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WO2001047033A1 - Transducteur photoelectrique et substrat pour transducteur photoelectrique - Google Patents

Transducteur photoelectrique et substrat pour transducteur photoelectrique Download PDF

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Publication number
WO2001047033A1
WO2001047033A1 PCT/JP2000/009056 JP0009056W WO0147033A1 WO 2001047033 A1 WO2001047033 A1 WO 2001047033A1 JP 0009056 W JP0009056 W JP 0009056W WO 0147033 A1 WO0147033 A1 WO 0147033A1
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WO
WIPO (PCT)
Prior art keywords
film
fine particles
photoelectric conversion
substrate
silica fine
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
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PCT/JP2000/009056
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English (en)
Japanese (ja)
Inventor
Tsuyoshi Otani
Toshifumi Tsujino
Yasunori Seto
Masahiro Hirata
Katsuhiko Kinugawa
Tetsuro Kawahara
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Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
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Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Publication of WO2001047033A1 publication Critical patent/WO2001047033A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/365—Coating different sides of a glass substrate

Definitions

  • the present invention relates to a substrate used for a photoelectric conversion device such as a solar cell panel. Further, the present invention relates to a photoelectric conversion device using the substrate.
  • photoelectric conversion devices generally used include a “thin film type” using amorphous silicon for the photoelectric conversion layer and a “crystal type” using silicon crystal.
  • Thin-film type photoelectric conversion devices consist of a transparent conductive film such as tin oxide, zinc oxide or tin-doped indium oxide (IT ⁇ ) on one main surface of a transparent substrate such as a glass plate or a resin sheet, and an amorphous A photoelectric conversion layer made of silicon is further added to aluminum, silver, or zinc oxide.
  • the crystal-type photoelectric conversion device has a structure in which a photoelectric conversion element composed of a single-crystal silicon / polycrystalline silicon wafer is sandwiched between two substrates and sealed.
  • the substrate on the light incident side must be transparent, and a glass plate is usually used (hereinafter, this transparent substrate is referred to as “cover glass”).
  • Tin oxide films formed by methods involving thermal decomposition and oxidation of raw materials such as chemical vapor deposition (CVD)
  • CVD chemical vapor deposition
  • transparent conductive films are frequently used as transparent conductive films in thin-film photoelectric conversion devices.
  • CVD chemical vapor deposition
  • a base film is provided to prevent the components from diffusing into the transparent conductive film and lowering the electrical conductivity of the transparent conductive film (increase in resistance).
  • a transparent thin film made of silica (Si ⁇ , etc.) is preferably used for the underlayer.
  • the transparent conductive film has a high transmittance (the photoelectric conversion layer More light), lower resistance (less loss when extracting the generated current), and contribution to light confinement in the photoelectric conversion layer.
  • a technique that can contribute to confinement there is known a method of forming irregularities of an appropriate size on the surface of a transparent conductive film (Japanese Patent Application Laid-Open No. 58-57756).
  • the photoelectric conversion rate of the thin-film photoelectric conversion device can be increased.
  • an anti-reflection film on a surface opposite to one main surface of the transparent substrate on which the transparent conductive film is formed, more light can be introduced into the photoelectric conversion layer.
  • a reflection suppressing film a single-layer film having a refractive index distribution is known.
  • a film containing silica fine particles having a particle size of 50 nm is formed on a glass surface by a sol-gel method.
  • the following literature5 shows that the solar transmittance is improved (2nd international Conierence on Coatiners on Glass, 1999, Elsevier Science, ISBN: 0-444-50247-5'255-260). Since high transmittance is naturally required for the antireflection film, fine particles having a relatively small particle size and uniform particle size as described in the above-mentioned literature have been used.
  • crystalline silicon such as microcrystal or polycrystal for the photoelectric conversion layer has attracted attention as a technique for dramatically increasing the photoelectric conversion rate of a thin film photoelectric conversion device.
  • the above transparent group The technology to increase the transmissivity by forming an anti-reflection film on one main surface of the body has a well-established feeling, as long as there is no fundamental component change such as using new materials that have never existed before However, it is considered difficult to expect effects beyond those shown in the above literature.
  • the present invention has been made in view of the above problems. Its purpose is to suppress more light to the photoelectric conversion layer and to suppress light confinement in the photoelectric conversion layer without depending on surface irregularities of the transparent conductive film. Another object of the present invention is to provide a substrate for a photoelectric conversion device including the same. Another object of the present invention is to provide a thin-film photoelectric conversion device having a photoelectric conversion layer made of crystalline silicon by using this substrate and having extremely high photoelectric conversion efficiency.
  • the present invention provides a substrate for a photoelectric conversion device in which a reflection suppressing film containing fine particles mainly composed of silica having a particle diameter of 30 O nm or less is formed on the main surface of a transparent substrate.
