CN104508183A - Film-forming method, porous film, photo-electrode, and dye-sensitized solar cell - Google Patents
Film-forming method, porous film, photo-electrode, and dye-sensitized solar cell Download PDFInfo
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- CN104508183A CN104508183A CN201480001982.4A CN201480001982A CN104508183A CN 104508183 A CN104508183 A CN 104508183A CN 201480001982 A CN201480001982 A CN 201480001982A CN 104508183 A CN104508183 A CN 104508183A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
This film-forming method comprises: producing porous particles through a step in which microparticles of an inorganic substance obtained from a raw material compound are synthesized in a solvent containing the raw material compound, and aggregated particles obtained by aggregating the microparticles are used to enhance the links between the microparticles contained in the aggregated particles; and blowing the porous particles onto a substrate to cause the substrate and the porous particles to join together, and the porous particles to join to each other, whereby a porous film composed of the inorganic substance on the substrate is formed.
Description
Technical field
The present invention relates to: by particle is formed on above-mentioned base material to base material winding-up comprise the porous film of above-mentioned particle film-forming method, by above-mentioned film-forming method the above-mentioned porous film formed, the optoelectronic pole possessing above-mentioned porous film and possess the dye-sensitized solar cell of above-mentioned optoelectronic pole.
The application in No. 2013-009210, the Japanese Patent Application of Japanese publication and CLAIM OF PRIORITY, quotes its content based on January 22nd, 2013 herein.
Background technology
As the formation method of porous film of optoelectronic pole forming dye-sensitized solar cell, known: the paste that the tackiness agent such as Titanium particles and high molecular polymer is mixed is coated on substrate, burnt till and formed the method for porous film.There is the advantage that can obtain porous film simply in the method, but owing to requiring thermotolerance to baseplate material, therefore there is the problem that the actual substrate used is limited to glass substrate.
Therefore, replace the method for being burnt till by paste, also study the method obtaining Titanium particles to comprise to substrate winding-up the masking body of titanium oxide.As such method, spray method, cold spray method, electrostatic spraying processes, hot spray process, aerosol deposition method (AD method) etc. can be enumerated.
As AD method in the past, patent documentation 1 ~ 3 can be enumerated.In patent documentation 1, as the Titanium particles (ultra micron hard brittle material) of winding-up, use and burnt till by 1 particle of the particle diameter by tens of about nm and condense for 2 particles about 50nm ~ 1 μm.2 particles have impact because winding-up to substrate produces and by boundary breaking, the feature easily pulverized.Therefore, obtain by the AD method of patent documentation 1 the masking body (dense film) that theoretical density is the compact substance of more than 95%.
In patent documentation 2 ~ 3, propose: by changing the making method of 2 particles used in the AD method of patent documentation 1, for obtaining the AD method of porous film instead of dense film.Specifically report: first, make 1 particle dispersion in the solution with tackiness agents such as high molecular polymers, make its dry solidification, obtain aggregate, further this aggregate is burnt till, obtain 1 particle thus and firmly sinter and form the sintered compact of the Porous of bulk.Then, with mortar, this sintered compact is pulverized, make it by the screen cloth of 25 μm further, obtain 2 particles being adjusted to about 20 μm sizes that can jet thus.Porous film is obtained by being jetted in the mode of carrying out colliding relative to the angle of substrate 60 ° by these 2 particles.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 3265481 publication
Patent documentation 2: Japanese Patent No. 4103470 publication
Patent documentation 3: Japanese Patent No. 4626829 publication
Summary of the invention
The problem that invention will solve
But, the words of the preparation method of 2 particles (winding-up particle) of patent documentation 2 ~ 3, even if make it be made particle diameter unification be less than 25 μm by screen cloth, be prepared as median size 20 μm, because the deviation of particle diameter is large, therefore in 2 particles bond strength each other, vesicularity of the porous film formed, also produce deviation.In addition, if median size is 2 particles of about 20 μm, then not only produce the masking effect forming film, and produce the injection effect reaming the film of formation, therefore masking efficiency step-down (film speed is slow), the more difficult thickness that makes is thickening.If obtain thick porous film and jet for a long time, the probability that the large footpath particle of accidental drill-through screen cloth is blowed also improves, and the possibility cracked in the porous film constantly formed also improves.In order to remove the particle in large footpath from winding-up particle and be a kind of unpractical method by the method that the opening of above-mentioned screen cloth narrows, this can produce blocking due to screen cloth, is difficult to the particle of a large amount of preparation winding-up.
The present invention makes in view of the above fact, and problem is to provide: the porous film easily can form the film-forming method of thick porous film than ever, being manufactured by this film-forming method, possess the optoelectronic pole of this porous film and possess the dye-sensitized solar cell of this optoelectronic pole.
Solve the means of problem
[1] a kind of film-forming method, it is characterized in that, comprise: use following aggregated particle, through the operation of the particulate comprised in described aggregated particle combination strengthening is each other made Porous particle, described Porous particle is jetted to base material, described base material is engaged with described Porous particle, and described Porous particle is engaged with each other, manufacture the porous film formed based on inorganic substance thus on the substrate; Described aggregated particle synthesizes in containing the solvent of starting compound with the particulate of the described starting compound described inorganic substance that are raw material and makes described particle coagulation.
Namely, a kind of film-forming method, it is characterized in that, comprise: use following aggregated particle, make, through the Porous particle operation of the combination strengthening each other of the particulate in described aggregated particle made, to base material winding-up, described base material to be engaged with described Porous particle, and described Porous particle is engaged with each other, manufactures the porous film formed based on described inorganic substance thus on the substrate; Described aggregated particle synthesizes in containing the solvent of starting compound with the particulate of the described starting compound described inorganic substance that are raw material and makes described particle coagulation.
[2] film-forming method according to above-mentioned [1], is characterized in that, by the operation of described particulate combination strengthening each other, makes the described particulate in described aggregated particle be engaged with each other under the condition of not filling described aggregated particle thick and fast.
