WO2016125803A1 - Élément de cellule solaire et procédé de fabrication correspondant - Google Patents

Élément de cellule solaire et procédé de fabrication correspondant Download PDF

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Publication number
WO2016125803A1
WO2016125803A1 PCT/JP2016/053093 JP2016053093W WO2016125803A1 WO 2016125803 A1 WO2016125803 A1 WO 2016125803A1 JP 2016053093 W JP2016053093 W JP 2016053093W WO 2016125803 A1 WO2016125803 A1 WO 2016125803A1
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Prior art keywords
electrode
solar cell
passivation film
substrate
cell element
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PCT/JP2016/053093
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English (en)
Japanese (ja)
Inventor
松島　徳彦
彰了 村尾
賢 北山
繁 後藤
誠一郎 稲井
求己 芝原
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京セラ株式会社
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Priority to CN201680007452.XA priority Critical patent/CN107360731B/zh
Priority to JP2016573386A priority patent/JP6336139B2/ja
Publication of WO2016125803A1 publication Critical patent/WO2016125803A1/fr

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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
    • H01L31/0224—Electrodes
    • 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
    • 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

Definitions

  • the present invention relates to a solar cell element and a manufacturing method thereof.
  • PERC Passivated Emitter Rear Cell
  • a solar cell element includes a semiconductor substrate having a first surface and a second surface located on the opposite side of the first surface, and a passivation film disposed on the second surface of the semiconductor substrate. And a first electrode in contact with the semiconductor substrate in a state of penetrating the passivation film at a plurality of locations.
  • the solar cell element is linearly arranged on the semiconductor substrate in a position not overlapping the first electrode in plan view, on the passivation film or in a state of penetrating the passivation film.
  • an electrical resistivity of the first electrode is smaller than an electrical resistivity of the third electrode.
  • a method for manufacturing a solar cell element according to an aspect of the present invention is a method for manufacturing a solar cell element having the above-described configuration, wherein after the conductive paste I is baked to form the first electrode, the conductive paste I is formed.
  • the third electrode is formed by baking the conductive paste II of the same material at a temperature lower than that of the conductive paste I.
  • FIG. 1 is a plan view showing an external appearance of a first surface side of a solar cell element according to an embodiment of the present invention.
  • FIG. 2 is a plan view showing an appearance of the second surface side of the solar cell element according to the embodiment of the present invention.
  • FIG. 3 is a cross-sectional view showing a cross-sectional state taken along the line X-X ′ of FIGS. 1 and 2.
  • 4A (a) to 4 (e) are enlarged sectional views showing a method for manufacturing a solar cell element according to an embodiment of the present invention.
  • 4B (f) to 4 (h) are enlarged cross-sectional views showing a method for manufacturing a solar cell element according to an embodiment of the present invention.
  • FIG. 5 is a cross-sectional view showing another cross-sectional state of the solar cell element according to the embodiment of the present invention.
  • FIG. 6 is a cross-sectional view showing a cross-sectional state of a solar cell element according to another embodiment.
  • FIG. 7 is a cross-sectional view showing a cross-sectional state of a solar cell element according to another embodiment.
  • ⁇ Solar cell element> 1 to 3 show a solar cell element 10 according to this embodiment.
  • the solar cell element 10 has a first surface 10a located mainly on the front (front) side where light is incident, and a second surface 10b located on the opposite side (back side) of the first surface 10a.
  • the substrate 1 that is a semiconductor substrate used for the solar cell element 10 similarly has a first surface 1a and a second surface 1b located on the opposite side of the first surface.
  • the substrate 1 is a first semiconductor layer 2 that is a one-conductivity type (for example, p-type) semiconductor region, and a reverse conductivity type (for example, n-type) semiconductor region that is provided on the first surface 1a side of the first semiconductor layer 2.
  • the p-type polycrystalline or single crystal silicon substrate has a thickness of about 100 to 250 ⁇ m, for example. If the shape of the substrate 1 is, for example, a substantially square shape with one side of about 150 to 200 mm in plan view, a solar cell module in which a large number of solar cell elements 10 having the substrate 1 are arranged can be easily produced. However, the planar shape and size of the substrate 1 are not limited.
  • an impurity such as boron or gallium is contained in the silicon substrate as a dopant element.
  • the second semiconductor layer 3 is provided on the first surface 10 a side in the first semiconductor layer 2.
  • the second semiconductor layer 3 is a semiconductor layer having a conductivity type opposite to that of the first semiconductor layer 2 (n-type in the case of the present embodiment), and the second semiconductor layer 3 is formed between the first semiconductor layer 2 and the second semiconductor layer 3. A pn junction is formed between them.
  • the second semiconductor layer 3 can be formed, for example, by containing an impurity such as phosphorus as a dopant element on the first surface 1a side of the substrate 1.
  • the light reflection can be reduced.
  • the height of the convex portion of the texture is about 0.1 to 10 ⁇ m, and the length between the tops of the adjacent convex portions is about 0.1 to 20 ⁇ m.
  • the solar cell element 10 includes an antireflection film 5 and a surface electrode 7 on the first surface 10a side. Further, a back electrode 8 and a passivation film 4 are provided on the second surface 10b side.