  • the particle size of the fine particles is from 300 to 60 O nm. It is suitable.
  • the antireflection film contains fine particles mainly composed of silica having a different particle diameter from fine particles mainly composed of silica having a particle diameter of 300 nm or more.
  • the particle diameter of fine particles mainly composed of silica having different particle diameters is preferably 50 to: I 50 nm.
  • the fine particles exist in a region of 60% or more of the main surface of the transparent substrate.
  • a transparent conductive film having a haze ratio of 10% or less may be formed on a surface opposite to the main surface of the transparent substrate.
  • FIG. 1 is a cross-sectional view of one embodiment of the substrate for a photoelectric conversion device of the present invention.
  • FIG. 2 is a schematic view showing an apparatus for producing a glass plate and a transparent conductive film.
  • FIG. 3 is an example of a diffusion transmission spectrum of a tin oxide film.
  • FIG. 4 is an example of the diffusion transmission spectrum of the photoelectric conversion device substrates of Examples 1 to 3.
  • FIG. 5 is a diagram illustrating a state in which the surface of the antireflection film manufactured in Example 2 is observed by SEM.
  • FIG. 1 is a cross-sectional view of one embodiment of the present invention.
  • an underlayer film 1 and a transparent conductive film 2 mainly composed of tin oxide are formed in this order on one main surface of a transparent substrate 5, and silica is mainly formed on the opposing surface.
  • An antireflection film 6 composed of fine particles (hereinafter referred to as “silicone fine particles”) and a binder (not shown) is formed.
  • silica fine particles 7 and 8 are formed on the surface of the antireflection film 6.
  • the antireflection film contains silica fine particles and a binder, and a void is formed between the fine particles. Due to the voids formed inside the film, the substantial refractive index of the antireflection film decreases. A decrease in the refractive index of the anti-reflection film is preferable from the viewpoint of improving the anti-reflection effect.
  • silica fine particles examples include silica fine particles synthesized by reacting silicon alkoxide with a basic catalyst such as ammonia by a sol-gel method, colloidal silica made from sodium gayate, etc., or fume synthesized in the gas phase. Dosilica or the like can be used. In order to improve the dispersibility of the raw material, the silica fine particles may contain a trace component other than silica.
  • the optical properties of the antireflection film depend on the particle size of the silica fine particles and the area ratio of the silica fine particles occupying the surface of the transparent substrate.
  • the particle size of the silica fine particles is accurately determined by measurement using a transmission electron microscope.
  • the average particle size of the individual particles that is, the average primary particle size, not the agglomerated particles (for example, secondary particles connected in a chain) is defined as the particle size.
  • the area ratio of the silica fine particles occupying the substrate surface can be determined by observation using a scanning electron microscope (SEM). If SEM is used, the approximate particle size can also be evaluated.
  • SEM scanning electron microscope
  • the reflectance of the anti-reflection film obtained by arranging the spherical fine particles on the substrate surface such that the center of the fine particles is arranged in a grid pattern is considered as follows, and is obtained. Assuming that the diameter of the silica fine particles is the film thickness, air occupies about half of the volume of the antireflection film.
  • the refractive index of silica is 1.45, Since the refractive index of air is 1.00, the refractive index of such an anti-reflection film is a substance having a refractive index of n1 and a volume of V1, and a substance having a refractive index of n2 and a volume of V2. Is calculated by the following equation which gives the refractive index n of the substance obtained by mixing That is,
  • V V 1 + V 2
  • the refractive index of the antireflection film made of the fine particles of silicic acid is calculated to be 1.22.
  • the refractive index calculated based on this formula is referred to as “apparent refractive index”.
  • the reflectance of the antireflection film is minimal when the following condition is satisfied between the refractive index of the antireflection film and the wavelength of the incident light.
  • ⁇ ⁇ d is called “optical thickness” of the antireflection film. Since the optical thickness is a component of the refractive index (apparent refractive index) of the antireflection film, its physical thickness d is smaller than the optical thickness. Therefore, in order to minimize the reflectance near the wavelength of 600 nm, at which the sensitivity of amorphous silicon becomes maximum, the thickness of the antireflection coating with the apparent refractive index of 1.2 d is about 120 nm. In addition, since the photoelectric conversion layer made of amorphous silicon or crystalline silicon has a wide absorption band from visible light to near-infrared light, the preferred particle size of the silica fine particles is 50% when calculated according to the above equation.
  • silica fine particles used in the reflection suppressing film of the photoelectric conversion device have a particle size of 50 to 15 O nm.
  • the present inventors have investigated the relationship between the particle size of the silicic acid fine particles and light scattering in the antireflection film, and found that when the particle size exceeds 20 O nm, the photoelectric conversion rate starts to increase, and 30 O nm From the vicinity, it was found that the change became remarkable.
