TWI398013B - Method and system for forming non-vacuum copper indium gallium sulphide selenium absorption layer and cadmium sulfide buffer layer - Google Patents

Description

Method and system for forming copper indium gallium sulphide selenium absorption layer and cadmium sulfide buffer layer without vacuum

The invention relates to a method and a system for forming a copper indium gallium sulfide selenium absorption layer and a cadmium sulfide buffer layer, in particular to perform a two-stage sulfur selenium reaction in a non-vacuum environment to form an excellent quality absorption layer.

In the international wave of green energy, copper-indium-gallium-selenide (CIGS) solar cells with quaternary compounds in thin-film solar cells are not limited by raw materials, can be fabricated on large-area flexible substrates, and have high conversion efficiency, especially The conversion efficiency of the cell can reach 20% and the conversion efficiency of the module can reach 14%. Therefore, it has been gradually developed by the new energy industry in various countries.

Referring to the first figure, a schematic diagram of a conventional technology copper indium gallium selenide solar cell. As shown in the first figure, the copper indium gallium selenide solar cell comprises a substrate 10, a back electrode layer 20, an absorbing layer 30, a buffer layer 40, a transparent conductive layer 50 and a front electrode layer 60 which are sequentially stacked from bottom to top, wherein incident Light L is injected into the copper indium gallium selenide solar cell from top to bottom.

The substrate 10 is generally glass, the back electrode layer 20 is made of metal molybdenum, and the absorption layer 30 is a quaternary compound containing copper, indium, gallium, and selenium to form an N-type semiconductor layer, and the buffer layer 40 contains zinc sulfide to form a P-type semiconductor layer. The transparent conductive layer (TCO) 50 includes indium tin oxide (ITO) or zinc oxide (ZnO), and the front electrode layer 60 may be made of nickel or aluminum, generally in the form of a grid, and a metal nickel layer is first formed on the transparent conductive layer 50. To avoid the formation of a high resistance metal oxide, followed by the formation of a metal aluminum layer.

A pn junction 35 is formed between the N-type absorber layer 30 and the P-type buffer layer 40 for absorbing incident light to generate a free electron hole pair, further causing the back electrode layer 20 to be a positive voltage and the front electrode layer 60 to be negative. The voltage is connected to the external load through the positive contact 22 and the negative contact 62 for outputting electric power.

The above-mentioned method for manufacturing the copper indium gallium selenide solar cell can adopt a vacuum process or a non-vacuum process, wherein the vacuum process mainly uses a sputtering method or an evaporation method, and although the product quality is good, the material utilization rate is low, the equipment is expensive, and the manufacturing is expensive. The high cost, non-vacuum process uses the Ink Process, which can greatly reduce the manufacturing cost, and has great potential for development. However, the compactness of the copper indium gallium selenide absorber layer is insufficient, often leading to the quaternary compound of copper indium gallium selenide. It is difficult to form larger particles, so that the grain boundary in the absorption layer is relatively large, and the light falling in the grain boundary cannot be successfully converted into usable electric energy, so that the conversion efficiency is not easily improved.

Therefore, there is a need for a method and system for improving the light absorption efficiency and photoelectric conversion efficiency of a copper indium gallium selenide absorber layer under non-vacuum and providing a well-matched cadmium sulfide buffer layer to form a preferred pn junction, thereby solving the above-mentioned conventional techniques. problem.

The main object of the present invention is to provide a non-vacuum method for forming a copper indium gallium sulphide selenide absorbing layer and a cadmium sulfide buffer layer, which is formed by coating a mixed slurry on a back electrode layer for a substrate having a back electrode layer under non-vacuum. The cloth layer, after preliminary drying, is solidified by a solid densification device, followed by a primary sulfurization reaction treatment and a primary selenization reaction treatment to form a primary copper indium gallium sulfide selenium layer, and then heat treatment to improve Lattice matching of the primary copper indium gallium sulphide selenide layer, followed by heterogeneous phase removal treatment using potassium cyanide or bromide to remove the heterogeneous cuprous selenide and copper sulphide, followed by post-stage sulfidation treatment and subsequent stages Selenization reaction to produce the desired copper indium gallium sulphide selenide absorption layer, and finally using a chemical bath water bath method to form a cadmium sulfide buffer layer on the copper indium gallium sulphide selenium absorption layer, and the copper indium gallium sulphide selenium absorption layer and The cadmium sulfide buffer layer can be applied to a copper indium gallium selenide solar cell, which can improve the light absorption efficiency and photoelectric conversion efficiency of the absorption layer, and improve the matching of the buffer layer to the absorption layer, thereby forming a shape between the absorption layer and the buffer layer. High-efficiency p-n junction, thereby reducing manufacturing costs and improve overall performance of CIGS solar cells.

