WO2018066016A1 - 高光電変換効率太陽電池の製造方法及び高光電変換効率太陽電池 - Google Patents
高光電変換効率太陽電池の製造方法及び高光電変換効率太陽電池 Download PDFInfo
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- WO2018066016A1 WO2018066016A1 PCT/JP2016/004492 JP2016004492W WO2018066016A1 WO 2018066016 A1 WO2018066016 A1 WO 2018066016A1 JP 2016004492 W JP2016004492 W JP 2016004492W WO 2018066016 A1 WO2018066016 A1 WO 2018066016A1
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- solar cell
- silicon substrate
- temperature
- semiconductor silicon
- electrode
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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
- 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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- 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
- 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
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
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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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
- H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
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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
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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
- H01L31/18—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
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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
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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
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- 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
- 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.
- FIG. 1 shows an overview viewed from the light-receiving surface side of a general high photoelectric conversion efficiency solar cell using a single crystal N-type silicon substrate. Moreover, the schematic diagram of the cross-sectional structure of this solar cell is shown in FIG.
- This solar cell 100 has a large number of electrodes having a width of one hundred to several tens of ⁇ m called finger electrodes 121 on the N-type substrate 110 as current collecting electrodes on the light receiving surface. The interval between adjacent finger electrodes is generally about 1 to 3 mm.
- 2 to 4 bus bar electrodes 122 are provided as current collecting electrodes for connecting the solar cells. Examples of a method for forming these electrodes (finger electrodes 121 and bus bar electrodes 122) include vapor deposition and sputtering.
- a metal paste obtained by mixing metal fine particles such as Ag in an organic binder is used.
- a method of printing using a plate or the like and performing heat treatment at several hundred degrees to adhere to the substrate is widely used.
- the portions other than the electrodes of the solar cell 100 are covered with an antireflection film 141 such as a silicon nitride film.
- a P-type diffusion layer 112 opposite to the conductivity type of the substrate is formed on the surface (light-receiving surface) of the substrate.
- Finger electrodes 131 are also formed on the back surface side, and portions other than the electrodes are covered with a film (back surface passivation film) 151 such as a silicon nitride film.
- An N-type diffusion layer 113 having the same conductivity type as the substrate is formed on the outermost layer on the back surface of the N-type substrate 110.
- FIG. 3 shows a schematic diagram of a cross-sectional structure when an N-type substrate is used as this solar cell.
- the light receiving surface of the N-type substrate 310 is covered with an antireflection film 341.
- N electrodes (N type finger electrodes) 335 and P electrodes (P type finger electrodes) 334 are alternately formed on the back surface of the solar cell 300.
- N-type diffusion layer 313 is formed only on the N-type substrate 310 just below the N-electrode 335, a P-type diffusion layer 312 is formed in most of the other regions, and a portion other than the electrode is a film (back surface) such as a silicon nitride film. (Passivation film) 351.
- a film back surface
- Passivation film 351.
- the present invention has been made in view of the above-described circumstances, and provides a method for manufacturing a solar cell in which a deterioration phenomenon in which the output of the solar cell is reduced simply by being left in the room temperature / atmosphere is suppressed. Objective.
- the present invention has been made to solve the above problems, and has a semiconductor silicon substrate of less than 100 ° C. having an electrode formed by firing an electrode precursor on at least one main surface and having a PN junction. And a method for annealing the semiconductor silicon substrate at 100 ° C. or higher and 450 ° C. or lower.
- the annealing treatment it is preferable to perform the annealing treatment for a time of 0.5 minutes or more.
- the effect of suppressing the deterioration phenomenon can be obtained more reliably, and a solar cell can be manufactured at a lower cost.
- the rate of temperature decrease from the maximum temperature to 450 ° C. is 50 ° C./second or more.
- the original initial characteristics of the solar cell can be enhanced by performing the firing step at such a temperature lowering rate.
- the present invention is particularly effective when the temperature lowering rate in the firing process is large as described above.
- the maximum temperature in firing the electrode precursor is 500 ° C. or higher and 1100 ° C. or lower.
- the electrode can be effectively baked by performing the baking step at such maximum temperature.
- a low-temperature curable conductive material that can be cured on the main surface of the semiconductor silicon substrate in a range of 100 ° C. to 450 ° C. Is applied in a pattern, and then, when the annealing treatment is performed, the low-temperature curable conductive material is simultaneously cured to form a conductor portion.
- the low temperature annealing treatment may be performed after the low temperature curable conductive material is applied in a pattern. This is particularly effective when the bus bar electrode is formed of a low-temperature curable conductive material.
- an insulating material that can be cured in a range of 100 ° C. or higher and 450 ° C. or lower is patterned on the main surface of the semiconductor silicon substrate. Then, when the annealing process is performed, the insulating material can be simultaneously cured to form an insulating film.
- the low temperature annealing treatment may be performed after the insulating material is applied in a pattern. This is particularly effective when manufacturing a back electrode type solar cell.
- the semiconductor silicon substrate is an N-type semiconductor silicon substrate.
- the solar cell manufacturing method of the present invention is more effective for the N type than for the P type.
- the present invention includes an electrode formed by firing an electrode precursor on at least one main surface, and anneals a semiconductor silicon substrate having a PN junction of less than 100 ° C. at 100 ° C. to 450 ° C.
- a solar cell that has been processed.
- the present invention is the above-described solar cell, wherein the initial short-circuit current value A measured within one day after the annealing treatment and the initial short-circuit current are measured for one week at room temperature.
- a short-circuit current value B measured after storage satisfies a relationship of B / A ⁇ 0.98.
