Zinc telluride n-doped target material and method for manufacturing the same

Abstract

The application discloses a zinc telluride N-doped target material and a preparation method thereof, and relates to the technical field of target material preparation. The preparation method comprises the following steps: zinc telluride powder, tellurium powder, zinc powder and zinc nitride powder are mixed according to a mass ratio of (50-70):(20-25):(3-10):(7-15), pre-pressing treatment is performed, and then vacuum hot-pressing treatment is performed, including sequentially performing a first temperature-rising and temperature-maintaining stage, a second temperature-rising and temperature-maintaining stage and a pressure-rising and pressure-maintaining and temperature-maintaining stage, and then being cooled to room temperature, so that the zinc telluride N-doped target material is obtained. The zinc telluride N-doped target material has high carrier concentration due to the nitrogen vacancies and zinc interstitials of zinc nitride, the zinc telluride has low resistivity due to the high carrier concentration, the zinc nitride doping introduces donor defects, the resistivity of the original zinc telluride is reduced, the density and purity of the prepared target material are improved, the conductivity and uniformity of the zinc telluride in film plating are improved, and the requirement for equipment is low and the production cost is saved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of target material preparation, in particular to a zinc telluride N-doped target material and a preparation method thereof. BACKGROUND

[0002] Zinc telluride (ZnTe) is an important member of the Ⅱ-Ⅵ semiconductor family, which has been widely used in green light-emitting diodes, solar cells, lithium batteries, and terahertz devices due to its excellent optoelectronic properties.

[0003] Zinc telluride is a P-type wide-bandgap semiconductor material with excellent optical properties, making it a promising material for thin-film solar sputtering coating applications. However, the purity, composition, relative density, electrical conductivity, cracking, and binding rate of zinc telluride targets used in thin-film solar sputtering coating applications are highly demanding. Therefore, it is crucial to develop a zinc telluride target with high purity, good electrical conductivity, and uniform composition for sputtering coating applications. SUMMARY

[0004] The present application provides a zinc telluride N-doped target material and a preparation method thereof to improve the purity, electrical conductivity, and composition uniformity of the target material, and to achieve a high relative density, making it suitable for sputtering coating applications.

[0005] To solve the above technical problems, one of the objectives of the present application is to provide a preparation method for a zinc telluride N-doped target material, comprising the following steps:

[0006] (1) Mix zinc telluride powder, tellurium powder, zinc powder, and zinc nitride powder in a mass ratio of (50-70):(20-25):(3-10):(7-15) to obtain a premix;

[0007] (2) Place the premix powder into a mold and perform pre-pressing treatment in a vacuum hot-pressing device;

[0008] (3) After pre-pressing, perform vacuum hot-pressing treatment, including a first temperature rising and holding stage, a second temperature rising and holding stage, and a pressure rising and holding stage. The first temperature rising and holding stage raises the temperature to 300-400℃, and the second temperature rising and holding stage raises the temperature to 500-550℃;

[0009] (4) After vacuum hot-pressing, reduce the temperature to room temperature to obtain the zinc telluride N-doped target material.

[0010] As a preferred scheme, in step (2), the pre-pressing pressure is 8-10T.

[0011] As a preferred scheme, in step (2), the pressure rising and holding stage raises the pressure to 23-25T.

[0012] Preferably, the holding time of the first temperature rising and holding stage is 20-30 min, the holding time of the second temperature rising and holding stage is 20-30 min, and the holding time of the pressure holding and holding stage is 60-90 min.

[0013] Preferably, the temperature rising rate of the first temperature rising and holding stage is 3-5℃ / min, and the temperature rising rate of the second temperature rising and holding stage is 8-10℃ / min.

[0014] Preferably, in step (1), the zinc telluride powder, the tellurium powder, the zinc powder and the zinc nitride powder are mixed under the condition of a protective gas, and the mixing time is 4-6 h.

[0015] Preferably, in step (4), after the vacuum hot pressing is completed, the temperature is lowered to below 450℃, the protective gas is introduced, and then the temperature is lowered to room temperature, thereby obtaining the zinc telluride N-doped target material.

[0016] Preferably, the protective gas is argon or nitrogen.

[0017] Preferably, the purity of the zinc telluride powder, the tellurium powder, the zinc powder and the zinc nitride powder is 5N or above.

[0018] To solve the above technical problems, a second object of the present application provides a zinc telluride N-doped target material.

