A phosphorus-doped cadmium selenide target and a method for producing the same

Abstract

The application discloses a phosphorus-doped cadmium selenide target material and a preparation method thereof, and belongs to the technical field of semiconductor materials. In the application, cadmium powder and red phosphorus powder are uniformly mixed, and then are subjected to two-stage heating and heat preservation treatment at a specific temperature to obtain cadmium phosphide powder suitable for preparing the phosphorus-doped cadmium selenide. Then, the cadmium phosphide powder is uniformly mixed with cadmium selenide powder, is put into a vacuum hot-pressing furnace, and is subjected to two-stage heating and heat preservation treatment at a specific pressure and temperature. Then, the mixture is hot-pressed, and finally is cooled to room temperature to obtain the phosphorus-doped cadmium selenide target material. The phosphorus-doped cadmium selenide target material has high relative density, uniform composition, a surface without defects, no pores and white spots, and low contents of free substances and oxygen.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor materials, in particular to a phosphorus-doped cadmium selenide target material and a preparation method thereof. BACKGROUND

[0002] Cadmiun selenide is a II-VI compound with a large band gap (Eg = 117 eV). Cadmium selenide single crystal is often used for laser detectors, various semiconductor light emitting elements and mid-infrared nonlinear optical devices due to its excellent mid-infrared and far-infrared optical properties.

[0003] Cadmium phosphide is a kind of p-type semiconductor material with excellent properties, direct band gap and narrow band gap, only 0.55 eV, and has strong light emission and light absorption in the ultraviolet-visible-infrared region, and has very good application prospect in photoelectric devices such as solar cells.

[0004] Studies have shown that by doping phosphorus elements in cadmium selenide to prepare new thin film solar materials, the band gap of cadmium selenide thin film solar materials can be effectively controlled, and the utilization rate of solar light of the battery in the full wave band is improved, but how to dope phosphorus elements in cadmium selenide has become a technical problem to be solved by the technical personnel in the field.

[0005] In view of this, the present application is proposed. SUMMARY

[0006] The present application aims to overcome the deficiencies in the prior art and provide a phosphorus-doped cadmium selenide target material and a preparation method thereof. The phosphorus-doped cadmium selenide target material has high relative density, uniform composition, no surface defects, no pores and white spots, and low free material and oxygen content.

[0007] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0009] (1) uniformly mixing cadmium powder and red phosphorus powder to obtain a mixed powder;

[0010] (2) placing the mixed powder into a tube furnace, heating to 400-600 DEG C, holding for 2-6 h, crushing, to obtain a mixed powder;

[0011] (3) placing the mixed powder into a tube furnace, heating to 400-500 DEG C, holding for 2-4 h, crushing, ball milling, and passing through a 100-325 mesh sieve to obtain cadmium phosphide powder;

[0012] (4) uniformly mixing the cadmium phosphide powder, cadmium selenide powder and active agent to obtain a precursor powder;

[0013] (5) Put the precursor powder into a vacuum hot pressing furnace, vacuumize, fill in nitrogen to stabilize the pressure in the furnace at 25-40 kPa, heat to 400-600℃, keep for 0.5-2 h, heat to 650-720℃, keep for 0.5-2 h;

[0014] (6) Press to 25-45 MPa, keep for 0.5-2 h;

[0015] (7) Release pressure, stop heating, cool to room temperature to obtain the phosphorus-doped cadmium selenide target.

[0016] As a preferred embodiment of the present application, the molar ratio of the cadmium powder and the red phosphorus powder is 3:(2-2.1).

[0017] As a preferred embodiment of the present application, the particle size of the cadmium powder in step (1) is 100-325 mesh.

[0018] As a preferred embodiment of the present application, the particle size of the red phosphorus powder in step (1) is 100-325 mesh.

[0019] As a preferred embodiment of the present application, the heating rate is 5-10℃ / min when heating to 400-600℃ in step (2).

[0020] As a preferred embodiment of the present application, the heating rate is 5-10℃ / min when heating to 400-500℃ in step (3).

[0021] As a preferred embodiment of the present application, at least one of the following (a)-(d) is satisfied:

[0022] (a) The mass ratio of the cadmium phosphide powder and the cadmium selenide powder is 1:(10-19);

[0023] (b) The mass of the active agent is 0-5% of the total mass of the cadmium phosphide powder and the cadmium selenide powder;

[0024] (c) The particle size of the cadmium selenide powder is 70-325 mesh;

[0025] (d) The particle size of the active agent is 100-325 mesh.

[0026] As a preferred embodiment of the present application, the active agent comprises selenium powder and cadmium powder, and the mass ratio of the selenium powder and the cadmium powder is 1:(1-2).

[0027] As a preferred embodiment of the present application, the heating rate is 5-10℃ / min when heating to 400-600℃ in step (5).

[0028] As a preferred embodiment of the present application, the temperature is raised to 650-720 DEG C in step (5) at a rate of 3-5 DEG C / min.

[0029] As a preferred embodiment of the present application, the pressure is raised to 25-45 MPa at a rate of 1-5 T / min.

[0030] As a preferred embodiment of the present application, the phosphorus-doped cadmium selenide target has a defect-free surface, a relative density of 90.3% or more, and an oxygen content of 952 ppm or less.

[0031] The present application also provides a phosphorus-doped cadmium selenide target prepared by the above method.

