Classifications

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  • C30—CRYSTAL GROWTH
  • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
  • C30B1/00—Single-crystal growth directly from the solid state
  • C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
  • C30B1/023—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing from solids with amorphous structure
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  • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
  • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
  • H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
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  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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  • C23C16/24—Deposition of silicon only
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  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/02—Elements
  • C30B29/06—Silicon
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  • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
  • H01L31/0264—Inorganic materials
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  • H01L31/03921—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic Table
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  • H01L31/04—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
  • H01L31/06—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
  • H01L31/072—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
  • H01L31/0745—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 comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
  • H01L31/0747—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 comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
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• • C—CHEMISTRY; METALLURGY
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  • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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Definitions

• the present invention relates to the production of crystalline silicon in a thin layer on a substrate, in particular but not exclusively for photo voltaic applications.
• the solar cells used in the photo voltaic application are, for about 90%, made from crystalline silicon wafers obtained from the cutting of an ingot. Also known are crystallization techniques of amorphous silicon, such as laser induced crystallization (LIC) or solid phase crystallization (SPC).
• LIC laser induced crystallization
• SPC solid phase crystallization
• the present invention improves the situation.
• the invention proposes a method of manufacturing a semiconductor component comprising crystalline silicon in a thin layer on a substrate.
• the process preferably comprises the steps:
• the thin layer of crystalline silicon may comprise, after annealing, a surface coating of silicon mixed with aluminum.
• the method may then comprise an additional step of etching the surface of said crystalline silicon thin film to remove said surface coating. Nevertheless, in certain possible applications, it may be advantageous to maintain this naturally forming coating.
• the substrate is made of an aluminum and silicon alloy initially comprising between 5 and 50% of silicon, and preferably between 12 and 50% of silicon. As described below, such a substrate is very simple to manufacture.
• the thermal annealing temperature is for example between 450 and 550 ° C, for durations of between twenty minutes and twelve hours, and to be applied to an amorphous silicon layer which may be of thickness between 1 and 10 micrometers.
• the crystalline silicon thin film obtained is more precisely a thin layer of P + doped polycrystalline silicon with aluminum.
• the method may advantageously furthermore comprise a step of depositing a second thin layer of silicon on said thin layer of crystalline silicon.
• the present invention also relates to a semiconductor component comprising crystalline silicon in a thin layer on a substrate.
• the substrate consists of an aluminum and silicon alloy, predominantly aluminum.
• the aforementioned thin film more precisely comprises poly-crystalline silicon, P + doped with aluminum.
• the component further comprises:
• Such a component then forms at least one photovoltaic cell including a solar panel.
• the second P-doped layer and the third N-doped layer are made of silicon (and in particular the N-doped layer can be made of amorphous silicon).
• the aluminum-doped P-doped polycrystalline silicon thin film may advantageously form a rear surface field layer (or "BSF" hereinafter).
• the substrate (mainly made of aluminum) can also form an optically reflective mirror.
• the cost of producing thin silicon layers is lower than that of platelets made of crystalline silicon.
• An electricity production price of less than 0.4 € / Wp is estimated for solar cells made from thin layers of silicon.
• a silicon-rich aluminum substrate produced at low cost, and used for the purposes of the invention as a catalyst for crystallizing amorphous silicon, has the advantage of being weaker. thermal budget than that of competing technologies such as laser-induced crystallization (LIC) or solid phase crystallization (SPC).
• LIC laser-induced crystallization
• SPC solid phase crystallization
• a so-called "aluminum-induced crystallization" (or AIC) technique which consists in depositing two layers of aluminum and silicon, respectively, on one another, in order to crystallize the silicon after annealing.
• AIC aluminum-induced crystallization
• such a technique uses very thin layers of aluminum and amorphous silicon (thicknesses of less than 200 nm) on a generally glass substrate.
• the interaction between the two layers results in a polysilicon layer that has at most the thickness of the amorphous silicon initial layer.
• this technique has many limitations to the growth of crystalline silicon layers suitable for applications of semiconductor components and especially for photo voltaic applications.
