WO2012161161A1 - 製膜方法、製膜体、及び色素増感太陽電池 - Google Patents
製膜方法、製膜体、及び色素増感太陽電池 Download PDFInfo
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- WO2012161161A1 WO2012161161A1 PCT/JP2012/062936 JP2012062936W WO2012161161A1 WO 2012161161 A1 WO2012161161 A1 WO 2012161161A1 JP 2012062936 W JP2012062936 W JP 2012062936W WO 2012161161 A1 WO2012161161 A1 WO 2012161161A1
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a film forming method for forming a porous film made of an inorganic substance on a substrate, a film forming body obtained by the film forming method, and a dye-sensitized solar cell provided with the film forming body.
- a porous film made of an oxide semiconductor such as titanium oxide on which a photosensitizing dye such as a ruthenium metal complex is adsorbed is used (Patent Document 1).
- a slurry or paste containing oxide semiconductor particles is applied onto a base material, and this is fired at a temperature lower than the melting point of the oxide semiconductor to thereby form oxide semiconductor particles. Films are formed in a state where they are in weak contact with each other.
- a binder such as ethyl cellulose
- the viscosity of the slurry or paste was adjusted, and the porosity of the film to be formed was increased to increase the adsorption area of the photosensitizing dye.
- a porous film is used.
- a method of surface-treating fine particles constituting a porous film is known.
- a method for forming a new titanium oxide film on a porous film by immersing the porous film made of titanium oxide formed as described above in a titanium tetrachloride aqueous solution and pulling it up, followed by heat treatment.
- This titanium oxide film is considered to play a role of enhancing the adhesion between titanium oxide particles constituting the porous film while providing a clean surface to the porous film.
- the base material that supports the conventional porous film needs to be a material that can withstand firing, it is difficult to use a plastic or a resin film as the base material.
- the time required for the firing process increases the time required for the entire manufacturing process of the porous membrane.
- the porous film formed by this method has a problem in that since the firing temperature is low, the adhesion between the oxide semiconductor particles is weakened, and the electron conductivity remains low.
- a binder is mix
- the present invention has been made in view of the above circumstances, and a method for forming a porous film made of an inorganic substance, which does not require a firing step, a film formed body manufactured by the film forming method, and a film formed body thereof
- An object is to provide a dye-sensitized solar cell provided.
- the present invention has the following aspects.
- inorganic fine particles are sprayed on a base material to join the base material and the fine particles, and the fine particles are joined to each other, whereby the inorganic material is porous on the base material.
- the ratio of the small particle and the large particle in the porous membrane small particle / large particle
- the film forming method according to the first aspect wherein the ratio is larger than the ratio (small particle / large particle) to the large particle.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 200 nm
- the average particle size R of the large particles is 0.2 ⁇ m ⁇ R ⁇ 200 ⁇ m.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 200 nm
- the average particle size R of the large particles is 1 ⁇ m ⁇ R ⁇ 200 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 200 nm, and the average particle size R of the large particles is 1 ⁇ m ⁇ R ⁇ 100 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 200 nm, and the average particle size R of the large particles is 1 ⁇ m ⁇ R ⁇ 50 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 100 nm, and the average particle size R of the large particles is 0.2 ⁇ m ⁇ R ⁇ 200 ⁇ m.
- the average particle size r of the small-sized particles is 1 nm ⁇ r ⁇ 100 nm, and the average particle size R of the large-sized particles is 1 ⁇ m ⁇ R ⁇ 200 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 100 nm, and the average particle size R of the large particles is 1 ⁇ m ⁇ R ⁇ 100 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 100 nm, and the average particle size R of the large particles is 1 ⁇ m ⁇ R ⁇ 50 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the average particle size r of the small particles is 1 nm ⁇ r ⁇ 100 nm, and the average particle size R of the large particles is 1 ⁇ m ⁇ R ⁇ 10 ⁇ m, Or it is the film forming method as described in the aspect of 2.
- the relative ratio (r / R) of the average particle size r of the small particles and the average particle size R of the large particles is (1/1000) ⁇ (r / R) ⁇ ( The film forming method according to any one of the first to eleventh aspects, which satisfies the relationship 1/5).
- the mixing ratio of the small-diameter particles to the large-diameter particles in the fine particles used when sprayed on the substrate is (parts by weight). It is the film forming method as described in an aspect.
- the treatment (operation) for spraying the inorganic fine particles onto the base material is performed by spraying the mixed particles containing the small diameter particles and the large diameter particles onto the base material, and The method according to any one of the first to thirteenth aspects, wherein the small-sized particles sprayed on the base material are collided with the large-sized particles to join the small-sized particles to form a film.
- a fifteenth aspect of the present invention is the film forming method according to any one of the first to fourteenth aspects, wherein the inorganic substance is an oxide semiconductor.
- a sixteenth aspect of the present invention is the film forming method according to any one of the first to fifteenth aspects, wherein the spraying is performed at room temperature.
- a seventeenth aspect of the present invention is the film forming method according to any one of the first to sixteenth aspects, wherein the substrate is made of a resin.
- An eighteenth aspect of the present invention is the film forming method according to any one of the first to seventeenth aspects, wherein the substrate is a film made of a resin.
- a nineteenth aspect of the present invention is the film forming method according to the seventeenth or eighteenth aspect, wherein a glass transition temperature (Tg) of the substrate made of the resin is less than 200 ° C.
- a twentieth aspect of the present invention is the film forming method according to any one of the first to nineteenth aspects, wherein the porous film is a porous film for a photoelectrode of a dye-sensitized solar cell.
- a twenty-first aspect of the present invention is a film-forming body obtained by the film-forming method described in any one of the first to twentieth aspects.
- a twenty-second aspect of the present invention is the film forming body according to the twenty-first aspect, wherein the content of the large-diameter particles in the porous film is 30% by volume or less.
- a twenty-third aspect of the present invention is the film forming body according to the twenty-first or twenty-second aspect, wherein the porosity of the porous film is 50 to 80%.
- a twenty-fourth aspect of the present invention is a photoelectrode provided with the film forming body according to any one of the twenty-first to twenty-third aspects.
- a twenty-fifth aspect of the present invention is a dye-sensitized solar cell comprising the film forming body according to any one of the twenty-first to twenty-third aspects.
- a conventional baking process is not required.
- a plastic, a resin film, etc. with comparatively low heat resistance can be used as a base material.
- a porous film can be formed on a substrate such as a plastic or resin film having relatively low heat resistance.
- a baking process is unnecessary at the time of manufacture and the required time for film formation can be shortened, it is excellent in manufacturing characteristics.
- mixed particles composed of small-sized particles and large-sized particles are sprayed onto the substrate, so that the large-sized particles collide with the small-sized particles accumulated on the surface of the substrate and the small-sized particles are used as the base.
- the small-sized particles are first deposited on the base material, and the large-sized particles can be hit from the first, and by applying large energy (mechanical impact force) to the small-sized particles, the small-sized particles are more sufficiently joined. be able to.
- a porous film can be formed more easily than in the past. That is, even when fine particles are sprayed at a lower speed than in the past, a porous film can be reliably formed.
- the so-called green compact has high strength and excellent electron conductivity.
- the film-forming body of the present invention is useful as a component of a photoelectrode because a porous film having excellent characteristics is disposed on the surface of a substrate. Since the dye-sensitized solar cell of the present invention includes the film forming body, it is excellent in photoelectric conversion efficiency. Moreover, if a film-forming body using a flexible substrate such as a resin film is used, a deformable dye-sensitized solar cell can be obtained.
- inorganic fine particles are sprayed onto a base material to join the base material and the fine particles, and the fine particles are joined to each other, whereby the porous inorganic material is formed on the base material. This is a method of forming a film.
- the inorganic substance examples include metal particles such as Pt, Ag, and Au, semiconductor particles such as Si, CdS, CdSe, CdTe, PbS, PbSe, ZnO, TiO 2 , In 2 O 3 , SnO 2 , and BaTiO 3 , and Well-known composite inorganic particle etc. are mentioned.
- the inorganic substance an oxide semiconductor excellent in electron conductivity and dye supporting property is preferable.
- the oxide semiconductor examples include titanium oxide (TiO 2 ), zinc oxide (ZnO), and strontium titanate (SrTiO 3 ). Among these, titanium oxide that is excellent in electron conductivity when a porous film is formed is preferable.
