Copper-indium-tin-selenium quaternary semiconductor alloy and preparation method and application thereof

Abstract

The invention belongs to the technical field of alloys, and particularly relates to a copper-indium-tin-selenium quaternary semiconductor alloy and a preparation method and application thereof. The atomic ratio of the elements in the alloy is as follows: copper is 2.2-3, indium is 0.7-1, tin is 0.7-1, and selenium is 4-5; the preparation method of the alloy comprises the following steps: according to the atomic ratio, the weighed raw materials are subjected to one-step smelting in a vacuum and protective atmosphere to obtain the copper-indium-tin-selenium semiconductor alloy. The prepared novel copper-indium-tin-selenium quaternary semiconductor alloy is a P-type semiconductor and can be applied to the photo-thermal and photoelectric conversion related fields such as solar cells.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of alloys, in particular to a copper-indium-tin-selenium quaternary semiconductor alloy and a preparation method and application thereof. BACKGROUND

[0002] Green energy and blue energy are two directions of clean energy. Tidal energy and ocean energy represent blue energy; solar energy and wind energy represent green energy. In recent years, solar energy has received extensive attention from the industry and the scientific community, the most important reason being that the use of solar energy is not limited by region and environment, and there are no security risks. Solar energy conversion can be divided into two main ways: photo-thermal conversion and photo-electric conversion. Among them, photo-electric conversion is favored because it can directly convert light energy into electrical energy through solar cells, and then through grid connection, the utilization of electrical energy in industry is completed. The scientific community focuses on the research and development of solar cell materials and devices with high photo-electric conversion efficiency, and the industry focuses on how to quickly scale up the preparation process of solar cells and component production; the core of the above two is the light-absorbing layer material of the solar cell, because this material determines the core properties of the solar cell, i.e. photo-electric conversion efficiency.

[0003] At present, silicon-based thin-film solar cells have been commercialized, and have good photo-electric conversion efficiency and long-term stability, but in the process of preparing high-purity silicon, the energy consumption is large, and the thickness of the light-absorbing layer of the silicon-based solar cell needs to be 100 microns. Exploring and discovering a thinner and more efficient solar cell light-absorbing layer material has become the focus of the industry.

[0004] The laboratory photo-electric conversion efficiency of thin-film solar cells represented by copper-indium-gallium-selenium exceeds 25% in a short time, and the photo-electric conversion efficiency of industrial components exceeds 16%, reaching a level comparable to silicon thin-film solar cells in terms of efficiency; but the light-absorbing layer film of copper-indium-gallium-selenium thin-film cells contains the metal elements indium and gallium, which are expensive and have a low content, limiting its use on a large scale. Therefore, finding a similar quaternary alloy that can partially replace indium and gallium has become the new focus of researchers and engineers; copper-indium-tin-selenium quaternary semiconductor material has a similar structure to copper-indium-gallium-selenium and is applied to thin-film solar cell light-absorbing layer materials, but in the preparation of copper-indium-tin-selenium, due to the large difference in melting point of metal copper, metal indium, metal tin and non-metallic element selenium, the sublimation loss of selenium element and the risk of explosion caused by large enthalpy change and heat release during the mixing reaction of metal elements and selenium. SUMMARY

[0005] In order to solve the above problems, the application provides a copper indium tin selenium quaternary semiconductor alloy material and a preparation method and application thereof. The copper indium tin selenium semiconductor alloy is prepared by a solid-liquid-solid reaction with copper selenide, metal indium and tin diselenide as metal precursors. The above method avoids the loss of selenium element sublimation and the explosion risk caused by large enthalpy change and heat release during the mixing reaction of metal elements and selenium, thereby ensuring the safety of the experiment. The prepared P-type semiconductor alloy can be used in the fields of solar cell photoelectricity, photo-thermal conversion and the like.

