Compound barium arsenic silicon and barium arsenic silicon photoelectric functional crystal and preparation method and application

Abstract

The present application relates to a kind of compound arsenic silicon barium and arsenic silicon barium photoelectric functional crystal and preparation method and application, the molecular formula of the compound is Ba2Si3As6, molecular weight is 808.47 g / mol, the molecular formula of the crystal is Ba2Si3As6, molecular weight is 808.47 g / mol, with asymmetric center, crystallize in orthorhombic Pna 21 space group, cell parameters are: a=9.9980 (14) Å, b=9.4084 (14) Å, c=12.1981 (17) Å, Z=4, V=1147.4 (3) Å 3 , high-temperature melt method, chemical vapor transport method, flux method or crucible drop method are made into crystal. The crystal has strong laser damage resistance, large second-order nonlinear optical effect, wide infrared transmission range and excellent photoelectric response characteristics, while having larger hardness, good mechanical properties, not easy to break and deliquesce, easy to process and save and other advantages, can be widely used to manufacture a series of high-performance photoelectric functional devices and equipment of high-efficiency solar cell, infrared nonlinear optical device and infrared photoelectric system.

Description

Technical Field

[0001] This invention belongs to the field of preparation of optoelectronic functional crystal materials, specifically relating to a compound barium arsenide silicon (Ba2Si3As6) and barium arsenide silicon optoelectronic functional crystals, their preparation methods and applications. Background Technology

[0002] Optoelectronic functional crystals are the core physical carriers for realizing photon energy and frequency conversion, and they have important applications in strategic fields such as photoelectric conversion (e.g., photovoltaic power generation in solar cells) and optical frequency conversion (e.g., mid- and far-infrared laser technology). Currently, next-generation advanced optoelectronic devices are evolving towards multifunctionality and high integration, which places extremely high demands on the comprehensive performance of underlying semiconductor materials. In the field of optical frequency conversion (infrared nonlinear optics), phosphorus-based materials such as ZnGeP2 and CdSiP2 perform excellently in the 3-5 μm wavelength range, but existing commercial materials face significant limitations in the long-wave infrared region with wavelengths greater than 10 μm: for example, chalcogenides such as AgGaS2 have low laser damage thresholds, while ZnGeP2 has limited infrared transmission range, making it difficult to meet the application requirements of high-power mid- and far-infrared laser systems. Meanwhile, in the field of photoelectric conversion (solar cells), breaking through the efficiency limits of existing photovoltaic devices also highly depends on the development of new semiconductor materials, which requires materials to simultaneously possess suitable bandgap widths, high light absorption coefficients, and excellent carrier transport characteristics. Therefore, developing multifunctional semiconductor optoelectronic materials that combine wide infrared transmission, high frequency doubling effect, and high photoelectric response has become an important challenge in the field of semiconductor materials.

[0003] Among numerous compound systems, arsenic compounds, particularly phosphorus compounds, exhibit great potential to simultaneously meet the aforementioned two major optoelectronic application requirements. This is because arsenic compounds possess unique electronic structures and suitable covalent bond characteristics: on the one hand, compared to isomorphic phosphides, arsenic compounds have greater hyperpolarizability, typically exhibiting larger nonlinear optical coefficients and wider infrared transmission ranges; on the other hand, their suitable bandgap characteristics and superior photon absorption capabilities theoretically make them ideal as key absorber layer materials for high-efficiency solar cells. However, currently known arsenic compound materials often face problems such as difficulty in precisely controlling the bandgap, low thermal conductivity, or difficulties in large-size crystal growth, which have become technical bottlenecks limiting their large-scale application in practical devices. To address this, this patent focuses on the exploration and development of novel arsenic compound materials. Through structural design, experimental synthesis, and innovative crystal growth processes, a novel ternary arsenic compound—barium arsenide—with excellent comprehensive performance has been successfully created. This material not only overcomes the limitations of traditional arsenides, such as low thermal conductivity and narrow band gap, but also, with its wide infrared transmission range, large second-order nonlinear optical effect, and excellent photoelectric response characteristics, it has become a highly promising key basic material. It can be used to manufacture a series of high-performance optoelectronic functional devices and equipment, such as infrared nonlinear optical devices (e.g., laser frequency conversion crystals and lasers), solar cells, and infrared optoelectronic systems (e.g., communication and guidance devices), providing important material support for the development of mid- and far-infrared lasers and new clean energy technologies. Summary of the Invention

[0004] The purpose of this invention is to provide a compound, barium arsenide silicon, with the molecular formula Ba₂Si₃As₆, a molecular weight of 808.47 g / mol, an asymmetric center, and crystallization in an orthorhombic crystal system. Pna Space group 21 was prepared using a high-temperature solid-state reaction method.