- the present invention is a solar cell comprising a semiconductor silicon substrate having a PN junction, and having an electrode formed by firing an electrode precursor on at least one main surface of the semiconductor silicon substrate,
- the initial short-circuit current value A measured within one day after the completion of the solar cell and the short-circuit current value B measured after the initial short-circuit current was measured and stored for 1 week at room temperature are B / A
- a solar cell that satisfies the relationship of ⁇ 0.98.
- the solar cell of the present invention is a solar cell in which the deterioration phenomenon that the output of the solar cell is lowered simply by being left in the room temperature and the atmosphere is suppressed.
- the present invention provides a solar cell module characterized in that the above-described solar cell is incorporated.
- the solar cell of the present invention can be built in the solar cell module.
- the present invention also provides a solar power generation system characterized by having the above solar cell module.
- the solar cell module incorporating the solar cell of the present invention can be used in a solar power generation system.
- the present invention also provides a method of firing the electrode precursor on the semiconductor silicon substrate by heating the semiconductor silicon substrate having the electrode precursor formed on at least one main surface and then lowering the temperature to below 100 ° C.
- a solar cell manufacturing apparatus comprising: a firing furnace for forming an electrode; and an annealing furnace for annealing a semiconductor silicon substrate treated in the firing furnace at 100 ° C. to 450 ° C.
- a solar cell is manufactured using such a solar cell manufacturing apparatus, it is possible to manufacture a solar cell in which the deterioration phenomenon that the output of the solar cell is reduced simply by leaving it in room temperature and in the atmosphere is suppressed. .
- the firing furnace and the annealing furnace are mechanically connected, and the semiconductor silicon substrate carried out of the firing furnace can be automatically stored in the annealing furnace.
- a solar cell is manufactured using such a solar cell manufacturing apparatus, a solar cell in which a deterioration phenomenon is automatically suppressed can be manufactured.
- the method for manufacturing a solar cell of the present invention it is possible to manufacture a high photoelectric conversion efficiency solar cell in which a deterioration phenomenon in which the output of the solar cell is lowered simply by being left in the room temperature and the atmosphere is suppressed.
- FIG. 6 is a diagram showing the correlation between annealing temperature, conversion efficiency, and conversion efficiency maintenance ratio obtained from Examples 1-1 to 1-6 and Comparative Examples 1-1 and 1-2. It is a graph which shows the correlation of annealing time, conversion efficiency, and conversion efficiency maintenance factor obtained from Example 2.
- FIG. 1 is a schematic diagram of a solar power generation system according to the present invention. It is a figure which shows the degradation phenomenon with time and the recovery by annealing according to the present invention.
- a substrate is prepared (step a).
- This semiconductor substrate silicon substrate can be prepared by the following sub-steps a-1 to a-4.
- a substrate made of semiconductor silicon is prepared (substep a-1).
- a PN junction is formed on a substrate made of semiconductor silicon (substep a-2).
- an electrode precursor is formed on at least one main surface of the substrate (substep a-3).
- Silver paste or the like can be used as the electrode precursor.
- Subsequent to sub-step a-3 by heating the substrate on which the electrode precursor is formed, the temperature is lowered to less than 100 ° C.
- the substrate may be cooled to a temperature similar to the ambient environment temperature).
- the electrode precursor is fired to form an electrode on the substrate (substep a-4.
- the formation of the electrode by firing the electrode precursor is also referred to as an electrode firing step).
- the manufacturing method of the solar cell of this invention can have another process suitably.
- the method for manufacturing a solar cell of the present invention includes a step (step b) of annealing the semiconductor silicon substrate prepared in step a as described above at 100 ° C. or higher and 450 ° C. or lower.
- step b By having the low-temperature annealing step for annealing the substrate at a relatively low temperature after the electrode firing step, the deterioration is recovered, and further, this treatment does not deteriorate over time. That is, according to the method for manufacturing a solar cell of the present invention, it is possible to manufacture a solar cell with high photoelectric conversion efficiency in which the deterioration phenomenon that the output of the solar cell is lowered simply by being left in the room temperature and the atmosphere is suppressed. .
- the solar cell having the structure illustrated in FIGS. 1 and 2 can be manufactured by such a solar cell manufacturing method, it can also be applied to solar cells having other structures.
- the temperature at which the annealing treatment is performed is 100 ° C. or higher and 450 ° C. or lower as described above. When the temperature is lower than 100 ° C., the annealing effect does not appear, and when the temperature is higher than 450 ° C., a problem occurs in the solar cell body, such as an increase in electrode contact resistance.
- the temperature of this low-temperature annealing treatment is preferably 150 ° C. or higher and 400 ° C. or lower, and more preferably 200 ° C. or higher and 300 ° C. or lower.
- the annealing treatment is preferably performed for a time of 0.5 minutes or longer.
- the time for the low-temperature annealing treatment is more preferably 1 minute or more, and further preferably 5 minutes or more.
- the low-temperature annealing treatment time is preferably 180 minutes or less, and more preferably 60 minutes or less in order to suppress manufacturing costs.
- the low temperature annealing treatment may be performed in several stages. That is, the low temperature annealing treatment can be performed once at a temperature of 100 ° C. or higher and 450 ° C. or lower, the temperature is lowered to around room temperature, and the low temperature annealing treatment can be performed again at a temperature of 100 ° C. or higher and 450 ° C. or lower. Also in that case, it is preferable that the total time of the low-temperature annealing treatment is 0.5 minutes or more and 60 minutes or less.
- the rate of temperature decrease from the maximum temperature to 450 ° C. is preferably 50 ° C./second or more.
- a temperature-fall rate shall be 50 degrees C / sec or more as mentioned above.
- the maximum temperature in the firing of the electrode precursor is 500 ° C. or higher and 1100 ° C. or lower.
- the temperature is 500 ° C. or higher, an annealing effect is easily obtained.
- the temperature is 1100 ° C. or lower, contamination from the firing furnace can be suppressed, and thus the annealing effect is easily obtained.