Another object of the present invention is to provide a system for forming a copper indium gallium sulphide selenide absorbing layer and a cadmium sulfide buffer layer without vacuum, comprising a mixing device, a coating layer forming device, a drying device, a densification device, and a primary sulfur selenium reaction. The device, the heat treatment device, the impurity phase cleaning device, the post-stage sulfur selenium reaction device and the cadmium sulfide buffer layer growth device are respectively subjected to mixing treatment, coating layer formation treatment, drying treatment, solidification treatment, primary sulfur selenium reaction treatment , heat treatment, impurity phase removal treatment, post-stage sulfur selenium reaction treatment and cadmium sulfide buffer layer growth treatment, and then sequentially form a copper indium gallium sulphide selenium absorption layer and a cadmium sulfide buffer layer on the metal molybdenum layer for high-performance Copper indium gallium selenide solar cell.

The embodiments of the present invention will be described in more detail below with reference to the drawings and the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;

Referring to the second figure, a flow chart of the method of the present invention. As shown in the second figure, the method of the present invention begins with step S10, and performs a mixing process under non-vacuum, including mixing copper indium gallium sulphide powder, a solvent and an additive to form a copper indium gallium sulphide slurry. The indium gallium sulphide powder may include CuIn, CuInGa, CuInSe, CuInGaSe, CuInS and CuS sulfide. At least one of gallium (CuInGaS) powder, the solvent may include at least one of an alcohol and an amine, and the additive may include at least one of a dispersant, an adhesive, and a leveling agent.

Next, proceeding to step S20, a coating layer forming process is performed to form a copper indium gallium sulfide selenium slurry coating layer on the back electrode layer 20 by using a copper indium gallium sulfide selenium slurry, the coating layer forming process including spray coating treatment, coating One of the cloth treatment and the immersion treatment, and the back electrode layer 20 is located on the upper surface of the substrate 10, and is subjected to a drying treatment in step S30, and is heated and heated to pre-dry and remove the copper indium gallium sulfide selenium slurry coating. The solvent in the layer.

Next, in step S40, the copper indium gallium sulfide selenium slurry coating layer after solvent removal is further densified, and may include one of a rolling treatment, a high pressure spray hydraulic treatment, and a high pressure jet compression treatment. Applying pressure to the copper indium gallium sulphide sulphide slurry coating layer to solidify the copper indium gallium sulphide sulphide slurry coating layer, and then proceeding to step S50 for primary sulfur selenium reaction, including sulfidation reaction and selenization reaction. The hydrogen sulfide and the hydrogen selenide may be respectively introduced, and the copper indium gallium sulfide selenium slurry coating layer may be used to generate sulfide and selenide at a temperature rise, thereby forming a primary copper indium gallium sulfide selenium absorption layer.

Next, a heat treatment is performed in step S60 for crystallization treatment of the primary copper indium gallium sulphide selenide absorption layer, which may be a rapid thermal process (RTP), which may include sequential rapid temperature crystallization treatment, Multi-stage constant temperature crystallization treatment and multi-stage cooling treatment to improve the crystal structure of the primary copper indium gallium sulphide selenide absorbing layer, and then proceed to step S70 for heterogeneous removal treatment, including the use of a heterogeneous scavenger to remove the primary copper indium gallium a compound of a hetero phase in the sulfur selenium absorption layer, comprising at least one of copper selenide (Cu ₂ Se) and copper sulfide (CuS), and the heterogeneous scavenger comprises sodium cyanide (NaCN) and potassium cyanide ( At least one of KCN) and bromide is washed and dried. Next, proceeding to step S80, a subsequent sulfur-selenium reaction treatment is performed, which is similar to the primary sulfur selenium reaction treatment in step S50, including a sulfurization reaction and a selenization reaction, so that the primary copper indium gallium sulfide selenium absorption layer is further subjected to sulfurization reaction and selenization. The reaction forms a copper indium gallium sulphide selenide absorbing layer of the latter stage, that is, a desired copper indium gallium sulphide selenide absorbing layer.