[0005] Another objective of this invention is to provide a barium arsenide silicon optoelectronic functional crystal with the molecular formula Ba₂Si₃As₆, a molecular weight of 808.47 g / mol, an asymmetric center, and crystallization in an orthorhombic crystal system. Pna Space group 21, cell parameters: a = 9.9980(14) Å, b = 9.4084(14) Å, c = 12.1981(17) Å, Z = 4, V = 1147.4(3) Å 3 .

[0006] Another objective of this invention is to provide a method for preparing a barium arsenide-silicon-barium Ba2Si3As6 optoelectronic functional crystal.

[0007] Another objective of this invention is to provide the use of the arsenic-silicon-barium Ba2Si3As6 optoelectronic functional crystal.

[0008] The present invention discloses a compound, barium arsenide silicon, with the molecular formula Ba₂Si₃As₆ and a molecular weight of 808.47 g / mol. This compound possesses an asymmetric center and crystallizes in an orthorhombic crystal system. Pna Space group 21 was prepared using a high-temperature solid-state reaction method.

[0009] The preparation method of the compound barium arsenide silicon adopts a high-temperature solid-state method, and the specific operation is carried out according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melt-sealed, wherein the Ba source material is elemental Ba, BaCl2, BaBr2 or BaI2; b. Place the sealed quartz tube from step a into a temperature-controlled muffle furnace, heat it to 800-950 ℃ at a rate of 20-30 ℃ / h, carry out a solid-phase reaction for 40-80 h, then cool it to 650 ℃ at a rate of 15-25 ℃ / h and turn off the furnace. After it cools naturally to room temperature, take out the sample, crush and grind it to obtain a powdered pure arsenic silicon barium sample.

[0010] A barium arsenide-silicon optoelectronic functional crystal, with the molecular formula Ba₂Si₃As₆ and a molecular weight of 808.47 g / mol, possesses an asymmetric center and crystallizes in an orthorhombic crystal system. Pna Space group 21, cell parameters: a = 9.9980(14) Å, b = 9.4084(14) Å, c = 12.1981(17) Å, Z = 4, V = 1147.4(3) Å 3 .

[0011] The preparation method of the aforementioned barium silicon arsenide optoelectronic functional crystal employs a high-temperature melt method, a chemical vapor transport method, a flux method, or a crucible lowering method to grow the crystal. The high-temperature melt method for growing barium silicon optoelectronic functional crystals is carried out according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Place the pure arsenic-silicon-barium sample obtained in step a into a quartz tube and evacuate to 10°C. -3 Pa was encapsulated in an oxyhydrogen flame and placed in a muffle furnace. The temperature was increased to 850-1000 ℃ at a rate of 13-24 ℃ / h and held at that temperature for 80-100 h. The temperature was then slowly reduced to 680 ℃ at a rate of 3-12 ℃ / h, and the furnace was turned off. After the temperature was allowed to cool naturally to room temperature, the quartz tube was cut open to obtain a black blocky barium arsenide silicon Ba2Si3As6 optoelectronic functional crystal. The chemical vapor transport method for growing barium arsenide-silicon optoelectronic functional crystals is performed according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Weigh the pure arsenic-silicon-barium sample obtained in step a and the transport agent iodine at a ratio of 1:0.06-0.12, mix thoroughly, and place into a quartz tube. Evacuate to 10°C. -3 Pa is encapsulated with an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 650-700 ℃ and a low temperature zone of 500-600 ℃. The growth of barium arsenide-silicon crystal is carried out through a horizontal or vertical gradient temperature field. The temperature is simultaneously raised to 650-700 ℃ in the high temperature zone and 500-600 ℃ in the low temperature zone at a rate of 24-32 ℃ / h. The growth cycle is 20-30 days. After the growth is completed, the temperature is slowly reduced to 400 ℃ at a rate of 10-16 ℃ / h and the tube furnace is turned off. After natural cooling to room temperature, the quartz tube is cut open to obtain black blocky barium arsenide-silicon-barium Ba2Si3As6 optoelectronic functional crystal at the low temperature end. The flux method for growing barium silicon photoelectric functional crystals is performed according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Mix the pure arsenic-silicon-barium sample obtained in step a with the flux at a mass ratio of 1:1-5, pack the mixture into a quartz tube, and evacuate to 10°C. -3 -10 -5 Pa was melted and sealed with an oxyhydrogen flame and placed in a crystal growth furnace. The temperature was increased to 650-750 ℃ ​​at a rate of 20-30 ℃ / h, and the reaction was maintained at this temperature for 70-100 h. Then, the temperature was reduced to 550 ℃ at a rate of 5-12 ℃ / h, and the tube growth furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black, blocky arsenic silicon barium Ba2Si3As6 optoelectronic functional crystal. The fluxing agent was As, BaCl2, BaBr2, BaI2, etc.