[0032] The present application has the advantages that: the cadmium powder and red phosphorus powder are mixed uniformly, and then subjected to two-stage heating and holding treatment at a specific temperature to obtain cadmium phosphide powder suitable for preparing phosphorus-doped cadmium selenide; the cadmium phosphide powder is mixed uniformly with cadmium selenide powder, and then subjected to two-stage heating and holding treatment at a specific pressure and temperature in a vacuum hot-pressing furnace, and then hot-pressed and cooled to room temperature to obtain a phosphorus-doped cadmium selenide target; the phosphorus-doped cadmium selenide target has a high relative density, uniform composition, defect-free surface, and no pores and white spots, and has a low content of free material and oxygen. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 X-ray diffraction pattern of the cadmium phosphide powder prepared in Example 1;

[0034] Figure 2 Ultrasonic C-scan image of the phosphorus-doped cadmium selenide target prepared in Example 1. DETAILED DESCRIPTION

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0036] In the present application, the technical features described in an open form include both a closed technical solution consisting of listed features and an open technical solution containing the listed features.

[0037] In the present application, when a numerical range is referred to, unless otherwise specified, the range is considered to be continuous and to include the minimum and maximum values of the range, as well as every value between the minimum and maximum values. Further, when a range is referred to as integers, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood as including any and all sub-ranges subsumed therein.

[0038] In the present application, the specific mixing method is not particularly limited as long as the desired mixture is uniformly mixed.

[0039] The components and raw materials used in the embodiments and comparative examples of the present application are commercially available unless otherwise specified, and the components and raw materials used in each parallel experiment are the same.

[0040] The embodiment of the present application provides a preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0041] (1) uniformly mixing cadmium powder and red phosphorus powder to obtain mixed powder;

[0042] (2) placing the mixed powder into a tube furnace, heating to 400-600 DEG C, and holding for 2-6 h, crushing, to obtain mixed powder;

[0043] (3) placing the mixed powder into a tube furnace, heating to 400-500 DEG C, and holding for 2-4 h, crushing, ball milling, and passing through a 100-325 mesh sieve, to obtain cadmium phosphide powder;

[0044] (4) uniformly mixing the cadmium phosphide powder, cadmium selenide powder and active agent to obtain precursor powder;

[0045] (5) placing the precursor powder into a vacuum hot pressing furnace, vacuumizing, filling nitrogen to stabilize the gas pressure in the furnace at 25-40 kPa, heating to 400-600 DEG C, holding for 0.5-2 h, heating to 650-720 DEG C, and holding for 0.5-2 h;

[0046] (6) pressurizing to 25-45 MPa, and holding for 0.5-2 h;

[0047] (7) releasing the pressure, stopping heating, and cooling to room temperature, to obtain the phosphorus-doped cadmium selenide target material.

[0048] The present application mixes cadmium powder and red phosphorus powder uniformly, then carries out two-stage heating and holding treatment at a specific temperature, to obtain cadmium phosphide powder suitable for preparing phosphorus-doped cadmium selenide, then mixes the cadmium phosphide powder with cadmium selenide powder uniformly, again carries out two-stage heating and holding treatment at a specific pressure and temperature in a vacuum hot-pressing furnace, then hot-presses, and finally cools to room temperature, to obtain a phosphorus-doped cadmium selenide target; the phosphorus-doped cadmium selenide target has high relative density, uniform composition, no defects on the surface, no pores and white spots, and low free phosphorus and cadmium contents.

[0049] The present inventors have found that, in the present application, the two-stage heating and holding treatment in steps (2) and (3) can effectively reduce the free diffusion of free phosphorus and cadmium in the phosphorus-doped cadmium selenide target, thereby fully discharging pores, effectively improving the relative density, making the surface free of pores and white spots, and reducing the oxygen content of the phosphorus-doped cadmium selenide target. If the two-stage holding treatment is not performed or only one-stage holding treatment is performed, the effect of the present application cannot be achieved.

[0050] The present inventors have also found that, if the temperature of the two-stage heating and holding treatment in steps (2) and (3) is too low, the synthesis effect is affected and the free phosphorus and cadmium in the cadmium selenide target cannot be effectively reduced; if the temperature is too high, part of the red phosphorus and cadmium selenide volatilize, thereby significantly reducing the performance. Therefore, the temperature of the two-stage heating and holding treatment in steps (2) and (3) needs to be controlled.

[0051] The present application creatively places the precursor powder into a vacuum hot-pressing furnace, stabilizes the pressure under the pressure of hot gas, and carries out two-stage heating and holding treatment, which can effectively avoid composition segregation, white spots and pores, reduce the oxygen content, and improve the density.

[0052] It should be noted that steps (1) to (4) are all performed in a protective atmosphere.

[0053] In one embodiment, the molar ratio of the cadmium powder to the red phosphorus powder is 3:(2-2.1), for example, 3:2, 3:2.02, 3:2.04, 3:2.05, 3:2.06, 3:2.08, 3:2.1, or a range formed by any two of the above values.

[0054] In one embodiment, the particle size of the cadmium powder in step (1) is 100-325 mesh, for example, 100 mesh, 125 mesh, 150 mesh, 175 mesh, 200 mesh, 225 mesh, 250 mesh, 275 mesh, 300 mesh, 325 mesh, or a range formed by any two of the above values.