- the maximum firing temperature is 550 ° C. or higher and 1000 ° C. or lower because a low contact resistance between the electrode and the substrate can be realized.
- the sintering of the electrode proceeds by setting the maximum firing temperature to 700 ° C. or higher, and the decrease in bulk lifetime is not manifested by setting it to 850 ° C. or lower, which is preferable because higher initial characteristics of the solar cell can be obtained. .
- FIG. 12 is a diagram showing the temporal change data of the short-circuit current (I SC ) of the solar cell created through the electrode firing step.
- Symbols ⁇ ⁇ ⁇ are different substrates, and the change in short-circuit current over time is shown with 0 immediately after firing. It can be seen that it decreases with the passage of days.
- the substrate after 17 days has been annealed, and the change in short-circuit current with time is shown as ⁇ ⁇ ⁇ , with 0 immediately after annealing.
- the short-circuit current is restored to the value immediately after firing, and further, no deterioration over time is observed.
- the above are specific examples of deterioration with time, recovery of deterioration by low-temperature annealing, and inhibition of deterioration phenomenon.
- the last high-temperature heat treatment process is often an electrode formation process.
- the electrode forming step is a step of printing and baking a paste containing silver powder or the like, and in particular, the baking step includes a step of lowering the temperature from a high temperature close to 800 ° C. to near room temperature in less than one minute.
- Cu copper
- Non-Patent Document 1 Cu in the silicon bulk forms precipitates in the bulk on the order of several hours even at room temperature.
- the atomic Cu forms precipitates with time, and this is considered to cause deterioration of the solar cell characteristics. That is, it is estimated that this is the cause of the output decrease with time.
- Patent Document 1 it is known that Cu in a silicon bulk diffuses to the substrate surface by performing heat treatment at room temperature to 400 ° C. a plurality of times.
- a low-temperature annealing treatment it is considered that Cu in the bulk moves and is fixed to the substrate surface, and is detoxified with respect to the solar cell characteristics. That is, this is presumed to be a cause of deterioration recovery and deterioration inhibition by low-temperature annealing.
- the elemental analysis of the solar cell in the substrate that deterioration over time was carried out in total dissolved ICP-MS (inductively coupled plasma mass spectrometry), either in a plurality of analysis Cu detection limit (1.9 ⁇ 10 12 / Cm 3 ) or less.
- ICP-MS inductively coupled plasma mass spectrometry
- the solar cell that has undergone the low-temperature annealing treatment according to the method of the present invention has its deterioration phenomenon suppressed, so that the structure of the solar cell itself changes as compared with the solar cell that has not undergone the low-temperature annealing treatment.
- any method of manufacturing a solar cell having the characteristics of the present invention can suppress the deterioration phenomenon that has occurred in the conventional solar cell anyway. .
- the low-temperature annealing step can be performed simultaneously with other low-temperature heat treatment in the solar cell manufacturing process. For example, after applying a low-temperature curable conductive material in a pattern, a low-temperature annealing treatment for suppressing solar cell deterioration can be performed.
- This method is effective when the bus bar electrode is formed of a low-temperature curable conductive material. More specifically, it can be as follows. That is, after a step of preparing a semiconductor silicon substrate by performing electrode firing (step a), a pattern of a low-temperature curable conductive material that can be cured in a range of 100 ° C. to 450 ° C. is formed on the main surface of the substrate. Apply to the shape.
- the conductor portion can be formed by simultaneously curing the low-temperature curable conductive material.
- This conductor part can be configured as, for example, a bus bar electrode.
- a low temperature annealing treatment for suppressing the deterioration of the solar cell can be performed.
- This is particularly effective when manufacturing a back electrode type solar cell. More specifically, it can be as follows. That is, after the step of preparing a semiconductor silicon substrate by performing electrode firing (step a), an insulating material curable in a range of 100 ° C. or higher and 450 ° C. or lower is applied in a pattern on the main surface of the substrate. To do. Thereafter, when the annealing treatment (step b) is performed, the insulating material can be simultaneously cured to form an insulating film.
- This insulating film can be configured, for example, as a film that separates the P electrode and the N electrode of the back electrode type solar cell.
- the annealing process is preferably performed at the stage of the substrate as described above, rather than after the solar cell module or string described below is manufactured.
- Modules and strings include solder and sealing material as constituent materials. Since these deteriorate in quality when exposed to a high temperature, they hinder the annealing. In addition, since the area of the individual increases, not only the apparatus becomes large, but also it becomes technically difficult to heat (anneal) uniformly.
- the substrate is preferably an N-type semiconductor silicon substrate. This is because the present invention is more effective for the N type than for the P type. Although the details of this reason are unknown, it is known that Cu in the P-type substrate starts to move to the surface at a temperature of about room temperature, and the deterioration phenomenon itself is relatively less likely to occur compared to the N-type substrate. it is conceivable that. However, the present invention can be applied to a P-type substrate without any problem.
- an as-cut single crystal ⁇ 100 ⁇ N-type silicon substrate having a specific resistance of 0.1 to 5 ⁇ ⁇ cm is prepared by doping high-purity silicon with a V-valent element such as phosphorus or arsenic / antimony.
- the single crystal silicon substrate may be manufactured by either the CZ (Czochralski) method or the FZ (floating zone) method.
- the silicon substrate prepared here is not necessarily monocrystalline silicon, but may be polycrystalline silicon.
- mechanical damage to the substrate surface formed during slicing and grinding can be caused by high-concentration alkali such as sodium hydroxide aqueous solution or potassium hydroxide aqueous solution having a concentration of 5 to 60%, or a mixed acid of hydrofluoric acid and nitric acid. Etch using Depending on the texture forming conditions in the next step, this mechanical damage removing step is not necessarily required and can be omitted.