Film-forming method according to above-mentioned [1], it is characterized in that, by in the operation of described particulate combination strengthening each other, under the condition of not filling described aggregated particle thick and fast, the described particulate in described aggregated particle is only made to be engaged with each other and not make described aggregated particle be engaged with each other.
[3] film-forming method according to above-mentioned [1] or [2], it is characterized in that, in the operation that the combination each other of described particulate is strengthened, burn till in temperature province more than the temperature that the position that can be contacted with each other by described particulate by solid state reaction is engaged, below the fusing point of described inorganic substance, thus described particulate is engaged with each other.
[4] film-forming method according to any one of above-mentioned [1] ~ [3], it is characterized in that, in the operation that the combination each other of described particulate is strengthened, forming the metal of described particulate by comprising or the reactive compounds of semi-conductor mixes with described aggregated particle, by described reactive compounds, described particulate mutual chemical being engaged.
[5] film-forming method according to any one of above-mentioned [1] ~ [4], is characterized in that, the median size of described aggregated particle and described Porous particle is 200nm ~ 2 μm.
[6] film-forming method according to any one of above-mentioned [1] ~ [5], is characterized in that, the median size of described particulate is 10nm ~ 100nm.
[7] film-forming method according to any one of above-mentioned [1] ~ [6], is characterized in that, in the described Porous particle of jetting to described base material, does not comprise the Porous particle that particle diameter is more than 5 μm.
That is, the film-forming method according to any one of above-mentioned [1] ~ [6], is characterized in that, in the Porous particle of described winding-up, does not comprise the Porous particle that particle diameter is more than 5 μm.[8] film-forming method according to any one of above-mentioned [1] ~ [7], is characterized in that, described porous film is the porous film of the optoelectronic pole of dye-sensitized solar cell.
[9] porous film, it is masking by the film-forming method according to any one of above-mentioned [1] ~ [8].
[10] optoelectronic pole, is characterized in that, possesses the porous film described in above-mentioned [9].
[11] dye-sensitized solar cell, is characterized in that, possesses the optoelectronic pole described in above-mentioned [10].
Invention effect
According to film-forming method of the present invention, use and make 1 particle (particulate) growth by liquid phase synthesizing method, make 2 particles (aggregated particle) of 1 particle coacervation further, therefore without the need to pulverizing making the bulk of 1 particles sintering, also without the need to making it pass through from screen cloth further with mortar as in the past.Stirred by limit in the reaction soln of liquid phase synthesis, while make particle growth, make this particulate aggregate with one another further, the aggregated particle with uniform particle diameter can be obtained.Aggregated particle is in the Porous state that particulate partly combines each other.Even if also its Porous can be maintained through the Porous particle bonding process of this particulate combination strengthening each other obtained to substrate collision.Consequently, vesicularity much higher hole plasma membrane can be obtained.In addition, Porous particle is in the same manner as aggregated particle, and particle diameter is unified, therefore can not be mixed with the particle in large footpath in winding-up particle, also produces hardly and sprays effect, therefore can effectively manufacture thick porous film.In addition, when forming thick porous film, also can make the region close with substrate and be same degree away from the vesicularity in the region of substrate, the vesicularity of film entirety can be made even.
Because film entirety is formed by the Porous particle of uniform particle sizes, therefore the structural strength of porous film of the present invention is high.Further, film entirety has much higher cell size.Therefore, the optoelectronic pole of pigment adsorptive capacity is added than ever.Consequently, the optoelectronic pole and the dye-sensitized solar cell that possess porous film of the present invention have excellent photoelectric transformation efficiency.
Accompanying drawing explanation
Fig. 1 is the schematic configuration diagram of the film forming apparatus can applied in the film-forming method of the first embodiment of the present invention.
Fig. 2 is the graph of the change of the pigment adsorptive capacity of the change of the thickness represented relative to porous film.
Embodiment
Below, based on preferred embodiment, with reference to accompanying drawing, the present invention is described, but the invention is not restricted to this embodiment.
It should be noted that, in this manual, particulate refers to the particle (primary particle) comprising inorganic substance.The particle that aggregated particle refers to above-mentioned particle coagulation and formed.Porous particle refers to and is burnt till by above-mentioned aggregated particle and the particle obtained.
" film-forming method "
The film-forming method of the first embodiment of the present invention uses following aggregated particle: containing (in liquid phase feed) in the solvent of starting compound, synthesize with the above-mentioned starting compound particulate (1 particle) comprising inorganic substance that is raw material and make above-mentioned particle coagulation, the aggregated particle formed thus.
Above-mentioned aggregated particle can be synthesized by known hydrothermal synthesis method, also can use commercially available product.The commercially available product of above-mentioned aggregated particle can be bought from such as Co., Ltd. of kingdom.In addition, as known hydrothermal synthesis method, following method can be applied: add autoclave using solid reaction material with as the aqueous solution that solvent or reactive material work, process under high-temperature and high-pressure conditions.By this process, solid reaction material dissolves and reacts to each other or react with the composition of the aqueous solution, and target particles can be made thus to separate out.Now, by making the condition such as kind, concentration, pH, stirring of temperature, the aqueous solution change, the particle shape, the state of aggregation that obtain can be controlled.As so known hydrothermal synthesis method, the method such as described in following reference can be enumerated.
< reference > water Hot method To I Ru セ ラ ミ Star Network ス powder synthesis (synthesis based on the ceramic powder of hydrothermal method), Liu Ze and road work, Nichias technology Times No. 2 No.353, pp1-7. in 2008; ア Na タ mono-ゼ type チ タ ヌ ア sosoloid Na ノ Li Quality To and ぼ す Tone shelf-regulating Conditions shadow Ring (preparation condition is on the impact of the character of anatase titanium dioxide sosoloid nanoparticle), the positive allusion quotation work in open country, Ai Zhi polytechnical university comprehensive technology research institute research report, 12nd phase, 2010.