[0055] In one embodiment, the particle size of the red phosphorus powder in step (1) is 100-325 mesh, for example, it can be 100 mesh, 125 mesh, 150 mesh, 175 mesh, 200 mesh, 225 mesh, 250 mesh, 275 mesh, 300 mesh, 325 mesh, or a range defined by any two of the above values.

[0056] In one embodiment, the temperature is raised to 400-600°C at a rate of 5-10°C / min in step (2), for example, it can be 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, or a range defined by any two of the above values.

[0057] In one embodiment, the temperature is raised to 400-500°C at a rate of 5-10°C / min in step (3), for example, it can be 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min, or a range defined by any two of the above values.

[0058] In one embodiment, the mass ratio of the cadmium phosphide powder and the cadmium selenide powder is 1:(10-19), for example, it can be 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or a range defined by any two of the above values. The inventors of the present application have found that the mass ratio of the cadmium phosphide powder and the cadmium selenide powder has a great influence on the effect. By controlling the mass ratio of the two within the range of the present application, segregation of components can be effectively avoided, the content of free substances can be reduced, white spots and pores can be avoided, the oxygen content can be reduced, and the density can be improved. If the content of cadmium phosphide is too high, cadmium phosphide will decompose at 700-800°C, which will result in too many pores, gas will be released during hot pressing and cannot be discharged, which will also result in too much free cadmium, white spots and pores, and an increase in oxygen content. If the content of cadmium phosphide is too low, the doping effect cannot be achieved, and the band gap of cadmium selenide cannot be controlled.

[0059] In one embodiment, the mass of the active agent is 0-5% of the total mass of the cadmium phosphide powder and the cadmium selenide powder, for example, it can be 0%, 0.5%, 1%, 2%, 3%, 4%, 5%, or a range defined by any two of the above values. When it is 0%, no active agent is added, and the purpose of adding selenium powder and cadmium powder is to improve the overall activity of the mixed powder, so that a target material with higher density can be obtained within a limited temperature range.

[0060] In one embodiment, the particle size of the cadmium selenide powder is 70-325 mesh, for example, it can be 70 mesh, 75 mesh, 100 mesh, 125 mesh, 150 mesh, 175 mesh, 200 mesh, 225 mesh, 250 mesh, 275 mesh, 300 mesh, 325 mesh or a range defined by any two of the above values.

[0061] In one embodiment, the particle size of the active agent is 100-325 mesh, for example, it can be 100 mesh, 125 mesh, 150 mesh, 175 mesh, 200 mesh, 225 mesh, 250 mesh, 275 mesh, 300 mesh, 325 mesh or a range defined by any two of the above values.

[0062] In one embodiment, the active agent comprises selenium powder and cadmium powder, and the mass ratio of the selenium powder to the cadmium powder is 1:(1-2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2 or a range defined by any two of the above values.

[0063] In one embodiment, when the temperature is raised to 400-600°C in step (5), the temperature raising rate is 5-10°C / min, for example, it can be 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min, 10°C / min or a range defined by any two of the above values.

[0064] In one embodiment, when the temperature is raised to 650-720°C in step (5), the temperature raising rate is 3-5°C / min, for example, it can be 3°C / min, 3.5°C / min, 4°C / min, 4.5°C / min, 5°C / min or a range defined by any two of the above values.

[0065] In one embodiment, when the pressure is raised to 25-45 MPa in the vacuum hot pressing furnace, the pressure raising rate is 1-5 T / min, for example, it can be 1 T / min, 2 T / min, 3 T / min, 4 T / min, 5 T / min or a range defined by any two of the above values.

[0066] In one embodiment, the phosphorus-doped cadmium selenide target has no defects on the surface, a relative density of greater than or equal to 90.3%, and an oxygen content of less than or equal to 952 ppm.

[0067] The application also provides a phosphorus-doped cadmium selenide target prepared by the above method.

[0068] The following examples are provided to facilitate an understanding of the present application. The examples are not intended to limit the scope of the claims.

[0069] Example 1

[0070] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0071] (1) 170-mesh cadmium powder and 170-mesh red phosphorus powder are uniformly mixed under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0072] (2) The mixed powder is loaded into a graphite boat and placed in a tube furnace, and is heated to 500℃ at a heating rate of 5℃ / min under nitrogen protection, and is kept for 4h, and is taken out after furnace cooling, and is crushed to obtain a mixed powder;

[0073] (3) The mixed powder is again loaded into a graphite boat and placed in a tube furnace, and is heated to 500℃ at a heating rate of 5℃ / min, and is kept for 4h, and is crushed, ball milled, and sieved through a 325-mesh sieve to obtain a cadmium phosphide powder;

[0074] (4) The cadmium phosphide powder obtained in step (3) and 325-mesh cadmium selenide powder are uniformly mixed according to a mass ratio of 1:10 under nitrogen protection to obtain a precursor powder;

[0075] (5) The precursor powder is loaded into a graphite mold and placed in a vacuum hot pressing furnace, and is vacuumed to 10 -2 Pa, nitrogen is filled to stabilize the pressure in the furnace at 30kPa, and is heated to 480℃ at a heating rate of 5℃ / min, and is kept for 1h, and is heated to 680℃ at a heating rate of 5℃ / min, and is kept for 1h;

[0076] (6) The pressure is increased to 45MPa at a pressure increasing rate of 2T / min, and is kept for 1h;

[0077] (7) The pressure is released, heating is stopped, and cooling is performed to room temperature to obtain a phosphorus-doped cadmium selenide target material.

