Synthesis process of gamma-phase indium selenide

Abstract

The invention discloses a synthesis process of gamma-phase indium selenide, and relates to the technical field of indium selenide. Comprising two main steps of synthesizing In4Se3 powder and further preparing gamma-phase indium selenide. The method comprises the following steps: synthesizing In4Se3 powder from high-purity selenium powder and indium powder in a normal-pressure tubular synthesis furnace; and reacting the In4Se3 powder with selenium powder to obtain the high-purity gamma-phase indium selenide. By optimizing the raw material ratio, atmosphere protection, ball-milling mixing and resin carbon adsorption, introduction of impurities is effectively reduced, selenium volatilization is prevented, and the phase composition uniformity and purity of indium selenide are improved. The prepared gamma-phase indium selenide has excellent photoelectric properties and thermal stability, and can be widely applied to the fields of photoelectric conversion and thermoelectric materials.

Description

Technical Field

[0001] The invention relates to the technical field of indium selenide, in particular to a synthesis process of gamma-phase indium selenide. Background Art

[0002] Indium selenide (In2Se3) is an important wide bandgap semiconductor material with excellent photoelectric and thermoelectric properties. It is widely used in photovoltaic devices, thermoelectric materials, photodetectors, infrared optical devices, etc. Different crystalline phases of indium selenide (including α phase, β phase, γ phase and δ phase) are suitable for different practical applications due to their differences in crystal structure and physical and chemical properties.

[0003] Among them, γ-phase indium selenide has important value in the field of high-performance optoelectronic materials and thermoelectric conversion due to its specific energy band structure and thermal stability. The energy gap of γ-In2Se3 is about 1.9 eV. The crystal structure of indium selenide depends on the preparation method. For example, KJ Chang et al. pointed out in "Growth of single-phase In2Se3by using metal organicchemical vapor deposition with dual-source precursors" that γ-In2Se3 can be prepared from trimethyl indium (InMe3) and hydrogen selenide (H2Se) by organic metal chemical vapor deposition.

[0004] Chemical vapor deposition is a method of producing indium selenide thin films through a vapor phase reaction of selenium and indium compounds. This method can achieve the preparation of high-purity materials and is suitable for the growth of large-area thin films. However, this method has high requirements for equipment, a complex process, and is suitable for the preparation of thin films rather than powder materials.

[0005] In addition, there are still many problems in the synthesis of high-purity γ-phase indium selenide:

[0006] Selenium volatilization problem: Selenium is easy to volatilize under high temperature conditions, resulting in an imbalance in the stoichiometric ratio of selenium and indium during the reaction, which in turn affects the phase composition and purity of the product.

[0007] Subphase generation: The polycrystalline characteristics of indium selenide make it easy to generate other crystalline phases (such as α phase or δ phase) during the synthesis process, affecting the purity and material properties of the γ phase.

[0008] Impurity issues: The purity of selenium and indium materials may not be sufficient to meet the high purity requirements of semiconductor materials. Even raw materials with nominal high purity (such as 4N or 4.5N) may contain trace amounts of metal impurities (such as iron, copper, nickel, etc.) and non-metallic impurities (such as oxides or sulfides); selenium is easily oxidized to form selenium dioxide (SeO2) under high temperature conditions. These oxides may remain in the product during the reaction, forming selenium oxide impurities, which in turn affects the semiconductor performance of the product. Summary of the invention

[0009] Based on the above background, this method develops a simple, efficient, low-energy, high-purity, uniform phase composition and suitable for large-scale production of γ-phase indium selenide synthesis process, which has important scientific research and industrial value. This method solves the problems of impurity introduction and secondary phase generation, while ensuring the crystal phase purity and particle size uniformity of the product to meet the needs of high-performance optoelectronic materials.

