WO2019153668A1 - 铜铟镓硒吸收层及其制备方法、太阳能电池及其制备方法 - Google Patents

铜铟镓硒吸收层及其制备方法、太阳能电池及其制备方法 Download PDF

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WO2019153668A1
WO2019153668A1 PCT/CN2018/098106 CN2018098106W WO2019153668A1 WO 2019153668 A1 WO2019153668 A1 WO 2019153668A1 CN 2018098106 W CN2018098106 W CN 2018098106W WO 2019153668 A1 WO2019153668 A1 WO 2019153668A1
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indium gallium
copper indium
copper
selenium
gallium selenide
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PCT/CN2018/098106
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English (en)
French (fr)
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叶亚宽
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北京铂阳顶荣光伏科技有限公司
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Priority to CN201880002666.7A priority Critical patent/CN110352499A/zh
Publication of WO2019153668A1 publication Critical patent/WO2019153668A1/zh

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Definitions

  • the present disclosure relates to the field of solar cell manufacturing technologies, and in particular, to a method for preparing a copper indium gallium selenide absorber layer and a method for preparing the solar cell.
  • Copper indium gallium selenide (CIGS) thin film solar cells are a new generation of solar cells with promising prospects. It has the advantages of high conversion efficiency, low cost, long life, good low light performance and strong radiation resistance. Since the 1990s, CIGS thin film solar cells have been the most efficient thin film solar cells in the laboratory. In 2016, ZSW in Germany increased the conversion efficiency of CIGS thin film solar cells to 22.6% in the laboratory. Since the conversion efficiency of CIGS thin film solar cells is close to that of crystalline silicon cells, CIGS thin film solar cells have great development prospects.
  • Some embodiments of the present disclosure provide a method for preparing a copper indium gallium selenide absorbing layer, comprising the steps of:
  • Step 100 sequentially forming a copper gallium alloy layer and an indium layer on the substrate to obtain a copper indium gallium prefabricated film;
  • Step 200 placing the copper indium gallium pre-formed film into a reaction chamber having a preset first temperature threshold; and introducing a selenium atmosphere having a preset first carrier gas flow value into the reaction chamber; The copper indium gallium prefabricated film is reacted in the selenium atmosphere of the first carrier gas flow value for a first predetermined period of time, such that the surface of the copper indium gallium prefabricated film forms an unsaturated In-Se binary phase and Cu-Se Yuan phase
  • Step 300 Passing a selenium atmosphere having a preset second carrier gas flow value smaller than a preset first carrier gas flow value into the reaction chamber; the surface is formed with an unsaturated In-Se binary phase And a Cu-Se binary phase copper indium gallium prefabricated film is reacted in a selenium atmosphere having the second carrier gas flow value for a second predetermined period of time, so that the selenium source contains a selenium source to the bottom of the copper indium gallium prefabricated film Diffusion, reacting with copper indium gallium contained on the surface of the copper indium gallium prefabricated film adjacent to the substrate to obtain a copper indium gallium selenide prefabricated film formed on the surface of the substrate;
  • Step 400 Annealing a copper indium gallium selenide pre-formed film formed on the surface of the substrate within a preset second temperature threshold and a third predetermined duration to obtain a copper indium gallium selenide absorber layer.
  • a back electrode is deposited on the substrate; the step 100 includes:
  • a copper gallium alloy layer and an indium layer are sequentially sputtered on the substrate on which the back electrode is deposited to obtain a copper indium gallium prefabricated film.
  • a back electrode is deposited on the substrate; the step 100 includes:
  • a copper gallium alloy layer and an indium layer are sequentially sputtered on the surface of the back electrode of the substrate such that the back electrode, the copper gallium alloy layer and the indium layer are laminated together to obtain a copper indium gallium prefabricated film.
  • the copper indium gallium prefabricated film comprises Cu, In, and Ga, and the molar ratio of Cu, In, and Ga included in the copper indium gallium prefabricated film satisfies: 0.8 ⁇ n Cu /(n In +n Ga ) ⁇ 0.96 and 0.25 ⁇ n Ga / (n In + n Ga ) ⁇ 0.35.
  • the second carrier gas flow value is less than the first carrier gas flow value.
  • the ratio of the first carrier gas flow value to the second carrier gas flow value is greater than five.
  • the first carrier gas flow value is greater than or equal to 5 slm and less than or equal to 15 slm, and the second carrier gas flow value is greater than zero and less than or equal to 2 slm.
  • the method for preparing the copper indium gallium selenide absorber layer further comprises:
  • the solid state selenium source is heated to a predetermined third temperature threshold in a vacuum or a set pressure inert gas to obtain a selenium atmosphere.
  • the preset first temperature threshold is 550 ° C ⁇ 580 ° C
  • the preset second temperature threshold is 500 ° C ⁇ 600 ° C
  • the preset third temperature threshold is 250 ° C ⁇ 470 ° C
  • the set pressure is 1 Pa to 1 atm.
  • the first preset duration is 25s to 35s
  • the second preset duration is 260s to 275s
  • the third preset duration is 5min to 30min.
  • the preset first temperature threshold is 620 ° C ⁇ 700 ° C
  • the preset second temperature threshold is 500 ° C ⁇ 600 ° C
  • the preset third temperature threshold is 380 ° C ⁇ 500 °C.
  • the first preset duration is 15 s to 25 s
  • the second preset duration is 15 s to 35 s
  • the third preset duration is 5 min to 30 min.
  • the copper indium gallium pre-formed film has a ramp rate in the course of the step 200, 300 of greater than 3 ° C/s.
  • the reaction chamber is a graphite reaction chamber.
  • the selenium atmosphere comprises: selenium vapor or hydrogen selenide gas.
  • the annealing treatment is performed in a vacuum or in a selenium atmosphere having a preset third carrier gas flow value; when the annealing treatment is performed with a preset third carrier gas flow value The selenium atmosphere is performed, and the preset third carrier gas flow value is less than a preset second carrier gas flow value.
  • Some embodiments of the present disclosure also provide a method of preparing a solar cell, comprising the method of preparing a copper indium selenium gallium absorbing layer provided by some embodiments disclosed above.
  • Some embodiments of the present disclosure also provide a copper indium gallium selenide absorber layer prepared by the method for preparing the copper indium gallium selenide absorber layer.
  • Some embodiments of the present disclosure also provide a solar cell comprising the copper indium gallium selenide absorber layer.
  • FIG. 1 is a flow chart of a method for preparing a copper indium gallium selenide absorber layer according to some embodiments of the present disclosure.
  • FIG. 2 is a flow chart of a method for preparing a copper indium gallium selenide absorber layer according to some embodiments of the present disclosure.
  • FIG 3 is a diagram showing the distribution of EDS spectrum components in the thickness direction of a copper indium gallium selenide absorber layer prepared by some embodiments of the present disclosure.
  • FIG. 4 is an X-ray diffraction pattern of a copper indium gallium selenide absorber layer prepared by a method for preparing a copper indium gallium selenide absorber layer according to some embodiments of the present disclosure.
  • FIG. 5 is a schematic structural diagram of a solar cell according to some embodiments of the present disclosure.
  • the preparation method of the CIGS absorption layer mainly includes a co-evaporation method, a post-sputtering selenization method (referred to as a two-step selenization method), and an electrochemical method.
  • a co-evaporation method a post-sputtering selenization method
  • an electrochemical method Compared with the co-evaporation method and the two-step selenization method, when the copper indium gallium selenide absorption layer prepared by the electrochemical method is applied to a solar cell, the stability and the highest conversion efficiency of the solar cell are relatively weak, resulting in electrochemical method.
  • the industrialization process for preparing copper indium gallium selenide absorption layer is relatively slow.
  • the co-evaporation method refers to evaporating four elements of Cu, In, Ga, and Se, and simultaneously depositing the four elements on the substrate and reacting to obtain a copper indium gallium selenide absorption layer.
  • the small area copper indium gallium selenide absorption layer prepared by the co-evaporation method is applied to a solar cell, and the solar cell has high conversion efficiency, but the uniformity of the copper indium gallium selenide absorption layer prepared by the above co-evaporation method is difficult to control,
  • the above co-evaporation method is difficult to be used in the preparation process of a large-area copper indium gallium selenide absorbing layer, which leads to a certain limitation of the industrial application of the solar cell, so that the solar cell cannot obtain high conversion efficiency.
  • the two-step selenization method refers to: first, using In 2 Se 3 target, Ga 2 Se 3 target, and Cu 2 Se target, sputtering In, Ga, and Cu on the surface of the substrate to obtain a copper indium gallium selenide pre-formed film. . Then, the copper indium gallium selenide pre-formed film is subjected to high-temperature heat treatment in a H 2 Se vapor atmosphere or a Se vapor atmosphere to obtain a CIGS absorption layer.
  • the copper indium gallium selenide absorbing layer is prepared by the above two-step selenization method, a saturated concentration of Se vapor is formed on the surface of the copper indium gallium prefabricated film, that is, the selenium atmosphere introduced into the reaction chamber causes the selenium vapor in the reaction chamber to be present. Saturated state.
  • the reaction enthalpy of Cu, In and Se is lower than that of Ga and Se, and the reaction rate of Cu, In and Se is faster.
  • Cu and In on the surface of the copper indium gallium prefabricated film can quickly and sufficiently react with the saturated selenium atmosphere, thereby obtaining a relatively stable In 2 Se 3 binary phase and a Cu 2 Se binary phase. Since the stable In 2 Se 3 binary phase and the Cu 2 Se binary phase have relatively small lattice voids, the Se element (Se element exists in the form of a selenium atmosphere) is blocked from the bottom of the copper indium gallium prefabricated film. Diffusion causes a decrease in the ability of the Se element to diffuse toward the bottom of the copper indium gallium prefabricated film.
