CN106471594A - The colouring method of porous plastid, optoelectronic pole and optical-electric module - Google Patents
The colouring method of porous plastid, optoelectronic pole and optical-electric module Download PDFInfo
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- CN106471594A CN106471594A CN201580036635.XA CN201580036635A CN106471594A CN 106471594 A CN106471594 A CN 106471594A CN 201580036635 A CN201580036635 A CN 201580036635A CN 106471594 A CN106471594 A CN 106471594A
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- base material
- pigment
- colouring method
- semiconductor layer
- porous plastid
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- 238000000034 method Methods 0.000 title claims abstract description 188
- 238000004040 coloring Methods 0.000 title claims abstract description 104
- 210000002706 plastid Anatomy 0.000 title claims abstract description 58
- 230000005693 optoelectronics Effects 0.000 title claims description 26
- 239000000463 material Substances 0.000 claims abstract description 182
- 239000000049 pigment Substances 0.000 claims abstract description 168
- 239000000243 solution Substances 0.000 description 134
- 239000004065 semiconductor Substances 0.000 description 102
- 206010070834 Sensitisation Diseases 0.000 description 46
- 230000008313 sensitization Effects 0.000 description 46
- 238000004043 dyeing Methods 0.000 description 38
- 230000008569 process Effects 0.000 description 32
- 210000004027 cell Anatomy 0.000 description 30
- 238000010586 diagram Methods 0.000 description 24
- 238000001035 drying Methods 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 230000007246 mechanism Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000006071 cream Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000002372 labelling Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCLXLZGAYCTHQJ-UHFFFAOYSA-N 1h-cyclohepta[b]pyridine Chemical compound C1=CC=CC=C2NC=CC=C21 HCLXLZGAYCTHQJ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BGOFCVIGEYGEOF-UJPOAAIJSA-N helicin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=CC=C1C=O BGOFCVIGEYGEOF-UJPOAAIJSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
- Optical Filters (AREA)
Abstract
A kind of colouring method of porous plastid, makes the porous plastid being formed on the surface of base material contact with the solution containing pigment, so that described porous plastid is dried it is characterised in that having following operation afterwards：While conveying described base material, so that described porous plastid and the described solution of the transport path setting along described base material is contacted, so that described porous plastid is dried downstream, this operation is carried out repeatedly.
Description
Technical field
The present invention relates to the colouring method of porous plastid in dye-sensitized solar cell, using this colouring method system
The optoelectronic pole made and the optical-electric module possessing this optoelectronic pole.
The Patent 2014-166630 CLAIM OF PRIORITY that the application is filed an application in Japan based on August in 2014 on the 19th,
Here cite its content.
Background technology
In recent years, solaode is attracted attention as the TRT of green energy resource, advance silicon class solaode and
The exploitation of dye-sensitized solar cell.Dye-sensitized solar cell is due to having high-photoelectric transformation efficiency and holding at a low price
Easily volume production, so its construction and manufacture method are widely studied.
Dye-sensitized solar cell is generally configured with optoelectronic pole, comparative electrode, electrolyte or dielectric substrate and constitutes.Make
For optoelectronic pole, generally by base material, transparency conducting layer, semiconductor layer, sensitization pigment and constitute.Semiconductor layer is as a rule
Porous construct.
In dye-sensitized solar cell, the Main Function of sensitization pigment is, by irradiated light stimulus, puts
Go out electronics.In addition, the Main Function of the semiconductor layer being made up of titanium oxide etc. is, provides and accept from energized sensitization pigment
The injection of electronics, conveys electronics to transparency conducting layer, and makes oxidation-reduction pair from electrolyte or dielectric substrate for the electronics
(acidifying unit) is to the reaction zone of sensitization pigment movement.
Towards described above dye-sensitized solar cell practical, recently, imported volume to volume mode (with
Under, be denoted as RtoR mode) dye-sensitized solar cell the positive sustainable development of continuous production, i.e. will be rolled into a roll
Base material untie and convey to direction, after forming element by various operations on base material or carrying out
Rolling is again wrapped around after the laminating each other of two or more base material or assembling.