The starting compound that above-mentioned liquid phase feed contains solvent and dissolves in a solvent or disperse.Above-mentioned raw materials compound is the compound containing the inorganic substance forming above-mentioned particulate.By such as using water as above-mentioned solvent, use TiCl
4as the hydrothermal synthesis method of above-mentioned raw materials compound, can obtain comprising the particulate of titanium oxide and the aggregated particle of this particle coagulation.
Above-mentioned inorganic substance are not particularly limited, but can enumerate the material of the porous film of the optoelectronic pole of such as known formation dye-sensitized solar cell.Specifically, the salt of the metal such as titanium, zinc or semi-conductor, this metal or semi-conductor or the halogenide etc. of this metal or semi-conductor can be exemplified.
The median size (major diameter average) forming the particulate (1 particle) of above-mentioned aggregated particle is not particularly limited, but preferred 1nm ~ 100nm, more preferably 5nm ~ 70nm, more preferably 10nm ~ 40nm.If the median size of above-mentioned particulate is more than 1nm, then easily obtain the aggregated particle of Porous, and the porous film of the sufficient specific surface area had for adsorbing sensitization pigment can be formed.If the median size of above-mentioned particulate is below 100nm, then can improves the bonding force between the particulate forming aggregated particle, the aggregated particle that physical strength is high can be obtained.
As the method for median size obtaining above-mentioned particulate, the major diameter by the multiple particulate of SEM Observe and measure can be enumerated and the method for averaging.Mensuration number when calculating mean value is more much more preferred, but can enumerate such as 30 ~ 100 aggregated particles, measures the major diameter of the above-mentioned particulate of each about 10 and calculates the method for mean value.
Above-mentioned aggregated particle is 2 particles that the particulate obtained by above-mentioned liquid phase synthesizing method is condensed further.The median size (major diameter average) of above-mentioned aggregated particle is not particularly limited, but preferably 0.1 μm ~ 5 μm, more preferably 0.2 μm ~ 2 μm, preferably 0.5 μm ~ 1.5 μm further.If the median size of above-mentioned aggregated particle is more than 0.1 μm, then easily can obtain the porous film with structural strength different from powder compact.That is, sufficient masking effect can easily be obtained.If the median size of above-mentioned aggregated particle is less than 5 μm, then can fully suppress to spray effect, the phenomenon that the porous film namely fully suppressing the aggregated particle of winding-up in advance to be formed is reamed by the aggregated particle of jetting afterwards.
As the method for median size obtaining above-mentioned aggregated particle, such as following method can be enumerated: with the method determined of peak value form of the volume mean diameter recorded by laser diffraction formula particle size distribution device distribution, by the major diameter of the multiple aggregated particle of SEM Observe and measure and the method for averaging.Mensuration number when calculating mean value is preferably The more the better, but can enumerate the major diameter the method calculating mean value that such as measure 30 ~ 100 aggregated particles.The particle diameter measuring above-mentioned aggregated particle is observed preferably by above-mentioned SEM.
In the present embodiment, in order to improve the structural strength of above-mentioned aggregated particle, carry out the joining process of the above-mentioned particulate combination strengthening each other by forming above-mentioned aggregated particle.As this joining process, preferably when using the tackiness agent containing high molecular polymer unlike patent documentation 2 ~ 3, above-mentioned aggregated particle being burnt till, more preferably only above-mentioned aggregated particle being burnt till (only above-mentioned aggregated particle being burnt till separately).Herein, above-mentioned high molecular polymer refers to that molecular weight (Mw) is the polymkeric substance of more than 1000.
Burning till in present embodiment, carries out, therefore without the need to burning till under the state of being filled thick and fast each other by above-mentioned aggregated particle for the object strengthening the particulate combination each other of having condensed.On the contrary, in order to prevent aggregated particle unnecessary combination each other, preferably burn till under the state not making above-mentioned aggregated particle fill thick and fast each other.Specifically, be preferably 3.7 ~ 4.1g/cm in the density of aggregated particle
3state under burn till.Due to this particularly important, be described in further detail therefore.
The above-mentioned tackiness agent burning till middle use in the past, uses for the object making unconjugated particle aggregate with one another.Further, in order to make particle state of aggregation each other reliable, be necessary before burning till, make the particle being attached with tackiness agent fill thick and fast each other.This tackiness agent burns mistake after burning till, and has the auxiliary particle function firmly sintered each other.But, the size of the sintered compact (bulk) that extremely difficult control obtains after burning till.Therefore, sintered compact is pulverized, use the operations unified for desired size (classification) such as strainer not lack further.
On the other hand, about the above-mentioned aggregated particle in present embodiment, owing to combining before burning till each other as the particulate of 1 particle, therefore do not need above-mentioned tackiness agent.By above-mentioned aggregated particle being burnt till under the condition not using above-mentioned tackiness agent, above-mentioned aggregated particle is not made to be bonded to one another thus, the particulate forming above-mentioned aggregated particle engages each other more firmly, the Porous particle of the structural strength of the above-mentioned aggregated particle that can be improved.Now, owing to not using above-mentioned tackiness agent, therefore do not form above-mentioned aggregated particle (2 particles) and firmly combine and the bulk (sintered compact) formed.Sintered compact in the past needs pulverizing afterwards, but can not produce such trouble in the present embodiment.In the present embodiment, by not using above-mentioned tackiness agent, even if also can obtain after burning till thus and the above-mentioned aggregated particle Porous particle that similarly particle diameter is consistent.
As long as the temperature province of burning till above-mentioned is that the temperature strengthening the combination each other of above-mentioned particulate is just not particularly limited, but preferably can be contacted with each other by above-mentioned particulate more than temperature that position engages by solid state reaction and temperature province below the fusing point of above-mentioned inorganic substance.Herein, " solid state reaction " refers to, in the temperature province below the melting temperature of above-mentioned particulate, above-mentioned particulate contact with each other position produce atom diffusion and combine again, above-mentioned particulate contact with each other position occur bonding reaction.