  • Cu and In at the bottom of the copper indium gallium prefabricated film also preferentially diffuse Ga onto the surface of the copper indium gallium prefabricated film, and react with Se to form the above-mentioned In 2 Se 3 binary phase and Cu 2 Se binary phase.
  • the obtained copper indium gallium selenide absorption layer is enriched at the bottom.
  • the fine Ga element of the grain causes the Ga element to be unevenly distributed in the copper indium gallium selenide absorption layer, thereby greatly reducing the performance of the copper indium gallium selenide absorption layer.
  • some embodiments of the present disclosure provide a method for preparing a copper indium gallium selenide absorbing layer.
  • the preparation method includes step 100 (S100), step 200 (S200), step 300 (S300), and step 400 (S400):
  • S200 placing a copper indium gallium prefabricated film into a reaction chamber having a preset first temperature threshold, and introducing a selenium atmosphere having a preset first carrier gas flow value into the reaction chamber, wherein the copper indium gallium prefabricated film has The first carrier gas flow rate is reacted in a selenium atmosphere for a first predetermined period of time such that a surface of the copper indium gallium pre-formed film forms an unsaturated In-Se binary phase and a Cu-Se binary phase.
  • the reaction chamber can be selected from a graphite reaction chamber.
  • the graphite reaction chamber has good thermal insulation and chemical stability under high temperature conditions.
  • the graphite reaction chamber reacts with oxygen at a high temperature to form a reducing atmosphere so that the metal in the reaction chamber is not oxidized.
  • the reaction chamber can also be other reaction chambers, which will not be enumerated here.
  • S300 introducing a selenium atmosphere having a preset second carrier gas flow value into the reaction chamber, the surface forming a copper indium gallium prefabricated with an unsaturated In-Se binary phase and a Cu-Se binary phase
  • the film is reacted in a selenium atmosphere having the second carrier gas flow value for a second predetermined period of time, such that the selenium source contained in the selenium atmosphere diffuses to the bottom of the copper indium gallium prefabricated film, and the copper contained in the copper indium gallium prefabricated film Indium gallium is reacted to obtain a copper indium gallium selenide pre-formed film formed on the surface of the substrate.
  • S400 annealing a copper indium gallium selenide pre-formed film formed on the surface of the substrate in a preset second temperature threshold and a third predetermined duration to obtain a copper indium gallium selenide absorption layer.
  • a selenium atmosphere having a first carrier gas flow value is introduced into the reaction chamber, so that the selenium atmosphere in the reaction chamber is at Higher concentration.
  • the copper indium gallium prefabricated film is maintained in the selenium atmosphere for a first predetermined period of time, the copper indium gallium prefabricated film forms a chemically bond-unsaturated In-Se binary on the surface of the copper indium gallium prefabricated film at a higher Se concentration. Phase and Cu-Se binary phase.
  • the unsaturated In-Se binary phase and the Cu-Se binary phase may further undergo selenization reaction with the selenium source to generate a saturated In in the first predetermined period of time. 2 Se 3 binary phase and Cu 2 Se binary phase. Thereafter, a selenium atmosphere of a second carrier gas flow value is introduced into the reaction chamber to form a copper indium gallium pre-formed film of a non-saturated In-Se binary phase and a Cu-Se binary phase at a lower flow rate of selenium atmosphere.
  • the reaction continues with the selenium source, so that the selenium source contained in the selenium atmosphere diffuses to the bottom of the copper indium gallium prefabricated film, and reacts with the copper indium gallium contained in the copper indium gallium prefabricated film to obtain copper indium gallium formed on the surface of the substrate.
  • the selenium pre-formed film ensures that the selenium element contained in the prepared copper indium gallium selenide pre-formed film is uniformly distributed in the thickness direction of the copper indium gallium selenide pre-formed film.
  • the surface forms an unsaturated In-Se binary phase and a Cu-Se binary phase of the copper indium gallium prefabricated film at a lower flow rate of selenium.
  • the atmosphere continues to react with the selenium source, and the selenization reaction enters the second process. Since the flow rate of the selenium atmosphere flowing into the reaction chamber in the second process is lowered, the surface Se concentration of the unsaturated In-Se binary phase and the Cu-Se binary phase on the surface of the copper indium gallium prefabricated film is lowered, and the concentration is low.
  • the selenium atmosphere flow is insufficient to provide a sufficient concentration of Se source for further selenization of the unsaturated In-Se binary phase and the Cu-Se binary phase on the surface of the copper indium gallium prefabricated film.
  • the In-Se binary phase and the Cu-Se binary phase have larger crystals from a lattice viewpoint.
  • the voids, therefore, the above-described In-Se binary phase and Cu-Se binary phase do not hinder the diffusion of the selenium source into the bottom of the copper indium gallium pre-formed film in the form of a selenium atmosphere.
  • the selenium atmosphere in the reaction chamber is maintained at a low concentration, so that the copper indium gallium prefabricated film is The second preset time period is maintained in the low concentration selenium atmosphere. Therefore, the selenium source diffuses to the bottom of the copper indium gallium prefabricated film through the lattice gap of the In-Se binary phase and the Cu-Se binary phase in the form of selenium vapor.
  • Se reacts with Cu, In and Ga at the bottom of the copper indium gallium prefabricated film to form an alloy phase, thereby avoiding the problem that the Ga element in the prepared copper indium gallium selenide absorption layer is enriched to the bottom, and the prepared copper is ensured.
  • the distribution of Ga elements in the indium gallium selenide absorber layer is relatively uniform, and the grain size of the Ga element increases.
  • the main purpose of the above annealing treatment is to release stress, increase material ductility and toughness, and produce a special microstructure.
  • the method for preparing the copper indium gallium selenide absorbing layer provided by some embodiments of the present disclosure is to anneal the copper indium gallium selenide pre-formed film obtained by the selenization reaction under a condition of a small amount of selenium atmosphere.
  • the final copper indium gallium selenide absorber layer obtained by annealing treatment not only has a large grain size, but also has good uniformity of Ga element distribution, which can solve the problem of stability and processing uniformity of large-area solar cells in related art. Control problem.
  • the substrate 10 described above is made of soda lime glass having a thickness of 2 mm to 3.2 mm.
  • a back electrode is deposited on the surface of the substrate 10.
  • a copper gallium alloy layer and an indium layer are sequentially formed on the substrate 10.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 300 nm to 1000 nm.
  • the above S100 when the back electrode is deposited on the substrate, the above S100 includes:
  • a copper gallium alloy layer and an indium layer are sequentially sputtered on the surface of the back electrode of the substrate such that the back electrode, the copper gallium alloy layer and the indium layer are laminated together to obtain a copper indium gallium prefabricated film.
  • the sputtering method is a magnetron sputtering method.
  • the magnetron sputtering method is a DC magnetron sputtering method or an intermediate frequency magnetron sputtering method.
  • the copper gallium alloy layer has a thickness of from 250 nm to 400 nm.
  • the thickness of the indium layer is 200 to 300 nm.
  • the copper indium gallium prefabricated film formed by the copper gallium alloy layer and the indium layer includes three elements of Cu, In, and Ga.
  • Pre-film copper indium gallium included Cu, In and Ga molar ratios satisfy: 0.8 ⁇ n Cu / (n In + n Ga) ⁇ 0.96 and 0.25 ⁇ n Ga / (n In + n Ga) ⁇ 0.35.
  • the thickness of the above copper gallium alloy layer is 300 nm.
  • the thickness of the indium layer was 250 nm.
  • the molar percentage of copper atoms in the copper gallium alloy layer was 75%, and the molar percentage of gallium atoms in the copper gallium alloy layer was 25%.
  • the molar ratio of Cu, In, and Ga included in the copper indium gallium prefabricated film satisfies: 0.8 ⁇ n Cu /(n In +n Ga ) ⁇ 0.96 and 0.25 ⁇ n Ga /(n In +n Ga ) ⁇ 0.35 .
  • the above copper indium gallium pre-formed film reacts with the selenium atmosphere to form a Cu-rich Cu x Se phase (x>1). Since the Cu x Se phase has a high chemical saturation and a small lattice gap between adjacent crystal phases, the Cu x Se phase hinders the selenium source from diffusing into the bottom of the copper indium gallium pre-formed film in the form of a selenium atmosphere.
  • the selenization ability is weaker in a low-concentration Se atmosphere, which leads to the enrichment of the fine-grained Ga element at the bottom of the copper-indium-gallium-selenium absorbing layer, so that the performance of the copper-indium-gallium-selenium absorbing layer Decreased significantly. Therefore, when the prepared copper indium gallium selenide absorber layer is applied to a solar cell, a high performance solar cell cannot be obtained.
  • the formed copper indium gallium selenide absorber layer contains a large amount of In-Se, Ga-Se binary phase.
  • the In-Se binary phase and the Ga-Se binary phase contained in the copper indium gallium selenide absorption layer are large, the copper indium gallium selenide quaternary phase of the chalcopyrite structure cannot be formed in the copper indium gallium selenide absorption layer, resulting in When the copper indium gallium selenide absorber layer is applied to a solar cell, the performance of the solar cell is degraded.
  • the first carrier gas flow rate value is greater than the second carrier gas flow rate value.
  • the concentration of the selenium atmosphere in the reaction chamber at the first predetermined duration reaction period is greater than the concentration at the second predetermined duration reaction period. Therefore, in the process of reacting the copper indium gallium prefabricated film in the selenium atmosphere having the first carrier gas flow value for the first predetermined period of time, the copper indium gallium prefabricated film rapidly reacts with the high concentration selenium atmosphere to be in the copper indium gallium
  • the surface of the pre-formed film forms an In-Se binary phase and a Cu-Se binary phase.
