WO2014148443A1 - 光起電力素子及びその製造方法 - Google Patents
光起電力素子及びその製造方法 Download PDFInfo
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- WO2014148443A1 WO2014148443A1 PCT/JP2014/057189 JP2014057189W WO2014148443A1 WO 2014148443 A1 WO2014148443 A1 WO 2014148443A1 JP 2014057189 W JP2014057189 W JP 2014057189W WO 2014148443 A1 WO2014148443 A1 WO 2014148443A1
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- silicon substrate
- pyramid
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 69
- 239000010703 silicon Substances 0.000 claims abstract description 69
- 238000005530 etching Methods 0.000 claims abstract description 55
- 239000010409 thin film Substances 0.000 claims abstract description 37
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 36
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
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- 150000001298 alcohols Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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- 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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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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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- H01L31/06—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
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- H01L31/077—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 PIN type, e.g. amorphous silicon PIN solar cells the devices comprising monocrystalline or polycrystalline materials
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
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- 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
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- 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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a photovoltaic device used in a silicon-based thin film heterojunction solar cell, and more particularly to a photovoltaic device that can be applied to a thin film with higher power generation efficiency and a method for manufacturing the photovoltaic device.
- photovoltaic power generation devices solar panels
- photovoltaic power generation devices solar panels
- This photovoltaic device has a plurality of photovoltaic elements (photovoltaic elements) 71 as shown in FIG.
- the photovoltaic element 71 has a p-type amorphous silicon thin film layer 74 on one surface (upper surface) of an n-type single crystal silicon substrate (c-Si) 72 via an intrinsic amorphous silicon layer (i layer) 73.
- Transparent conductive oxides Transparent Conductive Oxides
- Patent Document 1 discloses that the thickness of the intrinsic amorphous silicon layer 73 formed by plasma CVD covering the n-type single crystal silicon substrate 72 is formed by rounding the valley 84 portion of the pyramidal uneven portion 83. It is described that non-uniformity can be reduced and the efficiency (specifically, FF value) of a photovoltaic element can be improved.
- Patent Document 1 page 9, lines 20 to 31
- a pyramid having a depth of about 1 to 10 ⁇ m is formed by using 2 wt% sodium hydroxide for anisotropic etching and isopropyl alcohol for suppressing the generation of bubbles. Forming is also disclosed.
- isopropyl alcohol needs to be added because it evaporates, and it has a bad influence on the working environment, so it must be strictly controlled. Further, since isopropyl alcohol is expensive, the cost increases. Under such circumstances, Patent Document 1 does not disclose the function and performance of the photovoltaic element having a pyramidal protrusion having a depth of about 1 to 10 ⁇ m.
- Patent Document 1 a surfactant (for example, Shintrex manufactured by Nippon Oil & Fats Co., Ltd.) is used instead of isopropyl alcohol, and 1% by weight of the surfactant described above is added to 1.5% by weight NaOH aqueous solution.
- a surfactant for example, Shintrex manufactured by Nippon Oil & Fats Co., Ltd.
- 1% by weight of the surfactant described above is added to 1.5% by weight NaOH aqueous solution.
- an etching solution is used to manufacture a silicon substrate with an etching time of 30 minutes and a pyramidal concavo-convex portion having a width of 5 ⁇ m and a depth of 5 ⁇ m and having an excellent light confinement effect.
- the silicon substrate is immersed in an aqueous solution in which hydrofluoric acid and nitric acid are mixed, and isotropic etching is performed to give a rounded portion of 0.1 ⁇ m or more to the valley portion of the uneven portion.
- silane gas SiH is formed by plasma CVD. 4 ) is used to deposit an intrinsic amorphous silicon layer having a thickness of 50 to 200 angstroms.
- the present invention has been made in view of such circumstances, and a silicon substrate is etched without using an organic solvent that is harmful to the human body to form pyramidal concavo-convex portions, thereby increasing the photovoltaic power generation efficiency.
- An object is to provide an element and a method for manufacturing the element.