[0012] The crucible lowering method for growing barium silicon optoelectronic functional crystals is performed according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Place the pure arsenic-silicon-barium sample obtained in step a into a Φ25 mm × 240 mm quartz tube and evacuate to 10 °C. -3After Pa, the material is encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature is increased to 850-950 ℃ at a rate of 15-30 ℃ / h and held at that temperature for 50-80 h until the raw material is completely melted. Then, the crucible lowering furnace is vertically lowered at a rate of 0.1-2.0 mm / h to grow barium arsenide-silicon crystals. The cycle is 18-28 days. After the crystal growth is completed, the temperature is lowered to room temperature at a rate of 30-45 ℃ / h to obtain black blocky barium arsenide-silicon-barium Ba2Si3As6 optoelectronic functional crystals.

[0013] The application of the arsenic-silicon-barium optoelectronic functional crystal in the fabrication of infrared nonlinear optical devices, solar cells, and infrared optoelectronic systems.

[0014] The infrared nonlinear optical device solar cell is a high-performance optoelectronic functional device and equipment for communication and guidance.

[0015] The infrared optoelectronic system is a high-performance optoelectronic functional device and equipment for laser frequency conversion crystals and lasers.

[0016] The compound arsenic-silicon-barium Ba2Si3As6 of this invention is prepared according to the following chemical reaction formula: (1) 2Ba+3Si+6As=Ba2Si3As6; (2) 2BaCl2+3Si+6As=Ba2Si3As6+Cl2; (3) 2BaBr2+3Si+6As=Ba2Si3As6+Br2; (4) 2BaI2+3Si+6As=Ba2Si3As6+I2.

[0017] The preparation method of the arsenic silicon barium optoelectronic functional crystal described in this invention can obtain Ba2Si3As6 optoelectronic functional crystals with a size in the centimeter range; by using a large-size crucible and extending the growth time, Ba2Si3As6 optoelectronic functional crystals with a correspondingly larger size can be obtained.

[0018] The arsenic-silicon-barium (Ba2Si3As6) optoelectronic functional crystal described in this invention has advantages such as low cost and easy acquisition of large-size crystals. The obtained arsenic-silicon-barium (Ba2Si3As6) optoelectronic functional crystal and devices also have advantages such as strong resistance to laser damage, large second-order nonlinear optical effect, wide transmission band, wide arsenide optical bandgap, excellent photoelectric response characteristics, high hardness, good mechanical properties, resistance to breakage and deliquescence, and ease of processing and storage. This crystal can be used to manufacture a series of high-performance optoelectronic functional devices and equipment, such as infrared nonlinear optical devices (e.g., laser frequency conversion crystals, lasers), solar cells, and infrared optoelectronic systems (e.g., communication and guidance devices).

[0019] Based on the crystallographic data of the crystal, the crystal blank is oriented, and the crystal is cut according to the required angle, thickness and cross-sectional size. The light-transmitting surface of the crystal is polished, and it can then be used as an optoelectronic functional device. Attached Figure Description

[0020] Figure 1 This invention presents the photoelectric functional crystal structure of arsenic-silicon-barium Ba2Si3As6. It demonstrates that in this structure, all Si atoms are tetrahedral coordinated with As atoms, forming [SiAs4] units; while Ba atoms exhibit two different coordination forms, respectively constituting [Ba(1)As... 10 [SiAs4] tetrahedra and [Ba(2)As7] polyhedra (a); subsequently, three [SiAs4] tetrahedra are interconnected through corner sharing and edge sharing to form two different orientations (labeled A and B) of [Si3As9] trimers; these trimers further construct one-dimensional infinitely extending [Si-As] by sharing As atoms and As-As bonds. ∞ Chain (b, c); Meanwhile, [Ba(1)As 10 Through the sharing of As atoms, a three-dimensional [Ba(1)-As] structure is formed that runs through the entire structure. ∞ The framework consists of [Ba(2)As7], which exists in isolation and is distributed within the bc plane (d, e); the polyhedra of both types of Ba fill the one-dimensional [Si-As]. ∞ Within the three-dimensional framework channels constructed by the chain, the anionic skeleton charge is effectively balanced, thereby constructing a complete three-dimensional Ba2Si3As6 crystal structure (f). Figure 2 This is a comparison diagram of the experimental and theoretical values ​​of polycrystalline powder X-ray diffraction of the arsenic silicon barium Ba2Si3As6 crystal of the present invention. Figure 3 This is a schematic diagram of the second-order nonlinear optical effect signal of the arsenic-silicon-barium Ba2Si3As6 crystal of the present invention. In the particle size range of 180-212μm, Ba2Si3As6 exhibits a large second-order nonlinear optical coefficient, which is about 1.2 times that of the reference ZnGeP2. Figure 4 This is a schematic diagram of the working principle of the infrared nonlinear optical device of the present invention, wherein 1 is a laser, 2 is a convex lens, 3 is a Ba2Si3As6 optoelectronic functional crystal after crystal post-processing and optical processing, 4 is a prism, and 5 is a filter. Detailed Implementation