- titanium oxides used in the industry are roughly classified into anatase type and rutile type, and brookite type and amorphous titanium oxide are also known.
- titanium oxide is used as the inorganic substance, any of the above titanium oxides may be used.
- a porous film formed using mixed mixed particles tends to have a strength suitable for a photoelectrode of a dye-sensitized solar cell.
- rutile-type titanium oxide in addition to anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, or amorphous titanium oxide may be used.
- anatase type titanium oxide, brookite type titanium oxide or amorphous titanium oxide may be used as the large particle.
- the fine particles are mixed particles composed of small particles having an average particle size r ⁇ 0.2 ⁇ m and large particles having an average particle size R ⁇ 0.2 ⁇ m.
- the relative ratio (r / R) between the average particle size r of the small particles and the average particle size R of the large particles satisfies the relationship of (1/1000) ⁇ (r / R) ⁇ (1/5). .
- the average particle size r of the small particles is preferably 1 nm ⁇ r ⁇ 200 nm, more preferably 1 nm ⁇ r ⁇ 100 nm.
- a larger amount of dye (sensitizing dye) can be supported, and voids in which the electrolyte solution can more easily diffuse are easily formed in the porous film.
- the upper limit of the above range is preferably less than 200 nm, more preferably 100 nm or less, the small diameter particles tend to be joined. As a result, the electronic conductivity and strength of the porous film can be further improved.
- the average particle diameter R of the large particles is 200 nm ⁇ R ⁇ 200 ⁇ m, preferably 200 nm ⁇ R ⁇ 100 ⁇ m, more preferably 1 ⁇ m ⁇ R ⁇ 100 ⁇ m, still more preferably 1 ⁇ m ⁇ R ⁇ 50 ⁇ m, and more preferably 1 ⁇ m ⁇ R ⁇ 50 ⁇ m. 10 ⁇ m is even more preferable, and 1 ⁇ m ⁇ R ⁇ 5 ⁇ m is particularly preferable.
- the energy with which the large particles collide with the small particles can be increased when the mixed particles are sprayed onto the substrate.
- the bonding between the small diameter particles, the bonding between the small diameter particles and the base material, or the bonding between the small diameter particles and the large diameter particles can be performed more reliably.
- the electronic conductivity and strength of the porous film can be further improved.
- it can prevent that a large diameter particle scrapes off the porous membrane currently formed on the said base material at the time of film forming.
- the film formation speed can be increased.
- the average particle diameter r of the small particle is obtained as an average value of the particle diameters measured by observing a plurality of small particles with an electron microscope. In this case, the larger the number of small-diameter particles to be measured, the better. However, for example, 10 to 50 particles may be measured and the average may be obtained. Or the method of determining as a peak value of the particle diameter (volume average diameter) distribution obtained by the measurement of the laser diffraction type particle size distribution measuring apparatus is also mentioned.
- the average particle size R of the large particles is obtained by the same measuring method as the average particle size r of the small particles.
- the method for measuring the average particle size of the fine particles used in the present invention is not limited to the above two methods (electron microscope or laser diffraction particle size distribution measuring device), and may be measured by a measurement method different from these methods. . Even if the particle diameter measured by a method other than the above two methods is outside the above range, if it is measured by the above two methods and falls within the above particle diameter range, it is used in the present invention. Contained in fine particles of inorganic substances.
- the average particle size r of the small-sized particles constituting the mixed particles it is preferable because the measurement is easier before mixing with the large-sized particles.
- a particle size distribution curve of small particles which is obtained by a particle size distribution measuring device, it is preferable to fit assuming that the number of peaks in the range of the average particle size of less than 1 ⁇ m is one.
- the fitted particle size distribution curve with the number of the peaks as a plurality May be drawn. In this case, there are first small diameter particles, second small diameter particles, third small diameter particles,...
- the plurality of small diameter particles are collectively referred to as a small diameter particle group.
- the average particle diameter obtained by weighting by the abundance ratio of each small diameter particle corresponds to the “average particle diameter r of the small diameter particle” of the present invention. To do.
- the half width (full width at half maximum) of the peak in the particle size distribution curve of the small particle is preferably from 1 nm to less than 200 nm, more preferably from 1 nm to 100 nm, and even more preferably from 1 nm to 50 nm. It is preferable to use small-diameter particles having a peak with a narrow half-value width because it is easy to estimate the speed at the time of the spraying and the energy of the collision related to the speed, and the control of the spraying conditions becomes easier.
- the half width of the peak in the particle size distribution curve of the small particle is preferably determined based on the fitted distribution curve assuming that the number of the peak is one in the range of the average particle size of less than 1 ⁇ m.
- the number of the peaks is set as a plurality, and the half of each peak is The price range may be obtained.
- the half width of each peak is preferably in the above range.
- the average particle diameter R of the large-sized particles constituting the mixed particles it is preferable to perform the measurement before mixing with the small-sized particles because it is easier.
- a particle size distribution curve of large particles which is obtained by a particle size distribution measuring device, it is preferable to perform the fitting assuming that the number of peaks in the range of the average particle size of 1 ⁇ m or more is one.
- the fitted particle size distribution curve with the number of the peaks as a plurality May be drawn. In this case, the first large particle, the second large particle, the third large particle, etc.
- the average particle size of each large particle belonging to the large particle group the average particle size obtained by averaging the weighted ratios of the abundance ratio of each large particle is the “average particle size of large particles” of the present invention. R ".
- the full width at half maximum (full width at half maximum) of the peak in the particle size distribution curve of the large particle is preferably 0.2 ⁇ m or more and 500 ⁇ m or less, more preferably 0.2 ⁇ m or more and 250 ⁇ m or less, and further preferably 0.2 ⁇ m or more and 100 ⁇ m or less. It is preferable to use large-diameter particles having a peak with a narrow half-value width, because it becomes easy to estimate the speed at the time of spraying and the energy of the collision related to the speed, and control of the spraying conditions becomes easier.
- the half width of the peak in the particle size distribution curve of the large particle is preferably determined based on the fitted distribution curve assuming that the number of the peak is one in the range of the average particle size of 1 ⁇ m or more. On the other hand, if it is mathematically or logically appropriate to fit the number of the peaks as a plurality (for example, 2 to 5), the number of the peaks is set as a plurality, and the half of each peak is The price range may be obtained. Also in this case, the half width of each peak is preferably in the above range.
- the relative ratio (r / R) between the average particle diameter r of the small particles constituting the mixed particles and the average particle diameter R of the large particles is (1/1000) ⁇ (r / R) ⁇ (1/5).
- the relative ratio preferably satisfies the relationship of (1/750) ⁇ (r / R) ⁇ (1/10), and the relationship of (1/500) ⁇ (r / R) ⁇ (1/20) is satisfied. It is more preferable to satisfy
- the difference between the average particle diameter r of the small particle and the average particle diameter R of the large particle becomes clearer.
- the small particle and the large particle are made of the same inorganic substance (for example, titanium oxide)
- the difference in the average particle size becomes clearer because the weight of the individual particles of the small particle and the individual particles of the large particle This means that the difference becomes clearer.
- it is preferable to clarify the difference in weight because it is possible to more easily set spraying conditions considering the difference in weight. For example, when the difference in weight is relatively large, when the mixed particles are sprayed onto the base material to form a film, the collision energy given by the large particles to the small particles is much higher than the collision energy between the small particles. Can be large.
- the sprayed large-diameter particles collide with the small-diameter particles that have reached the base material or another adjacent particle, so that the collided small-diameter particles become the base material or By pressing or rubbing against another adjacent particle, the small diameter particle and the base material, or the small diameter particle and the adjacent another particle can be more reliably joined.
- the difference in weight is extremely large, the collided small-diameter particles may be shattered and it may be difficult to form a porous film.
- the degree to which the energy given by the large particle colliding with the small particle when the small particle is bonded to the base material or the adjacent another particle contributes It becomes relatively small.
- the mechanism that collides with and joins the base material or other adjacent particles by the kinetic energy inherent to the sprayed small-diameter particles prevails.
- the difference in weight can be within an appropriate range, and a porous film having further improved strength and electronic conductivity can be formed on the substrate. Can be formed into a film.