[0010] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0011] A synthesis process of γ-phase indium selenide, characterized in that it comprises the following steps:

[0012] S1: Synthesis of In4Se3 powder:

[0013] Weigh 46.44-61.92 parts of selenium powder and 9-12 parts of indium powder according to mass proportions;

[0014] The selenium powder and indium powder are transferred to a normal pressure tubular synthesis furnace, and the air is replaced by an inert gas, and the gas flow rate is controlled to be 0.1-1 L / min;

[0015] The reaction product is crushed and treated by air flow milling to obtain In4Se3 powder with a particle size of 10-45 μm;

[0016] S2: Synthesis of γ-phase InSe:

[0017] Add 30.96-41.28 parts of selenium powder to the prepared In4Se3 powder, and mix by ball milling to obtain a mixed powder;

[0018] The mixed powder is transferred to a normal pressure tubular synthesis furnace, 2-6 parts of resin carbon are added, the air is replaced by inert gas, and the gas flow rate is controlled to be 0.1-1 L / min;

[0019] Cool naturally to room temperature, take out the reaction product, filter it, and obtain γ-phase indium selenide;

[0020] The method for preparing the resin carbon in step S2 is:

[0021] (1) preparing the aqueous phase: adding 1000-1200 parts of water by weight to a reaction container, heating to 60-70° C., adding 1-3 parts of gelatin, 1-3 parts of sodium chloride, and 0.01-0.05 parts of methylene blue solution, stirring until completely dissolved and mixed uniformly, to prepare the aqueous phase for use;

[0022] (2) preparing the oil phase: adding 30-50 parts by weight of divinylbenzene, 0.2-0.5 parts by weight of methacryl cage silsesquioxane (CAS: 204591-17-2), 0.02-0.3 parts by weight of 4-vinylbenzocyclobutene, 5-8 parts by weight of styrene, 20-30 parts by weight of paraffin wax, and 0.4-0.8 parts by weight of benzoyl peroxide into a reaction container, stirring until uniform, to prepare the oil phase for later use;

[0023] (3) Synthesizing white resin balls: slowly add the prepared oil phase to the water phase, stir, heat to 80-100°C, stir for 7-15 hours to form resin, filter, dry, put the resin into 1000-1200 parts of gasoline, stir at 80-100°C for 4-7 hours, filter, dry, and obtain microporous white resin balls;

[0024] (4) Resin carbonization: Take the microporous resin white ball of step (3) and put it into the carbonization furnace, introduce nitrogen at a rate of 70-80cm3 / min, increase the temperature to 500°C at a rate of 15°C / min, keep it warm for 20-30min, continue to increase the temperature to 700°C at a rate of 15°C / min, keep it warm for 5-10min, continue to increase the temperature to 800°C at a rate of 15°C / min, keep it warm for 5-10min, turn off the nitrogen and introduce water vapor, keep it warm for 60-100min, cool naturally, and obtain resin carbon.

[0025] Preferably, the purity of the selenium powder and indium powder is not less than 99.99%.

[0026] Preferably, the inert gas in S1 and S2 is selected from one of nitrogen, argon or helium.

[0027] Preferably, the S1 is heated in two stages:

[0028] In the first stage, the temperature is raised to 180-200°C at a rate of 1-3°C / min and kept constant for 3-5 hours to allow selenium and indium to react fully and inhibit selenium volatilization;

[0029] In the second stage, the temperature is raised to 440-460°C at a rate of 2-5°C / min and maintained at a constant temperature for 3-5 hours to completely convert free selenium into In4Se3.

[0030] Preferably, the ball milling mixing parameters in step S2 are:

[0031] Material to ball mass ratio: 1:3 to 1:5;

[0032] Ball milling time: 10-30 minutes;

[0033] Ball mill speed: 150-300 rpm;

[0034] Ball milling atmosphere: nitrogen or argon;

[0035] Ball mill type: planetary ball mill or horizontal drum ball mill.

[0036] Preferably, the heating reaction in step S2 is carried out in two stages:

[0037] In the first stage, the temperature is raised to 190-210°C at a rate of 1-3°C / min and kept constant for 1.5-2.5 hours to allow selenium to react with In4Se3;

[0038] In the second stage, the temperature is raised to 590-610°C at a heating rate of 2-5°C / min and maintained at a constant temperature for 3.5-4.5 hours to completely convert indium selenide into the γ phase.

