WO2014014116A1 - Film de passivation, matériau de revêtement, élément de cellule solaire, et substrat de silicium auquel est fixé un film de passivation - Google Patents

Film de passivation, matériau de revêtement, élément de cellule solaire, et substrat de silicium auquel est fixé un film de passivation Download PDF

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WO2014014116A1
WO2014014116A1 PCT/JP2013/069706 JP2013069706W WO2014014116A1 WO 2014014116 A1 WO2014014116 A1 WO 2014014116A1 JP 2013069706 W JP2013069706 W JP 2013069706W WO 2014014116 A1 WO2014014116 A1 WO 2014014116A1
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oxide
passivation film
silicon substrate
vanadium
passivation
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PCT/JP2013/069706
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English (en)
Japanese (ja)
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服部　孝司
三江子 松村
浩孝 濱村
田中　徹
明博 織田
剛 早坂
敬司 渡邉
真年 森下
吉田　誠人
野尻　剛
倉田　靖
修一郎 足立
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日立化成株式会社
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Priority to CN201380037776.4A priority Critical patent/CN104488087B/zh
Priority to JP2014525900A priority patent/JP6434310B2/ja
Priority to KR20157003336A priority patent/KR20150038021A/ko
Publication of WO2014014116A1 publication Critical patent/WO2014014116A1/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
    • H01L31/0216—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
    • 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
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • 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
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a passivation film, a coating material, a solar cell element, and a silicon substrate with a passivation film.
  • the solar cell element is a photoelectric conversion element that converts solar energy into electric energy, and is expected to be further spread in the future as one of pollution-free and infinite renewable energy.
  • a solar cell element usually includes a p-type semiconductor and an n-type semiconductor, and generates electron-hole pairs inside the semiconductor by absorbing solar energy.
  • the generated electrons are transferred to the n-type semiconductor and the holes (holes) are transferred to the p-type semiconductor, and these are collected by the electrodes, whereby electric energy can be used outside.
  • the solar cell element it is important to increase efficiency so that solar energy can be converted into as much electric energy as possible and output.
  • Charge loss can occur for various reasons. In particular, the generated electrons and holes are recombined, and the charge is lost.
  • a crystalline silicon solar cell element that is currently mainstream uses a p-type silicon substrate 11 having a pyramid structure portion (not shown) for preventing reflection, which is called a texture.
  • the n layer 12 is formed on the back surface, and the p + layer 14 is formed on the back surface.
  • a silicon nitride (SiN) film 13 is provided as a light-receiving surface passivation film on the light-receiving surface side, and a silver collector electrode called a finger electrode 15 is formed.
  • an aluminum electrode 16 that also serves to suppress light transmission on the back surface is formed on the entire surface.
  • the silicon n layer 12 is generally formed by diffusing phosphorus into the silicon substrate 11 from a gas phase or a solid phase.
  • the p + layer 14 on the back surface is formed by applying heat of 700 ° C. or more at the contact portion between the aluminum and the p-type silicon substrate 11 when forming the aluminum electrode 16 on the back surface. Through this step, aluminum diffuses into the silicon substrate 11 to form an alloy, and the p + layer 14 is formed.
  • An electric field derived from a potential difference is formed at the interface between the p-type silicon substrate 11 and the p + layer 14.
  • This electric field generated by the p + layer 14 is mainly generated in the p-type silicon substrate 11, and of the holes and electrons diffused on the back surface, the electrons are reflected inside the p-type silicon substrate 11, and holes are formed. Is selectively passed through the p + layer 14. That is, this action brings about an effect of eliminating electrons and reducing recombination of holes and electrons at the back surface interface of the solar cell element.
  • a conventional solar cell element having such an aluminum alloy layer on the back surface is widely used as a structure of a solar cell element suitable for mass production because it is relatively easy to manufacture.
  • the back surface passivation type solar cell element is inherently present at the interface between the silicon substrate and the passivation film by covering the back surface of the solar cell element with a passivation film. The dangling bond can be terminated. That is, the back surface passivation type solar cell element does not attempt to reduce the carrier recombination rate due to the electric field generated at the p / p + interface, but reduces the density of recombination centers on the back surface itself, and the carrier (hole and hole). To recombine electrons).
  • a passivation film that suppresses the carrier recombination rate by lowering the carrier concentration by an electric field generated by a fixed charge in the passivation film is called a field effect passivation film.
  • a field effect passivation film that can move carriers away from the recombination centers by an electric field is effective.
  • an aluminum oxide film formed by ALD-CVD (Atomic Layer Deposition-Chemical Vapor Deposition) is known.
  • ALD-CVD Advanced Chemical Vapor Deposition
  • a technique using an aluminum oxide sol-gel coating film as a passivation film is known (for example, International Publication No. 2008/137174 pamphlet, JP 2009-194120 A and B). . Hoex, J. Schmidt, P. Pohl, M. C. M. van de Sanden, W. M. M. Kesseles, “Silicon surface passivation by atomic layer deposited Al2O3”, J Appl. Phys, 104, p.44 (2008)).
  • the ALD method has a problem that it is difficult to reduce the cost because the deposition rate is low and high throughput cannot be obtained. Furthermore, after forming the aluminum oxide film, a through hole for making contact with the electrode on the back surface is necessary, and some patterning technique is required.
  • the first problem to be solved by the present invention is to realize a passivation film having a long carrier lifetime and a negative fixed charge at a low cost.
  • a second problem is to provide a coating type material for realizing the formation of the passivation film.
  • a third problem is to realize a low-cost and highly efficient solar cell element using the passivation film at a low cost.
  • a fourth problem is to realize a silicon substrate with a passivation film that extends the carrier lifetime of the silicon substrate and has a negative fixed charge at low cost.
