WO2015083453A1 - 太陽電池の製造方法 - Google Patents

太陽電池の製造方法 Download PDF

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WO2015083453A1
WO2015083453A1 PCT/JP2014/077882 JP2014077882W WO2015083453A1 WO 2015083453 A1 WO2015083453 A1 WO 2015083453A1 JP 2014077882 W JP2014077882 W JP 2014077882W WO 2015083453 A1 WO2015083453 A1 WO 2015083453A1
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solar cell
dielectric film
manufacturing
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PCT/JP2014/077882
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English (en)
French (fr)
Japanese (ja)
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隼 森山
渡部　武紀
大塚　寛之
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信越化学工業株式会社
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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
    • H01L31/04—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
    • H01L31/068—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • 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
    • H01L31/068—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H01L31/0682—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
    • 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
    • H01L31/18—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
    • 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
    • Y02E10/547—Monocrystalline silicon PV 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a solar cell, and more particularly to a pn junction forming step.
  • a diffusion suppression mask such as a patterned SiO 2 layer is formed in advance on a silicon semiconductor substrate, a patterned diffusion layer is formed by performing a doping process, and a back junction solar cell Is made.
  • a method for manufacturing a solar cell includes a step of forming a dielectric film on a part of at least one surface of a silicon substrate, and a part or all of the dielectric film. a step of applying a p-type diffusion doping agent; and a step of diffusing the n-type dopant and the p-type dopant by one heat treatment.
  • the dielectric film is preferably a silicon oxide film.
  • the thickness of the dielectric film is preferably 10 to 150 nm.
  • the p-type dopant is preferably boron and the n-type dopant is preferably phosphorus.
  • the region where the n-type dopant diffuses and the region where the p-type dopant diffuses are preferably on the same surface of the silicon substrate.
  • FIG. 4 is a flowchart showing a process subsequent to the process of FIG. 3 in the embodiment. It is a flowchart which shows the process after the process of FIG. 3 in a comparative example.
  • FIG. 6 is a flowchart showing a process common to an example and a comparative example subsequent to the process of FIG. 4 or FIG. 5.
  • the conventional solar cell manufacturing method performs the diffusion treatment of the n-type diffusion dopant and the p-type diffusion dopant separately, two diffusion heat treatments are required, and a step of forming a diffusion suppression mask each time, Since the method includes a step of removing the mask after the doping process, the number of steps is complicated and the manufacturing cost is high.
  • the present inventors have made a p-type diffusion doping agent containing boron (boron) and an n-type diffusion doping agent containing phosphorus in a state where a dielectric film of 10 to 150 nm is formed on a silicon substrate. It was discovered that when boron is thermally diffused, boron dopant diffuses into the silicon substrate even in the presence of the dielectric film, but phosphorus dopant is blocked by the dielectric film and does not diffuse into the silicon substrate. . By utilizing this phenomenon, a process that conventionally required two diffusion heat treatments can be completed by one diffusion heat treatment, and the number of processes can be greatly omitted.
  • a semiconductor substrate 100 is prepared (FIG. 1A).
  • the semiconductor substrate 100 for example, an as-cut single crystal ⁇ 100 ⁇ p-type silicon substrate in which a high-purity silicon is doped with a group 3 element such as boron or gallium to have a specific resistance of 0.1 to 5 ⁇ ⁇ cm can be used.
  • the semiconductor substrate 100 may be a polycrystalline substrate as well as a single crystal, and may be an n-type silicon substrate instead of a p-type silicon substrate.
  • the slice damage on the surface of the semiconductor substrate 100 is etched using a high concentration alkali such as sodium hydroxide or potassium hydroxide having a concentration of 5 to 60%, or a mixed acid of hydrofluoric acid and nitric acid.
  • a texture having a random pyramid structure is formed on the surface (FIG. 1B). In the drawing, the textured uneven structure is omitted.
  • Texture is an effective method for reducing the reflectance of solar cells.
  • the texture is immersed for about 10 to 30 minutes in an alkali solution (concentration 1 to 10%, temperature 60 to 100 ° C.) such as heated sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, etc. It is formed. It is preferable to dissolve a predetermined amount of 2-propanol in the solution to promote the reaction. After the texture is formed, rinse with pure water and proceed to the next step.
  • an alkali solution concentration 1 to 10%, temperature 60 to 100 ° C.
  • the substrate is washed in an acidic aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, etc., or a mixture thereof. From an economical and efficient standpoint, it is preferred to wash in hydrochloric acid.
