WO2008010782A1 - The method of production of the photoelectric converter - Google Patents

The method of production of the photoelectric converter Download PDF

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Publication number
WO2008010782A1
WO2008010782A1 PCT/UA2007/000020 UA2007000020W WO2008010782A1 WO 2008010782 A1 WO2008010782 A1 WO 2008010782A1 UA 2007000020 W UA2007000020 W UA 2007000020W WO 2008010782 A1 WO2008010782 A1 WO 2008010782A1
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Prior art keywords
layer
substrate
porous silicon
silicon
type
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PCT/UA2007/000020
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French (fr)
Inventor
Vadim Volodimirovich Naumov
Oleksandra Mikolaevna Shmyrieva
Oleksandr Dmitrovich Skurtul
Mikola Mikolaevich Melnichenko
Vjacheslav Oleksandrovich Kochelap
Valentin Mikolaevich Golotjuk
Dmitro Vasilevich Lukomsky
Original Assignee
Vadim Volodimirovich Naumov
Shmyrieva Oleksandra Mikolaevn
Oleksandr Dmitrovich Skurtul
Mikola Mikolaevich Melnichenko
Kochelap Vjacheslav Oleksandro
Valentin Mikolaevich Golotjuk
Dmitro Vasilevich Lukomsky
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Application filed by Vadim Volodimirovich Naumov, Shmyrieva Oleksandra Mikolaevn, Oleksandr Dmitrovich Skurtul, Mikola Mikolaevich Melnichenko, Kochelap Vjacheslav Oleksandro, Valentin Mikolaevich Golotjuk, Dmitro Vasilevich Lukomsky filed Critical Vadim Volodimirovich Naumov
Publication of WO2008010782A1 publication Critical patent/WO2008010782A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • H01L31/0248—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
    • 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
    • H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
    • H01L31/0284—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table comprising porous silicon as part of the active layer(s)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • 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
    • 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