  • the antireflection film 5 can improve the photoelectric conversion efficiency of the solar cell element 10 by reducing the reflectance of the light irradiated on the first surface 10 a of the solar cell element 10.
  • the antireflection film 5 is made of, for example, an insulating film such as a silicon oxide, aluminum oxide, or silicon nitride layer, or a laminated film thereof.
  • an insulating film such as a silicon oxide, aluminum oxide, or silicon nitride layer, or a laminated film thereof.
  • a refractive index and thickness of the antireflection film 5 a refractive index and a thickness that can realize a low reflection condition with respect to light in a wavelength range that can be absorbed by the substrate 1 and contribute to power generation out of sunlight may be appropriately adopted. .
  • the antireflection film 5 made of silicon nitride is formed by PECVD (Plasma Enhanced Chemical Vapor Deposition) method
  • the refractive index is about 1.8 to 2.5 and the thickness is about 60 to 120 nm. can do.
  • the surface electrode 7 is an electrode provided on the first surface 1a side of the substrate 1 as shown in FIG.
  • the surface electrode 7 has several (for example, three in FIG. 1) bus bar electrodes 7a and a plurality of linear finger electrodes 7b.
  • the bus bar electrode 7 a is an electrode for taking out electricity obtained by photoelectric conversion to the outside of the solar cell element 10 on the first surface 1 a of the substrate 1.
  • the bus bar electrode 7a has a width of about 1 to 3 mm, for example. At least a part of the bus bar electrode 7a is electrically connected so as to cross the finger electrode 7b substantially perpendicularly.
  • the finger electrode 7b is an electrode for collecting the carriers generated by the light incident on the substrate 1 and transmitting them to the bus bar electrode 7a.
  • the finger electrodes 7b have a plurality of linear shapes, have a width of about 30 to 200 ⁇ m, for example, and are provided with an interval of about 1 to 3 mm.
  • the surface electrode 7 can be formed, for example, by applying a conductive paste containing silver as a main component into a desired shape by screen printing or the like and then baking it.
  • the main component indicates that the ratio of the total component is 50% or more, and the same applies to the following description.
  • the thickness of the surface electrode 7 formed by firing the conductive paste is about 10 to 40 ⁇ m.
  • the passivation film 4 is formed on substantially the entire surface of the substrate 1 on the second surface 1b side. As a result, the defect position causing the carrier recombination at the interface between the substrate 1 and the passivation film 4 can be reduced, and the recombination of minority carriers can be reduced.
  • the passivation film 4 is made of, for example, an insulating film such as silicon oxide, aluminum oxide, or silicon nitride layer, or a laminated film thereof. The thickness of the passivation film 4 is about 10 to 200 nm.
  • the passivation film 4 is a film having a negative fixed charge, such as an aluminum oxide layer formed by an ALD (Atomic Layer Deposition) method, is used as the passivation film 4. Good.
  • ALD Advanced Layer Deposition
  • the passivation film 4 having a negative fixed charge electrons which are minority carriers move away from the interface between the substrate 1 and the passivation film 4 due to the electric field effect, so that recombination of minority carriers is reduced.
  • the second semiconductor layer 3 is an n-type layer, a film having a positive fixed charge such as silicon nitride formed by PECVD or the like is used as the antireflection film 5. Good.
  • the back electrode 8 is an electrode provided on the second surface 1b side of the substrate 1 and includes a first electrode 8a, a second electrode 8b, and a third electrode 8c, as shown in FIGS.
  • the first electrode 8a penetrates the passivation film 4 at a number of locations. One end of the first electrode 8 a abuts on the second surface 1 b of the substrate 1, and carriers can be collected on the second surface 1 b of the substrate 1. The other end of the first electrode 8a is in contact with the third electrode 8c.
  • the shape of the first electrode 8a may be a dot (dot) shape or a belt shape (linear shape).
  • the diameter (or width) of the first electrode 8a is about 60 to 500 ⁇ m. If the first electrode 8a is composed of a plurality of electrode regions, the pitch between adjacent electrode regions may be about 0.3 to 2 mm.
  • the second electrode 8 b is an electrode for taking out the electricity obtained by photoelectric conversion on the second surface 1 b of the substrate 1 to the outside of the solar cell element 10.
  • the second electrode 8b is linearly disposed on the passivation film 4 at a position that does not overlap the first electrode 8a in plan view.
  • the second electrode 8b is linearly disposed on the substrate 1 in a state where the second electrode 8b does not overlap the first electrode 8a in plan view and penetrates the passivation film 4.
  • the thickness of the second electrode 8b is about 10 to 30 ⁇ m, and the width is about 1 to 7 mm.
  • a plurality of second electrodes 8b are formed and arranged in a straight line.
  • the 2nd electrode 8b contains the silver which can be soldered as a main component so that the tab copper foil which is a ribbon-shaped connection conductor can be connected easily in a solar cell module manufacturing process.
  • the second electrode 8b can be formed by, for example, applying a conductive paste containing silver as a main component in a desired shape by screen printing or the like, and then baking it.
  • the shape of the second electrode 8b may be a shape that conducts with the third electrode 8c. For example, it is possible to form a protrusion on the rectangular electrode body shown in FIG. 2 and to cover the protrusion with the third electrode 8c.
