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WO2015100480A1 - Procédé pour former des films minces cigs destinés aux cellules solaires et dispositif de sa mise en oeuvre - Google Patents

Procédé pour former des films minces cigs destinés aux cellules solaires et dispositif de sa mise en oeuvre Download PDF

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Publication number
WO2015100480A1
WO2015100480A1 PCT/BY2013/000013 BY2013000013W WO2015100480A1 WO 2015100480 A1 WO2015100480 A1 WO 2015100480A1 BY 2013000013 W BY2013000013 W BY 2013000013W WO 2015100480 A1 WO2015100480 A1 WO 2015100480A1
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layer
temperature
substrate
iii
layers
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Russian (ru)
Inventor
Владимир Яковлевич ШИРИПОВ
Сергей Павлович МАРЫШЕВ
Сергей Михайлович НАСТОЧКИН
Евгений Александрович ХОХЛОВ
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32899—Multiple chambers, e.g. cluster tools
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
    • H01J37/3405—Magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3417—Arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3426—Material
    • H01J37/3429—Plural materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/167—Photovoltaic cells having only PN heterojunction potential barriers comprising Group I-III-VI materials, e.g. CdS/CuInSe2 [CIS] heterojunction photovoltaic cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • the invention relates to a technology for the formation of thin semiconductor CIGS films for solar cells on sheet glass substrates and to devices for vacuum deposition that implement such a technology in mass industrial production.
  • a known method of recrystallization of CIGS films for solar cells including vacuum deposition of ultimately, a slightly copper-depleted layer of Cu (In, Ga) Se 2 (CIGS) on a substrate, including the formation on the surface of the substrate of the initial layer enriched with copper in the form a mixture of phases Cu (In, Ga) Se 2 - Cu x Se and subsequent application of a mixture of Cu (In, Ga) Se 2 - Cu x Se to the surface of the initial layer at an excess vapor pressure of Se and (In, Ga) and at the same time increasing the temperature of the substrate.
  • the specified method does not allow to obtain thin film structures homogeneously stable in thickness, and this, in turn, does not allow to obtain a structure with a high coefficient of transformation of solar energy into electricity. In addition, the method is extremely difficult to use with respect to large substrates.
  • the change in the heater power is caused by the fact that, at the end of the second stage, a free Cu 2-x Se phase appears on the surface of the film layer, the thermal emissivity of which is different from the thermal emissivity of the final Cu (In x Gai -x ) Se 2 compound slightly depleted in copper.
  • a change in thermal emission leads to a change in power dissipated and consumed to maintain a constant temperature, and this, in turn, allows us to estimate the amount of free phase Cu 2-x Se.
  • the production line for the implementation of this method is limited by the design, in which the film is applied from bottom to top, and the substrate of sheet glass is horizontally receiving surface down.
  • this design under conditions of a temperature of about 550 ° C, which is almost equal to the softening temperature of the glass, deformation of the substrate under the influence of gravitational forces or the sum of internal stresses in the deposited layers is inevitable;
  • a (InGa) 2 Se 3 layer is applied, the crystal lattice of which is not a chalcopyrite structure, which is necessary for the Cu (In x Gai -x ) Se 2 layer.
  • the transformation of the (InGa) 2 Se 3 layer formed in the first stage into a Cu (In x Gai -x ) Se 2 layer in the second stage is due to the diffusion of copper condensing on the surface of this layer.
  • the ratio of atomic concentrations Cu / (In + Ga) lies in the range of 0.88 - 0.92 at any point in the cross section of the layer, either adjust the diffusion rate of copper to the deposition rate, which is practically not feasible for the industrial method, or significantly reduce the deposition rate of copper in the second stage, which will significantly limit the performance of the process.
  • the thickness of the layer deposited in the first stage is close to half of the required thickness of the final layer, then at a rate of vacuum deposition acceptable for industrial production, inside the resulting Cu (In x Gai -x ) Se 2 layer, the gradient of the ratio Cu / (In + Ga), with a minimum at the boundary with the Mo layer.
  • the reproducibility of the technology in accordance with the existing method will be extremely low, due to the inability to control the diffusion rate of copper over time during the second stage.
  • the end of the second stage can be characterized by the presence of the Cu 2 phase on the film surface.
  • x Se of various thicknesses.