- high-concentration alkali such as sodium hydroxide aqueous solution or potassium hydroxide aqueous solution having a concentration of 5 to 60%, or a mixed acid of hydrofluoric acid and nitric acid.
- Texture is an effective way to reduce solar cell reflectivity.
- the texture is immersed for about 10 to 30 minutes in an alkali solution (concentration 1 to 10%, temperature 60 to 90 ° C.) such as heated sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, etc. Produced.
- an alkali solution concentration 1 to 10%, temperature 60 to 90 ° C.
- 2-propanol is dissolved in the solution to promote the reaction.
- a P-type diffusion layer is formed on the substrate.
- a vapor phase diffusion method and a coating diffusion method are used for the formation of the diffusion layer.
- gas-phase diffusion method and the placing in the heat treatment furnace in a state superimposed substrate as a set of two sheets, it enables a method of heat treatment at introducing a gas mixture of BBr 3 and the oxygen 950 ⁇ 1050 ° C. is there.
- Nitrogen and argon are suitable as the carrier gas.
- a coating method containing a boron source may be applied to the entire main surface of one of the substrates and heat-treated at 950 to 1050 ° C.
- the coating agent for example, an aqueous solution containing 1 to 4% boric acid as a boron source and 0.1 to 4% polyvinyl alcohol as a thickener can be used.
- an N-type diffusion layer is formed.
- a vapor phase diffusion method and a coating diffusion method either of which may be used.
- a method of heat-treating a substrate in a mixed gas atmosphere of 830 to 950 ° C. in a mixed gas of phosphorus oxychloride, nitrogen and oxygen by placing two substrates in a superposed state is possible.
- the coating diffusion method is a method in which a phosphorus-containing material is spin-coated or printed and then heat-treated, and any method may be used.
- the surface glass is removed with hydrofluoric acid or the like.
- an antireflection film is formed on the light receiving surface.
- a silicon nitride film or a silicon oxide film can be used as the antireflection film.
- a silicon nitride film a film of about 100 nm is formed using a plasma CVD apparatus.
- As the reaction gas monosilane (SiH 4 ) and ammonia (NH 3 ) are often mixed and used. However, nitrogen can be used instead of NH 3 , and the process pressure can be adjusted and the reaction gas diluted. Therefore, hydrogen may be mixed into the reaction gas.
- a CVD method may be used, but a film obtained by a thermal oxidation method can provide higher cell characteristics.
- a protective film with a silicon nitride film or a silicon oxide film on the back surface as well as the light receiving surface.
- a thin aluminum oxide film or thermal oxide film with a thickness of about 1 to 20 nm may be formed on the substrate surface in advance, and then the above silicon nitride film or silicon oxide film may be formed.
- a paste containing Ag powder is formed by a screen printing method. It is simplest to form the finger pattern and the bus bar electrode at the same time by using a comb-like printed pattern.
- the finger electrode width is preferably about 40 to 200 ⁇ m, and the bus bar electrode width is preferably about 0.5 to 2 mm.
- the screen surface printing method is also used to form the light receiving surface electrode, and an Ag paste in which Ag powder and glass frit are mixed with an organic binder is printed. It is simplest to form the finger pattern and the bus bar electrode at the same time by forming the printed pattern in a comb shape like the back surface.
- the finger electrode width is preferably about 40 to 100 ⁇ m, and the bus bar electrode width is preferably about 0.5 to 2 mm.
- the electrode and silicon are made conductive.
- the back electrode and the light-receiving surface electrode can be fired at one time or separately. Firing is usually carried out by treating at 700 to 850 ° C. for several seconds to several minutes.
- the cooling rate is also an important parameter, and it is desirable that the cooling rate be higher than 50 ° C./second.
- the rate of temperature decrease in the firing step refers to an average value from the peak temperature in the firing step to 450 ° C.
- the electrode-baked substrate is heated (annealed) at 100 to 450 ° C. for 1 to 60 minutes.
- the annealing method include indirect resistance heating, direct resistance heating, infrared heating, and high frequency induction heating.
- Indirect resistance heating is a method in which heat is transmitted from a heated heating element to a heated body
- direct resistance heating is a method in which current is directly applied to an object to be heated
- infrared heating is in which infrared energy is heated in the form of infrared rays.
- a method in which the material is directly charged and heated, and high frequency induction heating is a method in which electric energy is converted into a high frequency and directly heated into the heating material. Any of them may be used for heating, but indirect resistance heating will be described here.
- the heating device may be a batch type clean oven, a heating furnace, a simple oven with a heating space, a hot plate that heats the equipment surface, or a single-wafer walking beam method or a belt conveyor method. You can use it.
- the cells may be directly stacked and processed, or the cells may be stored in a container for processing.
- the number of processed sheets is preferably 1 to 400. A processing number of 400 or less is preferable because it is easy to handle in handling.
- the number of processed sheets is determined by the heat capacity of the cell and the capacity of the heat source, but generally it is preferably 1000 sheets or less.
- the present invention also provides a solar cell manufacturing apparatus suitable for manufacturing the solar cell.
- This solar cell manufacturing apparatus heats a semiconductor silicon substrate having an electrode precursor formed on at least one main surface, and then lowers the temperature to below 100 ° C., thereby firing the electrode precursor to form an electrode on the semiconductor silicon substrate.
- a firing furnace is provided.
- an annealing furnace is provided for annealing the semiconductor silicon substrate processed in the baking furnace at 100 ° C. or higher and 450 ° C. or lower.
- the transfer of the substrate from the firing furnace to the annealing furnace may be performed manually, but the substrate may be automatically moved by mechanically connecting the firing furnace and the annealing furnace. That is, in the above solar cell manufacturing apparatus, the firing furnace and the annealing furnace are mechanically connected, and the semiconductor silicon substrate carried out of the firing furnace can be automatically stored in the annealing furnace.