[0078] The X-ray diffraction pattern of the cadmium phosphide powder prepared in step (3) of the example is shown in FIG. 1, and the ultrasonic C-scan image of the phosphorus-doped cadmium selenide target material prepared in the example is shown in FIG. 2. Figure 1 Figure 2 It can be seen from the figure that the surface of the target material prepared in the example is defect-free, and there are no pores and white spots.

[0079] Example 2

[0080] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0081] (1) 170-mesh cadmium powder and 170-mesh red phosphorus powder are uniformly mixed under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0082] ​(2) The mixed powder is loaded into a graphite boat, and then is placed into a tube furnace. The temperature is raised to 500℃ at a rate of 5℃ / min under nitrogen protection, and is kept for 4h. The furnace is cooled down, and the product is taken out, crushed, and mixed powder is obtained.

[0083] (3) The mixed powder is loaded into a graphite boat again, and then is placed into a tube furnace. The temperature is raised to 500℃ at a rate of 5℃ / min, and is kept for 4h. The product is crushed, ball-milled, and is passed through a 325 mesh sieve, and cadmium phosphide powder is obtained.

[0084] (4) The cadmium phosphide powder obtained in step (3), 325 mesh cadmium selenide powder, 170 mesh selenium powder, and 170 mesh cadmium powder are mixed uniformly under nitrogen protection according to a mass ratio of 1:10:1:1.4, and precursor powder is obtained.

[0085] (5) The precursor powder is loaded into a graphite mold, and then is placed into a vacuum hot-pressing furnace. The vacuum is extracted to 10 -2 Pa, nitrogen is filled to stabilize the pressure in the furnace at 30kPa, the temperature is raised to 480℃ at a rate of 5℃ / min, and is kept for 1h. The temperature is raised to 680℃ at a rate of 5℃ / min, and is kept for 1h.

[0086] (6) The pressure is increased to 45MPa at a rate of 2T / min, and is kept for 1h.

[0087] (7) The pressure is released, heating is stopped, and the temperature is cooled to room temperature, and a phosphorus-doped cadmium selenide target is obtained.

[0088] Example 3

[0089] A preparation method of a phosphorus-doped cadmium selenide target comprises the following steps:

[0090] (1) 170 mesh cadmium powder and 170 mesh red phosphorus powder are mixed uniformly according to a molar ratio of 3:2.08 under nitrogen protection, and mixed powder is obtained.

[0091] (2) The mixed powder is loaded into a graphite boat, and then is placed into a tube furnace. The temperature is raised to 550℃ at a rate of 5℃ / min under nitrogen protection, and is kept for 2h. The furnace is cooled down, and the product is taken out, crushed, and mixed powder is obtained.

[0092] (3) The mixed powder is loaded into a graphite boat again, and then is placed into a tube furnace. The temperature is raised to 480℃ at a rate of 10℃ / min, and is kept for 4h. The product is crushed, ball-milled, and is passed through a 170 mesh sieve, and cadmium phosphide powder is obtained.

[0093] (4) The cadmium phosphide powder obtained in step (3), 325 mesh cadmium selenide powder, 170 mesh selenium powder, and 170 mesh cadmium powder are mixed uniformly under nitrogen protection according to a mass ratio of 6.5:78.3:1:1.4, and precursor powder is obtained.

[0094] (5) Put the precursor powder into a graphite mold, and then put it into a vacuum hot pressing furnace, and vacuumize to 10 -2 Pa, fill in nitrogen to stabilize the gas pressure in the furnace at 30 kPa, heat to 450℃ at a heating rate of 5℃ / min, keep for 1h, and then heat to 700℃ at a heating rate of 5℃ / min, keep for 1h;

[0095] (6) Pressurize to 45MPa at a pressurizing rate of 1T / min, and keep for 1h;

[0096] (7) Release the pressure, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0097] Example 4

[0098] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0099] (1) Mix 170 mesh cadmium powder and 170 mesh red phosphorus powder in a molar ratio of 3:2.1 under nitrogen protection to obtain a mixed powder;

[0100] (2) Put the mixed powder into a graphite boat, and then put it into a tube furnace, and heat to 500℃ at a heating rate of 5℃ / min under nitrogen protection, keep for 4h, cool down with the furnace, take out, crush, and obtain a mixed powder;

[0101] (3) Put the mixed powder into a graphite boat again, and then put it into a tube furnace, and heat to 450℃ at a heating rate of 10℃ / min, keep for 4h, crush, ball mill, and pass through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0102] (4) Mix the cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder in a mass ratio of 1:15 under nitrogen protection to obtain a precursor powder;

[0103] (5) Put the precursor powder into a graphite mold, and then put it into a vacuum hot pressing furnace, and vacuumize to 10 -2 Pa, fill in nitrogen to stabilize the gas pressure in the furnace at 30 kPa, heat to 420℃ at a heating rate of 5℃ / min, keep for 1h, and then heat to 680℃ at a heating rate of 3℃ / min, keep for 1h;

[0104] (6) Pressurize to 50MPa at a pressurizing rate of 1T / min, and keep for 1h;

[0105] (7) Release the pressure, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0106] Example 5

[0107] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0108] (1) Mix 170 mesh cadmium powder and 170 mesh red phosphorus powder uniformly under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0109] (2) Put the mixed powder into a graphite boat, and then put it into a tube furnace, and heat to 500℃ at a heating rate of 5℃ / min under nitrogen protection, keep for 4h, cool down with the furnace, take out, crush, and obtain a mixed powder;