  • the rate the transformation of this phase into chalcopyrite Cu (In x Ga ) -x ) Se 2 is controlled by the ratio of the deposition rate and the rate of mutual diffusion of the components, results are observed when a conducting phase Cu 2-x Se is present inside the finished layer (the deposition rate exceeded the diffusion rate of the components). If the diffusion and deposition rates are close to equilibrium, and the thickness of the Cu 2-x Se layer at the end of the second stage is too large, then the surface roughness at the end of the whole process is unacceptably large.
  • the maximum conversion efficiency in solar panels of this type is fixed in those cases when, on the surface of the Cu (In x Gai -x ) Se 2 layer, a layer is finally formed in which the ratio Cu / (In + Ga) ⁇ 0.4 , and its thickness does not exceed 20 - 50 nm.
  • the conductivity type undergoes a transformation from p to n, and, as a result, upon completion of the formation of the Cu (In x Ga] iX ) Se 2 layer, a very thin “built-in” homogeneous pn junction is automatically formed at its surface. This transition is stabilized by a subsequent operation — the deposition of the thinnest layer ( ⁇ 50 nm) of CdS from solutions.
  • paired magnetron targets are, respectively, copper selenide (CuSe 2 ) and a mixture of indium and gallium selenides.
  • the working gas in this case is argon.
  • paired magnetron targets are made of copper and indium gallium alloy, respectively.
  • the working gas in this case is a mixture of argon - hydrogen selenide (H 2 Se).
  • a device for the formation of a final layer of Cu (In x Ga 1-x ) Se 2 with a small copper deficiency is a sequence of several pairs of these magnetron targets in a vacuum corridor of a continuous line.
  • paired targets can be made in the form of planar cathodes or in the form of rotating cylindrical cathodes.
  • the substrate in this case, can be made both in the form of a sheet of glass, or in the form of a continuous tape of metal.
  • the required final composition of the Cu (In x Gai -x ) Se 2 layer is achieved by selecting the ratio of power dissipated in the target materials from copper selenide (pure copper) and indium / gallium selenides (indium / gallium alloy).
  • the distribution of the concentration ratio Cu / (In + Ga) becomes more uniform over the cross section of the final layer (the final layer is divided by the number of layers in accordance with the number of deposition stations, which may be more than three).
  • the problem solved by this invention is the creation of a method of forming thin-film layers of CIGS for solar cells on large substrates, which allows you to:
  • the number of layers is selected in the range from 5 to 1 1.
  • the problem is also solved by the fact that the temperature of the substrate is controlled by a non-contact pyrometer on the glass side.
  • the problem is also solved by the fact that a constant temperature of the substrate is supported by infrared emitters on the glass side, and as a parameter for the end of the deposition of a particular layer, the magnitude of the change in thermal radiation is used while maintaining a constant temperature of the substrate.
  • the problem is also solved by the fact that at a constant speed of movement of the workpiece in a vacuum corridor in the zone of application of the layer, the magnitude of the change in thermal radiation to maintain a constant substrate temperature is used as a parameter of the deposition rate of the layer.
  • the problem is also solved by the fact that at the positions forming even layers, the end of the process is determined after reaching the minimum radiation temperature and subsequently raising it by 0.8 - 6 ° C.
  • the end of the process is defined as the achievement of the maximum radiation temperature and its subsequent decrease by 1 ° - 5 ° C.
  • the problem is also solved by the fact that the power of the magnetron spray station is controlled depending on the magnitude of the change in heat flux from the heaters.
  • the problem is solved in that for the known device for the vacuum deposition of thin semiconductor films in the vacuum corridor of the production line with sequentially arranged spray stations equipped with planar or cylindrical DC magnetrons or twin magnetrons, and the control system according to the invention, in front of the first spray station and after the first spray station, heating chambers are placed, infrared heating elements and temperature measuring devices made in the form of optical pyrometers are installed on the side of the glass substrate on the spray station, and the control system contains heat flow sensors from heaters.
  • the problem is also solved by the fact that the pyrometers are multi-point.
  • the extended vacuum chamber is made in the form of two parallel rectilinear branches of the working and return, located in the same vacuum corridor, while the return branch serves to return products to the place of unloading, loading and cooling of products in vacuum.
  • a lock chamber for loading and unloading products is located on one side of the vacuum corridor.
  • FIG. 1 shows a diagram of a vacuum installation for applying a CIGS film in a vacuum to a sheet glass substrate in the manufacture of solar cells in vacuum.
  • FIG. 2 shows a deposition station with a magnetron.