  • a passivation film for use in a solar cell element having a silicon substrate comprising aluminum oxide and at least one oxide of vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
  • the carrier lifetime of the silicon substrate is increased and negative fixed charge is provided. Can do. The reason why the carrier lifetime becomes long is not clear, but one of the reasons may be termination of dangling bonds.
  • ⁇ 2> The passivation film according to ⁇ 1>, wherein a mass ratio of the vanadium group element oxide to the aluminum oxide (vanadium group element oxide / aluminum oxide) is 30/70 to 90/10. This can have a large stable negative fixed charge.
  • ⁇ 3> The passivation film according to ⁇ 1> or ⁇ 2>, in which a total content of the oxide of the vanadium group element and the aluminum oxide is 90% or more.
  • the oxide of the vanadium group element includes any of oxides of two or three kinds of vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide. Any one of ⁇ 1> to ⁇ 3> The passivation film according to claim 1.
  • ⁇ 5> Heat treatment of a coating-type material comprising: a precursor of aluminum oxide; and a precursor of an oxide of at least one vanadium group element selected from the group consisting of a precursor of vanadium oxide and a precursor of tantalum oxide.
  • the coating type material of the present invention for solving the second problem is as follows. ⁇ 6> an aluminum oxide precursor, and at least one vanadium group element oxide precursor selected from the group consisting of a vanadium oxide precursor and a tantalum oxide precursor, and having a silicon substrate A coating type material used for forming a passivation film of a solar cell element.
  • the solar cell element of the present invention for solving the third problem is as follows. ⁇ 7> a p-type silicon substrate; An n-type impurity diffusion layer formed on the first surface side which is the light-receiving surface side of the silicon substrate; A first electrode formed on the impurity diffusion layer; A passivation film formed on the second surface side opposite to the light receiving surface side of the silicon substrate and having an opening; A second electrode formed on the second surface side of the silicon substrate and electrically connected to the second surface side of the silicon substrate through the opening of the passivation film;
  • the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
  • a p-type impurity diffusion layer formed on part or all of the second surface side of the silicon substrate and doped with an impurity at a higher concentration than the silicon substrate,
  • the said passivation film is a solar cell element containing aluminum oxide and the oxide of the at least 1 sort (s) of vanadium group element selected from the group which consists of vanadium oxide and a tantalum oxide.
  • n-type impurity diffusion layer formed on a part or all of the second surface side of the silicon substrate and doped with impurities at a higher concentration than the silicon substrate, The solar cell element according to ⁇ 9>, wherein the second electrode is electrically connected to the n-type impurity diffusion layer through an opening of the passivation film.
  • ⁇ 11> The solar cell element according to any one of ⁇ 7> to ⁇ 10>, wherein a mass ratio of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 30/70 to 90/10 .
  • ⁇ 12> The solar cell element according to any one of ⁇ 7> to ⁇ 11>, wherein the total content of the oxide of the vanadium group element and the aluminum oxide in the passivation film is 90% or more.
  • the oxide of the vanadium group element includes an oxide of two or three vanadium group elements selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide, ⁇ 7> to ⁇ 12>
  • the solar cell element according to any one of the above.
  • the silicon substrate with a passivation film of the present invention for solving the fourth problem is as follows. ⁇ 14> a silicon substrate; The passivation film for a solar cell element according to any one of ⁇ 1> to ⁇ 5> provided on the entire surface or a part of the silicon substrate, A silicon substrate with a passivation film.
  • a passivation film having a long silicon carrier lifetime and a negative fixed charge can be realized at low cost.
  • a coating type material for realizing the formation of the passivation film can be provided.
  • a low-cost and highly efficient solar cell element using the passivation film can be realized.
  • a silicon substrate with a passivation film having a long carrier lifetime and a negative fixed charge can be realized at low cost.
  • the term “process” is not only an independent process, but is included in this term if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
  • the term “layer” includes a configuration of a shape formed in part in addition to a configuration of a shape formed on the entire surface when observed as a plan view.
  • the passivation film of the present embodiment is a passivation film used for a silicon solar cell element, and includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide. It is what was included.
  • the passivation film includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, thereby extending the carrier lifetime of the silicon substrate and negative fixed charge. Can have. Therefore, the passivation film of the present invention can improve the photoelectric conversion efficiency of the silicon solar cell element. Furthermore, since the passivation film of the present invention can be formed using a coating method or a printing method, the film formation process is simple and the film formation throughput is high. As a result, pattern formation is easy and cost reduction can be achieved.
  • the amount of fixed charges possessed by the passivation film can be controlled by changing the composition of the passivation film.
  • the vanadium group element is a Group 5 element in the periodic table, and is an element selected from vanadium, niobium, and tantalum.
  • the passivation film having the function of band bending by the fixed charge in the film [2] is called a field effect passivation film, and it works to prevent recombination by chasing either holes or electrons with the charge.
  • a field effect passivation film In a solar cell element using a normal p-type silicon substrate, electrons are extracted from the light-receiving surface side and holes are extracted from the back surface side among the generated carriers.
  • a field effect passivation film having a negative fixed charge is required in order to drive electrons back to the light receiving surface (for example, JP 2012-33759 A). Publication).
  • the fixed charge of the passivation film can be made negative by using the oxide of the vanadium group element and aluminum oxide in combination, and further, the oxide of the vanadium group element and the aluminum oxide
  • the mass ratio [oxide of vanadium group element / aluminum oxide] is set to 30/70 to 90/10, whereby a large stabilized negative fixed charge is obtained. Tend to be achieved.