For example, there is the dye-sensitized solar cell battle array that can manufacture by such a way disclosed in patent documentation 1
Row, i.e. form first electrode array and paired electrod-array respectively using RtoR mode, by these electrod-arrays assemble, close
Envelope, and carry out lamination processing (with reference to Figure 15 and Figure 20 etc.).
In addition, there being the manufacture of the dye-sensitized solar cell array possessing following manner to fill disclosed in patent documentation 2
Put, i.e. as described above, the flaky material of wound into rolls is untied, carry out photoelectricity pool unit in conveying in upstream side
Processing etc., and again wrap around into web-like in downstream.
Patent documentation 1：International Publication No. 2008/093117
Patent documentation 2：International Publication No. 2008/093111
Content of the invention
When manufacturing dye-sensitized solar cell, as described above, needing to make sensitization pigment support in Porous construction
Semiconductor layer, that is, dyeed.In the past, attempted by with once the contacting of solution containing sensitization pigment, make sensitization color
Element efficiently supports in semiconductor layer, but there is a problem of as follows, i.e. can not support the sensitization pigment of q.s or foot to be supported
If the sensitization pigment of enough amounts supports, activity time is elongated, or manufacturing process become complicated.
Carry out various researchs for the problems referred to above, supported in semiconductor layer recently as more effectively making sensitization pigment
Method it is known to repeatedly carry out the colouring method of following operation, i.e. make containing sensitization pigment solution connect with porous plastid
Touch, be then dried and so that sensitization pigment is supported in porous plastid.
However, porous plastid effectively, efficiently and is easily repeated to the contact of pigment and dry specific dyeing
Method is not suggested.
The present invention sets up in view of the foregoing, and its problem is to provide one kind can efficiently and easily make q.s
Pigment support the colouring method of porous plastid in porous plastid, the optoelectronic pole made using this colouring method and possess this
The optical-electric module of optoelectronic pole.
The colouring method of the porous plastid of the present invention makes the porous plastid and molten containing pigment being formed on the surface of base material
Liquid contacts, and so that described porous plastid is dried afterwards, wherein, has following operation：While conveying described base material, make described
Porous plastid is contacted with the described solution of the transport path setting along described base material, makes described Porous soma downstream
Dry, described operation is carried out repeatedly.
According to said method, only rely on conveying base material and porous plastid just can be repeated to the contact of solution and drying.
In the colouring method of the porous plastid of the present invention it is preferred that in above-mentioned operation, make the conveying of described base material
Direction (transport path) continuously bends along the vertical direction.
According to said method, even if expanding the length of base material it is also possible to suppression is implemented needed for the colouring method of the present invention
The increase of distance.
In the colouring method of the porous plastid of the present invention it is preferred that in above-mentioned operation, helically arrange described
The conveying direction (transport path) of base material.
According to said method, width extension, spiral forming transport path the axle along described base material is configured to
Every spiral all offsets, so making base material helically rotate and alternately repeatedly move forward and backward for one week to the direct of travel of base material
Ground conveying base material, therefore, it is possible to suppress further to implement the increase of the distance needed for the colouring method of the present invention.
It is preferred that with the width center of described base material as axle in the colouring method of the porous plastid of the present invention
Described base material is reversed by line, and is conveyed to a direction in rotation.
According to said method, by base material is reversed curl (that is, with the both ends of the length direction of base material as starting point
And become the state of coil buckling), and conveyed in rotation, porous plastid can be repeated and to the contact of solution and be dried.
The optoelectronic pole of the present invention is made using the colouring method of described porous plastid.
In addition, the optical-electric module of the present invention possesses described optoelectronic pole.
