WO2018123687A1 - 太陽電池および太陽電池の製造方法 - Google Patents

太陽電池および太陽電池の製造方法 Download PDF

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Publication number
WO2018123687A1
WO2018123687A1 PCT/JP2017/045304 JP2017045304W WO2018123687A1 WO 2018123687 A1 WO2018123687 A1 WO 2018123687A1 JP 2017045304 W JP2017045304 W JP 2017045304W WO 2018123687 A1 WO2018123687 A1 WO 2018123687A1
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Prior art keywords
finger electrode
fixing bar
insulating film
solar cell
firing
Prior art date
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PCT/JP2017/045304
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English (en)
French (fr)
Japanese (ja)
Inventor
浩一 上迫
傑也 新井
ミエ子 菅原
小林　賢一
秀利 小宮
正五 松井
潤 錦織
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アートビーム有限会社
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Priority to CN201780081471.1A priority Critical patent/CN110268531A/zh
Priority to KR1020197019096A priority patent/KR102227075B1/ko
Publication of WO2018123687A1 publication Critical patent/WO2018123687A1/ja

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/492—Bases or plates or solder therefor
    • H01L23/4924—Bases or plates or solder therefor characterised by the materials
    • 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
    • H01L31/02002—Arrangements for conducting electric current to or from the device in operations
    • 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
    • H01L31/042—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
    • 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
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • 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
    • 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 a region that generates a high electron concentration when light or the like is irradiated on a substrate is formed, an insulating film that transmits light or the like is formed on the region, and electrons are extracted from the region on the insulating film.
  • the present invention relates to a solar cell having a fixed bar in place of a conventional bus bar electrode and a method for manufacturing the solar cell, wherein a finger electrode forming an outlet is formed, and a plurality of finger electrodes are electrically connected to take out electrons to the outside. It is.
  • the vanadate glass which is a conductive glass filed by the present inventors, is used for the bus bar electrode to reduce the resistance value between the connection between the finger electrode and the externally taken out ribbon (lead wire), and the bus bar.
  • There are techniques for reducing the disappearance of electrons collected on electrodes Japanese Patent Application No. 2016-015873, Japanese Patent Application No. 2015-180720).
  • the above-described conventional conductive glass is used for the bus bar electrode to reduce the resistance value between the connection between the finger electrode and the externally extracted ribbon (lead wire), and to reduce the disappearance of the electrons collected on the bus bar electrode.
  • it is still not enough, and it is necessary to reduce the dependence of the baking process of conductive glass on the good and bad, and to improve it further by using general materials to achieve high efficiency. There was a problem that there was.
  • the inventors pay attention to the fact that the upper part of the finger electrode is exposed on the insulating film, and if a strip-like ribbon as an external terminal is directly connected to the exposed upper part of the finger electrode, the resistance component We found a configuration that reduces the leakage of electrons as well as the amount of leakage.
  • the resistance component between the finger electrode and the external terminal is reduced, and the fixing bar is formed by using an inexpensive material instead of an expensive material such as silver or conductive glass, which is a conventional bus bar electrode material.
  • connection terminals can be securely soldered to the back side of the solar cell substrate with a strong and inexpensive material.
  • the present inventors formed a region that generates a high electron concentration when light or the like is irradiated on the substrate, and formed an insulating film that transmits light or the like on the region, and the region on the insulating film
  • a finger electrode containing silver and lead is formed on an insulating film, and a portion of the finger electrode
  • a fixed bar is formed on the insulating film with a part having an allowance as an opening, and then fired, and an insulating film that is a film under the finger electrode is formed by the action of silver and lead contained in the finger electrode at the time of firing.
  • An electrically conductive passage is formed between the region penetrating through the finger electrode, and is firmly fixed to the insulating film by the action of the glass material contained in the fixing bar at the same time during firing. And so that to form a soldering good fixation bar.
  • the glass material is vanadate glass containing any one or more of vanadium and barium and tin and zinc or oxides thereof.
  • the firing is performed at the former temperature which is equal to or higher than the latter among the temperature for firing the finger electrode and the temperature for forming the fixing bar.
  • the firing is performed for 1 second or more and 60 seconds or less.
  • a portion having a margin is an opening
  • a portion having a predetermined width that is less affected by errors in forming the finger electrode and the fixing bar is set as an opening.