[0006] In order to achieve the above object, the application adopts the following technical scheme: The application aims to provide a preparation method of a copper indium tin selenium quaternary semiconductor alloy, comprising the following steps: S1. According to the atomic ratio of the element composition of the copper indium tin selenium quaternary semiconductor alloy, the atomic ratio of the element composition of the copper indium tin selenium quaternary semiconductor alloy is copper: indium: tin: selenium = 2.2-3: 0.7-1: 0.7-1: 4-5, and the corresponding mass of copper selenide, metal indium and tin diselenide is weighed; S2. Under vacuum conditions, the copper selenide, metal indium and tin diselenide are subjected to smelting under a protective gas atmosphere to obtain a copper indium tin selenium semiconductor alloy.

[0007] In a preferred embodiment of the application, the molar ratio of the copper selenide, metal indium and tin diselenide is 2.2-3: 0.7-1: 0.7-1.

[0008] In a preferred embodiment of the application, the protective gas is argon.

[0009] In a preferred embodiment of the application, the vacuum degree of the vacuum condition is 0.3*10 -5 Pa-0.5*10 -5 Pa.

[0010] In a preferred embodiment of the application, the smelting is performed in a step-by-step smelting manner, and the specific conditions are that the temperature is first raised to 650-780 DEG C, the copper selenide, metal indium and tin diselenide are completely melted, and then the temperature is raised to 850-950 DEG C for smelting for 30-60 min, and the copper indium tin selenium semiconductor alloy is obtained after cooling.

[0011] Another object of the application is to provide a copper indium tin selenium semiconductor alloy prepared by the above method.

[0012] A third object of the application is to provide an application of the above alloy in the preparation of a solar cell.

[0013] Compared with the prior art, the application has the beneficial effects that: 1. The application uses copper selenide, metal indium and tin diselenide as metal precursors, heats the quartz test tube by vacuum induction furnace, after reaching the melting point of the three substances, copper selenide, metal indium and tin diselenide occur solid-liquid fusion reaction, thereby preparing copper indium tin selenide semiconductor alloy, avoiding the sublimation of selenium element in the preparation process of the alloy, resulting in the loss of selenium element, at the same time, avoiding the use of metal elements and selenium mixture, the large enthalpy change in the reaction process, avoiding the risk of explosion caused by heat release, the safety loss of the experimenter and the surrounding experimental equipment and property. The new type of copper indium tin selenide quaternary semiconductor alloy prepared by the application is a P-type semiconductor, which can be applied to the fields of solar cell photoelectric and photo-thermal conversion.

[0014] 2. The application uses the method of vacuum induction heating, adopts solid phase heating reaction means, and prepares copper indium tin selenide semiconductor alloy, which is a P-type semiconductor. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 It is the XRD graph of copper indium tin selenide quaternary semiconductor alloy in embodiment 1 of the application. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0017] It should be noted that the professional terms used in the application are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the application. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the application can be purchased from the market or prepared by the existing method.

[0018] The laboratory photoelectric conversion efficiency of thin film solar cell represented by copper indium gallium selenide exceeds 25% in a short time, and the photoelectric conversion efficiency of industrial assembly exceeds 16%, reaching the level comparable to that of silicon thin film solar cell in efficiency; but the thin film of light absorbing layer of copper indium gallium selenide thin film cell contains metal elements indium and gallium with high price and low content, so that it is limited in large-scale use. Therefore, finding a similar quaternary alloy that can partially replace indium gallium becomes a new focus of researchers and engineers; the quaternary semiconductor material copper indium tin selenide is applied to the light absorbing layer material of thin film solar cell because of the similar structure to copper indium gallium selenide, but in the preparation process of copper indium tin selenide, because of the large difference between the melting points of metal copper, metal indium and metal tin and non-metallic element selenium, the selenium element is easy to volatilize, and the explosion is easy to occur when the four elements are mixed together, which causes the personnel injury, so how to quickly, simply and efficiently prepare copper indium tin selenide on a large scale becomes one of the difficult problems to be solved at present.