According to above-mentioned composition, can obtain by porous plastid being repeated to contact and the drying of solution in porous plastid
On supported q.s pigment optoelectronic pole.In addition, can obtain possessing this optoelectronic pole, and it is suitable to quantity-produced photoelectricity mould
Block.
According to the present invention, it is possible to provide efficiently and easily make the pigment of q.s support the porous plastid in porous plastid
Colouring method and the optoelectronic pole made using this colouring method, optical-electric module.The present invention is simultaneously achieved the pigment of q.s
Support and improving productivity.
Brief description
Fig. 1 is the skeleton diagram of the colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 2 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 3 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 4 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 5 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 6 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 7 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 8 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Fig. 9 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Figure 10 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Figure 11 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Figure 12 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Figure 13 is the skeleton diagram of the variation of colouring method of the porous plastid for first embodiment of the invention is described；
Figure 14 is the skeleton diagram of the colouring method of the porous plastid for second embodiment of the invention is described；
Figure 15 is the skeleton diagram of the colouring method of the porous plastid for third embodiment of the invention is described.
Description of symbols
10：Base material
11：Semiconductor layer (porous plastid)
12：Pigment solution (solution)
A：Axis
D1、D3：Direction
Specific embodiment
Hereinafter, referring to the drawings the colouring method of the porous plastid being suitable for embodiments of the present invention (below, is only denoted as
" colouring method ") illustrate.It should be noted that accompanying drawing used in the following description is schematic figure, length, width
And the ratio of thickness etc. is not limited to identical with material object, can suitably change.
The colouring method of the present invention is preferably applied to manufacture the situation of dye-sensitized solar cell by RtoR mode,
It is the method that can efficiently and easily make the sensitization pigment of q.s support the semiconductor layer in Porous construction." supporting pigment "
Refer to the meaning of " dyeing ".And, supporting of pigment for example can be carried out by the absorption of pigment.
Therefore, in the applicable the embodiments of the present invention below illustrating, as dye-sensitized solar cell, explanation
The object being manufactured using colouring method.But, dye-sensitized solar cell is the colouring method manufacture using the present invention
One of object, object is not limited to dye-sensitized solar cell.In addition, sensitization pigment is also the dyeing of the present invention
One of pigment used in method, in the colouring method of the present invention, pigment used is not particularly limited.
Dye-sensitized solar cell (omitting diagram) possesses following construction, i.e. on the surface of base material successively lamination
The semiconductor layer that conductive layer and the titanium oxide that constructed by Porous etc. form, the interval configuration separating regulation supports in titanium oxide layer
The optoelectronic pole of dye-sensitized solar cell of sensitization pigment (pigment) and define platinum (Pt) etc. on the surface of base material
Electric conductor membrane comparative electrode, and in these gap filling electrolytes.
The colouring method of the present invention has following operation, i.e. makes the semiconductor layer being formed on the surface of base material and contains
Solution (below, being denoted as " the pigment solution ") contact of sensitization pigment, makes porous plastid be dried making described base material downstream.With
Under, this operation is denoted as " dyeing process ".In addition, in the colouring method of the present invention, following operation is carried out repeatedly, i.e.
While conveying base material, make described porous plastid and contact with the pigment solution arranging along transport path, make this many downstream
Hole plastid is dried.
" drying " here is not necessarily required to completely remove the solvent being used for pigment solution, as long as being capable of the present invention's
Purpose is it is also possible to residual solvent.For example, by the solvent that contains in dried base material amount (drying will before base material
The quality of quality-dried base material) with respect to the solvent containing in the base material before drying amount (drying to start before base material
Quality-contact with pigment solution before base material quality) the residual solvent amount that defines of ratio (quality %) in 90 mass %
Following situation is also contained in dry state.
Generally be dried so that residual solvent amount be 60 mass % below preferably, below more preferably 30 mass %, more
Below more preferably 10 mass %, below particularly preferably 3 mass %.When below residual solvent amount about 3 mass %,
It is difficult to produce the transfer to conveying roller for the solvent, thus preferably.It is highly preferred that residual solvent amount is below about 2 mass %.