[0021] Any feature disclosed in this specification, unless specifically stated otherwise, may be replaced by other equivalent or similar features. Unless specifically stated otherwise, each feature is merely one example of a series of equivalent or similar features. The descriptions are merely to aid in understanding the invention and should not be construed as limiting the invention.

[0022] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments. Example 1

[0023] The compound Ba2Si3As6 was prepared by a high-temperature solid-state reaction method using the chemical reaction formula 2Ba + 3Si + 6As = Ba2Si3As6. The specific operation is as follows: 1.699 g of elemental Ba, 0.521 g of elemental Si, and 2.780 g of elemental As were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to a vacuum level of 10 using a vacuum pump. -3 -10 -5 After Pa, perform melt sealing; The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 930 °C at a rate of 22 °C / h for a solid-phase reaction for 60 h. Then, it was cooled to 650 °C at a rate of 18 °C / h and the furnace was turned off. After the sample was allowed to cool naturally to room temperature, it was removed and crushed and ground to obtain a powdered Ba2Si3As6 compound. Example 2

[0024] The compound Ba2Si3As6 was prepared by a high-temperature solid-state reaction method using the chemical reaction formula 2BaCl2 + 3Si + 6As = Ba2Si3As6 + Cl2. The specific operation is carried out according to the following steps: 2.191 g of BaCl2, 0.443 g of elemental Si, and 2.365 g of elemental As were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to a vacuum level of 10 using a vacuum pump. -3 -10 -5 After Pa, perform melt sealing; The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 900 °C at a rate of 25 °C / h for a solid-phase reaction for 80 h. The furnace was then cooled to 650 °C at a rate of 20 °C / h and the furnace was turned off. After the sample was allowed to cool naturally to room temperature, it was removed and crushed and ground to obtain a powdered Ba2Si3As6 compound. Example 3

[0025] The compound Ba2Si3As6 was prepared by a high-temperature solid-state reaction method using the chemical reaction formula 2BaBr2 + 3Si + 6As = Ba2Si3As6 + Br2. The specific operation is carried out according to the following steps: 2.634 g of BaBr2, 0.373 g of elemental Si, and 1.992 g of elemental As were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to a vacuum level of 10 using a vacuum pump. -3-10 -5 After Pa, perform melt sealing; The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 850 °C at a rate of 27 °C / h for a solid-phase reaction for 50 h. Then, it was cooled to 650 °C at a rate of 23 °C / h and the furnace was turned off. After the sample was allowed to cool naturally to room temperature, it was removed and crushed and ground to obtain a powdered Ba2Si3As6 compound. Example 4

[0026] The compound Ba2Si3As6 was prepared by a high-temperature solid-state reaction method using the chemical reaction formula 2BaI2 + 3Si + 6As = Ba2Si3As6 + I2. The specific operation is carried out according to the following steps: 2.972 g of BaI₂, 0.320 g of elemental Si, and 1.708 g of elemental As were mixed thoroughly and placed into a 25 mm × 240 mm quartz glass tube. The quartz tube was then evacuated to a vacuum level of 10 using a vacuum pump. -3 -10 -5 After Pa, perform melt sealing; The sealed quartz tube was placed in a temperature-controlled muffle furnace and heated to 800 °C at a rate of 30 °C / h for a solid-phase reaction for 75 h. Then, it was cooled to 650 °C at a rate of 25 °C / h and the furnace was turned off. After the sample was allowed to cool naturally to room temperature, it was removed and crushed and ground to obtain a powdered Ba2Si3As6 compound. Example 5

[0027] The high-temperature melt method for growing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 1 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 980 ℃ at a rate of 16 ℃ / h, held at that temperature for 80 h, and then slowly cooled to 680 ℃ at a rate of 6 ℃ / h before the furnace was turned off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ3.8mm×3.2 mm. Example 6