  • the hydrochloric acid solution may be mixed with 0.5 to 5% hydrogen peroxide and heated to 60 to 90 ° C. for washing. Thereafter, the substrate is rinsed with pure water, and the substrate is dried to obtain the solar cell substrate 101.
  • a dielectric film 102 is formed on both surfaces of the solar cell substrate 101 (FIG. 1C).
  • a silicon oxide film formed by thermal oxidation is used as the dielectric film 102.
  • a thermal oxide film having a thickness of 10 to 150 nm is formed on the solar cell substrate 101 by heat treatment for 4 minutes to 7 hours in a high temperature heat treatment furnace at 900 to 1100 ° C. in an oxygen atmosphere.
  • oxide film formation methods include wet oxidation and pyrogenic oxidation, as well as methods such as introducing gases such as HCl and Cl 2 , whichever method is used. Good.
  • the dielectric film 102 is coated on the entire surface of the substrate with a coating agent such as siloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraethylorthosilicate alone or a mixture thereof, and is heated at a temperature of about 100 to 300 ° C. It may be formed by drying on a plate for several minutes, or an oxide film may be formed using atmospheric pressure CVD or the like.
  • a coating agent such as siloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraethylorthosilicate alone or a mixture thereof. It may be formed by drying on a plate for several minutes, or an oxide film may be formed using atmospheric pressure CVD or the like.
  • an etching paste 103 containing phosphoric acid is applied using a dispenser (FIG. 1D), and an opening 104 is formed in a part of the dielectric film 102. (FIG. 1 (e)). Note that the etching paste 103 may be applied by printing.
  • the opening 104 may be formed by using a photolithography technique, and the opening 104 can be formed even by ink-jet printing a coating solution containing a small amount of hydrofluoric acid.
  • the openings 104 preferably have a width of about 50 to 400 ⁇ m, and are preferably formed at intervals of 1 to 5 mm.
  • a p-type diffusion doping agent 106 containing, for example, boron is applied to a region where the opening 104 is not provided in the dielectric film 102 by a dispenser or printing. Again, the paste may be applied by printing.
  • a p-type diffusion doping agent containing a trivalent element such as gallium or indium may be used. However, it is preferable to use a p-type diffusion doping agent containing boron from the viewpoint of cost.
  • the width of the p-type diffusion doping agent 106 is preferably about 50 to 1000 ⁇ m, and preferably formed at intervals of 1 to 5 mm.
  • the printing position of the p-type diffusion doping agent 106 is preferably separated from the opening 104 by at least about 10 ⁇ m.
  • an n-type diffusion doping agent 105 containing phosphorus is applied onto the opening 104 by a dispenser or printing (FIG. 1 (f)).
  • a dispenser or printing FOG. 1 (f)
  • an n-type diffusion doping agent 105 containing a pentavalent element such as arsenic or antimony may be used.
  • an n-type diffusion doping agent 105 containing phosphorus is used from the viewpoint of cost and ease of material handling. It is preferable.
  • a dielectric film 102 exists directly under the p-type diffusion dopant 106, but if the dielectric film thickness is up to 150 nm, a trivalent p-type dopant such as boron penetrates the dielectric film 102 during thermal diffusion.
  • a p-type dopant region 108 can be formed that can be diffused into the semiconductor substrate.
  • pentavalent n-type diffusion doping agent 105 such as phosphorus is an oxide containing an n-type dopant, such as diphosphorus pentoxide, scattered from the paste during heat treatment, and an n-type doping region is formed in a region other than the paste printing portion.
  • the dielectric film 102 is formed in a region other than the region where the n-type diffusion dopant 105 is applied as in the present invention, the dielectric film 102 enters the p-type dopant substrate.
  • the p-type doping region 108 and the n-type doping region 107 can be formed only immediately below the paste application.
  • the heat treatment is preferably performed for about 10 to 120 minutes in a heat treatment furnace at 800 to 1000 ° C. in an inert gas atmosphere such as argon or nitrogen, and a mixed gas in which oxygen is mixed may be used.
  • an inert gas atmosphere such as argon or nitrogen
  • a mixed gas in which oxygen is mixed may be used.
  • the n-type diffusion doping agent 105 containing phosphorus may be formed by a vapor phase diffusion method using phosphorus oxychloride or the like, or the n-type diffusion doping agent 105 containing phosphorus is spin-coated and heat-treated. It may be formed.
  • the glass layer containing the p-type dopant and / or the n-type dopant and the dielectric film 102 formed on the surface are removed with several percent to several tens percent hydrofluoric acid or the like (FIG. 1 (h)).