Definitions

  • the invention belongs to the sphere of semiconductor optoelectronic technique, in particular, to the photoelectric converter production technology, i.e. silicon-based solar cells converting solar radiation into low-cost electricity.
  • the methods of production of crystalline silicon based photoelectric converters are known, which allow creation of multi-layered semiconductor structures with electron-hole junctions enabling photoelectric conversion of solar light energy into electric current and voltage.
  • These methods of photoelectric converter production involve a series of coordinated technological procedures that includes such technological processes as 1) chemical etching of the source cut out silicon plates for removing mechanical damages, 2) acid treatment for alkali refuses neutralization, 3) thermal diffusion of boron and phosphorous into the bulk of the substrate for doping the source silicon and forming the semiconductor junction, 4) oxidizing the substrate surfaces, 5) depositing the masking layer onto the back surface, 6) chemical removal of the oxide and surface silicon layer from the top side; texturing the top surface for enhancing the efficiency of solar light absorption, deposition of the antireflective coating for lowering the optical losses, and, finally, metallization and formation of ohmic contacts.
  • Photoelectric converters with high efficiency of about 23-25% could be produced if the source material is of high quality (with high doping level and without defects) and the properly selected technological processes are accomplished under extra-pure laboratory conditions using high-precision technological equipment.
  • a disadvantage of the known methods of production of the efficient PECs on the basis of crystalline silicon of high semiconductor quality is a complex fabrication technology that involves high number of expensive technological procedures. That is why the technology of photoelectric converter fabrication is usually simplified in industrial conditions in order to reduce the production costs. But this also reduces efficiency, so that the commercial PECs have essentially lower efficiency (usually 15-16%) than the laboratory ones.
  • a method of production of the thick film contact with the reduced transient resistance for silicon solar cells which include the following technological procedures: chemical etching the source silicon plates after cutting in order to remove mechanical damages, acid treatment for alkali refuses neutralization, texturing the substrate surface in order to reduce the optical losses, diffusion of boron from the gaseous phase, oxidizing the substrate surfaces, depositing the mask layer onto the back surface, chemical removal of the oxide and surface layer of silicon from the top side; texturing the top surface and deposition of the antireflective coating for lowering the optical losses; creation of n + -layer; metallization and formation of ohmic contacts.
  • the resulting photoelectric converters have the following parameters: open-circuit voltage 590 mV, density of short circuit current 30 mA/cm 2 , efficiency 13,2%.
  • a disadvantage of the stated method is the necessity of an additional high-temperature oxidizing, which leads to worsening the recombination parameters of the substrate and, as a result, to reducing the efficiency of the photoelectric converters. Besides, it is necessary to form the masking layer and to carry out two separate procedures of texturing.
  • the method of gettering the contaminants is known, where a porous silicon layer is formed electro-chemically at one of the sides of silicon plate [Patent of the USA 3929529, Proponiak M. R. Method for gettering contaminants in monocrystalline silicon] and then the structure with the porous silicon layer undergoes annealing in the non-oxidizing medium under temperature and temporal conditions sufficient for diffusion of the contaminants from the bulk of plate into the porous silicon.
  • the nearest analogue is the method of solar cell manufacturing on the basis of single crystal silicon (see Patent of Russia M» 2139601 cl . HOl L 31/18 from October, 28 1999 Zaks M. B., Kolomoets G.Yu., Pinov A. B., Sitnikov A.M., Solodukha O.I. «A method of production of a solar cell with N + -P-P + structure») , which allowed to reduce the number of technological procedures and to increase the efficiency of photoelectric converters.
  • This method includes the following procedures:
  • a disadvantage of this method is the necessity to carry out the high-temperature processes of simultaneous diffusion of boron and phosphorus (at the temperature of 1000 0 C) and high-temperature diffusion of phosphorus (at the temperature of 830 0 C) , that lead to the formation of defects in the source material and decrease the life time of charge carriers. This, in turn, reduces the efficiency of photoelectric converters.
  • Such method of manufacturing does not provide any passivation and does not favor the improvement of the antireflection properties of the top surface of a photoelectric converter.