[0110] (3) Put the mixed powder into a graphite boat again, and then put it into a tube furnace, and heat to 500℃ at a heating rate of 5℃ / min, keep for 4h, crush, ball mill, and pass through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0111] (4) Mix the cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder uniformly under nitrogen protection according to a mass ratio of 1:19 to obtain a precursor powder;

[0112] (5) Put the precursor powder into a graphite mold, and then put it into a vacuum hot pressing furnace, and vacuumize to 10 -2 Pa, fill nitrogen to stabilize the pressure in the furnace at 30kPa, heat to 480℃ at a heating rate of 5℃ / min, keep for 1h, and then heat to 680℃ at a heating rate of 5℃ / min, keep for 1h;

[0113] (6) Pressurize to 45MPa at a pressurizing rate of 2T / min, and keep for 1h;

[0114] (7) Release the pressure, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target material.

[0115] Example 6

[0116] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0117] (1) Mix 170 mesh cadmium powder and 170 mesh red phosphorus powder uniformly under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0118] (2) Put the mixed powder into a graphite boat, and then put it into a tube furnace, and heat to 400℃ at a heating rate of 5℃ / min under nitrogen protection, keep for 6h, cool down with the furnace, take out, crush, and obtain a mixed powder;

[0119] (3) Put the mixed powder into a graphite boat again, and then put it into a tube furnace, and heat to 600℃ at a heating rate of 5℃ / min, keep for 4h, crush, ball mill, and pass through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0120] (4) The cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are mixed uniformly in a mass ratio of 1:10 under nitrogen protection to obtain a precursor powder;

[0121] (5) The precursor powder is loaded into a graphite mold, and then placed into a vacuum hot pressing furnace, vacuumed to 10 -2 Pa, nitrogen is filled to stabilize the gas pressure in the furnace at 30 kPa, heated to 480°C at a heating rate of 5°C / min, and held for 1 h, then heated to 680°C at a heating rate of 5°C / min, and held for 1 h;

[0122] (6) Pressurized to 45 MPa at a pressurization rate of 2T / min, and held for 1 h;

[0123] (7) Pressure relief, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0124] Example 7

[0125] A method for preparing a phosphorus-doped cadmium selenide target, comprising the following steps:

[0126] (1) 170 mesh cadmium powder and 170 mesh red phosphorus powder are mixed uniformly in a molar ratio of 3:2 under nitrogen protection to obtain a mixed powder;

[0127] (2) The mixed powder is loaded into a graphite boat, and then placed into a tube furnace, heated to 500°C at a heating rate of 5°C / min under nitrogen protection, held for 4 h, cooled with the furnace, taken out, and crushed to obtain a mixed powder;

[0128] (3) The mixed powder is again loaded into a graphite boat, and then placed into a tube furnace, heated to 500°C at a heating rate of 5°C / min, held for 4 h, crushed, ball milled, and passed through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0129] (4) The cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are mixed uniformly in a mass ratio of 1:10 under nitrogen protection to obtain a precursor powder;

[0130] (5) The precursor powder is loaded into a graphite mold, and then placed into a vacuum hot pressing furnace, vacuumed to 10 -2 Pa, nitrogen is filled to stabilize the gas pressure in the furnace at 30 kPa, heated to 600°C at a heating rate of 5°C / min, and held for 0.8 h, then heated to 720°C at a heating rate of 5°C / min, and held for 0.5 h;

[0131] (6) Pressurized to 45 MPa at a pressurization rate of 2T / min, and held for 1 h;

[0132] (7) Pressure relief, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0133] Comparative Example 1

[0134] Comparative Example 1 is different from Example 1 in that Comparative Example 1 does not undergo the heat soaking treatment of step (3) of Example 1, i.e. Comparative Example 1 only undergoes a soaking treatment, and is the same as Example 1 in other aspects.

[0135] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0136] (1) uniformly mix 170-mesh cadmium powder and 170-mesh red phosphorus powder in a molar ratio of 3:2 under nitrogen protection to obtain a mixed powder;

[0137] (2) load the mixed powder into a graphite boat, and then place the graphite boat into a tube furnace, heat the graphite boat to 500℃ at a heating rate of 5℃ / min under nitrogen protection, and then cool the graphite boat with the furnace, take out the graphite boat, crush the graphite boat, and obtain a mixed powder;

[0138] (3) pass the mixed powder through a 325-mesh sieve to obtain cadmium phosphide powder;

[0139] (4) uniformly mix the cadmium phosphide powder obtained in step (3) and 325-mesh cadmium selenide powder in a mass ratio of 1:10 under nitrogen protection to obtain a precursor powder;

[0140] (5) load the precursor powder into a graphite mold, and then place the graphite mold into a vacuum hot pressing furnace, vacuumize the vacuum hot pressing furnace to 10 -2 Pa, fill nitrogen to stabilize the pressure in the furnace at 30kPa, heat the furnace to 480℃ at a heating rate of 5℃ / min, and then heat the furnace to 680℃ at a heating rate of 5℃ / min, and then heat the furnace for 1h;

[0141] (6) pressurize the vacuum hot pressing furnace to a pressure of 45MPa at a pressurizing rate of 2T / min, and then maintain the pressure for 1h;

[0142] (7) release the pressure, stop heating, and cool the furnace to room temperature to obtain a phosphorus-doped cadmium selenide target material.