In addition, being not particularly limited to specific drying meanss, can take and make use of natural drying, air-supply to be dried, add
Heated drying or the known method of aftermentioned such air knife or hot ply rolling (ラ ミ ロ Le) etc., and select felicity condition to enter
OK, to become residual solvent amount as described above.
(first embodiment)
Hereinafter, the first embodiment of the present invention is described with reference to Fig. 1～Figure 13.Fig. 1 is for present embodiment is described
The skeleton diagram of colouring method.
As shown in figure 1, the colouring method of present embodiment has following operation, i.e. make base material 10 surface 10a,
The semiconductor layer 11 (porous plastid) of the Porous construction being formed at least one side in the 10b of the back side contacts with pigment solution 12,
Section makes semiconductor layer 11 be dried behind.Here, " surface " refers to the direction of the base material 10 when dyeing process starts plate upward
Face.On the other hand, " back side " refer to when dyeing process starts base material 10 be directed downward plate face.
As the material of base material 10, as long as can process strip and or bendable or can roll up, and it is real to be suitable to RtoR mode
The quantity-produced material of existing dye-sensitized solar cell, is not particularly limited.As this material, preferably have
There is pliability.As concrete example, polyethylene terephthalate (PET) can be enumerated.
Be suitable for the colouring method of present embodiment in the surface 10a, back side 10b of base material 10 and the face dyeed successively
Lamination is formed with conductive layer (omitting diagram) and semiconductor layer 11.
As the material of conductive layer, for example, can include：Tin indium oxide/stannum oxide (ITO), fluorine-doped tin oxide (FTO),
Zinc oxide, stannum oxide, tin-antiomony oxide (ATO), tin indium oxide/zinc oxide (IZO), gallium oxide/zinc oxide (GZO), titanium oxide etc.
Transparent conductive body or be processed in the metals such as the titanium of shape of a mesh, platinum, gold, silver, copper, chromium, nickel, tungsten, ferrum, aluminum or these metals
Alloy of two or more metals etc., is not particularly limited.Even if in these materials, point out from conductivity and high this of transparency
Send out ITO preferred, FTO is particularly preferred from thermostability and the good this point of weatherability.
The material of semiconductor layer 11 and thickness be not particularly limited it is contemplated that the performance of dye-sensitized solar cell and
Design etc. is suitably selected.As the material of semiconductor layer 11, titanium oxide (TiO can be enumerated2).In the case of being somebody's turn to do, semiconductor layer
11 thickness preferably more than 1 μm and less than 30 μm, more preferably more than 3 μm and less than 20 μm.By by semiconductor layer 11
Thickness sets within the above range, and the photoelectric transformation efficiency of dye-sensitized solar cell improves.
When semiconductor layer 11 is the Porous titanium oxide layer being made up of titanium oxide, for example can be by being coated with the electrically conductive
Cream containing titanium oxide simultaneously carries out heat treated (that is, burning till) and is formed.
The coating process of the cream containing titanium oxide is not particularly limited, and example can go out silk screen print method, spin-coating method, scraper plate
The known methods such as method, doctor blade method.
As the cream containing titanium oxide, preferably coordinate the cream of Titanium particles, organic bond resin and solvent.Enter
And it is also possible to as needed, be combined with these materials and disappear for the heating forming space part in Porous titanium oxide layer
Property resin particle or various additives.
The surface area of Porous titanium oxide layer is bigger, more can effectively support sensitization pigment.Therefore preferred raw material is oxygen
The surface area changing titanium particle is the bigger the better.From the purpose of the surface area increasing Titanium particles, the primary particle size of titanium oxide
(volume average particle size) is the smaller the better.
For example, the primary particle size of Titanium particles be preferably more than 3nm and below 500nm, more preferably more than 3nm and
Below 200nm.