  • the potential barriers in the photoelectric converter structure are formed only in one direction, which decreases the total efficiency of photoelectric converter.
  • the obtained value of the efficiency 16,6% at high level of the short circuit current density 36 mA/cm 2 is far from the possible efficiency for the single- crystal silicon photoelectric converters.
  • the aim of the considering invention is the enhancement of photoelectric converter efficiency and the reducing of power inputs for its manufacturing due to the performance of the doping process at relatively low temperature (less than 780 0 C) , the processes of gettering and stable hydrogen saturation of the surface layer, the formation of 3D potential barriers, the reducing of the optical reflection from the top surface and the enhancement of the IR radiation reflection from the back surface.
  • the manufacturing of the photoelectric converter is realized in a following sequence (see Fig.l) :
  • the suggested method does not include any additional high-temperature process of oxidizing and, moreover, provides the performance of the process of potential barriers formation at relatively low temperature (less than 780 °C) . This does not reduce the life-time of charge carriers, but on the contrary enhances this parameter due to gettering and saturation of the surface layer by hydrogen. Just this is the advantage of the proposed method as compared to the nearest analogue.
  • the proposed method not only decreases the power inputs and improves the quality of a source silicon, but also provides fundamentally new service properties of the photoelectric converter: - an effective passivation of the surface due to stable hydrogen content in the surface layer;
  • the density of short-circuit current of PEC produced by the suggested method could be as high as 41 mA/cm 2 , the open- circuit voltage - 650 mV and the conversion efficiency — 20%.
  • the standard substrates were of SDB-I single-crystal silicon (grown by the Czochralski method, p-type conductivity, ⁇ 100> orientation, resistivity ⁇ 1 Ohm- cm, life time of charge carriers ⁇ 10 ⁇ s — typical parameters of the so-called «solar» silicon) .
  • the source plates were pseudosquares 102,8x102,8 mm 2 , 300 ⁇ m thick.
  • the initial layer of porous silicon on the both sides of the substrate has been grown by chemical etching for 4-5 min in an acid etchant of the following composition: 1 part of hydrofluoric acid, 3 parts of nitric acid, 6 parts of deionized ' water.
  • the phosphorosilicate and borosilicate emulsions were deposited onto the face and back surfaces, respectively.
  • the simultaneous diffusion of boron and phosphorus into the bulk of the substrate was carried out in diffusive furnace at 800 0 C for 60 min in nitrogen atmosphere.
  • a doped p + -type layer of 30 Ohm/0 surface resistivity has been formed at the back side.
  • the texturing of the face side was carried out by etching in hot solution of 2% potassium hydrate and 4% isopropyl alcohol at 80 0 C for 10 min, the surface n + -layer being simultaneously removed from the face side.
  • the oxide films that refused after diffusion were removed using 10% solution of hydrofluoric acid.
  • the secondary layer of the porous silicon on the textured top surface was grown by the method of chemical etching prior to the initial diffusion of boron and phosphorus.
  • the method of electrochemical anodizing in the solution 1 part of hydrofluoric acid and 1 part of isopropyl alcohol for 12 ⁇ 4 min at current density of 25+5mA/cm 2 has been used for the similar purposes.
  • Secondary diffusion of phosphorus into the bulk of the substrate has been carried out from gaseous phase though the porous silicon layer in diffusive furnace at 780 0 C for 35 min.
  • the doped n-type layer of 80-85 Ohm/D surface resistivity has been formed at the top side within the porous silicon layer.
  • the layer of porous silicon grown by chemical etching for 0.5 min after plasmochemical etching served as antireflective coating. Then the ohmic contacts were formed by stenciling. For this the contact bars of silver-aluminum paste were deposited onto the back side of the substrate, the rest of the surface being covered by aluminum paste. The contact grid of silver paste was deposited onto the top side of the substrate. Then, this unit was annealed at 850 0 C in a conveyer furnace. As a result, the contact bars 2 mm wide were obtained at the top surface and contact bars 5 mm wide were obtained at the back surface. Photoelectric converters produced by such method were studied and tested using metrologically certified equipment both in laboratory and industrial conditions. The following parameters were obtained: 1) open-circuit voltage 640 ⁇ 15 mV, 2) short-circuit current density 39 ⁇ 2.0 itiA/cm 2 ,
  • the produced photoelectric converters were used as component parts of PEC modules and solar batteries, which were successfully tested under bench and field conditions.