• the silicon-rich aluminum substrate can be advantageously used as a support during the manufacture of photovoltaic cells manufactured from the stack of thin silicon layers.
• a substrate plays the role, in this application to the manufacture of photovoltaic cells, both rear contact and reflector after complete manufacture of the cells.
• the aluminum substrate can play the role of optical mirror, to promote the light-matter interaction in the overlying thin layers. It should be noted here, however, that an initially pure aluminum substrate can not be used as an alternative, due to diffusion of uncontrolled silicon during the elaboration of the overlying silicon layers.
• the crystallized layer after annealing then comprises crystalline silicon doped with aluminum, and then forms a P + layer usually used as back surface field (or "BSF" for "back surface field") of a photo voltaic cell.
• this crystalline silicon layer can serve as a seed for the deposition of a P-doped overlying layer, for example silicon (for example amorphous or micro-amorphous silicon, or even polycrystalline silicon), which is thicker. and formed by growth on the polycrystalline layer.
• a P-doped overlying layer for example silicon (for example amorphous or micro-amorphous silicon, or even polycrystalline silicon), which is thicker. and formed by growth on the polycrystalline layer.
• TCO type transparent layer
• the silicon-rich aluminum substrate constitutes a reflective and conductive support for deposited silicon thin films in an application to the manufacture of photovoltaic cells.
• a substrate initially acting as a catalyst for the crystallization of amorphous silicon makes it possible to obtain a continuous layer of polycrystalline silicon that can be used as a rear surface field (BSF) of a solar cell, and this by using a low thermal budget.
• BSF rear surface field
• FIG. 1 illustrates an exemplary embodiment of the method according to the invention, of crystallization of amorphous silicon on a substrate of silicon-rich aluminum
• FIG. 2 schematically illustrates a solar cell comprising a P + doped thin layer obtained by implementing the method of the invention.
• the invention provides a low temperature crystallization process of an amorphous silicon film on a silicon-rich aluminum substrate.
• the silicon-rich aluminum substrate is used as a catalyst for the crystallization of amorphous silicon and provides a continuous layer of polycrystalline silicon that can be used as a back surface field (BSF) of photovoltaic solar cells.
• BSF back surface field
• a pure aluminum substrate is not suitable for direct use because of the high diffusivity and solubility of silicon in aluminum.
• the use of the silicon-rich aluminum substrate thus makes it possible to limit the diffusion and crystallization of amorphous silicon on the surface.
• Such a method makes it possible to obtain a crystalline silicon film a few microns thick directly on a silicon-rich aluminum substrate.
• the method comprises three steps:
• a chemical etching process for etching the residual surface layer consisting essentially of aluminum and silicon in order to access the underlying polycrystalline layer.
• the crystallization of the amorphous silicon on a silicon-rich aluminum substrate can be obtained as follows.
• a deposit of the intrinsic amorphous silicon 110 is carried out in a reactor, for example of the PECVD type (for "Plasma Enhanced Chemical Vapor Deposition") or other, on a silicon-rich aluminum substrate 10. Thicknesses included between 1 and ⁇ are deposited at a growth rate of the order of 50 to 100 nm / s, for example about 90 nm / s.
• the filing conditions can be of the type:
• a substrate temperature of between 200 and 300 ° C., preferably of the order of 250 ° C.
• argon-type neutral gas of between 20 and 50 sccm, preferably of the order of 35 sccm,
• the annealing is carried out in a conventional tubular furnace under controlled nitrogen flow (flow rate of the order of 120 sccm) at temperatures of between 450 ° C. and 550 ° C., as for example in embodiments at 490 ° C, 520 ° C or 550 ° C and durations of between twenty minutes and twelve hours.
• flow rate of the order of 120 sccm
• temperatures of between 450 ° C. and 550 ° C., as for example in embodiments at 490 ° C, 520 ° C or 550 ° C and durations of between twenty minutes and twelve hours.
• the higher the annealing temperature the shorter the annealing time.
• the melting point of the substrate is only slightly higher or close to 550 ° C.