  • Accordance particle diameter of the silica fine particles increases as this, where n the degree physician light scattering is increased, the haze ratio is the number of fingers indicating the ratio of scattered transmitted light, larger the value Indicates that transmitted light is scattered.
  • Photoelectric It is generally believed that the more scattered light introduced into the conversion layer, the more effective it is in confining light. Therefore, focusing on light confinement, it seems that the larger the particle size of the silica fine particles, the better.
  • the particle size exceeds 1 m the adhesion between the silica fine particles and the transparent substrate is reduced, so that the durability of the antireflection film is reduced.
  • the particle size of the silica fine particles should be 200 to 100 O in consideration of light confinement and durability. nm force Considered reasonable. Further, considering the light scattering by the above-described antireflection film and the adhesiveness between the silica fine particles and the transparent substrate from the viewpoint of practicality, the particle size of the silica fine particles is from 300 to 600 nm. Seems appropriate. As described above, the optical function exerted by the anti-reflection film changes depending on the particle size of the silica fine particles.
  • the anti-reflection having various optical characteristics can be obtained. It is believed that a film is obtained. For example, when the above-described silica fine particles having a particle diameter of 300 to 60 O nm and silica fine particles having a particle diameter of 50 to 15 O nm are combined, light scattering is generated and the reflectance is too low. It is expected that not high films will be obtained. However, this antireflection film exerts more functions than the above-mentioned combination of the functions of the fine particles of each particle diameter. In other words, the combination of the two types of silica microparticles is thought to produce only an effect that compromises the respective functions, but the experimental results disappointed.
  • the haze ratio of the antireflection film shows an intermediate value of that of only silica fine particles of each particle size.
  • the photoelectric conversion rate is higher than that of only particles of each particle size. The reason why such a result is obtained is not necessarily clear, but the present inventors speculate as follows. That is, when fine particles having different particle sizes are mixed, the larger fine particles are dispersed and scattered on the transparent substrate, and a gap is formed between the fine particles. Occurs.
  • the same effect can be obtained by using silica fine particles with a wide particle size distribution, or by laminating the anti-reflection film with a thicker silica fine particle. It is thought to be played.
  • silica fine particles having a wide particle size distribution are used, the number of fine particles satisfying the relationship between the reflectance and the wavelength decreases, so that the reflectance of the antireflection film increases, and the amount of light incident on the photoelectric conversion layer decreases. Eventually, the photoelectric conversion rate decreases. From this, it is considered that the silica fine particles preferably have a uniform particle size as much as possible.
  • the silica fine particles have a particle size of 30 O nm, those having a particle size distribution of about ⁇ 10% are commercially available.
  • the thickness of the anti-reflection film is increased to deposit the fine particles, the strength of the anti-reflection film decreases, and the durability of the anti-reflection film does not reach a practical level. It is conceivable to increase the amount of binder in the anti-reflection coating to increase its strength, but this causes a new problem that the gap between fine particles becomes smaller and the apparent refractive index rises. From these facts, it is considered that the thickness of the antireflection film is preferably 1 to 2 times the particle size of the large fine particles.
  • the particle diameter ratio of each fine particle is preferably 3 or more. If the particle size ratio is 3 or more, small fine particles can enter the gaps between the large fine particles.
  • silica fine particles of less than SO nrn induce an increase in reflectance, and silica fine particles of more than 100 O nm have poor adhesion to the transparent substrate, and the durability of the antireflection film is low. Lower. Therefore, this particle size ratio is preferably Is preferably 20 or less, that is, 3 to 20.
  • the type of transparent substrate is not particularly limited, and various types of transparent substrates such as a glass plate and a resin plate conventionally used as a transparent substrate of a photoelectric conversion device can be used.
  • the binder improves the adhesion between the silica fine particles and between the silica fine particles and the transparent substrate.
  • the binder is preferably at least one metal oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide and tantalum oxide.
  • An alkoxide containing at least one metal selected from Si, Al, Ti, Zr, and Ta is preferable as a material for the binder from the viewpoint of film strength and chemical stability.
  • the refractive index of the binder affects the reflectance. Therefore, a silicon alkoxide having a small refractive index, particularly a silicon tetraalkoxide or an oligomer thereof is preferable as the raw material.
  • metal alkoxides may be used as the raw material of the binder, and even if other than metal alkoxides, M (OH) n (M is a metal atom, n is determined based on the valence of the metal by hydrolysis)
  • the metal compound is not particularly limited as long as it is a metal compound from which a reaction product represented by a natural number, for example, 1 to 4) is obtained. Examples of such metal compounds include metal halides and metal compounds having an isocyanate group, an acyloxy group, an aminoxy group, and the like.
  • the anti-reflection film is formed, for example, by applying a coating solution containing silica fine particles and a metal compound such as a metal alkoxide to the surface of the substrate and baking the coating solution. At this time, the weight ratio between the silica fine particles and the binder is preferably in the range of 50:50 to 85:15.