  • the In-Se binary phase and the Cu-Se binary phase have not yet reached further selenization reaction to form the In 2 Se 3 binary phase and the Cu 2 Se binary phase, in the reaction chamber.
  • the selenium atmosphere is reduced from the first carrier gas flow value to the second carrier gas flow value, and the selenium atmosphere of the copper indium gallium prefabricated film in which the In-Se binary phase and the Cu-Se binary phase are formed is formed on the surface.
  • the concentration is low, which not only does not cause the In-Se binary phase and the Cu-Se binary phase formed on the surface of the copper indium gallium prefabricated film to rapidly form a saturated In 2 Se 3 binary phase and a Cu 2 Se binary phase.
  • the selenium source required for the formation of the copper indium gallium selenide quaternary phase is prepared by reacting a copper indium gallium prefabricated film having an In-Se binary phase and a Cu-Se binary phase formed thereon.
  • the Se element diffuses to the bottom of the copper indium gallium pre-formed film in which the In-Se binary phase and the Cu-Se binary phase are formed in the form of a selenium atmosphere, thereby ensuring the Ga contained in the prepared copper indium gallium selenide absorption layer.
  • the elements are evenly distributed.
  • the ratio of the first carrier gas flow value to the second carrier gas flow value is greater than five.
  • the unit of carrier gas flow value is slm, which is the abbreviation of standard litre per minute, which refers to the carrier gas flow rate of 1L/min under standard state (1 atmosphere, 25 degrees Celsius). Slm said.
  • the concentration of the selenium atmosphere at the first carrier gas flow value in the reaction chamber is higher, and the copper indium gallium pre-formed film is at the higher selenium.
  • the first preset time period is reacted at the atmospheric concentration. Since the first predetermined duration is short, the surface of the copper indium gallium prefabricated film forms an unsaturated In-Se binary phase and a Cu-Se binary phase.
  • the concentration of the selenium atmosphere in the reaction chamber at the second carrier gas flow value is low, so that the Se atoms pass through the unsaturated In-Se binary phase and Cu-Se II.
  • the lattice gap of the element phase rapidly diffuses to the bottom of the copper indium gallium prefabricated film and reacts with Cu, In and Ga at the bottom of the copper indium gallium prefabricated film, thereby avoiding the phenomenon that the Ga element is enriched at the bottom of the copper indium gallium selenide absorption layer.
  • the selenium atmosphere described above is a selenium vapor or a hydrogen selenide (H 2 Se) gas, and is of course not limited to the two listed.
  • the method for preparing the copper indium gallium selenide absorber layer further includes:
  • the solid selenium source In a vacuum or an inert gas with a set pressure, the solid selenium source is heated to a preset third temperature threshold to obtain a selenium atmosphere, which facilitates subsequent flow control of the selenium atmosphere carrier gas into the reaction chamber.
  • the inert gas can be nitrogen or argon.
  • the solid selenium source is elemental selenium
  • the selenium atmosphere is selenium vapor.
  • the selenium atmosphere at the first carrier gas flow rate and the selenium atmosphere at the second carrier gas flow rate are obtained by heating the solid selenium source to a preset third temperature threshold in a vacuum or a set pressure inert gas. Therefore, the selenium atmosphere at the first carrier gas flow value and the selenium atmosphere at the second carrier gas flow value are only different in the selenium atmosphere flow rate.
  • the above-described copper indium gallium pre-formed film has an average heating rate in the reaction chamber of greater than 3 ° C/s.
  • the temperature rising rate block is about 15 ° C / s -20 ° C / s
  • the second preset time period is slow in the reaction stage, and the copper indium gallium prefabricated film is controlled in the first preset duration and the second
  • the average heating rate of the preset duration is maintained at a relatively high level, such as above 3 ° C / s, so that the selenium atmosphere is maintained at a higher diffusion and reaction rate.
  • the rate of temperature rise of the above copper indium gallium pre-formed film in the reaction chamber depends on two factors, one of which is the temperature of the reaction chamber itself.
  • the reaction chamber radiates heat transfer to the copper indium gallium prefabricated film.
  • the second is the temperature of the selenium atmosphere, and the selenium atmosphere transfers heat to the copper indium gallium prefabricated film by convection.
  • the predetermined first temperature threshold is 550 ° C to 580 ° C. In the range of 550 ° C ⁇ 580 ° C, the copper indium gallium pre-formed film is fully reacted with the selenium atmosphere to obtain a high-performance copper indium gallium selenide absorber layer with good Ga element distribution.
  • the preset third temperature threshold is 250 ° C ⁇ 470 ° C to ensure the formation of a high temperature selenium atmosphere, and facilitate the subsequent reaction of the selenium atmosphere with the above copper indium gallium prefabricated film.
  • the above set pressure is 1 Pa to 1 atm.
  • the first predetermined duration is 25 s to 35 s, and the surface of the copper indium gallium prefabricated film forms a non-saturated In-Se binary phase and a Cu-Se binary phase in a relatively short time.
  • the first preset duration is 30s.
  • the second preset duration is 260s-275s.
  • a second carrier gas flow selenium atmosphere is introduced into the reaction chamber, and the surface is formed with an unsaturated In-Se binary phase and Cu.
  • the -Se binary phase copper indium gallium prefabricated film is in a low concentration selenium atmosphere for a relatively long time. Since the unsaturated In-Se binary phase and the Cu-Se binary phase on the surface of the copper indium gallium prefabricated film have a large lattice gap, the Se element diffuses toward the bottom of the copper indium gallium prefabricated film, thereby avoiding the Ga element in the copper. The phenomenon of enrichment at the bottom of the indium gallium selenide absorber layer.
  • a selenium atmosphere is introduced into the reaction chamber at a second carrier gas flow rate for a second predetermined period of time of 260 s to 275 s, which complements the copper indium gallium pre-formed film containing the unsaturated In-Se binary phase and the Cu-Se binary phase.
  • the second preset duration is preferably 270 s.
  • the preset second temperature threshold is 500 ° C to 600 ° C
  • the third predetermined duration is 5 min to 30 min, so that the copper indium gallium prefabricated film is sufficiently subjected to high temperature annealing treatment.
  • the rate of temperature rise of the copper indium gallium pre-formed film in the reaction chamber is greater than 3 ° C / s and less than or equal to 6 ° C / s.
  • the Se source in the selenium atmosphere maintains a high diffusion rate between the surface and the bottom of the copper indium gallium prefabricated film, and the flow rate of the selenium atmosphere matches the heating rate of the reaction chamber, thereby The reaction speed of the copper indium gallium prefabricated film and the selenium source contained in the selenium atmosphere is controlled.
  • the method for preparing the copper indium gallium selenide absorber layer of the above implementation has a larger operating window of process parameters, which is beneficial to process parameter control. .
  • the preset first temperature threshold may be 620 ° C to 700 ° C. In the range of 620 ° C to 700 ° C, the copper indium gallium pre-formed film is sufficiently reacted with the selenium atmosphere to obtain a high-performance copper indium gallium selenide absorbing layer having a good Ga element distribution.
  • the preset second temperature threshold is 500 ° C to 600 ° C.
  • the preset third temperature threshold is 380 ° C to 500 ° C to form a high temperature selenium atmosphere, and the heat contained in the selenium atmosphere is used to supplement the heat required for the reaction between the copper indium gallium prefabricated film and the selenium source contained in the selenium atmosphere, thereby facilitating high temperature.
  • the selenium atmosphere is subsequently fully reacted with the above copper indium gallium prefabricated film.
  • the first preset duration is 15s to 25s.
  • the second preset duration is 15s to 35s.
  • the surface of the copper indium gallium pre-formed film forms an unsaturated In-Se binary phase in a shorter time (the first predetermined duration)
  • the Cu-Se binary phase the Se element is diffused to the bottom of the copper indium gallium prefabricated film for a long time (the second predetermined duration), thereby preventing the Ga element from being rich at the bottom of the prepared copper indium gallium selenide absorption layer.
  • the selenium source required for the formation of the CIGS quaternary phase is complemented by the copper indium gallium pre-formed film reaction for a long time (second preset duration).
  • the rate of temperature rise of the copper indium gallium pre-formed film in the reaction chamber is greater than 6 ° C / s.
  • the heating rate of the copper indium gallium pre-formed film in the reaction chamber is greater than 6 ° C / s, the heating rate of the copper indium gallium pre-formed film in the reaction chamber is relatively fast, so that the selenium source is The rapid diffusion rate in the bottom of the copper indium gallium prefabricated film is relatively fast. Therefore, the distribution of Ga element in the copper indium gallium selenide absorption layer prepared by the preparation method of the copper indium gallium selenide absorption layer provided by some embodiments described above is uniform. Thereby ensuring the performance of the prepared copper indium gallium selenide absorption layer is higher.
  • the second temperature threshold is 580 ° C
  • the third preset duration is 5 min. ⁇ 30min.
  • the annealing treatment is performed in a vacuum or in a selenium atmosphere having a predetermined third carrier gas flow rate.
  • the preset third carrier gas flow value is less than a preset second carrier gas flow value to further improve the above
  • the degree of reaction between the copper indium gallium contained in the copper indium gallium selenide pre-formed film and the selenium source contained in the selenium atmosphere is less than a preset second carrier gas flow value to further improve the above.
  • a copper gallium alloy layer and an indium layer are sequentially formed on the surface of the back electrode of the substrate.