[0028] The high-temperature melt method for growing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 2 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 950 °C at a rate of 19 °C / h, held at that temperature for 90 h, and then slowly cooled to 680 °C at a rate of 8 °C / h before the furnace was turned off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ4.5 mm × 3.6 mm. Example 7

[0029] The high-temperature melt method for growing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 3 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 920 °C at a rate of 22 °C / h, held at that temperature for 95 h, and then slowly cooled to 680 °C at a rate of 10 °C / h before the furnace was turned off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ5.0 mm × 4.5 mm. Example 8

[0030] The high-temperature melt method for growing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 4 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 Pa was encapsulated in an oxyhydrogen flame, placed in a muffle furnace, heated to 880 ℃ at a rate of 24 ℃ / h, held at that temperature for 100 h, and then slowly cooled to 680 ℃ at a rate of 12 ℃ / h before the furnace was turned off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ4.8 mm × 3.6 mm. Example 9

[0031] The chemical vapor transport method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder obtained in Example 1 and elemental iodine were weighed at a ratio of 1:0.06 and placed into a quartz tube with a diameter of 25 mm × 240 mm. The tube was then evacuated to 10 °C. -3The sample was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 700 °C and a low temperature zone of 600 °C. Crystal growth of Ba2Si3As6 was carried out through a horizontal gradient temperature field. The temperature was simultaneously increased to 700 °C in the high temperature zone and 600 °C in the low temperature zone at a rate of 25 °C / h, with a growth cycle of 24 days. After the growth was completed, the temperature was slowly reduced to 400 °C at a rate of 12 °C / h and the tube furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open, and a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ5.8 mm × 4.6 mm was obtained at the low temperature end. Example 10

[0032] The chemical vapor transport method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder obtained in Example 2 and elemental iodine were weighed at a ratio of 1:0.08 and placed into a quartz tube with a diameter of 25 mm × 240 mm. The tube was then evacuated to 10 °C. -3 The quartz tube was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 680 °C and a low temperature zone of 590 °C. Crystal growth of Ba2Si3As6 was carried out through a horizontal gradient temperature field. The temperature was simultaneously increased to 680 °C in the high temperature zone and 590 °C in the low temperature zone at a rate of 27 °C / h, with a growth cycle of 20 days. After the growth was completed, the temperature was slowly reduced to 400 °C at a rate of 15 °C / h and the tube furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open, and a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ4.4 mm × 4.0 mm was obtained at the low temperature end. Example 11

[0033] The chemical vapor transport method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder obtained in Example 3 and elemental iodine were weighed at a ratio of 1:0.1 and placed into a quartz tube with a diameter of 25 mm × 240 mm. The tube was then evacuated to 10 °C. -3 The quartz tube was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 660 °C and a low temperature zone of 540 °C. Crystal growth of Ba2Si3As6 was carried out through a horizontal gradient temperature field. The temperature was simultaneously increased to 660 °C in the high temperature zone and 540 °C in the low temperature zone at a rate of 30 °C / h, with a growth cycle of 28 days. After the growth was completed, the temperature was slowly reduced to 400 °C at a rate of 13 °C / h and the tube furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open, and a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ6.4 mm × 5.6 mm was obtained at the low temperature end. Example 12

[0034] The chemical vapor transport method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder obtained in Example 4 was weighed together with elemental iodine at a ratio of 1:0.12 and placed into a quartz tube with a diameter of 25 mm × 240 mm. The tube was then evacuated to a vacuum of 1000 mm. -3 The quartz tube was encapsulated in an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 700 °C and a low temperature zone of 560 °C. Crystal growth of Ba2Si3As6 was carried out through a horizontal gradient temperature field. The temperature was simultaneously increased to 700 °C in the high temperature zone and 560 °C in the low temperature zone at a rate of 24 °C / h, with a growth cycle of 23 days. After the growth was completed, the temperature was slowly reduced to 400 °C at a rate of 16 °C / h and the tube furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open, and a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ7.2 mm × 6.3 mm was obtained at the low temperature end. Example 13

[0035] The flux growth method for preparing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder obtained in Example 1 was mixed with elemental As flux at a mass ratio of 1:1 and then packed into a 25 mm × 240 mm quartz tube. The mixture was then evacuated to 10 °C. -3 -10 -5 The quartz tube was melted and sealed with an oxyhydrogen flame and then placed in a crystal growth furnace. The temperature was increased to 750 °C at a rate of 22 °C / h and kept at a constant temperature for 80 h. The temperature was then reduced to 550 °C at a rate of 8 °C / h and the tube growth furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ5.0 mm × 4.5 mm. Example 14