[0039] Analysis of mechanism and technical effect:

[0040] 1. Structure and function of acryl cage silsesquioxane

[0041] Acryl cage silsesquioxane is a cage compound containing eight carbon-carbon double bonds. This structure makes it highly reactive and can be used as a super crosslinker.

[0042] Due to the presence of eight carbon-carbon double bonds, the propylene cage silsesquioxane can provide new cross-linking nodes, thereby optimizing the microporous structure of the resin carbon. This optimized microporous structure is more conducive to the adsorption of gas impurities and improves the adsorption performance of the material.

[0043] Technical effect: Through the cross-linking effect of propylene cage silsesquioxane, the microporous structure of the resin carbon is improved, which increases its ability to adsorb impurities, thereby facilitating the preparation of high-purity γ-phase indium selenide.

[0044] 2. Structure and function of benzocyclobutene functional group

[0045] Structural characteristics: 4-vinylbenzocyclobutene is a compound with a rigid structure. The benzocyclobutene functional group in its structure provides high strength and thermal stability.

[0046] Reinforcement: The rigid structure of 4-vinylbenzocyclobutene can improve the strength of the resin ball, which is crucial for the subsequent roasting process. During the roasting process, the resin ball is converted into resin carbon, which helps to maintain the strength of the carbon material.

[0047] Technical effect: By introducing 4-vinylbenzocyclobutene, the strength of resin carbon is significantly improved, which is particularly important for its application in high temperature and high pressure environments. At the same time, this also helps to improve the wear resistance and chemical corrosion resistance of resin carbon.

[0048] 3. Comprehensive analysis

[0049] Synergistic effect: The combined use of acryl cage-type silsesquioxane and benzocyclobutene functional groups can optimize the micropore structure and enhance the strength in the resin carbon material, thereby achieving better adsorption and mechanical properties.

[0050] Application areas: This composite material has broad application prospects in the fields of adsorbing impurities and preparing high-purity γ-phase indium selenide.

[0051] Technical Effects

[0052] Compared with the traditional process, the present invention effectively avoids the volatilization loss of selenium by heating the reaction in stages, ensuring the high purity and stability of indium selenide. The purity of the raw materials is controlled, and resin carbon is added for adsorption. The prepared γ-phase indium selenide product has the characteristics of high purity (>99.99%) and uniform phase composition, which significantly improves its photoelectric performance. DETAILED DESCRIPTION

[0053] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0054] The sources of the reagents used in the embodiments of the present invention can be purchased from the market unless otherwise specified. The purity of selenium powder and indium powder in this method is 99.99%. Selenium powder was purchased from Shanghai Ketuo Chemical Technology Co., Ltd.; indium powder was purchased from Hunan Zhongcai Shengte New Material Technology Co., Ltd.

[0055] The embodiment is detected by the following method:

[0056] X-ray diffraction (XRD) analysis

[0057] Purpose: To detect the crystal phase composition of the product and confirm the formation of γ-phase indium selenide and the content of the secondary phase.

[0058] Equipment: D / MAX 2500 X-ray diffractometer.

[0059] Parameters: Cu Kα radiation, scanning range 10°-80°, scanning rate 0.02° / s.

[0060] Example 1

[0061] A synthesis process of γ-phase indium selenide, characterized in that it comprises the following steps:

[0062] S1: Synthesis of In4Se3 powder:

[0063] Weigh 46.44 g of selenium powder and 9 g of indium powder;

[0064] The selenium powder and indium powder were transferred into a normal pressure tubular synthesis furnace, and the air was replaced by an inert gas, and the gas flow rate was controlled to be 0.3 L / min;

[0065] The reaction product is crushed and treated by air flow milling to obtain In4Se3 powder with a particle size of 10 to 45 μm.