The crystal type of Titanium particles can for Detitanium-ore-type, rutile-type, brucite type any one.When titanium oxide grain
When the crystal type of son is Detitanium-ore-type, when being used for the manufacture of dye-sensitized solar cell as present embodiment, its
Reactivity ratio's rutile-type is high, and the electron injection of autosensibilization pigment is more effective, thus preferably.
For to the shape of the containing ratio of the primary particle size in Titanium particles or Titanium particles, the cream containing titanium oxide
The organic bond resin that is adjusted of viscosity or solvent etc. in detail and optimum condition is for example in (Japan) franchise the
Disclosed in No. 5444195 publications.
Porous titanium oxide layer can be formed as described above by using the cream containing titanium oxide and carry out heat treated,
But gas can also be conveyed by helium etc. to form thin layer, pass through aerosol to blow attached titanium oxide microparticle to base material at a high speed
Sedimentation (AD method) and formed.So, as long as the forming method of semiconductor layer 11 is suitable to the material of semiconductor layer 11 and pigment is quick
The manufacture method of change type solaode, is not limited to burn till or AD method.
The sensitization pigment (omitting diagram) supporting in semiconductor layer 11 is not particularly limited it is contemplated that the material of semiconductor layer 11
The performance of matter or dye-sensitized solar cell and design etc. and suitably select.
As the preferred sensitization pigment supporting on quasiconductor, cis- two (thiocyanogen)-two (2,2 '-connection can be included
Pyridine -4,4 '-dioctyl phthalate) close ruthenium (II), cis- two (sulfur cyanogen)-two (2,2 '-bipyridyl -4,4 '-dioctyl phthalate) close ruthenium
(II) double 4-butyl ammoniums (below, being abbreviated as N719), three (thiocyanogens)-(4,4 ', 4 "-three carboxyl -2,2 '：6 ',
2 "-ter cycloheptapyridine) close the ruthenium class pigments such as the three -4-butyl ammonium (melanin) of ruthenium.Wherein, as particularly preferred ruthenium class color
Element, can enumerate N719.
Sensitization pigment can be used alone one kind it is also possible to and with two or more.And with the case of two or more, only
According to purpose, the combination of various materials and ratio are suitably selected.
As long as the Vehicle Composition in pigment solution is suitably selected according to the species of the sensitization pigment using, do not have
Especially limit, for example, can be alcohols, nitrile, ethers, lipid, ketone, hydro carbons, halogenated hydrocarbon etc..
The water content of the solvent in pigment solution is more low better, preferably uses desiccant etc. and imposes anhydrous process.Logical
Cross reduction water content, can suppress to be sensitized the obstruction that supports of pigment further, sensitization pigment is supported in quasiconductor with good state
Layer 11.
The concentration of the sensitization pigment of pigment solution is preferably less than 10mmol/L, more preferably below 2mmol/L, more enters one
Step is preferably 1mmol/L, particularly preferably 0.8mmol/L, more particularly preferably 0.5mmol/L.By pigment will be sensitized
Upper limit of concentration value is set as above-mentioned value, the precipitation of pigment when can suppress dyeing process further, particularly be dried, and pigment is with more
Good state supports in semiconductor layer 11.The concentration limit value of sensitization pigment is not particularly limited, but from making sensitization pigment more
Efficiently support in semiconductor layer 11 this point, the concentration limit value of sensitization pigment is preferably 0.1mM.
As shown in figure 1, in the dyeing process of present embodiment, when along arrow D1 direction conveying base material 10, making base material
10 transport path continuously bends along the vertical direction with respect to arrow D1 direction.Here, " above-below direction " is the arrow representing in Fig. 1
Head D2 direction.The transporting velocity of base material 10 is for example assumed to be 0.01m/, and to divide above and 200m/ to divide following, but preferably considers for reality
Apply the size of the device of the colouring method of present embodiment and performance and set, be not particularly limited.