  • the passivation film of the present invention can be formed using a coating method or a printing method, the film formation process is simple and the film formation throughput is high. As a result, in the present embodiment, pattern formation is easy and cost reduction can be achieved.
  • the mass ratio of the oxide of vanadium group element to aluminum oxide is preferably 35/65 to 90/10, from the viewpoint that the negative fixed charge can be stabilized, and is preferably 50/50 to 90/10. More preferably.
  • the mass ratio of vanadium group element oxide and aluminum oxide in the passivation film is determined by energy dispersive X-ray spectroscopy (EDX), secondary ion mass spectrometry (SIMS), and high frequency inductively coupled plasma mass spectrometry (ICP-MS). ) Can be measured. Specific measurement conditions are as follows in the case of ICP-MS, for example. Dissolving the passivation film in acid or alkaline aqueous solution, atomizing this solution and introducing it into Ar plasma, measuring the wavelength and intensity by spectroscopically analyzing the light emitted when the excited element returns to the ground state, Element qualification is performed from the obtained wavelength, and quantification is performed from the obtained intensity.
  • EDX energy dispersive X-ray spectroscopy
  • SIMS secondary ion mass spectrometry
  • ICP-MS high frequency inductively coupled plasma mass spectrometry
  • the total content of the vanadium group element oxide and aluminum oxide in the passivation film is preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of maintaining good characteristics.
  • the components other than the oxide of vanadium group elements and aluminum oxide in the passivation film increase, the effect of negative fixed charges increases.
  • components other than vanadium group oxide and aluminum oxide may be contained as organic components from the viewpoint of improving the film quality and adjusting the elastic modulus.
  • the presence of the organic component in the passivation film can be confirmed by elemental analysis and measurement of the FT-IR of the film.
  • vanadium oxide As the oxide of the vanadium group element, it is preferable to select vanadium oxide (V 2 O 5 ) from the viewpoint of obtaining a larger negative fixed charge. Since vanadium oxide has a negative fixed charge larger than that of tantalum oxide, carrier recombination can be more effectively prevented.
  • the passivation film may include two or three vanadium group oxides selected from the group consisting of vanadium oxide, niobium oxide, and tantalum oxide as the vanadium group element oxide.
  • the passivation film is preferably obtained by heat-treating a coating-type material, and can be obtained by forming a coating-type material using a coating method or a printing method, and then removing organic components by heat treatment. More preferred. That is, the passivation film may be obtained as a heat-treated product of a coating type material containing an aluminum oxide precursor and a vanadium group element oxide precursor. Details of the coating type material will be described later.
  • the coating type material of the present embodiment is a coating type material used for a passivation film for a solar cell element having a silicon substrate, and includes a precursor of aluminum oxide, a precursor of vanadium oxide, and a precursor of tantalum oxide. And a precursor of an oxide of at least one vanadium group element selected from the group.
  • a precursor of the oxide of the vanadium group element contained in the coating material a precursor of vanadium oxide (V 2 O 5 ) is selected from the viewpoint of the negative fixed charge of the passivation film formed from the coating material. It is preferable.
  • the coating type material is composed of two or three vanadium group elements selected from the group consisting of vanadium oxide precursors, niobium oxide precursors and tantalum oxide precursors as vanadium group oxide precursors. An oxide precursor may also be included.
  • the aluminum oxide precursor can be used without particular limitation as long as it produces aluminum oxide.
  • As the aluminum oxide precursor it is preferable to use an organic aluminum oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and a chemically stable viewpoint.
  • Examples of the organic aluminum oxide precursor include aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , Kojundo Chemical Laboratory Co., Ltd., SYM-AL04.
  • the precursor of the oxide of the vanadium group element can be used without particular limitation as long as it generates an oxide of the vanadium group element.
  • the vanadium group element oxide precursor is preferably an organic vanadium group oxide oxide precursor from the viewpoint of uniformly dispersing aluminum oxide on the silicon substrate and chemically stable. .
  • organic vanadium oxide precursors examples include vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13), High Purity Chemical Laboratory, V-02 can be mentioned.
  • organic tantalum oxide precursors include tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12), Kojundo Chemical Laboratory, Ta-10-P Can be mentioned.
  • organic niobium oxide precursors examples include niobium (V) ethoxide (structural formula: Nb (OC 2 H 5 ) 5 , molecular weight: 318.21), High Purity Chemical Laboratory, Nb-05. Can be mentioned.
  • a passivation film By forming a coating type material containing an organic vanadium group oxide precursor and an organic aluminum oxide precursor using a coating method or a printing method, and then removing the organic components by a heat treatment, A passivation film can be obtained. Therefore, as a result, a passivation film containing an organic component may be used.
  • the content of the organic component in the passivation film is more preferably less than 10% by mass, still more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
  • the solar cell element (photoelectric conversion device) of the present embodiment has a passivation film (insulating film, protective insulating film) described in the first embodiment in the vicinity of the photoelectric conversion interface of the silicon substrate, that is, aluminum oxide and oxidized It has a film containing at least one oxide of a vanadium group element selected from the group consisting of vanadium and tantalum oxide.
  • a vanadium group element selected from the group consisting of vanadium and tantalum oxide.
  • FIGS. 2 to 5 are sectional views showing first to fourth configuration examples of the solar cell element using a passivation film on the back surface of the present embodiment.
  • silicon substrate crystalline silicon substrate, semiconductor substrate
  • silicon substrate either single crystal silicon or polycrystalline silicon
  • a p-type crystalline silicon substrate or an n-type crystalline silicon substrate may be used.
  • silicon substrate 1 either p-type crystalline silicon or n-type crystalline silicon may be used. From the viewpoint of further exerting the effects of the present invention, p-type crystalline silicon is more suitable.