[0066] S2: Synthesis of γ-phase InSe:

[0067] Add 30.96 g of selenium powder to the prepared In4Se3 powder, and mix by ball milling to obtain a mixed powder;

[0068] The mixed powder was transferred to a normal pressure tubular synthesis furnace, 2 g of resin carbon was added, and the air was replaced by inert gas, and the gas flow rate was controlled to be 0.3 L / min;

[0069] Naturally cool to room temperature, take out the reaction product, filter it, and obtain γ-phase indium selenide;

[0070] The method for preparing the resin carbon in step S2 is:

[0071] (1) preparing the aqueous phase: adding 1000 g of water to a reaction vessel, heating to 60° C., adding 1 g of gelatin, 1 g of sodium chloride, and 0.01 g of methylene blue solution, stirring until completely dissolved and mixed uniformly, to prepare the aqueous phase for use;

[0072] (2) preparing the oil phase: adding 30 g of divinylbenzene, 0.2 g of methyl acryloyl cage silsesquioxane (CAS: 204591-17-2), 0.02 g of 4-vinylbenzocyclobutene, 5 g of styrene, 20 g of paraffin wax, and 0.4 g of benzoyl peroxide into a reaction container, stirring until uniform, to prepare the oil phase for later use;

[0073] (3) Synthesizing white resin balls: slowly add the prepared oil phase to the water phase, stir, heat to 80°C, stir for 7 hours to form a resin, filter, dry, put the resin into 1000g gasoline, stir at 80°C for 4 hours, filter, dry, and obtain microporous white resin balls;

[0074] (4) Resin carbonization: Take the microporous resin white ball from step (3) and put it into the carbonization furnace at 70 cm 3 / min nitrogen gas was introduced, the temperature was raised to 500°C at a rate of 15°C / min, and kept warm for 20 min. The temperature was further raised to 700°C at a rate of 15°C / min, and kept warm for 5 min. The temperature was further raised to 800°C at a rate of 15°C / min, and kept warm for 5 min. The nitrogen gas was turned off and water vapor was introduced, and the temperature was kept warm for 60 min. The resin carbon was obtained by natural cooling.

[0075] The inert gas in S1 and S2 is selected from nitrogen.

[0076] The S1 performs heating reaction in two stages:

[0077] In the first stage, the temperature is raised to 180°C at a rate of 1°C / min and kept constant for 3 hours to allow selenium and indium to react fully and inhibit selenium volatilization;

[0078] In the second stage, the temperature is raised to 440°C at a heating rate of 2°C / min and maintained at this temperature for 3 hours to completely convert the free selenium into In4Se3.

[0079] The ball milling mixing parameters in step S2 are:

[0080] Material to ball mass ratio: 1:3;

[0081] Ball milling time: 10 minutes;

[0082] Ball milling speed: 150 rpm;

[0083] Ball milling atmosphere: nitrogen;

[0084] Ball mill type: planetary ball mill.

[0085] The heating reaction is carried out in two stages in step S2:

[0086] In the first stage, the temperature was raised to 190°C at a rate of 1°C / min and kept constant for 1.5 hours to allow selenium to react with In4Se3;

[0087] In the second stage, the temperature is raised to 590°C at a heating rate of 2°C / min and maintained at this temperature for 3.5 hours to completely convert indium selenide into the γ phase.

[0088] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 97.9% of the product indium selenide, and the diffraction peak intensity of the subphase accounted for 2.1%.

[0089] Example 2

[0090] A synthesis process of γ-phase indium selenide, characterized in that it comprises the following steps:

[0091] S1: Synthesis of In4Se3 powder:

[0092] Weigh 51.6 g of selenium powder and 10 g of indium powder;

[0093] The selenium powder and indium powder were transferred into a normal pressure tubular synthesis furnace, and the air was replaced by an inert gas, and the gas flow rate was controlled to be 0.6 L / min;

[0094] The reaction product is crushed and treated by air flow milling to obtain In4Se3 powder with a particle size of 10 to 45 μm;

[0095] S2: Synthesis of γ-phase InSe:

[0096] Add 34.4 g of selenium powder to the prepared In4Se3 powder, and mix by ball milling to obtain a mixed powder;

[0097] The mixed powder was transferred to a normal pressure tubular synthesis furnace, 4 g of resin carbon was added, and the air was replaced by inert gas, and the gas flow rate was controlled to be 0.5 L / min;

[0098] Cool naturally to room temperature, take out the reaction product, filter it, and obtain γ-phase indium selenide;