- the photovoltaic device according to the first invention that meets the above-described object includes a silicon substrate having a large number of pyramidal irregularities formed on the surface by anisotropic etching, and chemical vapor deposition on the pyramidal irregularities.
- a photovoltaic device comprising an amorphous silicon thin film formed
- the average length of the diagonal line of the pyramid which is defined by the following formula and forms the pyramidal uneven portion is smaller than 5 ⁇ m.
- Average length of diagonal line (2 ⁇ area of field of view / number of vertices of pyramid of field of view) 0.5
- the etching process for positively forming R in the valleys of the concavo-convex portions is not performed.
- the width here refers to the length of the side, and the average length of the diagonal line in this case
- the thickness is about 7 ⁇ m.
- the photovoltaic element according to a second aspect of the present invention is the photovoltaic element according to the first aspect of the present invention, wherein a lamination of at least an amorphous silicon thin film that is directly bonded to at least the silicon substrate by the chemical vapor deposition method is the silicon element.
- the substrate temperature is higher than 180 ° C. and not higher than 220 ° C.
- a photovoltaic element according to a third invention is the photovoltaic element according to the first or second invention, wherein the thickness of the silicon substrate is in the range of 70 to 120 ⁇ m.
- a photovoltaic element according to a fourth invention is the photovoltaic element according to the first to third inventions, wherein a finger electrode is formed on the surface, and the thickness of the finger electrode is in the range of 1 to 5 ⁇ m. .
- the photovoltaic element according to a fifth aspect is the photovoltaic element according to the first to fourth aspects, wherein the average length of the diagonal line is in the range of 2 to 4 ⁇ m.
- the photovoltaic element according to a sixth aspect is the photovoltaic element according to the first to fifth aspects, wherein the open circuit voltage is 720 mV or more.
- a solar cell module according to a seventh aspect includes the photovoltaic element according to the first to sixth aspects. And the solar cell system which concerns on 8th invention is equipped with the solar cell module which concerns on 7th invention.
- a method for producing a photovoltaic device comprising: a silicon substrate having a large number of pyramidal irregularities formed on the surface by anisotropic etching; and a chemical vapor deposition method formed on the pyramidal irregularities.
- a method for producing a photovoltaic device comprising an amorphous silicon thin film comprising: The anisotropic etching using a mixed solution of an alkali, an additive containing at least one of an alcohol derivative and a surfactant, and water without using isopropyl alcohol is performed on the silicon substrate before etching.
- an etching step for obtaining the silicon substrate is defined, which is defined by the following formula, and the average length of the diagonal lines of the pyramids forming the pyramidal uneven portions is smaller than 5 ⁇ m.
- Average length of diagonal line (2 ⁇ area of field of view / number of vertices of pyramid of field of view) 0.5
- the method for producing a photovoltaic element according to the tenth invention is the method for producing a photovoltaic element according to the ninth invention, wherein the alkali concentration of the mixed solution is, for example, 0.2 to 2 in terms of NaOH.
- the etching step further includes a cleaning step of immersing the pre-etched silicon substrate in the mixed solution for 10 to 20 minutes and cleaning the silicon substrate as the etching step.
- the silicon pieces or reaction products generated during the etching are reattached to the silicon substrate, and fine roughness is generated on the surface of the silicon substrate. Can be prevented.
- an alcohol derivative a compound obtained from alcohol, such as carboxylic acid, aldehyde, ester, etc., preferably harmless to human body
- the etching reaction on the surface of the silicon substrate can be moderately suppressed, and a large number of pyramidal uneven portions can be effectively formed on the surface of the silicon substrate.
- the concentration of the alkaline solution such as sodium hydroxide or potassium hydroxide is 0.2 to 2% by mass (in terms of sodium hydroxide, preferably less than 1% by mass), and the concentration of the additive is 0.05 to 0.5% by mass.