Finally, in step S90, a cadmium sulfide buffer layer growth treatment, a substrate scraping treatment, and a cleaning and drying treatment are performed, wherein the cadmium sulfide buffer layer growth treatment is performed by a chemical bath deposition (CBD) in step S80. The generated copper indium gallium sulphide selenium absorption layer is immersed in an aqueous solution containing sulfur and cadmium to form a cadmium sulfide buffer layer on the copper indium gallium sulphide selenium absorption layer, wherein the aqueous solution comprises chlorinated salt, ammonia water (NH ₃ ) and Sulfur (SC(NH ₂ ) ₂ )), and the chloride may include cadmium chloride (CdCl ₂ ), cadmium sulfate (CdSO ₄ ), cadmium iodide (CdI ₂ ), and cadmium diacetate (Cd (CH _{3 )} At least one of COO) ₂ ). The substrate scraping process scrapes off the edges and back of the substrate to remove excess material.

The method of the invention is characterized in that the two-stage sulfur selenium reaction is carried out in a non-vacuum environment to improve the quality of the copper indium gallium sulfide selenium absorption layer, wherein the sulfur selenium reaction comprises sequential sulfurization reaction and selenization reaction, and is first Before the primary sulfur selenium reaction in the stage, the dried copper indium gallium sulfide selenium slurry coating layer is subjected to a densification treatment, thereby reducing the number of grain boundaries to improve the photoelectric conversion efficiency.

Another feature of the method of the present invention is that, during the first stage of the primary sulfur selenium reaction and the second stage of the subsequent stage sulfur selenium reaction, rapid thermal annealing treatment and impurity phase removal treatment are sequentially performed, wherein the rapid thermal annealing treatment It is used to improve the crystal structure of the primary copper indium gallium sulfide selenium absorption layer produced by the primary sulfur selenium reaction, thereby reducing or eliminating possible internal stress and improving lattice matching, while the impurity phase removal treatment is used to remove copper which will hinder copper. The indium gallium sulphide selenide absorber layer is subjected to photoelectric conversion of heterogeneous cuprous selenide and copper sulfide to further improve photoelectric conversion.

Referring to the third figure, a schematic diagram of the system of the present invention. As shown in the third figure, the system of the present invention includes a mixing device 110, a coating layer forming device 120, a drying device 130, a solidifying device 140, a primary sulfur selenium reaction device 150, a heat treatment device 160, and a phase cleaning device. 170. The post-stage sulfur-selenium reaction device 180 and the cadmium sulfide buffer layer growth device 190 are respectively subjected to mixing treatment, coating layer formation treatment, drying treatment, solidification treatment, primary sulfur selenium reaction treatment, heat treatment, and impurity phase removal. The treatment, the post-stage sulfur selenium reaction treatment and the cadmium sulfide buffer layer growth treatment further form a copper indium gallium sulfide selenium absorption layer and a cadmium sulfide buffer layer on the metal molybdenum layer.

The mixing device 110 can include at least one powder tank 112, at least one solvent tank 114, and a mixing tank 116, wherein the at least one powder tank 112 is used for accommodating a plurality of powders, including copper indium alloy (CuIn), copper indium. At least one of a gallium compound (CuInGa), copper indium selenide (CuInSe), copper indium gallium selenide (CuInGaSe), copper indium sulfide (CuInS), and copper indium gallium sulfide (CuInGaS) powder, the at least one solvent tank The 114 system is for accommodating a solvent and an additive, the solvent comprising at least one of an alcohol and an amine, the additive may include at least one of a dispersing agent, an adhesive, and a leveling agent, and the mixing tank 116 is utilized. A stirring device (not shown) uniformly mixes the powder in the at least one powder tank 112 and the solvent of the at least one solvent tank 114 with an additive to produce a copper indium gallium sulfide selenium slurry.