  • the single crystal silicon or polycrystalline silicon used for the silicon substrate 1 may be any material, but single crystal silicon or polycrystalline silicon having a resistivity of 0.5 ⁇ ⁇ cm to 10 ⁇ ⁇ cm is preferable.
  • n is obtained by doping (adding) a group V element such as phosphorus on the light-receiving surface side (upper side, first surface, surface in the figure) of the p-type silicon substrate 1.
  • a mold diffusion layer 2 is formed.
  • a pn junction is formed between the silicon substrate 1 and the diffusion layer 2.
  • a light receiving surface antireflection film 3 such as a silicon nitride (SiN) film, and a first electrode 5 (light receiving surface side electrode, first surface electrode, upper surface electrode) using silver (Ag) or the like. , Surface electrode) is formed.
  • the light receiving surface antireflection film 3 may also have a function as a light receiving surface passivation film. By using the SiN film, both functions of the light receiving surface antireflection film and the light receiving surface passivation film can be provided.
  • the solar cell element of the present invention may or may not have the light-receiving surface antireflection film 3.
  • the light receiving surface of the solar cell element is preferably formed with a concavo-convex structure (texture structure) in order to reduce the reflectance on the surface, but the solar cell element of the present invention has a texture structure. Even if it does not have.
  • a BSF (Back Surface Field) layer 4 which is a layer doped with a group III element such as aluminum or boron is formed on the back side of the silicon substrate 1 (the lower side, the second side, and the back side in the figure).
  • the solar cell element of the present invention may or may not have the BSF layer 4.
  • Electrodes 6 back surface side electrode, second surface electrode, back surface electrode are formed.
  • the contact region (the surface on the back surface side of the silicon substrate 1 when the BSF layer 4 is not provided) and the second electrode 6 are electrically connected.
  • a passivation film 7 (passivation layer) containing aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide is provided in a portion excluding the opening OA). Is formed.
  • the passivation film 7 of the present invention can have a negative fixed charge. Due to this fixed charge, electrons which are minority carriers among the carriers generated in the silicon substrate 1 by light rebound to the surface side. For this reason, a short circuit current increases and it is anticipated that photoelectric conversion efficiency will improve.
  • the second electrode 6 is formed on the entire surface of the contact region (opening OA) and the passivation film 7.
  • the second electrode 6 is formed only in the region (opening OA).
  • the second electrode 6 may be formed only on the contact region (opening OA) and part of the passivation film 7. Even with the solar cell element having the configuration shown in FIG. 3, the same effect as that of FIG. 2 (first configuration example) can be obtained.
  • the BSF layer 4 is formed only on a part of the back side including the contact region (opening OA portion) with the second electrode 6, and FIG. 2 (first configuration example). Thus, it is not formed on the entire back surface side. Even with the solar cell element having such a configuration (FIG. 4), the same effect as that of FIG. 2 (first configuration example) can be obtained. Further, according to the solar cell element of the third configuration example of FIG. 4, the BSF layer 4, that is, the impurity is doped at a higher concentration than the silicon substrate 1 by doping a group III element such as aluminum or boron. Since the area is small, it is possible to obtain higher photoelectric conversion efficiency than that in FIG. 2 (first configuration example).
  • FIG. 5 a fourth configuration example shown in FIG. 5 will be described.
  • the second electrode 6 is formed on the entire surface of the contact region (opening OA) and the passivation film 7, but in FIG. 5 (fourth configuration example), the contact The second electrode 6 is formed only in the region (opening OA).
  • the second electrode 6 may be formed only on the contact region (opening OA) and part of the passivation film 7. Even with the solar cell element having the configuration shown in FIG. 5, the same effect as that of FIG. 4 (third configuration example) can be obtained.
  • the second electrode 6 when the second electrode 6 is applied by a printing method and baked at a high temperature to form the entire surface on the back side, a convex warpage tends to occur in the temperature lowering process. Such warpage may cause damage to the solar cell element, which may reduce the yield. Further, the problem of warpage increases as the silicon substrate becomes thinner. The cause of this warp is that stress is generated because the second electrode 6 made of metal (for example, aluminum) has a larger thermal expansion coefficient than the silicon substrate, and the shrinkage in the temperature lowering process is correspondingly large.
  • metal for example, aluminum
  • the electrode structure tends to be symmetrical vertically. This is preferable because stress due to the difference in thermal expansion coefficient is not easily generated. However, in that case, it is preferable to provide a separate reflective layer.
  • a texture structure is formed on the surface of the silicon substrate 1 shown in FIG.
  • the texture structure may be formed on both sides of the silicon substrate 1 or only on one side (light receiving side).
  • the damaged layer of the silicon substrate 1 is removed by immersing the silicon substrate 1 in a heated potassium hydroxide or sodium hydroxide solution.
  • a texture structure is formed on both surfaces or one surface (light receiving surface side) of the silicon substrate 1 by immersing in a solution containing potassium hydroxide and isopropyl alcohol as main components.
  • this step may be omitted.
  • a phosphorus diffusion layer (n + layer) is formed as the diffusion layer 2 on the silicon substrate 1 by thermal diffusion of phosphorus oxychloride (POCl 3 ) or the like.
  • the phosphorus diffusion layer can be formed, for example, by applying a coating-type doping material solution containing phosphorus to the silicon substrate 1 and performing heat treatment. After the heat treatment, the phosphorus glass layer formed on the surface is removed with an acid such as hydrofluoric acid, whereby a phosphorus diffusion layer (n + layer) is formed as the diffusion layer 2.
  • the method for forming the phosphorus diffusion layer is not particularly limited.