  • the opening is equal to or slightly narrower than the contact part of the tip of the ultrasonic soldering iron when the external terminal is ultrasonically soldered on the finger electrode and the fixing bar.
  • the contact part of the contact is not directly touching the insulating film.
  • solder material for soldering the external terminal to the finger electrode and the fixing bar includes at least one of tin, tin oxide, zinc, and zinc oxide.
  • solder material is added with one or more of copper and silver as an additive as required.
  • the external terminals are soldered to the finger electrodes and the fixing bar by ultrasonic soldering.
  • the external terminals are strip-shaped ribbons.
  • aluminum is formed on the entire surface of the back side opposite to the front side where the substrate region, insulating film, finger electrodes, and fixing bar are provided, and external terminals on the back side are soldered or ultrasonically soldered to this. .
  • the external terminals on the back side are fired by forming a fixed bar on the back side of aluminum corresponding to almost the same position as the front side fixed bar or at any position, and soldering the external terminals on the back side Alternatively, ultrasonic soldering is performed.
  • the upper part of the finger electrode is exposed on the oxide film, the upper part of the finger electrode and the strip-shaped ribbon that is the external terminal are electrically connected directly. Therefore, a highly efficient solar cell is obtained.
  • connection terminals can be securely soldered to the back side of the solar cell substrate with a strong and inexpensive material.
  • 1 to 3 show a configuration diagram of one embodiment of the present invention.
  • a nitride film 3 is an insulating film formed on a substrate (wafer) 1.
  • the finger electrode 5 is formed by printing and sintering a paste of silver and lead (lead glass) on the nitride film 3 to break through the nitride film 3 by a known firing and between the high-concentration electron region. An electrically conductive path is formed to take out electrons to the outside (described later).
  • the fixing bar 6 is provided in the present invention, and the finger electrode 5 is an opening, and is firmly fixed to the nitride film 3, and the external terminal (strip-shaped ribbon) is soldered well. This is for reducing leakage of electrons taken out from the finger electrode 5 (described later).
  • the fixed bar area 61 is an area for forming the fixed bar 6 (described later).
  • FIG. 1 shows a partially enlarged schematic diagram of the finger electrode 5 and the fixing bar 6 from the upper side of the wafer.
  • the illustrated rectangular substrate (silicon substrate, wafer) was used for the experiment.
  • a rectangular size of 48 mm was used (the numerical value is one example).
  • the finger electrodes 5 are provided in a large number at a predetermined interval in the lateral direction, and are sintered to form an electrically conductive path between the high concentration electron regions by firing. (It will be described later).
  • the fixed bar region 61 is a region where a fixed bar 6 to be described later is formed with a predetermined width in a direction perpendicular to the finger electrode 5 as indicated by a dotted line in the figure.
  • FIG. 2 shows a partially enlarged schematic example of the finger electrode 5 and the fixing bar 6 from the upper side of the wafer.
  • the fixing bar 6 is formed in the fixing bar region 61 of FIG. 1, and here, as shown in the figure, a plurality of band-like portions having openings of the finger electrodes 5 are provided. is there.
  • a plurality of ones having a width of 2.0 mm, a length of 1.2 mm, and an opening with the finger electrode 5 of about 0.5 mm are provided.
  • the fixing bar 6 is formed by screen printing, and then sintered to firmly adhere to the nitride film 3 and improve soldering (described later).
  • FIG. 3 shows an enlarged schematic sectional view of the finger electrode 5 and the fixing bar 6 from the side surface of the wafer.
  • the finger electrode 5 is screen-printed and sintered, penetrates the underlying nitride film 3 by firing and forms an electrically conductive path with the lower high-concentration electron region as shown in the figure.
  • a protrusion of about 40 nm is normally formed as an upper part (head) in the upward direction (described later).
  • the fixing bar 6 is employed in the present invention, and is screen-printed with a paste containing vanadate glass and melted by simultaneous heating at the time of sintering of the finger electrode 5 to firmly adhere to the nitride film 3 And the surface is formed so as to be easily soldered (described later).
  • the fixing bar 6 is desirably highly electrically insulating, because electrons flowing through the ribbon do not leak to the substrate or the like.
  • the fixing bar 6 is adjusted so as to be formed at a height (about 20 nm here) lower than the height (about 40 nm here) of the upper part (head) of the finger electrode 5 as shown in the drawing (screen printing). It is desirable to adjust the concentration of the paste containing the vanadate glass at the time).