Illustrate following composition in Fig. 1, i.e. in advance base material 10 surface 10a successively lamination and formed conductive layer and
Base material 10 is untied by semiconductor layer 11 afterwards from the web-like base material 10R1 of wound into rolls, with respect to arrow D1 direction to upper and lower
Continuous bending, wound into rolls after multiple dyeing process, become web-like base material 10R2 again.However, conductive layer and half
The formation of conductor layer 11 can also be carried out after untiing base material 10 from web-like base material 10R1 and before implementing dyeing process.
In the dyeing process of present embodiment, the transport path along the base material 10 of continuous bending in the vertical direction sets
Put pigment solution 12.
Conveying roller R, R ..., R is equally spaced on the conveying direction (arrow D1 direction) of base material 10.Adjacent conveying
Roller R, R configure different position upper in vertical direction (arrow D2 direction) each other.
The conveying roller R in upside for the configuration and configuration separate the distance of regulation in the conveying roller R of downside and set.
The conveying roller R of downside is arranged on the depth location of regulation with respect to solution tank 18.
The conveying roller R of upside is arranged on the top of the peristome of solution tank 18.
Base material passes through the lower section of conveying roller R of downside and then covers the mode of the top of conveying roller R of upside below 10
Alternately it is placed on adjacent conveying roller R.
By arrange in this wise conveying roller R, R ..., R and base material 10, can when to web-like base material 10R2 conveying base material 10,
Form transport path that following action is repeated, i.e. send downwards base material 10 in curved substrates afterwards upwards
Side sends (continuously bending along the vertical direction).
In the solution tank 18 being accommodated with pigment solution 12, in transport path, it is configured with the conveying roller R of downside, thus exist
From position P1 to position P2, composition semiconductor layer 11 contacts with pigment solution 12 and (that is, base material 10 be impregnated in pigment solution
12) contact site 35, is pulled up and dry doing constituting base material 10 from position P2 to position P1 from pigment solution 12
Dry portion 36.
By such configuration, when to arrow D1 direction conveying base material 10, in the upper table of base material 10 and pigment solution 12
The position P1 that face (liquid level) connects, base material 10 initially enters in pigment solution 12, and pigment solution 12 starts to connect with semiconductor layer 11
Touch.
Afterwards, in the conveying direction position P2 that period is connected with the upper surface of pigment solution 12 upward of base material 10,
Base material 10 separates from pigment solution 12, and semiconductor layer 11 is exposed in the air.
By exposing in atmosphere semiconductor layer 11, semiconductor layer 11 is dried.
As described above, the position that position P1 is semiconductor layer 11 to start to pigment solution 12 contact, position P2 is and pigment
The contact of solution 12 terminates and starts the position of the drying of semiconductor layer 11.
In the dyeing process of present embodiment, only pass through to convey base material 10, you can will contact with pigment solution 12
The transport path of contact site 35 and drying section 36 alternate repetition being pulled up from contact site 35 and being dried passes through.
Suitably carry out cleaning operation in the colouring method of present embodiment it is also possible to after having carried out dyeing process.
Clean operation is the operation being carried out for the purpose of reducing the unnecessary sensitization pigment supporting on semiconductor layer 11, is
This purpose and the process that carries out all belongs to clean operation.As the method for the unnecessary sensitization pigment reducing semiconductor layer 11,
Ultrasonic cleansing can be enumerated, using the cleaning of the organic solvent such as ethanol, with combination of brush brush or these methods etc., but do not limit
In these methods.Clean operation can carry out it is also possible in the dyeing process carrying out stipulated number after each dyeing process
After implement.That is, the opportunity carrying out cleaning operation is not particularly limited.
By carrying out cleaning operation, the aesthetic property of semiconductor layer 11 improves.
As described above, in the colouring method of present embodiment, while will be vertically square to contact site 35 and drying section 36
To alternately repeatedly being formed, while switching the conveying direction of base material 10 between contact site 35 and drying section 36.Thus, only
By base material 10 is placed in transport path, semiconductor layer 11 can be made to contact with pigment solution 12 in contact site 35, set
It is dried in drying section 36 downstream, thus dyeing process is carried out repeatedly.