  • the phosphorus diffusion layer may be formed so that the depth from the surface of the silicon substrate 1 is in the range of 0.2 ⁇ m to 0.5 ⁇ m, and the sheet resistance is in the range of 40 ⁇ / ⁇ (ohm / square) to 100 ⁇ / ⁇ . preferable.
  • a BSF layer 4 on the back surface side is formed by applying a coating-type doping material solution containing boron, aluminum or the like to the back surface side of the silicon substrate 1 and performing heat treatment.
  • a coating-type doping material solution containing boron, aluminum or the like for the application, methods such as screen printing, ink jet, dispensing, spin coating and the like can be used.
  • the BSF layer 4 is formed by removing the layer of boron glass, aluminum or the like formed on the back surface with hydrofluoric acid, hydrochloric acid or the like.
  • the method for forming the BSF layer 4 is not particularly limited.
  • the BSF layer 4 is preferably formed so that the concentration range of boron, aluminum, etc.
  • the solar cell element of the present invention may or may not have the BSF layer 4, this step may be omitted.
  • both the diffusion layer 2 on the light receiving surface and the BSF layer 4 on the back surface are formed using a coating-type doping material solution
  • the above-described doping material solution is applied to both surfaces of the silicon substrate 1 and diffused.
  • the phosphorus diffusion layer (n + layer) and the BSF layer 4 as the layer 2 may be formed in a lump, and then the phosphorus glass, boron glass, etc. formed on the surface may be removed in a lump.
  • a silicon nitride film as the light-receiving surface antireflection film 3 is formed on the diffusion layer 2.
  • the method for forming the light receiving surface antireflection film 3 is not particularly limited.
  • the light-receiving surface antireflection film 3 is preferably formed to have a thickness in the range of 50 to 100 nm and a refractive index in the range of 1.9 to 2.2.
  • the light-receiving surface antireflection film 3 is not limited to a silicon nitride film, and may be a silicon oxide film, an aluminum oxide film, a titanium oxide film, or the like.
  • the surface antireflection film 3 such as a silicon nitride film can be produced by a method such as plasma CVD or thermal CVD, and is preferably produced by plasma CVD that can be formed in a temperature range of 350 ° C. to 500 ° C.
  • the passivation film 7 includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide.
  • an organometallic decomposable coating material from which aluminum oxide can be obtained after firing and a precursor represented by a commercially available organometallic decomposition coating material from which an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide is obtained after firing.
  • a material including a body (passivation material) is applied and heat-treated (fired) (see Embodiment 1).
  • the formation of the passivation film 7 can be performed as follows, for example.
  • the thickness of the passivation film 7 formed by the above method is usually about several tens of nanometers as measured by an ellipsometer.
  • the coating type material is applied to a predetermined pattern including the contact area (opening OA) by a method such as screen printing, offset printing, inkjet printing, or dispenser printing.
  • the above coating type material is pre-baked in the range of 80 ° C. to 180 ° C. after evaporation to evaporate the solvent, and then in a nitrogen atmosphere or in air at 600 ° C. to 1000 ° C. for 30 minutes to 3 hours. It is desirable to perform a degree of heat treatment (annealing) to form a passivation film 7 (oxide film).
  • the opening (contact hole) OA is formed on the BSF layer 4 in a dot shape or a line shape.
  • the passivation film 7 used in the solar cell element has a mass ratio of oxide of vanadium group element to aluminum oxide (oxide of vanadium group element / aluminum oxide) of 30. It is preferably within the range of / 70 to 90/10, more preferably within the range of 35/65 to 90/10, and even more preferably within the range of 50/50 to 90/10. Thereby, the negative fixed charge can be stabilized.
  • the total content of vanadium group element oxide and aluminum oxide is 90% or more.
  • the 1st electrode 5 is formed by forming the paste which has silver (Ag) as a main component on the light-receiving surface antireflection film 3 by screen printing, and performing heat processing (fire through).
  • the shape of the 1st electrode 5 may be arbitrary shapes, for example, may be a well-known shape which consists of a finger electrode and a bus-bar electrode.
  • the 2nd electrode 6 which is an electrode of the back side is formed.
  • the 2nd electrode 6 can be formed by apply
  • the shape of the second electrode 6 is desirably the same shape as the shape of the BSF layer 4, a shape covering the entire back surface, a comb shape, a lattice shape, or the like.
  • the first electrode 5 and the second electrode 6 are printed by first printing pastes for forming the first electrode 5 and the second electrode 6 that are electrodes on the light receiving surface side, and then performing heat treatment (fire-through). The electrodes 6 may be formed together.
  • the BSF layer 4 is formed in a contact portion between the second electrode 6 and the silicon substrate 1 in a self-alignment manner. Is formed.
  • the BSF layer 4 may be separately formed by applying a coating-type doping material solution containing boron, aluminum or the like to the back side of the silicon substrate 1 and then heat-treating it. .
  • the diffusion layer 2 is formed by a layer doped with a group III element such as boron
  • the BSF layer 4 is formed by doping a group V element such as phosphorus.
  • a leakage current flows through a portion where the inversion layer formed at the interface due to the negative fixed charge and the metal on the back surface are in contact with each other, and the conversion efficiency may be difficult to increase.
  • FIG. 6 is a cross-sectional view illustrating a configuration example of a solar cell element using the light-receiving surface passivation film of the present embodiment.
  • the diffusion layer 2 on the light receiving surface side is p-type doped with boron and collects holes on the light receiving surface side and electrons on the back surface side of the generated carriers. Therefore, it is preferable that the passivation film 7 having a negative fixed charge is on the light receiving surface side.
  • An antireflection film made of SiN or the like may be further formed on the passivation film 7 by CVD or the like.