  • the ratio of the binder is too large, the fine particles are buried in the binder, and the unevenness due to the fine particles and the porosity in the film are reduced. On the other hand, if the ratio of the binder is too small, the adhesiveness between the transparent substrate and the fine particles and between the fine particles is reduced.
  • the coating liquid may be prepared by mixing a hydrolyzate of a metal compound with fine particles of silica, but is preferably prepared by hydrolyzing a hydrolyzable metal compound in the presence of fine silica particles. . This is because the film strength is significantly improved. For example, when a metal alkoxide is hydrolyzed in the presence of silica fine particles, a condensation reaction between silanol groups on the surface of the silica fine particles and the metal alkoxide is promoted in the coating solution. This condensation reaction not only enhances the adhesion between the silica fine particles, but also enhances the reactivity of the surface of the silica fine particles to enhance the adhesive force between the fine particles and the glass substrate.
  • the coating liquid is prepared by mixing a hydrolyzable metal compound, a hydrolysis catalyst, water and a solvent, preferably in the presence of silica fine particles, and hydrolyzing the metal compound.
  • the hydrolysis can be carried out, for example, by stirring the mixture at room temperature for 1 hour or more to carry out the reaction, or by stirring the mixture at a temperature higher than room temperature, for example, 40 to 80 minutes for 10 to 50 minutes.
  • the obtained coating solution may be diluted with an appropriate solvent according to the coating method.
  • Hydrolysis catalysts include mineral acids such as hydrochloric acid and nitric acid and acid catalysts such as acetic acid. Is preferred. When an acid catalyst is used, the metal alkoxide reacts easily to form M (OR) n, thereby providing abundant reaction products that effectively act as a binder. With basic catalysts, hydrolysis is rate-limiting and the condensation reaction is faster. For this reason, the reaction product of the alkoxide is reduced to fine particles, or the metal alkoxide is consumed for the growth of the particle diameter of the fine particles, and the number of products acting as a binder is reduced.
  • the amount of the catalyst to be added is preferably from 0.001 to 4 in a molar ratio to the metal compound serving as the binder.
  • the amount of water required for the hydrolysis is preferably from 0.1 to 100 in molar ratio to the metal compound. If the amount of water added is less than 0.1 in a molar ratio, hydrolysis of the metal compound is not sufficiently promoted. On the other hand, if the amount of water added is greater than 100 in terms of molar ratio, the stability of the liquid will be reduced.
  • the solvent is not particularly limited as long as it can dissolve the metal compound.
  • Alcohols such as methanol, ethanol, propanol, and butanol
  • cellosolves such as ethylcellosolve, butylcellosolve, and propylcellosolve
  • ethylene Glycols such as glycol and hexylene glycol
  • the concentration of the metal compound dissolved in the solvent is preferably 20% by weight or less, and more specifically, 1 to 20% by weight.
  • the ratio of the fine particles of the silicon force to the metal compound in the coating solution is determined by changing the metal compound to the corresponding metal oxide (eg, SiO ⁇ AO ⁇ TiO 2, Zr0 in terms of 2, Ta 2 0 5), 0 5 at a weight ratio: 5 0-9 9: 1 is not preferred.
  • the coating solution is prepared by hydrolyzing a metal compound in the presence of silica fine particles, the above weight ratio is more preferably 66:34 to 95: 5, and further preferably 75: 5. 25 to 90: 10
  • the weight ratio is more preferably 50:50 to 85:15, and even more preferably 60:40 to 50:50. 7 5: 25
  • the coating liquid is applied to a glass substrate and heated, whereby a dehydration-condensation reaction of a metal compound hydrolyzate, vaporization and burning of volatile components proceed, and a reflection suppressing film is formed on the glass substrate.
  • the method of applying the coating liquid to the glass substrate is not particularly limited, but may be a method using an apparatus such as a spin-coat, a mouth-coat, a spray-coat, a curtain-coat, or the like.
  • Various methods such as a lifting method (dip coating method) and a flow coating method (flow coating method), and screen printing, gravure printing, and curved surface printing can be used.
  • cleaning and surface modification may be performed.
  • Methods for cleaning and surface modification include degreasing with an organic solvent such as alcohol, acetone or hexane, cleaning with an alkali or acid, and polishing.
  • Surface polishing with an abrasive, ultrasonic cleaning, ultraviolet irradiation treatment, ultraviolet ozone treatment or plasma treatment can be mentioned.
  • the heat treatment after the application is effective in improving the adhesion between the antireflection film substantially consisting of silica fine particles and the binder and the transparent substrate.
  • the heating temperature expressed in terms of the maximum temperature, is preferably 200 ° C or higher, more preferably 400 ° C or higher, particularly preferably 600 ° C or higher, and 180 ° C or lower. Below is preferred. In general, at 200 ° C. or higher, the solvent component of the coating liquid evaporates, and the gelation of the film proceeds to generate an adhesive force. Above 400 ° C, the organic components remaining in the film are almost completely eliminated by combustion.