  • the third electrode 8c is in contact with each of the first electrode 8a and the second electrode 8b and electrically connects them.
  • the third electrode 8c covers a part of the second electrode 8b, the passivation film 4, and the first electrode 8a.
  • the third electrode 8c can transmit the electricity collected by the first electrode 8a to the second electrode 8b.
  • the third electrode 8c is formed on substantially the entire surface excluding a part of the region where the second electrode 8b of the second surface 1b of the substrate 1 is formed, for example, so as to cover all the first electrodes 8a.
  • the thickness of the third electrode 8c is about 15 to 50 ⁇ m.
  • the electrical resistivity of the first electrode 8a is smaller than the electrical resistivity of the third electrode 8c.
  • the electrical resistivity of the first electrode 8a is 10 to 24 ⁇ 10 ⁇ . 8 is about [Omega] m
  • the electrical resistivity of the third electrode 8c is 38 ⁇ 75 ⁇ 10 -8 ⁇ m order.
  • the electrical resistivity of the third electrode 8c occupying a wide area of the back electrode 8 is made larger than the electrical resistivity of the first electrode 8a, the following effects can be expected.
  • a solar cell module including a large number of solar cell elements 10 for example, when a part of the light receiving surface is shaded, the shaded solar cell element functions as a diode. For this reason, a large reverse bias current may flow through the solar cell element 10 in a shaded area. At this time, if a large reverse bias current flows for a long time, the semiconductor junction (pn junction) of the solar cell element 10 tends to deteriorate.
  • the electrical resistivity of the third electrode 8c is made approximately 1.5 to 7 times larger than the electrical resistivity of the first electrode 8a, thereby increasing the electrical resistivity of the entire back electrode 8. .
  • the reverse electrode current having a large electrical resistivity as a whole makes the reverse bias current small and hardly flows. can do.
  • a pn junction part becomes difficult to deteriorate and can provide the solar cell element 10 and solar cell module with high reliability.
  • the electrical resistivity can be easily measured by using a sheet resistance measuring instrument, a step meter, a microprobe, etc., and calculated from the sheet resistance and thickness of the electrode. Can do.
  • the BSF layer 13 can be formed on the substrate 1 by forming the first electrode 8a with a conductive paste containing aluminum.
  • the conductive paste is baked at a predetermined temperature profile having a maximum temperature equal to or higher than the melting point of aluminum.
  • the first electrode 8 a is formed, and interdiffusion occurs between the aluminum in the conductive paste and the substrate 1, and the BSF in which the aluminum diffuses in the substrate 1 at a higher concentration than the first semiconductor layer 2.
  • Layer 13 is formed. Since aluminum can be a p-type dopant, the concentration of the dopant contained in the BSF layer 13 is higher than the concentration of the dopant contained in the first semiconductor layer 2.
  • the dopant element is present at a concentration higher than the concentration of the dopant element that is doped to make the first semiconductor layer 2 have one conductivity type.
  • the BSF layer 13 has a role of forming an internal electric field on the second surface 1b side of the substrate 1 and reducing a decrease in photoelectric conversion efficiency due to minority carrier recombination in the vicinity of the surface of the second surface 1b of the substrate 1. is doing.
  • the BSF layer 13 can be formed, for example, by diffusing a dopant element such as boron or aluminum on the second surface 1b side of the substrate 1.
  • the concentrations of the dopant elements contained in the first semiconductor layer 2 and the BSF layer 13 are about 5 ⁇ 10 15 to 1 ⁇ 10 17 atoms / cm 3 and 1 ⁇ 10 18 to 5 ⁇ 10 21 atoms / cm 3 , respectively. Can do.
  • the solar cell element 10 of the present embodiment is disposed on the substrate 1 having the first surface 1a and the second surface 1b located on the opposite side of the first surface 1a, and the back surface of the substrate 1.
  • a passivation film 4 and a back electrode 8 disposed on the back surface of the substrate 1 are provided.
  • the back electrode 8 includes a first electrode 8a, a second electrode 8b, and a third electrode 8c.
  • the first electrode 8 a penetrates the passivation film 4 at a number of locations and is in contact with the substrate 1.
  • the second electrode 8b is linearly disposed on the substrate 1 so as not to overlap the first electrode 8a in plan view, on the passivation film 4 or through the passivation film 4.
  • the third electrode 8c covers a part of the periphery of the second electrode 8b and the like, the passivation film 4 and the first electrode 8a, and the first electrode 8a and the second electrode 8b. It touches. Thereby, even if a part of 3rd electrode 8c peels, a carrier is.
  • the second electrode 8b can be reached through another portion of the third electrode 8c provided in a planar shape. For this reason, it is possible to provide the solar cell element 10 in which the photoelectric conversion efficiency is unlikely to decrease.
  • a substrate 1 is prepared as shown in FIG. 4A (a).
  • the substrate 1 may be, for example, single crystal silicon or polycrystalline silicon.
  • the substrate 1 is produced by, for example, an existing CZ method or a casting method.
  • an example in which a p-type polycrystalline silicon substrate is used as the substrate 1 will be described.
  • an ingot of polycrystalline silicon is produced by a casting method.