  • FIG. 3 to 11 show a graph of the variation in heat flux at the spray stations 1 to 9.
  • FIG. 12 and 13 are integrated plots of the variation in heat flow temperature for sputtering a nine- and eleven-layer film.
  • FIG. 15 is a typical SEM image of a cleaved CIGS film.
  • FIG. 16 is an X-ray diffraction pattern of a two-layer CIGS-Mo structure on a glass substrate
  • the installation consists of two vacuum corridors 1 and 2 connected by a transport system 3.
  • the transport system 3 is made by known solutions and is, for example, a chain conveyor on which the snap-in 6 is mounted for fixing the substrate 7.
  • heating elements 8, pyrometers 9 for measuring temperature and heat sensors are installed on the substrate side about flow 10.
  • the heat flux sensors 10 are installed only at the spraying positions where the magnetrons are installed 11.
  • the heat flux sensors 10 are connected to the control system (not shown) by magnetrons 1 through control units 12 1.
  • the control unit 14 receives and analyzes the signals from the pyrometers 9 and controls the power sent to the heating elements 8 to ensure a constant temperature of the substrate 7. After turning the conveyor in the cooling vacuum corridor 2, the workpieces, moving forward, cool to the temperature necessary to extract them from the vacuum chamber. The extraction is carried out in the lock chamber 4, combined with a device for turning the conveyor. A layer of molybdenum 15 is preliminarily applied to the substrate 7, and a layer of a thin film (not shown) is applied during the passage through the spraying positions.
  • the technological process of vacuum deposition of a CIGS film consisting of 9 sequentially sprayed layers is as follows.
  • the glass substrate 7 with a molybdenum layer 15 previously sprayed onto its surface is placed in the lock chamber 4 at room temperature and pumped out with a vacuum pump to pressure of the order of 1-10 Pa. Then the substrate is transferred to the first heating chamber, in which the temperature of the substrate is brought to 370 ° C.
  • FIG. Figure 3 shows the temperature profile of the heat flux sensor, which records the change in the heat flux of the heaters, and therefore the power consumed by them during the deposition process of the first layer while maintaining a constant substrate temperature of 370 ° C. The moment of completion of the spraying process is determined after reaching the maximum heat flux temperature and lowering the temperature by 1 ° C. Then the substrate is moved to a second heating chamber, in which the temperature of the substrate is raised to 550 ° C.
  • FIG. 4 shows the temperature profile of the heat flux sensor during the deposition process of the second layer while maintaining a constant substrate temperature of 550 ° C. The moment of completion of the deposition process is determined after reaching a radiation temperature of a minimum and a subsequent rise in temperature by 3 ° C.
  • the substrate is transferred to a third spray station, on which the next copper-depleted layer is deposited onto its surface by spraying a target whose composition is identical to the target composition of the first spray station.
  • FIG. 5 shows the temperature profile of the heat flux sensor during the deposition of the third layer while maintaining a constant substrate temperature of 550 ° C. End time the spraying process is determined after reaching the maximum radiation temperature and lowering the temperature by 5 ° C.
  • FIG. 6 shows the temperature profile of the heat flux sensor during the deposition process of the fourth layer while maintaining a constant substrate temperature of 550 ° C. The moment of completion of the spraying process is determined after reaching a radiation temperature of a minimum and a subsequent rise in temperature by 6 ° C.
  • Figure 7 shows the temperature profile of the heat flux sensor during the fifth layer deposition process while maintaining a constant substrate temperature of 550 ° C. The end of the deposition process is determined after reaching the radiation maximum temperature and lowering the temperature by 5 ° C.
  • the substrate is transferred to the sixth spray station, on which a copper-enriched layer is deposited onto its surface by spraying a target whose composition is identical to the target composition of the second and fourth spray stations.
  • On Fig shows the temperature profile of the heat flow sensor during the deposition process of the sixth layer while maintaining a constant substrate temperature of 550 ° C. The moment of completion of the spraying process is determined after reaching a radiation temperature of a minimum and a subsequent rise in temperature by 2 ° C.
  • Figure 9 shows the temperature heat flow sensor profile during the seventh layer deposition process while maintaining a constant substrate temperature of 550 ° C. The moment of completion of the deposition process is determined after reaching the radiation maximum temperature and lowering the temperature by 2 ° C.
  • FIG. 10 shows the temperature profile of the heat flux sensor during the eighth layer deposition process while maintaining a constant substrate temperature of 550 ° C. The moment of completion of the spraying process is determined after reaching a radiation temperature of a minimum and a subsequent rise in temperature by 1 ° C.