- a walking beam type or belt conveyor type firing furnace and a walking beam type or belt conveyor type annealing furnace can be used by synchronizing the substrate transfer operation.
- the fired substrate can be temporarily stored in a heat-resistant container, or the substrates can be directly stacked and stored in a batch-type furnace. Is also possible. Regardless of whether the method is manual or automatic, the substrate temperature needs to be lower than 100 ° C. in order to stabilize the handling of the substrate.
- the finger electrode and the bus bar electrode are formed simultaneously.
- the finger electrode and the bus bar electrode may be formed separately. Since it is not necessary to reduce the contact resistance between the bus bar electrode and the substrate, a low temperature curing type conductive paste can be used as the material of the bus bar electrode.
- a low temperature curing type conductive paste can be used as the material of the bus bar electrode.
- one or more kinds of conductive substances selected from Ag, Cu, Au, Al, Zn, In, Sn, Bi, and Pb, and epoxy resin, acrylic resin, polyester resin, phenol resin, and silicone resin What consists of the material containing 1 or more types of resin selected from can be used.
- the above Ag paste is applied by printing or a dispenser and formed (fired) by a fire-through method, and then the paste is used to print or dispense a bus bar electrode by using the paste. Apply and dry the precursor.
- the substrate temperature at the time of forming the bus bar electrode precursor needs to be less than 100 ° C. If this is heated at 100 ° C. or higher and 450 ° C. or lower, not only bus bar electrodes can be formed, but also the effect of preventing deterioration can be obtained.
- the processing method in this case may be a batch type, but if a single wafer type, for example, a walking beam type or a belt conveyor type, is used, the processing becomes smooth.
- the low-temperature annealing for suppressing the deterioration of the solar cell is preferably 0.5 minutes or more and 60 minutes or less as described above, but at the same time when the low temperature curable conductive material is cured, it is 1 minute or more. More preferably, it is more preferably 5 minutes or longer. This is because it becomes easier to cure the low-temperature curable conductive material.
- the temperature of the low-temperature annealing can be further optimized within a range of 100 ° C. or more and 450 ° C. or less, which is a temperature range in which the solar cell deterioration can be suppressed, depending on the type of the low-temperature curable conductive material.
- a P-type diffusion layer is formed on the entire back surface of the substrate by the method described above on the substrate that has been subjected to texture formation as described above.
- the substrate is thermally oxidized, or a silicon nitride film or a silicon oxide film is formed on both sides of the substrate. These films function as a diffusion mask for subsequent phosphorus diffusion.
- the mask formed on the back surface is opened in a pattern.
- the simplest pattern is a parallel line with substantially equal intervals.
- a physical opening may be performed with a laser or a dicer, or a chemical opening may be performed by using an etching paste or a photoresist.
- the P + layer in the opening is etched by dipping in an aqueous solution of KOH or NaOH.
- phosphorus is diffused by the method described above, and an N + layer is formed only in the opening. This is immersed in HF or the like to remove the mask and the glass formed during diffusion.
- the substrate is cleaned and both surfaces are passivated with an aluminum oxide film, a silicon nitride film, or the like.
- Print electrode paste on both PN diffusion layers can be made to follow the pattern of the diffusion layer. That is, it is most convenient to use parallel lines in which the electrodes of the PN are alternately arranged. This is fired to fire through. The conditions are the same as described above.
- bus bar electrodes are formed. Since it is necessary to electrically connect the P bus bar electrode only to the P finger electrode and the N bus bar electrode only to the N finger electrode, the insulating material is printed in a pattern before forming the bus bar electrode. That is, an insulating material is printed at least at the intersection between the P bus bar electrode and the N finger electrode and at the intersection between the N bus bar electrode and the P finger electrode.
- Insulating material contains at least one resin selected from silicone resin, polyimide resin, polyamideimide resin, fluororesin, phenol resin, melamine resin, urea resin, polyurethane, epoxy resin, acrylic resin, polyester resin and poval resin It is preferable that it consists of the material to do.
- the substrate temperature at the time of applying the insulating material needs to be less than 100 ° C.
- this is heated at 100 to 450 ° C. (low temperature annealing).
- the low-temperature annealing time may be 0.5 to 60 minutes, but may be adjusted depending on the type of insulating material.
- the low-temperature annealing time can be set to 1 minute to 100 minutes.
- the temperature of the low-temperature annealing can be further optimized within a range of 100 ° C. or higher and 450 ° C. or lower, which is a temperature range in which the solar cell deterioration can be suppressed, depending on the type of insulating material.
- bus bar electrode is formed using a material as shown above, a high photoelectric conversion efficiency back electrode type solar cell in which deterioration is suppressed can be produced.
- the case of the N-type substrate has been described as an example.
- the case of the P-type substrate it can be realized only by exchanging the P-type and the N-type in the above description.
- the solar cell manufactured by the above method has an electrode formed by firing an electrode precursor on at least one main surface, and a semiconductor silicon substrate having a PN junction and having a PN junction of less than 100 ° C. is not less than 100 ° C. and not less than 450 It is a solar cell that has been annealed at a temperature of 0 ° C. or lower.
- Such a solar cell of the present invention is a solar cell in which the deterioration phenomenon that the output of the solar cell is lowered simply by being left in the room temperature and the atmosphere is suppressed.
- the solar cell of the present invention has an initial short-circuit current value A measured within one day after the annealing treatment, and a short-circuit current value measured after storing the initial short-circuit current for 1 week at room temperature.
- a solar cell that satisfies the relationship B / A ⁇ 0.98 with the value B can be obtained (see FIG. 12).