  • the electrical resistivity of the ingot may be about 1 to 5 ⁇ ⁇ cm, for example.
  • boron may be added as the dopant element.
  • the ingot is sliced using a wire saw device to obtain a large number of substrates 1.
  • the substrate 1 has, for example, a square shape with a side of about 160 mm square and a thickness of about 200 ⁇ m. Thereafter, in order to remove the mechanical damage layer and the contamination layer on the cut surface of the substrate 1, the surface of the substrate 1 may be etched by a very small amount with an aqueous solution such as NaOH, KOH, hydrofluoric acid, or hydrofluoric nitric acid.
  • an aqueous solution such as NaOH, KOH, hydrofluoric acid, or hydrofluoric nitric acid.
  • a texture may be formed on the first surface 1a of the substrate 1 in order to reduce light reflection.
  • a texture formation method a wet etching method using an alkaline solution such as NaOH or an acid solution such as hydrofluoric acid, or a dry etching method using a RIE (Reactive Ion Etching) method or the like can be used.
  • an n-type second semiconductor layer 3 is formed on the first surface 1a of the textured substrate 1.
  • the second semiconductor layer 3 is a coating thermal diffusion method in which paste-like P 2 O 5 is applied to the surface of the substrate 1 and thermally diffused, and a gas phase using gaseous POCl 3 (phosphorus oxychloride) as a diffusion source. It is formed by a thermal diffusion method or the like.
  • the second semiconductor layer 3 is formed to have a thickness of about 0.1 to 2 ⁇ m and a sheet resistance value of about 40 to 200 ⁇ / ⁇ .
  • the substrate 1 is heat-treated for about 5 to 30 minutes at a temperature of about 600 to 800 ° C.
  • the substrate 1 is heat-treated for about 10 to 40 minutes at a high temperature of about 800 to 900 ° C. in an inert gas atmosphere such as argon or nitrogen. As a result, phosphorus diffuses from the PSG to the substrate 1, and the second semiconductor layer 3 is formed on the first surface 1 a side of the substrate 1.
  • PSG phosphosilicate glass
  • the second semiconductor layer 3 formed on the second surface 1b side is etched. Remove. Thereby, the p-type first semiconductor layer 2 is exposed on the second surface 1b side.
  • the second semiconductor layer 3 formed on the second surface 1b side is removed by immersing only the second surface 1b side of the substrate 1 in a hydrofluoric acid solution. Thereafter, PSG adhering to the first surface 1a side of the substrate 1 when the second semiconductor layer 3 is formed is removed by etching. At this time, the second semiconductor layer 3 formed on the side surface of the substrate 1 may also be removed.
  • a passivation film 4 made of, for example, aluminum oxide is formed on the second surface 1b of the first semiconductor layer 2 as shown in FIG. 4A (d).
  • a method for forming the passivation film 4 for example, an ALD method, a PECVD method, or the like can be used. However, the passivation effect can be increased by using the ALD method excellent in the coverage of the surface of the substrate 1.
  • the substrate 1 on which the second semiconductor layer 3 is formed is placed in the chamber of the film forming apparatus. Then, in a state where the substrate 1 is heated in a temperature range of 100 ° C. to 250 ° C., a plurality of series of steps of supplying the aluminum source gas, removing the aluminum source exhaust, supplying the oxidizing gas, and removing the oxidizing agent are performed. Repeat once. Thereby, the passivation film 4 made of aluminum oxide can be formed.
  • the aluminum raw material for example, trimethylaluminum (TMA), triethylaluminum (TEA), or the like can be used. Moreover, water, ozone gas, etc.
  • the passivation film 4 is also formed on the entire periphery including the first surface 1 a of the first semiconductor layer 2 and the side surface of the substrate 1.
  • the unnecessary passivation film 4 may be removed by etching with hydrofluoric acid (HF) or the like.
  • an antireflection film 5 made of, for example, a silicon nitride film is formed on the first surface 1a side of the substrate 1.
  • the antireflection film 5 is formed using, for example, PECVD method or sputtering method.
  • the substrate 1 is heated in advance at a temperature higher than the temperature during film formation.
  • a mixed gas of silane (SiH 4 ) and ammonia (NH 3 ) is supplied to the heated substrate 1 after being diluted with nitrogen (N 2 ).
  • the reaction pressure in the chamber is set to 50 to 200 Pa, and plasma is formed by glow discharge decomposition, whereby the antireflection film 5 is formed.
  • the film forming temperature at this time is about 350 to 650 ° C.
  • a frequency of 10 to 500 kHz is used as the frequency of the high frequency power source necessary for glow discharge.
  • the gas flow rate supplied to the chamber is appropriately determined depending on the size of the chamber.
  • the flow rate of the gas supplied to the chamber is, for example, in the range of 150 to 6000 sccm.
  • the flow ratio B / A between the flow rate A of silane and the flow rate B of ammonia may be 0.5-15.
  • the front surface electrode 7 bus bar electrode 7a and finger electrode 7b, sub finger electrode 7c
  • the back surface electrode 8 first electrode 8a, The second electrode 8b and the third electrode 8c
  • the first paste 16 is made of, for example, a metal powder containing silver as a main component (for example, a main metal component is composed of only silver powder having a particle size of about 0.05 to 20 ⁇ m, preferably about 0.1 to 5 ⁇ m, and has a silver content). About 65 to 85 mass% of the total mass of the conductive paste).