  • the ribbon 7 shown in the figure preferably ultrasonic soldering
  • it is completely soldered so as to cover the upper part (head) of the finger electrode 5 to reduce contact resistance and mechanical strength. It is possible to strengthen (so that the ribbon 7 does not peel when pulled).
  • the lower limit is that the solder slope shown in FIG. 3 is not too steep and is within the screen printing overlay accuracy so that the solder material is not cut (determined by experiment).
  • the upper limit of the width between the finger electrode 5 and the fixed bar 6 is the ribbon width (the width of the fixed bar 6).
  • the lower limit is about 0.8, the upper limit.
  • ultrasonic soldering is about 2W. If it is too large, the N + emitter (high-concentration electron region) is damaged. If it is small, solder adhesion cannot be obtained (the solder adhesion is defined to be 0.2 N or more, and in the present invention, 0.5 N or more). Therefore, the optimum W number is determined by experiment (ultrasonic soldering iron (trowel (It depends on the length, width, etc.)
  • the requirement for soldering the fixing bar 6 and the finger electrode 5 and the ribbon (external terminal) is that the adhesiveness between the finger electrode 5 (silver) and the fixing bar 6 (vanadate glass) needs to be good. is there.
  • solder material suitable for it an alloy of tin and zinc, an alloy of tin and copper, an alloy of tin and silver, etc. are used.
  • the ultrasonic output when ultrasonically soldering the ribbon (pre-soldered) to the fixing bar 6 and the finger electrode 5 is preferably about 2 W as described above. Ultrasonic soldering does not require higher temperatures than necessary. Moreover, it is not necessary to raise the temperature of the useless part outside the soldering area, and performance degradation due to useless surrounding temperature rise can be prevented.
  • the ribbon (external terminal) is a wire made of copper at the center, and the outside is covered with a solder material (pre-soldered).
  • the entire back side of the substrate is coated with aluminum, so that the ribbon is ultrasonically soldered directly or after being formed in the same manner as the fixing bar 6 described above.
  • the formation of the fixing bar 6 is, in the experiment, -Using a paste mainly composed of vanadate glass, it was formed by screen printing and sintering.
  • Material examples Glass paste of vanadium, barium, (tin or zinc, or both (or oxides thereof)).
  • the requirements for forming the fixing bar 6 are: (1) Good adhesion to the solder material used (2) Good electrical insulation (3) Material, screen printing thickness, sintering temperature, etc. so as to satisfy good adhesion to the nitride film 3 Is determined experimentally.
  • S1 prepares a Si substrate (tetravalent). This prepares a wafer to be a solar cell substrate (tetravalent).
  • S2 creates a P-type (trivalent) substrate 1. This is to form P-type (trivalent) by diffusing boron or the like into the Si substrate (tetravalent) of S1.
  • N + type a high concentration electron region
  • S4 forms the nitride film 3 on the N + region (high electron concentration region) on the front side of the substrate 1.
  • the nitride film 3 is usually about 60 nm. As a result, the N + region (high electron concentration region) is protected by the nitride film 3.
  • an aluminum film 4 is formed on the back side of the substrate 1 by vapor deposition, sputtering, or the like.
  • the aluminum film 4 is a portion that becomes an electrode on the back side of the solar cell.
  • S5 prints finger electrodes.
  • the shape of the finger electrode 5 in FIGS. 1 to 3 described above is screen-printed using a paste made of silver or lead glass.
  • S6 performs solvent blowing. This is performed by heating at 100 to 120 ° C. for about 1 hour to completely remove the solvent contained in the screen-printed paste.
  • the fixed bar 6 is printed.
  • the shape of the fixing bar 6 in FIGS. 1 to 3 described above is screen-printed using a paste containing vanadate glass.
  • S8 performs solvent removal of the fixing bar. This is performed by heating at 100 to 120 ° C. for about 1 hour to completely remove the solvent contained in the screen-printed paste.
  • S9 performs firing.
  • firing is performed under conditions that cause fire-through of the finger electrode 5.
  • the finger electrode 5 is screen-printed on the nitride film 3 using a paste made of silver or lead glass (silver / lead glass paste) in S5 and S6, and similarly not overlapped in S7 and S8.
