WO2013129044A1 - Procédé de fabrication d'alliage pour cellule solaire à base de cigs - Google Patents

Procédé de fabrication d'alliage pour cellule solaire à base de cigs Download PDF

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WO2013129044A1
WO2013129044A1 PCT/JP2013/052699 JP2013052699W WO2013129044A1 WO 2013129044 A1 WO2013129044 A1 WO 2013129044A1 JP 2013052699 W JP2013052699 W JP 2013052699W WO 2013129044 A1 WO2013129044 A1 WO 2013129044A1
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alloy
temperature
manufacturing
cigss
solar cells
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Japanese (ja)
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賢二 吉野
章 永岡
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株式会社日本マイクロニクス
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Priority to JP2014502094A priority Critical patent/JP6002207B2/ja
Priority to CN201380010987.9A priority patent/CN104245572B/zh
Publication of WO2013129044A1 publication Critical patent/WO2013129044A1/fr

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    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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    • H—ELECTRICITY
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Definitions

  • the present invention relates to a CIGS quaternary alloy using copper, indium, gallium and selenium as raw materials as an alloy for solar cells used in a solar cell using a compound semiconductor for a light absorption layer, and copper, indium, gallium, selenium and sulfur.
  • the present invention relates to a method for producing a CIGS quaternary alloy using as a raw material, and a method for producing a solar cell using a sputtering target produced from a CIGS quaternary alloy or a CIGSS quaternary alloy.
  • a solar cell is an element that converts solar light energy into electric power. Photoelectrons due to the internal photoelectric effect are generated by sunlight irradiated to the pn-junction semiconductor interface, and the photoelectrons move in a certain direction due to the rectifying action by the pn junction. Can function as a battery.
  • the movement of electrons and holes due to the photovoltaic force can be taken out by attaching an electrode to the n-type semiconductor and the p-type semiconductor, with the n-type semiconductor side serving as a negative electrode and the p-type semiconductor side serving as a positive electrode.
  • Solar cells are roughly classified into three types: silicon-based, compound-based, and organic-based, and silicon is the most widely used. Recently, compound-based solar cells are thin and have little change over time. Is expected to increase, and development is progressing.
  • silicon copper (hereinafter referred to as Cu), indium (hereinafter referred to as In), gallium (hereinafter referred to as Ga), selenium (hereinafter referred to as Se), sulfur (hereinafter referred to as S).
  • a group I-III-VI group 2 compound called chalcopyrite is used as a group I-III-VI group 2 compound called chalcopyrite.
  • Typical examples include copper indium diselenide CuInSe 2 (hereinafter referred to as CIS), copper indium diselenide / gallium Cu (In, Ga) Se 2 (hereinafter referred to as CIGS), and diselene / copper indium sulfide / gallium Cu. (In, Ga) (S, Se) 2 (hereinafter referred to as CIGSS) (see Patent Document 1).
  • Chalcopyrite compound semiconductors have the characteristics of being both p-type and n-type semiconductors, and are direct transition semiconductors, so they have excellent light absorption characteristics, and the forbidden band width is from 3.5 eV of aluminum sulphide copper CuAlS 2 . , Which covers a wide wavelength range of 0.8 eV of tellurium / indium copper CuInTe 2 , it is possible to produce light emitting and light receiving elements from the infrared region to the ultraviolet region.
  • a polycrystalline CIGS solar cell is reported to have a conversion efficiency of 20.3% by taking advantage of excellent light absorption characteristics (see Non-Patent Document 1).
  • CIS films, CIGS films, and CIGSS films that serve as light absorption layers.
  • Typical methods include vapor deposition methods based on vacuum processes (see Patent Document 2, etc.) and selenium.
  • Patent Document 3 etc. There exists a chemical conversion method (refer patent document 3 etc.).
  • a manufacturing method of a CIGS film which is a typical compound semiconductor will be described below.
  • FIG. 20 shows a manufacturing process of a three-stage method, which is a kind of vapor deposition method.
  • FIG. 21 shows the temperature control state at this time.
  • In, Ga, and Se are vapor-deposited on a substrate in the first stage to form (In, Ga) 2 Se 3 .
  • the substrate temperature is raised, and only Cu and Se are vapor-deposited simultaneously, and film formation is performed until the composition of the entire film becomes an excessive Cu composition.
  • the film in the second stage is in a two-phase coexistence state of the liquid phase Cu 2 Se and the solid phase CIGS, and Cu 2 Se acts as a flux and the crystal grains A sudden increase in particle size occurs. Since Cu 2 Se has low resistance, the film is irradiated with each flux of In, Ga, and Se as a third stage so that the final composition becomes an (In, Ga) excess composition.
  • the first stage is 350 to 400 ° C.
  • the second stage is 500 to 550 ° C.
  • precise temperature management is required for the CIGS film composition control. It is requested.