  • the heating time is preferably from 5 seconds to 5 hours, more preferably from 30 seconds to 1 hour.
  • the photoelectric conversion rate of the photoelectric conversion device is improved by the reflection suppressing effect of the reflection suppressing film.
  • the reflectance of the transparent substrate on which the anti-reflection film is formed is preferably not more than 3.5%, and is preferably not more than 3.5%, expressed as the reflectance not including the reflection of the opposing surface (the surface on which the transparent conductive film was formed). The following is more preferable, and the most preferable is 0.5% or less.
  • a water-repellent film or an anti-fogging film may be further formed on the reflection suppressing film. By coating with a water-repellent film, water-repellent performance can be obtained, and dirt-removing property is also improved.
  • the antireflection film is formed on the main surface of the transparent substrate of the thin-film or crystal-type photoelectric conversion device, thereby realizing the above-described transmittance and high light confinement. Also, the silica fine particles are firmly fixed to the transparent substrate by the binder. Therefore, it shows high durability. Further, since the irregularities derived from the silica fine particles are formed on the surface of the antireflection film, this film has extremely high durability.
  • the underlayer 1 is preferably a two-layer film composed of a first underlayer 1a and a second underlayer 1b, or a single-layer film.
  • the first base layer la preferably contains tin oxide as a main component.
  • the second underlayer 1b preferably contains at least one of silicon oxide and aluminum oxide as a main component, and is particularly preferably a silicon oxide film.
  • a film containing silicon oxide, SiOC, aluminum oxide, or the like as a main component, or a film made of a composite oxide of silicon oxide and tin oxide is preferable.
  • the transparent conductive film 2 is preferably a film containing tin oxide as a main component, and more preferably a material to which a predetermined amount of an element such as fluorine is added for improving conductivity.
  • the transparent conductive film 2 is preferably formed by a method involving a thermal decomposition oxidation reaction of a raw material.
  • Preferred thicknesses of the respective films shown in FIG. 1 are exemplified below.
  • a method of sequentially depositing each film on the glass ribbon surface using the heat of the glass ribbon in the float glass manufacturing process may be applied to each of the above films.
  • a spray method in which the raw material liquid is atomized and supplied to the glass ribbon surface
  • a CVD method in which the raw material is vaporized and supplied to the glass ribbon surface.
  • the surface on which the transparent conductive film is to be formed is float glass top. It is preferable that the surface on which the antireflection film is formed be the bottom surface of the float glass.
  • the bottom surface of the float glass is more excellent in flatness than the top surface. For example, when a reflection suppressing film is formed by a roll coating method, it is easy to control unevenness.
  • FIG. 2 shows an embodiment of an apparatus for forming a transparent conductive film on the surface of the glass ribbon by the CVD method.
  • a predetermined number of glass ribbons flow out of the melting furnace 11 into the tin float tank 12 and immediately above the glass ribbon 10 which is formed into a belt shape in the tin bath 15 and moves.
  • 6 in the illustrated form, five coaters 16a, 16a, 16c, 16c, 16d, 16e) are arranged. From these moments, the vaporized raw material adjusted according to the type of film to be formed is supplied, and each film (for example, the first surface) is applied to the glass ribbon 10 surface (top surface; tin non-contact surface).
  • the transparent conductive film formed to be thicker than both underlayers is formed using a plurality of layers.
  • the temperature of the glass ribbon 10 is controlled by a heater and a cooler (not shown) arranged in the tin float tank 12 so that the temperature becomes a predetermined temperature immediately before the temperature 16.
  • the predetermined temperature of the glass ribbon is preferably 6 ° C. to 75 ° C., and more preferably 63 ° C. to 75 ° C.
  • the glass ribbon 10 on which each film is formed in this way is pulled up by the roll 17 and cooled in the annealing furnace 13.
  • tin raw materials include monobutyltin trichloride, tin tetrachloride, dimethyltin dichloride, dibutyltin dichloride, dioctyltin dichloride, and tetra. Methyltin and the like.
  • organotin chlorides such as monobutyltin trichloride and dimethyltin dichloride are particularly suitable. Oxygen, water vapor, dry Dry air or the like may be used as the oxidizing material.
  • fluorine raw material include hydrogen fluoride, trifluoroacetic acid, bromotrifluoromethane, and chlorodifluoromethane.
  • the silicon raw materials include monosilane, disilane, trisilane, monochlorosilane, 1,2-dimethylsilane, 1,1,2-trimethyldisilane, 1, Examples include 1,2,2-tetramethyldisilane, tetramethylorthosilicate, and tetraethylorthosilicate.
  • oxygen, steam, dry air, carbon dioxide, carbon monoxide, nitrogen dioxide, ozone, or the like may be used.