- the mixing ratio of small particles: large particles is preferably 0.1 parts by weight: 99.9 parts by weight to 99.9 parts by weight: 0.1 parts by weight, and 0.5 parts by weight. : 99.5 parts by weight to 50 parts by weight: 50 parts by weight is more preferable, and 1 part by weight: 99 parts by weight to 20 parts by weight: 80 parts by weight is still more preferable.
- the large-diameter particles can be more reliably collided with the small-diameter particles on the substrate. As a result, the strength and electronic conductivity of the porous film formed on the substrate can be further enhanced.
- the film-forming method of the present invention uses a porous film in which fine particles are bonded to each other by spraying small-sized particles and large-sized particles, which are fine particles of at least two kinds of inorganic substances having different average particle sizes, onto the substrate. It is a method of forming a film on top. Examples of the method of spraying the small-sized fine particles and the large-sized fine particles onto the substrate include a method of spraying mixed particles composed of small-sized particles and large-sized particles onto the substrate.
- the fine particles may include small particles and particles obtained by pulverizing small particles, and large particles and particles obtained by pulverizing large particles.
- the relative ratio satisfies the relationship of (1/1000) ⁇ (r / R) ⁇ (1/5), so that among the fine particles constituting the porous film, the small diameter
- the ratio of particles broken by particles and / or small-diameter particles can be 50% by volume or more.
- the ratio can be further increased by setting the range of the relative ratio to a suitable range or adjusting the mixing ratio of the mixed particles to a suitable range.
- the content ratio of the large-diameter particles and / or the particles obtained by breaking the large-diameter particles in the porous film formed on the substrate can be 50% by volume or less, preferably 40% by volume or less. More preferably, it can be made into 30 volume% or less.
- the content ratio of the large-diameter particles or the particles obtained by pulverizing the large-diameter particles in the porous film is determined by observing the cross-section of the porous film with an electron microscope.
- the content rate may be determined by determining that the large-diameter particles are crushed particles.
- the ratio of the large diameter particles in the mixed particles before spraying is larger than the ratio of the small diameter particles.
- the smaller diameter particles contribute more to the formation of the porous film, and therefore the proportion of the smaller diameter particles is larger than the proportion of the larger diameter particles. preferable.
- the ratio between the small-sized particles and the large-sized particles after joining often increases more than the ratio of the small-sized particles and large-sized particles in the fine particles used when sprayed on the substrate. . That is, it means that the ratio of the small particle / large particle after bonding is larger than the ratio of the small particle / large particle used when spraying the substrate (before bonding). This is because, as described above, a part of the large-sized particles sprayed onto the base material during the thin film formation is used only for the small-sized particle strike, and therefore, without forming the porous film, It is thought that it is to be.
- the said base material in particular is not restrict
- the transparent base material used for the photoelectrode of a dye-sensitized solar cell is mentioned.
- the transparent substrate include a substrate made of glass or plastic, a resin film, and the like.
- Examples of the glass that is the material of the substrate include soda lime glass, borosilicate glass, quartz glass, borosilicate glass, Vycor glass, non-alkali glass, blue plate glass, and white plate glass.
- a substrate having a glass transition temperature (Tg) of less than 200 ° C. for example, resin Substrate, resin film, etc. can be used, more base materials can be used than before, and various dye-sensitized solar cells can be produced according to the purpose and application Become.
- Tg glass transition temperature
- the plastic that is the material of the substrate examples include polyacrylic resin, polycarbonate resin, polyester resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, and polyamide resin.
- polyester resins particularly polyethylene terephthalate (PET) are produced and used in large quantities as transparent heat-resistant films.
- the substrate is preferably a PET film.
- the surface of the base material is preferably coated with a metal oxide used for a transparent conductive substrate of a known dye-sensitized solar cell.
- a metal oxide used for a transparent conductive substrate of a known dye-sensitized solar cell.
- ITO indium oxide / tin oxide
- FTO fluorine-doped tin oxide
- ATO antimony-doped tin oxide
- IZO indium oxide / zinc oxide
- GZO gallium oxide / zinc oxide
- Etc may be formed in advance on the surface of the substrate.
- the porous film is preferably formed by being laminated on the metal oxide layer.
- the metal oxide layer may be a single layer or a plurality of layers.
- Examples of the method of spraying the mixed particles, which are fine particles, onto the substrate include an aerosol deposition method (AD method) using a carrier gas, an electrostatic fine particle coating method in which the mixed particles are accelerated by electrostatic force, a cold spray method, and the like.
- AD method aerosol deposition method
- the AD method is preferred because it is easy to adjust the spraying speed and it is easy to adjust the strength and film thickness of the porous film to be formed.
- the AD method is a method in which fine particles are accelerated to a subsonic to supersonic speed by a carrier gas such as helium and sprayed onto a substrate. Further, due to this collision, a new surface is formed on the surface of the base material and the surface of the fine particles, and the base material and the fine particles are joined mainly on the new surface. Due to the collision of the fine particles, a new surface is formed on the surface of the fine particles, and the fine particles are joined mainly on the new surface. At this time, by appropriately adjusting the speed of spraying, it is possible to adjust the degree of crushing of the small diameter particles and the large diameter particles. Usually, the higher the speed of spraying, the greater the degree of breakage of small and large particles.
- the opening diameter of the spray nozzle (the diameter of the opening or the length of one side of the opening) can be adjusted. As the opening diameter is increased, the spraying speed can be decreased.
- the spraying speed can be increased. For example, it is possible to easily accelerate to about several hundreds m / s by blowing fine particles (small particle or large particle) conveyed through a gas through a nozzle opening having an opening diameter of 1 mm or less.
- the film forming method according to the present invention preferably satisfies the following (i) and (ii).
- Large-sized particles are not crushed or hardly crushed by impact generated when sprayed onto a substrate.
- Small-sized particles are not deformed by being struck against large-sized particles, or large-sized particles that are hardly deformed. When crushed by impact, the crushed large-diameter particles are taken into the film, and the strength and electrical conductivity of the formed porous film may be lowered.
- the case of (i) is preferable.
- the formed thin film may not be a porous film but may be a dense film. Therefore, the case (ii) is preferable.
- fine particles are bonded means a state in which new surfaces are formed on the surfaces of adjacent fine particles and are in close contact with each other.
- This close contact state can also be expressed as a state of being fused and bonded (fused).
- the “joined state” and the “contact state” are clearly different.
- an SEM photograph is taken at a magnification (for example, 50,000 to 200,000 times) that allows observation of the entire particle (the entire particle enters the observation field)
- a gap is formed at the boundary between the bonded particles.
- a state of close contact is observed. It can be determined that the region in which the closely attached circumferences are continuously connected is one form of the joined state.
- FIG. 2 is a schematic cross-sectional view showing an example of a film forming process by the film forming method according to the present invention.
- a state is shown in which mixed particles composed of small-diameter particles 21 and large-diameter particles 26 are sprayed onto the surface of the base material 24 to join the fine particles 22 to form a porous film 23.
- the relative sizes of the small-diameter particles 21, the large-diameter particles 26, and the fine particles 22 in FIG. 2 are merely examples, and are not limited thereto.
- porous film 23 is drawn so as to be composed of fine particles 22 smaller than the small-diameter particles 21, the fine particles 22 are not necessarily smaller than the small-diameter particles 21, and the small-diameter particles 22 and / or the large-diameter particles are not necessarily included.
- the porous film 23 may be formed in a state where the original shape is maintained without being broken.
- FIG. 3 is a schematic cross-sectional view showing an example of a film forming process by spraying only the small-diameter particles 31 instead of the mixed particles as the fine particles to be sprayed.
- Small particles 31 are sprayed onto the surface of the substrate 34, and the small particles 31 and the fine particles 32 made of particles obtained by pulverizing the small particles 31 form the thin film 33.
- the thin film 33 is a porous film or a dense thin film.
- the speed of the mixed particles accelerated by the carrier gas is preferably 10 to 650 m / s, more preferably 10 to 250 m / s, and still more preferably 10 to 150 m / s.
- the porous membrane is more crushed without being excessively crushed. Can be easily formed.
- the lower limit of the above range among the mixed particles to be sprayed, mainly small-diameter particles are surely bonded to the base material or fine particles already bonded, and have sufficient strength and electron-conductive porous properties. A film can be formed more easily.
- the speed of the mixed particles accelerated by the carrier gas is within the above range, the kind of the base material, the average particle size r of the small particles, the particle size R of the large particles, and the inorganic substance forming the small particles and the large particles What is necessary is just to adjust suitably according to the kind of this.