[0099] The method for preparing the resin carbon in step S2 is:

[0100] (1) preparing the aqueous phase: adding 1100 g of water to a reaction vessel, heating to 65° C., adding 2 g of gelatin, 2 g of sodium chloride, and 0.03 g of methylene blue solution, stirring until completely dissolved and mixed uniformly, to prepare the aqueous phase for use;

[0101] (2) preparing the oil phase: adding 40 g of divinylbenzene, 0.3 g of methyl acryloyl cage silsesquioxane (CAS: 204591-17-2), 0.1 g of 4-vinylbenzocyclobutene, 6 g of styrene, 25 g of paraffin wax, and 0.6 g of benzoyl peroxide into a reaction container, stirring until uniform, to prepare the oil phase for later use;

[0102] (3) Synthesizing white resin balls: slowly add the prepared oil phase to the water phase, stir, heat to 90°C, stir for 10 hours to form a resin, filter, dry, put the resin into 1100g gasoline, stir at 90°C for 5 hours, filter, dry, and obtain microporous resin balls;

[0103] (4) Resin carbonization: Take the microporous resin white ball from step (3) and put it into the carbonization furnace at 75 cm 3 / min nitrogen gas was introduced, the temperature was increased to 500°C at a rate of 15°C / min, and kept warm for 25 min. The temperature was further increased to 700°C at a rate of 15°C / min, and kept warm for 7 min. The temperature was further increased to 800°C at a rate of 15°C / min, and kept warm for 7 min. The nitrogen gas was turned off and water vapor was introduced, and the temperature was kept warm for 80 min. The mixture was cooled naturally to obtain resin carbon.

[0104] The inert gas in S1 and S2 is selected from nitrogen.

[0105] The S1 performs heating reaction in two stages:

[0106] In the first stage, the temperature is raised to 190°C at a rate of 2°C / min and kept constant for 4 hours to allow selenium and indium to react fully and inhibit selenium volatilization;

[0107] In the second stage, the temperature is raised to 450°C at a heating rate of 3°C / min and maintained at this temperature for 4 hours to completely convert free selenium into In4Se3.

[0108] The ball milling mixing parameters in step S2 are:

[0109] Material to ball mass ratio: 1:4;

[0110] Ball milling time: 20 minutes;

[0111] Ball milling speed: 200 rpm;

[0112] Ball milling atmosphere: nitrogen;

[0113] Ball mill type: planetary ball mill.

[0114] The heating reaction is carried out in two stages in step S2:

[0115] In the first stage, the temperature was raised to 200°C at a rate of 2°C / min and kept constant for 2 hours to allow selenium to react with In4Se3;

[0116] In the second stage, the temperature is raised to 600°C at a heating rate of 3°C / min and maintained at this temperature for 4 hours to completely convert indium selenide into the γ phase.

[0117] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 98.1% of the product indium selenide, and the diffraction peak intensity of the secondary phase accounted for 1.9%.

[0118] Example 3

[0119] A synthesis process of γ-phase indium selenide, characterized in that it comprises the following steps:

[0120] S1: Synthesis of In4Se3 powder:

[0121] Weigh 51.6 g of high-purity selenium powder and 10 g of indium powder;

[0122] The selenium powder and indium powder were transferred into a normal pressure tubular synthesis furnace, and the air was replaced by an inert gas, and the gas flow rate was controlled to be 0.8 L / min;

[0123] The reaction product is crushed and treated by air flow milling to obtain In4Se3 powder with a particle size of 10 to 45 μm;

[0124] S2: Synthesis of γ-phase InSe:

[0125] Add 34.4 g of selenium powder to the prepared In4Se3 powder and mix by ball milling;

[0126] The mixed powder was transferred to a normal pressure tubular synthesis furnace, 4 g of resin carbon was added, and the air was replaced by inert gas, and the gas flow rate was controlled to be 0.8 L / min;

[0127] Cool naturally to room temperature, take out the reaction product, filter it, and obtain γ-phase indium selenide;

[0128] The method for preparing the resin carbon in step S2 is:

[0129] (1) preparing the aqueous phase: adding 1100 g of water to a reaction vessel, heating to 65° C., adding 2 g of gelatin, 2 g of sodium chloride, and 0.03 g of methylene blue solution, stirring until completely dissolved and mixed uniformly, to prepare the aqueous phase for use;

[0130] (2) preparing the oil phase: adding 40 g of divinylbenzene, 0.4 g of methyl acryloyl cage silsesquioxane (CAS: 204591-17-2), 0.2 g of 4-vinylbenzocyclobutene, 7 g of styrene, 25 g of paraffin wax, and 0.6 g of benzoyl peroxide into a reaction container, stirring until uniform, to prepare the oil phase for later use;

[0131] (3) Synthesizing white resin balls: slowly add the prepared oil phase to the water phase, stir, heat to 90°C, stir for 12 hours to form a resin, filter, dry, put the resin into 1100g gasoline, stir at 90°C for 6 hours, filter, dry, and obtain microporous resin white balls;

[0132] (4) Resin carbonization: Take the microporous resin white ball from step (3) and put it into the carbonization furnace at 75 cm 3 / min, nitrogen was introduced, the temperature was increased to 500°C at a rate of 15°C / min, and kept warm for 25 min, then the temperature was further increased to 700°C at a rate of 15°C / min, and kept warm for 8 min, then the temperature was further increased to 800°C at a rate of 15°C / min, and kept warm for 8 min, then the nitrogen was turned off and water vapor was introduced, and the temperature was kept warm for 80 min. Then the mixture was cooled naturally to obtain resin carbon.

[0133] The inert gas in S1 and S2 is selected from nitrogen.

[0134] The S1 performs heating reaction in two stages:

[0135] In the first stage, the temperature is raised to 190°C at a rate of 2°C / min and kept constant for 4 hours to allow selenium and indium to react fully and inhibit selenium volatilization;

[0136] In the second stage, the temperature is raised to 450°C at a heating rate of 4°C / min and maintained at this temperature for 4 hours to completely convert free selenium into In4Se3.

[0137] The ball milling mixing parameters in step S2 are:

[0138] Material to ball mass ratio: 1:4;

[0139] Ball milling time: 20 minutes;

[0140] Ball milling speed: 250 rpm;

[0141] Ball milling atmosphere: nitrogen;

[0142] Ball mill type: planetary ball mill.

[0143] The heating reaction is carried out in two stages in step S2:

[0144] In the first stage, the temperature was raised to 200°C at a rate of 2°C / min and kept constant for 2 hours to allow selenium to react with In4Se3;

[0145] In the second stage, the temperature is raised to 500°C at a heating rate of 4°C / min and kept constant for 4 hours to completely convert indium selenide into the γ phase.

[0146] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 98.4% of the product indium selenide, and the diffraction peak intensity of the secondary phase accounted for 1.6%.

[0147] Example 4

[0148] A synthesis process of γ-phase indium selenide, characterized in that it comprises the following steps:

[0149] S1: Synthesis of In4Se3 powder:

[0150] Weigh 61.92 g of selenium powder and 12 g of indium powder;

[0151] The selenium powder and indium powder were transferred into a normal pressure tubular synthesis furnace, and the air was replaced by an inert gas, and the gas flow rate was controlled to be 1 L / min;

[0152] The reaction product is crushed and treated by air flow milling to obtain In4Se3 powder with a particle size of 10 to 45 μm;

[0153] S2: Synthesis of γ-phase InSe:

[0154] Add 41.28 g of selenium powder to the In4Se3 powder prepared above, and mix by ball milling to obtain a mixed powder;

[0155] The mixed powder was transferred to a normal pressure tubular synthesis furnace, 6 g of resin carbon was added, and the air was replaced by inert gas, and the gas flow rate was controlled to be 1 L / min;

[0156] Cool naturally to room temperature, take out the reaction product, filter it, and obtain γ-phase indium selenide;

[0157] The method for preparing the resin carbon in step S2 is:

[0158] (1) preparing the aqueous phase: adding 1200 g of water to a reaction vessel, heating to 70° C., adding 3 g of gelatin, 3 g of sodium chloride, and 0.05 g of methylene blue solution, stirring until completely dissolved and mixed uniformly, to prepare the aqueous phase for use;