  • the produced CIGS thin film has a chalcopyrite structure, and has a large grain size and a crystallographically high quality thin film crystal.
  • FIG. 22 shows a manufacturing process of a CIGS thin film by a selenization method.
  • Selenization method Mo an In a sputtering method on the (molybdenum) layer, to form a laminated film of Cu (Ga), and the laminated film at a substrate temperature of 400 ⁇ 550 °C, H 2 diluted with Ar (argon)
  • a CuInSe 2 thin film having a particle size of about 3 ⁇ m is formed by treatment in a gas containing Se (hydrogen selenide) for several hours.
  • the group VI element is S (sulfur)
  • it is processed in an S atmosphere.
  • H 2 Se (hydrogen sulfide) gas By reacting with H 2 Se (hydrogen sulfide) gas at 400 ° C. or higher, a Cu (In, Ga) Se 2 film is obtained.
  • the selenization method is a method suitable for forming a uniform CIGS film over a wide area.
  • the manufacture of the CIS film is the same as the CIGS film manufacturing method, but Ga is not used as the material.
  • a compound having an amino group and a hydroxy group as a functional group is used as a solvent to dissolve each chalcogenide of Cu, In, and Ga, and Cu, In, and Ga.
  • a step of preparing a complex containing at least one of S and Se which are constituents of chalcogenide a step of applying the complex to the surface of a substrate and drying to form a complex film, and the complex
  • the film is heat-treated in a reducing atmosphere containing hydrogen, nitrogen, or a mixed gas thereof, and the surface of the substrate is mainly composed of at least one of Cu, In, and Ga, and S and Se.
  • a method of manufacturing the thin film is proposed (see Patent Document 4).
  • the production of the light absorption layer by vapor deposition depends on the other production process, which is difficult to control because the vaporization temperature and vaporization rate of each substance are different and the composition ratio of the CIGS film is difficult to produce accurately.
  • the apparatus is complicated and expensive, resulting in high cost, and the film forming speed is slow and the productivity is low.
  • the CIGS film is produced by the selenization method because the H 2 Se gas is harmful to the human body, and when it is processed in the H 2 Se gas, the Se gas penetrates onto the surface of the substrate, and the temperature rise process As a result, an Se compound is generated on the surface of the substrate, and the Se compound has a high resistance, so that there is a problem in that the performance of the manufactured solar cell is deteriorated. Further, since Se enters and reacts in the Cu, In laminated film, volume expansion occurs, and the adhesion force at the interface of the substrate / CIGS film is weakened.
  • Patent Document 5 proposes the following method.
  • Cu, In, Ga, and Se are weighed so as to have concentrations of 25%, 20%, 5%, and 50%, respectively, put into a quartz amble, vacuum-sealed, sealed, and set in a furnace.
  • the temperature in the furnace is from room temperature to 100 ° C. with a heating rate of 5 ° C./min, then up to 400 ° C., the heating rate is 1 ° C./min, up to 550 ° C., up to 5 ° C./min, up to 650 ° C.
  • the temperature rise rate is 1.66 ° C./min, and the temperature is maintained at 650 ° C. for 8 hours, and then the inside of the furnace is cooled to room temperature over 12 hours.
  • the CIGS sintered body thus obtained was passed through 120 mesh and then hot-pressed.
  • the hot-press conditions were from room temperature to 750 ° C. with a temperature increase rate of 10 ° C./min, and after reaching 750 ° C., 30 After 200 minutes, pressurize at 200 kgf / cm 2 for 2 hours and 30 minutes, stop the pressure, and return to room temperature by natural cooling.
  • Patent Document 6 a sputtering target is produced by using the following method in order to suppress an explosion caused by a reaction between In and Se.
  • FIG. 23 is an example of temperature control at the time of CIGS sputtering target manufacturing, and includes a first melting step S1, an intermediate melting step Sm, and a second melting step S2.
  • heating is performed to a temperature of 150 to 200 ° C. over 1 hour, and in the first melting step S1, the temperature is maintained at a temperature of 150 to 200 ° C. for 5 hours.
  • it is heated to a temperature of 500 to 650 ° C. over 1 hour, and is maintained at a temperature of 500 to 650 ° C. for 1 hour in the intermediate melting step Sm.
  • it is slowly heated to a temperature of 1000 to 1100 ° C. over 2 hours, and is maintained at a temperature of 1000 to 1100 ° C. for 1 hour in the second melting step S2.
  • Se is heated to 670 ° C.
  • Ga is added to the obtained Cu—Se—In ternary alloy molten metal, and the temperature is raised to 1000 ° C. to prepare a Cu—In—Ga—Se quaternary alloy molten metal, which is cast into a mold and ingot. Is made. This ingot is pulverized to 100 mesh under with a dry pulverizer to produce a Cu—In—Ga—Se quaternary alloy powder, and this Cu—In—Ga—Se quaternary alloy powder is pressured in an Ar atmosphere. : Cu-In-Ga-Se quaternary alloy sputtering target with extremely low compositional segregation is manufactured by hot pressing under conditions of 600 MPa, temperature: 200 ° C., and holding for 1.5 hours.