  • the first paste 16 further includes an organic vehicle (for example, about 5 to 15% by mass of the total mass of the conductive paste) and a glass frit (for example, about 0.05 to 10% by mass of the total mass of the conductive paste).
  • the first paste 16 is applied to the first surface 1a of the substrate 1 using screen printing. After this application, the solvent is evaporated and dried at a predetermined temperature.
  • the second electrode 8b which is the back electrode 8 is formed using a conductive powder (second paste 17) containing a metal powder composed solely of silver as a main component, an organic vehicle, glass frit, and the like.
  • the component of the second paste 17 may be the same as that of the first paste 16.
  • a coating method of the second paste 17 for example, a screen printing method or the like can be used. After this application, the solvent is evaporated and dried at a predetermined temperature.
  • the first electrode 8 a is formed using the third paste (conductive paste I) 18.
  • the third paste 18 is a metal powder containing aluminum as a main component (for example, the main metal component is composed only of an aluminum powder having a particle size of about 0.05 to 20 ⁇ m, preferably about 0.1 to 5 ⁇ m, and has an aluminum content. About 65 to 80% by mass of the total mass of the conductive paste).
  • the third paste 18 further includes an organic vehicle (for example, about 5 to 15% by mass of the total mass of the conductive paste) and a glass frit (for example, about 0.05 to 10 atomic% of the total mass of the conductive paste, the components are About 40 to 60 atomic% of lead, about 20 to 40 atomic% of silicon, about 1 to 5 atomic% of phosphorus, and about 7 to 15 atomic% of boron.
  • the third paste 18 is applied in a dotted or linear manner at a predetermined position on the second surface 1b at a position away from the already applied second paste 17.
  • a coating method a screen printing method or the like can be used. After this application, the solvent may be evaporated and dried at a predetermined temperature.
  • the substrate 1 on which the first paste 16, the second paste 17 and the third paste 18 are applied has a maximum temperature of about 750 to 950 ° C. in the baking furnace, and the maximum temperature is several tens of seconds to several tens of minutes.
  • the first firing is performed while maintaining. As a result, each conductive paste is sintered, and the first electrode 8a and the second electrode 8b of the front electrode 7 and the back electrode 8 are formed as shown in FIG. 4B (g).
  • the first paste 16 fires through the antireflection film 5 and is connected to the n-type second semiconductor layer 3 on the first surface 1 a of the substrate 1 to form the surface electrode 7.
  • the third paste 18 also fires through the passivation film 4 and is connected to the p-type first semiconductor layer 2 on the second surface 1b to form the first electrode 8a.
  • the BSF layer 13 is also formed.
  • the second paste 17 is baked to form the second electrode 8b.
  • the second paste 17 may be formed on the passivation film 4 without fire-through the passivation film 4 as shown in FIG.
  • the passivation film 4 may be formed on the first semiconductor layer 2 by fire-through.
  • the presence or absence of fire-through can be adjusted by appropriately selecting the glass frit component in the second paste 17.
  • the passivation film 4 when the passivation film 4 is fire-through, it is possible to use a SiO 2 —BiO 3 —PbO-based glass frit for the glass frit.
  • the passivation film 4 when the passivation film 4 is not fire-through, it is possible to use B 2 O 3 —SiO 2 —ZnO glass frit for the glass frit.
  • the third electrode 8 c is formed using a fourth paste (conductive paste II) 19.
  • the fourth paste 19 has a metal powder containing aluminum as a main component (for example, about 65 to 80% by mass of the total mass of the conductive paste).
  • the fourth paste 19 further contains an organic vehicle (for example, about 5 to 15% by mass of the total mass of the conductive paste) and glass frit (for example, about 5 to 25% by mass of the total mass of the conductive paste).
  • the composition of the glass frit is about 0.05 to 10 mass% of the total mass of the conductive paste, the components are about 40 to 60 atomic% of lead, silicon is about 20 to 40 atomic%, phosphorus is about 1 to 5 atomic%, About 7 to 15 atomic% of boron).
  • the fourth paste 19 is applied onto the second surface 1b so as to come into contact with the already formed first electrode 8a and the end of the second electrode 8b. At this time, by applying to almost the entire surface of the second surface 1b where the second electrode 8b is not formed, it is possible to contact the end of the second electrode 8b without strict alignment.
  • the coating method a screen printing method or the like can be used. After this application, the solvent may be evaporated and dried at a predetermined temperature.
  • the substrate 1 coated with the fourth paste 19 is subjected to the second baking in a baking furnace at a temperature lower than the first baking condition of 600 to 700 ° C. for several tens of seconds to several tens of minutes. Do.
  • the third electrode 8 c is formed on the second surface 1 b side of the substrate 1.
  • the firing temperature of the fourth paste 19 for forming the third electrode 8c is equal to the third paste for forming the first electrode 8a. Lower than the firing temperature of 18. For this reason, the third electrode 8c is less likely to be denser than the first electrode 8a, and the third electrode 8c has a higher electrical resistivity than the first electrode 8a.