  • a highly reactive raw material such as monosilane is used, the reactivity may be controlled by adding an unsaturated hydrocarbon gas such as ethylene, acetylene or toluene.
  • aluminum materials include trimethylaluminum, aluminum triisopopropoxide, and getylaluminum chloride.
  • the oxidizing raw material include oxygen, steam, and dry air.
  • the surface of the transparent conductive film may be provided with irregularities.
  • the surface irregularities of the transparent conductive film when the surface irregularities of the transparent conductive film become large, crystal growth of crystalline silicon is inhibited. Therefore, the surface irregularities are preferably not more than 10% in terms of a haze ratio. Further, the surface irregularities of the transparent conductive film can also be formed by etching or the like.
  • the method for manufacturing the thin film type or crystal type photoelectric conversion device is not particularly limited, and other structures may be used if the antireflection film is formed by the above-described means.
  • the component can be manufactured by a known means.
  • the method of measuring the transmittance and the haze of the substrate for a photoelectric conversion device in the examples is as follows.
  • the transmittance at 400 to 110 nm was measured, and the average value was determined.
  • HGM-2DP integrating sphere light transmittance measuring device
  • JIS Japanese Industrial Standard
  • a 1 Ocm square ordinary float glass (2.8 mm thick) was used as a transparent substrate for forming the anti-reflective film.
  • the glass plate was washed and dried, and a silicon dioxide film and a fluorine-doped tin oxide film were deposited in this order using a belt-conveying normal pressure CVD apparatus.
  • the silicon dioxide film was formed by heating a glass plate to 550 ° C. and supplying monosilane, oxygen and nitrogen. Its film thickness was 50 nm.
  • the glass on which the silicon dioxide film is formed is heated to 600 ° C, and a mixed gas comprising dimethyltin dichloride, water vapor, oxygen, hydrofluoric acid, and nitrogen is supplied. Formed. Its film thickness was 45 O nm.
  • the glass substrate with a transparent conductive film thus obtained had a transmittance T1 of 78.3% and a haze ratio H1 of 4.5%.
  • Example 1 First silica fine particle dispersion (Nippon Shokubai Co., Ltd. “Siphos Yuichi KE—W10” average primary particle size 11 1 Onm solids 15%) 5 6.67 g, ethilse Mouth Solve 33.7 g Then, 1 g of concentrated hydrochloric acid and 5.2 g of tetraethoxysilane were sequentially added, and the mixture was reacted with stirring for 24 hours to prepare a first silica fine particle hydrolyzed liquid. In addition, a second silica fine particle dispersion (Nippon Shokubai Co., Ltd.
  • a coating solution was prepared by mixing 12 g of the first hydrolyzed silica fine particle solution, 18 g of the second hydrolyzed silica fine particle solution, 40 g of ethylene glycol, and 30 g of ethyl ethyl solvent.
  • This coating solution was applied to the glass surface of the glass substrate with a transparent conductive film (the surface facing the transparent conductive film) by spin coating.
  • the number of revolutions was set to 120 Or.pm.
  • the maximum temperature of the glass substrate in the electric furnace was 52 Ot :.
  • Example 3 Silica fine particle dispersion ("KE-W50" manufactured by Nippon Shokubai Co., Ltd., average primary particle size: 55 Onm solids: 20%) While stirring 40 g, add ethyl acetate 52.1 g, concentrated hydrochloric acid lg and tetraethoxy 6.9 g of silane was added sequentially, and reacted while stirring for 240 minutes, to prepare a hydrolyzed silica fine particle solution. 30 g of this hydrolyzed silica fine particle solution was diluted by adding 30 g of ethyl acetate solvent and 40 g of hexylene glycol to prepare a coating solution. Using this coating liquid, a reflection suppressing film was formed in the same manner as in Example 1 except that the spin speed was set to 100 rpm.
  • KE-W50 manufactured by Nippon Shokubai Co., Ltd., average primary particle size: 55 Onm solids: 20%
  • Silica fine particle dispersion (“KE_W30”, manufactured by Nippon Shokubai Co., Ltd., average primary particle size 30 Onm, solid content 20%) While stirring 35 g, add 52.1 g of ethylcellosolve, 1 g of concentrated hydrochloric acid and 10 g of tetraethoxysilane. .4 g were sequentially added and reacted while stirring for 300 minutes to prepare a hydrolyzed silica fine particle solution. To 30 g of this hydrolyzed silica fine particle was added 30 g of ethyl ethyl solvent and 40 g of hexylene glycol for dilution to prepare a coating solution. Using this coating liquid, a reflection suppressing film was formed in the same manner as in Example 1 except that the spin rotation speed was set to 100 Or.p.m. (Comparative Example 1)
  • Silica fine particle dispersion (“KE-W10” manufactured by Nippon Shokubai Co., Ltd., average primary particle size: 110 nm, solid content: 15%) While stirring 45 g, add 48.3 g of ethyl ethyl cellulose, 1 g of concentrated hydrochloric acid and 5.7 g of tetraethoxysilane was sequentially added, and the mixture was reacted with stirring for 4 hours to prepare a hydrolyzed silica fine particle solution. 35 g of this hydrolyzed silica fine particle solution was diluted with 30 g of diacetone alcohol and 3 ⁇ -hexylene glycol to prepare a coating solution. Using this coating liquid, a reflection suppressing film was formed in the same manner as in Example 1 except that the spin speed was set to 1200 rpm. (Comparative Example 2)
  • a reflection suppressing film was formed in the same manner as in Example 1 except that the spin speed was set at 100 Or.p.m.