  • Patent Document 7 also proposes a method of forming a CIGS thin film by filling CIGS crystal powder into an evaporation source of a chamber and heating it at 1000 to 1400 ° C., and depositing the evaporated CIGS crystal powder on a substrate. .
  • producing a CIGS or CIGSS sputtering target is a manufacturing technology that can form a CIGS or CIGSS light absorption layer by one sputtering and that does not use hydrogen selenide gas and hydrogen sulfide gas harmful to the human body. This contributes to cost reduction of manufacturing equipment, improvement of productivity and safety.
  • the melting step is performed by heating Cu, In, Ga, and Se to a temperature at which all of In and Ga are dissolved and lower than the melting point of Se.
  • the second melting step S2 for producing a Cu—In—Ga—Se quaternary alloy molten metal by heating to a temperature and between the first melting step S1 and the second melting step S2, the molten metal is made of Se.
  • the CIGS solar cell has a forbidden band width of about 1.2 eV, and in order to further increase the efficiency, it was necessary to set it to 1.4 to 1.5 eV that best suits the wavelength of sunlight. . There is also a problem of reducing the amount of Se harmful to the human body as much as possible.
  • the present invention provides a method for producing a CIGS sputtering target, which prevents In from chemically reacting with Se and burns and explodes, is easy to control temperature, and has high productivity, and the CIGS sputtering target. It aims at providing the manufacturing method of the used solar cell.
  • the present invention provides a CIGS quaternary alloy manufacturing method in which S is added to a CIGS quaternary alloy, a CIGSS sputtering target and a manufacturing method thereof, and a CIGSSS 5 having a higher forbidden band width with respect to a conventional CIGS sputtering target. It aims at providing the preparation method of the solar cell using the CIGSS sputtering target by a ternary alloy.
  • a sputtering target for producing a light absorption layer of a solar cell in one step by sputtering is a sputtering target of a CIGS quaternary alloy composed of copper, indium, gallium and selenium, and copper, indium, gallium, selenium and sulfur. It is a sputtering target by the CIGSS ternary system alloy which used as a component.
  • the CIGS quaternary alloy and the CIGSSS quaternary alloy are collectively referred to as solar cell alloys.
  • CIGSS ternary alloy which is an alloy for solar cells, is prepared by mixing copper, indium, gallium, selenium, and sulfur as raw materials, vacuum-sealing the ampule in vacuum, heating the ampule, and starting the raw material in the ampule And a CIGSS crystallization step of crystallizing the material by melt growth.
  • the raw material of copper, indium and gallium may be indium gallium copper (CIG) crystal, and the CIG crystal may be pulverized to be powdered. Thereby, a high quality crystal is obtained in the crystallization with S or Se.
  • Indium gallium copper crystal is a vacuum sealing process in which copper, indium and gallium are mixed as raw materials and vacuum sealed in an ampoule, and a CIG crystallization process in which the ampoule is heated to crystallize the raw material in the ampoule by melt growth And made from.
  • ⁇ ⁇ CIG quaternary alloy crystals can be produced by mixing selenium alone into the pulverized CIG crystal, vacuum-sealing the ampule, heating the ampule, and crystallizing the raw material in the ampule by melt growth.
  • the ampoule is carbon coated to prevent the precipitation of impurities.
  • Ampoule is made of quartz glass.
  • the CIGSS crystallization process having a composition of copper, indium, gallium, selenium, and sulfur includes a first step of maintaining the temperature at 180 to 220 ° for a certain time by increasing the temperature, and a first step for maintaining the temperature at 1000 to 1100 ° for a certain time. Has two steps.
  • the CIG crystallization process in the case of producing and pulverizing the CIG crystal includes a process of maintaining the temperature at 1000 to 1100 ° for a predetermined time by increasing the temperature.
  • the temperature is raised to 100 ° C. or lower for 1 hour, the temperature of 1000 to 1100 ° C. is maintained for 6 hours or more, and the temperature is increased to 1 hour. Temperature control is performed to lower the temperature above 100 ° C. and return to room temperature.
  • the obtained solar cell alloy is sliced into a CIGS sputtering target and a CIGS sputtering target. Further, after the obtained solar cell alloy is pulverized and pulverized, it is put into a mold or the like having a desired shape, bulked by press processing, and then sliced to produce a sputtering target.
  • the CIGS sputtering target or CIGS sputtering target manufactured in this way is used as a material for the light absorption layer.
  • the CIGS thin film or the CIGS thin film is formed on the back electrode that is installed and laminated on the glass substrate.