  • Figure 1 1 shows the temperature profile of the heat flux sensor during the deposition process of the ninth layer while maintaining a constant substrate temperature of 550 ° C. The moment of completion of the deposition process is determined after reaching the radiation maximum temperature and lowering the temperature by 2 ° C.
  • the substrate using the transport system 3 is moved to the rotary chamber and then to the cooling vacuum corridor 2, in which the substrate 7 with the film 15 is moved to the discharge position 4 and cooled to a temperature of 90 - 105 ° C. Then the substrate is moved to the lock chamber 4, let in air and removed from the vacuum installation.
  • CIGS films In the process of vacuum deposition of a CIGS film, two types of targets are used with different percentages of Cu, In, Ga.
  • the composition of the targets is determined based on the following considerations.
  • the Cu2 – x Se phase precipitates in the film volume, which, due to the metallic nature of the conductivity, shunts the absorber material and the region of the - - - transition.
  • the CIGS film is a mixture of the a and ⁇ phases and is characterized by an increased resistivity, which leads to a decrease in the efficiency of CIGS as an absorber.
  • Cu-In-Ga and Cu-Ga targets are used.
  • the use of the Cu-In-Ga target for sputtering the first layer is due to the need to form a seed layer on the molybdenum contact layer in composition and structure close to chalcopyrite.
  • the temperature of the substrate at which this layer is sprayed is slightly lower than on the other layers and is 340 - 400 ° C. This is due to the fact that, at elevated temperatures above 400 ° C, large internal stresses arise in the sprayed layer and film peeling occurs at the boundary with molybdenum. In addition, at such temperatures, film growth in the form of pillars (columnar growth) is observed, which leads to the appearance of leakage currents along the grain boundaries in the final structure of the solar cell and a decrease in its efficiency. At temperatures below 340 ° C, the process of the germinal layer slows down sharply and does not provide the required grain structure.
  • the first CIGS layer has a copper and gallium depleted composition
  • the total number of layers should be odd, since when spraying even layers on the surface of the growing film, there is a Cu 2-x Se phase with a metallic conductivity. It must be neutralized with a layer with a reduced copper content.
  • it is required to create an increased concentration of indium selenides in the surface layer of CIGS ⁇ 40-60 nm thick (ratio [Cu / N] ⁇ 0.4). This makes it possible to invert the natural p- chalcopyrite conductivity into i-type conductivity.
  • a hidden homogeneous ⁇ -transition is formed under the CIGS surface, which in the finished device, together with the subsequently deposited heterogeneous layer of sulfur cadmium ⁇ -type conductivity, will determine the parameters of the solar cell diode.
  • this is quite simple to do, for example, by lowering the power on the Cu-In-Ga target of the last layer.
  • a gradient of the [Ga / III] ratio is provided with a minimum at the surface and a maximum towards the boundary with molybdenum.
  • the internal electric field of the CIGS film is formed, which contributes to the efficient transfer of charges to external contacts.
  • Fig.14 shows the profiles of the ratios [Cu / III] and [Ga / III] obtained from the numerical data of the Auger analysis during deep etching of the formed structure by the primary ion beam.
  • the number of layers and, accordingly, spray stations depends on the thickness of the CIGS film and for a film thickness of 1.3 - 2.0 ⁇ m is from 5 to 11.
  • the thickness of the first layer cannot be selected more than 0.4 - 0.5 ⁇ m, since more thick films have weak adhesion to the molybdenum layer due to internal stresses, and further thickness growth is possible only with an increase in the total number of layers.
  • On Fig presents a typical SEM image of a chip CIGS film sprayed on a molybdenum layer, which serves as the back contact electrode in the structure of the solar cell.
  • CIGS film sprayed by the proposed method has a dense coarse-grained structure in the form of equidistant grains with dimensions of the order of the thickness of the deposited layer. Grain boundaries are very rare, extending from the CIGS surface to the molybdenum layer, which is important from the point of view of reducing leakage currents along the grain boundaries in the structure of the solar cell.
  • Fig presents x-ray two-layer structure of CIGS-Mo on a glass substrate.
  • the ratio and high intensity of lines 204/220 and 312 of sample 422-SM297-290 are close to the values characteristic of polycrystalline chalcopyrite.
  • a significant amount of the phase corresponds to chalcopyrite strongly textured along the axis 112. From the point of view of the quality of the> -and transition in the device, the structure of the obtained layer is close to optimal.