  • the metal particles in the electrode can be in good contact with each other, and the porosity in the electrode can be reduced, which can be dense. For this reason, the electrical resistivity of the first electrode 8a decreases, and the contact resistance with the substrate 1 can decrease.
  • the third electrode 8c formed with a large area is formed at a low firing temperature, the porosity can be increased and the thermal contraction in the hole portion can be reduced. For this reason, at the time of manufacture of the solar cell element 10, the curvature by the difference with the thermal expansion coefficient of the board
  • the peak temperature of the first firing is set higher than the peak temperature of the second firing.
  • the electrical resistivity of the first electrode 8a can be made smaller than the electrical resistivity of the third electrode 8c.
  • the electrode forming step is performed after the surface electrode 7 (bus bar electrode 7a and finger electrode 7b, subfinger electrode 6c) having similar components and the second electrode 8b of the back electrode 8 are formed. Firing for forming the three electrodes 8c and the first electrode 8a may be performed separately.
  • ⁇ Modification 1> As shown in FIG. 6, in the embodiment according to the first modification, a first silicon oxide film 11 thinner than the passivation film 4 is interposed between the passivation film 4 and the substrate 1 on the second surface 10 b side. Yes. Since other configurations are the same as those of the above-described embodiment, description thereof is omitted.
  • the photoelectric conversion efficiency of the solar cell element can be further improved.
  • the source gas by the ALD method include N, N, N ′, N ′, tetraethylsilanediamine ⁇ H 2 Si [N (C 2 H 5 ) 2 ] 2 > gas, ozone (O 3 ), water vapor, and the like. Can be used to form a film.
  • the thickness of the first silicon oxide film 11 is made thinner than that of the passivation film 4.
  • the negative fixed charge of aluminum oxide forming the passivation film 4 becomes superior to the positive fixed charge of the first silicon oxide film 11. Then, it is possible to make it difficult to lower the passivation effect of the passivation film 4.
  • the film thickness of the first silicon oxide film 11 is desirably less than half the film thickness of the passivation film 4.
  • the thickness of the first silicon oxide film 11 is about 20 nm.
  • the film thickness of the first silicon oxide film 11 is preferably less than half the film thickness of the passivation film 4.
  • the second silicon oxide film 12 aluminum or the like can be made difficult to diffuse into the passivation film 4 when the third electrode 8c is formed. Thereby, the passivation effect of the passivation film 4 can be further improved.
  • the second silicon oxide film 12 it is desirable to use an ALD method having excellent coverage as in the case of the first silicon oxide film 11.
  • the film thickness of the second silicon oxide film 12 is less than half the film thickness of the passivation film 4 as described above.
  • the thickness of the second silicon oxide film 12 is desirably about 20 nm.
  • the metal component of the conductive paste (third paste 18) for forming the first electrode 8a mainly contains aluminum and further contains silver. Since other configurations are the same as those of the above-described embodiment, description thereof is omitted.
  • the third paste 18 uses a main metal component made of only aluminum, it is considered that an oxide film is formed on the surface of the first electrode 8a when the first electrode 8a is baked. At this time, the contact resistance in the connection part of the 1st electrode 8a and the 3rd electrode 8c increases, and the photoelectric conversion efficiency of the solar cell element 10 may fall. On the other hand, by adding silver to the third paste 18, it becomes difficult to form a surface oxide film in firing, and the contact resistance at the connection portion between the first electrode 8 a and the third electrode 8 c can be reduced. it can.
  • the metal component of the third paste 18 is preferably such that the mass% of silver is larger than the mass% of aluminum.
  • the presence of aluminum makes it possible to form a good BSF layer 13, and the presence of silver makes it difficult to form an oxide film on the surface of the first electrode 8a.
  • silver in the metal component is about 70 to 99.5% by mass and aluminum is about 0.5 to 30% by mass. Thereby, a good BSF layer 13 can be formed, and the oxide film formation on the surface of the first electrode 8a can be further reduced.
  • the 3rd paste 18 which concerns on the modification 3 is the same as that of embodiment mentioned above except the composition of a metal component.
  • the metal component of the conductive paste (second paste 17) for forming the second electrode 8b includes silver as a main component, and further includes aluminum.
  • Other configurations are the same as those in the above-described embodiment.
  • ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Aluminum is added to the second paste 17 in addition to silver.
  • a BSF layer can be formed also in the 1st semiconductor layer 2 of the board
  • FIG. And the recombination of the minority carrier of a BSF layer part can be reduced, and the further improvement in photoelectric conversion efficiency can be aimed at.
  • silver in the metal component is about 85 to 99.5% by mass and aluminum is about 0.5 to 15% by mass.
  • a good BSF layer 13 can be formed on the first semiconductor layer 2 of the substrate 1 immediately below the second electrode 8b, and soldering to the second electrode 8b is also possible.
  • the conductivity for forming the conductive paste (third paste 18) and the second electrode 8b for forming the first electrode 8a as shown in ⁇ Modification 3> and ⁇ Modification 4> above.
  • the paste may be made of the same material. Accordingly, the third paste 18 and the second paste 17 can be simultaneously printed by the screen printing method, and the number of steps in the manufacturing process of the solar cell element 10 can be reduced.