  • the alloy for solar cells can be mounted in a vacuum evaporation apparatus as a material for forming a light absorption layer of a solar cell, and a CIGSS thin film or a CIGS thin film can be formed on a back electrode laminated on a glass substrate.
  • a CIGSS sputtering target or CIGS sputtering target for forming a light absorption layer of a solar cell by a sputtering process in one process is obtained. Furthermore, the CIGSS sputtering target can reduce the amount of Se harmful to the human body as compared with the conventional CIGS sputtering target. Further, in the CIGSS ternary alloy manufacturing process, S and Se are vacuum-enclosed together with other raw materials, and crystals are grown by melt growth by heating, so that they can be manufactured by a safe process with little risk of combustion and explosion.
  • a CIGS quaternary alloy having a wider band gap can be obtained as compared with the CIGS quaternary alloy reported conventionally.
  • a light absorption layer can be produced in one process without using hydrogen sulfide gas or selenium sulfide gas, and it is safe and efficient. A good solar cell manufacturing process can be obtained.
  • a CIGS quaternary alloy sputtering target used in a sputtering apparatus for forming a light absorption layer of a CIGS solar cell can also be produced by a safe production process that does not involve the risk of combustion or explosion. For this reason, high-precision and complicated temperature control is not performed, and the productivity is improved and the cost is reduced.
  • the CIGS quaternary alloy sputtering target produced by this production method in a sputtering apparatus the light absorption layer of the CIGS solar cell can be produced in one process, and the production process is more than that in the three-stage method.
  • XRD measurement result of CIGS quaternary alloy Results of Raman shift measurement of CIGS quaternary alloy
  • a CIGSS ternary alloy which is a material of a light absorption layer in which S is added to CIGS and the band gap width is adapted to sunlight
  • a CIGSS sputtering target is produced from the CIGSS quinary alloy, and the CIGSS sputtering target.
  • the present invention relates to a method for manufacturing a CIGSS solar cell, in which a light absorption layer is manufactured in one process.
  • the present invention produces a CIGS quaternary alloy with high productivity that suppresses the chemical reaction between In and Se, and uses a CIGS sputtering target with the CIGS quaternary alloy to form a light absorption layer in one process.
  • the present invention relates to a CIGS solar cell to be manufactured.
  • FIG. 1 is a flowchart 10 showing the concept of a method for producing a CIGSS sputtering target.
  • step S1 Cu, In, Ga, S, and Se are used as raw materials, weighed and mixed according to the elemental composition ratio, and sealed in an ampoule.
  • step S2 the ampoule in which the raw material is vacuum-sealed is heated to melt the raw material and crystallize by melt growth.
  • the crystals obtained here are CIGSS polycrystals.
  • the CIGSS polycrystal is sliced to complete a CIGSS sputtering target.
  • the obtained CIGSS sputtering target has a forbidden band width of 1.4 eV compared to about 1.0 eV for conventional CIS and about 1.2 eV for CIGS, and is used as a light absorption layer material for solar cells. Thus, a light absorption layer with good conversion efficiency can be obtained.
  • a compound semiconductor used as a material of a p-type semiconductor that functions as a light absorption layer of a solar cell is two kinds of elements that are equidistant from the IV group across the IV group (Si, Ge, etc.) in the periodic table of elements.
  • a compound When a compound is produced, it utilizes the property that a similar chemical bond is formed and becomes a semiconductor. It is an I-III-VI group 2 element belonging to the adamantine series, and its crystal structure is a chalcopyrite structure.
  • FIG. 2 shows the chalcopyrite type crystal structure 20.
  • Each of the group I Cu, group III Ga, In, and VI group S and Se atoms shown in FIG. 2 is tetracoordinate and has a tetragonal crystal structure.
  • Chalcopyrite type semiconductors have a forbidden band width ranging from 0.26 to 3.5 eV, but the I-III-VI Group 2 element has strong ionicity but mobility of I-IV- weaker than the V 2 group, Thus, a typical CIS and CIGS which have been conventionally used, operating at lower than desired bandgap.
  • the forbidden band width of the chalcopyrite type compound crystal used in the present invention is 1.04 eV for CIS, 1.68 eV for CGS, and 1.53 eV for CuInS.
  • the mobility of a p-type semiconductor is high it is desirable, each of the mobility, CIS is 50cm 2 / V ⁇ s, CGS is 40cm 2 / V ⁇ s, CuInS Is 15 cm 2 / V ⁇ s.
  • CuInS 2 has an ideal forbidden band width, but has low mobility for use as a solar cell.
  • CIS and CIGS which are currently widely used as light absorbing layers, use Se that is harmful to the human body, so there is an expectation to reduce Se as much as possible. Proposed.