- the film forming method of the present invention is a method capable of forming a film in a room temperature environment.
- the normal temperature refers to a temperature sufficiently lower than the melting point of the mixed particles, and is substantially 200 ° C. or lower. It is preferable that the temperature of the normal temperature environment is equal to or lower than the melting point of the base material.
- the temperature of the room temperature environment is preferably less than the Vicat softening temperature.
- the ultrafine particle beam deposition method and apparatus disclosed in International Publication No. WO01 / 27348A1 or the brittle material ultrafine particle low temperature molding method and apparatus disclosed in Japanese Patent No. 3265481
- the present invention may be applied without departing from the spirit of the present invention.
- the film forming method of the present invention it is not necessary to apply internal strain in advance to the mixed particles to be sprayed.
- the mixed particles have an appropriate strength, a porous film in which voids are sufficiently formed can be formed without excessively pulverizing the mixed particles during spraying. Thereby, a porous film having a large specific surface area can be formed.
- an aerosol generator in order to prevent the mixed particles from aggregating to form secondary particles before spraying, an aerosol generator, a classifier, and / or used in the ultrafine particle beam deposition method are used. Or you may use a crusher.
- the porosity of the porous film to be formed can be adjusted by the spraying speed and spraying angle of the mixed particles, but the average particle diameter r and average particle diameter R of the mixed particles are as described above. It is possible to adjust more effectively by setting the value within a suitable range.
- the method for preparing the mixed fine particles is not particularly limited.
- the small diameter particles and the large diameter particles may be uniformly mixed with a ball mill or the like before spraying on the substrate.
- the film-forming body of the present invention comprises at least a porous film formed by the film-forming method described above and the base material.
- the porous film is a porous film having voids (also referred to as pores or pores) that can carry the dye of the dye-sensitized solar cell.
- the porosity of the porous membrane (also referred to as porosity, porosity, or porosity) is preferably 50% or more, more preferably 50 to 85%, still more preferably 50 to 80%, and more preferably 50 to 65%. Particularly preferred. If it is at least the lower limit of the above range, more dye can be supported.
- strength of a porous membrane can be strengthened more as it is below the upper limit of the said range.
- the porous film is formed on the substrate, and the thickness of the porous film is preferably 1 ⁇ m to 200 ⁇ m, more preferably 2 ⁇ m to 100 ⁇ m, and 5 ⁇ m to 50 ⁇ m. More preferably.
- the probability that the dye supported on the porous film absorbs light energy can be further increased, and the photoelectric conversion efficiency in the dye-sensitized solar cell can be further improved.
- the amount is not more than the upper limit of the above range, the exchange between the bulk electrolyte (electrolyte in the solar battery cell) and the electrolyte in the porous film is more efficiently performed by diffusion, and the photoelectric conversion efficiency can be further improved. .
- the porosity of the porous film constituting the film-forming body of the present invention is increased stepwise or continuously in the film thickness direction away from the substrate.
- the titanium oxide paste manufactured by Pexel is commercially available as a porous titanium oxide layer can be formed by low-temperature baking at 110 ° C. for 5 minutes.
- a porous semiconductor layer can be formed by the low temperature firing (see Chemistry Letters Vol. 36, No. 6 (2007), etc.).
- Such low-temperature baking is a mild temperature compared to the conventional baking temperature of 500 ° C., but it is still difficult to use a resin substrate or a resin film as a base material.
- the following method is mentioned.
- a dye described later is dissolved in a solvent, and a tetrabutylammonium cation (hereinafter sometimes referred to as TBA) is further added to prepare a dye solution.
- TBA tetrabutylammonium cation
- the film forming body can be used as a photoelectrode by immersing the film forming body in this dye solution and adsorbing the dye and TBA to the porous film.
- the dye is not particularly limited, and sensitizing dyes generally used in dye-sensitized solar cells can be used.
- the dye include cis-di (thiocyanato) -bis (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II) (hereinafter sometimes referred to as N3), N3 bis-TBA salt ( N719), tri (thiocyanato)-(4,4 ′, 4 ′′ -tricarboxy-2,2 ′: 6 ′, 2 ′′ -terpyridine) ruthenium tris-tetrabutylammonium salt (black dye) Ruthenium dye systems, etc.).
- the dye examples include coumarin, polyene, cyanine, hemicyanine, thiophene, indoline, xanthene, carbazole, perylene, porphyrin, phthalocyanine, merocyanine, catechol and squarylium.
- organic pigments can be mentioned.
- a donor-acceptor composite dye combining these dyes can also be used as the dye.
- a solvent used for preparing the dye solution it is possible to use one or a mixture of two or more of various solvents such as alcohol, nitrile, ether, ester, ketone, hydrocarbon, halogenated hydrocarbon and the like. it can.
- the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, and ethylene glycol.
- the nitrile include acetonitrile and propionitrile.
- the ether include dimethyl ether, diethyl ether, ethyl methyl ether, and tetrahydrofuran.
- Examples of the ester include ethyl acetate, propyl acetate, and butyl acetate.
- Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone.
- Examples of the hydrocarbon include pentane, hexane, heptane, octane, cyclohexane, toluene, and xylene.
- Examples of the halogenated hydrocarbon include methylene chloride and chloroform.
- N3 or N719 is used as the dye, it is preferable to use, for example, a mixed solvent of t-butyl alcohol (t-BuOH) and acetonitrile (MeCN) as a solvent for preparing the dye solution.
- t-BuOH t-butyl alcohol
- MeCN acetonitrile
- the TBA cation added to the dye solution is preferably added to the dye solution in a state where a hydroxylated TBA or a TBA salt is dissolved or dispersed in an appropriate solvent.
- TBA salt include brominated TBA (TBAB) and iodinated TBA (TBAI).
- the amount of TBA cation added to the dye solution is preferably in the range of 0.1 to 3.0 equivalents, more preferably in the range of 0.3 to 2.5 equivalents, per mole of the dye contained in the dye solution. A range of 0.5 to 1.5 equivalents is more preferable.
- the amount of TBA cation added is less than 0.1 equivalent, the effect of adding TBA cation is insufficient, and the photoelectric conversion efficiency becomes the same as when TBA cation is not added.
- the added amount of TBA cation exceeds 3.0 equivalents, the effect of adding TBA cation reaches its peak, which is not preferable.
- the concentration of the dye is not particularly limited, but is usually preferably in the range of 0.05 to 1.0 mM, more preferably in the range of 0.1 to 0.5 mM.
- the method for immersing the film-forming body in the dye solution is not particularly limited, and the film-forming body is immersed in the dye solution in a container, held at a constant temperature for a certain time, and then the film-forming body is pulled up. Is mentioned.
- a method of continuously charging, dipping and pulling up while moving the film-forming body into the dye solution is also included.
- the temperature of the dye solution during immersion is not particularly limited.
- the temperature is preferably 10 to 90 ° C.
- the immersion time is preferably 30 minutes to 50 hours. What is necessary is just to set the combination of immersion temperature and immersion time according to the combination of the kind of inorganic substance which comprises the pigment
- the dye-sensitized solar cell of the present invention is provided with the film-forming body or a photoelectrode comprising the film-forming body.
- a counter electrode, a separator, an electrolyte (electrolyte), and the like used in a known dye-sensitized solar cell can be used.
- Example 1 Small particles (average particle size: 30 nm) and large particles (average particle size: 2.31 ⁇ m) were mixed to prepare fine particles for spraying.
- Each of the fine particles for spraying was sprayed at a speed of 150 m / s to form a porous film (thickness 10 ⁇ m) made of titanium oxide on the glass substrate on which the transparent conductive film (FTO) was formed by the AD method.
- Table 1 shows the mixing ratio (weight ratio) between the small-diameter particles and the mixed particles in each Example and Comparative Example.
- Table 2 shows the characteristics of the film obtained by film formation.
- Comparative Example 1 As a result of Comparative Example 1, when only large particles (average particle size: 2.31 ⁇ m) were used, no film was formed. As a result of Comparative Example 2, when only small-diameter particles (average particle diameter: 30 nm) were used, no compaction was caused by the large-diameter particles, resulting in a green compact. And since the adhesiveness of particle
- Example 1 to 3 good porous membranes were obtained. From this, it can be seen that, when the small-diameter particles and the large-diameter particles are mixed, a porous film in which the small-diameter particles are joined together by hitting with the large-diameter particles is obtained. Further, in the porous membranes of Examples 1 to 3, good power generation efficiency was obtained.
