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WO2012169602A1 - Substrat comprenant un film conducteur transparent fixé sur celui-ci - Google Patents

Substrat comprenant un film conducteur transparent fixé sur celui-ci Download PDF

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Publication number
WO2012169602A1
WO2012169602A1 PCT/JP2012/064725 JP2012064725W WO2012169602A1 WO 2012169602 A1 WO2012169602 A1 WO 2012169602A1 JP 2012064725 W JP2012064725 W JP 2012064725W WO 2012169602 A1 WO2012169602 A1 WO 2012169602A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide layer
substrate
conductive film
tin oxide
silicon oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/064725
Other languages
English (en)
Japanese (ja)
Inventor
林　英明
高橋　亮
池田　徹
志堂寺　栄治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2012169602A1 publication Critical patent/WO2012169602A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
    • H10F71/1385—Etching transparent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/30—Coatings
    • H10F77/306—Coatings for devices having potential barriers
    • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
    • H10F77/315—Coatings for devices having potential barriers for photovoltaic cells the coatings being antireflective or having enhancing optical properties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/42—Optical elements or arrangements directly associated or integrated with photovoltaic cells, e.g. light-reflecting means or light-concentrating means
    • H10F77/488—Reflecting light-concentrating means, e.g. parabolic mirrors or concentrators using total internal reflection
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H10F77/707—Surface textures, e.g. pyramid structures of the substrates or of layers on substrates, e.g. textured ITO layer on a glass substrate
    • 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
    • Y02E10/52—PV systems with concentrators