  • the present invention is a sputtering target made of a CIGSS ternary alloy in which the forbidden band width is 1.4 eV and the amount of Se is reduced with respect to CIGS, and CIS, CGS and CuInS 2 which are basic three crystals are mixed. It is thought that the structure is configured as follows. That is, CIS having a forbidden band width of 1.04 eV and CGS having a forbidden band width of 1.68 eV are mixed to form a polycrystal of CIGS having a forbidden band width of 1.2 eV. This is considered to be a mixed structure of CuInS 2 polycrystal having a band width of 1.54 eV.
  • FIG. 3 is a flowchart 24 showing a method for producing a SIGSS ternary alloy.
  • step S11 as a preparation, a quartz ampule is prepared. Quartz ampules are washed with aqua regia and hydrofluoric acid, and the moisture is evaporated in a dryer. After soaking in acetone, heat with a burner and remove wrinkles. As a result, the quartz ampule is carbon-coated, and precipitation of impurities can be prevented.
  • step S12 Cu, In, and Ga are washed using hydrochloric acid or the like, and the element atom number ratio of Cu, In, and Ga is 1: 0.8: 0.2, and the element atom number ratio of S and Se. Is weighed to 0.2: 0.8 and sealed in a carbon-coated quartz amble.
  • the element atomic ratio of Se and S is determined by design according to the function, and can be set to x: (1-x), where x is 0 ⁇ x ⁇ 1. When x is 0 or 1, it is a quaternary alloy and is not considered in this embodiment.
  • step S13 the quartz amble in which the raw material is vacuum-sealed is placed in an electric furnace for heating.
  • the heater in the furnace is energized to generate heat, and as a first temperature step, the temperature is raised to 200 ° C. and maintained for a certain period of time. Further, in step 15, the temperature is raised to 1050 ° C. as the second temperature step, the high temperature state is maintained for a certain time, and the raw material is polycrystallized, and then the furnace temperature is lowered to room temperature in step S16. Thereby, a CIGSS ternary alloy is obtained.
  • FIG. 4 is a diagram specifically showing the production state 30 by the electric furnace used in the production process described in FIG.
  • a heater 34 for heating in the electric furnace 32, and the heater 34 generates heat due to energization from the outside and raises the temperature in the furnace.
  • a quartz amble 38 in which a raw material 36 is vacuum-sealed is placed inside the electric furnace 32. The furnace temperature is controlled by an external control device (not shown).
  • FIG. 5 shows a temperature control state 40 in the electric furnace in the production process of the SIGSS ternary alloy.
  • a quartz ampule in which the raw materials of Cu, In, Ga, S, and Se are vacuum-sealed is placed in the furnace, and the heater is energized to raise the furnace temperature.
  • the first temperature step is raised to about 200 ° C. and the second temperature step is raised to 1050 ° C.
  • the temperature rise to 200 ° C. is increased to 200 ° C. in 2 hours.
  • This state is maintained for about 12 hours and then raised to 1050 ° C. in 6 hours.
  • This high temperature state is kept constant for about 24 hours. This maintaining time has a high degree of freedom, and strict time management is not required.
  • return to room temperature within 6 hours. Example 2
  • Example 1 raw materials that are elemental components of the CIGSS ternary alloy were mixed, but Se and S have a low melting point, and it is necessary to precisely control the temperature in order to obtain a high-quality polycrystal. For this reason, CIG polycrystal by Cu, In, and Ga is produced, CIGSS polycrystal is produced by mixing this CIG polycrystal and Se and S.
  • FIG. 6 is a flowchart 42 of a CIGSS ternary alloy production method for producing a CIGSS polycrystal by preparing a CIG polycrystal and preparing CIGSS polycrystal by mixing Se and S with this CIG polycrystal.
  • a quartz ampoule for producing a CIG ternary alloy and a quartz ampoule for producing a CIGS quaternary alloy are prepared. Quartz ampules are washed with aqua regia and hydrofluoric acid, and the moisture is evaporated in a dryer. After soaking in acetone, heat with a burner and remove wrinkles.
  • Step S22 Cu, In, and Ga are washed with hydrochloric acid or the like, and the carbon atom-coated quartz is weighed so that the atomic ratio of Cu, In, and Ga is 1: 0.8: 0.2. Vacuum-fill the amble.
  • step S23 the quartz amble in which the raw material is vacuum-sealed is placed in an electric furnace for heating.
  • the heater in the furnace is energized to generate heat, the temperature is raised to 1050 ° C., the high temperature state is maintained for a certain time, and the raw material is polycrystallized, and then the furnace temperature is rapidly cooled within 6 hours in step S24. This is to obtain a high-quality CIG crystal.
  • step S25 the obtained CIG crystal is pulverized and pulverized to be sufficiently mixed with S and Se.
  • the CIG crystal powdered in step S26 and the atomic ratio of S and Se are weighed so as to be 0.2: 0.8, and the amount of raw materials is mixed and sealed in a quartz ampule.