- the treatment temperature is preferably 75 to 90 ° C. If the etching time is long, the production efficiency decreases. Therefore, it is preferable to adjust the concentration ratio of the alkali reagent (alkali) and the additive so that the etching process is completed in about 10 to 20 minutes. For example, when the pyramidal uneven portions are formed small and dense in a short time, the concentration of the additive may be increased while the concentration of the alkali reagent is decreased.
- the alkali concentration is set to 5% by mass or more to increase the etching rate to increase the isotropic property, and the damaged layer on the surface of the substrate generated in the silicon substrate slicing step is removed. After the damage layer is removed, it is preferable to carry out the etching step in which the anisotropy is strengthened to form the uneven portion.
- a photovoltaic device having higher power generation efficiency (Pmax) than the conventional photovoltaic device can be provided, and the length of the diagonal line of the concavo-convex portion is smaller than that of the conventional photovoltaic device.
- Substrate manufacturing time is short, and production efficiency can be increased.
- the etching amount is small, a thinner silicon substrate can be used, and the silicon substrate material can be reduced.
- the depth (height) of the concavo-convex portion is also reduced, the thickness of the collector electrode formed on the surface of the photovoltaic element can be reduced, and the amount of the collector electrode material (for example, silver) used can be reduced. it can.
- a photovoltaic device 10 constitutes an amorphous silicon thin film heterojunction solar cell, and has an n-type single crystal silicon substrate (c-Si) in the center.
- the p-type amorphous silicon thin film layer 13 is formed on the upper surface of the silicon substrate 11 via the intrinsic amorphous silicon thin film layer (i layer) 12.
- i layer intrinsic amorphous silicon thin film layer
- Transparent conductive oxides (Transparent Conductive Oxides) 16 and 17 are provided under the thin film layer 15, and comb-shaped collector electrodes (finger electrodes) 18 and 19 are provided on the respective surfaces.
- the upper and lower surfaces of the silicon substrate 11 are subjected to uneven processing by anisotropic etching by a chemical method in order to make light confinement due to diffused reflection of light more effective. That is, the silicon substrate before etching sliced in the (100) plane (the damaged layer is removed) is, for example, 0.2 to 2% by mass (more preferably 0.5 to 1.5% by mass, A large number of pyramidal irregularities can be formed by dipping in an alkaline aqueous solution (mixed solution) containing less than 1% by mass of sodium hydroxide or equivalent potassium hydroxide. This uneven portion is generated because the etching rate of the (111) plane is remarkably smaller than other crystal orientations. When the alkali concentration of the mixed solution is as high as about 5% by mass, for example, exceeding 2% by mass, isotropic etching proceeds and it becomes difficult to form a large number of pyramidal irregularities.
- the alkali concentration of the mixed solution is as high as about 5% by mass, for example, exceeding 2% by mass
- isopropyl alcohol when an aqueous isopropyl alcohol solution is used as the etching solution (mixed solution), as described above, the isopropyl alcohol volatilizes and deteriorates the working environment. Therefore, isopropyl alcohol is not used, and at least the alcohol derivative and the surfactant are used.
- One type of additive is used.
- As a boiling point of an alcohol derivative and surfactant 100 degreeC or more is preferable.
- this additive for example, “ALKA-TEX” commercially available from GP Solar can be used.
- “ALKA-TEX ZERO” in the “ALKA-TEX” series of GP Solar is used.
- a mixed solution of an alkali such as sodium hydroxide or potassium hydroxide, “ALKA-TEX ZERO” (an example of an additive containing at least one of an alcohol derivative and a surfactant), and water is used as an etching solution.
- an alkali such as sodium hydroxide or potassium hydroxide
- AKA-TEX ZERO an example of an additive containing at least one of an alcohol derivative and a surfactant
- water is used as an etching solution.
- pyramidal uneven portions A to E having different sizes are formed as shown in FIGS. 3 to 7 in order.