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  • Computer Hardware Design (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

The invention belongs to the semiconductor optoelectronic technique, in particular, to the technology of production of the photoelectric converters, i.e. silicon-based solar elements that convert solar radiation into electric power and are used as economical sources of electricity. The method of production of the photoelectric converter on the base of p-type silicon substrate, which includes the procedures of the formation of p+-layer on the back surface of substrate and n- layer on the face surface with the subsequent formation of the contacts, wherein porous silicon layer additionally is grown, herein the layer of p+-type being formed on the back surface of substrate during simultaneous diffusion of boron and phosphorus from the preliminary deposited onto the back and face surfaces of substrate borosilicate and phosphorosilicate emulsions respectively, with the layer of n+-type being simultaneously formed on the face surface; then the layer of n+-type is selectively removed and n-layer is formed on the face surface of substrate through the layer of porous silicon.

Description

THE METHOD OF PRODUCTION OF THE PHOTOELECTRIC CONVERTER
The invention belongs to the sphere of semiconductor optoelectronic technique, in particular, to the photoelectric converter production technology, i.e. silicon-based solar cells converting solar radiation into low-cost electricity.
The methods of production of crystalline silicon based photoelectric converters are known, which allow creation of multi-layered semiconductor structures with electron-hole junctions enabling photoelectric conversion of solar light energy into electric current and voltage. These methods of photoelectric converter production involve a series of coordinated technological procedures that includes such technological processes as 1) chemical etching of the source cut out silicon plates for removing mechanical damages, 2) acid treatment for alkali refuses neutralization, 3) thermal diffusion of boron and phosphorous into the bulk of the substrate for doping the source silicon and forming the semiconductor junction, 4) oxidizing the substrate surfaces, 5) depositing the masking layer onto the back surface, 6) chemical removal of the oxide and surface silicon layer from the top side; texturing the top surface for enhancing the efficiency of solar light absorption, deposition of the antireflective coating for lowering the optical losses, and, finally, metallization and formation of ohmic contacts. Photoelectric converters with high efficiency of about 23-25% (i.e. close to the theoretical limit for crystalline silicon solar cells - A.Goetzberger, J.Knobloch, Bernard Voss, Crystalline Silicon Solar Cells, N.Y. : John Willey & Sons) could be produced if the source material is of high quality (with high doping level and without defects) and the properly selected technological processes are accomplished under extra-pure laboratory conditions using high-precision technological equipment.
A disadvantage of the known methods of production of the efficient PECs on the basis of crystalline silicon of high semiconductor quality is a complex fabrication technology that involves high number of expensive technological procedures. That is why the technology of photoelectric converter fabrication is usually simplified in industrial conditions in order to reduce the production costs. But this also reduces efficiency, so that the commercial PECs have essentially lower efficiency (usually 15-16%) than the laboratory ones.
The methods of photoelectric converters production are known (e.g., Patent of Russia N' 2139600 cl . HOl L 31/18 from October, 28 1999, Zaks M. B., Kolomoets G. Yu., Pinov A. B., Sitnikov A.M., Solodukha O.I. «A method of production of the thick film contact with the reduced transient resistance for silicon solar cells») , which include the following technological procedures: chemical etching the source silicon plates after cutting in order to remove mechanical damages, acid treatment for alkali refuses neutralization, texturing the substrate surface in order to reduce the optical losses, diffusion of boron from the gaseous phase, oxidizing the substrate surfaces, depositing the mask layer onto the back surface, chemical removal of the oxide and surface layer of silicon from the top side; texturing the top surface and deposition of the antireflective coating for lowering the optical losses; creation of n+-layer; metallization and formation of ohmic contacts. The resulting photoelectric converters have the following parameters: open-circuit voltage 590 mV, density of short circuit current 30 mA/cm2, efficiency 13,2%.
A disadvantage of the stated method is the necessity of an additional high-temperature oxidizing, which leads to worsening the recombination parameters of the substrate and, as a result, to reducing the efficiency of the photoelectric converters. Besides, it is necessary to form the masking layer and to carry out two separate procedures of texturing. The method of gettering the contaminants is known, where a porous silicon layer is formed electro-chemically at one of the sides of silicon plate [Patent of the USA 3929529, Proponiak M. R. Method for gettering contaminants in monocrystalline silicon] and then the structure with the porous silicon layer undergoes annealing in the non-oxidizing medium under temperature and temporal conditions sufficient for diffusion of the contaminants from the bulk of plate into the porous silicon. Then the plate is oxidized at 1173 K and the layer of porous silicon containing contaminants is removed by chemical or mechanical treatment. Here, the layer of porous silicon acts exclusively as a getter of contaminants without any optimization of its properties with regard to its application in photoelectric converter technologies . The nearest analogue is the method of solar cell manufacturing on the basis of single crystal silicon (see Patent of Russia M» 2139601 cl . HOl L 31/18 from October, 28 1999 Zaks M. B., Kolomoets G.Yu., Pinov A. B., Sitnikov A.M., Solodukha O.I. «A method of production of a solar cell with N+-P-P+ structure») , which allowed to reduce the number of technological procedures and to increase the efficiency of photoelectric converters.
This method includes the following procedures:
- simultaneous diffusion of boron and phosphorous from the borosilicate and phosphorosilicate films, respectively, deposited onto the back and top surfaces;
- chemical removal of the oxide films from the both sides of the substrate;
- texturing of the top surface; - formation of n-layer;
- formation of current-collecting contacts.