[0019] Based on this, first, the application provides a preparation method of copper indium tin selenide quaternary semiconductor alloy, comprising the following steps: S1, according to the atomic ratio of the element composition of the copper indium tin selenide quaternary semiconductor alloy, the atomic ratio of the element composition of the copper indium tin selenide quaternary semiconductor alloy is: copper: indium: tin: selenium = 2.2~3: 0.7~1: 0.7~1: 4~5, and the corresponding mass of copper selenide, metal indium and tin diselenide is taken.

[0020] S2, under vacuum condition, copper selenide, metal indium and tin diselenide are subjected to smelting under protective gas atmosphere to obtain copper indium tin selenide semiconductor alloy.

[0021] The application uses copper selenide, metal indium and tin diselenide as metal precursors, heats the quartz test tube by using a vacuum induction furnace, after reaching the melting points of the three substances, the copper selenide, metal indium and tin diselenide occur solid-phase fusion reaction, thereby preparing the copper indium tin selenide semiconductor alloy, avoiding the sublimation and volatilization of selenium element in the component during the preparation process of the alloy, causing the loss of selenium element, at the same time, avoiding the use of mixing of metal elemental elements and selenium, the large enthalpy change in the reaction process, avoiding the danger of explosion caused by the heat release of the reaction, and the safety loss of the experimental personnel and the surrounding experimental equipment and property. The new copper indium tin selenide quaternary semiconductor alloy prepared by the application is a P-type semiconductor, and the phase analysis of the same is carried out to obtain the phase uniform copper indium tin selenide material, which can be applied to the fields of solar cell photoelectric or photo-thermal conversion.

[0022] The molar ratio of the copper selenide, metal indium and tin diselenide is 2.5~3: 0.8~1: 0.8~1.

[0023] The protective gas is argon.

[0024] The vacuum degree of the vacuum condition is 0.3*10-5 Pa~0.5×10 -5 Pa.

[0025] The smelting adopts a sectional smelting mode, and specific conditions are as follows: first, the temperature is raised to 650-780 DEG C, after the copper selenide, metal indium and tin diselenide are completely melted, the temperature is raised to 850-950 DEG C for smelting for 30-60 min, and then the copper indium tin selenide semiconductor alloy is obtained by cooling.

[0026] Secondly, the application provides the copper indium tin selenide semiconductor alloy prepared by the above method.

[0027] Finally, the application provides application of the above copper indinium tin selenide quaternary semiconductor alloy in preparation of a solar cell.

[0028] The copper indium tin selenide quaternary semiconductor alloy prepared by the application is a P-type semiconductor alloy, can be used as a P-type light-absorbing layer of a solar cell, and can be used in a thin-film solar cell by constructing a PN junction with an N-type layer semiconductor film such as a cadmium sulfide film, a zinc sulfide film or the like, and can also be used in a solar energy light-heat conversion refrigeration application.

[0029] The application will be further described below by means of specific examples.

[0030] Example 1 A preparation method of a copper indium tin selenide quaternary semiconductor alloy comprises the following steps: 3 mol of copper selenide, 1 mol of metal indium and 1 mol of tin diselenide are loaded into a quartz glass test tube, the quartz glass test tube is vacuumized, sealed and placed into a vacuum induction furnace; the vacuum induction furnace is vacuumized, and then protective gas nitrogen or argon is introduced to make the vacuum degree of the vacuum induction furnace be 0.4*10 -5 Pa, then the temperature is raised to 665 DEG C, after the three raw materials are melted, the temperature is raised to 885 DEG C, smelting is carried out for 45 min, and the furnace is slowly cooled to obtain the copper indium tin selenide semiconductor alloy.

[0031] The analysis result of the atomic ratio of copper indium tin selenide is as follows: copper (Cu): 2.98, indium (In): 0.99, tin (Sn): 0.98, and selenium (Se): 4.97.