[0036] The flux growth method for preparing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder obtained in Example 2 was mixed with elemental As flux at a mass ratio of 1:2 and then packed into a 25 mm × 240 mm quartz tube. The mixture was then evacuated to 10 °C. -3 -10 -5 The quartz tube was melted and sealed with an oxyhydrogen flame and then placed in a crystal growth furnace. The temperature was increased to 720 °C at a rate of 25 °C / h and kept at a constant temperature for 90 h. The temperature was then reduced to 550 °C at a rate of 5 °C / h and the tube growth furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ6.6 mm × 5.5 mm. Example 15

[0037] The flux growth method for preparing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder obtained in Example 3 was mixed with the flux BaCl2 at a mass ratio of 1:3 and then packed into a 25 mm × 240 mm quartz tube. The tube was then evacuated to 10 °C. -3 -10 -5 Pa was melted and sealed with an oxyhydrogen flame and placed in a crystal growth furnace. The temperature was increased to 700 °C at a rate of 27 °C / h and kept at a constant temperature for 100 h. Then the temperature was reduced to 550 °C at a rate of 10 °C / h and the tube growth furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ4.2 mm × 3.3 mm. Example 16

[0038] The flux growth method for preparing Ba2Si3As6 optoelectronic functional crystals is carried out according to the following steps: The pure Ba2Si3As6 powder obtained in Example 4 was mixed with flux BaI2 at a mass ratio of 1:4 and then packed into a 25 mm × 240 mm quartz tube. The tube was then evacuated to 10 °C. -3 -10 -5 Pa was melted and sealed with an oxyhydrogen flame and placed in a crystal growth furnace. The temperature was increased to 660 °C at a rate of 30 °C / h and kept at a constant temperature for 75 h. Then the temperature was reduced to 550 °C at a rate of 6 °C / h and the tube growth furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ4.8 mm × 3.5 mm. Example 17

[0039] The crucible lowering method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 1 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 950 °C at a rate of 15 °C / h and held at that temperature for 70 h until the raw material was completely melted. Then, the crucible lowering furnace was vertically lowered at a rate of 0.5 mm / h to grow barium arsenide-silicon crystals for 25 days. After the crystal growth was completed, the temperature was lowered to room temperature at a rate of 30 °C / h to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ6.6 mm × 4.5 mm. Example 18

[0040] The crucible lowering method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 2 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 920 °C at a rate of 20 °C / h and held at that temperature for 60 h until the raw material was completely melted. Then, the crucible lowering furnace was vertically lowered at a rate of 1.0 mm / h to grow barium arsenide-silicon crystals for 22 days. After the crystal growth was completed, the temperature was lowered to room temperature at a rate of 35 °C / h to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ5.9 mm × 4.3 mm. Example 19

[0041] The crucible lowering method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 3 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 880 °C at a rate of 25 °C / h and held at that temperature for 80 h until the raw material was completely melted. Then, the crucible lowering furnace was vertically lowered at a rate of 1.5 mm / h to grow barium arsenide-silicon crystals for 27 days. After the crystal growth was completed, the temperature was lowered to room temperature at a rate of 40 °C / h to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ7.8 mm × 6.5 mm. Example 20

[0042] The crucible lowering method for growing Ba2Si3As6 optoelectronic functional crystals is performed according to the following steps: The pure Ba2Si3As6 powder sample obtained in Example 4 was placed into a 25 mm × 240 mm quartz tube and evacuated to 10 °C. -3 After Pa, the material was encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature was increased to 850 °C at a rate of 30 °C / h and held at that temperature for 65 h until the raw material was completely melted. Then, the crucible lowering furnace was vertically lowered at a rate of 2.0 mm / h to grow barium arsenide silicon crystals. The cycle was 23 days. After the crystal growth was completed, the temperature was lowered to room temperature at a rate of 45 °C / h to obtain a black blocky Ba2Si3As6 optoelectronic functional crystal with dimensions of Φ5.0 mm × 3.7 mm. Example 21

[0043] Place any of the Ba2Si3As6 optoelectronic functional crystals obtained in Examples 5-20 into Figure 4The device shown is located at position 3. At room temperature, using a Q-switched Ho:Tm:Cr:YAG laser as the light source, with infrared light of 2090 nm incident on the light source, the output wavelength is 1045 nm frequency-doubled light. Under the same conditions, the output laser intensity is 1.2 times that of commercial material ZnGeP2. Example 22