  • the transmittance T 2 and the haze H 2 of the transparent conductive film and the glass substrate with a reflection suppressing film manufactured in Examples 1 to 4 and Comparative Examples 1 and 2 were measured, and the change ⁇ T before and after the formation of the reflection suppressing film was measured.
  • ⁇ were determined by the following equations. That is, the following ⁇ T and ⁇ indicate the optical characteristics of the antireflection film.
  • Fig. 3 shows an example of the relationship between the haze ratio of the transparent conductive film and the diffusion transmission spectrum (in the thin-film photoelectric conversion device, the light of amorphous silicon in the photoelectric conversion layer is shown in Fig. 3).
  • the absorption band is mainly in the short wavelength range of the visible light range of 400 to 60 orn.
  • a tin oxide film when used as the transparent conductive film, light confinement in the photoelectric conversion layer can be easily generated by increasing the haze ratio of the tin oxide film.
  • the antireflection film of the present invention when the haze ratio is increased by increasing the number of fine particles having a large particle diameter, the diffuse transmittance not only in the short wavelength region but also in the long wavelength region of 60 O nm or more is increased. Can be. Examples are Example 1 (fine particle diameter 110 nm + 300 nm), Example 2 (fine particle diameter 110 nm + 550 nm) and Example 3 (fine particle diameter 55 nm).
  • Fig. 4 shows the diffuse transmission spectrum of the manufactured glass substrate with a reflection suppressing film and a transparent conductive film.
  • the sensitivity of the photoelectric conversion layer When the sensitivity of the photoelectric conversion layer is in the visible light range, it is sufficient to express the surface roughness of the transparent conductive film, that is, its haze ratio, as a standard for measuring the degree of light confinement in the photoelectric conversion layer. In other words, the higher the haze ratio, the greater the light confinement effect.
  • thin-film photoelectric conversion devices with microcrystalline or polycrystalline silicon in the photoelectric conversion layer, crystalline photoelectric conversion devices, or solar cells, such as IS in which the sensitivity of the photoelectric conversion layer includes a wavelength range longer than visible light. It is necessary to judge the degree of light confinement in the photoelectric conversion layer not by the haze ratio but by the diffusion transmission spectrum.
  • the antireflection film of the present invention not only achieves a high haze ratio but also exhibits a high diffuse transmittance in a wide wavelength range. That is, the antireflection film can realize high light confinement there regardless of the material of the photoelectric conversion layer.
  • the present invention has the following effects because it is configured as described above.
  • the photoelectric conversion rate of the photoelectric conversion device can be increased.
  • the particle size of the silica fine particles can be set to 300 to 600 runs, a substrate for a photoelectric conversion device having excellent physical durability such as abrasion resistance can be obtained.
  • Effective light confinement in the photoelectric conversion layer is achieved by forming a reflection suppression film containing silica fine particles with a particle size of 30 O nm or more and silica fine particles with different particle sizes on the main surface of the transparent substrate. And the photoelectric conversion rate can be further increased. Further, by setting the particle size of the silica fine particles having different particle sizes to 50 to 15 O nm, the reflectance of the reflection suppressing film from visible light to near-infrared light can be effectively reduced.
  • silica fine particles are present in a region of 60% or more of the main surface of the transparent substrate, a substrate for a photoelectric conversion device that effectively exhibits various functions such as suppression of reflection, increase in transmittance, and improvement in durability can be obtained.
  • a transparent conductive film having a haze ratio of 10% or less is formed on the surface of the transparent substrate facing the key surface, a substrate suitable for a photoelectric conversion device having a photoelectric conversion layer made of crystalline silicon can be obtained.
  • a photoelectric conversion device having a high photoelectric conversion rate can be obtained according to the present invention.
  • the present invention may include other specific forms without departing from the spirit and essential characteristics thereof.