When above-mentioned aggregated particle comprises titanium oxide, above-mentioned firing temperature preferably 400 ~ 1000 DEG C, is more preferably 500 ~ 800 DEG C, preferably 500 ~ 600 DEG C further.In this firing temperature, firing time preferably 1 hour ~ 24 hours, more preferably 3 hours ~ 12 hours, preferably 5 hours ~ 12 hours further.
The median size of above-mentioned Porous particle is preferably roughly the same with above-mentioned aggregated particle.Even if burnt till by above-mentioned aggregated particle as mentioned above, if do not use tackiness agent, be above-mentioned firing temperature and above-mentioned firing time, then aggregated particle also bonds each other hardly.In addition, even if suppose that above-mentioned aggregated particle is attached to each other by above-mentioned burning till, insecure due to its attachment, therefore by broken slightly and the size of original aggregated particle can be got back to simply.
The density of above-mentioned Porous particle is not particularly limited, but is preferably 3.3 ~ 4.2g/cm
3, be more preferably 3.5 ~ 4.2g/cm
3, more preferably 3.7 ~ 4.1g/cm
3.
If density is above-mentioned scope, then easily can obtain vesicularity much higher hole plasma membrane.
When above-mentioned Porous particle comprises titanium oxide, the Mohs' hardness of this Porous particle is preferably in the scope of 5.5 ~ 6.0.
If the Mohs' hardness of above-mentioned scope, then suppress, by the pulverizing of the Porous particle caused of jetting, easily to form the porous film of the vesicularity maintaining Porous particle.
As the structural strength in order to improve above-mentioned aggregated particle by forming the process of the above-mentioned particulate combination strengthening each other of above-mentioned aggregated particle, also can carry out replacing above-mentioned burning till based on chemically treated joint.
Specifically, such as, can using containing forming the metal of above-mentioned particulate or the reactive compounds of semi-conductor, above-mentioned reactive compounds being mixed with above-mentioned aggregated particle, utilizes above-mentioned reactive compounds to be engaged by above-mentioned particulate mutual chemical.As above-mentioned reactive compounds, the compound being promoted reaction by light or heat can be used.
When above-mentioned particulate is the particulate comprising titanium oxide, such as TiCl can be enumerated as above-mentioned reactive compounds
4.This aggregated particle be impregnated in the TiCl that concentration is 0.05 ~ 0.1mol/L
4the aqueous solution 30 minutes, 60 ~ 100 DEG C of heating 30 minutes ~ 2 hours (or irradiating UV light while heating), the combination each other of the particulate in aggregated particle can be strengthened thus.Now, be bonded to each other to not allow aggregated particle and form bulk, stirring the heating of above-mentioned aqueous solution limit by limit, aggregated particle can be suppressed thus to be engaged with each other.
< is based on the masking > of AD method
Below, the film-forming method of the porous film as the first embodiment of the present invention is described with reference to Fig. 1.
It should be noted that, the accompanying drawing used in the following description is schematic diagram, and the ratio of length, width and thickness etc. can be not identical with the article of reality, can appropriate change.
Fig. 1 is the pie graph of the film forming apparatus 60 that can be applied to present embodiment.Wherein, as long as the film forming apparatus used in the film-forming method of present embodiment is to base material winding-up as the device of the above-mentioned Porous particle of the raw material of porous film, can be not limited to the formation shown in Fig. 1.
< film forming apparatus >
Film forming apparatus 60 possesses gas-holder 55, transporting tube 56, nozzle 52, base station 63 and masking room 51.
In gas-holder 55, be filled with for making Porous particle 54 accelerate to the gas (hereinafter referred to as transport gas) that base material 53 is jetted.
One end of transporting tube 56 is connected with gas-holder 55.The transport gas supplied from gas-holder 55 supplies to transporting tube 56.
In transporting tube 56, from leading portion side, be disposed with mass flow controller 57, aerosol generator 58, the deployment conditions of the Porous particle 54 transported in gas can be adjusted to appropriate pulverizer 59 and classifier 61.By pulverizer 59, Porous particle 54 can be removed each other because of state that moisture etc. adheres to.In addition, even if hypothesis exists the Porous particle passed through from pulverizer 59 with the state of attachment, also this particle can be removed with classifier 61.
By mass flow controller 57, the flow of the transport gas supplied from gas-holder 55 to transporting tube 56 can be adjusted.In aerosol generator 58, be filled with Porous particle 54.When manufacturing the porous film of dye-sensitized solar cell, the Porous particle 54 before winding-up can be made to adsorb sensitization pigment in advance.Porous particle 54 disperses in the transport gas supplied by mass flow controller 57, transports to pulverizer 59 and classifier 61.
Nozzle 52 is configured with in the mode omitting base material 53 on illustrated opening portion and base station 63 facing.The other end of transporting tube 56 is connected with nozzle 52.Transport gas containing Porous particle 54 sprays from the opening portion of nozzle 52 to base material 53.
In the mode that base material 53 face 72 abuts with the upper surface 73 of base station 63, be placed with base material 53.In addition, another face 71 (masking face) of base material 53 and the opening portion of nozzle 52 facing.Porous particle 54 and the masking face of spraying together with the transport gas from nozzle 52 are collided, and manufacture the porous film comprising Porous particle 54.
The component of base station 63 forming film forming apparatus 60 is preferably formed by following material, that is, according to the median size of Porous particle 54, hardness, injecting velocity and suitably control the material of Porous particle 54 collision energy each other on masking face 71.If such component, then due to improve Porous particle 54 with the adaptation in masking face 71 and the Porous particle 54 piled up easily engage each other, therefore easily can make vesicularity much higher hole plasma membrane.