  • a polycrystalline silicon substrate doped with boron having a square side of about 156 mm and a thickness of about 200 ⁇ m in plan view was prepared.
  • the substrate 1 was obtained by subjecting an ingot produced by a casting method to processing such as slicing using a wire saw device. Further, the surface layer portion of the substrate 1 having a thickness of about 10 ⁇ m was etched using an aqueous sodium hydroxide solution to remove the damaged layer on the surface layer portion of the substrate 1. Then, the surface of the substrate 1 was cleaned. The following processing was performed on the substrate 1 thus prepared.
  • a fine texture was formed on the first main surface 7a side of the substrate 1 by using the RIE method.
  • phosphorus is diffused by vapor phase thermal diffusion using phosphorus oxychloride (POCl 3 ) as a diffusion source on the substrate 1 to form an n-type semiconductor layer having a sheet resistance of about 60 to 100 ⁇ / ⁇ , A pn junction was formed.
  • the n-type semiconductor layer formed on the side surface of the substrate 1 and the second main surface 7b side was removed with a hydrofluoric acid solution. Thereafter, the remaining PSG was removed with a hydrofluoric acid solution.
  • an n-type second semiconductor layer 3 was formed on the p-type first semiconductor layer 2 of the substrate 1 as shown in FIG. 4A (c).
  • a passivation film 4 made of aluminum oxide was formed on the entire surface of the substrate 1 by an ALD method to a thickness of about 15 nm.
  • the substrate 1 was held upright in the chamber of the ALD apparatus, and the temperature of the substrate 1 was maintained at about 200 ° C. under reduced pressure.
  • Trimethylaluminum (TMA) was used as a source gas, and N 2 , He, and H 2 were used as a carrier gas and a purge gas. Ozone was used as the oxidizing gas.
  • the passivation film 4 includes a supply process (P1), a diffusion process (gas sealing process) (P2), an exhaust process (P3), an oxidizing gas supply process (P4), a diffusion process (gas sealing process) (P5) and The steps P1 to P6 of the exhaust step (P6) were repeated a plurality of times.
  • the time required for each step per cycle of P1 to P6 is as follows: P1: about 1 second, P2: about 3 seconds, P3: about 5 seconds, P4: about 1 second, P5: about 2 seconds, P6: about 3 Seconds.
  • the film-forming time (cycle number) was determined from the film-forming speed calculated beforehand.
  • antireflection made of a silicon nitride film having a refractive index of 1.9 to 2.1 and a film thickness of about 70 to 90 nm is formed on the first surface 1a of the substrate 1 by PECVD.
  • a film 5 was formed. This is because the inside of the chamber of the PECVD apparatus is set to about 500 ° C., a mixed gas of silane (SiH 4 ) and ammonia (NH 3 ) is diluted with nitrogen (N 2 ), and is plasmatized by glow discharge decomposition to form silicon nitride. Was deposited.
  • a conductive paste (silver paste) mainly composed of silver and made of glass frit, an organic vehicle, or the like is formed on the first surface side electrode (first bus bar electrode) as shown in FIG. 8 and the first collector electrode 9) were applied and dried. Also on the second main surface 7b side, the silver paste was applied to the pattern of the second bus bar electrode 10 as shown in FIG. 2 (b) and dried. Further, an electrode conductive paste (aluminum paste) mainly composed of aluminum on the second main surface 7b side and made of glass frit, an organic vehicle, or the like is a pattern of the second collector electrode 11 as shown in FIG. And then dried.
  • the substrate 1 that had been coated with silver paste and aluminum paste and dried was baked at a peak temperature (about 750 ° C.) for about 10 minutes to form a first surface side electrode and a second surface side electrode.
  • the first bus bar electrode 8 had a width of about 1.7 mm and a thickness of about 11 ⁇ m.
  • the first current collecting electrode 9 had a width of about 0.05 mm and a thickness of about 11 ⁇ m.
  • the second bus bar electrode 10 had a width of about 3.5 mm and a thickness of about 10 ⁇ m.
  • the thickness of the 2nd current collection electrode 11 was about 33 micrometers. In this way, a solar cell element was produced.
  • the 1st paste 16 for formation of the surface electrode 7 (the bus-bar electrode 7a and the finger electrode 7b, the sub finger electrode 7c) is formed in the 1st surface 1a of the board
  • the first paste 16 a paste containing about 80% by mass of silver, about 14% by mass of SiO 2 —Bi 2 O 3 —PbO-based glass frit and about 6% by mass of an organic vehicle was used.
  • the organic vehicle used ethyl cellulose as the binder and diethylene glycol monobutyl ether acetate as the organic solvent.
  • the paste film thickness immediately after printing the first paste 16 was about 18 ⁇ m. After this application, the first paste 16 was dried at a temperature of about 140 ° C. for about 3 minutes to evaporate the solvent.
  • the second paste 17 for forming the second electrode 8b of the back electrode 8 was applied to the pattern as shown in FIG. 2 using a screen printing method.
  • the second paste 17 used was the same component as the first paste 16.
  • the paste film thickness immediately after printing of the second paste 17 was about 17 ⁇ m.