  • the form disclosed in this specification is not restrictive, and the scope of the present invention is indicated not by the above description but by the appended claims, and all modifications within the scope equivalent to the invention described in the claims are to be made. Shall also be included here.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Geochemistry & Mineralogy (AREA)
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Abstract

L'invention concerne un substrat destiné à un transducteur photoélectrique comprenant un corps transparent doté d'une surface principale garnie d'un revêtement antireflet contenant des particules fines à base de silice dont la taille est supérieure à 300 nm. De préférence, le revêtement antireflet contient également des particules à base de silice présentant une taille différente de celle des particules susmentionnées. Une couche photoélectrique constituée d'un film de silicium cristallin peut être formée sur ledit substrat, d'où l'obtention d'un transducteur photoélectrique présentant une haute efficacité photoélectrique.
PCT/JP2000/009056 1999-12-20 2000-12-20 Transducteur photoelectrique et substrat pour transducteur photoelectrique Ceased WO2001047033A1 (fr)

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JP36180899 1999-12-20
JP11/361808 1999-12-20
JP2000017310 2000-01-26
JP2000/17310 2000-01-26

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Cited By (6)

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WO2008137412A1 (fr) * 2007-05-01 2008-11-13 Jacobs Gregory F Dispositifs photovoltaïques et éléments de toiture photovoltaïques comprenant des granules et des toits pour les recevoir
CN102270667A (zh) * 2011-07-27 2011-12-07 保定天威英利新能源有限公司 提高n型单晶硅光伏电池发电效率的组件及其制造方法
WO2016051718A1 (fr) * 2014-09-30 2016-04-07 日本板硝子株式会社 Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique
WO2016181794A1 (fr) * 2015-05-08 2016-11-17 富士フイルム株式会社 Stratifié pour traitement de placage, procédé de fabrication de stratifié conducteur, capteur d'écran tactile, et écran tactile
JPWO2016002215A1 (ja) * 2014-06-30 2017-04-27 日本板硝子株式会社 低反射コーティング、低反射コーティング付き基板および光電変換装置
KR20180091113A (ko) * 2009-12-18 2018-08-14 가부시키가이샤 한도오따이 에네루기 켄큐쇼 광 센서를 포함하는 표시 장치 및 그 구동 방법

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JPH02175601A (ja) * 1988-09-09 1990-07-06 Hitachi Ltd 超微粒子
JPH02177573A (ja) * 1988-12-28 1990-07-10 Matsushita Electric Ind Co Ltd 光起電力装置
JPH11274536A (ja) * 1998-03-26 1999-10-08 Mitsubishi Chemical Corp 太陽電池用基板
EP1058320A2 (fr) * 1999-05-31 2000-12-06 Kaneka Corporation Module de cellules solaires

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JPH02175601A (ja) * 1988-09-09 1990-07-06 Hitachi Ltd 超微粒子
JPH02177573A (ja) * 1988-12-28 1990-07-10 Matsushita Electric Ind Co Ltd 光起電力装置
JPH11274536A (ja) * 1998-03-26 1999-10-08 Mitsubishi Chemical Corp 太陽電池用基板
EP1058320A2 (fr) * 1999-05-31 2000-12-06 Kaneka Corporation Module de cellules solaires

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008137412A1 (fr) * 2007-05-01 2008-11-13 Jacobs Gregory F Dispositifs photovoltaïques et éléments de toiture photovoltaïques comprenant des granules et des toits pour les recevoir
KR20180091113A (ko) * 2009-12-18 2018-08-14 가부시키가이샤 한도오따이 에네루기 켄큐쇼 광 센서를 포함하는 표시 장치 및 그 구동 방법
US10360858B2 (en) 2009-12-18 2019-07-23 Semiconductor Energy Laboratory Co., Ltd. Display device including optical sensor and driving method thereof
KR102020739B1 (ko) * 2009-12-18 2019-09-10 가부시키가이샤 한도오따이 에네루기 켄큐쇼 광 센서를 포함하는 표시 장치 및 그 구동 방법
US10796647B2 (en) 2009-12-18 2020-10-06 Semiconductor Energy Laboratory Co., Ltd. Display device including optical sensor and driving method thereof
CN102270667A (zh) * 2011-07-27 2011-12-07 保定天威英利新能源有限公司 提高n型单晶硅光伏电池发电效率的组件及其制造方法
JPWO2016002215A1 (ja) * 2014-06-30 2017-04-27 日本板硝子株式会社 低反射コーティング、低反射コーティング付き基板および光電変換装置
WO2016051718A1 (fr) * 2014-09-30 2016-04-07 日本板硝子株式会社 Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique
JPWO2016051718A1 (ja) * 2014-09-30 2017-07-13 日本板硝子株式会社 低反射コーティング、低反射コーティング付ガラス板、低反射コーティングを有するガラス板、ガラス基板、および光電変換装置
WO2016181794A1 (fr) * 2015-05-08 2016-11-17 富士フイルム株式会社 Stratifié pour traitement de placage, procédé de fabrication de stratifié conducteur, capteur d'écran tactile, et écran tactile

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