Base material 53 preferably comprises: the Porous particle 54 of winding-up be absorbed in masking face 71 and do not run through, material that can be closely sealed with Porous particle 54.As such base material 53, such as resin masking (resin film-making) can be enumerated.Due to can masking at normal temperatures by AD method, therefore do not require that base material 53 has the thermotolerance of height.As long as suitably carry out the selection of base material 53 more specifically according to the film forming condition such as material, injecting velocity of Porous particle 54, the purposes of porous film.
Masking room 51 is provided with in order to be filmed under reduced atmosphere.Vacuum pump 62 is connected with masking room 51, as required by decompression in masking room 51.
In addition, in masking room 51, possesses the illustrated base station crosspoint of omission.
< blowing method >
Below, an example of the blowing method of Porous particle 54 is described.
First, make vacuum pump 62 operate and reduce pressure in masking room 51.Pressure in masking room 51 is not particularly limited, and is preferably set to 5 ~ 1000Pa.By being decompressed to this degree, suppress the convection current in masking room 51, Porous particle 54 is easy to the predetermined portion winding-up transfiguration in masking face 71.
Then, from gas-holder 55, transport gas is supplied to transporting tube 56, transported flow velocity and the flow of gas by mass flow controller 57 adjustment.As transport gas, such as O can be used
2, N
2, the common gas such as Ar, He or air.
As long as suitably set the flow velocity and flow that transport gas according to the material of the Porous particle 54 of jetting from nozzle 52, median size, flow velocity and flow.
Porous particle 54 is filled in aerosol generator 58, Porous particle 54 is scattered in the transport gas of flowing in transporting tube 56, accelerates.With subsonic speed ~ ultrasonic speed, Porous particle 54 is sprayed from the opening portion of nozzle 52, be laminated in the masking face 71 of base material 53.Now, Porous particle 54 can be set as such as 10 ~ 1000m/s to the injecting velocity in masking face 71.But this speed is not particularly limited, as long as suitably set according to the material of base material 53.
By continuing to carry out jetting until the porous film comprising Porous particle 54 reaches the thickness of regulation, the continuous collision of Porous particle 54 has been absorbed in the Porous particle 54 in the masking face 71 of base material 53 thus, form newborn face on the surface of Porous particle 54 each other by Porous particle 54 collision each other, Porous particle 54 engages in this newborn face each other.Rise owing to not producing the integrally fused such temperature of Porous particle 54 when Porous particle 54 collision each other, therefore formed hardly in newborn face and comprise vitreous grain boundary layer.
When the porous film of Porous particle 54 becomes thickness (such as 1 μm ~ 100 μm) of regulation, stop the winding-up of the Porous particle 54 from nozzle 52.
By above operation, the masking face 71 of base material 53 manufactures the porous film comprising the thickness of the regulation of Porous particle 54.
Be illustrated the film-forming method based on AD method above, but film-forming method of the present invention is not limited to AD method.The known spray method as powder blowing process, cold spray method, electrostatic spraying processes, hot spray process etc. can be used, above-mentioned Porous particle is jetted to base material, manufactures porous film thus.
" porous film "
The porous film of the second embodiment of the present invention is the porous film formed on base material by the film-forming method of the first embodiment.Because film entirety is formed by the Porous particle of uniform particle sizes, therefore the structural strength of this porous film is high.Further, film entirety has much higher cell size.Therefore, the optoelectronic pole that pigment adsorptive capacity adds than ever is obtained.Consequently, the optoelectronic pole and the dye-sensitized solar cell that possess porous film of the present invention have excellent photoelectric transformation efficiency.
The purposes of the porous film of present embodiment is not limited to optoelectronic pole, can the widespread use make use of the species adsorbs of porous structure, in purposes that material supports.
" optoelectronic pole "
The optoelectronic pole of the 3rd embodiment of the present invention is the optoelectronic pole being adsorbed with sensitization pigment in the porous film of the second embodiment.The kind of sensitization pigment is not particularly limited, and can apply known pigment.In the third embodiment, porous film is preferably formed on transparent conductive substrate.
Except using the porous film of the second embodiment, the optoelectronic pole of the 3rd embodiment can be manufactured by ordinary method.
" dye-sensitized solar cell "
The dye-sensitized solar cell of the 4th embodiment of the present invention possess the 3rd embodiment optoelectronic pole, to electrode and electrolytic solution or dielectric substrate.Electrolytic solution is preferably sealed in optoelectronic pole by sealing material and between electrode.
As the base material forming the porous film forming optoelectronic pole, resin molding or resin sheet that surface defines nesa coating can be used in.As above-mentioned resin (plastics), preferably there is the material of the perviousness of visible ray, such as polyacrylic, polycarbonate, polyester, polyimide, polystyrene, polyvinyl chloride, polymeric amide etc. can be enumerated.Among these, polyester, particularly polyethylene terephthalate (PET) are produced in a large number as transparency and heat-proof film and use.By using so resinous substrate, thin and light flexible dye-sensitized solar cell can be manufactured.
Above-mentioned electrolytic solution can apply the known electrolytic solution used in dye-sensitized solar cell.Be dissolved with redox couple (ionogen) in the electrolytic solution.In the electrolytic solution, without departing from the scope of spirit of the present invention, other additives such as weighting agent, tackifier can be contained.
In addition, dielectric substrate (solid electrolyte layer) can be applied and replace electrolytic solution.Above-mentioned dielectric substrate has the function same with electrolytic solution, is any one state in gel or solid state.As above-mentioned dielectric substrate, can application examples as following dielectric substrate, that is: add gelating agent or tackifier in the electrolytic solution, as required except desolventizing, the dielectric substrate thus Electrolyte Gel or solidification obtained.By using the dielectric substrate of gel or solid state, need not worry that electrolytic solution spills from dye-sensitized solar cell thus.
Except using the optoelectronic pole of the 3rd embodiment, the dye-sensitized solar cell of the 4th embodiment can be made by ordinary method.