  • the silicon substrate with a passivation film of the present embodiment is composed of a silicon substrate and the passivation film described in the first embodiment provided on the entire surface or part of the silicon substrate, that is, aluminum oxide, vanadium oxide, and tantalum oxide. And a film containing at least one oxide of a vanadium group element selected from the group consisting of:
  • the passivation film includes aluminum oxide and an oxide of at least one vanadium group element selected from the group consisting of vanadium oxide and tantalum oxide, thereby extending the carrier lifetime of the silicon substrate and negative fixed charge.
  • the characteristics (photoelectric conversion efficiency) of the solar cell element can be improved.
  • Example 1 ⁇ When vanadium oxide is used as the oxide of vanadium group element> [Example 1] 3.0 g of a commercially available organometallic thin film coating type material (Co., Ltd., High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass%) from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing) 6.0 g of a commercially available organometallic thin film coating type material [Vitamin Purity Laboratory, V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) is obtained by heat treatment (firing) By mixing, a passivation material (a-1) as a coating type material was prepared.
  • passivation of passivation material (a-1) on one side of a 725 ⁇ m thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) from which a natural oxide film was previously removed with hydrofluoric acid having a concentration of 0.49% by mass It was applied and placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing vanadium oxide and vanadium oxide [vanadium oxide / aluminum oxide 63/37 (mass%)]. It was 51 nm when the film thickness was measured with the ellipsometer. When the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
  • the passivation material (a-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to a heat treatment (firing) at 650 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured with a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the carrier lifetime was 380 ⁇ s.
  • the decrease in carrier lifetime (from 400 ⁇ s to 380 ⁇ s) was within ⁇ 10%, and the decrease in carrier lifetime was small.
  • the passivation film obtained by heat-treating (firing) the passivation material (a-1) showed a certain degree of passivation performance and a negative fixed charge.
  • Example 2 In the same manner as in Example 1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass] %] And a commercially available organic metal thin film coating type material [Vitamin Purity Laboratory, V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) can be obtained by heat treatment is changed in ratio. Then, the passivation materials (a-2) to (a-7) shown in Table 1 were prepared.
  • each of the passivation materials (a-2) to (a-7) was applied to one side of a p-type silicon substrate and heat-treated (fired) to produce a passivation film.
  • the voltage dependence of the capacitance of the obtained passivation film was measured, and the fixed charge density was calculated therefrom.
  • the carrier lifetime was measured using a sample obtained by applying a passivation material on both sides of a p-type silicon substrate and performing heat treatment (firing).
  • the passivation materials (a-2) to (a-7) are all negative after the heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film. It was found that all the passivation films obtained from the passivation materials (a-2) to (a-7) stably show negative fixed charges and can be suitably used as a passivation for a p-type silicon substrate. .
  • Example 3 As a compound for obtaining vanadium oxide (V 2 O 5 ) by heat treatment (firing), commercially available vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13) is 1 0.02 g (0.010 mol) and a compound obtained from aluminum oxide (Al 2 O 3 ) by heat treatment (calcination), commercially available aluminum triisopropoxide (structure: Al (OCH (CH 3 ) 2 ) 3 , A passivation material (b-1) having a concentration of 5% by mass was prepared by dissolving 2.04 g (0.010 mol) of molecular weight: 204.25) in 60 g of cyclohexane.
  • the passivation material (b-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (firing) at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain silicon.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 400 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (sintering) the passivation material (b-1) exhibited a certain degree of passivation performance and a negative fixed charge.
  • Example 4 1.52 g (0.0075 mol) of commercially available vanadium (V) oxytriethoxide (structural formula: VO (OC 2 H 5 ) 3 , molecular weight: 202.13) and commercially available aluminum triisopropoxide (structural formula : Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25), 1.02 g (0.005 mol) and 10 g of novolak resin were dissolved in 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to passivate. Material (b-2) was prepared.
  • the passivation material (b-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 170 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by curing the passivation material (b-2) exhibited a certain degree of passivation performance and a negative fixed charge.
  • tantalum oxide is used as the oxide of vanadium group element>
  • Commercially available organometallic thin film coating type material [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing) and oxidation by heat treatment
  • a commercially available organometallic thin film coating type material [Tapuro Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10 mass%] from which tantalum (Ta 2 O 5 ) can be obtained is mixed at a different ratio, and Passivation materials (c-1) to (c-6) shown in Fig. 2 were prepared.
  • Each of the passivation materials (c-1) to (c-6) is a 725 ⁇ m-thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ) from which the natural oxide film has been removed in advance with hydrofluoric acid having a concentration of 0.49% by mass.
  • (Cm) was spin-coated on one side, placed on a hot plate, and pre-baked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 700 ° C. for 30 minutes in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and tantalum oxide. Using this passivation film, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • each of the passivation materials (c-1) to (c-6) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
  • the passivation materials (c-1) to (c-6) are all negative after heat treatment (firing). Since it showed a fixed charge and a certain carrier lifetime, it was suggested that it functions as a passivation film.
  • Example 6 As a compound from which tantalum oxide (Ta 2 O 5 ) can be obtained by heat treatment (firing), 1.18 g (0.002) of commercially available tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12) is obtained. As a compound from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), commercially available aluminum triisopropoxide (structural formula: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25 2.04 g (0.010 mol) was dissolved in cyclohexane 60 g to prepare a passivation material (d-1) having a concentration of 5% by mass.
  • a passivation material d-1 having a concentration of 5% by mass.