  • the sputtering method is a DC magnetron sputtering method.
  • the substrate is made of soda lime glass having a thickness of 2 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 700 nm.
  • a copper gallium alloy layer and an indium layer are sequentially formed on the surface of the back electrode of the substrate.
  • the sputtering method is an intermediate frequency magnetron sputtering method.
  • the substrate is made of soda lime glass having a thickness of 3 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 1000 nm.
  • the elemental selenium was heated to 400 ° C under vacuum to obtain selenium vapor.
  • the sputtering method is an intermediate frequency magnetron sputtering method.
  • the substrate is made of soda lime glass having a thickness of 2.5 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 300 nm.
  • a copper gallium alloy layer and an indium layer are sequentially formed on the surface of the back electrode of the substrate.
  • the sputtering method is a DC magnetron sputtering method.
  • the substrate is made of soda lime glass having a thickness of 2.5 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 500 nm.
  • the method for preparing a copper indium gallium selenide absorbing layer includes the following steps: S100: sequentially sputtering a copper gallium alloy layer and an indium layer on a substrate on which a back electrode is deposited to obtain a copper indium gallium prefabricated film.
  • a copper gallium alloy layer and an indium layer are sequentially formed on the surface of the back electrode of the substrate.
  • the sputtering method is a DC magnetron sputtering method.
  • the substrate 10 is made of soda lime glass having a thickness of 3.2 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 500 nm.
  • the method for preparing a copper indium gallium selenide absorbing layer includes the following steps: S100: sequentially sputtering a copper gallium alloy layer and an indium layer on a substrate on which a back electrode is deposited to obtain a 300 nm copper indium gallium prefabricated film. .
  • a copper gallium alloy layer and an indium layer are sequentially formed on the surface of the back electrode of the substrate.
  • the sputtering method is a DC magnetron sputtering method.
  • the substrate is made of soda lime glass having a thickness of 2 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 300 nm.
  • a copper gallium alloy layer and an indium layer are sequentially formed on the surface of the back electrode of the substrate.
  • the sputtering method is a DC magnetron sputtering method.
  • the substrate is made of soda lime glass having a thickness of 3.2 mm.
  • the back electrode is a metal molybdenum layer formed of metal molybdenum.
  • the metal molybdenum layer has a thickness of 800 nm.
  • the copper indium gallium prefabricated film was placed in a reaction chamber at 650 ° C (the temperature rising rate of the reaction chamber was 9 ° C / s). 5 slm of hydrogen selenide gas was introduced into the reaction chamber. The copper indium gallium prefabricated film was reacted in 5 slm of hydrogen selenide gas for 18 s, so that the surface of the copper indium gallium prefabricated film formed an In-Se binary phase and a Cu-Se binary phase.
  • Fig. 3 is a graph showing the distribution of EDS spectrum components in the thickness direction of the copper indium gallium selenide absorption layer of Ga(III). 4 shows an X-ray diffraction pattern of a copper indium gallium selenide absorber layer prepared by a method for preparing a copper indium gallium selenide absorber layer.
  • PR_1 in FIG. 3 and FIG. 4 is a copper indium gallium selenide absorption layer prepared by a two-step selenization method
  • PR_2-PR_4 is a copper indium gallium selenide absorption prepared by the preparation methods described in the above first to third embodiments.
  • Floor is a copper indium gallium selenide absorption prepared by the preparation methods described in the above first to third embodiments.
  • the distribution gradient of Ga(III) included in the copper indium gallium selenide absorber layer represented by the above PR1-PR4 from the surface of the pre-formed film to the bottom portion in the thickness direction is gradually decreased. Therefore, the preparation method of the copper indium gallium selenide absorbing layer provided by the implementation of the present disclosure effectively alleviates the problem of Ga(III) enrichment at the bottom of the copper indium gallium selenide absorbing layer.
  • the copper indium gallium selenide absorber layer represented by the above PR1 is a copper indium gallium selenide absorber layer in which a copper indium selenide phase is separated from a copper indium gallium selenide phase.
  • the copper indium gallium selenide absorbing layer represented by the above PR4 is a copper indium gallium selenide absorbing layer of a single phase.