The coating layer forming device 120 may be one of a spraying device for performing a spray coating process, a coating device for performing a coating process, and an infusion device for performing a soaking process. The spraying device may include an ultrasonic nozzle, an ultrasonic controller and a pneumatic flow controller (not shown) for uniformly spraying the copper indium gallium sulfide selenium slurry of the mixing tank 116 to the back electrode on the upper surface of the substrate 10. The layer is formed to form a copper indium gallium sulfide selenium slurry coating layer, and the lower surface of the substrate 10 is supported and driven by a plurality of rollers 12 to advance.

Further, the coating apparatus may include a slurry extruder and a doctor blade, wherein the slurry extruder extrudes the copper indium gallium sulfide selenium slurry onto the back electrode layer, and the doctor blade is used to remove excess copper indium gallium sulfide Slurry to achieve the desired thickness. The immersion device comprises a immersion tank and a scraper, and the immersion tank is provided with a copper indium gallium sulphide selenide slurry, and after the copper indium gallium sulphide selenide slurry is immersed in the back electrode layer, the excess copper indium gallium sulphide selenide slurry is removed by a scraper. To achieve the desired thickness.

The drying device 130 may include at least one of a heating wire, a high-frequency radiation source, and an infrared source (not shown) for pre-drying and removing the solvent in the copper indium gallium sulfide selenium slurry coating layer.

The solidification device 140 may include a rolling device for performing a rolling process, a high pressure spray hydraulic device for performing a high pressure spray hydraulic pressure process, and a high pressure jet press device for performing a high pressure jet press treatment. One. The third figure is an example of a rolling device. The display device 140 can include at least one roller 142 for densifying the copper indium gallium sulfide selenium slurry coating layer.

In addition, the high-pressure spray hydraulic device may include a liquid compressor and a nozzle, and the liquid compressor is used to increase the pressure of the spray liquid, and then sprayed onto the coating layer of the copper indium gallium sulfide selenium slurry through the nozzle, thereby applying pressure, the spray The liquid can be water. The high pressure jet compression device may include a gas compressor for increasing the pressure of the jet, and then spraying the nozzle onto the coating layer of the copper indium gallium sulphide slurry to apply pressure, the jet may be air One of nitrogen, nitrogen and argon.

The primary sulfur selenium reaction device 150 may include a primary sulfurization reaction device and a primary selenization reaction device (not shown), respectively introducing hydrogen sulfide and hydrogen selenide and heating the copper indium gallium sulfide selenium slurry coating layer at elevated temperature. The primary sulfurization reaction treatment and the primary selenization reaction treatment form a primary copper indium gallium sulfide selenium absorption layer.

The heat treatment device 160 may be a rapid thermal annealing treatment device, which may include a rapid temperature rising crystallization section, a multi-stage constant temperature crystallization section, and a multi-stage cooling section (not shown) for sequentially absorbing the primary copper indium gallium sulfide selenium. The layer is subjected to rapid temperature crystallization treatment, multi-stage constant temperature crystallization treatment and multi-stage cooling treatment to reduce or eliminate possible internal stress and improve the crystal structure of the primary copper indium gallium sulfide selenium absorption layer.

The impurity phase removing device 170 may include an etching tank and a cleaning and drying device (not shown), wherein the etching tank accommodates an etching solution containing at least one of sodium cyanide (NaCN), potassium cyanide (KCN) and bromide. One of the compounds for removing impurities in the primary copper indium gallium sulphide selenide absorbing layer, including at least one of cuprous selenide and copper sulphide, and cleaning and drying by a cleaning and drying device to further improve copper Crystal quality of indium gallium sulphide selenide absorber layer.