  • an antireflection film 109 is formed on the front surface (light receiving surface) of the substrate, and a protective film 110 is formed on the back surface (non-light receiving surface) (FIG. 1 (i)).
  • a thermal oxide film is used as the antireflection film 109 and the protective film 110.
  • the thermal oxide film may be formed by any method such as dry oxidation, wet oxidation, pyrogenic oxidation at 950 to 1100 ° C. for about 5 to 120 minutes, or introduction of a gas such as HCl or Cl 2 .
  • a silicon oxide film having a thickness of 90 to 150 nm is formed on the light receiving surface by any one of these methods. If it is out of this range, the reflectance becomes high, and problems such as a short circuit current decrease occur.
  • an SiN x (silicon nitride) film may be used in addition to the thermal oxide film.
  • a method of forming the SiN x film for example, there is a method of forming the SiN x film by about 100 nm using a plasma CVD apparatus.
  • the reaction gas monosilane (SiH 4 ) and ammonia (NH 3 ) are often mixed and used, but nitrogen may be used instead of NH 3 .
  • both an oxide film functioning as a passivation film and an SiN x film functioning as an antireflection film may be laminated.
  • an electrode is formed (FIG. 1 (j)).
  • An n-type electrode 111 is formed on the n-type doping region 107, and a p-type electrode 112 is formed on the p-type doping region 108.
  • These electrodes can be formed by any of vapor deposition, sputtering, plating, ink jet, and screen printing.
  • a silver paste in which silver (Ag) powder and glass frit are mixed with an organic binder is screen-printed, and then the silver powder is passed through the SiN x film by heat treatment (fire-through), and the electrode and silicon are made conductive.
  • the n-type doping region is formed in the region other than the opening 104. It does n’t happen at all. Therefore, in the conventional method for manufacturing a solar cell, the diffusion heat treatment that had to be performed separately twice for the n-type diffusion dopant 105 and the p-type diffusion dopant 106 is made one diffusion heat treatment. Can do.
  • the manufacturing method of the present invention is applied to the manufacturing process of the back junction solar cell in which the electrode is not formed on the light receiving surface of the silicon substrate and the electrode is formed only on the back surface has been described.
  • the solar cell manufacturing method of the present invention can also be used in a manufacturing process of a solar cell in which an emitter is provided on one side and a base is provided on the opposite side.
  • a second embodiment of the present invention will be described with reference to FIG.
  • the dielectric film 202 is formed on both surfaces of the solar cell substrate 201 obtained by removing the damage layer and forming the texture structure on the semiconductor substrate 200 by the same method as described in the first embodiment (FIG. 2 (a) to (c)).
  • an opening 204 is formed in a part of one surface of the dielectric film 202.
  • the surface provided with the opening 204 is referred to as a back surface (non-light receiving surface), and the opposite surface is referred to as a front surface (light receiving surface).
  • an etching paste 203 containing phosphoric acid is applied or printed using a dispenser (FIG. 2D), and an opening 204 can be formed in a part of the dielectric film 202 (FIG. 2D).
  • the opening 204 may be formed using a photolithography technique, or may be formed by inkjet printing a coating liquid containing a trace amount of hydrofluoric acid.
  • the width of the opening 204 is preferably about 50 to 400 ⁇ m, and preferably formed at an interval of 1 to 5 mm.
  • phosphorus-containing n-type diffusion doping agent 205 is applied on the formed opening 204 with a dispenser or printed (FIG. 2F).
  • an n-type diffusion doping agent 205 containing a pentavalent element such as arsenic or antimony may be used.
  • an n-type diffusion doping agent 205 containing phosphorus is used. It is preferable to use it.
  • the n-type diffusion doping agent 205 may be printed on the entire back surface (non-light-receiving surface) without being patterned, and the n-type diffusion doping agent 205 may be printed on the entire back surface (non-light-receiving surface). Spin coating may be applied.
  • the n-type diffusion doping agent 205 may not be provided on the back surface, and only the opening 204 may be provided, and vapor phase diffusion may be performed using phosphorus oxychloride or the like in the next step.
  • p-type diffusion doping agent 206 containing boron is applied or printed using a dispenser.
  • a p-type diffusion doping agent 206 containing a trivalent element such as gallium or indium may be used.
  • the width of the p-type diffusion dopant 206 is preferably about 50 to 1000 ⁇ m, and preferably formed at intervals of 1 to 5 mm.
  • the paste may be applied to the entire surface (light receiving surface), or the p-type diffusion doping agent 206 may be spin applied to the entire surface (light receiving surface).