  • the full width at half maximum of the diffraction peak of the copper indium gallium selenide absorber layer represented by the above PR1-PR4 is gradually decreased, indicating that the internal grain size of the copper indium gallium selenide absorber layer is gradually increased.
  • the embodiment of the present disclosure further provides a method for preparing a solar cell, and the method for preparing the solar cell includes the method for preparing the solar energy absorbing layer described in the above embodiment.
  • the method for preparing the solar cell provided by the embodiment of the present disclosure has the same beneficial effects as the method for preparing the solar cell absorbing layer provided by the above embodiment, and will not be described herein.
  • the carrier gas flow rate, the first temperature threshold, the second temperature threshold, and the second temperature threshold of the selenium atmosphere introduced above are controlled.
  • the first preset duration, the second preset duration, the set pressure and the like, the selenium element passes through the surface of the copper indium gallium prefabricated film to form an unsaturated In-Se binary phase and the Cu-Se binary phase copper indium
  • the bottom diffusion of the gallium prefabricated film avoids the problem that the gallium element is enriched to the bottom of the prepared copper indium gallium selenide absorber layer, thereby increasing the grain size of the copper indium gallium selenide absorber layer.
  • some embodiments of the present disclosure also provide a copper indium gallium selenide absorber layer 100.
  • the copper indium gallium selenide absorber layer 100 is prepared by the above method for preparing a copper indium gallium selenide absorber layer.
  • the copper indium gallium selenide absorber layer 100 provided by some embodiments of the present disclosure has the same beneficial effects as the method for preparing the copper indium gallium selenide absorber layer described above, and details are not described herein.
  • the solar cell 1 includes the above-described copper indium gallium selenide absorbing layer 100.
  • the solar absorbing layer 1 provided by some embodiments of the present disclosure has the same beneficial effects as the method for preparing the copper indium gallium selenide absorbing layer described above, and details are not described herein.
  • the solar cell 1 includes not only the copper indium gallium selenide absorber layer 100 but also the back electrode 110. And the front electrode 120.
  • the copper indium gallium selenide layer 100 is located between the front electrode 110 and the back electrode 120.
  • the solar cell 1 includes a front electrode 120 in addition to the copper indium gallium selenide absorber layer 100.
  • the front electrode 110 is located on a surface of the copper indium gallium selenide absorber layer 100 away from the back electrode 110.

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Abstract

一种铜铟镓硒吸收层的制备方法包括：在基底上依次形成铜镓合金层和铟层构成的铜铟镓预制膜。将铜铟镓预制膜放入具有第一温度阈的反应腔中。向反应腔中通入具有第一载气流量值的硒气氛，使铜铟镓预制膜在第一时长内反应，以在铜铟镓预制膜表面形成非饱和的In-Se二元相和Cu-Se二元相。向反应腔内通入具有第二载气流量值的硒气氛，使得表面形成有非饱和的In-Se二元相和Cu-Se二元相的铜铟镓预制膜在第二预设时长内反应，获得铜铟镓硒预制膜。在预设的第二温度阈和第三预设时长内对铜铟镓硒预制膜进行退火处理，获得太阳能电池吸收层。

Description

铜铟镓硒吸收层及其制备方法、太阳能电池及其制备方法
本申请要求于2018年2月8日提交中国专利局、申请号为201810128936.0、发明名称为“太阳能电池吸收层的制备方法和太阳能电池的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及太阳能电池制造技术领域，尤其涉及一种铜铟镓硒吸收层的制备方法和太阳能电池的制备方法。
背景技术
铜铟镓硒(简称CIGS)薄膜太阳能电池是新一代具有发展前景的太阳能电池。它具有转换效率高、成本低、寿命长、弱光性能好、抗辐射能力强等优点。自20世纪90年代以来，CIGS薄膜太阳能电池一直是实验室转换效率最高的薄膜太阳能电池。2016年德国ZSW在实验室中将CIGS薄膜太阳能电池的转换效率提升至22.6％。由于CIGS薄膜太阳能电池的转换效率与晶硅电池的转换效率较为接近，因此，CIGS薄膜太阳能电池具有较大的发展前景。
发明内容
本公开一些实施方案提供了一种铜铟镓硒吸收层的制备方法，包括如下步骤：
步骤100：在基底上依次形成铜镓合金层和铟层，获得铜铟镓预制膜；
步骤200：将所述铜铟镓预制膜放入具有预设的第一温度阈的反应腔中；向所述反应腔中通入具有预设的第一载气流量值的硒气氛；所述铜铟镓预制膜在所述第一载气流量值的硒气氛中反应第一预设时长，使得所述铜铟镓预制膜的表面形成非饱和的In-Se二元相和Cu-Se二元相；
步骤300：向所述反应腔内通入具有小于预设的第一载气流量值的预设的第二载气流量值的硒气氛；所述表面形成有非饱和的In-Se二元相和Cu-Se二元相的铜铟镓预制膜在具有所述第二载气流量值的硒气氛中反应第二预设时长，使得硒气氛所含有的硒源向铜铟镓预制膜的底部扩散，与 铜铟镓预制膜邻近基底的表面所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜；
步骤400：在预设的第二温度阈和第三预设时长内对所述基底表面形成的铜铟镓硒预制膜进行退火处理，获得铜铟镓硒吸收层。
在一些实施方案中，所述基底上沉积有背电极；所述步骤100包括：
在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得铜铟镓预制膜。
在一些实施方案中，所述基底上沉积有背电极；所述步骤100包括：
在所述基底的背电极的表面依次溅射铜镓合金层和铟层，使得所述背电极、铜镓合金层和铟层层叠在一起，获得铜铟镓预制膜。
在一些实施方案中，所述铜铟镓预制膜包括Cu、In和Ga，所述铜铟镓预制膜所包括的Cu、In和Ga的摩尔比值满足：0.8＜n Cu/(n In+n Ga)＜0.96和0.25≤n Ga/(n In+n Ga)≤0.35。
在一些实施方案中，所述第二载气流量值小于所述第一载气流量值。
在一些实施方案中，所述第一载气流量值与所述第二载气流量值的比大于5。
在一些实施方案中，第一载气流量值大于等于5slm且小于等于15slm，第二载气流量值大于0且小于等于2slm。
在一些实施方案中，在所述步骤200之前，所述铜铟镓硒吸收层的制备方法还包括：
在真空或设定气压的惰性气体中，将固态硒源加热至预设的第三温度阈内，获得硒气氛。
在一些实施方案中，所述预设的第一温度阈为550℃～580℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为250℃～470℃，所述设定气压为1Pa～1atm。
在一些具体实施方案中，所述第一预设时长为25s～35s，所述第二预设时长为260s～275s，所述第三预设时长为5min～30min。
在一些实施方案中，所述预设的第一温度阈为620℃～700℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为380℃～500℃。
在一些具体实施方案中，所述第一预设时长为15s～25s，所述第二预设时长为15s～35s，所述第三预设时长为5min～30min。
在一些实施方案中，所述铜铟镓预制膜在所述步骤200，300反应进程中的升温速率大于3℃/s。
在一些实施方案中，所述反应腔为石墨反应腔。
在一些实施方案中，所述硒气氛包括：硒蒸气或硒化氢气体。
在一些实施方案中，所述退火处理是真空或是在通有预设的第三载气流量值的硒气氛中进行；当所述退火处理是在通有预设的第三载气流量值的硒气氛中进行，所述预设的第三载气流量值小于预设的第二载气流量值。
本公开一些实施方案还提供了一种太阳能电池的制备方法，包括上述公开的一些实施方案提供的铜铟硒镓吸收层的制备方法。