[0159] (2) preparing the oil phase: adding 50 g of divinylbenzene, 0.5 g of methyl acryloyl cage silsesquioxane (CAS: 204591-17-2), 0.3 g of 4-vinylbenzocyclobutene, 8 g of styrene, 30 g of paraffin wax, and 0.8 g of benzoyl peroxide into a reaction container, stirring until uniform, to prepare the oil phase for later use;

[0160] (3) Synthesizing white resin balls: slowly add the prepared oil phase to the water phase, stir, raise the temperature to 100°C, stir for 15 hours to form a resin, filter, dry, put the resin into 1200g gasoline, stir at 100°C for 7 hours, filter, dry, and obtain microporous resin white balls;

[0161] (4) Resin carbonization: Take the microporous resin white ball of step (3) and put it into the carbonization furnace, introduce nitrogen at a rate of 80 cm3 / min, increase the temperature to 500°C at a rate of 15°C / min, keep it warm for 30 min, continue to increase the temperature to 700°C at a rate of 15°C / min, keep it warm for 10 min, continue to increase the temperature to 800°C at a rate of 15°C / min, keep it warm for 10 min, turn off the nitrogen and introduce water vapor, keep it warm for 100 min, cool naturally, and obtain resin carbon.

[0162] The inert gas in S1 and S2 is selected from nitrogen.

[0163] The S1 performs heating reaction in two stages:

[0164] In the first stage, the temperature is raised to 200°C at a rate of 3°C / min and kept constant for 5 hours to allow selenium and indium to react fully and inhibit selenium volatilization;

[0165] In the second stage, the temperature is raised to 460°C at a heating rate of 5°C / min and maintained at this temperature for 5 hours to completely convert the free selenium into In4Se3.

[0166] The ball milling mixing parameters in step S2 are:

[0167] Material to ball mass ratio: 1:5;

[0168] Ball milling time: 30 minutes;

[0169] Ball milling speed: 300 rpm;

[0170] Ball milling atmosphere: nitrogen;

[0171] Ball mill type: planetary ball mill.

[0172] The heating reaction is carried out in two stages in step S2:

[0173] In the first stage, the temperature was raised to 210°C at a rate of 3°C / min and kept constant for 2.5 hours to allow selenium to react with In4Se3;

[0174] In the second stage, the temperature is raised to 610°C at a heating rate of 5°C / min and kept constant for 4.5 hours to completely convert indium selenide into the γ phase.

[0175] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 98.9% of the product indium selenide, and the diffraction peak intensity of the secondary phase accounted for 1.1%.

[0176] Comparative Example 1

[0177] The only difference between this comparative example and Example 1 is that no resin carbon is added.

[0178] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 94.1% of the product indium selenide, and the diffraction peak intensity of the secondary phase accounted for 5.9%.

[0179] Comparative Example 2

[0180] The only difference between this comparative example and Example 1 is that no methacryl cage-type silsesquioxane is added during the preparation of the resin carbon.

[0181] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 95.4% of the product indium selenide, and the diffraction peak intensity of the secondary phase accounted for 4.6%.

[0182] Comparative Example 3

[0183] The only difference between this comparative example and Example 1 is that 4-vinylbenzocyclobutene is not added during the preparation of the resin carbon.

[0184] After testing, it was found that the diffraction peak intensity of the γ phase accounted for 95.1% of the product indium selenide, and the diffraction peak intensity of the secondary phase accounted for 4.9%.

[0185] It can be seen from the above test results that the present invention has significant technical advantages in synthesizing high-purity γ-phase indium selenide.