[0143] Comparative Example 2

[0144] Comparative Example 2 is different from Example 1 in that the soaking treatment temperature of steps (2) and (3) of Comparative Example 2 is different, and is the same as Example 1 in other aspects.

[0145] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0146] (1) uniformly mix 170-mesh cadmium powder and 170-mesh red phosphorus powder in a molar ratio of 3:2 under nitrogen protection to obtain a mixed powder;

[0147] (2) The mixed powder is loaded into a graphite boat, and then put into a tube furnace, and heated to 350℃ at a heating rate of 5℃ / min under nitrogen protection, and kept for 4h, and then cooled with the furnace, taken out, and crushed to obtain a mixed powder;

[0148] (3) The mixed powder is loaded into a graphite boat again, and then put into a tube furnace, and heated to 350℃ at a heating rate of 5℃ / min, and kept for 4h, and then crushed, ball milled, and sieved through a 325 mesh screen to obtain a mixed powder containing cadmium phosphide powder (the composition of the mixed powder is cadmium powder + phosphorus powder + cadmium phosphide powder) ;

[0149] (4) The mixed powder containing cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are uniformly mixed under nitrogen protection according to a mass ratio of 1:10 to obtain a precursor powder;

[0150] (5) The precursor powder is loaded into a graphite mold, and then put into a vacuum hot pressing furnace, and vacuumized to 10 -2 Pa, nitrogen is filled to stabilize the pressure in the furnace at 30kPa, and heated to 480℃ at a heating rate of 5℃ / min, and kept for 1h, and then heated to 680℃ at a heating rate of 5℃ / min, and kept for 1h;

[0151] (6) The pressure is increased to 45MPa at a pressure increasing rate of 2T / min, and kept for 1h;

[0152] (7) The pressure is released, heating is stopped, and cooled to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0153] Comparative Example 3

[0154] Comparative Example 3 is different from Example 1 in that the holding treatment temperature of steps (2) and (3) of Comparative Example 3 is different, and other aspects are the same.

[0155] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0156] (1) 170 mesh cadmium powder and 170 mesh red phosphorus powder are uniformly mixed under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0157] (2) The mixed powder is loaded into a graphite boat, and then put into a tube furnace, and heated to 650℃ at a heating rate of 5℃ / min under nitrogen protection, and kept for 4h, and then cooled with the furnace, taken out, and crushed to obtain a mixed powder;

[0158] (3) The mixed powder is loaded into a graphite boat again, and then put into a tube furnace, and heated to 550℃ at a heating rate of 5℃ / min, and kept for 4h, and then crushed, ball milled, and sieved through a 325 mesh screen to obtain a mixed powder containing cadmium phosphide powder (the composition of the mixed powder is cadmium powder + phosphorus powder + cadmium phosphide powder) ;

[0159] (4) The cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are mixed uniformly under nitrogen protection at a mass ratio of 1:10 to obtain a precursor powder;

[0160] (5) The precursor powder is loaded into a graphite mold, and then placed into a vacuum hot pressing furnace, vacuumized to 10 -2 Pa, nitrogen is filled to stabilize the gas pressure in the furnace at 30 kPa, heated to 480℃ at a heating rate of 5℃ / min, and kept for 1 h, and then heated to 680℃ at a heating rate of 5℃ / min, and kept for 1 h;

[0161] (6) Pressurized to 45 MPa at a pressurization rate of 2T / min, and kept for 1 h;

[0162] (7) Pressure relief, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0163] Comparative Example 4

[0164] Comparative Example 4 is different from Example 1 in that the mass ratio of cadmium phosphide powder and cadmium selenide powder in Comparative Example 4 is different, and the others are the same.

[0165] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0166] (1) The 170 mesh cadmium powder and the 170 mesh red phosphorus powder are mixed uniformly under nitrogen protection at a molar ratio of 3:2 to obtain a mixed powder;

[0167] (2) The mixed powder is loaded into a graphite boat, and then placed into a tube furnace, heated to 500℃ at a heating rate of 5℃ / min under nitrogen protection, kept for 4 h, cooled with the furnace, taken out, and crushed to obtain a mixed powder;

[0168] (3) The mixed powder is loaded into a graphite boat again, and then placed into a tube furnace, heated to 500℃ at a heating rate of 5℃ / min, kept for 4 h, broken, ball milled, and passed through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0169] (4) The cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are mixed uniformly under nitrogen protection at a mass ratio of 1:8 to obtain a precursor powder;

[0170] (5) The precursor powder is loaded into a graphite mold, and then placed into a vacuum hot pressing furnace, vacuumized to 10 -2 Pa, nitrogen is filled to stabilize the gas pressure in the furnace at 30 kPa, heated to 480℃ at a heating rate of 5℃ / min, and kept for 1 h, and then heated to 680℃ at a heating rate of 5℃ / min, and kept for 1 h;

[0171] (6) pressurize to 45 MPa at a pressurizing rate of 2 T / min, and keep pressure for 1 h;

[0172] (7) release pressure, stop heating, and cool to room temperature to obtain the phosphorus-doped cadmium selenide target.

[0173] Comparative Example 5

[0174] Comparative Example 5 is different from Example 1 in that the mass ratio of the cadmium phosphide powder and the cadmium selenide powder in Comparative Example 5 is different, and the others are the same.