  • passivation of passivation material (d-1) to one side of a 725 ⁇ m thick 8-inch p-type silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) with natural oxide film removed beforehand with hydrofluoric acid at a concentration of 0.49% by mass It was applied and placed on a hot plate and prebaked at 120 ° C. for 3 minutes. Thereafter, heating was performed at 700 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and tantalum oxide. When the film thickness was measured with an ellipsometer, it was 40 nm. As a result of elemental analysis, it was found that Ta / Al / C 75/22/3 (wt%). When the FT-IR of the passivation film was measured, a very few peaks due to alkyl groups were observed in the vicinity of 1200 cm ⁇ 1 .
  • the passivation material (d-1) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 610 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating the passivation material (d-1) showed a certain degree of passivation performance and a negative fixed charge.
  • Example 7 As a compound for obtaining tantalum oxide (Ta 2 O 5 ) by heat treatment (firing), 1.18 g (0.005 mol) of commercially available tantalum (V) methoxide (structural formula: Ta (OCH 3 ) 5 , molecular weight: 336.12) ) And aluminum oxide (Al 2 O 3 ) obtained by heat treatment (firing), a commercially available aluminum triisopropoxide (structure: Al (OCH (CH 3 ) 2 ) 3 , molecular weight: 204.25) 1.02 g (0.005 mol) and 10 g of novolak resin were dissolved in a mixture of 10 g of diethylene glycol monobutyl ether acetate and 10 g of cyclohexane to prepare a passivation material (d-2).
  • the passivation material (d-2) was applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and subjected to heat treatment (baking) at 600 ° C. for 1 hour in a nitrogen atmosphere to obtain silicon.
  • a sample in which both surfaces of the substrate were covered with a passivation film was produced.
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540). As a result, the carrier lifetime was 250 ⁇ s.
  • the same 8-inch p-type silicon substrate was measured by passivation using the iodine passivation method, and the carrier lifetime was 1100 ⁇ s.
  • the passivation film obtained by heat-treating (sintering) the passivation material (d-2) exhibited a certain degree of passivation performance and a negative fixed charge.
  • the passivation film containing aluminum oxide and vanadium oxide and the passivation film containing aluminum oxide and tantalum oxide exhibit negative fixed charges and have an effect of improving the carrier lifetime due to the passivation. It has been found.
  • a passivation film containing aluminum oxide and two or three vanadium group oxides selected from the group consisting of vanadium oxide, niobium oxide and tantalum oxide as oxides of vanadium group elements is examined as follows. did.
  • Example 8 Commercially available organometallic thin film coating material that can be obtained by heat treatment (firing) aluminum oxide (Al 2 O 3 ) [High Purity Chemical Laboratory Co., Ltd., SYM-AL04, concentration 2.3 mass%], heat treatment (firing) Commercially available organic metal thin film coating material (VCO, Ltd., V-02, concentration 2 mass%) from which vanadium oxide (V 2 O 5 ) can be obtained by heat treatment, and tantalum oxide (Ta 2 O 5 ), a commercially available organometallic thin film coating type material [High Purity Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10% by mass] is mixed to form a passivation material (e -1) was prepared (see Table 3).
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
  • aluminum oxide Al 2 O 3
  • heat treatment firing
  • Niobium oxide Nb 2 O
  • VCO high purity chemical research laboratory V-02, concentration 2 mass%
  • vanadium oxide V 2 O 5
  • heat treatment firing
  • e-2 passivation material
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%] from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (firing), heat treatment (firing) Niobium oxide (Nb) by commercially available organometallic thin film coating material [Tapurio Chemical Lab. Ta-10-P, concentration 10% by mass] from which tantalum oxide (Ta 2 O 5 ) can be obtained, and heat treatment (firing) 2 O 5 ), a commercially available organometallic thin film coating material [High Purity Chemical Laboratory Nb-05, concentration 5 mass%] is mixed to form a passivation material (e-3) which is a coating material Was prepared (see Table 3).
  • organometallic thin film coating type material High purity chemical research laboratory SYM-AL04, concentration 2.3 mass%
  • aluminum oxide Al 2 O 3
  • heat treatment firing
  • Tantalum oxide Ti 2 O 5
  • heat treatment Niobium oxide
  • a commercially available organometallic thin film coating type material [Co., Ltd., High Purity Chemical Laboratory Ta-10-P, concentration 10% by mass] and heat treatment (firing).
  • a commercially available organometallic thin film coating type material [High purity chemical research laboratory Nb-05, concentration 5 mass%] was mixed to prepare a passivation material (e-4) as a coating type material (see Table 3). ).
  • each of the passivation materials (e-1) to (e-4) is a 725 ⁇ m thick 8-inch p-type film in which the natural oxide film is previously removed with a hydrofluoric acid having a concentration of 0.49% by mass.
  • a silicon substrate (8 ⁇ ⁇ cm to 12 ⁇ ⁇ cm) was spin-coated on one side, placed on a hot plate, and prebaked at 120 ° C. for 3 minutes. Thereafter, a heat treatment (firing) was performed at 650 ° C. for 1 hour in a nitrogen atmosphere to obtain a passivation film containing aluminum oxide and two or more vanadium group element oxides.
  • each of the passivation materials (e-1) to (e-4) is applied to both sides of an 8-inch p-type silicon substrate, pre-baked, and heat-treated (fired) at 650 ° C. for 1 hour in a nitrogen atmosphere. )
  • the carrier lifetime of this sample was measured by a lifetime measuring device (Kobelco Research Institute, Inc., RTA-540).