The porous film forming the second embodiment of the optoelectronic pole of the 3rd embodiment is compared with the porous film formed by powder blowing process in the past, and homogeneity and the pigment adsorptivity of the homogeneity of structural strength, structure, vesicularity, vesicularity are all excellent.Consequently, the weather resistance of the optoelectronic pole of the 3rd embodiment and the dye-sensitized solar cell of the 4th embodiment and photoelectric transformation efficiency can be made to improve.
Embodiment
Then, by embodiment, the present invention will be described in more detail, but the invention is not restricted to these examples.
[embodiment 1]
Buy commercially available aggregated particle and use, the mean value that described aggregated particle comprises 1 particle diameter is about the TiO of the particle coagulation to about 1 μm of 15nm
2.By this aggregated particles of cleaning such as Purified Waters, spread out on bucket (バ ッ ト) not fill aggregated particle mode each other thick and fast and make it dry.The above-mentioned aggregated particle of the median size of about 1 of dried powdery μm is dropped into reagent bottle and temporary safe-keeping.
Then, the aggregated particle 10g of this dried powdery is dropped into volume 150cm
3the container of oxidation aluminum.Now pressure is not applied, for comprising the state in gap to a certain degree between particle to powder.In addition, now tackiness agent is not used.
In air atmosphere, burn till 5 hour at 500 DEG C with this state, obtain comprising the median size TiO that unification is about 1 μm in the same manner as above-mentioned aggregated particle
2porous particle.
The density of the Porous particle obtained is 3.8g/cm
3.
By AD method, this Porous particle is jetted on the PEN substrate being formed with ito film, manufacture and comprise TiO
2porous film.Thickness at random can adjust in the scope of 0.1 μm ~ 30 μm.
[embodiment 2]
Buy commercially available aggregated particle and use, the mean value that described aggregated particle comprises 1 particle diameter is about the TiO of the particle coagulation to about 1 μm of 30nm
2.By this aggregated particles of cleaning such as Purified Waters, the mode of not filling thick and fast each other with aggregated particle spreads out and makes it dry on bucket.The above-mentioned aggregated particle of the median size of about 1 of dried powdery μm is dropped into reagent bottle and temporary safe-keeping.
Then, the aggregated particle 10g of this dried powdery is dropped into volume 150cm
3the container of oxidation aluminum.Now pressure is not applied, for comprising the state in gap to a certain degree between particle to powder.In addition, now tackiness agent is not used.
Burn till 5 hours at 500 DEG C in air atmosphere with this state, obtain comprising the median size TiO that unification is about 1 μm in the same manner as above-mentioned aggregated particle
2porous particle.
The density of the Porous particle obtained is 4.0g/cm
3.
By AD method, this Porous particle is jetted on the PEN substrate being formed with ito film, makes and comprise TiO
2porous film.Thickness at random can adjust in the scope of 0.1 μm ~ 30 μm.
[embodiment 3]
Buy commercially available aggregated particle and use, the particle coagulation that the mean value that described aggregated particle comprises 1 particle diameter is about 15nm is the TiO of about 1 μm
2.By this aggregated particles of cleaning such as Purified Waters, the mode of not filling thick and fast each other with aggregated particle spreads out and makes it dry on bucket.The above-mentioned aggregated particle of the median size of about 1 of dried powdery μm to be dropped in reagent bottle and temporary safe-keeping.
Then, the aggregated particle 10g of this dried powdery is dropped into volume 150cm
3the container of oxidation aluminum.Now pressure is not applied, for comprising the state in gap to a certain degree between particle to powder.In addition, now tackiness agent is not used.
In air atmosphere, burn till 5 hour at 300 DEG C with this state, obtain comprising the median size TiO that unification is about 1 μm in the same manner as above-mentioned aggregated particle
2porous particle.
The density of the Porous particle obtained is 3.7g/cm
3.
By AD method, this Porous particle is jetted on the PEN substrate being formed with ito film, manufacture and comprise TiO
2porous film.Thickness can adjust arbitrarily in the scope of 0.1 μm ~ 30 μm.
[comparative example 1]
The mean value of made by known Verneuil method 1 particle diameter is about the TiO of 15nm
2the mean value of particle and 1 particle diameter is the TiO of 2 μm
2the particle that particle mixes with 10:90 (volume ratio) uses without burning till, and by AD method, to the above-mentioned mixed particle of PEN substrate winding-up being formed with ito film, manufactures and comprises TiO
2porous film.Thickness can adjust arbitrarily in the scope of 0.1 μm ~ 30 μm.
But, owing to not making the TiO of 1 particle
2particle bonds and directly jets and masking, the TiO in the porous film therefore obtained
2particle joint each other only depends on collision energy during winding-up.Therefore, need strongly to jet to obtain sufficient collision energy.But if strongly jet, the vesicularity of porous film reduces, and can become dense film in extreme situations.In addition, collision energy is jetted the size of particle, the material (hardness) of substrate are driven.Like this, neither be impossible although adjust vesicularity by means of only the intensity of collision energy, very difficult.
[comparative example 2]
Use the TiO that the mean value of 1 particle diameter made by known Verneuil method is 15nm
2particle, uses this particle without burning till, by AD method, to jet above-mentioned particle to the PEN substrate being formed with ito film, attempts making and comprises TiO
2porous film.But, the powder compact of fragile structure can only be obtained.
[comparative example 3]
Be the TiO of 15nm by the mean value of 1 particle diameter made by known Verneuil method
2particle mixes with 97:3 (weight ratio) with polyoxyethylene glycol (PEG) (Mw:6000) as tackiness agent.At room temperature make this mixture dry solidification, obtain the aggregate after 1 particle coacervation.After this aggregate is burnt till 5 hours at 500 DEG C, pulverized by the block of mortar by the sintered compact obtained, make it by the screen cloth of 25 μm, make thus and comprise TiO
2porous particle.
The median size of the Porous particle obtained is about 10 μm.Use this Porous particle, by AD method, the PEN substrate being formed with ito film is jetted above-mentioned Porous particle and make and comprise TiO
2film (thickness 1.8 μm).