- the solar cell of the present invention can have the following structure and characteristics. That is, this solar cell includes a semiconductor silicon substrate having a PN junction. Moreover, it has the electrode formed by baking an electrode precursor on the at least one main surface of a semiconductor silicon substrate. Moreover, the initial short-circuit current value A measured within one day after the completion of the solar cell, and the short-circuit current value B measured after storing the initial short-circuit current for one week at room temperature, Satisfies the relationship B / A ⁇ 0.98.
- Such a solar cell of the present invention is a solar cell in which the deterioration phenomenon that the output of the solar cell is lowered simply by being left in the room temperature and the atmosphere is suppressed.
- the solar cell manufactured by the above method can be used for manufacturing a solar cell module.
- FIG. 8 shows an overview of an example of a solar cell module in which a solar cell manufactured by the above method is incorporated. Although the example of the solar cell module which incorporated the back electrode type high photoelectric conversion efficiency solar cell is shown in FIG. 8, it is not restricted to this,
- the solar cell manufactured by the manufacturing method of the solar cell of this invention is a solar cell. Can be used for modules.
- the solar cell 400 manufactured by the above method has a structure in which the solar cell module 460 is tiled.
- FIG. 9 corresponds to a schematic diagram of the back side of the inside of the module which is not normally touched by human eyes. Also, finger electrodes and bus bar electrodes are not shown.
- the P bus bar of the adjacent solar cell 400 (the bus bar electrode connected to the finger electrode joined to the P type layer of the substrate) and the N bus bar (the N type layer of the substrate) are connected by a tab lead wire 461 or the like.
- FIG. 10 shows a schematic cross-sectional view of the solar cell module 460.
- the string is configured by connecting a plurality of solar cells 400 to the bus bar electrode 422 and the lead wires 461.
- the string is usually sealed with a light-transmitting filler 472 such as EVA (ethylene vinyl acetate), the non-light-receiving surface side is a weather-resistant resin film 473 such as PET (polyethylene terephthalate), and the light-receiving surface is soda lime glass.
- the light-receiving surface protective material 471 having high translucency and high mechanical strength is used.
- the filler 472 polyolefin, silicone, or the like can be used in addition to the EVA.
- FIG. 11 shows a basic configuration of a photovoltaic power generation system in which modules of the present invention are connected.
- a plurality of solar cell modules 16 are connected in series by wiring 15 and supply generated power to an external load circuit 18 via an inverter 17.
- the system may further include a secondary battery that stores the generated power.
- a phosphorus-doped ⁇ 100 ⁇ N-type as-cut silicon substrate having a length and width of 156 ⁇ 156 mm, a thickness of 200 ⁇ m, and a specific resistance of 1 ⁇ ⁇ cm was prepared as a semiconductor substrate.
- the damaged layer of the silicon substrate was removed with a heated potassium hydroxide aqueous solution.
- the substrate was dipped in an aqueous solution containing potassium hydroxide and 2-propanol to form a texture on the substrate surface. Then, it was immersed in an aqueous solution of 1% hydrochloric acid and 1% hydrogen peroxide maintained at 80 ° C. for 5 minutes, rinsed with pure water for 5 minutes, and then dried in a clean oven.
- a P-type diffusion layer was formed on the substrate.
- Two substrates were stacked and placed in a heat treatment furnace, a mixed gas of BBr 3 , oxygen and argon was introduced and heat treatment was performed at 1000 ° C. for 10 minutes.
- N-type diffusion layer was formed.
- Two substrates were stacked and placed in a heat treatment furnace, and heat-treated at 900 ° C. for 40 minutes in a mixed gas atmosphere of phosphorus oxychloride, nitrogen and oxygen.
- the glass on the surface was removed with 25% hydrofluoric acid and washed in an aqueous solution of 1% hydrochloric acid and 1% hydrogen peroxide.
- thermal oxidation was performed by treating these silicon substrates at 900 ° C. for 40 minutes in an oxygen atmosphere, and a 20 nm thick thermal oxide film was formed on both surfaces of the substrate.
- an antireflection film or a passivation film made of a silicon nitride film was formed on both surfaces of the thermal oxide film.
- a plasma CVD method was used, and a mixed gas of monosilane and ammonia was used as a reaction gas.
- the film thickness of the light receiving surface was 80 nm and the refractive index was 2.0.
- the film thickness of the non-light-receiving surface was 80 nm and the refractive index was 2.2.
- silver paste was screen-printed with a comb-like pattern on the entire non-light-receiving surface and dried. Thereafter, a silver paste was screen-printed in a comb-like pattern on the light receiving surface and dried.
- the silver paste is obtained by dispersing silver powder in an organic solvent. Heat treatment was performed for about 10 seconds in an air atmosphere at 840 ° C. to sinter silver. In this sintering step, the temperature was decreased from 840 ° C. to 450 ° C. at a temperature decrease rate of 50 ° C./second or more, and further to room temperature (environment temperature).
- Examples 1-1 to 1-6, Comparative Examples 1-1 and 1-2 The substrate was allowed to stand in a belt furnace at 25 ° C. (Comparative Example 1-1), 100 ° C. (Example 1-1), 200 ° C. (Example 1-2), 250 ° C. (Example 1-3), Annealing was performed at 300 ° C. (Example 1-4), 400 ° C. (Example 1-5), 450 ° C. (Example 1-6), and 500 ° C. (Comparative Example 1-2) for 20 minutes.
- Example 2 The substrate was allowed to stand in a belt furnace and annealed at 200 ° C. for 10, 30 seconds, 1, 10, 40, 60 minutes.