- Specific procedures are (1) H 2 O rinse (room temperature), (2) NaOH (5 mass%, 85 ° C.), (3) H 2 O rinse (room temperature), (4) NaOH / ALKA-TEX ZERO (Table 1), (5) H 2 O rinse (room temperature), (6) HCl / H 2 O 2 / H 2 O (volume ratio 1: 1: 5, 80 ° C.), (7) H 2 O rinse ( Room temperature), (8) HF / H 2 O (5 mass%, room temperature), and (9) H 2 O rinse (room temperature).
- the cut-out thickness of the silicon substrate is 180 ⁇ m, and the finished thickness of the silicon substrate after etching is 165 ⁇ m.
- the thickness of the silicon substrate before etching can be reduced, and the thickness (average thickness) of the finished silicon substrate can be set to 70 to 120 ⁇ m. As a result, a thinner and more economical photovoltaic device can be provided.
- the average length L of the diagonals of the pyramids forming the pyramidal uneven portions A to E is (2 ⁇ area of field of view / number of vertices of pyramids of field of view) 0.5
- pyramidal uneven portions having L of 7 ⁇ m (A), 5 ⁇ m (B), 4 ⁇ m (C), 3 ⁇ m (D), and 2 ⁇ m (E) are formed.
- (A) to (E) correspond to the silicon substrates shown in FIGS.
- 3 to 7 are laser microscope images measured using an OLYMPUS laser microscope OLS4000.
- the average length L of the diagonal line the field of view of the laser microscope image per measurement is 128 ⁇ m ⁇ 128 ⁇ m.
- the number of vertices of the pyramid within the visual field range was counted, and the average length L of the diagonals of the pyramid forming the pyramidal uneven portion was calculated.
- the average length L of the diagonal line was calculated by counting the number of vertices of the pyramid of the laser microscope image at one place near the center of the silicon substrate and at four places from the center of the silicon substrate, that is, four places.
- the concentration of etching solution, etching time, and temperature are shown in Table 1.
- an amorphous silicon thin film (that is, an intrinsic amorphous system) is formed on the surface of the silicon substrate 11 on which these pyramidal uneven portions A to E are formed by plasma CVD (an example of chemical vapor deposition).
- a silicon thin film layer (i layer) 12, a p-type amorphous silicon thin film layer 13, an intrinsic amorphous silicon thin film layer (i layer) 14, and an n-type amorphous silicon thin film layer 15) are formed.
- the raw material gas in the plasma CVD method for example, in the case of forming the p-type amorphous-based silicon thin film layer 13, it is possible to use a mixed gas of SiH 4, H 2, and PH 3 and B 2 H 6.
- the frequency is, for example, about 13.56 MHz or about 40.68 MHz, more preferably about 40.68 MHz
- the reaction pressure is 5 Pa or more and less than 300 Pa
- 50 Pa or more and less than 200 Pa is more preferable
- RF or VHF power for example less than about 1 mW / cm 2 or more 500 mW / cm 2, less than about 5 mW / cm 2 or more 100 mW / cm 2 is more preferable.
- the temperature of the silicon substrate 11 when laminating each amorphous silicon thin film can be over 180 ° C. and 220 ° C. or less (forming temperature).
- the effect of controlling the formation temperature is that a thin film (intrinsic amorphous silicon thin film layer (i layer) 12, amorphous silicon thin film layer (i layer) 14) directly bonded to the silicon substrate 11 having fine irregularities on the surface. ) Becomes particularly prominent. That is, the generation of a local epitaxial film in the groove portion of the uneven portion can be suppressed.
- Table 2 shows the relationship between the average length L of the diagonals of the pyramids of the pyramidal irregularities A to E and the short circuit current density, the open circuit voltage, the fill factor, and the conversion efficiency.
- the average length of the diagonal lines (C) of 4 ⁇ m and (D) of 3 ⁇ m were high.
- the difference in the short-circuit current density is due to the low reflectivity from the silicon substrate surface.
- (A) where the average length of the diagonal lines is 7 ⁇ m and (B) where the average length is 5 ⁇ m the (100) surface on which the concave and convex portions are not formed remains on the silicon substrate surface (solid circles in the figure) and the concave and convex portions There is a portion where the portion is over-etched (dotted circle in the figure). These are considered to be factors that increase the reflectance.