Definitions

  • Patent Document 1 includes a discontinuous peak portion (so-called small peak portion) having a bottom surface diameter of 0.2 to 2 ⁇ m formed of a first oxide portion and a second oxide on a glass substrate.
  • This substrate with a transparent conductive film has a structure in which the transparent conductive oxide film has a double textured structure of large irregularities due to the peaks and fine irregularities of the continuous layer. Therefore, according to this board
  • a substrate with a transparent conductive film of the present invention includes a substrate made of glass containing alkali, a titanium oxide layer mainly composed of titanium oxide formed on the substrate, A silicon oxide layer mainly composed of silicon oxide having a thickness of 15 to 40 nm formed on the titanium oxide layer, and a density of 0.3 to 2 / ⁇ m 2 is formed on the silicon oxide layer.
  • the substrate with a transparent conductive film of the present invention having the above-described structure is suitably formed with a tin oxide crest that is a large unevenness in the substrate with a transparent conductive film having a double textured structure having large unevenness and fine unevenness on the surface.
  • This makes it possible to ensure a high haze ratio (light scattering property) over a wide wavelength band from the visible light range to the near infrared light range.
  • haze ratio light scattering property
  • substrate with a transparent conductive film which has the characteristic that a haze rate is 30% or more also in 800 nm can be obtained.
  • substrate 10 with an electrically conductive film of this invention it is not limited for the board
  • a curved shape may be sufficient and an irregular shape may be sufficient.
  • the incident light can be appropriately scattered and incident on the solar cell without reflecting it, and for example, the light use efficiency in the solar cell can be improved.
  • the light reflection preventing performance of the substrate with conductive film 10 can be improved by combining with the silicon oxide layer 16 described later.
  • the method for forming the titanium oxide layer 14 is not particularly limited, and any known forming method (film forming method) can be used. As an example, a method by atmospheric pressure (normal pressure) CVD using vaporized tetraisopropoxy titanium or further nitrogen gas is exemplified. Further, the titanium oxide layer 14 is online in a glass plate manufacturing process such as atmospheric pressure CVD (bus CVD) in a float bath or atmospheric pressure CVD (rare CVD) in a slow cooling furnace in a glass plate manufacturing process by a float method. on-line). Alternatively, after the glass plate is manufactured, it may be formed off-line on the surface of the cut glass plate using a belt conveyor furnace or the like.
  • any known forming method film forming method
  • a method by atmospheric pressure (normal pressure) CVD using vaporized tetraisopropoxy titanium or further nitrogen gas is exemplified.
  • the titanium oxide layer 14 is online in a glass plate manufacturing process such as atmospheric pressure CVD (bus CVD) in a float
  • the diameter of the bottom surface of the peak portion 18 described later means the diameter of the peak portion 18 if it is hemispherical, and in the case of a substantially hemispherical shape, the diameter of a circle having the same area as the area of the bottom surface portion of the substantially hemispherical shape. means.
  • the height of the peak portion 18 is the same as the radius in the case of a hemisphere, and in the case of a substantially hemisphere, it means a hemispheric radius having the same volume as the substantially hemispherical volume.
  • the peak part 18 and the adjacent peak part 18 are not in contact, but are formed discontinuously with a gap.
  • the conductive film-equipped substrate 10 of the present invention has the peak portions 18 scattered on the silicon oxide layer 16 and the intermediate oxide layer 20 thereon.
  • the tin oxide layer 24 is formed on the intermediate oxide layer 20. Further, the tin oxide layer 24 has fine unevenness on the entire surface. Therefore, the tin oxide layer 24 has two types of unevenness, which are greatly different in size, that is, the large unevenness caused by the peak portion 18 and the unevenness finer than the large unevenness on the surface of the tin oxide layer 24 itself, that is, It has a double texture structure.
  • the formation density of the peaks 18 can be controlled by using hydrogen chloride gas in combination with the formation of the peaks 18. Specifically, as the amount of hydrogen chloride supplied at the time of forming the peak 18 increases, the density of the peak 18 decreases.
  • the alkali barrier effect by the silicon oxide layer 16 is further reduced. That is, by forming the silicon oxide layer 16 on the titanium oxide layer 14, the silicon oxide layer 16 has a fine unevenness, and the alkali component deposited from the substrate 12 made of glass containing an alkali component is silicon oxide. It will be easier to slip over the layer 16. As a result, the alkali component of the uppermost surface layer of the silicon oxide layer 16 slightly increases, and the formation density of the peaks 18 can be improved.
  • the titanium oxide layer 14 under the silicon oxide layer 16 the amount of alkali components present on the formation surface when forming the ridges 18, that is, the surface of the silicon oxide layer 16, is increased. Therefore, it is possible to form a high-density mountain portion 18.
  • the present invention has been made by obtaining such knowledge, and has a titanium oxide layer 14 and a silicon oxide layer 16 having a thickness of 15 to 40 nm formed on the surface of the titanium oxide layer 14. With such a configuration, a sufficient amount of an alkaline component is supplied to the surface of the silicon oxide layer 16 when forming the peak portion 18 while ensuring a sufficient alkali barrier action, 18 can be suitably formed. Further, in the present invention, by setting the density of the peaks 18 to 0.3 to 2 / ⁇ m 2 , high light scattering properties are realized not only for visible light but also for light in the near infrared region of about 800 nm. At the same time, the light reflection preventing property is prevented from being adversely affected.
  • the thickness of the titanium oxide layer 14 is not particularly limited.
  • the film thickness of the titanium oxide layer 14 is too thin, the effect of forming the titanium oxide layer 14 cannot be sufficiently exhibited, and the target formability of the peak 18 may not be obtained.
  • the thickness of the titanium oxide layer 14 is too thick, light absorption on the short wavelength side increases and the light use efficiency when used in solar cells and the like is adversely affected, and the antireflection performance is adversely affected. There is a possibility that inconveniences such as not being able to supply a sufficient amount of alkali at the time of forming the ridges 18 may occur.
  • the thickness of the titanium oxide layer 14 is preferably 8 to 12 nm, and particularly preferably 9 to 11 nm.
  • Example 1 A soda-lime glass plate having a size of 330 ⁇ 300 mm and a thickness of 1.1 mm was prepared as the substrate 12. While the substrate 12 is conveyed at a speed of 1 m / min by a belt conveyor furnace, a titanium oxide layer 14, a silicon oxide layer 16, a mountain portion 18, an intermediate oxide layer 20, and a tin oxide layer 24 are sequentially formed. Thus, a substrate 10 with a conductive film as shown in FIG. 1 was produced.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Chemical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention a pour objet de fournir un substrat sur lequel un film conducteur transparent équilibrant une valeur de turbidité élevée et des propriétés empêchant la réflexion de la lumière est fixé grâce à la fourniture d'un substrat sur lequel les éléments suivants sont présents : une couche comprenant de l'oxyde de titane comme principal constituant ; une couche présentant une épaisseur de 10 à 30 nm et comprenant de l'oxyde de silicium comme principal constituant ; des sections en forme de montagnes discontinues comprenant de l'oxyde d'étain ; une couche d'oxyde d'étain permettant de recouvrir la couche comprenant de l'oxyde de silicium comme principal constituant et les sections en forme de montagnes ; et une couche d'oxyde comprenant un oxyde présentant une composition différente de celle de la couche d'oxyde d'étain et positionnée entre la couche d'oxyde d'étain et la couche comprenant un oxyde de silicium comme principal constituant et les sections en forme de montagnes.
PCT/JP2012/064725 2011-06-08 2012-06-07 Substrat comprenant un film conducteur transparent fixé sur celui-ci Ceased WO2012169602A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-128312 2011-06-08
JP2011128312 2011-06-08