[0044] Take any one of the Ba2Si3As6 optoelectronic functional crystals obtained in Examples 5-20, and follow the instructions... Figure 4 As shown, the components are arranged at position 3, where 1 is a laser, 2 is a convex lens, 3 is a Ba2Si3As6 optoelectronic functional crystal, 4 is a prism, and 5 is a filter. The laser beam emitted by the laser 1 passes through the convex lens 2 and enters the Ba2Si3As6 crystal 3. The resulting outgoing laser beam passes through the prism 4 and the filter 5 to obtain the desired laser beam. Example 23

[0045] Using any one of the Ba2Si3As6 polycrystalline powders or crystal fragments obtained in Examples 1-20 as the target material, a Ba2Si3As6 crystalline thin film is deposited on a transparent conductive glass (FTO or ITO) substrate as a light absorption layer using magnetron sputtering technology, and a metal back electrode is further deposited to form a Ba2Si3As6-based thin-film solar cell. Example 24

[0046] Using any of the Ba2Si3As6 polycrystalline powders or crystal fragments obtained in Examples 1-20 as evaporation source materials, a Ba2Si3As6 light-absorbing layer is prepared on a semiconductor substrate using high-vacuum electron beam evaporation or thermal evaporation processes, and then assembled into a solar cell device with a heterojunction structure. Example 25

[0047] Using any of the Ba2Si3As6 polycrystalline powders or crystal fragments obtained in Examples 1-20 as the target material, a Ba2Si3As6 thin film is epitaxially grown on a flexible polymer (such as a PI film) or flexible metal foil substrate using pulsed laser deposition (PLD) technology to prepare a flexible thin-film solar cell. Example 26

[0048] Using any of the Ba2Si3As6 polycrystalline powders or crystal fragments obtained in Examples 1-20 as the target material, a physical vapor deposition process is used to grow them on the back of a wide bandgap solar cell (such as a silicon-based cell or a wide bandgap perovskite cell) to construct a tandem tandem solar cell, with the Ba2Si3As6 layer serving as the bottom cell absorption layer for absorbing long-wavelength spectra. Example 27

[0049] Any of the Ba2Si3As6 optoelectronic functional crystals obtained in Examples 5-20 are directionally cut and mechanically and chemically polished to form complete single-crystal wafers of a specific thickness, which are directly used as the semiconductor light-absorbing layer of a Schottky junction solar cell, and a transparent conductive film and metal grid electrodes are deposited on its surface.

[0050] Devices made using the Ba2Si3As6 optoelectronic functional crystal of this invention can be a series of high-performance optoelectronic functional devices and equipment, such as infrared nonlinear optical devices (e.g., laser frequency conversion crystals, lasers, frequency multipliers, up / down frequency converters, optical parametric oscillators and optical parametric amplifiers), solar cells, and infrared optoelectronic systems (e.g., infrared communication and laser guidance devices).

Claims

1. A compound, barium arsenide, characterized in that... The compound has the molecular formula Ba₂Si₃As₆, a molecular weight of 808.47 g / mol, an asymmetric center, and crystallizes in an orthorhombic crystal system. Pna Space group 21 was prepared using a high-temperature solid-state reaction method.

2. The method for preparing the compound barium arsenide according to claim 1, characterized in that... The high-temperature solid-state method is employed, and the specific operation is carried out according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melt-sealed, wherein the Ba source material is elemental Ba, BaCl2, BaBr2 or BaI2; b. Place the sealed quartz tube from step a into a temperature-controlled muffle furnace, heat it to 800-950 ℃ at a rate of 20-30 ℃ / h, carry out a solid-phase reaction for 40-80 h, then cool it to 650 ℃ at a rate of 15-25 ℃ / h and turn off the furnace. After it cools naturally to room temperature, take out the sample, crush and grind it to obtain a powdered pure arsenic silicon barium sample.

3. A barium arsenide silicon photoelectric functional crystal, characterized in that, The crystal has the molecular formula Ba₂Si₃As₆, a molecular weight of 808.47 g / mol, an asymmetric center, and crystallizes in an orthorhombic crystal system. Pna Space group 21, cell parameters: a = 9.9980(14) Å, b = 9.4084(14) Å, c = 12.1981(17) Å, Z = 4, V = 1147.4(3) Å 3 .