Then attempt making the porous film with the thickness of more than 10 μm, but be mixed with the particle in the large footpath much more than 10 μm in the particle of winding-up, spray effect and have the advantage, thick porous film can not be obtained.
The mensuration > of < specific surface area
By the film-forming method of embodiment 1, embodiment 2 and comparative example 1, make multiple porous films that thickness is different, compare its vesicularity.For the comparison of vesicularity, evaluate by comparing pigment adsorptive capacity.Specifically, each porous film be impregnated in the solution comprising N719 pigment, after pigment is adsorbed, impregnate porous plasma membrane in another solvent, makes the pigment being adsorbed in porous film depart from.Measure the amount of pigment of this disengaging, calculate the pigment adsorptive capacity (pigment adsorption density) of the per unit volume of each porous film, thus many cell sizes.Show its result in fig. 2.
In the porous film obtained by the film-forming method of embodiment 1 and embodiment 2, even if Thickness Variation, pigment adsorption density also can not change, roughly necessarily.Even if this represents the Thickness Variation making porous film, its vesicularity also keeps certain.In addition, the pigment adsorption density of the porous film of embodiment 1 is higher than the pigment adsorption density of embodiment 2, and specific surface area is large.This represents that, because the median size of 1 particle used in the film-forming method of embodiment 1 is less than the median size of embodiment 2, therefore specific surface area becomes large.Therefore, show: by adjusting the median size of 1 particle used in film-forming method of the present invention, the vesicularity of the porous film obtained can be controlled.
On the other hand, in the porous film that the film-forming method by comparative example 1 obtains, pigment adsorption density changes according to thickness, and film is thicker, and pigment adsorption density more reduces.This suggests the brittle deformation that particle occurs in masking, the crushed and densification of the porous structure of porous film.
The mensuration > of < photoelectric transformation efficiency η
The porous film obtained by film-forming method by embodiment 1, embodiment 2, comparative example 1 and comparative example 3 uses as the optoelectronic pole of dye-sensitized solar cell, determines its efficiency of conversion.As to electrode, be used in the glass substrate of one side with platinum.Use N719 as pigment, use AN50 (SOLARONIX Inc.) as electrolytic solution, to make solar battery cell by ordinary method.Use commercially available solar simulator to determine the photoelectric transformation efficiency of each solar battery cell possessing each porous film.Its result displayed in Table 1.
Measurement result shows: the solar battery cell employing the porous film of embodiment 1 and embodiment 2 demonstrates higher photoelectric transformation efficiency than the solar battery cell of the porous film employing comparative example 1.Think that this result reflects that the pigment adsorption density (vesicularity) of the porous film of embodiment 1 and embodiment 2 is higher than comparative example 1.In addition, because the thickness of the porous film of comparative example 3 is thin, therefore photoelectric transformation efficiency is low.This result shows: the porous film obtained by film-forming method of the present invention is useful as the optoelectronic pole of dye-sensitized solar cell.
[table 1]
| Masking result | Thickness | Conversion efficiency | |
| Embodiment 1 | Porous film | 13.2μm | 6.3％ |
| Embodiment 2 | Porous film | 12.7μm | 5.8％ |
| Embodiment 3 | Porous film | 13.0μm | 5.1％ |
| Comparative example 1 | Porous film | 13.4μm | 4.2％ |
| Comparative example 2 | Powder compact | - | - |
| Comparative example 3 | Porous film | 1.8μm | 1.2％ |
[summary of embodiment and comparative example]
The thicker porous film of thickness is obtained by the film-forming method of embodiment 1 and 2.Because its specific surface area is large, pigment adsorptive capacity is many, therefore demonstrates high-photoelectric transformation efficiency η.Be aware of in addition: the embodiment 1 that the median size of 1 particle used in masking is little has the specific surface area larger than embodiment 2, therefore by the median size of reduction 1 particle, its specific surface area can be increased.
Also can obtain the thicker porous film of thickness in the same manner as embodiment 1 and 2 by the film-forming method of comparative example 1, but its specific surface area is less than embodiment, photoelectric transformation efficiency η is also poor.In addition, as mentioned above, owing to controlling the vesicularity of porous film by means of only the particle collision energy each other of winding-up, the condition exerting to study winding-up is therefore needed.
In comparative example 2, due to the particle of the little 15nm of median size of only jetting, therefore become the powder compact of only build-up of particles.The fragile structure of powder compact, to the degree of easily peeling off from substrate, does not have the intensity that can use as the porous film of dye-sensitized solar cell.
In comparative example 3,1 particle will be fixed with tackiness agent and the block of sintering is pulverized further and obtains particle, by this particle masking, therefore not obtain thick porous film.As its reason, the median size of the particle of winding-up is about 10 μm, in this winding-up particle, be also mixed with the particle being greater than 10 μm, therefore masking effect and injection effect phase antagonism in masking, and film growth stops.In addition, the phenomenon that film is broken in midway is also observed under some film forming condition.
Each formation in each embodiment described above and their combination etc. are examples, without departing from the scope of spirit of the present invention, can carry out forming additional, omit, displacement and other change.In addition, the invention is not restricted to each embodiment, only limited by the scope of claim (claim).
Utilizability in industry
Film-forming method of the present invention, porous film, possess above-mentioned porous film optoelectronic pole and employ the dye-sensitized solar cell of above-mentioned optoelectronic pole can widespread use in the field of solar cell.