A disadvantage of this method is the necessity to carry out the high-temperature processes of simultaneous diffusion of boron and phosphorus (at the temperature of 1000 0C) and high-temperature diffusion of phosphorus (at the temperature of 830 0C) , that lead to the formation of defects in the source material and decrease the life time of charge carriers. This, in turn, reduces the efficiency of photoelectric converters. Such method of manufacturing does not provide any passivation and does not favor the improvement of the antireflection properties of the top surface of a photoelectric converter. The potential barriers in the photoelectric converter structure are formed only in one direction, which decreases the total efficiency of photoelectric converter. The obtained value of the efficiency 16,6% at high level of the short circuit current density 36 mA/cm2 is far from the possible efficiency for the single- crystal silicon photoelectric converters. The aim of the considering invention is the enhancement of photoelectric converter efficiency and the reducing of power inputs for its manufacturing due to the performance of the doping process at relatively low temperature (less than 780 0C) , the processes of gettering and stable hydrogen saturation of the surface layer, the formation of 3D potential barriers, the reducing of the optical reflection from the top surface and the enhancement of the IR radiation reflection from the back surface.
The manufacturing of the photoelectric converter is realized in a following sequence (see Fig.l) :
- growth of a porous silicon layer;
- simultaneous diffusion of boron and phosphorus from the borosilicate and phosphorosilicate emulsions, respectively, earlier deposited onto the back and top surfaces; - chemical removal of the oxide films from the both surfaces of the substrate;
- texturing the top surface of the photoelectric converter;
- growth of porous silicon layer; - formation of n-layer;
- growth of porous silicon layer;
- formation of current-collecting contacts.
The essence of the invention suggested is illustrated by the scheme, in which the operation-routing sequence of photoelectric converter production is presented schematically .
The suggested method does not include any additional high-temperature process of oxidizing and, moreover, provides the performance of the process of potential barriers formation at relatively low temperature (less than 780 °C) . This does not reduce the life-time of charge carriers, but on the contrary enhances this parameter due to gettering and saturation of the surface layer by hydrogen. Just this is the advantage of the proposed method as compared to the nearest analogue.
The proposed method not only decreases the power inputs and improves the quality of a source silicon, but also provides fundamentally new service properties of the photoelectric converter: - an effective passivation of the surface due to stable hydrogen content in the surface layer;
- an effective separation of photoproduced charge carriers due to formation of the 3D potential barriers;
- a reducing of optical reflection from the PEC top surface due to new geometry;
- an enhancement of the IR reflection from the PEC back surface;
- the UV to visible reradiation. This causes an enhancement of photosensitivity both in short- and long-wave spectral ranges. As a result, the density of short-circuit current of PEC produced by the suggested method could be as high as 41 mA/cm2, the open- circuit voltage - 650 mV and the conversion efficiency — 20%.
So, an essential increase of the photoelectric converter quality and reduction of the manufacturing power inputs are reached due to the set and sequence of the procedures stated above in the method suggested. It should be noted that the proposed additional operations concerning the growth of porous silicon layers by chemical etching or chemical anodizing are performed at room temperature and during short time and allow extensive treatment and automation. This provides almost negligible influence of the labor expenditures of the efficient PEC manufacturing.
An example of the particular performance.
The standard substrates were of SDB-I single-crystal silicon (grown by the Czochralski method, p-type conductivity, <100> orientation, resistivity ~1 Ohm- cm, life time of charge carriers ~10 μs — typical parameters of the so-called «solar» silicon) . The source plates were pseudosquares 102,8x102,8 mm2, 300 μm thick. The initial layer of porous silicon on the both sides of the substrate has been grown by chemical etching for 4-5 min in an acid etchant of the following composition: 1 part of hydrofluoric acid, 3 parts of nitric acid, 6 parts of deionized' water. Then the phosphorosilicate and borosilicate emulsions were deposited onto the face and back surfaces, respectively. The simultaneous diffusion of boron and phosphorus into the bulk of the substrate was carried out in diffusive furnace at 800 0C for 60 min in nitrogen atmosphere. As a result, a doped p+-type layer of 30 Ohm/0 surface resistivity has been formed at the back side. The texturing of the face side was carried out by etching in hot solution of 2% potassium hydrate and 4% isopropyl alcohol at 80 0C for 10 min, the surface n+-layer being simultaneously removed from the face side. The oxide films that refused after diffusion were removed using 10% solution of hydrofluoric acid. The secondary layer of the porous silicon on the textured top surface was grown by the method of chemical etching prior to the initial diffusion of boron and phosphorus. The method of electrochemical anodizing in the solution 1 part of hydrofluoric acid and 1 part of isopropyl alcohol for 12±4 min at current density of 25+5mA/cm2 has been used for the similar purposes. Secondary diffusion of phosphorus into the bulk of the substrate has been carried out from gaseous phase though the porous silicon layer in diffusive furnace at 780 0C for 35 min. As a result, the doped n-type layer of 80-85 Ohm/D surface resistivity has been formed at the top side within the porous silicon layer. The layer of porous silicon grown by chemical etching for 0.5 min after plasmochemical etching served as antireflective coating. Then the ohmic contacts were formed by stenciling. For this the contact bars of silver-aluminum paste were deposited onto the back side of the substrate, the rest of the surface being covered by aluminum paste. The contact grid of silver paste was deposited onto the top side of the substrate. Then, this unit was annealed at 850 0C in a conveyer furnace. As a result, the contact bars 2 mm wide were obtained at the top surface and contact bars 5 mm wide were obtained at the back surface. Photoelectric converters produced by such method were studied and tested using metrologically certified equipment both in laboratory and industrial conditions. The following parameters were obtained: 1) open-circuit voltage 640±15 mV, 2) short-circuit current density 39±2.0 itiA/cm2,
3) power at maximal load 2.05±0.1 Wt,
4) efficiency 19±1 %, which meet the requirements of high-effective low-cost silicon photoelectric converters.
The data presented for the standard testing conditions: lighting power of 1000 Wt/m2, spectral composition of radiation AMI.5, temperature of 25 °C.
The produced photoelectric converters were used as component parts of PEC modules and solar batteries, which were successfully tested under bench and field conditions.
High operational characteristics corresponding to requirements of the ISO international standards have been demonstrated. So, the presented data give evidence for significant advantages of the new method of photoelectric converter production as compared to the known prototypes, since it provides better technical characteristics at lower production costs .