[0019] Compared with the prior art, the embodiments of the present application have the following beneficial effects:

[0020] The zinc telluride N-doped target material provided by the present application has high carrier concentration due to the nitrogen vacancies and zinc interstitials of the zinc nitride itself, and the carrier concentration is high, so the resistivity is low. The doping of the zinc nitride introduces donor defects, which reduces the resistivity of the original zinc telluride, improves the density and purity of the prepared target material, improves the conductivity and uniformity of the zinc telluride in the film, and has low requirements for equipment and saves production cost. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0022] Embodiment one

[0023] A preparation method of a zinc telluride N-doped target material includes the following steps:

[0024] (1) mixed zinc telluride powder with purity of 5N, tellurium powder, zinc powder, zinc nitride powder according to mass ratio of 50:25:10:15, passed 5L / min argon, argon passing time was 10min, mixed for 4h by using three-dimensional homogenizing machine to obtain premix;

[0025] (2) put the premix powder into graphite mold, then put into vacuum hot pressing furnace, and carried out pre-pressing treatment with pre-pressing pressure of 8T;

[0026] (3) after pre-pressing, started heating, heated to 300℃ at 3℃ / min, after 30min, continued to heat to 500℃ at 10℃ / min, after 20min, increased pressure to 23T, and kept for 60min;

[0027] (4) after vacuum hot pressing, decreased temperature to 450℃, started passing argon protective gas, and continued to decrease to room temperature, thus obtained zinc telluride doped N target material.

[0028] Example Two

[0029] A preparation method of zinc telluride doped N target material, comprising the following steps:

[0030] (1) mixed zinc telluride powder with purity of 5N, tellurium powder, zinc powder, zinc nitride powder according to mass ratio of 60:23:7:10, passed 5L / min argon, argon passing time was 10min, mixed for 4h by using three-dimensional homogenizing machine to obtain premix;

[0031] (2) put the premix powder into graphite mold, then put into vacuum hot pressing furnace, and carried out pre-pressing treatment with pre-pressing pressure of 9T;

[0032] (3) after pre-pressing, started heating, heated to 320℃ at 4℃ / min, after 25min, continued to heat to 530℃ at 9℃ / min, after 25min, increased pressure to 24T, and kept for 75min;

[0033] (4) after vacuum hot pressing, decreased temperature to 450℃, started passing argon protective gas, and continued to decrease to room temperature, thus obtained zinc telluride doped N target material.

[0034] Example Three

[0035] A preparation method of zinc telluride doped N target material, comprising the following steps:

[0036] (1) mixed zinc telluride powder with purity of 5N, tellurium powder, zinc powder, zinc nitride powder according to mass ratio of 70:20:3:7, passed 5L / min argon, argon passing time was 10min, mixed for 4h by using three-dimensional homogenizing machine to obtain premix;

[0037] (2) Put the premix powder into a graphite mold, and then into a vacuum hot pressing furnace, and perform pre-pressing treatment, with a pre-pressing pressure of 10T;

[0038] (3) After the pre-pressing is completed, start heating, with a temperature rising rate of 5℃ / min to 400℃, and after 30min of heat preservation, continue to rise the temperature to 550℃ at a rate of 8℃ / min, and after 30min of heat preservation, increase the pressure to 25T, and perform 90min of heat preservation and pressure preservation;

[0039] (4) After the vacuum hot pressing is completed, the temperature is decreased to 450℃, argon protection gas is introduced, and the temperature is continuously decreased to room temperature, thereby obtaining the zinc telluride N-doped target material.

[0040] Comparative Example 1

[0041] A preparation method of a zinc telluride N-doped target material, comprising the following steps:

[0042] (1) Mix zinc telluride powder, tellurium powder, zinc powder and zinc nitride powder with a purity of 5N according to a mass ratio of 70:20:3:7, introduce 5L / min of argon, and the argon introduction time is 10min, and mix for 4h by using a three-dimensional homogenizer, thereby obtaining a premix;

[0043] (2) Put the premix powder into a graphite mold, and then into a vacuum hot pressing furnace, and perform pre-pressing treatment, with a pre-pressing pressure of 15T;

[0044] (3) After the pre-pressing is completed, start heating, with a temperature rising rate of 5℃ / min to 400℃, and after 30min of heat preservation, continue to rise the temperature to 550℃ at a rate of 8℃ / min, and after 30min of heat preservation, increase the pressure to 30T, and perform 90min of heat preservation and pressure preservation;

[0045] (4) After the vacuum hot pressing is completed, the temperature is decreased to 450℃, argon protection gas is introduced, and the temperature is continuously decreased to room temperature, thereby obtaining the zinc telluride N-doped target material.