本公开一些实施方案还提供了一种铜铟镓硒吸收层，采用所述的铜铟镓硒吸收层的制备方法制得。
本公开一些实施方案还提供了一种太阳能电池，包括所述的铜铟镓硒吸收层。
附图说明
下面结合附图对本公开的具体实施方式作进一步详细的说明。
图1为本公开一些实施方式提供的铜铟镓硒吸收层的制备方法的流程图。
图2为本公开一些实施方式提供的铜铟镓硒吸收层的制备方法的流程图。
图3为本公开一些实施例所制备的铜铟镓硒吸收层在铜铟镓硒吸收层厚度方向的EDS能谱成分分布图。
图4为本公开一些实施例铜铟镓硒吸收层的制备方法所制备的铜铟镓硒吸收层的X射线衍射图谱。
图5为本公开一些实施例提供的太阳能电池的结构示意图。
具体实施方式
下面详细描述本公开的实施方式，所述实施方式的实施例在附图中示出。下面通过参考附图描述的实施例方式是示例性地，仅用于解释本公开， 而不能解释为对本公开的限制。
相关技术中，CIGS吸收层的制备方法主要有共蒸发法、溅射后硒化法(简称两步硒化法)以及电化学法等。相对于共蒸发法和两步硒化法，采用电化学法所制得的铜铟镓硒吸收层应用于太阳能电池时，太阳能电池的稳定性和最高转换效率都比较弱，导致采用电化学法制备铜铟镓硒吸收层的产业化进程比较缓慢。
共蒸发法是指：蒸发Cu、In、Ga、Se四种元素，使该四种元素同时沉积在基底并进行反应，得到铜铟镓硒吸收层。采用共蒸发法制备的小面积铜铟镓硒吸收层应用于太阳能电池，太阳能电池具有较高的转换效率，但是，上述共蒸发法所制备的铜铟镓硒吸收层的均匀性难以控制，使得上述共蒸发法难以用于大面积的铜铟镓硒吸收层的制备过程中，导致太阳能电池的产业化应用受到一定局限，使得太阳能电池无法获得高转换效率。
两步硒化法是指：首先，采用In 2Se 3靶材、Ga 2Se 3靶材和Cu 2Se靶材，在基材表面溅射In、Ga和Cu，得到铜铟镓硒预制膜。然后，在H 2Se蒸气气氛或者Se蒸气气氛下对铜铟镓硒预制膜进行高温热处理，获得CIGS吸收层。
采用上述两步硒化法制备铜铟镓硒吸收层时，在上述铜铟镓预制膜表面形成饱和浓度的Se蒸气，即，向反应腔内通入的硒气氛使得反应腔内的硒蒸汽呈现饱和状态。在两步硒化法制备铜铟镓硒吸收层的过程中，相较于Ga与Se的反应焓，Cu、In与Se的反应焓更低，进而Cu、In与Se的反应速率更快，因此，铜铟镓预制膜表面的Cu和In能够快速充分地与饱和的硒气氛反应，从而获得相对稳定的In 2Se 3二元相和Cu 2Se二元相。由于稳定的In 2Se 3二元相和Cu 2Se二元相具有的晶格空隙相对较小，因此，会阻碍Se元素(Se元素以硒气氛的形态存在)向铜铟镓预制膜的底部扩散，导致Se元素向铜铟镓预制膜的底部扩散的能力下降。而铜铟镓预制膜底部的Cu和In也会优先于Ga向铜铟镓预制膜表面扩散，并与Se反应形成上述的In 2Se 3二元相和Cu 2Se二元相。基于上述In 2Se 3二元相和Cu 2Se二元相对Se元素产生的阻碍扩散作用，以及Cu和In更优先与Se充分反应的机理，使得获得的铜铟镓硒吸收层底部富集 了晶粒细小的Ga元素，造成Ga元素在铜铟镓硒吸收层中分布不均，从而大大降低铜铟镓硒吸收层的性能。
针对上述问题，如图1所示，本公开一些实施方式提供了一种铜铟镓硒吸收层的制备方法。所述制备方法包括步骤100(S100)、步骤200(S200)、步骤300(S300)和步骤400(S400)：
S100：在基底上依次形成铜镓合金层和铟层，获得铜铟镓预制膜。
S200：将铜铟镓预制膜放入具有预设的第一温度阈的反应腔中，向反应腔中通入具有预设的第一载气流量值的硒气氛，铜铟镓预制膜在具有该第一载气流量值的硒气氛中反应第一预设时长，使得铜铟镓预制膜的表面形成非饱和的In-Se二元相和Cu-Se二元相。
反应腔可以选择石墨反应腔。石墨反应腔在高温条件下具有良好的绝热性和化学稳定性。石墨反应腔在高温下与氧反应生成还原性气氛，以使得反应腔内金属不被氧化。当然，反应腔也可以是其他反应腔，在此不再一一列举。
S300：向所述反应腔内通入具有预设的第二载气流量值的硒气氛，所述表面形成有非饱和的In-Se二元相和Cu-Se二元相的铜铟镓预制膜在具有该第二载气流量值的硒气氛中反应第二预设时长，使得硒气氛所含有的硒源向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在预设的第二温度阈和第三预设时长内对基底表面形成的铜铟镓硒预制膜进行退火处理，获得铜铟镓硒吸收层。
在本公开的上述实施方式中，将制备好的铜铟镓预制膜放入反应腔后，向反应腔内通入具有第一载气流量值的硒气氛，使得反应腔内的硒气氛处在较高的浓度。当铜铟镓预制膜在此硒气氛中维持第一预设时长，使得铜铟镓预制膜在较高的Se浓度条件下，铜铟镓预制膜的表面形成化学键不饱和的In-Se二元相和Cu-Se二元相。由于第一预设时长较短，因此，不饱和的In-Se二元相和Cu-Se二元相在第一预设时长内还未来得及与硒源进一步发生硒化反应而生成饱和的In 2Se 3二元相和Cu 2Se二元相。此后，向反应腔内通入第二载气流量值的硒气氛，使得表面形成非饱和的In-Se二元相和 Cu-Se二元相的铜铟镓预制膜在较低流量的硒气氛中继续与硒源发生反应，使得硒气氛所含有的硒源向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜，以保证所制备的铜铟镓硒预制膜所含有的硒元素在铜铟镓硒预制膜的厚度方向分布比较均匀。
示例性地，当第二载气流量值小于第一载气流量值时，表面形成非饱和的In-Se二元相和Cu-Se二元相的铜铟镓预制膜在较低流量的硒气氛中继续与硒源发生反应，硒化反应进入第二进程。由于在第二进程中通入反应腔的硒气氛流量降低，因此，处于铜铟镓预制膜表面的不饱和In-Se二元相和Cu-Se二元相的表面Se浓度降低，较低的硒气氛流量不足以提供足够浓度的Se源供铜铟镓预制膜表面的不饱和In-Se二元相和Cu-Se二元相进一步硒化。另一方面，由于该In-Se二元相和Cu-Se二元相部分化学键未饱和，从晶格角度来说，上述In-Se二元相和Cu-Se二元相具有较大的晶格空隙，因此，上述In-Se二元相和Cu-Se二元相不会阻碍硒源以硒气氛的形式向铜铟镓预制膜的底部扩散。换句话说，由于向反应腔内通入具有预设的低流量(第二载气流量值)的硒气氛时，反应腔室中的硒气氛保持在较低浓度，使铜铟镓预制膜在低浓度的硒气氛中维持第二预设时长，因此，硒源以硒蒸汽的形式通过上述In-Se二元相和Cu-Se二元相的晶格间隙向铜铟镓预制膜的底部扩散，使得Se与铜铟镓预制膜底部的Cu、In和Ga反应，形成合金相，从而避免了所制备的铜铟镓硒吸收层中Ga元素向底部富集的问题，保证了所制备的铜铟镓硒吸收层中Ga元素分布比较均匀，且Ga元素晶粒尺寸增大。
上述退火处理的主要目的是释放应力、增加材料延展性和韧性、产生特殊显微结构。本公开一些实施例提供的铜铟镓硒吸收层的制备方法，是在通有少量硒气氛的条件下对硒化反应得到的铜铟镓硒预制膜进行退火处理。经过退火处理获得的最终铜铟镓硒吸收层不仅具有较大的晶粒尺寸，而且还具有良好的Ga元素分布均匀性，可解决相关技术中大面积太阳能电池的稳定性及加工均匀性等难以控制的问题。
在一些实施方式中，上述基底10采用2mm～3.2mm厚度的钠钙玻璃制成。基底10表面沉积有背电极。在基底10上依次形成铜镓合金层和 铟层。
在一些实施方式中，上述背电极为金属钼所形成的金属钼层。金属钼层的厚度为300nm～1000nm。
在一些实施方式中，当上述基底上沉积有背电极时，上述S100包括：
在上述基底的背电极的表面依次溅射铜镓合金层和铟层，使得背电极、铜镓合金层和铟层层叠在一起，获得铜铟镓预制膜。所述溅射方法为磁控溅射方法。磁控溅射方法为直流磁控溅射方法或中频磁控溅射方法。
在一些实施方式中，上述铜镓合金层的厚度为250nm～400nm。铟层的厚度为200～300nm。铜镓合金层和铟层所形成的铜铟镓预制膜包括Cu、In和Ga三种元素。铜铟镓预制膜所包括的Cu、In和Ga的摩尔比值满足：0.8＜n Cu/(n In+n Ga)＜0.96和0.25≤n Ga/(n In+n Ga)≤0.35。
例如：上述铜镓合金层的厚度为300nm。铟层的厚度为250nm。铜镓合金层中铜原子的摩尔百分比为75％，铜镓合金层中镓原子的摩尔百分比为25％。此时，铜铟镓预制膜所包括的Cu、In和Ga的摩尔比值满足：0.8＜n Cu/(n In+n Ga)＜0.96和0.25≤n Ga/(n In+n Ga)≤0.35。
当n Cu/(n In+n Ga)＝0.96时，上述铜铟镓预制膜与硒气氛反应容易形成富Cu的Cu xSe相(x＞1)。由于Cu xSe相化学饱和度较高，相邻晶相间的晶格空隙较小，因此，Cu xSe相阻碍硒源以硒气氛的形式向铜铟镓预制膜的底部扩散。相比铜、铟、镓在低浓度Se气氛下的硒化能力更弱，进而导致铜铟镓硒吸收层的底部容易富集呈现细小晶粒的Ga元素，以致铜铟镓硒吸收层的性能显著下降。因此，当所制备的铜铟镓硒吸收层应用于太阳能电池时，无法获得高性能的太阳能电池。
当n Cu/(n In+n Ga)＝0.80时，所形成的铜铟镓硒吸收层含有较多的In-Se、Ga-Se二元相。当铜铟镓硒吸收层所含有的In-Se二元相和Ga-Se二元相较多时，铜铟镓硒吸收层内无法形成黄铜矿结构的铜铟镓硒四元相，导致该铜铟镓硒吸收层应用于太阳能电池时，太阳能电池的性能下降。
在一些实施方式中，上述第一载气流量值大于第二载气流量值。当第一载气流量值大于第二载气流量值时，反应腔内处在第一预设时长反应时段时的硒气氛浓度大于处在第二预设时长反应时段时的浓度。因此，上 述铜铟镓预制膜在具有第一载气流量值的硒气氛中反应第一预设时长的过程中，上述铜铟镓预制膜与高浓度的硒气氛迅速反应，以在铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。但因第一预设时长较短，In-Se二元相和Cu-Se二元相还没来得及进一步硒化反应生成In 2Se 3二元相和Cu 2Se二元相，反应腔内的硒气氛通入量即由第一载气流量值降为第二载气流量值，该表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜所处的硒气氛浓度较低，其不仅不会使得铜铟镓预制膜表面所形成的In-Se二元相和Cu-Se二元相快速形成饱和的In 2Se 3二元相和Cu 2Se二元相，而且还补足表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜反应生成铜铟镓硒四元相所需的硒源。上述Se元素以硒气氛的形式向表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜的底部扩散，从而保证所制备的铜铟镓硒吸收层所含有的Ga元素分布均匀。
在一些具体实施方式中，第一载气流量值与第二载气流量值的比大于5。载气流量值的单位是slm，其是standard litre per minute的英文缩写，是指标准状态(1个大气压，25摄氏度下)下1L/min的载气流量，以下载气流量值的单位均采用slm表示。
示例性地，当第一载气流量值大于等于5slm且小于等于15slm时，反应腔内处在第一载气流量值的硒气氛浓度较高，且铜铟镓预制膜在该较高的硒气氛浓度下反应第一预设时长。由于第一预设时长较短，以使得铜铟镓预制膜的表面形成不饱和的In-Se二元相和Cu-Se二元相。当第二载气流量值大于0且小于等于2slm时，反应腔内处在第二载气流量值的硒气氛浓度较低，使得Se原子通过不饱和In-Se二元相和Cu-Se二元相的晶格空隙向铜铟镓预制膜底部快速扩散，并与铜铟镓预制膜底部的Cu、In和Ga反应，从而避免了Ga元素在铜铟镓硒吸收层底部富集的现象。
在一些实施方式中，上述硒气氛为硒蒸气或硒化氢(H 2Se)气体，当然不限于所列举的这两种。在一些实施方式中，如图2所示，上述S200之前，上述铜铟镓硒吸收层的制备方法还包括：