Claims

Claims
1. The method of production of the photoelectric converter on the base of p-type silicon substrate, which includes the procedures of the formation of p+-layer on the back surface of substrate and n- layer on the face surface with the subsequent formation of the contacts, characterized in that porous silicon layer additionally is grown, herein the layer of p+-type being formed on the back surface of substrate during simultaneous diffusion of boron and phosphorus from the preliminary deposited onto the back and face surfaces of substrate borosilicate and phosphorosilicate emulsions respectively, with the layer of n+-type being simultaneously formed on the face surface; then the layer of n+-type is selectively removed and n-layer is formed on the face surface of substrate through the layer of porous silicon.
2. The method of claim 1, wherein the layer of porous silicon is grown before the formation of p+-type layer on the back surface of substrate.
3. The method of claim 1, wherein the removing of n+- layer and the subsequent growing of the layer of porous silicon are performed in the same solution.
4. The method of claims 1, 2 or 3, wherein the process of the selective removing of n+-layer and the growing of the porous silicon layer are performed by anodizing of silicon substrate with its preliminary treatment in peroxide- ammoniac solution.
5. The method of claim 4, wherein the anodizing of silicon substrate is performed at current density 25+5 mA/cm2 for 12±4 min. in the solution of the following composition: 1 part of hydrofluoric acid, 1 part of isopropyl alcohol.
6. The method of claim 1, wherein the additional texturing of the surface is performed after removing of n+- layer.
7. The method of claim 1, 2 or 3, wherein the process of the selective removing of n+-layer and the growing of porous silicon layer are performed by chemical etching at the temperature 30+100C for 0.5-5 min. in the solution: 1 part of hydrofluoric acid, 3 parts of nitric acid, 6±1 parts of deionized water.
8. The method of claim 1, wherein at least one layer of porous silicon is grown by chemical etching after formation of n- layer.
PCT/UA2007/000020 2006-07-21 2007-03-30 The method of production of the photoelectric converter WO2008010782A1 (en)

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EP1968123A3 (en) * 2007-02-28 2010-06-02 Centrotherm Photovoltaics Technology GmbH Method for manufacturing silicon solar cells
WO2012025511A1 (en) * 2010-08-27 2012-03-01 Universität Konstanz Method for producing a solar cell having a textured front face and corresponding solar cell
RU2469439C1 (en) * 2011-06-23 2012-12-10 Общество с ограниченной ответственностью "Солнечный ветер" Method of making solar cell with double-sided sensitivity
CN102925982A (en) * 2012-11-15 2013-02-13 英利能源（中国）有限公司 Solar cell and diffusion method of solar cell
CN109378357A (en) * 2018-09-06 2019-02-22 横店集团东磁股份有限公司 A kind of PERC double-side solar cell wet-etching technology
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CN109378357A (en) * 2018-09-06 2019-02-22 横店集团东磁股份有限公司 A kind of PERC double-side solar cell wet-etching technology
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