[0046] Comparative Example 2

[0047] A preparation method of a zinc telluride target material, comprising the following steps:

[0048] (1) Mix zinc telluride powder, tellurium powder and zinc powder with a purity of 5N according to a mass ratio of 70:20:3, introduce 5L / min of argon, and the argon introduction time is 10min, and mix for 4h by using a three-dimensional homogenizer, thereby obtaining a premix;

[0049] (2) Put the premix powder into a graphite mold, and then into a vacuum hot pressing furnace, and perform pre-pressing treatment, with a pre-pressing pressure of 10T;

[0050] (3) after the pre-pressing is finished, heating is started, the temperature is increased to 400 DEG C at 5 DEG C / min, after 30 min of keeping the temperature, the temperature is continuously increased to 550 DEG C at 8 DEG C / min, after 30 min of keeping the temperature, the pressure is increased to 25T, and 90 min of keeping the temperature and pressure is performed;

[0051] (4) after the vacuum hot-pressing is finished, the temperature is decreased to 450 DEG C, argon protection gas is started to be introduced, and the temperature is continuously decreased to room temperature, thereby obtaining the zinc telluride target material.

[0052] Comparative Example Three

[0053] A preparation method of a zinc telluride N-doped target material comprises the following steps:

[0054] (1) zinc telluride powder, tellurium powder, zinc powder and zinc nitride powder with a purity of 5N are mixed according to a mass ratio of 75:18:2:5, 5L / min argon is introduced, the argon introduction time is 10 min, a three-dimensional homogenizer is used for mixing for 4h, and a premix is obtained;

[0055] (2) the premix powder is placed into a graphite mold, and then placed into a vacuum hot-pressing furnace, and pre-pressing is performed, and the pre-pressing pressure is 10T;

[0056] (3) after the pre-pressing is finished, heating is started, the temperature is increased to 400 DEG C at 5 DEG C / min, after 30 min of keeping the temperature, the temperature is continuously increased to 550 DEG C at 8 DEG C / min, after 30 min of keeping the temperature, the pressure is increased to 25T, and 90 min of keeping the temperature and pressure is performed;

[0057] (4) after the vacuum hot-pressing is finished, the temperature is decreased to 450 DEG C, argon protection gas is started to be introduced, and the temperature is continuously decreased to room temperature, thereby obtaining the zinc telluride target material.

[0058] Comparative Example Four

[0059] A preparation method of a zinc telluride N-doped target material comprises the following steps:

[0060] (1) zinc telluride powder, tellurium powder, zinc powder and zinc nitride powder with a purity of 5N are mixed according to a mass ratio of 75:18:2:5, 5L / min argon is introduced, the argon introduction time is 10 min, a three-dimensional homogenizer is used for mixing for 4h, and a premix is obtained;

[0061] (2) the premix powder is placed into a graphite mold, and then placed into a vacuum hot-pressing furnace, and pre-pressing is performed, and the pre-pressing pressure is 10T;

[0062] (3) after the pre-pressing is finished, heating is started, the temperature is increased to 400 DEG C at 5 DEG C / min, after 30 min of keeping the temperature, the temperature is continuously increased to 550 DEG C at 8 DEG C / min, after 30 min of keeping the temperature, the pressure is increased to 25T, and 90 min of keeping the temperature and pressure is performed;

[0063] (4) After the vacuum hot pressing is finished, the temperature is decreased to 450 DEG C, argon protective gas is introduced, and the temperature is continuously decreased to room temperature, to obtain the zinc telluride doped N target material.

[0064] Comparative Example Five

[0065] A preparation method of a zinc telluride doped N target material, comprising the following steps:

[0066] (1) Zinc telluride powder with a purity of 5N, tellurium powder, zinc powder and zinc nitride powder are mixed according to a mass ratio of 70:20:3:7, 5L / min argon is introduced, the argon introduction time is 10 min, a three-dimensional homogenizing machine is used for mixing for 4 h, to obtain a premix;

[0067] (2) The premix powder is put into a graphite mold, and then put into a vacuum hot pressing furnace, to perform pre-pressing treatment, and the pre-pressing pressure is 10T;

[0068] (3) After the pre-pressing is finished, heating is started, the temperature is increased to 400 DEG C at a rate of 5 DEG C / min, after 30 min of heat preservation, the temperature is continuously increased to 600 DEG C at a rate of 8 DEG C / min, after 30 min of heat preservation, the pressure is increased to 25T, and 90 min of heat preservation and pressure preservation are performed;

[0069] (4) After the vacuum hot pressing is finished, the temperature is decreased to 450 DEG C, argon protective gas is introduced, and the temperature is continuously decreased to room temperature, to obtain the zinc telluride doped N target material.