- rutile type titanium oxide particles (rutile degree 95%, average particle size 2.31 ⁇ m, purity 99.9%, manufactured by Mitsuwa Chemical Co., Ltd.) were used.
- the conditions of the AD method used here are as follows.
- a film was formed using the film forming apparatus 10 shown in FIG.
- the mixed particles 4 were sprayed from the nozzle 2 having a rectangular opening of 5 mm ⁇ 0.5 mm to the glass substrate 3 at an injection speed of 150 m / s.
- Helium which is a carrier gas, was supplied from the cylinder 5 to the carrier pipe 6, and the flow rate was adjusted by the mass flow controller 7.
- the mixed particles for spraying were loaded into the aerosol generator 8, dispersed in a carrier gas, conveyed to the crusher 9 and the classifier 11, and sprayed from the nozzle 2 onto the substrate 3.
- a pump 12 is connected to the film forming chamber 1, and the film forming chamber is set to a negative pressure.
- a counter electrode made of glass with platinum coating was placed over the glass so as not to enter air, and the photoelectrode and the counter electrode were sandwiched with a double clip and pressed to obtain a simple cell of a dye-sensitized solar cell.
- the effective area was 4 mm square.
- the reason why the photoelectric conversion efficiency of the dye-sensitized solar cell according to Example 1 is excellent is that the porous film of the film forming body constituting the dye-sensitized solar cell has strength, electron conductivity, dye adsorbability, and electrolyte solution. It is because it is excellent in diffusibility.
- FIG. 5 shows an image taken at a magnification of about 100,000 times on the surface of the porous membrane that has been cut off smoothly by ion milling. It can be seen that the new surfaces of the fine particles are bonded together.
- the SEM photograph which imaged this cross section by about 20,000 times magnification is shown in FIG.
- the results of analyzing this SEM photograph are shown in FIGS.
- the porous film is mainly composed of small-diameter particles and fine particles obtained by pulverizing small-diameter particles, and the ratio of large-diameter particles contained in the porous film is 20.7%. It was estimated that the ratio of small and large particles in the porous membrane was higher than the ratio of small and large particles in the fine particles used when sprayed on the substrate.
- Example 4 Next, the average particle size of the small particles was changed from 30 nm to 200 nm (0.2 ⁇ m), and the influence of the small particle size was confirmed.
- Table 3 shows the characteristics of the film obtained by film formation.
- a simple cell of a solar cell has a power generation efficiency that can function as a battery, but by using small-sized particles having an average particle size of less than 0.2 ⁇ m, a simple cell of a dye-sensitized solar cell obtained from the film forming body can be used. The cell was found to have higher power generation efficiency.
- the film forming method in Example 4 was performed by the same film forming method as in Example 1 except that the average particle diameter of the small diameter particles was changed to 200 nm (0.2 ⁇ m).
- manufacture of the simple cell of a dye-sensitized solar cell, evaluation of photoelectric conversion efficiency (electric power generation efficiency), the measurement of the porosity, and the measurement of a particle ratio were performed by the method similar to Example 1.
- Example 5 [Production of PEN film and production of simple cell] A film was formed in the same manner as in Example 2 except that the substrate was changed to a PEN film (glass transition temperature (Tg): 126 ° C., with ITO coating) instead of the glass substrate. Furthermore, the simple cell of the dye-sensitized solar cell produced using this film forming body was produced, and the solar cell characteristic was compared. The characteristics of the obtained film and the characteristics of the simple cell of the dye-sensitized solar cell are shown in Table 4 together with Example 2. In addition, manufacture of the simple cell of the dye-sensitized solar cell in Example 5, evaluation of photoelectric conversion efficiency (power generation efficiency), the measurement of the porosity, and the measurement of a particle ratio were performed by the method similar to Example 1.
- Tg glass transition temperature
- ITO coating glass transition temperature
- the film can be formed on a PEN film having a Tg of 126 ° C. No particular damage was seen on the film.
- the porosity and power generation efficiency were not significantly different from those of the glass substrate (Example 2). From this, it is understood that a porous film that is the same as that on glass can be formed even on a resin film that cannot be heated.