The post-sulfur-selenium reaction device 180 is similar to the primary sulfur-selenium reaction device 150, and may include a post-stage vulcanization reaction device and a post-stage selenization reaction device (not shown) for respectively performing the primary copper indium gallium sulfide selenium absorption layer. The post-stage vulcanization reaction treatment and the post-stage selenization reaction treatment form a copper indium gallium sulphide selenide absorbing layer of the latter stage, that is, a desired copper indium gallium sulphide selenide absorbing layer.

The cadmium sulfide buffer layer growth device 190 may include a cadmium sulfide growth soaking device, a substrate scraping device, and a cleaning and drying device (not shown), wherein the cadmium sulfide growth soaking device houses an aqueous solution containing sulfur and cadmium to make the latter stage When the copper indium gallium sulphide selenide absorption layer is immersed in the aqueous solution, a cadmium sulfide buffer layer is grown on the copper indium gallium sulphide selenide absorption layer of the subsequent stage, and the substrate scraping device scrapes off the edge and the back surface of the substrate. Excess material, and the cleaning and drying device is used to clean and dry the cadmium sulfide buffer layer. The aqueous solution includes a chloride salt, ammonia water, and thiourea, and the chloride salt may include at least one of cadmium chloride, cadmium sulfate, cadmium iodide, and cadmium diacetate.

The system of the present invention is characterized in that it can be operated in a non-vacuum atmospheric environment to form a high-quality copper indium gallium sulphide selenium absorbing layer and a cadmium sulfide buffer layer for use in a copper indium gallium selenide solar cell.

The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, and any modifications or alterations to the present invention made in the spirit of the same invention. All should still be included in the scope of the intention of the present invention.

10. . . Substrate

12. . . Wheel

20. . . Back electrode layer

twenty two. . . Positive contact

30. . . Absorbing layer

35. . . P-n junction

40. . . The buffer layer

50. . . Transparent conductive layer

60. . . Front electrode layer

62. . . Negative contact

110. . . Mixing device

112. . . Powder slot

114. . . Solvent tank

116. . . Mixing tank

120. . . Coating layer forming device

130. . . Drying device

140. . . Solidification device (roller device)

142. . . Wheel

150. . . Primary sulfur selenium reaction unit

160. . . Heat treatment device (rapid thermal annealing treatment device)

170. . . Miscellaneous phase cleaning device

180. . . Subsequent sulfur-selenium reaction device

190. . . Cadmium sulfide buffer layer growth device

L. . . Incident light

S10. . . Mixed processing

S20. . . Coating layer formation treatment

S30. . . Drying treatment

S40. . . Solidification

S50. . . Primary sulfur selenium reaction treatment

S60. . . Heat treatment (rapid thermal annealing treatment)

S70. . . Miscellaneous phase removal

S80. . . Subsequent sulfur and selenium reaction treatment

S90. . . Cadmium sulfide buffer layer growth treatment

The first picture is a schematic diagram of a conventional technology copper indium gallium selenide solar cell.

The second figure is a flow chart of the method of the invention.

The third figure is a schematic diagram of the system of the present invention.

S10. . . Mixed processing

S20. . . Coating layer formation treatment

S30. . . Drying treatment

S40. . . Solidification

S50. . . Primary sulfur selenium reaction treatment

S60. . . Heat treatment (rapid thermal annealing treatment)

S70. . . Miscellaneous phase removal

S80. . . Subsequent sulfur and selenium reaction treatment

S90. . . Cadmium sulfide buffer layer growth treatment

Claims (19)