  • Example 9 In the same manner as in Example 1, a commercially available organometallic thin film coated material from which aluminum oxide (Al 2 O 3 ) can be obtained by heat treatment (calcination) [High Purity Chemical Laboratory, SYM-AL04, concentration 2.3 mass] %] And a commercially available organic metal thin film coating type material [Vitamin Purity Chemical Laboratory Co., Ltd., V-02, concentration 2 mass%] from which vanadium oxide (V 2 O 5 ) is obtained by heat treatment (firing), or heat treatment Commercially available organic metal thin film coating type material [Tapuro Chemical Laboratory Co., Ltd., Ta-10-P, concentration 10 mass%] from which tantalum oxide (Ta 2 O 5 ) can be obtained by (firing) is applied by coating. Passivation materials (f-1) to (f-8) as mold materials were prepared (see Table 4).
  • each of the passivation materials (f-1) to (f-9) was applied to one side of a p-type silicon substrate, and then heat treatment (firing) was performed to produce a passivation film, Using this, the voltage dependence of the capacitance was measured, and the fixed charge density was calculated therefrom.
  • each of the passivation materials (f-1) to (f-9) was applied to both surfaces of a p-type silicon substrate, and a sample obtained by heat treatment (firing) was used. career lifetime was measured. The results obtained are summarized in Table 4.
  • a passivation film containing aluminum oxide and vanadium oxide and a passivation film containing aluminum oxide and tantalum oxide exhibit a negative fixed charge, and have an effect of improving the carrier lifetime by the passivation.
  • the mass ratio of vanadium oxide to aluminum oxide is 30/70 to 90/10, more preferably 35/65 to 90/10, which improves carrier lifetime and provides a stable negative fixed charge. It is more preferable from the viewpoint of achieving both.
  • the mass ratio of tantalum oxide to aluminum oxide is 30/70 to 90/10, more preferably 35/65 to 90/10, which improves carrier lifetime and provides stable negative fixed charge. It is more preferable from the viewpoint of achieving both.
  • the passivation film elements other than oxides of vanadium group elements in the film (here, vanadium oxide or tantalum oxide) and aluminum oxide are included as organic components from elemental analysis and FT-IR measurement results of the film. It can be seen that the content (mass) of the vanadium group element oxide (here vanadium oxide or tantalum oxide) and aluminum oxide in the passivation film is 90% or more, more preferably 95% or more. Therefore, it tends to maintain better characteristics as a passivation film.
  • a passivation film containing aluminum oxide and an oxide of two or more vanadium group elements exhibits a negative fixed charge and has an effect of improving the carrier lifetime due to passivation.
  • Example 10 Using a single crystal silicon substrate with boron as a dopant as the silicon substrate 1, a solar cell element having the structure shown in FIG. 4 was produced. After the surface of the silicon substrate 1 was textured, a coating type phosphorous diffusion material was applied only to the light receiving surface side, and a diffusion layer 2 (phosphorus diffusion layer) was formed by heat treatment. Thereafter, the coating type phosphorus diffusing material was removed with dilute hydrofluoric acid.
  • a SiN film was formed by plasma CVD on the light receiving surface side as the light receiving surface antireflection film 3.
  • the passivation material (a-1) prepared in Example 1 was applied to the region excluding the contact region (opening OA) on the back surface side of the silicon substrate 1 by an inkjet method.
  • heat treatment was performed to form a passivation film 7 having an opening OA.
  • a sample using the passivation material (c-1) prepared in Example 5 was separately prepared as the passivation film 7.
  • a paste mainly composed of silver was screen-printed on the light-receiving surface antireflection film 3 (SiN film) formed on the light-receiving surface side of the silicon substrate 1 in the shape of predetermined finger electrodes and bus bar electrodes.
  • a paste mainly composed of aluminum was screen-printed on the entire surface.
  • heat treatment fire-through
  • electrodes first electrode 5 and second electrode 6
  • aluminum is diffused into the opening OA on the back surface to form the BSF layer 4.
  • the fire-through process in which the SiN film is not perforated is described.
  • the opening OA is first formed in the SiN film by etching or the like, and then the silver electrode is formed. You can also
  • the passivation film 7 is not formed in the above manufacturing process, an aluminum paste is printed on the entire back surface, the p + layer 14 corresponding to the BSF layer 4 and the electrode 16 corresponding to the second electrode.
  • a solar cell element having the structure of FIG.
  • characteristic evaluation a short circuit current, an open circuit voltage, a fill factor, and conversion efficiency
  • the characteristic evaluation was performed according to JIS-C-8913 (fiscal 2005) and JIS-C-8914 (fiscal 2005). The results are shown in Table 5.
  • the solar cell element having the passivation film of the present invention has both the short-circuit current and the open-circuit voltage increased, and the conversion efficiency (photoelectric conversion efficiency) is maximum as compared with the solar electronic element not having the passivation film. It has been found that the effect of the present invention can be obtained with an improvement of 0.6%.

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Abstract

L'invention concerne un film de passivation qui s'utilise dans un élément de cellule solaire comportant un substrat de silicium, et contient un oxyde d'aluminium et un ou plusieurs types d'oxydes d'éléments du groupe vanadium sélectionnés dans un groupe constitué d'un oxyde de vanadium et d'un oxyde de tantale.
PCT/JP2013/069706 2012-07-19 2013-07-19 Film de passivation, matériau de revêtement, élément de cellule solaire, et substrat de silicium auquel est fixé un film de passivation WO2014014116A1 (fr)

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CN201380037776.4A CN104488087B (zh) 2012-07-19 2013-07-19 钝化膜、涂布型材料、太阳能电池元件及带钝化膜的硅基板
JP2014525900A JP6434310B2 (ja) 2012-07-19 2013-07-19 パッシベーション膜、塗布型材料、太陽電池素子及びパッシベーション膜付シリコン基板
KR20157003336A KR20150038021A (ko) 2012-07-19 2013-07-19 패시베이션 막, 도포형 재료, 태양 전지 소자 및 패시베이션 막이 형성된 실리콘 기판

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