- the film forming method of the present invention does not require a firing step, and therefore the time required for film formation can be shortened. Moreover, since it can form into a film at normal temperature, it is clear that a porous film can be formed on base materials, such as a plastics and a resin film.
- the film forming method of the present invention can be widely used for the production of dye-sensitized solar cells.
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Abstract
Description
本発明の第1の態様は、無機物質の微粒子を基材に吹き付けて、前記基材と前記微粒子とを接合させると共に、前記微粒子同士を接合させることによって、前記基材上に無機物質の多孔質膜を製膜する方法であって、前記微粒子は、異なる平均粒子径を有する少なくとも2種の微粒子である小径粒子と大径粒子とからなる、前記無機物質の多孔質膜を製膜する方法である。
本発明の第2の態様は、多孔質膜中の前記小径粒子と前記大径粒子との割合(小径粒子/大径粒子)が、前記基材に吹き付ける際に使用した微粒子中の前記小径粒子と前記大径粒子との割合(小径粒子/大径粒子)よりも増加している、前記第1の態様に記載の製膜方法である。
本発明の第3の態様は、前記小径粒子の平均粒子径rが、1nm≦r<200nmであり、かつ、前記大径粒子の平均粒子径Rが、0.2μm≦R≦200μmである、前記第1又は2の態様に記載の製膜方法である。
本発明の第4の態様は、前記小径粒子の平均粒径rが、1nm≦r<200nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦200μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第5の態様は、前記小径粒子の平均粒径rが、1nm≦r<200nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦100μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第6の態様は、前記小径粒子の平均粒径rが、1nm≦r<200nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦50μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第7の態様は、前記小径粒子の平均粒径rが、1nm≦r≦100nmであり、かつ、前記大径粒子の平均粒子径Rが、0.2μm≦R≦200μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第8の態様は、前記小径粒子の平均粒径rが、1nm≦r≦100nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦200μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第9の態様は、前記小径粒子の平均粒径rが、1nm≦r≦100nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦100μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第10の態様は、前記小径粒子の平均粒径rが、1nm≦r≦100nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦50μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第11の態様は、前記小径粒子の平均粒子径rが、1nm≦r≦100nmであり、かつ、前記大径粒子の平均粒子径Rが、1μm≦R≦10μmである、前記1又は2の態様に記載の製膜方法である。
本発明の第12の態様は、前記小径粒子の平均粒子径rと前記大径粒子の平均粒子径Rの相対比(r/R)が、(1/1000)≦(r/R)≦(1/5)の関係を満たす、前記第1~11のいずれか1つの態様に記載の製膜方法である。
本発明の第13の態様は、前記基材に吹き付ける際に使用した微粒子中の前記小径粒子:前記大径粒子の混合比が、(重量部)である前記第1~12のいずれか1つの態様に記載の製膜方法である。
本発明の第14の態様は、前記無機物質の微粒子を基材に吹き付ける処理(操作)が、前記小径粒子と前記大径粒子とを含む混合粒子の前記基材への吹き付けによって行われ、かつ、前記基材に吹き付けられた前記小径粒子に対して、前記大径粒子を衝突させることによって、前記小径粒子同士を接合して製膜する前記第1~13のいずれか1つの態様に記載の製膜方法である。
本発明の第15の態様は、前記第1~14のいずれか1つの態様において、前記無機物質が、酸化物半導体である製膜方法である。
本発明の第16の態様は、前記吹き付けを常温で行う、前記第1~15のいずれか1つの態様に記載の製膜方法である。
本発明の第17の態様は、前記基材が樹脂からなる前記第1~16のいずれか1つの態様に記載の製膜方法である。
本発明の第18の態様は、前記基材が樹脂からなるフィルムである前記第1~17のいずれか1つの態様に記載の製膜方法である。
本発明の第19の態様は、前記樹脂からなる基材のガラス転移温度(Tg)が、200℃未満である前記第17又は18の態様に記載の製膜方法である。
本発明の第20の態様は、前記多孔質膜が色素増感太陽電池の光電極用の多孔質膜である前記第1~19のいずれか1つの態様に記載の製膜方法である。
本発明の第21の態様は、前記第1~20のいずれか1つの態様に記載の製膜方法によって得られた製膜体である。
本発明の第22の態様は、前記多孔質膜中の前記大径粒子の含有率が、30体積%以下である前記第21の態様に記載の製膜体である。
本発明の第23の態様は、前記多孔質膜の空隙率が50~80%である前記第21又は22の態様に記載の製膜体である。
本発明の第24の態様は、前記第21~23のいずれか1つの態様に記載の製膜体を備えた光電極である。
本発明の第25の態様は、前記第21~23のいずれか1つの態様に記載の製膜体を備えた色素増感太陽電池である。
また、本発明の製膜方法では小径粒子及び大径粒子からなる混合粒子を基材に吹き付けることによって、基材表面に積もった小径粒子の上に大径粒子が衝突して該小径粒子を基材表面又は隣接する別の小径粒子に確実に接合させることができる。すなわち、小径粒子がまず基材上に堆積し、その上から大径粒子を打ち付けることができ、大きなエネルギー(機械的衝撃力)を小径粒子に与えることによって、小径粒子をより一層充分に接合させることができる。
この結果、従来よりも容易に多孔質膜を製膜できる。すなわち、従来よりも低速で微粒子の吹き付けを行った場合でも、確実に多孔質膜を製膜できる。
本発明の製膜体によれば、無機物質の粒子同士が互いに確実に接合し、多孔質膜を形成しているため、いわゆる圧粉体とは異なり、強度が高く、電子伝導性に優れる。この接合によって、多孔質膜内に色素吸着サイトとなる空隙が形成されるため、色素吸着性に優れる。その空隙は電解液が拡散することにも適しているため、電解液の拡散性に優れる。
本発明の製膜体は、優れた特性を有する多孔質膜を基材の表面に配しているため、光電極の構成部品として有用である。
本発明の色素増感太陽電池は、前記製膜体を備えているため、光電変換効率に優れる。
また、樹脂フィルム等の柔軟な基材を使用した製膜体を用いれば、変形可能な色素増感太陽電池とすることもできる。
<<製膜方法>>
本発明の製膜方法は、無機物質の微粒子を基材に吹き付けて、前記基材と前記微粒子とを接合させると共に、前記微粒子同士を接合させることによって、前記基材上に無機物質の多孔質膜を製膜する方法である。
前記無機物質としては、電子伝導性及び色素の担持性により優れた酸化物半導体が好ましい。前記酸化物半導体としては、酸化チタン(TiO2)、酸化亜鉛(ZnO)、チタン酸ストロンチウム(SrTiO3)等が挙げられる。これらの中でも、多孔質膜を形成した時に電子伝導性に優れる酸化チタンが好ましい。
前記無機物質として酸化チタンを用いる場合、上記いずれの酸化チタンを用いてもよい。
混合された混合粒子を使用して形成した多孔質膜は、色素増感太陽電池の光電極に適した強度を有するものとなりやすい。
上記範囲の下限値以上であることにより、色素(増感色素)をより多く担持でき、電解液がより拡散しやすい空隙が前記多孔質膜に形成されやすい。
上記範囲の上限が好ましくは200nm未満、より好ましくは100nm以下であることにより、前記小径粒子同士で接合した状態となりやすい。
この結果、当該多孔質膜の電子伝導性及び強度が一層向上しうる。
上記範囲の下限値以上であることにより、前記混合粒子を基材に吹き付ける際の、大径粒子が小径粒子に衝突するエネルギーをより大きくすることができる。
この結果、前記吹き付けによる製膜において、小径粒子同士の接合、小径粒子と基材との接合、又は小径粒子と大径粒子との接合をより確実に行える。この結果、当該多孔質膜の電子伝導性及び強度が一層向上しうる。
上記範囲の上限値以下であることにより、製膜時に前記基材上に形成されつつある多孔質膜を、大径粒子が削り取ってしまうことを防止できる。これにより、前記吹き付けによって着実に製膜を進行させられるので、製膜スピードを速めることができる。また、前記小径粒子同士で接合した状態となりやすい。
前記大径粒子の平均粒子径Rは、前記小径粒子の平均粒子径rと同じ測定方法で求められる。
なお、本発明に用いられる微粒子の平均粒子径の測定方法は、前記2つの方法(電子顕微鏡又はレーザー回折式粒度分布測定装置)には限られず、これらとは異なる測定方法によって測定してもよい。前記2つの方法以外の方法によって測定した粒子径が、上述の範囲外であっても、前記2つの方法によって測定すれば、上述の粒子径の範囲に入ってくるのであれば、本発明に用いられる無機物質の微粒子に含まれる。