A non-vacuum method for forming a copper indium gallium sulphide selenium absorbing layer and a cadmium sulfide buffer layer, wherein a copper indium gallium sulphide selenide absorbing layer and a cadmium sulfide buffer are sequentially formed on a back electrode layer on a substrate under non-vacuum Layer, the method comprises the following sequential steps: a mixing treatment, mixing copper indium gallium sulphide powder, solvent and additives to form a copper indium gallium sulphide selenide slurry; a coating layer forming treatment, the system is copper indium gallium a sulfur selenium slurry is coated on the back electrode layer to form a copper indium gallium sulfide selenium slurry coating layer, and the coating layer forming process includes one of a spray coating process, a coating process, and a soaking process; The treatment is performed by heating and heating to pre-dry and remove the solvent in the coating layer of the copper indium gallium sulfide selenium slurry; a solidification treatment, including a rolling treatment, a high pressure spray hydraulic treatment, and a high pressure jet compression treatment. One, by applying pressure on the copper indium gallium sulfide selenium slurry coating layer, the copper indium gallium sulfide selenium slurry coating layer is densified; a primary sulfur selenium reaction treatment, including a sulfurization reaction and a selenization reaction , respectively, hydrogen sulfide and hydrogen selenide are introduced, and are heating up The copper indium gallium sulfide selenium slurry coating layer is made to generate sulfide and selenide to form a primary copper indium gallium sulfide selenium absorption layer; a heat treatment for performing crystallization treatment of the primary copper indium gallium sulfide selenium absorption layer; Miscellaneous phase removal treatment, using a heterogeneous scavenger to remove the heterogeneous compound in the primary copper indium gallium sulphide selenide absorption layer, cuprous selenide and copper sulfide, and washing and drying; a post-stage sulfur selenium reaction treatment Similar to the primary sulfur selenium reaction treatment, including the sulfurization reaction and the selenization reaction, the primary copper indium gallium sulfide selenium absorption layer is further subjected to a sulfurization reaction and a selenization reaction to form a copper indium gallium sulfide selenium absorption layer of the latter stage. That is, the required copper indium gallium sulphide selenide absorption layer; and a cadmium sulfide buffer layer growth treatment, the copper indium gallium sulphide selenium absorption layer is immersed in an aqueous solution containing sulfur and cadmium by a chemical bath water bath method, The cadmium sulfide buffer layer is formed on the copper indium gallium sulfide selenium absorber layer. According to the method of claim 1, wherein the copper indium gallium sulphide powder comprises copper indium alloy (CuIn), copper indium gallium compound (CuInGa), copper indium selenide (CuInSe), and copper indium gallium selenide. At least one of (CuInGaSe), copper indium sulfide (CuInS), and copper indium gallium sulfide (CuInGaS) powder. The method of claim 1, wherein the solvent comprises at least one of an alcohol and an amine. The method of claim 1, wherein the additive comprises at least one of a dispersant, an adhesive, and a leveling agent. The method of claim 1, wherein the heat treatment is a rapid thermal annealing treatment, the crystallization treatment comprising at least one of a rapid temperature crystallization treatment, a multi-stage constant temperature crystallization treatment, and a multi-stage cooling crystallization treatment. The method of claim 1, wherein the compound of the heterophase comprises at least one of cuprous selenide and copper sulfide. The method of claim 1, wherein the heterogeneous scavenger comprises at least one of sodium cyanide, potassium cyanide, and bromide. The method of claim 1, wherein the aqueous solution comprises a chloride salt, an ammonia water, and a sulfur urine, and the chloride salt comprises at least one of cadmium chloride, cadmium sulfate, cadmium iodide, and cadmium diacetate. . The method of claim 1, wherein the cadmium sulfide buffer growth treatment further comprises scraping the edges and the back of the substrate to remove excess material. A non-vacuum system for forming a copper indium gallium sulphide selenide absorbing layer and a cadmium sulfide buffer layer, sequentially forming a copper indium gallium sulphide selenium absorbing layer and a cadmium sulfide buffer on a back electrode layer on a substrate under non-vacuum a layer, and the lower surface of the substrate is supported and driven by a plurality of rollers, the system comprising: a mixing device comprising at least one powder tank, at least one solvent tank and a mixing tank, thereby performing a mixing process, the at least one The powder tank is for accommodating a plurality of powders, and the powder comprises at least one of a copper indium alloy, a copper indium gallium compound, copper indium selenide, copper indium gallium selenide, copper indium sulfide, and copper indium gallium sulfide. The at least one solvent tank is used for accommodating the solvent and the additive, and the mixing