  • the subsequent manufacturing method of the CIGSS ternary alloy is the same as in Steps S14 to S16 of Example 1.
  • a quartz ampule in which the raw materials are vacuum-sealed is placed in an electric furnace, and the heater is energized to raise the furnace temperature.
  • step S27 the temperature is raised to about 200 ° C.
  • step S28 the temperature is raised to 1050 ° C. Thereafter, the temperature is returned to room temperature in step S29.
  • FIG. 7 shows the temperature control state 44 in the electric furnace in the production process of the SIGSS ternary alloy of Example 2.
  • a quartz ampule in which the raw materials of Cu, In, and Ga are vacuum-sealed in a furnace at room temperature, the heater is energized and the furnace temperature is raised to 1050 ° C. The temperature was raised for 12 hours. The high temperature state of 1050 ° C. was maintained for 24 hours, and then returned to room temperature within 6 hours.
  • the first temperature step is raised to about 200 ° C.
  • the second temperature step is raised to 1050 ° C.
  • the temperature rise to 200 ° C. is increased to 200 ° C. in 2 hours. This state is maintained for about 12 hours and then raised to 1050 ° C. in 6 hours. This high temperature state is kept constant for about 24 hours. This maintaining time has a high degree of freedom, and strict time management is not required.
  • the SIGSS quinary alloy produced by these production methods was evaluated by XRD and Raman spectroscopy.
  • XRD can evaluate crystallinity from the diffraction pattern of X-rays scattered by the arrangement state of atoms / molecules of a substance by irradiating an analysis sample with X-rays of a certain wavelength.
  • Raman spectroscopy is a method of analyzing a molecular structure by Raman scattering (inelastic scattering) in which a substance is irradiated with light and scattered from scattered light to a wavelength different from incident light by molecular vibration.
  • FIG. 8 shows the XRD measurement result 46 of the CIGSS ternary alloy.
  • the X-ray diffraction pattern of the CIGSS ternary alloy has peaks at 2 ⁇ of about 27 °, 45 °, 53 °, 65 °, 72 °, and 82 °. This is consistent with the ICDD CIGSS reference pattern shown simultaneously in FIG. The intensity is also a sharp peak, indicating that a good CIGSS crystal is obtained.
  • FIG. 9 shows a Raman shift measurement result 48 by Raman spectroscopy.
  • the mode indicated by the Raman shift of 177 cm ⁇ 1 is the A 1 mode, and the vertex at 259 cm ⁇ 1 is the highest transverse optical B 2 (T0) mode.
  • This result shows the good crystallinity of the CIGSS ternary alloy.
  • the obtained CIGSS ternary alloy is a CIGSS polycrystal, which can be used as a material for forming a light absorption layer of a solar cell, and can be used to manufacture a safe solar cell that does not use sulfur gas or selenium gas harmful to the human body. It becomes.
  • this CIGSS ternary alloy In order to install this CIGSS ternary alloy in a sputtering apparatus for forming a light absorption layer of a solar cell, it is used as a CIGSS sputtering target, but the obtained CIGSS quinary alloy is used as a CIGSS sputtering target. Is sliced to obtain a CIGSS sputtering target. Moreover, after pulverizing and pulverizing the obtained CIGSS ternary alloy, it is put into a mold having a desired shape adapted to a sputtering apparatus, bulked by press processing, and sliced to produce a CIGSS sputtering target. You can also.
  • a CIGSS quaternary alloy production method for producing a CIGSS polycrystal by preparing a CIGSS polycrystal by preparing a CIGSS polycrystal by mixing the CIG polycrystal with Se and S is a CIGS quaternary by mixing only Se to the pulverized CIG polycrystal.
  • a system alloy can be produced.
  • FIG. 10 is a flowchart showing in detail a method for producing a CIGS quaternary alloy.
  • Step S31 a quartz ampule for producing a CIG ternary alloy and a quartz ampule for producing a CIGS quaternary alloy are prepared. Quartz ampules are washed with aqua regia and hydrofluoric acid, and the moisture is evaporated in a dryer. After soaking in acetone, heat with a burner and remove wrinkles. As a result, the quartz ampule is carbon-coated, and precipitation of impurities can be prevented.
  • step S32 Cu, In and Ga are washed with hydrochloric acid or the like, and weighed so that the atomic ratio is 1: 0.8: 0.2, and vacuum-sealed in a carbon-coated quartz amble.
  • step S33 the quartz amble in which the raw material is vacuum-sealed is placed in an electric furnace for heating.
  • the heater in the furnace is energized to generate heat, and the temperature is raised to 1050 ° C.
  • the high temperature state of 1050 ° C. is maintained for a certain period of time, and after the raw material is polycrystallized, the furnace temperature is lowered to room temperature in step S35.
  • a CIG ternary alloy is obtained.