[0032] Example 2 A preparation method of a copper indium tin selenide quaternary semiconductor alloy comprises the following steps: 2.5 mol of copper selenide, 1 mol of metal indium and 1 mol of tin diselenide are loaded into a quartz glass test tube, the quartz glass test tube is vacuumized, sealed and placed into a vacuum induction furnace; the vacuum induction furnace is vacuumized, and then protective gas nitrogen or argon is introduced to make the vacuum degree of the vacuum induction furnace be 0.4*10 -5Pa, and then heated to 678℃, after the three raw materials are melted, heated to 890℃, smelting 40min, slow cooling with the furnace, to obtain copper indium tin selenium semiconductor alloy.

[0033] The analysis results of copper indium tin selenium atomic ratio are: copper (Cu): 2.5, indium (In): 0.98, tin (Sn): 0.99, selenium (Se): 4.49.

[0034] Example 3 A preparation method of a copper indium tin selenium quaternary semiconductor alloy, comprising the following steps: 2.8mol of copper selenide, 0.8mol of metal indium and 0.9mol of tin diselenide are loaded into a quartz glass test tube, the quartz glass test tube is vacuumized, sealed and placed in a vacuum induction furnace; the vacuum induction furnace is vacuumized, and then protective gas nitrogen or argon is introduced, so that the vacuum degree in the vacuum induction furnace is 0.4*10 -5 Pa, and then heated to 660℃, after the three raw materials are melted, heated to 860℃, smelting 35min, slow cooling with the furnace, to obtain copper indium tin selenium semiconductor alloy.

[0035] The analysis results of copper indium tin selenium atomic ratio are: copper (Cu): 2.77, indium (In): 0.78, tin (Sn): 0.89, selenium (Se): 4.58.

[0036] Example 4 A preparation method of a copper indium tin selenium quaternary semiconductor alloy, comprising the following steps: 2.6mol of copper selenide, 0.9mol of metal indium and 0.95mol of tin diselenide are loaded into a quartz glass test tube, the quartz glass test tube is vacuumized, sealed and placed in a vacuum induction furnace; the vacuum induction furnace is vacuumized, and then protective gas nitrogen or argon is introduced, so that the vacuum degree in the vacuum induction furnace is 0.4*10 -5 Pa, and then heated to 710℃, after the three raw materials are melted, heated to 920℃, smelting 50min, slow cooling with the furnace, to obtain copper indium tin selenium semiconductor alloy.

[0037] The analysis results of copper indium tin selenium atomic ratio are: copper (Cu): 2.55, indium (In): 0.89, tin (Sn): 0.93, selenium (Se): 4.47.

[0038] Example 5 A preparation method of a copper indium tin selenium quaternary semiconductor alloy, comprising the following steps: The three raw materials of 2.7 mol of copper selenide, 0.95 mol of metallic indium and 0.8 mol of tin diselenide are loaded into a quartz glass test tube, the quartz glass test tube is vacuumized, sealed, and placed in a vacuum induction furnace; the vacuum induction furnace is vacuumized, and then protective gas nitrogen or argon is introduced, so that the vacuum degree in the vacuum induction furnace is 0.4×10 -5 Pa, and then heated to 700 DEG C, and after the three raw materials are melted, heated to 930 DEG C, and smelted for 55 min, and slowly cooled in the furnace, to obtain a copper indium tin selenide semiconductor alloy.

[0039] The analysis result of the atomic ratio of copper indium tin selenide is: copper (Cu): 2.68, indium (In): 0.92, tin (Sn): 0.78, and selenium (Se): 4.27.

[0040] Since the copper indium tin selenide quaternary semiconductor alloys prepared in Examples 1-5 have similar structures and basically the same performance, the copper indium tin selenide quaternary semiconductor alloy prepared in Example 1 is taken as an example for further description, and the result analysis is as follows.