  • the fixing bar 6 is screen-printed on the nitride film 3 using a paste containing vanadate glass (vanadate glass paste)
  • both are simultaneously fired (heated).
  • the firing conditions include the former (fire through with silver / lead glass paste) firing temperature and the latter (dissolution / adhesion of vanadate glass paste) temperature (a kind of brazing temperature).
  • the former is higher than or equal to the latter.
  • the former firing temperature fire-through firing temperature
  • baking is performed in a range of 750 ° C. to 850 ° C. for 1 to 60 seconds (heating is performed using a far-infrared lamp, and optimum conditions are determined by experiment).
  • pre-soldering is performed.
  • the solder material is pre-soldered with ultrasonic soldering iron from above the finger electrode 5 and the fixing bar 6 fired in S9.
  • S11 performs ribbon attachment.
  • the ribbon is soldered from the pre-soldering in S10 (refer to the description of FIG. 3 for details). Note that ultrasonic soldering may be performed directly on the finger electrode 5 and the fixing bar 6 using a pre-soldered ribbon.
  • the ribbon on the back side is attached.
  • a ribbon is ultrasonically soldered to the aluminum film 4 formed on the back side of the substrate 1 in S4 of FIG.
  • the pre-soldered ribbon may be ultrasonically soldered directly to the aluminum film 4 of S4 in the figure, or, like the fixing bar 6, the fixing bar on the back side having an opening is screen-printed. After firing and firmly fixing, both the ribbon, the fixing bar and the aluminum film 4 may be ultrasonically soldered to increase the strength.
  • FIG. 8 shows a specific example of the present invention and a conventional example.
  • FIG. 8 (a) shows a photograph of an example of the split type of the present invention. This shows an example (referred to as a split type) in which the fixed bar 6 is separated from the finger electrode 5 and the fixed bar 6 is divided in the length direction.
  • FIG. 8B shows a photograph of an example of the touch bar type of the present invention. This shows an example in which the fixing bar 6 is in contact with the finger electrode 5 and the fixing bar 6 is divided in the length direction (referred to as a touch bar type).
  • the touch bar type of FIG. 8B is used when the accuracy (positioning, etc.) of the fixed bar 6 during screen printing and the accuracy (positioning, etc.) of the finger electrode 5 during screen printing are large. It is preferable to select the split side in FIG. 8A so that the accuracy error is not affected.
  • the tip is slightly smaller than the tip size (length direction) when ultrasonic soldering, as described above. As a result, it is possible to prevent a situation such as contact with the underlying nitride film 3 and destroying it, so that good soldering can be performed.
  • FIG. 8 shows an example in which a finger electrode is present under a conventional bus bar electrode.
  • the strip-shaped bus bar electrode is formed by screen-printing and baking a paste containing silver and lead glass so as to be orthogonal to the finger electrode, so that the finger electrode protrudes above the bus bar electrode. It is not possible to solder the ribbon directly to the finger electrode of the present invention, and as a result, the electrons are taken out via the finger electrode-bus bar electrode-ribbon, so the resistance of the path cannot be reduced, resulting in As a disadvantage, the efficiency of the solar cell is reduced.
  • FIG. 1 is a configuration diagram of one embodiment of the present invention (partially enlarged schematic diagram of finger electrodes 5 and fixing bars 6 from the upper side of a wafer).
  • FIG. 1 is a configuration diagram of an embodiment of the present invention (an example of an enlarged schematic cross-sectional view of a portion of a finger electrode 5 and a fixing bar 6 from a side surface of a wafer). It is the process flow (the 1) of this invention. It is the process flow (the 2) of this invention. It is the process flow (the 3) of this invention. It is the process flow (the 4) of this invention. It is the specific example of this invention, and a prior art example.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
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PCT/JP2017/045304 2016-12-30 2017-12-18 太陽電池および太陽電池の製造方法 WO2018123687A1 (ja)

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CN201780081471.1A CN110268531A (zh) 2016-12-30 2017-12-18 太阳能电池及太阳能电池的制造方法
KR1020197019096A KR102227075B1 (ko) 2016-12-30 2017-12-18 태양전지 및 태양전지의 제조방법

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JP2016257471A JP2018110178A (ja) 2016-12-30 2016-12-30 太陽電池および太陽電池の製造方法

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