  • step S36 the CIG ternary alloy is taken out from the quartz amble lowered to room temperature, and the CIG ternary alloy is pulverized. At this time, a uniform fine powder is obtained through the mesh.
  • Such crystal powder does not chemically react with Se because In is crystallized together with Cu and Ga.
  • step S37 the pulverized CIG ternary alloy and Se are weighed at a ratio of the elemental atomic ratio of 1: 2, sealed in a carbon-coated quartz amble, and placed in an electric furnace in step S38.
  • step 39 the furnace temperature is raised to 1050 ° C., and the temperature of 1050 ° C. is maintained for a certain period of time. After polycrystallization, the furnace temperature is lowered to room temperature in step S40. Take out.
  • FIG. 11 shows a temperature control state 52 in the electric furnace in the CIGS quaternary alloy production process.
  • the electric furnace shown in FIG. 4 is used as the electric furnace.
  • a quartz amble in which Cu, In, and Ga raw materials are vacuum-sealed is placed in a furnace, and a heater is energized to raise the furnace temperature.
  • the temperature rise is raised to 1050 ° C. in 12 hours, for example.
  • the temperature raising time may be 12 hours or less, and may be 6 hours to 12 hours.
  • the temperature is kept constant for about 24 hours while maintaining 1050 ° C.
  • Even in this high temperature state the temperature is 1000 ° C. to 1100 ° C. and polycrystallizes in about 12 to 24 hours. This maintaining time has a high degree of freedom, and strict time management is not required.
  • energization of the heater is stopped and the furnace temperature is lowered by natural temperature drop. Decrease in time within 6 hours.
  • the CIG polycrystal thus obtained is returned to room temperature and then pulverized, further mixed with Se, vacuum sealed in a quartz amble, and again placed in the furnace.
  • the temperature is raised from room temperature to 1050 ° C., for example, in 10 hours. This state of 1050 ° C. is maintained for about 24 hours. Strict control is not required for this time, and the subsequent temperature decrease to room temperature may be rapid cooling.
  • FIG. 12 is an appearance of the CIGS quaternary alloy powder 54 obtained by pulverizing the CIGS quaternary alloy obtained according to the present invention.
  • the CIGS quaternary alloy powder 54 in FIG. 12 is in a state before being bulked by pressure processing.
  • FIG. 13 shows the XRD measurement results of the CIGS quaternary alloy.
  • the X-ray diffraction pattern of the CIGS quaternary alloy has peaks at 2 ⁇ of about 26.5 °, 44.5 °, 52.5 °, 65 °, 71 °, and 82 °. This is consistent with the ICDD CIGS reference pattern shown simultaneously in FIG. The intensity is also a sharp peak, indicating that a good CIGS crystal is obtained.
  • FIG. 14 shows a Raman shift measurement result 58 of a CIGS quaternary alloy by Raman spectroscopy.
  • FIG. 15 is a diagram showing a structure 60 of the CIGSS solar cell.
  • Blue glass is used for the glass substrate 62 and Mo (molybdenum) is used as the back electrode 64.
  • the light absorption layer 66 is composed of a CIGSS thin film. Since the CIGSS thin film is a direct transition type semiconductor, the light absorption coefficient is large, the forbidden band width is around 1.4 eV, and the conversion efficiency is high.
  • An n-type buffer layer 58 is formed on the p-type CIGSS thin film that is the light absorption layer 66 to function as a solar cell. For example, cadmium sulfide CdS is used for the buffer layer 68.
  • a surface electrode 70 is formed on the top by ZnO (zinc oxide) or the like. Further, an extraction electrode (not shown) is provided.
  • FIG. 16 shows a conceptual diagram of one-process formation 74 of a light absorption layer by sputtering using a CIGSS sputtering target prepared according to the present invention.
  • a CIGSS thin film to be the light absorption layer 66 is formed on the back electrode 64 by sputtering and attaching CIGSS sputtered atoms.
  • FIG. 17 is a diagram for explaining a production state 80 of the light absorption layer by the sputtering apparatus.
  • the sputtering apparatus 82 is provided with an opening for performing vacuum suction 84, an opening for injecting Ar (argon) gas 86, and an opening for injecting cooling water 92.
  • a Mo substrate 96 on which a back electrode is formed of Mo on a glass substrate is placed on the sample stage 94.
  • a CIGSS sputtering target 90 attached to the electrode 88 is installed on the upper part of the sputtering apparatus 82.
  • a DC power source 102 is connected to the electrode 88 and the sample stage 94 with the sample stage 94 as a plus.
  • FIG. 18 is a flowchart showing an example of a solar cell manufacturing method 110 for forming a CIGSS thin film in one process using a CIGSS sputtering target.
  • step S51 Mo is formed on the soda glass substrate by sputtering.
  • step S52 the back electrode is cut and patterned for series connection of each cell.