- a portion where the uneven portion is over-etched (dotted line circle frame in the figure) is also confirmed in (E) where the average length of the diagonal line is 2 ⁇ m.
- the average length of the diagonal line (C) of 4 ⁇ m and (D) of 3 ⁇ m were high.
- the high open circuit voltage is due to the high minority carrier lifetime.
- the average length L of the diagonal of the pyramid forming the pyramid-shaped irregularities is defined as (2 ⁇ the area of the visual field range / the number of vertices of the pyramid of the visual field range) 0.5 , the average length L of the diagonal is less than 5 ⁇ m It is necessary to be 2 ⁇ m or more (more preferably 3 ⁇ m or more) and 4 ⁇ m or less.
- the portion where the concavo-convex portion is not formed or the portion where the concavo-convex portion is over-etched increases, and the maximum output of the photovoltaic element cannot be exhibited.
- the average length L of diagonal lines where uneven portions are densely formed is preferably in the range of 2 ⁇ m or more and less than 5 ⁇ m. If the average length L of the diagonal line is smaller than 5 ⁇ m, particularly in the range of 2 to 4 ⁇ m, the etching amount in the depth direction can be reduced to less than 3.5 ⁇ m (single side), so the thickness of the silicon substrate is thin ( For example, it is suitable for 60 to 200 ⁇ m, more preferably 70 to 120 ⁇ m), and the amount of silicon used can be reduced. In addition, the average length L of the diagonal of the pyramid is also closely related to the depth of the surface irregularities.
- a collector electrode pattern in which the collector electrodes 18 and 19 (finger electrodes) are thin is also possible.
- the amount of silver paste used can be reduced and a solar cell can be provided at a lower cost.
- gravure offset printing is preferably used as a method for forming a finger electrode having a small thickness.
- the thickness of the finger electrode is preferably 1 ⁇ m or more. When the finger thickness is smaller than 1 ⁇ m, the implementation becomes difficult and the electrical resistance increases.
- Non-Patent Document 1 it is shown that when a local epitaxial film is formed in the groove (valley) portion of the concavo-convex portion, the surface recombination rate is four times faster, which is a factor for greatly reducing the open circuit voltage. ing. Although the details are unknown, the groove portion of the concavo-convex portion is less likely to cause surface diffusion of radical species and overlaps with the local stress described in Non-Patent Document 1, and the groove portion of the concavo-convex portion It is presumed that a local epitaxial film is formed.
- the technique described in Patent Document 1 can improve not only the fill factor but also the open-circuit voltage because the formation of the uneven portion in a round shape suppresses the formation of a local epitaxial film in the groove portion of the uneven portion. Presumed to have been.
- the size of the pyramidal concavo-convex portion is increased, a portion where the (100) surface where the concavo-convex portion is not formed is left on the surface of the silicon substrate is generated, and the open circuit voltage is reduced.
- the etching time is extended to reduce the (100) plane portion, a portion where the uneven portion is over-etched is likely to occur, and the fill factor is lowered.
- Non-Patent Document 1 shows that the (100) plane has a surface recombination rate 40 times faster than the (111) plane, and the exposure of the (100) plane is significantly open, even if it is a small area. It is considered that the voltage is lowered.
- the average length L of the diagonal of the pyramid forming the pyramidal uneven portion is defined as (2 ⁇ the area of the visual field range / the number of vertices of the pyramid of the visual field range) 0.5
- the average length L is in the range of 2 ⁇ m or more and less than 5 ⁇ m, and a high open circuit voltage of 720 mV or more is obtained despite the increase in the groove portion of the concavo-convex portion.
- This result also relates to the fact that when the amorphous silicon thin film is formed on the silicon substrate by the chemical vapor deposition method, the temperature of the silicon substrate is higher than 180 ° C. and not higher than 220 ° C. . If it is carried out at a relatively high temperature, the surface diffusion of radical species becomes active, and it becomes difficult to form a local epitaxial film in the groove portion of the uneven portion. Thereby, it is considered that a high open-circuit voltage can be obtained by enjoying the merit of the fact that the (100) plane is hardly exposed.