[0041] In order to detect the performance of the alloy prepared in the application, the alloy prepared in Example 1 is subjected to XRD test, and the result is shown in Figure 1 As shown in Figure 1 It can be seen that the copper indium tin selenide alloy prepared in Example 1 has a uniform phase structure.

[0042] In addition, the alloy prepared in Example 1 is subjected to Hall effect test at room temperature (298 K) and a magnetic field intensity of 5000 Gauss with different current intensities, and the result is shown in Table 1.

[0043] Table 1: Hall effect test result of copper indium tin selenide Note: the Hall coefficient is positive, representing that the semiconductor of this type is a P-type semiconductor; otherwise, the Hall coefficient is negative, representing that the semiconductor of this type is an N-type semiconductor.

[0044] As shown in Table 1, the bulk Hall coefficient of the alloy prepared in Example 1 is positive, indicating that the copper indium tin selenide alloy prepared in Example 1 is a P-type semiconductor. The P-type semiconductor alloy can be used as a P-type light-absorbing layer of a solar cell, and through the action with an N-type layer semiconductor thin film such as a cadmium sulfide thin film, a zinc sulfide thin film, etc., a PN junction is constructed, which is used in a thin film solar cell, and can also be used in solar light-heat conversion refrigeration applications.

[0045] It is to be understood that every range of values disclosed herein is to be understood to encompass any and every sub-range of values within the range. Although the preferred embodiments of the invention have been described above, it will be appreciated that those skilled in the art, on consideration of this disclosure, will be able to devise additional embodiments that, although not explicitly described or shown herein, nonetheless fall within the scope of the present invention. Accordingly, the appended claims are intended to include within their scope all such alternatives, modifications and variations as fall within the scope of the present invention. Various features and aspects of the present invention will become apparent from the following examples, which are intended only to exemplify the invention. It should be understood, of course, that in the various examples of the present invention, the specific phrasing of the claims will depend on the exact nature of the claims sought.

[0046] Obviously, numerous modifications and variations of the present application are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the present application can be practiced otherwise than as specifically described herein.

Claims

1. A method for preparing a copper indium tin selenide quaternary semiconductor alloy, characterized in that, Includes the following steps: Based on the atomic ratios of the elements in the copper indium tin selenide (CIDS) quaternary semiconductor alloy, the atomic ratios of the elements in the CIDS quaternary semiconductor alloy are as follows: Copper:Indium:Tin:Selenium = 2.2~3:0.7~1:0.7~1:4~5, weigh out the corresponding masses of copper selenide, metallic indium and tin diselenide respectively; Copper indium tin selenide, metallic indium, and tin diselenide are smelted under vacuum conditions in a protective gas atmosphere to obtain a copper indium tin selenide semiconductor alloy.

2. The method for preparing the copper indium tin selenide quaternary semiconductor alloy according to claim 1, characterized in that, The molar ratio of copper selenide, metallic indium, and tin diselenide is 2.2~3:0.7~1:0.7~1.

3. The method for preparing the copper indium tin selenide quaternary semiconductor alloy according to claim 1, characterized in that, The vacuum level under vacuum conditions is 0.3 × 10⁻⁶. -5 Pa ~ 0.5 × 10 -5 Pa.

4. The method for preparing the copper indium tin selenide quaternary semiconductor alloy according to claim 1, characterized in that, The smelting process is carried out in stages. The specific conditions are as follows: first, the temperature is raised to 650℃~780℃, and after copper selenide, metallic indium and tin diselenide are completely melted, the temperature is raised to 850℃~950℃ and smelted for 30min~60min. After cooling, copper indium tin selenide semiconductor alloy is obtained.

5. A copper indium tin selenide quaternary semiconductor alloy, characterized in that, It is prepared by the method described in any one of claims 1 to 4.

6. The application of the copper indium tin selenide quaternary semiconductor alloy of claim 5 in the fabrication of solar cells.

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