- Example 3 The bus bar electrode was formed separately from the finger electrode using a low-temperature curable silver paste. Specifically, after forming the antireflection film / passivation film on the front and back surfaces in the same manner as in Examples 1-1 to 1-6 and Comparative Examples 1-1 and 1-2, a parallel linear pattern was formed on the front and back surfaces. Only the finger electrodes were screen printed and dried. This was heat-treated in an air atmosphere at 840 ° C. for about 10 seconds to sinter silver. In this sintering step, the temperature was decreased from 840 ° C. to 450 ° C. at a temperature decrease rate of 50 ° C./second or more, and further to room temperature (environment temperature). As the bus bar electrode, three epoxy silver pastes were printed on the front and back surfaces, respectively, and dried. The substrate was allowed to stand in a belt furnace and annealed at 200 ° C. for 1, 5, 10, 30, 60 minutes.
- Example 4 The back electrode type solar cell was produced using this application. After producing the boron diffusion in the same manner as in Example 1, thermal oxidation was performed at 1000 ° C. for 3 hours to form a thermal oxide film on both sides. A thermal oxide film was opened in parallel lines at intervals of 1.4 mm on the boron diffusion surface using an etching paste, and immersed in a 25% 70 ° C. aqueous KOH solution for 6 minutes to etch the P + layer in the opening. A phosphorous diffusion / passivation film was formed thereon by the same method as in Example 1. On the non-light-receiving surface, only the finger electrodes having a parallel line pattern with an interval of 0.7 mm along the N + region were screen-printed and dried.
- the temperature was decreased from 840 ° C. to 450 ° C. at a temperature decrease rate of 50 ° C./second or more, and further to room temperature (environment temperature).
- An insulating material intended to insulate the opposite bus bar electrodes was screen printed in a pattern on all finger electrodes at three locations on one finger electrode and dried. Silicone manufactured by Shin-Etsu Chemical Co., Ltd. was used as the insulating material.
- six epoxy-based silver pastes were printed as bus bar electrodes so as to be orthogonal to the existing finger electrodes, dried, and the substrate was allowed to stand in a belt furnace and annealed at 200 ° C. for 30 minutes.
- FIG. 4 summarizes the results of Examples 1-1 to 1-6 and Comparative Examples 1-1 and 1-2.
- the initial conversion efficiency decreases at 500 ° C. This is probably because if the annealing temperature is too high, a defect occurs in the electrode contact.
- the maintenance rate decreases only at 25 ° C. This is because a deterioration phenomenon has occurred. In order to prevent deterioration, the annealing temperature needs to be 100 ° C. or higher.
- FIG. 5 summarizes the results of Example 2.
- the initial characteristics are the same for all conditions.
- the maintenance rate is slightly reduced only for 10 seconds. This is because a deterioration phenomenon has occurred.
- the annealing time is preferably 30 seconds or longer.
- FIG. 6 summarizes the results of Example 3.
- the initial characteristics are low at 1 minute. This is probably because the bus bar electrode material could not be cured.
- the maintenance rates are all the same and no deterioration is observed. Therefore, the effect of preventing deterioration by the low temperature annealing treatment of the present invention is obtained.
- FIG. 7 summarizes the results of Example 4.
- Initial properties are low at 100 ° C and 350 ° C.
- the cause is considered to be insufficient curing of the insulating material. This is probably because oxidation (combustion) of the insulating material has progressed at 350 ° C.