- the above-mentioned effect is obtained by using “ALKA-TEX ZERO”.
- “TAD70” manufactured by Hayashi Junyaku Kogyo Co., Ltd. is similarly obtained, and the average length of the diagonal line is obtained. It is thought to be universal with respect to height.
- the main point of the present invention is that the method and the agent for performing anisotropic etching by setting the average length of the diagonal line of the pyramidal uneven portion of the silicon substrate within a specific range is not a problem.
- “Silicon substrate etching method”, JP 2009-206335 A, “Si anisotropic etching solution composition”, JP 2012-227304 A, “Etching solution composition and etching method” The "" technology is of course applicable.
- the solar cell module of this invention is comprised including the photovoltaic element demonstrated above. That is, the basic structure of a solar cell module (solar cell panel) is a structure in which a plurality of photovoltaic elements connected in series are sandwiched between a surface panel such as glass and a back sheet via a sealing material. Become. For example, a technique of “photovoltaic battery electrode, photovoltaic battery, and photovoltaic module” described in JP-T-2005-536894 can be applied. In combination with a collector electrode pattern in which the thickness of the finger electrode is reduced (for example, a thickness of 1 to 5 ⁇ m), the resistance can be reduced, and a more efficient solar cell module can be provided.
- a collector electrode pattern in which the thickness of the finger electrode is reduced (for example, a thickness of 1 to 5 ⁇ m)
- the resistance can be reduced, and a more efficient solar cell module can be provided.
- a solar cell system is comprised by providing the required number of this solar cell module. Terminals for connection, control means such as a control circuit, and the like are appropriately attached to the solar cell module and the solar cell system.
- the present invention is not limited to the above-described embodiment, and the configuration thereof can be changed without changing the gist of the present invention.
- the “amorphous” in the present invention means not only an amorphous body but also a microcrystalline body, and can be replaced as appropriate.
- power can be generated by receiving light from the front and back surfaces of the silicon substrate. However, when receiving light from only the front side, the configuration of the back surface can be further simplified.