一方、当該ピークの数を複数(例えば2つ~5つ)であるとしてフィッティングした方が、数学的若しくは論理的に妥当である場合は、当該ピークの数を複数として、フィッティングした粒径分布曲線を描いてもよい。この場合、当該ピーク数に応じて複数の平均粒子径r1、r2、r3・・・をもった第一小径粒子、第二小径粒子、第三小径粒子・・・が存在することになる。これらの複数の小径粒子をまとめて小径粒子群と呼ぶ。小径粒子群に属する各小径粒子の平均粒子径について、各小径粒子の存在比によって重み付けをして平均して得られた平均粒子径が、本発明の「小径粒子の平均粒子径r」に相当する。
一方、当該ピークの数を複数(例えば2つ~5つ)であるとしてフィッティングした方が、数学的若しくは論理的に妥当である場合は、当該ピークの数を複数として、フィッティングした粒径分布曲線を描いてもよい。この場合、当該ピーク数に応じて複数の平均粒子径R1、R2、R3・・・をもった第一大径粒子、第二大径粒子、第三大径粒子・・・が存在することになる。これらの複数の大径粒子をまとめて大径粒子群と呼ぶ。大径粒子群に属する各大径粒子の平均粒子径について、各大径粒子の存在比によって重み付けをして平均して得られた平均粒子径が、本発明の「大径粒子の平均粒子径R」に相当する。
本発明において、前記重量の差をより明確にすることによって、前記重量の差を考慮した吹き付け条件の設定をより容易に行えるので好ましい。例えば、前記重量の差が比較的大きい場合であると、前記混合粒子を基材に吹き付けて製膜する際、小径粒子同士の衝突エネルギーよりも、大径粒子が小径粒子へ与える衝突エネルギーを格段に大きくすることができる。すなわち、製膜過程において、前記基材又は隣接する別の粒子の上に到達した小径粒子に対して、吹き付けられた大径粒子が衝突することによって、衝突された前記小径粒子が前記基材又は前記隣接する別の粒子に押し付けられて若しくは擦り付けられて、前記小径粒子と前記基材、又は前記小径粒子と前記隣接する別の粒子へ、より確実に接合できる。
前記相対比(r/R)が前記関係を満たすものとすることによって、前記重量の差を適切な範囲とすることができ、強度及び電子伝導性が一層優れた多孔質膜を前記基材上に製膜できる。
上記範囲であると、基材上において、小径粒子に対して大径粒子をより確実に衝突させることができる。この結果、基材上に製膜される多孔質膜の強度及び電子伝導性を一層高められる。
前記微粒子は、小径粒子及び小径粒子が砕けた粒子、並びに大径粒子及び大径粒子が砕けた粒子が含まれ得る。
前記多孔質膜中の大径粒子及び大径粒子が砕けた粒子の含有率を少なくするほど、当該多孔質膜を構成する微粒子の粒径を揃えることができ、当該多孔質膜の強度及び電子伝導性を高められるので、好ましい。
また、多孔質膜の製膜効率の点からは、多孔質膜の形成には小径粒子の方がより多く寄与しているため、小径粒子の割合が大径粒子の割合に比べて多い方が好ましい。
前記透明基材としては、例えばガラス若しくはプラスチックからなる基板及び樹脂製フィルム等が挙げられる。
また、この衝突により、基材表面と微粒子表面に新生面が形成されて、主にこの新生面において、基材と微粒子とが接合する。
微粒子同士の衝突によって、互いの微粒子表面に新生面が形成されて、主にこの新生面において微粒子同士が接合する。この際、吹き付けの速度を適宜調整することによって、小径粒子及び大径粒子の砕ける程度を調整することができる。通常、高速で吹き付けるほど、小径粒子及び大径粒子の砕ける程度は大きくなる。
前記微粒子同士の衝突においては、微粒子が溶融するような温度上昇は発生し難いため、微粒子同士が接合した界面には、ガラス質からなる粒界層は実質的に存在しない。前記微粒子の吹き付けを継続することによって、次第に、基材表面に多数の微粒子が接合してなる多孔質膜が形成される。形成された多孔質膜は、色素増感太陽電池の光電極として充分な強度及び電子伝導性を有するので、焼成による焼き締めを必要としない。
前記吹き付けの速度を調整する方法としては、例えば吹き付けノズルの開口径(開口部の直径又は開口部の一辺の長さ)を調整することによって行うことができる。前記開口径を広げるほど、吹き付け速度を遅くすることができ、前記開口径を狭めるほど、吹き付け速度を速めることができる。例えば、ガス搬送された微粒子(小径微粒子又は大径微粒子)を1mm以下の開口径のノズル口を通して吹きつけることによって、数百m/s程度まで容易に加速できる。
(i)大径粒子が、基材への吹き付け時に生じる衝撃で砕けないか、ほとんど砕けない
(ii)小径粒子が、大径粒子に打ち付けられることによって変形しないか、ほとんど変形しない
大径粒子が衝撃で砕けると、砕けた大径粒子が膜中に取り込まれ、形成される多孔質膜の強度及び電気伝導性が低くなる場合があるため、上記(i)の場合が好ましい。また、小径粒子が大径粒子に打ち付けられることによって変形すると、形成される薄膜は、多孔質膜とならず、緻密な膜となる場合があるため、上記(ii)の場合が好ましい。
多くの場合、粒子同士が接合した面においては、粒子表面が溶融してできるガラス質からなる粒界層は実質的には無い。
通常、電子顕微鏡で観察した場合に、「接合状態」と単に「接触している状態」とは明らかに異なることが見て取れる。微粒子全体が観察できる(観察視野に微粒子全体が入る)程度の倍率(例えば5万~20万倍)のSEM写真を撮った場合、接合状態にある微粒子同士の境界には、隙間が形成されておらず密着している様子が観察される。密着した周長が連続して繋がっている領域は、接合状態の一形態であると判断できる。
上記範囲の上限値以下であることにより、前記吹き付ける混合粒子のうち、主に小径粒子が、基材又は既に接合している微粒子に衝突した際に、過度に砕けることなく、多孔質膜をより容易に形成できる。
上記範囲の下限値以上であることにより、前記吹き付ける混合粒子のうち、主に小径粒子が、基材又は既に接合している微粒子に確実に接合して、充分な強度及び電子伝導性の多孔質膜を形成することがより容易にできる。
前記搬送ガスによって加速する前記混合粒子の速度は、上記範囲内において、基材の種類、小径粒子の平均粒子径r、大径粒子の粒子径R、並びに小径粒子及び大径粒子をなす無機物質の種類等に応じて適宜調整すればよい。
前記常温環境の温度は、前記基材の融点以下であることが好ましい。前記基材が樹脂製である場合は、前記常温環境の温度はビカット軟化温度未満であることが好ましい。
本発明の製膜体は、前述した製膜方法によって形成した多孔質膜及び前記基材を少なくとも備えたものである。
前記多孔質膜の空隙率(空孔率、細孔率又は多孔度とも呼ばれる)は、50%以上が好ましく、50~85%がより好ましく、50~80%が更に好ましく、50~65%が特に好ましい。
上記範囲の下限値以上であると、色素をより多く担持することができる。上記範囲の上限値以下であると多孔質膜の強度をより強固にすることができる。
上記範囲の下限値以上であると、前記多孔質膜に担持させた色素が光エネルギーを吸収する確率を一層高めることができ、色素増感太陽電池における光電変換効率を一層向上できる。また、上記範囲の上限値以下であると、バルクの電解質(太陽電池セル内の電解質)と多孔質膜内の電解質との交換が、拡散によって一層効率よく行われ、光電変換効率を一層向上できる。
このような低温焼成は、従来の500℃の焼成温度に比べて穏やかな温度ではあるが、基材として樹脂製の基板又は樹脂製のフィルムを用いることは、やはり困難である。
まず、後述する色素を溶剤に溶かし、さらにテトラブチルアンモニウムカチオン(以下、TBAということがある)を添加して色素溶液を調製する。この色素溶液に前記製膜体を浸漬して、前記多孔質膜に色素及びTBAを吸着させることによって、前記製膜体を光電極とすることができる。
前記アルコールとしては、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、イソブチルアルコール、t-ブチルアルコール、エチレングリコールなどが挙げられる。
前記ニトリルとしては、アセトニトリル、プロピオニトリルなどが挙げられる。
前記エーテルとしては、ジメチルエーテル、ジエチルエーテル、エチルメチルエーテル、テトラヒドロフランなどが挙げられる。
前記エステルとしては、酢酸エチル、酢酸プロピル、酢酸ブチルなどが挙げられる。
前記ケトンとしては、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトンなどが挙げられる。
前記炭化水素としては、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、トルエン、キシレンなどが挙げられる。
前記ハロゲン化炭化水素としては、塩化メチレン、クロロホルムなどが挙げられる。
前記TBA塩としては、臭化TBA(TBAB)、ヨウ化TBA(TBAI)などが挙げられる。
以上の操作によって、本発明にかかる製膜体を構成する多孔質膜に、前記色素及びTBAを吸着させた、色素増感太陽電池用の光電極が得られる。
小径粒子(平均粒子径:30nm)と大径粒子(平均粒子径:2.31μm)を混合して、吹き付け用の微粒子を調製した。各吹き付け用の微粒子を150m/sの速度で吹き付けて、透明導電膜(FTO)が形成されたガラス基板上に、AD法によって酸化チタンからなる多孔質膜(厚さ10μm)を製膜した。
各実施例及び比較例における小径粒子と混合粒子との混合比(重量比)を表1に示す。
比較例2の結果の通り、小径粒子(平均粒子径:30nm)のみを用いた場合には、大径粒子による打ち付けがないため、圧粉体となった。そして、粒子同士の密着性が低く、良好な電子伝導性が得られないために発電効率が低くなった。
また、発電効率は、大径粒子の混合比率が高い方が良い結果となった。このことから、大径粒子を多く混合することによって、小径粒子に対して大径粒子をより確実に衝突させることができ、良好な多孔質膜が得られることがわかる。
小径粒子:大径粒子=10:90の実施例2で発電効率は7.06%となった。
実施例1~3では、良好な多孔質膜が得られた。このことから、小径粒子と大径粒子を混合すると、大径粒子による打付けによって小径粒子同士が接合された多孔質膜が得られることがわかる。
さらに、実施例1~3の多孔質膜では、いずれも良好な発電効率が得られた。
表1の大径粒子としてルチル型酸化チタン粒子(ルチル化率95%、平均粒子径2.31μm、純度99.9%、三津和化学社製)を使用した。
表1の小径粒子としてアナターゼ型酸化チタン粒子(型番=P25、ルチル化率30%、平均粒子約30nm、日本アエロジル社製)を使用した。