在真空或设定气压的惰性气体中，将固态硒源加热至预设的第三温度阈内，获得硒气氛，方便后续向反应腔中通入硒气氛载气的流量控制。 惰性气体可以为氮气或氩气。当固态硒源为单质硒时，硒气氛为硒蒸气。由于处在上述第一载气流量的硒气氛和处在第二载气流量的硒气氛均是在真空或设定气压的惰性气体中将固态硒源加热至预设的第三温度阈内获得的，因此，上述处在第一载气流量值的硒气氛和处在第二载气流量值的硒气氛只是硒气氛流速上有所区别。
在一些实施方式中，上述铜铟镓预制膜在反应腔中的平均升温速率大于3℃/s。在第一预设时长反应阶段升温速率块，约为15℃/s-20℃/s，第二预设时长反应阶段升温速率慢，控制铜铟镓预制膜在第一预设时长与第二预设时长的平均升温速率保持在较高水平，如3℃/s以上，以使得硒气氛保持在较高的扩散及反应速度。上述铜铟镓预制膜在反应腔中的升温速率取决于两个因素，其一是反应腔自身所具有的温度。反应腔对铜铟镓预制膜起辐射传热作用。其二是硒气氛的温度，硒气氛对铜铟镓预制膜通过对流传热。
在一些实施方式中，上述预设的第一温度阈为550℃～580℃。在550℃～580℃范围内，铜铟镓预制膜与硒气氛充分反应，以获得具有良好的Ga元素分布的高性能铜铟镓硒吸收层。上述预设的第三温度阈为250℃～470℃，以保证形成高温硒气氛，便于硒气氛后续与上述铜铟镓预制膜反应。上述设定气压为1Pa～1atm。
上述第一预设时长为25s～35s，上述铜铟镓预制膜的表面在相对短的时间内形成非饱和的In-Se二元相和Cu-Se二元相。例如：第一预设时长为30s。
上述第二预设时长为260s～275s，在该第二预设时长反应阶段，向反应腔内通入第二载气流量的硒气氛，上述表面形成有不饱和In-Se二元相和Cu-Se二元相的铜铟镓预制膜在相对长时间内处在低浓度的硒气氛中。由于铜铟镓预制膜表面的不饱和In-Se二元相和Cu-Se二元相晶格间隙较大，因此，Se元素向铜铟镓预制膜的底部方向扩散，从而避免Ga元素在铜铟镓硒吸收层的底部富集的现象。以第二载气流量在第二预设时长260s～275s内向反应腔通入硒气氛，补足了与包含不饱和In-Se二元相和Cu-Se二元相的铜铟镓预制膜反应生成铜铟镓硒四元相时所需的硒源，以生成均匀的铜铟镓锡膜层。例如：本实施方式中第二预设时长优选为270s。
上述预设的第二温度阈为500℃～600℃，上述第三预设时长为5min～30min，以对上述铜铟镓预制膜充分进行高温退火处理。
在该实施方式中，上述铜铟镓预制膜在反应腔中的升温速率大于3℃/s且小于等于6℃/s。在该升温速率条件下，一方面硒气氛中的Se源在铜铟镓预制膜的表面及底部之间保持较高的扩散速率，并使得硒气氛的流量与反应腔的升温速率相匹配，从而控制铜铟镓预制膜与硒气氛所含有的硒源的反应速度。
另外，由上述实施方式所公开的第一预设时长和第二预设时长可以看出，上述实现方式的铜铟镓硒吸收层的制备方法的工艺参数操作窗口较大，有利于工艺参数控制。
在另一些实施方式中，上述预设的第一温度阈可以为620℃～700℃。在620℃～700℃范围内，以保证上述铜铟镓预制膜与硒气氛充分反应，从而获得具有良好的Ga元素分布的高性能铜铟镓硒吸收层。上述预设的第二温度阈为500℃～600℃。上述预设的第三温度阈为380℃～500℃，以形成高温硒气氛，利用硒气氛所含有的热量补充铜铟镓预制膜与硒气氛所含有的硒源反应所需的热量，便于高温硒气氛后续与上述铜铟镓预制膜充分反应。
上述第一预设时长为15s～25s。上述第二预设时长为15s～35s。当第一预设时长为15s～25s，第二预设时长为15s～35s，在反应温度较高的条件下，有利于缩短上述铜铟镓预制膜与硒气氛的反应时间，以提高上述铜铟镓预制膜与硒气氛所含有的硒源的反应效率。
由上可见，由于上述第二预设时长大于第一预设时长，使得在较短的时间(第一预设时长)内上述铜铟镓预制膜的表面形成非饱和的In-Se二元相和Cu-Se二元相，在较长时间(第二预设时长)内使Se元素向铜铟镓预制膜的底部扩散，从而避免Ga元素在所制备的铜铟镓硒吸收层的底部富集的问题。同时，由于上述第二预设时长大于第一预设时长，因此，在较长时间(第二预设时长)内补足上述铜铟镓预制膜反应生成CIGS四元相时所需的硒源。
在此实施方式中，上述铜铟镓预制膜在反应腔中的升温速率大于 6℃/s。在当铜铟镓预制膜在反应腔中的升温速率大于6℃/s时，该反应腔的升温速率下，铜铟镓预制膜在反应腔中的升温速率相对较快，使得硒源向在铜铟镓预制膜底部内的快速扩散速度比较快，因此，上述一些实施方式所提供的铜铟镓硒吸收层的制备方法所制备的铜铟镓硒吸收层内Ga元素分布呈现均匀化趋势，从而保证制备的铜铟镓硒吸收层性能更高。
在一些实施方式中，为了改善硒元素在上述铜铟镓预制膜的扩散速度，以获得高性能的铜铟镓硒吸收层，上述第二温度阈为580℃，上述第三预设时长为5min～30min。
在一些实施方式中，上述退火处理是在真空或是在通有预设的第三载气流量值的硒气氛中进行。当所述退火处理是在通有预设的第三载气流量值的硒气氛中进行，所述预设的第三载气流量值小于预设的第二载气流量值，以进一步提高上述铜铟镓硒预制膜所含有的铜铟镓与硒气氛所含有的硒源的反应程度。下面结合实施例对本公开实施方式提供的铜铟镓硒吸收层的制备方法进行详细说明。
实施例一
本实施例提供的一种铜铟镓硒吸收层的制备方法包括以下步骤：
S100：在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得700nm的铜铟镓预制膜。
在S100中，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为直流磁控溅射方法。基底采用2mm厚度的钠钙玻璃制成。背电极为金属钼所形成的金属钼层。金属钼层的厚度为700nm。铜铟镓预制膜所包括的Cu、In和Ga的摩尔比值满足：n Cu/(n In+n Ga)＝0.82和n Ga/(n In+n Ga)＝0.25。
在氮气保护下，将单质硒在1Pa的压力下加热至250℃，获得硒蒸气。
S200：将铜铟镓预制膜放入550℃的反应腔(反应腔的升温速率为4℃/s)。在所述反应腔中通入5slm的硒蒸气。铜铟镓预制膜在5slm的硒蒸气中反应35s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。
S300：向所述反应腔内通入1slm的硒蒸气。所述表面形成有In-Se 二元相和Cu-Se二元相的铜铟镓预制膜在1slm的硒蒸气中反应275s，使得硒蒸气所含有的Se向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在真空环境中，于500℃的温度下对基板表面形成的铜铟镓硒预制膜进行30min退火处理，获得铜铟镓硒吸收层。
实施例二
本实施例提供的一种铜铟镓硒吸收层的制备方法包括以下步骤：
S100：在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得铜铟镓预制膜。
在S100中，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为中频磁控溅射方法。基底采用3mm厚度的钠钙玻璃制成。背电极为金属钼所形成的金属钼层。金属钼层的厚度为1000nm。铜铟镓预制膜所包括的Cu、In和Ga的摩尔值满足：n Cu/(n In+n Ga)＝0.92和n Ga/(n In+n Ga)＝0.3。
在真空条件下，将单质硒加热至400℃，获得硒蒸气。
S200：将铜铟镓预制膜放入580℃的反应腔(反应腔的升温速率为5℃/s)。在所述反应腔中通入10slm的硒蒸气。铜铟镓预制膜在10slm的硒蒸气中反应35s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。
S300：向所述反应腔内通入2slm的硒蒸气。所述表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜在2slm的硒蒸气中反应260s，使得硒蒸气所含有的Se向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在0.5slm的硒蒸气流量环境中，于600℃的温度下对基板表面形成的铜铟镓硒预制膜进行5min的退火处理，获得铜铟镓硒吸收层。
实施例三
本实施例提供的一种铜铟镓硒吸收层的制备方法包括下述步骤：
S100，在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得铜铟镓预制膜。此时，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为中频磁控溅射方法。基底采用2.5mm厚度的钠钙玻璃制成。 背电极为金属钼所形成的金属钼层。金属钼层的厚度为300nm。铜铟镓预制膜所包括的Cu、In和Ga的摩尔值满足：n Cu/(n In+n Ga)＝0.9和n Ga/(n In+n Ga)＝0.36。
在氩气保护下，将单质硒在0.8Pa的压力下加热至380℃，获得硒蒸气。
S200：将铜铟镓预制膜放入550℃的反应腔(反应腔的升温速率为6℃/s)。在所述反应腔中通入15slm的硒蒸气。铜铟镓预制膜在15slm的硒蒸气中反应30s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。
S300：向所述反应腔内通入1.5slm的硒蒸气。所述表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜在1.5slm的硒蒸气中反应265s，使得硒蒸气所含有的Se向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在真空环境中，于540℃的温度下对基板表面形成的铜铟镓硒预制膜进行18min的退火处理，获得铜铟镓硒吸收层。
实施例四
本实施例提供的一种铜铟镓硒吸收层的制备方法包括下述步骤：
S100：在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得铜铟镓预制膜。
在S100中，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为直流磁控溅射方法。基底采用2.5mm厚度的钠钙玻璃制成。背电极为金属钼所形成的金属钼层。金属钼层的厚度为500nm。铜铟镓预制膜所包括的Cu、In和Ga的原子比值满足：n Cu/(n In+n Ga)＝0.9和n Ga/(n In+n Ga)＝0.36。
在氩气保护下，将单质硒在0.8Pa的压力下加热至470℃，获得硒蒸气。
S200：将铜铟镓预制膜放入620℃的反应腔(反应腔的升温速率为8℃/s)。在所述反应腔中通入7slm的硒蒸气。铜铟镓预制膜在7slm的硒蒸气中反应25s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se 二元相。
S300：向所述反应腔内通入1.2slm的硒蒸气。所述表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜在1.2slm的硒蒸气中反应35s，使得硒蒸气所含有的Se向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在0.5slm的硒蒸气流量环境中，于580℃的温度下对基板表面形成的铜铟镓硒预制膜进行24min的退火处理，获得铜铟镓硒吸收层。
实施例五
本实施例提供的一种铜铟镓硒吸收层的制备方法包括下述步骤：S100：在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得铜铟镓预制膜。