- the maintenance rates are all the same and no deterioration is observed. Therefore, the effect of preventing deterioration by the low temperature annealing treatment of the present invention is obtained.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.
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Abstract
Description
まず、半導体基板として、縦横156×156mm、厚さ200μm、比抵抗1Ω・cmのリンドープ{100}N型アズカットシリコン基板を用意した。次に、加熱した水酸化カリウム水溶液により該シリコン基板のダメージ層を除去した。次に、水酸化カリウムと2-プロパノールを含む水溶液中に浸漬し、基板表面にテクスチャ形成を行った。その後、80℃に保った1%の塩酸と1%の過酸化水素の水溶液中に5分浸漬し、純水で5分リンス後、クリーンオーブンにて乾燥させた。
上記基板をベルト炉内で静置させ25℃(比較例1-1)、100℃(実施例1-1)、200℃(実施例1-2)、250℃(実施例1-3)、300℃(実施例1-4)、400℃(実施例1-5)、450℃(実施例1-6)、500℃(比較例1-2)の各条件で20分間アニールした。
上記基板をベルト炉内で静置させ200℃で10、30秒、1、10、40、60分アニールした。
バスバー電極を低温硬化型銀ペーストを用いて、フィンガー電極と別形成した。具体的には、表裏面の反射防止膜・パッシベーション膜形成まで実施例1-1~1-6、比較例1-1、1-2と同様に作製した後、表裏面に平行線状パターンのフィンガー電極のみをスクリーン印刷し、乾燥した。これを840℃の空気雰囲気下で10秒程度熱処理し、銀を焼結させた。この焼結工程では、840℃から450℃まで50℃/秒以上の降温速度で降温し、さらに室温(環境温度)まで降温した。バスバー電極として、エポキシ系の銀ペーストを、表裏面にそれぞれ3本印刷し乾燥させ、該基板をベルト炉内で静置させ200℃で1、5、10、30、60分アニールした。
本願を用いて裏面電極型太陽電池を作製した。ボロン拡散まで実施例1と同様に作製した後、1000℃3時間の熱酸化を行って両面に熱酸化膜を形成した。ボロン拡散面に対し、エッチングペーストを用いて1.4mm間隔の平行線状に熱酸化膜を開口し、25%70℃のKOH水溶液に6分間浸漬して開口部のP+層をエッチングした。これに実施例1と同じ方法でリン拡散・パッシベーション膜形成を行った。非受光面に、N+領域に沿うように0.7mm間隔の平行線状パターンのフィンガー電極のみをスクリーン印刷し、乾燥した。これを840℃の空気雰囲気下で10秒程度熱処理し、銀を焼結させた。この焼結工程では、840℃から450℃まで50℃/秒以上の降温速度で降温し、さらに室温(環境温度)まで降温した。相反するバスバー電極との絶縁を目的とした絶縁材料を、1本のフィンガー電極に対し3箇所、全フィンガー電極に対しパターン状にスクリーン印刷し乾燥した。絶縁材料は信越化学工業株式会社製のシリコーンを用いた。該基板をベルト炉内で静止させ100、150、200、250、300、350℃の各条件で5分間アニールした。最後にバスバー電極として、エポキシ系の銀ペーストを、既設のフィンガー電極に直交するように6本印刷し乾燥させ、該基板をベルト炉内で静置させ200℃で30分アニールした。
以上のようにして得られた太陽電池のサンプルについて、山下電装株式会社製ソーラーシミュレータを用いてAM1.5スペクトル、照射強度100mW/cm2、25℃の条件下で、電流電圧特性を測定し光電変換効率を求めた。さらに、室温・大気雰囲気中放置して1週間後に同一条件で再測定した。特性の維持率を、1週間後の変換効率を初期の変換効率で除したものとして定義した。すなわち、以下の計算式に従う。
維持率=(1週間後の変換効率)/(初期の変換効率)
得られた結果を、左軸を初期変換効率、右軸を維持率として図4、図5、図6及び図7に示す。
Claims (14)
- 少なくとも一方の主表面上に電極前駆体を焼成することにより形成された電極を有し、PN接合を有する100℃未満の半導体シリコン基板を準備する工程と、
前記半導体シリコン基板を100℃以上450℃以下でアニール処理する工程と
を有することを特徴とする太陽電池の製造方法。 - 前記アニール処理を0.5分以上の時間で行うことを特徴とする請求項1に記載の太陽電池の製造方法。
- 前記電極前駆体の焼成において、最高温度から450℃までの降温速度を50℃/秒以上とすることを特徴とする請求項1又は請求項2に記載の太陽電池の製造方法。
- 前記電極前駆体の焼成における最高温度を500℃以上1100℃以下とすることを特徴とする請求項1から請求項3のいずれか1項に記載の太陽電池の製造方法。
- 前記半導体シリコン基板を準備する工程の後、前記半導体シリコン基板の主表面上に、100℃以上450℃以下の範囲で硬化可能な低温硬化型導電材料をパターン状に塗布し、
その後、前記アニール処理を行う際に、同時に前記低温硬化型導電材料の硬化を行って導電体部を形成することを特徴とする請求項1から請求項4のいずれか1項に記載の太陽電池の製造方法。 - 前記半導体シリコン基板を準備する工程の後、前記半導体シリコン基板の主表面上に、100℃以上450℃以下の範囲で硬化可能な絶縁材料をパターン状に塗布し、
その後、前記アニール処理を行う際に、同時に前記絶縁材料の硬化を行って絶縁膜を形成することを特徴とする請求項1から請求項5のいずれか1項に記載の太陽電池の製造方法。 - 前記半導体シリコン基板をN型半導体シリコン基板とすることを特徴とする請求項1から請求項6のいずれか1項に記載の太陽電池の製造方法。
- 少なくとも一方の主表面上に電極前駆体を焼成することにより形成された電極を有し、PN接合を有する100℃未満の半導体シリコン基板を、100℃以上450℃以下でアニール処理されたものであることを特徴とする太陽電池。
- 請求項8に記載の太陽電池であって、
前記アニール処理がなされた後1日以内に測定した初期の短絡電流の値Aと、該初期の短絡電流を測定してから室温で1週間保管した後に測定した短絡電流の値Bとが、B/A≧0.98の関係を満たすものであることを特徴とする太陽電池。 - 請求項8又は請求項9に記載の太陽電池が内蔵されていることを特徴とする太陽電池モジュール。
- 請求項10に記載の太陽電池モジュールを有することを特徴とする太陽光発電システム。
- 少なくとも一方の主表面上に電極前駆体が形成された半導体シリコン基板を加熱した後100℃未満に降温することにより、前記電極前駆体を焼成して前記半導体シリコン基板上に電極を形成する焼成炉と、
該焼成炉にて処理された半導体シリコン基板を100℃以上450℃以下でアニール処理するアニール炉と
からなることを特徴とする太陽電池製造装置。 - 前記焼成炉と前記アニール炉は機械的に接続され、前記焼成炉から搬出された前記半導体シリコン基板を自動で前記アニール炉に収納するものであることを特徴とする請求項12に記載の太陽電池製造装置。
- PN接合を有する半導体シリコン基板を具備し、前記半導体シリコン基板の少なくとも一方の主表面上に電極前駆体を焼成することにより形成された電極を有する太陽電池であって、
前記太陽電池の完成後1日以内に測定した初期の短絡電流の値Aと、該初期の短絡電流を測定してから室温で1週間保管した後に測定した短絡電流の値Bとが、B/A≧0.98の関係を満たすものであることを特徴とする太陽電池。
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KR102599917B1 (ko) | 2023-11-09 |
TW201814917A (zh) | 2018-04-16 |
EP3333901A1 (en) | 2018-06-13 |
US20180337303A1 (en) | 2018-11-22 |
JPWO2018066016A1 (ja) | 2018-10-04 |
KR20190055818A (ko) | 2019-05-23 |
CN109844960A (zh) | 2019-06-04 |
US20200227584A1 (en) | 2020-07-16 |
CN109844960B (zh) | 2022-11-29 |
EP3333901A4 (en) | 2019-02-27 |
EP3333901B1 (en) | 2020-12-30 |
US11538957B2 (en) | 2022-12-27 |
TWI631717B (zh) | 2018-08-01 |
JP6285612B1 (ja) | 2018-02-28 |
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