According to above-mentioned colouring method, start from initial position P1 to the position P2 near downstream from conveying, partly lead
Body layer 11 is immersed in pigment solution 12, and what semiconductor layer 11 impregnated has partly all reliably supported sensitization pigment.Then, certainly
Base material 10 conveying start initial position P2 make semiconductor layer 11 from pigment solution 12 separate, from this position P2 near
The position P1 of trip side makes it be dried, thus only promptly removing the solvent in pigment solution 12.
Then, when edge above-below direction change base material 10 conveying direction, side continuously bendingly convey base material 10 when, under
One position P1, semiconductor layer 11 is immersed in pigment solution 12 again.Now, the sensitization pigment in pigment solution 12 is again dipped into
Semiconductor layer 11, is securely joined with quasiconductor and is supported.Start with secondary position P1's from the conveying of base material 10
Downstream close proximity P2, makes the semiconductor layer 11 of this state separate, be dried from pigment solution 12, thus again only by color
Solvent in plain solution 12 promptly removes.
By carrying out repeatedly sensitization pigment to the dyeing of semiconductor layer 11, make the sensitization pigment in pigment solution 12 reliable
Ground reach semiconductor layer 11 inside, when the manufacture of the dye-sensitized solar cell that RtoR mode is realized, even if
Conveying base material 10 is it is also possible to effectively make sensitization pigment support in semiconductor layer 11 at short notice at high speed.
It should be noted that preferably, the number of times carrying out dyeing process considers species or the semiconductor layer 11 of sensitization pigment
Composition, the transporting velocity of base material 10 etc. and set.From the viewpoint of the pigment supporting q.s, preferably carry out more than twice
Dyeing process, more preferably carry out more than three times.With regard to the upper limit of this number of times, because the method for the present invention is substantially continuous
Manufacture method, even if increasing this number of times it is also difficult to such problem that produces that manufacturing time is elongated or manufacturing process complicates, so
It is not particularly limited.That is, even if increasing and carrying out the number of times of dyeing process it is also difficult to produce long-timeization manufacturing, the increasing of operation
Plus, efficiency be also one of the advantages of the present invention the problems such as decline.
In addition, in the colouring method of present embodiment, due to conveying direction (transport path) the vertically side of base material 10
Bend to continuous, even if so expanding the length of base material 10 it is also possible to suppress the increasing implementing required distance of colouring method
Greatly.That is, can achieve the device of colouring method for implementing present embodiment, the space saving of equipment.
Therefore, it is possible to improve the dyeing side employing the dyeing process to semiconductor layer 11 for the sensitization pigment and present embodiment
The manufacture efficiency of the dye-sensitized solar cell of method.
Then, the variation of the colouring method of present embodiment is described.Fig. 2～Figure 13 is for present embodiment is described
The skeleton diagram of the modification of colouring method.It should be noted that the colouring method in the expression present embodiment of Fig. 2～Figure 13
The in figure of variation, is constituted to the element identical with expression in Fig. 1 of the colouring method for present embodiment is described
Key element, marks same labelling and the description thereof will be omitted.
In the colouring method of present embodiment, when making base material 10 continuously bend along the vertical direction it is also possible to need not be as
Fig. 1 is illustratively alternately placed in adjacent conveying roller R.Although not shown, in part specified in transport path, also may be used
Pass through the lower section of the adjacent conveying roller R in downside to skip the transport path R of upside.So, the not continuous bending to base material 10
Shape or make the method for wearing under the method, the set location of conveying roller R, base material 10 that base material 10 continuously bends be particularly limited.
In addition, conveying roller R, R ..., R equally spaced can not also set along the conveying direction (arrow D1 direction) of base material 10
Put.Adjacent conveying roller R, R can also configure positions different in vertical direction each other.As long as base material 10 can be made along upper
Lower direction Curved Continuous are rolled over, conveying roller R, R ..., the configuration of R is not particularly limited.By the big transport road of this degree of freedom
The setting in footpath, the practicality of the colouring method of present embodiment improves further.