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Abstract
Description
また、特許文献1(9頁20~31行目)に、異方性エッチングに2重量%の水酸化ナトリウムと、気泡の発生を抑えるイソプロピルアルコールを用いて深さが1~10μm程度のピラミッドを形成することも開示されている。しかし、イソプロピルアルコールは気化するので注ぎ足す必要があり、作業環境に悪影響があるので厳重に管理する必要があることが記載されている。また、イソプロピルアルコールは高価であるため、コストが増大する。このような事情から、特許文献1には、1~10μm程度の深さを有するピラミッド状の凸部を有する光起電力素子の作用、性能については全く開示されていない。
更に、ピラミッド状凹凸部の形状を大きくすると、より厚めなシリコン基板が必要となり、透明導電酸化物の上に形成する櫛形の集電極に使用する金属ペースト(通常、銀ペースト)の使用量が増加するという問題があることも判った。
なお、非特許文献1については後述する。
以下の式で定義され、前記ピラミッド状凹凸部を形成するピラミッドの対角線の平均長さが5μmより小さくなっている。
対角線の平均長さ=(2×視野範囲の面積/視野範囲のピラミッドの頂点数)0.5
第1の発明に係る光起電力素子においては、凹凸部の谷部に積極的にRを形成するエッチング処理は行っていない。
なお、特許文献1に記載されている幅5μm深さ5μmのピラミッド状の凹凸部の場合、ここでいう幅とは辺の長さを指しているものと推測され、この場合の対角線の平均長さは約7μmとなる。
第4の発明に係る光起電力素子は、第1~第3の発明に係る光起電力素子において、表面にフィンガー電極が形成されており、該フィンガー電極の厚みは1~5μmの範囲にある。
第6の発明に係る光起電力素子は、第1~第5の発明に係る光起電力素子において、開放電圧が720mV以上である。
そして、第8の発明に係る太陽電池システムは、第7の発明に係る太陽電池モジュールを備えている。
エッチング前シリコン基板に対して、イソプロピルアルコールを使用しないで、アルカリと、アルコール誘導体及び界面活性剤の少なくとも1種類を含む添加剤と、水との混合液を用いた前記異方性エッチングをすることにより、前記シリコン基板を得るエッチング工程を有し、以下の式で定義され、前記ピラミッド状凹凸部を形成するピラミッドの対角線の平均長さが5μmより小さくなっている。
対角線の平均長さ=(2×視野範囲の面積/視野範囲のピラミッドの頂点数)0.5
更に、エッチング量が少ないので、より薄いシリコン基板を使用でき、シリコン基板の材料が少なくて済む。
そして、凹凸部の深さ(高さ)も小さくなるので、光起電力素子の表面に形成する集電極の厚みも薄くて済み、集電極の材料(例えば、銀)の使用量も減らすことができる。
図1に示すように、本発明の一実施の形態に係る光起電力素子10は、非晶質系シリコン薄膜ヘテロ接合太陽電池を構成し、中央にn型単結晶のシリコン基板(c-Si、以下、単にシリコン基板という)11を有し、その上面に、真性非晶質系シリコン薄膜層(i層)12を介してp型非晶質系シリコン薄膜層13を、シリコン基板11の下面に真性非晶質系シリコン薄膜層(i層)14を介してn型非晶質系シリコン薄膜層15を備え、p型非晶質系シリコン薄膜層13の上及びn型非晶質系シリコン薄膜層15の下にそれぞれ透明導電酸化物(Transparent Conductive Oxide)16、17を有し、それぞれの表面に櫛形の集電極(フインガー電極)18、19を有している。
また、エッチング液の濃度、エッチング時間、温度については、表1の通りである。
ピラミッド状凹凸部A~Eのピラミッドの対角線の平均長さLと、短絡電流密度、開放電圧、フィルファクタ、変換効率との関係を表2に示す。
対角線の平均長さが7μmの(A)と5μmの(B)には、凹凸部が形成されていない(100)面がシリコン基板表面に残っている箇所(図中の実線丸枠)があり、少数キャリアライフタイムの減少要因となっているものと考えられる。
本発明は前記した実施の形態に限定されるものではなく、本発明の要旨を変更しない範囲でその構成を変更することもできる。例えば、本発明における「非晶質系」とは、非晶質体のみならず、微結晶体を含む意味であり、適時入れ替えることも可能である。
例えば、前記実施の形態においては、シリコン基板の表裏面から受光して発電が可能であるが、表側のみから受光する場合は、裏面の構成をより簡略にすることができる。
Claims (10)
- 異方性エッチングにより表面に多数のピラミッド状凹凸部が形成されたシリコン基板と、前記ピラミッド状凹凸部上に化学気相成長法によって形成される非晶質系シリコン薄膜を備える光起電力素子において、
以下の式で定義され、前記ピラミッド状凹凸部を形成するピラミッドの対角線の平均長さが5μmより小さくなっていることを特徴とする光起電力素子。
対角線の平均長さ=(2×視野範囲の面積/視野範囲のピラミッドの頂点数)0.5 - 請求項1記載の光起電力素子において、前記化学気相成長法による少なくとも前記シリコン基板と直接接合する非晶質系シリコン薄膜の積層が前記シリコン基板の温度が180℃を超え220℃以下の状態で行われていることを特徴とする光起電力素子。
- 請求項1又は2記載の光起電力素子において、前記シリコン基板の厚みが70~120μmの範囲にあることを特徴とする光起電力素子。
- 請求項1~3のいずれか1項に記載の光起電力素子において、表面にフィンガー電極が形成されており、該フィンガー電極の厚みは1~5μmの範囲にあることを特徴とする光起電力素子。