在S100中，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为直流磁控溅射方法。基底10采用3.2mm厚度的钠钙玻璃制成。背电极为金属钼所形成的金属钼层。金属钼层的厚度为500nm。铜铟镓预制膜所包括的Cu、In和Ga的原子比值满足：n Cu/(n In+n Ga)＝0.82和n Ga/(n In+n Ga)＝0.3。
在氩气保护下，将单质硒在0.4Pa的压力下加热至500℃，获得硒蒸气。
S200：将铜铟镓预制膜放入640℃的反应腔(反应腔的升温速率为7℃/s)。在所述反应腔中通入10slm的硒蒸气。铜铟镓预制膜在10slm的硒蒸气中反应15s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。
S300：向所述反应腔内通入1slm的硒蒸气。所述表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜在1slm的硒蒸气中反应25s，使得硒蒸气所含有的Se向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在0.2slm的硒蒸气流量环境中，于580℃的温度下对基板表面形成的铜铟镓硒预制膜进行24min的退火处理，获得铜铟镓硒吸收层。
实施例六
本实施例提供的一种铜铟镓硒吸收层的制备方法包括下述步骤：S100：在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得300nm的铜铟镓预制膜。
在S100中，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为直流磁控溅射方法。基底采用2mm厚度的钠钙玻璃制成。背电极为金属钼所形成的金属钼层。金属钼层的厚度为300nm。铜铟镓预制膜所包括的Cu、In和Ga的原子比值满足：n Cu/(n In+n Ga)＝0.92和n Ga/(n In+n Ga)＝0.3。
S200：将铜铟镓预制膜放入670℃的反应腔(反应腔的升温速率为10℃/s)。在所述反应腔中通入12slm的硒化氢气体。铜铟镓预制膜在12slm的硒化氢气体中反应15s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。
S300：向所述反应腔内通入1slm的硒化氢气体。所述表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜在1slm的硒化氢气体中反应35s，使得硒化氢气体所含有的硒化氢向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在真空环境中，于500℃的温度下对铜铟镓硒预制膜进行30min的退火处理，获得铜铟镓硒吸收层。
实施例七
本实施例提供的一种铜铟镓硒吸收层的制备方法包括下述步骤：
S100：在沉积有背电极的基底上依次溅射铜镓合金层和铟层，获得800nm的铜铟镓预制膜。
在S100中，铜镓合金层和铟层依次形成在基底的背电极的表面。溅射方法为直流磁控溅射方法。基底采用3.2mm厚度的钠钙玻璃制成。背电极为金属钼所形成的金属钼层。金属钼层的厚度为800nm。铜铟镓预制膜所包括的Cu、In和Ga的原子比值满足：n Cu/(n In+n Ga)＝0.90和n Ga/(n In+n Ga)＝0.25。
S200：将铜铟镓预制膜放入650℃的反应腔(反应腔的升温速率为 9℃/s)。在所述反应腔中通入5slm的硒化氢气体。铜铟镓预制膜在5slm的硒化氢气体中反应18s，使得铜铟镓预制膜的表面形成In-Se二元相和Cu-Se二元相。
S300：向所述反应腔内通入1slm的硒化氢气体。所述表面形成有In-Se二元相和Cu-Se二元相的铜铟镓预制膜在1slm的硒化氢气体中反应15s，使得硒化氢气体所含有的硒化氢向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜。
S400：在0.7slm的硒化氢气体流量环境中，在600℃的温度下对基板表面形成的铜铟镓硒预制膜进行5min的退火处理，获得铜铟镓硒吸收层。
图3示出了Ga(III)在铜铟镓硒吸收层厚度方向的EDS能谱成分分布析图。图4示出了铜铟镓硒吸收层的制备方法所制备的铜铟镓硒吸收层的X射线衍射图谱。图3和图4中的PR_1为采用两步硒化法所制备的铜铟镓硒吸收层，PR_2-PR_4依次为采用上述实施例一至实施例三所述的制备方法制备的铜铟镓硒吸收层。
从图3可知，上述PR1-PR4所代表的铜铟镓硒吸收层所包括的Ga(III)沿着厚度方向从预制膜表面到底部的分布梯度逐渐减小。因此，采用本公开实现方式所提供的铜铟镓硒吸收层的制备方法有效缓解了Ga(III)在铜铟镓硒吸收层的底部富集的问题。
从图4可知，上述PR1代表的铜铟镓硒吸收层为铜铟硒物相与铜铟镓硒物相分离的铜铟镓硒吸收层。上述PR4代表的铜铟镓硒吸收层为单一物相的铜铟镓硒吸收层。而且，上述PR1-PR4所代表的铜铟镓硒吸收层的衍射峰的半高宽逐步下降，表明铜铟镓硒吸收层的内部晶粒尺寸逐步增大。
本公开实施方式还提供了一种太阳能电池的制备方法，该太阳能电池的制备方法包括上述实施方式所述的太阳能吸收层的制备方法。
与相关技术相比，本公开实施方式提供的太阳能电池的制备方法与上述实施方式提供的太阳能吸收层的制备方法的有益效果相同，在此不做赘 述。
由上可见，在本公开实施方式提供的铜铟镓硒吸收层的制备方法及太阳能电池的制备方法中，控制上述通入的硒气氛的载气流量、第一温度阈、第二温度阈、第一预设时长、第二预设时长、设定压力等参数，使硒元素穿过上述铜铟镓预制膜表面所形成的不饱和In-Se二元相和Cu-Se二元相向铜铟镓预制膜底部扩散，避免了镓元素在所制备的铜铟镓硒吸收层的向底部富集的问题，从而提高了铜铟镓硒吸收层的晶粒尺寸。
如图5所示，本公开一些实施方式还提供了一种铜铟镓硒吸收层100。该铜铟镓硒吸收层100采用上述铜铟镓硒吸收层的制备方法制得。
与相关技术相比，本公开一些实施例方式提供的铜铟镓硒吸收层100与上述铜铟镓硒吸收层的制备方法的有益效果相同，在此不做赘述。
如图5所示，本公开一些实施方式还提供了一种太阳能电池1。该太阳能电池1包括上述铜铟镓硒吸收层100。
与相关技术相比，本公开一些实施例方式提供的太阳能吸收层1与上述铜铟镓硒吸收层的制备方法的有益效果相同，在此不做赘述。
在一些实施方式中，如图5所示，如果上述铜铟镓硒层100的基底10没有沉积有背电极110，那么上述太阳能电池1不仅包括铜铟镓硒吸收层100，还包括背电极110和前电极120。所述铜铟镓硒层100位于所述前电极110和背电极120之间。
在一些实施方式中，如图5所示，如果上述铜铟镓硒层100的基底10沉积有背电极120，那么上述太阳能电池1除了铜铟镓硒吸收层100，还包括前电极120。该前电极110位于所述铜铟镓硒吸收层100远离背电极110的表面。
以上依据图式所示的实施例详细说明了本公开的构造、特征及作用效果，以上所述仅为本公开的较佳实施例，但本公开不以图面所示限定实施范围，凡是依照本公开的构想所作的改变，或修改为等同变化的等效实施例，仍未超出说明书与图示所涵盖的精神时，均应在本公开的保护范围内。

Claims (17)

  1. 一种铜铟镓硒吸收层的制备方法，包括如下步骤：
    步骤100：在基底上依次形成铜镓合金层和铟层，获得铜铟镓预制膜；
    步骤200：将所述铜铟镓预制膜放入具有预设的第一温度阈的反应腔中，向所述反应腔中通入具有预设的第一载气流量值的硒气氛，所述铜铟镓预制膜在具有所述第一载气流量值的硒气氛中反应第一预设时长，使得所述铜铟镓预制膜的表面形成非饱和的In-Se二元相和Cu-Se二元相；
    步骤300：向所述反应腔内通入预设的第二载气流量值的硒气氛，所述表面形成有非饱和的In-Se二元相和Cu-Se二元相的铜铟镓预制膜在具有所述第二载气流量值的硒气氛中反应第二预设时长，使得硒气氛所含有的硒源向铜铟镓预制膜的底部扩散，并与铜铟镓预制膜所含有的铜铟镓反应，获得形成在基底表面的铜铟镓硒预制膜；
    步骤400：在预设的第二温度阈和第三预设时长内对所述基底表面形成的铜铟镓硒预制膜进行退火处理，获得铜铟镓硒吸收层。
  2. 根据权利要求1所述的铜铟镓硒吸收层的制备方法，其中，所述基底上沉积有背电极；
    所述步骤100包括：在所述基底的背电极的表面依次溅射铜镓合金层和铟层，使得所述背电极、铜镓合金层和铟层层叠在一起，获得铜铟镓预制膜。
  3. 根据权利要求1所述的铜铟镓硒吸收层的制备方法，其中，所述铜铟镓预制膜包括Cu、In和Ga，所述铜铟镓预制膜所包括的Cu、In和Ga的摩尔比值满足：0.8＜n Cu/(n In+n Ga)＜0.96，0.25≤n Ga/(n In+n Ga)≤0.35。
  4. 根据权利要求3所述的铜铟镓硒吸收层的制备方法，其中，所述第二载气流量值小于所述第一载气流量值。
  5. 根据权利要求3所述的铜铟镓硒吸收层的制备方法，其中，所述第一载气流量值与所述第二载气流量值的比值大于5。
  6. 根据权利要求5所述的铜铟镓硒吸收层的制备方法，其中，第一载气流量值大于等于5slm且小于等于15slm，第二载气流量值大于0且小于等于2slm。
  7. 根据权利要求1所述的铜铟镓硒吸收层的制备方法，其中，在所述步骤 200之前，所述铜铟镓硒吸收层的制备方法还包括：
    在真空或设定气压的惰性气体中，将固态硒源加热至预设的第三温度阈内，获得硒气氛。
  8. 根据权利要求7所述的铜铟镓硒吸收层的制备方法，其中，所述预设的第一温度阈为550℃～580℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为250℃～470℃，所述设定气压为1Pa～1atm。
  9. 根据权利要求8所述的铜铟镓硒吸收层的制备方法，其中，所述第一预设时长为25s～35s，所述第二预设时长为260s～275s，所述第三预设时长为5min～30min。
  10. 根据权利要求7所述的铜铟镓硒吸收层的制备方法，其中，所述预设的第一温度阈为620℃～700℃，所述预设的第二温度阈为500℃～600℃，所述预设的第三温度阈为380℃～500℃，所述设定气压为1Pa～1atm。
  11. 根据权利要求10所述的铜铟镓硒吸收层的制备方法，其中，所述第一预设时长为15s～25s，所述第二预设时长为15s～35s，所述第三预设时长为5min～30min。
  12. 根据权利要求8或10所述的铜铟镓硒吸收层的制备方法，其中，所述步骤200中所述铜铟镓预制膜在反应腔中的平均升温速率大于3℃/s。
  13. 根据权利要求1所述的铜铟镓硒吸收层的制备方法，其中，所述硒气氛包括硒蒸气和/或硒化氢气体。
  14. 根据权利要求4～6任一项所述的铜铟镓硒吸收层的制备方法，其中，所述退火处理是在真空或是在通有预设的第三载气流量值的硒气氛中进行；当所述退火处理是在通有预设的第三载气流量值的硒气氛中进行，所述预设的第三载气流量值小于预设的第二载气流量值。
  15. 一种太阳能电池的制备方法，包括如权利要求1～14任一项所述的铜铟镓硒吸收层的制备方法。
  16. 一种铜铟镓硒吸收层，采用权利要求1～14任一项所述的铜铟镓硒吸收层的制备方法制得。
  17. 一种太阳能电池，包括如权利要求16所述的铜铟镓硒吸收层。
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EP3527687A1 (en) 2019-08-21
KR20190096285A (ko) 2019-08-19
CN108305906B (zh) 2019-09-03
AU2018241050A1 (en) 2019-08-22
US20190245103A1 (en) 2019-08-08
JP2019140392A (ja) 2019-08-22

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