Publications (1)

Publication Number Publication Date
WO2012169602A1 true WO2012169602A1 (fr) 2012-12-13

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PCT/JP2012/064725 Ceased WO2012169602A1 (fr) 2011-06-08 2012-06-07 Substrat comprenant un film conducteur transparent fixé sur celui-ci

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JP (1) JPWO2012169602A1 (fr)
TW (1) TW201305084A (fr)
WO (1) WO2012169602A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016017650A1 (fr) * 2014-08-01 2016-02-04 旭硝子株式会社 Substrats de support avec pellicule inorganique ainsi que stratifié de verre, procédé de fabrication de ceux-ci, et procédé de fabrication de dispositif électronique
JPWO2015093029A1 (ja) * 2013-12-17 2017-03-16 日本板硝子株式会社 ガラス板の製造方法及びガラス板
CN112186048A (zh) * 2019-07-05 2021-01-05 Ａｇｃ株式会社 透明电极基板和太阳能电池
EP3925070A4 (fr) * 2019-02-11 2022-04-06 Shkalim, Reuven Panneau supérieur transparent ondulé pour augmenter ou diminuer la collecte de rayonnement solaire et procédés associés

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI556002B (zh) * 2014-08-05 2016-11-01 群創光電股份有限公司 抗反射結構及電子裝置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004102677A1 (fr) * 2003-05-13 2004-11-25 Asahi Glass Company, Limited Substrat conducteur transparent pour batterie solaire et procede de production dudit substrat
WO2005027229A1 (fr) * 2003-08-29 2005-03-24 Asahi Glass Company, Limited Base dotee d'un film conducteur transparent et son procede de production
WO2010016468A1 (fr) * 2008-08-05 2010-02-11 旭硝子株式会社 Substrat à film conducteur transparent et cellule solaire utilisant le substrat
WO2011013775A1 (fr) * 2009-07-30 2011-02-03 旭硝子株式会社 Substrat conducteur transparent pour cellules solaires et cellule solaire
JP2012084843A (ja) * 2010-09-17 2012-04-26 Asahi Glass Co Ltd 透明導電性酸化物膜付き基体、および光電変換素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004102677A1 (fr) * 2003-05-13 2004-11-25 Asahi Glass Company, Limited Substrat conducteur transparent pour batterie solaire et procede de production dudit substrat
WO2005027229A1 (fr) * 2003-08-29 2005-03-24 Asahi Glass Company, Limited Base dotee d'un film conducteur transparent et son procede de production
WO2010016468A1 (fr) * 2008-08-05 2010-02-11 旭硝子株式会社 Substrat à film conducteur transparent et cellule solaire utilisant le substrat
WO2011013775A1 (fr) * 2009-07-30 2011-02-03 旭硝子株式会社 Substrat conducteur transparent pour cellules solaires et cellule solaire
JP2012084843A (ja) * 2010-09-17 2012-04-26 Asahi Glass Co Ltd 透明導電性酸化物膜付き基体、および光電変換素子

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015093029A1 (ja) * 2013-12-17 2017-03-16 日本板硝子株式会社 ガラス板の製造方法及びガラス板
WO2016017650A1 (fr) * 2014-08-01 2016-02-04 旭硝子株式会社 Substrats de support avec pellicule inorganique ainsi que stratifié de verre, procédé de fabrication de ceux-ci, et procédé de fabrication de dispositif électronique
EP3925070A4 (fr) * 2019-02-11 2022-04-06 Shkalim, Reuven Panneau supérieur transparent ondulé pour augmenter ou diminuer la collecte de rayonnement solaire et procédés associés
US12143063B2 (en) 2019-02-11 2024-11-12 Reuven SHKALIM Corrugated transparent top panel for either increasing or decreasing harvesting of solar radiation and methods thereof
CN112186048A (zh) * 2019-07-05 2021-01-05 Ａｇｃ株式会社 透明电极基板和太阳能电池

Also Published As

Publication number Publication date
JPWO2012169602A1 (ja) 2015-02-23
TW201305084A (zh) 2013-02-01

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