[0175] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0176] (1) uniformly mix 170-mesh cadmium powder and 170-mesh red phosphorus powder in a molar ratio of 3:2 under nitrogen protection to obtain a mixed powder;

[0177] (2) load the mixed powder into a graphite boat, and then put it into a tube furnace, heat to 500℃ at a heating rate of 5℃ / min under nitrogen protection, keep for 4 h, cool down with the furnace, take out, crush, and obtain a mixed powder;

[0178] (3) load the mixed powder into a graphite boat again, and then put it into a tube furnace, heat to 500℃ at a heating rate of 5℃ / min, keep for 4 h, crush, ball mill, and pass through a 325-mesh sieve to obtain cadmium phosphide powder;

[0179] (4) uniformly mix the cadmium phosphide powder obtained in step (3) and 325-mesh cadmium selenide powder in a mass ratio of 1:25 under nitrogen protection to obtain a precursor powder;

[0180] (5) load the precursor powder into a graphite mold, and then put it into a vacuum hot pressing furnace, vacuumize to 10 -2 Pa, fill nitrogen to stabilize the pressure in the furnace at 30 kPa, heat to 480℃ at a heating rate of 5℃ / min, keep for 1 h, and then heat to 680℃ at a heating rate of 5℃ / min, keep for 1 h;

[0181] (6) pressurize to 45 MPa at a pressurizing rate of 2 T / min, and keep pressure for 1 h;

[0182] (7) release pressure, stop heating, and cool to room temperature to obtain the phosphorus-doped cadmium selenide target.

[0183] Comparative Example 6

[0184] Comparative Example 6 is different from Example 1 in that only one heating and keeping step is performed in step (5) of Comparative Example 6, and the others are the same.

[0185] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0186] (1) Mix 170 mesh cadmium powder and 170 mesh red phosphorus powder uniformly under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0187] (2) Put the mixed powder into a graphite boat, and then put it into a tube furnace, and heat it to 500℃ at a heating rate of 5℃ / min under nitrogen protection, keep it for 4h, cool it with the furnace, take it out, crush it, and obtain a mixed powder;

[0188] (3) Put the mixed powder into a graphite boat again, and then put it into a tube furnace, and heat it to 500℃ at a heating rate of 5℃ / min, keep it for 4h, crush it, ball mill it, and pass it through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0189] (4) Mix the cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder uniformly under nitrogen protection according to a mass ratio of 1:10 to obtain a precursor powder;

[0190] (5) Put the precursor powder into a graphite mold, and then put it into a vacuum hot pressing furnace, and vacuumize it to 10 -2 Pa, fill nitrogen to stabilize the pressure in the furnace at 30kPa, and heat it to 480℃ at a heating rate of 5℃ / min;

[0191] (6) Pressurize it to 45MPa at a pressurizing rate of 2T / min, and keep it for 1h;

[0192] (7) Release the pressure, stop heating, and cool it to room temperature to obtain a phosphorus-doped cadmium selenide target material.

[0193] Comparative Example 7

[0194] Comparative Example 7 is different from Example 1 in that the two-stage heat preservation temperatures in step (5) of Comparative Example 7 are different from those of Example 1, and the others are the same.

[0195] A preparation method of a phosphorus-doped cadmium selenide target material, comprising the following steps:

[0196] (1) Mix 170 mesh cadmium powder and 170 mesh red phosphorus powder uniformly under nitrogen protection according to a molar ratio of 3:2 to obtain a mixed powder;

[0197] (2) Put the mixed powder into a graphite boat, and then put it into a tube furnace, and heat it to 500℃ at a heating rate of 5℃ / min under nitrogen protection, keep it for 4h, cool it with the furnace, take it out, crush it, and obtain a mixed powder;

[0198] (3) Put the mixed powder into a graphite boat again, and then put it into a tube furnace, and heat it to 500℃ at a heating rate of 5℃ / min, keep it for 4h, crush it, ball mill it, and pass it through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0199] (4) The cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are mixed uniformly in a mass ratio of 1:10 under nitrogen protection to obtain a precursor powder;

[0200] (5) The precursor powder is loaded into a graphite mold, and then placed into a vacuum hot pressing furnace, vacuumized to 10 -2 Pa, nitrogen is filled to stabilize the gas pressure in the furnace at 30 kPa, heated to 300°C at a heating rate of 5°C / min, and kept for 1 h, then heated to 600°C at a heating rate of 5°C / min, and kept for 1 h;

[0201] (6) Pressurized to 45 MPa at a pressurizing rate of 2T / min, and kept for 1 h;

[0202] (7) Pressure relief, stop heating, and cool to room temperature to obtain a phosphorus-doped cadmium selenide target.

[0203] Comparative Example 8

[0204] Comparative Example 8 is different from Example 1 in that the two-stage heat preservation temperatures in step (5) of Comparative Example 8 are different from those of Example 1, and the others are the same.