Nomenclature
51 ... masking room, 52 ... nozzle, 53 ... base material, 54 ... Porous particle, 55 ... tank, 56 ... transporting tube, 57 mass flow controllers, 58 ... aerosol generator, 59 ... pulverizer, 60 ... film forming apparatus, 61 ... classifier, 62 ... vacuum pump, 63 ... base station, 71 ... masking face, 72 ... the face, 73 of the opposition side in masking face ... the mounting surface (upper surface) of base station
Claims (11)
1. a film-forming method, it is characterized in that, comprise: use following aggregated particle, through the operation of the particulate comprised in described aggregated particle combination strengthening is each other made Porous particle, described Porous particle is jetted to base material, described base material is engaged with described Porous particle, and described Porous particle is engaged with each other, manufacture the porous film formed based on inorganic substance thus on the substrate; Described aggregated particle synthesizes in containing the solvent of starting compound with the particulate of the described starting compound described inorganic substance that are raw material and makes described particle coagulation.
2. film-forming method according to claim 1, is characterized in that, by the operation of described particulate combination strengthening each other, makes the described particulate in described aggregated particle be engaged with each other under the condition of not filling described aggregated particle thick and fast.
3. film-forming method according to claim 1 and 2, it is characterized in that, in the operation that the combination each other of described particulate is strengthened, burn till in temperature province more than the temperature that the position that can be contacted with each other by described particulate by solid state reaction is engaged, below the fusing point of described inorganic substance, thus described particulate is engaged with each other.
4. the film-forming method according to any one of claims 1 to 3, it is characterized in that, in the operation that the combination each other of described particulate is strengthened, forming the metal of described particulate by comprising or the reactive compounds of semi-conductor mixes with described aggregated particle, utilizing described reactive compounds to be engaged by described particulate mutual chemical.
5. the film-forming method according to any one of Claims 1 to 4, is characterized in that, the median size of described aggregated particle and described Porous particle is 200nm ~ 2 μm.
6. the film-forming method according to any one of Claims 1 to 5, is characterized in that, the median size of described particulate is 10nm ~ 100nm.
7. the film-forming method according to any one of claim 1 ~ 6, is characterized in that, in the described Porous particle of jetting to described base material, does not comprise the Porous particle that particle diameter is more than 5 μm.
8. the film-forming method according to any one of claim 1 ~ 7, is characterized in that, described porous film is the porous film of the optoelectronic pole of dye-sensitized solar cell.
9. a porous film, it is masking by the film-forming method according to any one of claim 1 ~ 8.
10. an optoelectronic pole, is characterized in that, possesses porous film according to claim 9.
11. 1 kinds of dye-sensitized solar cells, is characterized in that, possess optoelectronic pole according to claim 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2013-009210 | 2013-01-22 | ||
| JP2013009210 | 2013-01-22 | ||
| PCT/JP2014/051253 WO2014115763A1 (en) | 2013-01-22 | 2014-01-22 | Film-forming method, porous film, photo-electrode, and dye-sensitized solar cell |
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| CN104508183A true CN104508183A (en) | 2015-04-08 |
| CN104508183B CN104508183B (en) | 2017-07-18 |
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| CN201480001982.4A Active CN104508183B (en) | 2013-01-22 | 2014-01-22 | Film-forming method, multiple aperture plasma membrane, optoelectronic pole and dye-sensitized solar cell |
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|---|---|
| JP (1) | JPWO2014115763A1 (en) |
| KR (1) | KR20150110455A (en) |
| CN (1) | CN104508183B (en) |
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| JP2020152951A (en) * | 2019-03-19 | 2020-09-24 | 積水化学工業株式会社 | Forming method for ceramic film, manufacturing apparatus for ceramic film, and film type flexible solar battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003208901A (en) * | 2002-01-16 | 2003-07-25 | Nissan Motor Co Ltd | Porous oxide film, its manufacturing method and cell of fuel cell using the same |
| JP2004039286A (en) * | 2002-06-28 | 2004-02-05 | Toto Ltd | Method for manufacturing optical semiconductor electrode and photoelectric conversion element |
| CN101127374A (en) * | 2007-09-11 | 2008-02-20 | 西安交通大学 | Making method for flexible dye sensitized solar battery nano crystal thin film |
| CN101289223A (en) * | 2008-03-26 | 2008-10-22 | 重庆大学 | Method for preparing titanic oxide nano powder with visual light catalytic activity |
| JP2012241244A (en) * | 2011-05-20 | 2012-12-10 | National Institute Of Advanced Industrial Science & Technology | Film-formed body, photoelectrode provided with the film-formed body, and dye-sensitized solar cell provided with the photoelectrode |
-
2014
- 2014-01-22 JP JP2014558592A patent/JPWO2014115763A1/en active Pending
- 2014-01-22 TW TW103102411A patent/TW201439375A/en unknown
- 2014-01-22 KR KR1020157002174A patent/KR20150110455A/en not_active Application Discontinuation
- 2014-01-22 WO PCT/JP2014/051253 patent/WO2014115763A1/en active Application Filing
- 2014-01-22 CN CN201480001982.4A patent/CN104508183B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003208901A (en) * | 2002-01-16 | 2003-07-25 | Nissan Motor Co Ltd | Porous oxide film, its manufacturing method and cell of fuel cell using the same |
| JP2004039286A (en) * | 2002-06-28 | 2004-02-05 | Toto Ltd | Method for manufacturing optical semiconductor electrode and photoelectric conversion element |
| CN101127374A (en) * | 2007-09-11 | 2008-02-20 | 西安交通大学 | Making method for flexible dye sensitized solar battery nano crystal thin film |
| CN101289223A (en) * | 2008-03-26 | 2008-10-22 | 重庆大学 | Method for preparing titanic oxide nano powder with visual light catalytic activity |
| JP2012241244A (en) * | 2011-05-20 | 2012-12-10 | National Institute Of Advanced Industrial Science & Technology | Film-formed body, photoelectrode provided with the film-formed body, and dye-sensitized solar cell provided with the photoelectrode |
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| WO2014115763A1 (en) | 2014-07-31 |
| CN104508183B (en) | 2017-07-18 |
| JPWO2014115763A1 (en) | 2017-01-26 |
| TW201439375A (en) | 2014-10-16 |
| KR20150110455A (en) | 2015-10-02 |
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