[0070] Performance detection test

[0071] 1. The density of the target material in the examples and the comparative examples is measured by using a wax sealing method, the relative density is calculated based on the true density, and the test statistical results are shown in Table 1.

[0072] 2. The impurity content of the target material in the examples and the comparative examples is measured by using IPC, so as to determine the purity of the material, and the test results are shown in Table 1.

[0073] 3. The resistivity of the target material in the examples and the comparative examples is tested by using a four-probe method, which is used to measure low resistivity and high resistivity materials, the measurement range is (0.0001-19000 ohm*cm) and is relatively accurate, the resistivity is very good when less than 8000 ohm*cm, and the conductivity is relatively good, and the test results are shown in Table 1.

[0074] 4. The sample in the examples and the comparative examples is combusted and converted into N2 in a pure oxygen environment and a corresponding reagent by using a weight method, is conveyed by a carrier gas helium through a special separation tube and is separated by using a gas chromatography principle, is detected by a thermal conductivity detector (TCD), and the N content in the sample is measured and shown in Table 1.

[0075] Table 1-Performance detection results of the target material in the examples and the comparative examples of the application

[0076]

[0077]

[0078] It can be known from the comparison of the performance detection results of example 3 and comparative examples 1, 2 and 4-5 in table 1 that if the pressure of vacuum hot pressing is higher, the relative density of the target material will decrease, the N content will also decrease, and the final resistivity cannot meet the higher requirements.

[0079] It can be known from the comparison of the performance detection results of example 3 and comparative examples 1, 2 and 4-5 in table 1 that if the pressure of vacuum hot pressing is higher, the relative density of the target material will decrease, the N content will also decrease, and the final resistivity cannot meet the higher requirements.

[0080] It can be known from the comparison of the performance detection results of example 3 and comparative examples 1, 2 and 4-5 in table 1 that if the pressure of vacuum hot pressing is higher, the relative density of the target material will decrease, the N content will also decrease, and the final resistivity cannot meet the higher requirements.

[0081] The above-described specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above-described specific embodiments are merely examples of the present application and are not intended to limit the protection scope of the present application. It is particularly pointed out that any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a zinc telluride N-doped target, characterized in that: The following steps are involved: (1) zinc telluride powder, tellurium powder, zinc powder, and zinc nitride powder are mixed in a mass ratio of (50-70): (20-25): (3-10): (7-15) to obtain a premix, wherein the purity of the zinc telluride powder, tellurium powder, zinc powder, and zinc nitride powder is 5N or higher; (2) Place the premix powder into a mold and perform pre-pressing in a vacuum hot pressing device; (3) After the pre-pressing is completed, vacuum hot pressing treatment is carried out, including the first heating and holding stage, the second heating and holding stage, and the pressure-raising and holding stage. The temperature is raised to 300-400°C in the first heating and holding stage, and the temperature is raised to 500-550°C in the second heating and holding stage. (4) After vacuum hot pressing, the temperature is cooled to room temperature to obtain the zinc telluride doped N target; In step (3), the pressure is increased to 23-25 ​​tons during the pressure-raising and temperature-maintaining stages.

2. The method for preparing a zinc telluride N-doped target according to claim 1, wherein: In step (2), the pre-pressing pressure is 8-10 tons.

3. The method for preparing a zinc telluride N-doped target according to claim 1, wherein: The holding time of the first heating and holding stage is 20-30 minutes, the holding time of the second heating and holding stage is 20-30 minutes, and the holding time of the pressure rising and holding stage is 60-90 minutes.

4. The method for preparing a zinc telluride N-doped target according to claim 3, wherein: The heating rate of the first heating and holding stage is 3-5°C / min, and the heating rate of the second heating and holding stage is 8-10°C / min.

5. The method for preparing a zinc telluride N-doped target according to claim 1, wherein: In step (1), zinc telluride powder, tellurium powder, zinc powder and zinc nitride powder are mixed under protective gas conditions for a mixing time of 4-6 hours.

6. The method for preparing a zinc telluride N-doped target according to claim 1, wherein: In step (4), after the vacuum hot pressing is completed, the temperature is lowered to below 450°C and protective gas is introduced, and then the temperature is lowered to room temperature to obtain the zinc telluride doped N target.

7. The method for preparing a zinc telluride N-doped target according to claim 5 or 6, characterized in that: The protective gas is argon.

8. A zinc telluride N-doped target obtained by the method for preparing a zinc telluride N-doped target according to any one of claims 1 to 7.

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