[0205] A preparation method of a phosphorus-doped cadmium selenide target, comprising the following steps:

[0206] (1) 170 mesh cadmium powder and 170 mesh red phosphorus powder are mixed uniformly in a molar ratio of 3:2 under nitrogen protection to obtain a mixed powder;

[0207] (2) The mixed powder is loaded into a graphite boat, and then placed into a tube furnace, heated to 500°C at a heating rate of 5°C / min under nitrogen protection, kept for 4 h, cooled with the furnace, taken out, and crushed to obtain a mixed powder;

[0208] (3) The mixed powder is loaded into a graphite boat again, and then placed into a tube furnace, heated to 500°C at a heating rate of 5°C / min, kept for 4 h, broken, ball milled, and passed through a 325 mesh sieve to obtain a cadmium phosphide powder;

[0209] (4) The cadmium phosphide powder obtained in step (3) and 325 mesh cadmium selenide powder are mixed uniformly in a mass ratio of 1:10 under nitrogen protection to obtain a precursor powder;

[0210] (5) The precursor powder is loaded into a graphite mold, and then placed into a vacuum hot pressing furnace, vacuumized to 10 -2 Pa, nitrogen is filled to stabilize the gas pressure in the furnace at 30 kPa, heated to 650°C at a heating rate of 5°C / min, and kept for 1 h, then heated to 800°C at a heating rate of 5°C / min, and kept for 1 h;

[0211] (6) pressurizing to 45 MPa at a pressurizing rate of 2T / min, and keeping pressure for 1h;

[0212] (7) releasing pressure, stopping heating, and cooling to room temperature to obtain the phosphorus-doped cadmium selenide target.

[0213] Test Example

[0214] The relative density, surface defects, and oxygen content of the target materials of the examples and Comparative Example 1 are shown in Table 1.

[0215] The test method for the relative density is as follows: first, the hot-pressed phosphorus-doped cadmium selenide target is sampled in a size of 30*20*15 cm, washed, polished, and dried for 6h, and then sealed with wax and tested for actual density by the drainage method. The ratio of the actual density to the theoretical density is the relative density.

[0216] The surface defects are observed by ultrasonic C-scan images.

[0217] The test method for the oxygen content is as follows: the phosphorus-doped cadmium selenide target sample is dried and broken into powder, vacuum-packed, and then tested for oxygen content by an oxygen meter.

[0218] Table 1

[0219]

[0220]

[0221] As can be seen from Table 1, the phosphorus-doped cadmium selenide target has high relative density, uniform composition, no surface defects, no pores and white spots, and low free oxygen content.

[0222] The phosphorus-doped cadmium selenide target prepared by the method has a relative density of greater than or equal to 90.3% and an oxygen content of less than or equal to 952 ppm.

[0223] It should be finally noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A method for producing a phosphorus-doped cadmium selenide target material, characterized by, The method comprises the following steps: (1) uniformly mixing cadmium powder and red phosphorus powder to obtain mixed powder; (2) placing the mixed powder into a tube furnace, heating to 400-600 DEG C, holding for 2-6 hours, crushing, obtaining mixed powder; (3) placing the mixed powder into a tube furnace, heating to 400-500 DEG C, holding for 2-4 hours, crushing, ball milling, and passing through a 100-325 mesh sieve to obtain cadmium phosphide powder; (4) uniformly mixing the cadmium phosphide powder, cadmium selenide powder and active agent to obtain precursor powder; (5) placing the precursor powder into a vacuum hot pressing furnace, vacuumizing, filling nitrogen to stabilize the pressure in the furnace at 25-40 kPa, heating to 400-600 DEG C, holding for 0.5-2 hours, heating to 650-720 DEG C, holding for 0.5-2 hours; (6) pressurizing to 25-45 MPa, holding for 0.5-2 hours; (7) depressurizing, stopping heating, and cooling to room temperature to obtain phosphorus-doped cadmium selenide target material. The mass ratio of the cadmium phosphide powder and the cadmium selenide powder is 1:(10-19).

2. The method of producing a phosphorus-doped cadmium selenide target according to claim 1, characterized by, The molar ratio of the cadmium powder and the red phosphorus powder is 3:(2-2.1).

3. The method of producing a phosphorus-doped cadmium selenide target according to claim 1, characterized by, In the step (1), the particle size of the cadmium powder is 100-325 mesh; and / or In the step (1), the particle size of the red phosphorus powder is 100-325 mesh.

4. The method for preparing the phosphorus-doped cadmium selenide target according to claim 1, characterized in that, In the step (2), when heating to 400-600 DEG C, the heating rate is 5-10 DEG C / min; and / or In the step (3), when heating to 400-500 DEG C, the heating rate is 5-10 DEG C / min.

5. The method for preparing the phosphorus-doped cadmium selenide target according to claim 1, characterized in that, At least one of the following (a)-(c): (a) the mass of the active agent is 0-5% of the total mass of the cadmium phosphide powder and the cadmium selenide powder; (b) the particle size of the cadmium selenide powder is 70-325 mesh; (c) the particle size of the active agent is 100-325 mesh.

6. The method of producing a phosphorus-doped cadmium selenide target according to claim 1, wherein The active agent comprises selenium powder and cadmium powder, and the mass ratio of the selenium powder and the cadmium powder is 1:(1-2).

7. The method of producing a phosphorus-doped cadmium selenide target according to claim 1, wherein In the step (5), when heating to 400-600 DEG C, the heating rate is 5-10 DEG C / min; and / or In the step (5), when heating to 650-720 DEG C, the heating rate is 3-5 DEG C / min.

8. The method of producing a phosphorus-doped cadmium selenide target according to claim 1, wherein The phosphorus-doped cadmium selenide target material has no defects on the surface, a relative density greater than or equal to 90.3%, and an oxygen content less than or equal to 952 ppm.

9. A phosphorus-doped cadmium selenide target material, characterized by, Prepared by the method of any one of claims 1-8.

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