  • the diffusion heat treatment is performed in the state where the n-type diffusion doping agent 205 and the p-type diffusion doping agent 206 are applied as shown in FIG.
  • the dielectric film 202 exists directly under the p-type diffusion dopant 206, as described above, if the film thickness is up to 150 nm, trivalent p-type dopants such as boron are transmitted through the dielectric film 202 during thermal diffusion.
  • the p-type dopant region 208 can be formed by diffusing into the semiconductor substrate.
  • an n-type doping region 207 can be formed in a portion where the dielectric film 202 is not formed (FIG. 2G).
  • pentavalent n-type diffusion doping agent 205 such as phosphorus is formed by diffusing an oxide containing an n-type dopant from the paste during heat treatment to form an n-type doping region 207 in a region other than the paste application portion.
  • the dielectric film 2020 by forming the dielectric film 2020 in a region other than the region where the n-type diffusion doping agent 205 is printed, the dielectric film 202 diffuses the n-type dopant into the substrate. Can be inhibited.
  • the heat treatment is preferably performed for about 10 to 120 minutes in a heat treatment furnace at 800 to 1000 ° C. in an inert gas atmosphere such as argon or nitrogen, and a mixed gas in which oxygen is mixed may be used.
  • an inert gas atmosphere such as argon or nitrogen
  • a mixed gas in which oxygen is mixed may be used.
  • the glass layer and the dielectric film 202 containing p dopant and / or n dopant formed on the surface are removed with several to several tens of% hydrofluoric acid or the like (FIG. 2 (h)).
  • an antireflection film 209 is formed on the front surface of the substrate, and a protective film 210 is formed on the back surface (FIG. 2 (i)).
  • a thermal oxide film may be used as the antireflection film 209.
  • the thermal oxide film may be formed by any method such as dry oxidation, wet oxidation, pyrogenic oxidation at 950 to 1100 ° C. for about 5 to 120 minutes, or introduction of a gas such as HCl or Cl 2 .
  • a silicon oxide film of 90 to 150 nm is formed on the light receiving surface by any of these methods. If it is out of this range, the reflectance becomes high, and problems such as a short circuit current decrease occur.
  • an SiN x film may be used in addition to the thermal oxide film.
  • a method of forming the SiN x film for example, there is a method of forming the SiN x film by about 100 nm using a plasma CVD apparatus.
  • the reaction gas monosilane (SiH 4 ) and ammonia (NH 3 ) are often mixed and used, but nitrogen may be used instead of NH 3 .
  • an oxide film functioning as a passivation film and an SiN x film functioning as an antireflection film may be formed.
  • an electrode is formed (FIG. 2 (j)).
  • An n-type electrode 211 is formed on the n-type doping region 207, and a p-type electrode 212 is formed on the p-type doping region 208.
  • These can be formed by any of vapor deposition, sputtering, plating, ink jet, and screen printing.
  • a silver paste in which silver powder and glass frit are mixed with an organic binder is screen-printed, and then the silver powder is passed through the SiN x film by heat treatment (fire-through) to make the electrode and silicon conductive.
  • the back surface is a comb electrode similar to the light-receiving surface, it can be used as a double-sided solar cell.
  • the present invention can be used not only for back junction solar cells but also for manufacturing solar cells in which one surface is an emitter and the other surface is a pace.
  • the diffusion heat treatment that had to be performed separately twice for the n-type diffusion doping agent 205 and the p-type diffusion doping agent 206 is performed as one diffusion heat treatment. can do. Also in this manufacturing method, since the region other than the opening 204 is covered with the dielectric film 202 during the thermal diffusion treatment, no n-type doping region is formed in the region other than the opening 204, and the characteristics thereby The decline of the will not occur.
  • FIG. 4 shows a process subsequent to the process of FIG. 3 in the embodiment.
  • FIG. 5 shows a process subsequent to the process of FIG. 3 in the comparative example.
  • FIG. 6 shows a process common to the embodiment and the comparative example subsequent to the process of FIG. 4 or FIG.
  • examples and comparative examples will be described with reference to FIGS.
  • a phosphorus-doped ⁇ 100 ⁇ n-type as-cut silicon substrate 300 having a thickness of 200 ⁇ m and a specific resistance of 1 ⁇ ⁇ cm was prepared, and the damaged layer was removed with a hot concentrated potassium hydroxide aqueous solution (FIG. 3A).
  • a texture was formed by dipping in an aqueous solution of potassium hydroxide / 2-propanol. In the drawing, the textured uneven structure is omitted.