  • the inventive method allows us to solve all six problems stated in the present description, to obtain the optimal integral composition of the material, to ensure its homogeneity, as well as to collect material with high efficiency of converting solar energy into electricity.
  • the inventive method allows for reliable reproducibility and stability of the technology in mass production on large substrates while reducing production costs.

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  • Plasma & Fusion (AREA)
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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
  • Photovoltaic Devices (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne la technologie de formation de films minces semi-conducteurs CIGS pour cellules solaires sur des substrats en verre en feuilles et des dispositifs de pulvérisation à vide qui mettent en œuvre cette technologie dans des conditions de fabrication de masse. L'objectif atteint par cette invention est la mise au point d'un procédé pour former des couches CIGS à film mince pour cellules solaires sur des substrats de grandes dimensions qui permet, dans des conditions de fabrication de masse, d'obtenir une composition de matériau intégrale efficace et d'assurer une efficacité de conversion d'énergie solaire en électricité ainsi qu'une reproductibilité fiable de la technologie dans une production de masse sur de grands substrats, avec une baisse de coût de revient de la production. L'objectif visé est réalisé en ce que dans un procédé connu de formation de films minces CIGS le matériau est appliqué par couches subséquentes au moyen d'un procédé de pulvérisation réactive dans des vapeurs de sélénium atomique en utilisant des stations de pulvérisation à magnétrons disposées en séquence, on utilise en tant que stations à magnétrons dans des positions formant des couches impaires l'alliage Cu-In-Ga, dans lequel les rapports des concentrations atomiques Cu/(In+Ga) [Cu/III] и Ga/(In+Ga) [Ga/III] sont sélectionnés dans des limites [Cu/III] = 0,47 - 0,51 a [Ga/III] = 0,25 - 0,3, et l'on utilise en tant que stations à magnétrons dans des positions formant des couches paires l'alliage Cu-Ga, dans lequel les rapports des concentrations atomiques Cu/Ga = 2,5 - 2,8. Il existe d'autres différences du procédé par rapport au prototype.
PCT/BY2013/000013 2013-12-30 2013-12-30 Procédé pour former des films minces cigs destinés aux cellules solaires et dispositif de sa mise en oeuvre Ceased WO2015100480A1 (fr)

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RU2347298C1 (ru) * 2007-06-28 2009-02-20 Государственное научно-производственное объединение "Научно-практический центр Национальной академии наук Беларуси по материаловедению"(ГО"НПЦ НАН Беларуси по материаловедению") СПОСОБ ПОЛУЧЕНИЯ Cu(In, Ga)(S, Se)2 ТОНКИХ ПЛЕНОК
CN101383389A (zh) * 2008-10-07 2009-03-11 苏州富能技术有限公司 铜铟镓硒硫或铜铟镓硒或铜铟镓硫薄膜太阳能电池吸收层的制备方法及镀膜设备
US7544884B2 (en) * 2002-09-30 2009-06-09 Miasole Manufacturing method for large-scale production of thin-film solar cells
US20100297835A1 (en) * 2009-05-22 2010-11-25 Industrial Technology Research Institute Methods for fabricating copper indium gallium diselenide (cigs) compound thin films
CN102386283A (zh) * 2011-11-18 2012-03-21 陈群 Cigs太阳能光伏电池制备方法

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US7544884B2 (en) * 2002-09-30 2009-06-09 Miasole Manufacturing method for large-scale production of thin-film solar cells
RU2347298C1 (ru) * 2007-06-28 2009-02-20 Государственное научно-производственное объединение "Научно-практический центр Национальной академии наук Беларуси по материаловедению"(ГО"НПЦ НАН Беларуси по материаловедению") СПОСОБ ПОЛУЧЕНИЯ Cu(In, Ga)(S, Se)2 ТОНКИХ ПЛЕНОК
CN101383389A (zh) * 2008-10-07 2009-03-11 苏州富能技术有限公司 铜铟镓硒硫或铜铟镓硒或铜铟镓硫薄膜太阳能电池吸收层的制备方法及镀膜设备
US20100297835A1 (en) * 2009-05-22 2010-11-25 Industrial Technology Research Institute Methods for fabricating copper indium gallium diselenide (cigs) compound thin films
CN102386283A (zh) * 2011-11-18 2012-03-21 陈群 Cigs太阳能光伏电池制备方法

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