[0186] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A synthesis process of γ-phase indium selenide, characterized in that: The following steps are involved: S1: Synthesis of In4Se3 powder: Weigh 46.44-61.92 parts of selenium powder and 9-12 parts of indium powder according to mass proportions; The selenium powder and indium powder are transferred to a normal pressure tubular synthesis furnace, and the air is replaced by an inert gas, and the gas flow rate is controlled to be 0.1-1 L / min; The reaction product is crushed and treated by air flow milling to obtain In4Se3 powder with a particle size of 10-45 μm; S2: Synthesis of γ-phase InSe: Add 30.96-41.28 parts of selenium powder to the prepared In4Se3 powder, and mix by ball milling to obtain a mixed powder; The mixed powder is transferred to a normal pressure tubular synthesis furnace, 2-6 parts of resin carbon are added, the air is replaced by inert gas, and the gas flow rate is controlled to be 0.1-1 L / min; Cool naturally to room temperature, take out the reaction product, filter it, and obtain γ-phase indium selenide; The resin carbon preparation adopts acryl cage-type silsesquioxane as a super cross-linking agent.

2. The synthesis process of γ-phase indium selenide according to claim 1, characterized in that: The purity of the selenium powder and indium powder is not less than 99.99%.

3. The synthesis process of γ-phase indium selenide according to claim 1, characterized in that: The inert gas in S1 and S2 is selected from one of nitrogen, argon or helium.

4. The synthesis process of γ-phase indium selenide according to claim 1, characterized in that: The S1 performs heating reaction in two stages: In the first stage, the temperature is raised to 180-200°C at a rate of 1-3°C / min and kept constant for 3-5 hours to allow selenium and indium to react fully and inhibit selenium volatilization; In the second stage, the temperature is raised to 440-460°C at a rate of 2-5°C / min and maintained at a constant temperature for 3-5 hours to completely convert free selenium into In4Se3.

5. The synthesis process of γ-phase indium selenide according to claim 1, characterized in that: The ball milling mixing parameters in step S2 are: Material to ball mass ratio: 1:3 to 1:5; Ball milling time: 10-30 minutes; Ball mill speed: 150-300 rpm; Ball milling atmosphere: nitrogen or argon; Ball mill type: planetary ball mill or horizontal drum ball mill.

6. The synthesis process of γ-phase indium selenide according to claim 1, characterized in that: The heating reaction is carried out in two stages in step S2: In the first stage, the temperature is raised to 190-210°C at a rate of 1-3°C / min and kept constant for 1.5-2.5 hours to allow selenium to react with In4Se3; In the second stage, the temperature is raised to 590-610°C at a heating rate of 2-5°C / min and maintained at a constant temperature for 3.5-4.5 hours to completely convert indium selenide into the γ phase.

7. The synthesis process of γ-phase indium selenide according to claim 1, characterized in that: The method for preparing the resin carbon in step S2 is: (1) preparing the aqueous phase: adding 1000-1200 parts of water by weight to a reaction container, heating to 60-70° C., adding 1-3 parts of gelatin, 1-3 parts of sodium chloride, and 0.01-0.05 parts of methylene blue solution, stirring until completely dissolved and mixed uniformly, to prepare the aqueous phase for use; (2) preparing an oil phase: adding 30-50 parts by weight of divinylbenzene, 0.2-0.5 parts by weight of methacryl cage silsesquioxane, 0.02-0.3 parts by weight of 4-vinylbenzocyclobutene, 5-8 parts by weight of styrene, 20-30 parts by weight of paraffin wax, and 0.4-0.8 parts by weight of benzoyl peroxide into a reaction container, stirring until uniform, to prepare an oil phase for later use; (3) Synthesizing white resin balls: slowly add the prepared oil phase to the water phase, stir, raise the temperature to 80-100°C, stir for 7-15 hours to form resin, filter, dry, put the resin into 1000-1200 parts of gasoline, stir at 80-100°C for 4-7 hours, filter, dry, and obtain microporous white resin balls; (4) Resin carbonization: Take the microporous resin white ball from step (3) and put it into the carbonization furnace at 70-80 cm 3 / min, introduce nitrogen, increase the temperature to 500°C at a rate of 15°C / min, keep warm for 20-30min, continue to increase the temperature to 700°C at a rate of 15°C / min, keep warm for 5-10min, continue to increase the temperature to 800°C at a rate of 15°C / min, keep warm for 5-10min, turn off the nitrogen, introduce water vapor, keep warm for 60-100min, cool naturally, and obtain resin carbon.