- 請求項1~4のいずれか1項に記載の光起電力素子において、前記対角線の平均長さは、2~4μmの範囲にあることを特徴とする光起電力素子。
- 請求項1~5のいずれか1項に記載の光起電力素子において、開放電圧が720mV以上であることを特徴とする光起電力素子。
- 請求項1~6のいずれか1項に記載の光起電力素子を備えたことを特徴とする太陽電池モジュール。
- 請求項7記載の太陽電池モジュールを含むことを特徴とする太陽電池システム。
- 異方性エッチングにより表面に多数のピラミッド状凹凸部が形成されたシリコン基板と、前記ピラミッド状凹凸部上に化学気相成長法によって形成される非晶質系シリコン薄膜を備える光起電力素子の製造方法であって、
エッチング前シリコン基板に対して、イソプロピルアルコールを使用しないで、アルカリと、アルコール誘導体及び界面活性剤の少なくとも1種類を含む添加剤と、水との混合液を用いた前記異方性エッチングをすることにより、前記シリコン基板を得るエッチング工程を有し、
以下の式で定義され、前記ピラミッド状凹凸部を形成するピラミッドの対角線の平均長さが5μmより小さくなっていることを特徴とする光起電力素子の製造方法。
対角線の平均長さ=(2×視野範囲の面積/視野範囲のピラミッドの頂点数)0.5 - 請求項9記載の光起電力素子の製造方法において、前記混合液のアルカリ濃度は、NaOH換算で0.2~2質量%であり、
前記エッチング工程として、前記混合液に10~20分、前記エッチング前シリコン基板を浸漬し、
前記シリコン基板の洗浄処理を行う洗浄工程をさらに有することを特徴とする光起電力素子の製造方法。
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- 2014-03-17 WO PCT/JP2014/057189 patent/WO2014148443A1/ja active Application Filing
- 2014-03-17 CN CN201480016819.5A patent/CN105144399A/zh active Pending
- 2014-03-17 US US14/777,772 patent/US20160284888A1/en not_active Abandoned
- 2014-03-17 AU AU2014239493A patent/AU2014239493A1/en not_active Abandoned
- 2014-03-17 JP JP2015506776A patent/JP5945066B2/ja not_active Expired - Fee Related
- 2014-03-17 EP EP14768001.1A patent/EP2978026A4/en not_active Withdrawn
- 2014-03-17 KR KR1020157029976A patent/KR20150133243A/ko not_active Application Discontinuation
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RU2590284C1 (ru) * | 2015-04-10 | 2016-07-10 | Общество с ограниченной ответственностью "НТЦ тонкопленочных технологий в энергетике при ФТИ им. А.Ф. Иоффе", ООО "НТЦ ТПТ" | Солнечный элемент |
RU2632267C2 (ru) * | 2016-03-10 | 2017-10-03 | Общество с ограниченной ответственностью "НТЦ тонкопленочных технологий в энергетике при ФТИ им. А.Ф. Иоффе", ООО "НТЦ ТПТ" | Структура фотопреобразователя на основе кристаллического кремния и линия по его производству |
JP2018117124A (ja) * | 2017-01-17 | 2018-07-26 | エルジー エレクトロニクス インコーポレイティド | 太陽電池の製造方法 |
US10593558B2 (en) | 2017-01-17 | 2020-03-17 | Lg Electronics Inc. | Method of manufacturing solar cell |
Also Published As
Publication number | Publication date |
---|---|
TWI596790B (zh) | 2017-08-21 |
EP2978026A4 (en) | 2016-12-07 |
JPWO2014148443A1 (ja) | 2017-02-16 |
KR20150133243A (ko) | 2015-11-27 |
AU2014239493A1 (en) | 2015-10-29 |
TW201448244A (zh) | 2014-12-16 |
US20160284888A1 (en) | 2016-09-29 |
CN105144399A (zh) | 2015-12-09 |
EP2978026A1 (en) | 2016-01-27 |
JP5945066B2 (ja) | 2016-07-05 |
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