaction vessel in step a is placed in a pit muffle furnace, heated from room temperature to 400-500 ° C at a rate of 10-50 ° C / h, kept warm for 30-120 hours, and then heated to 600-900 ° C at a rate of 5-40 ° C / h, and kept warm for 30-120 hours; c. Cool down to room temperature at a rate of 1-10°C / h to prepare a sulfide gallium zinc barium nonlinear optical crystal.

7. The method according to claim 5, characterized in that The specific operation of the Bridgman method (crucible descent method) is carried out in the following steps: a. Heating the single-phase polycrystalline powder of the barium gallium zinc sulfide compound obtained according to any one of claims 1 to 3 or the mixture of the single-phase polycrystalline powder of the barium gallium zinc sulfide compound obtained according to any one of claims 1 to 3 and a flux to obtain a mixed melt, and cooling or growing at a constant temperature to prepare a barium gallium zinc sulfide nonlinear optical crystal; Alternatively, a mixture of the barium element in the barium-containing compound, the zinc element in the zinc-containing compound, the gallium element in the gallium-containing compound, and the sulfur (selenium) element in the sulfur (selenium) compound in a molar ratio of 3.75-4.25:0.3-1.2:3.75-4.25:10-16 or a mixture of the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur (selenium)-containing compound with a flux is directly heated to melt to obtain a mixed solution, and then the temperature is reduced or the growth is constant to prepare a chalcogenide gallium zinc barium nonlinear optical crystal. b. Place the crucible containing the mixture prepared in step a into a crystal growth furnace, slowly lower it, and pass the crucible through a heating furnace with a certain temperature gradient, controlling the furnace temperature to be slightly higher than the melting point of the material; select a suitable heating zone, when the crucible passes through the heating zone, the material in the crucible is melted, and when the crucible continues to descend, the temperature at the bottom of the crucible first drops below the melting point and begins to crystallize, and the crystal continues to grow as the crucible descends, thereby preparing a sulfide gallium zinc barium nonlinear optical crystal.

8. The method according to claim 7, characterized in that The molar ratio of the sulfide gallium zinc barium compound single-phase polycrystalline powder or the sulfide gallium zinc barium compound single-phase polycrystalline powder to the flux is 1:0.1-30; or the molar ratio of the barium-containing compound, the zinc-containing compound, the gallium-containing compound and the sulfur (selenium)-containing compound to the flux is 3.75-4.25:0.3-1.2:3.75-4.25:10-16:0.1-30; The single flux includes one or more of S(Se), Ba, BaS(BaSe), BaS2(BaSe2), BaS3(BaSe3), Zn, ZnS(ZnSe), Ga, GaS(GaSe), Ga2S3(Ga2Se3), and the composite flux includes Ba-S(Se), Ba-ZnS(ZnSe), Ba-GaS(GaSe), Ba-Ga2S3(Ga2Se3), BaS(BaSe)-S(Se), BaS2(BaSe2)-S(Se), BaS3(BaSe3)-S (Se), Zn-S(Se), Zn-Ga, Zn-GaS(GaSe), Zn-Ga2S3(Ga2Se3), ZnS(ZnSe)-S(Se), ZnS(ZnSe)-Ga, ZnS(ZnSe)-GaS(GaSe), ZnS One or more of (ZnSe)-Ga2S3(Ga2Se3), Ga-S(Se), Ga-GaS(GaSe), Ga-Ga2S3(Ga2Se3), GaS(GaSe)-S(Se), Ga2S3(Ga2Se3)-S(Se).

9. The method according to claim 8, characterized in that: The molar ratio of Ba to S (Se) in the Ba-S (Se) system of the composite flux is 2-5:1-10; the molar ratio of Ba to ZnS (ZnSe) in the Ba-ZnS (ZnSe) system is 1-4:1-10; the molar ratio of Ba to GaS (GaSe) in the Ba-GaS (GaSe) system is 2-5:1-6; the molar ratio of Ba to Ga2S3 (Ga2Se3) in the Ba-Ga2S3 (Ga2Se3) system is 2-5:1-4; BaS (BaSe) -S (S e) The molar ratio of BaS (BaSe) to S (Se) in the system is 2-7:1-6; the molar ratio of BaS2 (BaSe2) to S (Se) in the BaS2 (BaSe2)-S (Se) system is 2-7:1-4; the molar ratio of BaS3 (BaSe3) to S (Se) in the BaS3 (BaSe3)-S (Se) system is 2-7:1-3; the molar ratio of ZnS (ZnSe) to S (Se) in the ZnS (ZnSe)-S (Se) system is 2-7:1-1 0; the molar ratio of ZnS to Ga in the Zn-Ga system is 0.5-7:1-6; the molar ratio of Zn to GaS (GaSe) in the Zn-GaS (GaSe) system is 0.5-7:1-4; the molar ratio of ZnS (ZnSe) to Ga2S3 (Ga2Se3) in the ZnS (ZnSe)-Ga2S3 (Ga2Se3) system is 0.5-7:1-3; the molar ratio of Ga to S (Se) in the Ga-S (Se) system is 2-5:1-10; Ga-GaS (GaSe) The molar ratio of Ga to GaS (GaSe) in the system is 2-5:1-6; the molar ratio of Ga to Ga2S3 (Ga2Se3) in the Ga-Ga2S3 (Ga2Se3) system is 2-5:1-4; the molar ratio of GaS (GaSe) to S (Se) in the GaS (GaSe)-S (Se) system is 2-5:1-4:1-10; the molar ratio of Ga2S3 (Ga2Se3) to S (Se) in the Ga2S3 (Ga2Se3)-S (Se) system is 2-5:1-10.

10. The use of the barium gallium zinc chalcogenide nonlinear optical crystal according to claim 4, characterized in that: The sulfide gallium zinc barium nonlinear optical crystal is used for preparing a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.

Images