図1に記載の製膜装置10を使用して製膜した。製膜室1内において、5mm×0.5mmの長方形の開口部を持つノズル2からガラス基板3に対して、150m/sの噴射速度で混合粒子4を吹き付けた。
搬送ガスであるヘリウムをボンベ5から搬送管6へ供給し、その流速をマスフロー制御器7で調整した。吹き付け用の混合粒子をエアロゾル発生器8に装填し、搬送ガスに分散させて、解砕器9および分級器11へ搬送し、ノズル2から基板3へ噴射した。製膜室1にはポンプ12が接続されており、製膜室内を陰圧にした。
二次粒子(凝集粒子)の形成を防ぐために真空乾燥によって、混合粒子から水分を予め除去した微粒子を使用した。約10分間の噴射中、ステージ13を水平に動かして、ガラス基板3上に、均一な厚さの多孔質膜が形成されるようにした。
次に、実施例1~3、及び比較例2で製膜したガラス基板を、0.3mMに調製した色素(N719、ソラロニクス社製)のアルコール溶液に、室温で24時間浸漬した。
次に、色素を担持した多孔質膜およびガラス基板からなる光電極をアルコールで軽く洗浄した後、薄膜の周りに30μm厚みのシリコンゴムのスペーサーを配し、電解液(Iodolyte50、ソラロニクス社製)を注いだ。続いて、空気が入らないように、白金コーティング付きガラスからなる対極を被せて、ダブルクリップで光電極と対極とを挟んで圧着し、色素増感太陽電池の簡易セルを得た。有効面積は4mm角とした。
I‐V特性測定装置を備えたソーラーシミュレーター(AM1.5、100mW/cm2)を用いて、作製した各簡易セルの電池性能として、光電変換効率(発電効率)を指標として評価した。
その結果、実施例1~3、及び比較例2の光電変換効率は順に7.06%、3.48%、2.01%、1.92%であった。この結果から、実施例1~3の多孔質膜を備えた製膜体が光電極として優れていることが明らかである。
実施例1~3で作成した製膜体の多孔質膜の空隙率は、窒素吸着測定の方法で測定したところ、それぞれ55%、61%、53%であった。得られた膜の空隙率を表1に示す。同様の方法で、比較例1及び2で得られた製膜体の多孔質膜の空隙率を測定したところ、比較例1は膜が形成されなかったため、また、比較例2は圧粉体であったため、いずれも空隙率の測定は不可能であった。
小径粒子:大径粒子=10:90の比率を有する混合粒子を用いて作製した実施例1の製膜体の多孔質膜の断面を電子顕微鏡で観察し、SEM写真を撮ったところ(図5参照)、当該多孔質膜を構成する微粒子同士が接合していることを確認できた。図5は、多孔質膜の破断面をイオンミリングによって平滑に削りだした面を約10万倍の倍率で撮像したものである。微粒子の新生面同士が接着している様子がわかる。この断面を約2万倍の倍率で撮像したSEM写真を図6に示す。このSEM写真を解析した結果を図7、8に示す。図7、8より、当該多孔質膜は、主に小径粒子及び小径粒子が砕けた微粒子からなるものであり、当該多孔質膜に含まれる大径粒子の割合は、20.7%であると見積もられ、多孔質膜中の小径粒子と大径粒子との割合が、基材に吹き付ける際に使用した微粒子中の小径粒子と大径粒子の割合よりも増加していることがわかった。
次に、小径粒子の平均粒子径を30nmから200nm(0.2μm)に変更し、小径粒子サイズの影響を確認した。混合粒子における混合比率は小径粒子:大径粒子=10:90とした。
製膜して得られた膜の特性を表3に示す。
なお、実施例4における製膜方法は、小径粒子の平均粒子径を200nm(0.2μm)に変更した以外は、実施例1と同様の製膜方法により行った。また、色素増感太陽電池の簡易セルの製造、光電変換効率(発電効率)の評価、空隙率の測定及び粒子比率の測定は、実施例1と同様の方法により行った。
[PENフィルムを用いた製膜、簡易セルの製造]
基材をガラス基板に代えて、PENフィルム(ガラス転移温度(Tg):126℃、ITOコーティング付)に変更した以外は、実施例2と同様の方法により製膜した。さらに、この製膜体を用いて作製した色素増感太陽電池の簡易セルを作製し、太陽電池特性を比較した。
得られた膜の特性、及び色素増感太陽電池の簡易セルの特性を実施例2と共に表4に示す。
なお、実施例5における色素増感太陽電池の簡易セルの製造、光電変換効率(発電効率)の評価、空隙率の測定及び粒子比率の測定は、実施例1と同様の方法により行った。
また、空隙率や発電効率についてもガラス基板の場合(実施例2)と比べて大きな差は見られなかった。このことから、高熱をかけることができない樹脂フィルム上にも、ガラス上と変わらない多孔質膜を製膜できていることがわかる。
Claims (15)
- 無機物質の微粒子を基材に吹き付けて、前記基材と前記微粒子とを接合させると共に、前記微粒子同士を接合させることによって、前記基材上に無機物質の多孔質膜を製膜する方法であって、
前記微粒子は、異なる平均粒子径を有する少なくとも2種の微粒子である小径粒子と大径粒子とからなる前記無機物質の多孔質膜を製膜する方法。 - 多孔質膜中の前記小径粒子と大径粒子との割合(小径粒子/大径粒子)が、前記基材に吹き付ける際に使用した微粒子中の前記小径粒子と前記大径粒子の割合(小径粒子/大径粒子)よりも増加していることを特徴とする請求項1に記載の製膜方法。
- 前記小径粒子の平均粒子径rが、1nm≦r<200nmであり、かつ、前記大径粒子の平均粒子径Rが、0.2μm≦R≦100μmである請求項1又は2に記載の製膜方法。
- 前記小径粒子の平均粒子径rと、前記大径粒子の平均粒子径Rの相対比(r/R)が、(1/1000)≦(r/R)≦(1/5)の関係を満たす、請求項~3のいずれか一項に記載の製膜方法。
- 前記基材に吹き付ける際に使用した微粒子中の前記小径粒子:前記大径粒子の混合比が、0.1:99.9~99.9:0.1(重量部)である請求項1~4のいずれか一項に記載の製膜方法。
- 前記無機物質の微粒子を基材に吹き付ける処理が、前記小径粒子と前記大径粒子とを含む混合粒子の前記基材への吹き付けによって行われ、かつ、前記基材に吹き付けられた前記小径粒子に対して、前記大径粒子を衝突させることによって、前記小径粒子同士を接合して製膜する請求1~5のいずれか一項に記載の製膜方法。
- 前記無機物質が、酸化物半導体である請求項1~6のいずれか一項に記載の製膜方法。
- 前記吹き付けを常温で行うことを特徴とする請求項1~7のいずれか一項に記載の製膜方法。
- 前記基材が樹脂からなることを特徴とする請求項1~8のいずれか一項に記載の製膜方法。
- 前記樹脂からなる基材のガラス転移温度(Tg)が200℃未満である請求項9に記載の製膜方法。
- 前記多孔質膜が、色素増感太陽電池の光電極用の多孔質膜であることを特徴とする請求項1~10のいずれか一項に記載の製膜方法。
- 前記1~11のいずれか一項に記載の製膜方法によって得られたことを特徴とする製膜体。
- 前記多孔質膜中の前記大径粒子の含有率が、30%体積以下であることを特徴とする請求項12に記載の製膜体。
- 請求項12又は13に記載の製膜体を備えたことを特徴とする光電極。
- 請求項12又は13に記載の製膜体を備えたことを特徴とする色素増感太陽電池。
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JP2013513447A JP5322017B2 (ja) | 2011-05-20 | 2012-05-21 | 製膜方法、製膜体、及び色素増感太陽電池 |
EP12790324.3A EP2712683B1 (en) | 2011-05-20 | 2012-05-21 | Film forming method |
US14/117,999 US9721733B1 (en) | 2011-05-20 | 2012-05-21 | Method for forming a dye-sensitized solar cell having a porous film of an inorganic substance on a base material by spraying dry fine particles of an inorganic substance on the base material |
CN201280035294.0A CN103797554B (zh) | 2011-05-20 | 2012-05-21 | 制膜方法、制膜体及色素增敏太阳能电池 |
KR1020137032836A KR101419671B1 (ko) | 2011-05-20 | 2012-05-21 | 제막 방법, 제막체, 및 색소 증감 태양 전지 |
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WO2016136950A1 (ja) * | 2015-02-26 | 2016-09-01 | 積水化学工業株式会社 | 半導体膜の製造方法、及び色素増感太陽電池 |
JP2017512125A (ja) * | 2014-02-13 | 2017-05-18 | ユニベルシテ ピエール エ マリー キュリー (パリ6)Universite Pierre Et Marie Curie (Paris 6) | 表面をコーティングするための方法及びその方法を実行するための装置 |
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CN115117179A (zh) * | 2022-06-10 | 2022-09-27 | 华中科技大学 | 一种可印刷的多孔光学薄膜及其制备方法与应用 |
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KR101419671B1 (ko) | 2014-07-30 |
CN103797554B (zh) | 2017-09-01 |
KR20140008528A (ko) | 2014-01-21 |
TWI502761B (zh) | 2015-10-01 |
JP5322017B2 (ja) | 2013-10-23 |
TW201251101A (en) | 2012-12-16 |
JPWO2012161161A1 (ja) | 2014-07-31 |
EP2712683A1 (en) | 2014-04-02 |
CN103797554A (zh) | 2014-05-14 |
US9721733B1 (en) | 2017-08-01 |
EP2712683A4 (en) | 2015-02-25 |
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