4. The method for preparing the arsenic-silicon-barium optoelectronic functional crystal according to claim 3, characterized in that... Crystals are grown using the high-temperature melt method, chemical vapor transport method, flux method, or crucible lowering method. The high-temperature melt method for growing barium silicon optoelectronic functional crystals is carried out according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Place the pure arsenic-silicon-barium sample obtained in step a into a quartz tube and evacuate to 10°C. -3 Pa was encapsulated in an oxyhydrogen flame and placed in a muffle furnace. The temperature was increased to 850-1000 ℃ at a rate of 13-24 ℃ / h and held at that temperature for 80-100 h. The temperature was then slowly reduced to 680 ℃ at a rate of 3-12 ℃ / h, and the furnace was turned off. After the temperature was allowed to cool naturally to room temperature, the quartz tube was cut open to obtain a black blocky barium arsenide silicon Ba2Si3As6 optoelectronic functional crystal. The chemical vapor transport method for growing barium arsenide-silicon optoelectronic functional crystals is performed according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Weigh the pure arsenic-silicon-barium sample obtained in step a and the transport agent iodine at a ratio of 1:0.06-0.12, mix thoroughly, and place into a quartz tube. Evacuate to 10°C. -3 Pa is encapsulated with an oxyhydrogen flame and placed in a tube furnace for chemical vapor transport at a high temperature zone of 650-700 ℃ and a low temperature zone of 500-600 ℃. The growth of barium arsenide-silicon crystal is carried out through a horizontal or vertical gradient temperature field. The temperature is simultaneously raised to 650-700 ℃ in the high temperature zone and 500-600 ℃ in the low temperature zone at a rate of 24-32 ℃ / h. The growth cycle is 20-30 days. After the growth is completed, the temperature is slowly reduced to 400 ℃ at a rate of 10-16 ℃ / h and the tube furnace is turned off. After natural cooling to room temperature, the quartz tube is cut open to obtain black blocky barium arsenide-silicon-barium Ba2Si3As6 optoelectronic functional crystal at the low temperature end. The flux method for growing barium silicon photoelectric functional crystals is performed according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Mix the pure arsenic-silicon-barium sample obtained in step a with the flux at a mass ratio of 1:1-5, pack the mixture into a quartz tube, and evacuate to 10°C. -3 -10 -5 Pa was melted and sealed with an oxyhydrogen flame and placed in a crystal growth furnace. The temperature was increased to 650-750 ℃ ​​at a rate of 20-30 ℃ / h, and the reaction was maintained at this temperature for 70-100 h. Then, the temperature was reduced to 550 ℃ at a rate of 5-12 ℃ / h, and the tube growth furnace was shut off. After natural cooling to room temperature, the quartz tube was cut open to obtain black blocky arsenic silicon barium Ba2Si3As6 optoelectronic functional crystals. The fluxes were As, BaCl2, BaBr2, and BaI2. The crucible lowering method for growing barium silicon optoelectronic functional crystals is performed according to the following steps: a. Mix the Ba source material, elemental Si, and elemental As evenly according to the molar ratio Ba∶Si∶As=2∶3∶6, and place the mixture into a Φ25 mm×240 mm quartz glass tube. Evacuate the quartz tube to a vacuum degree of 10 using a vacuum pump. -3 -10 -5 Pa is melted and sealed, then placed in a temperature-controlled muffle furnace and heated to 800-950 ℃ at a rate of 20-30 ℃ / h for solid-phase reaction for 40-80 h. The furnace is then turned off and allowed to cool naturally to room temperature before the sample is removed and crushed and ground to obtain a powdered pure arsenic silicon barium sample. The Ba source material is metallic elemental Ba, BaCl2, BaBr2 or BaI2. b. Place the pure arsenic-silicon-barium sample obtained in step a into a Φ25 mm × 240 mm quartz tube and evacuate to 10 °C. -3 After Pa, the material is encapsulated with an oxyhydrogen flame and placed in a crucible lowering furnace. The temperature is increased to 850-950 ℃ at a rate of 15-30 ℃ / h and held at that temperature for 50-80 h until the raw material is completely melted. Then, the crucible lowering furnace is vertically lowered at a rate of 0.1-2.0 mm / h to grow barium arsenide-silicon crystals. The cycle is 18-28 days. After the crystal growth is completed, the temperature is lowered to room temperature at a rate of 30-45 ℃ / h to obtain black blocky barium arsenide-silicon-barium Ba2Si3As6 optoelectronic functional crystals.

5. The use of the arsenic-silicon-barium optoelectronic functional crystal as described in claim 3 in the fabrication of infrared nonlinear optical devices, solar cells, and infrared optoelectronic systems.

6. The use as described in claim 5, characterized in that... The infrared nonlinear optical device solar cell is a high-performance optoelectronic functional device and equipment for communication and guidance.

7. The use as described in claim 5, characterized in that... The infrared optoelectronic system is a high-performance optoelectronic functional device and equipment for laser frequency conversion crystals and lasers.

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