• the annealing temperature should be limited to about 550 ° C, and, if necessary (depending on the thickness amorphous Si layer or other parameter), to increase the duration of annealing.
• a physicochemical phenomenon can possibly be explained as follows. Silicon atoms of the amorphous layer have a sufficiently high energy to leave their bond and diffuse towards the substrate. They interact with it aluminum, which promotes their crystallization. These atoms then use just the amount of energy needed for their crystallization, and release the excess. Simultaneously, silicon atoms of the substrate are released and move towards the interface with the layer to also initiate crystallization. Furthermore, the amount of aluminum that can also migrate to the overlying layer is limited by a "natural" barrier constituted by an oxide layer (for example Al 2 O 3 alumina) at the same time. interface between the substrate and the overlying amorphous silicon layer.
• oxide layer for example Al 2 O 3 alumina
• a polycrystalline silicon layer 11 is formed on the silicon-rich aluminum substrate 10.
• a surface layer 111 of aluminum-silicon mixture that it is then necessary to strip in a third subsequent step.
• this third step S3 the Silicon / Aluminum mixture created on the top of the substrate is etched in a solution of HN0 3 , HF, H 2 O (in exemplary proportions of the order of 72.5 ml / 1.5 ml / 28 ml).
• HN0 3 a solution of HN0 3 , HF, H 2 O
• FIG. 1 at the end of this step S3, there remains a layer 11 of P + doped poly-crystalline silicon with aluminum, on the silicon-rich aluminum substrate 10.
• a possible prior step S0 to obtain the silicon-rich aluminum substrate 10. In reality, such a substrate is very simple to manufacture because aluminum and silicon are very miscible and Al-Si alloy is very easy to achieve .
• the absorbent layer of the cell can be created by depositing amorphous silicon, or micro-amorphous, or by epitaxial growth of a thicker polycrystalline film, on the first crystalline film obtained at the same time. from step S3 above.
• FIG. 2 Reference is then made to FIG. 2 to describe the structure of a photovoltaic cell comprising such layers.
• the photovoltaic cell comprises in particular:
• the substrate 10 and the layer 11 form characteristic elements of a semiconductor component within the meaning of the invention (and directly obtained by the implementation of the method of the invention), in particular but not exclusively for a photovoltaic application.
• the cell may further comprise a layer of silicon 12 (P-doped), which may be amorphous or crystalline, the underlying layer 11 forming a seed to promote the deposition of this layer 12. It can be provided by in addition to the deposition of an additional layer 13, doped N (for example doped amorphous silicon), to constitute the "diode” corresponding to the complete cell. Conventionally, provision is furthermore made for a layer 14 of conductive transparent oxide (or TCO), typically made of ITO (Indium-tin-oxygen) or zinc oxide ZnO, on which metal contacts 15 of the cell are deposited.
• TCO conductive transparent oxide
• ITO Indium-tin-oxygen
• ZnO zinc oxide
• the aluminum plates used as substrates can be produced in an industrial manner (pouring, extrusion, etc.), thus without any industrial limit.
• the amorphous silicon film precursor to crystallization is produced from a gas (silane), but alternatively it is possible to use also trichlorosilane (first by-product of the combustion of sand, so widely available).
• Annealing furnaces for heat treatment and crystallization are widely used in electronics, photovoltaics and metallurgy. Consequently, there is no limit to the method of the invention in order to obtain such a layer 11 deposited on the substrate 10.
• the limit in temperature elevation of the aluminum substrate at about 550 ° C. maximum. In this case, however, it suffices to extend the duration of the anneals and the durations of possible deposits by epitaxy, if necessary.
• the present invention is not limited to the embodiments described above by way of example; it extends to other variants.
• an annealing furnace optimized to crystallize plates in large series for periods of a few hours (between 20 minutes to 12 minutes). hours as previously described).
• a passivation of the defects in a hydrogen atmosphere at low temperature makes it possible to improve the performances.
• P doping of the second silicon layer for example.
• it may be an I (intrinsic) or N doping.
• the third N-doped (amorphous) silicon layer may be more particularly n + doped.

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