tank uniformly mixes the powder in the at least one powder tank and the solvent of the at least one solvent tank with the additive to produce copper indium. a gallium-sulfur-selenium slurry; a coating layer forming device comprising: a spraying device for performing a spray coating process, a coating device for performing a coating process, and one of an infusion device for performing a soaking treatment, and further Copper indium gallium a selenium slurry forms a copper indium gallium sulphide sulphide slurry coating layer on the back electrode layer; a drying device for predrying and removing the solvent in the copper indium gallium sulphide sulphide slurry coating layer; a device for solidifying the copper indium gallium sulfide selenium slurry coating layer, the solidification device comprising a rolling device for performing a rolling process, and a high pressure spray hydraulic pressure for performing a high pressure spray hydraulic pressure treatment a device and one of a high pressure jet compression device for performing high pressure jet compression treatment; a primary sulfur selenium reaction device comprising a primary sulfurization reaction device and a primary selenization reaction device, respectively introducing hydrogen sulfide and hydrogen selenide The copper indium gallium sulfide selenium slurry coating layer is subjected to a primary sulfurization reaction treatment and a primary selenization reaction treatment at a temperature rise to form a primary copper indium gallium sulfide selenium absorption layer; a heat treatment device for performing primary copper indium Crystallization treatment of the gallium sulphide selenium absorption layer; a heterophase removal device comprising an etching tank and a cleaning and drying device, the etching tank accommodating the etching liquid to remove the impurity phase compound in the primary copper indium gallium sulphide selenium absorption layer, The cleaning and drying device The primary copper indium gallium sulfide selenium absorption layer is washed and dried; a post-stage sulfur selenium reaction device, similar to the primary sulfur selenium reaction device, includes a post-stage sulfurization reaction device and a post-stage selenization reaction device. The primary copper indium gallium sulphide selenide absorption layer is subjected to a post-sulfidation treatment and a subsequent selenization reaction to form a copper indium gallium sulphide selenide absorption layer, that is, the required copper indium gallium sulphide sulphide. An absorbing layer; and a cadmium sulfide buffer layer growing device, comprising a cadmium sulfide growth soaking device, a substrate scraping device, and a cleaning and drying device, wherein the cadmium sulfide growth soaking device houses an aqueous solution containing sulfur and cadmium to make the latter stage When the copper indium gallium sulphide selenide absorption layer is immersed in the aqueous solution, a cadmium sulfide buffer layer is grown on the copper indium gallium sulphide selenide absorption layer of the subsequent stage, and the substrate scraping device is used to scrape off the edge of the substrate. And the excess material on the back side, the cleaning and drying device is used for cleaning and drying the cadmium sulfide buffer layer. The system of claim 10, wherein the solvent comprises at least one of an alcohol and an amine. The system of claim 10, wherein the additive comprises at least one of a dispersant, an adhesive, and a leveling agent. The system of claim 10, wherein the spraying device comprises an ultrasonic jet nozzle, an ultrasonic controller, and a pneumatic flow controller, the coating device comprising a slurry extruder and a scraper, the soaking device comprising a soaking tank And scraper. The system of claim 10, wherein the drying device comprises at least one of a heating wire, a high-frequency radiation source, and an infrared source. The system of claim 10, wherein the rolling device comprises at least one roller, the high pressure spray hydraulic device comprising a liquid compressor for increasing the pressure of the spray liquid and spraying the spray liquid to the copper indium gallium sulfide slurry a nozzle on the coating layer, the spray is water, the high pressure jet compression device includes a gas compressor that increases the pressure of the jet, and a nozzle that sprays the jet onto the coating layer of the copper indium gallium sulphide slurry. The jet is one of air, nitrogen and argon. The system of claim 10, wherein the heat treatment is a rapid thermal annealing treatment, the crystallization treatment comprising at least one of a rapid temperature crystallization treatment, a multi-stage constant temperature crystallization treatment, and a multi-stage cooling crystallization treatment. The system of claim 10, wherein the etching solution comprises at least one of sodium cyanide, potassium cyanide, and bromide. The system of claim 10, wherein the compound of the heterophase comprises at least one of cuprous selenide and copper sulfide. The system according to claim 10, wherein the aqueous solution comprises a chloride salt, an ammonia water and a sulfur urine, and the chloride salt comprises at least one of cadmium chloride, cadmium sulfate, cadmium iodide and cadmium diacetate. .