  • the substrate 300 was washed in a hydrochloric acid / hydrogen peroxide mixed solution to prepare 100 solar cell substrates 301 (FIG. 3B).
  • the obtained solar cell substrate 301 was heat-treated in an oxygen atmosphere at 1000 ° C. for 90 minutes to form a 70 nm silicon oxide film 302 on both surfaces of the substrate (FIG. 3C).
  • phosphoric acid-containing etching paste 303 was applied using a dispenser (FIG. 3D) to form openings 304.
  • the openings 304 were formed in a line shape having a width of 200 ⁇ m and an interval of 1.5 mm (FIG. 3E).
  • n-type diffusion doping agent 305 containing phosphorus was applied to the opening 304 using the dispenser (FIG. 3 (f)).
  • 50 substrates 300 are processed by the method of the embodiment (FIGS. 4A and 4B), and the remaining 50 substrates are processed by the method of the comparative example.
  • FIGGS. 5A to 5G 50 solar cells produced by the production methods of Examples and Comparative Examples were produced. Each manufacturing method will be described below with reference to the drawings.
  • Boron-containing p-type diffusion doping agent 306 was applied to 50 substrates 300 processed up to FIG. 3F using a dispenser. Further, the p-type diffusion doping agent 306 is formed in a line shape having a width of 400 ⁇ m and an interval of 1.5 mm, and is formed with an interval of 200 ⁇ m from the n-type diffusion doping agent 305 (FIG. 4A )).
  • thermal diffusion treatment was performed (FIG. 4 (b)).
  • the thermal diffusion treatment was performed in a heat treatment furnace in an argon atmosphere at 950 ° C. for 30 minutes.
  • the thermal oxide film 302 was formed once again.
  • the same heat treatment as in FIG. 3C was performed, and a 70 nm silicon oxide film 302 was again formed on both surfaces of the substrate (FIG. 5C).
  • the opening 304 is formed in a line shape having a width of 400 ⁇ m and an interval of 1.5 mm, and is spaced 200 ⁇ m from the n-type doping region 307 formed in FIG. Formed.
  • a p-type diffusion doping agent 306 containing boron was applied to the opening 304 by using a dispenser (FIG. 5 (f)) and subjected to thermal diffusion treatment (FIG. 5 (g)).
  • the thermal diffusion treatment was performed for 30 minutes in a heat treatment furnace in an argon atmosphere at 950 ° C.
  • an antireflection film 309 and a protective film 310 were formed on all the substrates (FIG. 6B).
  • a thermal oxide film was formed on both surfaces of the substrate by performing heat treatment for 40 minutes in a heat treatment furnace in an oxygen atmosphere of 900 ° C.
  • an antireflection film 309 and a protective film 310 were formed by depositing a SiN x film of about 80 nm on both surfaces of the substrate using a plasma CVD apparatus.
  • an n-type electrode 311 was formed on the n-type doping region 307, and a p-type electrode 312 was formed on the p-type doping region 308 (FIG. 6C).
  • a silver electrode paste containing silver powder and glass frit is screen-printed, the silver powder is passed through the SiN x film by heat treatment (fire through), and the electrode and silicon are made conductive to make the n-type electrode 311 and the p-type electrode 312. Formed.
  • Table 1 shows the measurement results of electric characteristics (average value of 50 sheets each) of the solar cell produced as described above when irradiated with pseudo sunlight of 25 ° C., 100 mW / cm 2 and spectrum AM 1.5 global.
  • the open-circuit voltage was greatly improved, and a solar cell with high conversion efficiency was produced. This is because the number of times of high-temperature heat treatment is less in the example than in the comparative example, and it is difficult to reduce the bulk lifetime.
  • the n-type doping region can be prevented from being formed in the region other than the n-type doping region, and the shape factor can be increased.
  • the conversion efficiency can be further increased.
  • the manufacturing method of the solar cell described above is used, not only the process can be largely omitted, but also the conversion efficiency of the solar cell can be improved.
  • the manufacturing process can be greatly shortened.
  • the number of high-temperature heat treatment steps can be reduced, a decrease in bulk lifetime can be prevented, an open circuit voltage can be increased, and conversion efficiency can be increased.
  • the p-type and n-type dopants can be selectively diffused in the substrate because the dielectric film is protected except for the region where the n-type doped region is formed. This contributes to an increase in the form factor and can further increase the conversion efficiency.
  • the method for manufacturing a solar cell according to the present invention enables efficient manufacturing by reducing the number of steps.

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PCT/JP2014/077882 2013-12-05 2014-10-21 太陽電池の製造方法 WO2015083453A1 (ja)

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