  • step S53 as described with reference to FIG. 17, a CIGSS light absorption layer is formed in one process using a sputtering apparatus.
  • step S54 the formed CIGS light absorption layer is immersed in a strong alkaline aqueous solution, and a buffer layer is formed by a solution growth method. Subsequently, in step S55, the CIGSS light absorption layer and the buffer layer are shaved to form a pattern.
  • step S56 a transparent conductive film layer is formed on the buffer layer by using ZnO or the like using, for example, an MOCVD (Metal Organic Chemical Deposition) apparatus.
  • step S57 the conductive film layer is shaved again and patterned.
  • step S58 a buster electrode made of aluminum or the like is soldered to the back electrode, and a layer laminated on the glass substrate is sealed with a cover glass to complete a CIGSS solar cell.
  • the CIGSS solar cell manufacturing method using the CIGSS sputtering target using the CIGSS ternary alloy according to the present invention has been described.
  • the CIGSS quinary alloy according to the present invention can also be used for forming a light absorption layer by a vacuum deposition method. .
  • FIG. 19 is a diagram for explaining a production state of a light absorption layer by a vacuum deposition method using a CIGSS ternary alloy according to the present invention.
  • FIG. 19A is a plan view of the vacuum deposition apparatus 120, which includes a vacuum chamber 122, a diffusion pump 124, a mechanical booster pump 126, and an oil rotary pump 128.
  • the light absorption layer is formed by the CIGSS ternary alloy according to the present invention.
  • the air inside the vacuum chamber 122 is evacuated and vacuumed by the diffusion pump 124 and the oil rotary pump 128.
  • the mechanical booster pump 126 is configured such that two mayu rotors in a casing enter a drive gear at the shaft end and rotate synchronously in opposite directions.
  • the gas entering from the intake port is confined in the space between the casing and the rotor, and is released into the atmosphere from the exhaust port side by the rotation of the rotor. For this reason, the exhaust speed can be significantly increased by combining the mechanical booster pump 126 with the diffusion pump 124 and the oil rotary pump 128.
  • FIG. 19B shows a state where a light absorption layer is formed on the Mo substrate 96 by vapor deposition from the CIGSS ternary alloy 138 in the vacuum chamber 122 of the vacuum vapor deposition apparatus 120.
  • the vacuum chamber 122 includes a tungsten board 130 on which a Mo substrate 96 and a CIGSS ternary alloy 138 are mounted, and a heater 132. Further, a shutter 136 that stops film formation when the thickness of the light absorbing layer reaches a predetermined thickness is provided.
  • the CIGSS ternary alloy 138 as a vapor deposition sample is put in the tungsten boat 130, and then the evacuation is performed by rotating the diffusion pump 124, the oil rotary pump 128, and the mechanical booster pump 126.
  • the heater power supply 134 is turned on and a current is supplied to the heater 132 to heat it.
  • the shutter 136 is opened. Thereby, the vapor deposition material from the CIGSS ternary alloy 138 starts vapor deposition on the Mo substrate 96 to form a film.
  • the shutter 136 is closed and the vapor deposition is finished.
  • the light absorption layer can be formed also by the vacuum vapor deposition method using the vacuum vapor deposition apparatus.
  • a CIGS solar cell can be produced by a sputtering method or a vacuum evaporation method in the same manner as the method for producing a solar cell using a CIGS quaternary alloy.
  • this invention includes the appropriate deformation

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Abstract

　Le procédé de fabrication d'un alliage pour cellule solaire selon l'invention consiste à mélanger des matières premières du cuivre, de l'indium, du gallium, du sélénium et du soufre, à sceller sous vide lesdites matières dans une ampoule, à chauffer l'ampoule, et à cristalliser les matières premières dans l'ampoule par une croissance par fusion. Les matières premières du cuivre, de l'indium et du gallium sont transformées en cristaux de cuivre, d'indium, de gallium (CIG), et ces cristaux CIG peuvent être broyés ou pulvérisés. Ainsi, il est possible d'obtenir des cristaux de qualité élevée lors de la cristallisation avec S ou Se. Les cristaux de cuivre, de gallium, d'indium sont préparés en deux étapes: une étape de scellement sous vide lors laquelle les matières premières du cuivre, de l'indium et du gallium sont mélangées et scellées sous vide dans une ampoule; et une étape de cristallisation CIG lors de laquelle l'ampoule est chauffée, et les matières premières dans l'ampoule sont cristallisées par une croissance par fusion. Les cristaux CIG peuvent être broyés, et s'ils sont mélangés uniquement avec du sélénium, ils peuvent être transformés en alliage quaternaire.
PCT/JP2013/052699 2012-02-27 2013-02-06 Procédé de fabrication d'alliage pour cellule solaire à base de cigs WO2013129044A1 (fr)

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