  • the second paste 17 was dried at a temperature of about 140 ° C. for about 3 minutes to evaporate the solvent.
  • a third paste 18 for forming the first electrode 8a of the back electrode 8 was applied using a screen printing method.
  • the third conductive paste 18 an aluminum powder having an average particle size of about 0.1 to 5 ⁇ m and having an aluminum content of about 75% by mass of the total mass of the third paste was used.
  • glass frit about 5 atomic% of the total mass of the conductive paste, components are about 50 atomic% of lead, about 30 atomic% of silicon, about 2 atomic% of phosphorus, and about 10 atomic% of boron
  • an organic vehicle about 10% by mass of the total mass of the conductive paste
  • the paste film thickness immediately after printing the second paste 17 was about 28 to 34 ⁇ m.
  • the maximum temperature is a temperature I (600 ° C.), a temperature II (650 ° C.), a temperature III (700 ° C.), a temperature IV (750 ° C.), and a temperature V (800 ° C.).
  • the temperature VI 850 ° C.
  • the temperature VII 900 ° C.
  • the temperature VIII 950 ° C.
  • the temperature IX 1000 ° C.
  • a fourth paste 19 for forming the third electrode of the back current collector 8 was applied by screen printing.
  • the fourth paste 19 had the same components as the third paste 18.
  • the paste film thickness immediately after printing the fourth paste 19 was about 31 to 42 ⁇ m.
  • the substrate 1 on which the fourth paste 19 was applied was subjected to second baking.
  • the maximum temperature is a temperature A (600 ° C.), a temperature B (650 ° C.), a temperature C (700 ° C.), a temperature D (750 ° C.), and a temperature E (800 ° C.).
  • the temperature F (850 ° C.), the temperature G (900 ° C.), and the temperature H (950 ° C.) were maintained for about 20 seconds.
  • the maximum temperature was less than 600 ° C. (temperature A) such as 550 ° C., the second firing could not be performed because the temperature was too low.
  • the temperatures I to VIII and A to H are median values and have a range of plus or minus 10 ° C. For example, when the temperature is 700 ° C., the temperature is in the range of 690 to 710 ° C.
  • the photoelectric conversion efficiency was measured under the conditions of irradiation of AM (Air Mass) 1.5 and 100 mW / cm 2 , and the average was calculated for the solar cell element produced as described above.
  • Table 1 shows the standard value of the photoelectric conversion efficiency when the first firing condition and the second firing condition are combined. This standard value is indicated by an index with the average value of the measurement results of all the solar cell elements as 100. However, a horizontal bar indicates a case where the conductive paste was not fired well and the photoelectric conversion efficiency could not be measured due to electrode peeling or oxidation.
  • the result of baking performed at temperatures E to H is the same as that at temperature D, and is omitted.
  • the maximum temperature of the first baking is not less than 750 ° C. and not more than 950 ° C. (temperature IV to VIII) and the maximum temperature of the second baking is not less than 600 ° C. and not more than 700 ° C. (temperature A to C). It was found that firing was possible.
  • the maximum temperature of the first baking is 750 ° C. or more and 900 ° C. or less (temperatures IV to VII), and the maximum temperature of the second baking is 650 ° C. or more and 700 ° C. or less (temperature B To C).
  • the electrical resistivity of the first electrode 8a is in the range of 10 to 24 ⁇ 10 ⁇ 8 ⁇ m
  • the electrical resistance of the third electrode 8c The rate was found to be in the range of 38 to 75 ⁇ 10 ⁇ 8 ⁇ m.
  • the electrical resistivity of the 1st electrode 8a electrode was smaller than the electrical resistivity of the 3rd electrode 8c.

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  • Electromagnetism (AREA)
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Abstract

La présente invention concerne, selon un mode de réalisation, un élément de cellule solaire comprenant : un substrat semi-conducteur présentant une première surface et une seconde surface située à l'opposé de la première surface; un film de passivation disposé sur la seconde surface du substrat semi-conducteur; des premières électrodes en contact avec le substrat semi-conducteur dans un état de pénétration dans le film de passivation au niveau d'une pluralité de positions; une deuxième électrode disposée en ligne droite sur le substrat semi-conducteur, sur le film de passivation ou dans un état de pénétration dans le film de passivation, à un emplacement qui ne chevauche pas les premières électrodes en vue plane; et une troisième électrode couvrant le film de passivation, les premières électrodes et une partie de la deuxième électrode de manière à être en contact avec les premières électrodes et la deuxième électrode. La résistance électrique des premières électrodes est inférieure à celle de la troisième électrode.
PCT/JP2016/053093 2015-02-02 2016-02-02 Élément de cellule solaire et procédé de fabrication correspondant WO2016125803A1 (fr)

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JP5822952B2 (ja) * 2011-12-27 2015-11-25 京セラ株式会社 太陽電池および太陽電池の製造方法
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JP2005353836A (ja) * 2004-06-10 2005-12-22 Kyocera Corp 太陽電池素子及びこれを用いた太陽電池モジュール
WO2009139222A1 (fr) * 2008-05-14 2009-11-19 シャープ株式会社 Pile solaire et procédé de fabrication de pile solaire
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