In addition, in the colouring method of present embodiment, as long as solution tank 18 is closely set with the transport path of base material 10
Put, so that semiconductor layer 11 contacts the stipulated time with pigment solution 12.As shown in Fig. 2 for example in the back side 10b of base material 10
Setting semiconductor layer 11 and in the case that back side 10b side is dyeed it is also possible to so that the pigment solution 12 of solution tank 18
The mode that upper surface can be contacted with back side 10b sets the position of the transfer position that solution tank 18 is with respect to base material 10.
As shown in Fig. 2 (that is, will be contacted by the relative position changing the transport path with respect to base material 10 for the solution tank 18
Portion 15 is set as irreducible minimum), the contact area between back side 10b and pigment solution 12 reduces, thus can get following effect,
That is, can suppress the usage amount of pigment solution 12 that the manufacturing cost of dye-sensitized solar cell is greatly reduced.
In addition, for example being intended to be set to grow as far as possible by the contact site 35 of transport path and be set to drying section 36 short
In the case of, as long as the prescribed depth in pigment solution 12 by the conveying roller R configuration of downside, and increase contact site 35 with respect to dry
The ratio in dry portion 36.
In addition, when wanting to obtain more drying time in the colouring method of present embodiment, as shown in figure 3,
With the opportunity of regulation and time, the transport path of base material 10 can be made with respect to solution tank 18 relatively in the conveying of base material 10
Ground is temporarily separated along arrow D4 direction, so that drying section 36 is intermittently expanded.In the case of being somebody's turn to do, can be by the transport path 10 of base material 10
Fixing, make solution tank 18 with respect to this path along arrow D4 direction close to or separate the set location it is also possible to by solution tank 18
Fixing, make the transport path of base material 10 with respect to this position along arrow D4 direction close to or separate.Generally in this case, pass through
So that the state shown in Fig. 1 and the state shown in Fig. 2 is alternately repeated, implement colouring method.
In addition, the expansion of the drying section 36 realized by the relative movement of transport path and solution tank 18 both can be conveyed with side
Base material 10 side is carried out, or it is also possible to convey base material 10 off and on, carries out during the conveying of base material 10 stops.In side conveying
In the case that base material 10 side carries out the expansion of drying section 36 realized by the relative movement of transport path and solution tank 18 it is considered to
The opportunity of relative movement, so that any position of the length direction in base material 10 for the semiconductor layer 11 (porous plastid) is all molten with pigment
Liquid 12 contacts same time, and same time is dried.
In either method, non-with the pigment solution 12 of solution tank 18 from the transport path of base material 10 as illustrated in fig. 3
The state of contact, contact to a part for the transport path of base material 10 as illustrated in fig. 1 with the pigment solution 12 of solution tank 18
During state, the semiconductor layer 11 that is immersed in pigment solution 12 all supports sensitization pigment.
As shown in figure 3, by the relative position changing base material 10 and solution tank 18, can get following effect, i.e. can
It is easily controlled pigment solution 12 to the frequency of exposure of semiconductor layer 11.By this effect, can suitably increase and decrease pigment solution 12 to
The frequency of exposure of semiconductor layer 11, shortens dyeing time, even if the size reducing device also can increase frequency of exposure.
In addition, it is also possible to replacing solution tank 18 and using the solution of example in Fig. 4 in the colouring method of present embodiment
Case 28, wherein, liquor box 28 is received pigment solution 12 and is formed with, in the position of regulation, the hole that can discharge pigment solution 12
Portion 29.In the case of being somebody's turn to do, in the way of the plate face being formed with the base material 10 of semiconductor layer 11 being abutted with hole portion 29, with respect to base
The transport path of material 10 arranges liquor box 28 in relatively suitable position.Illustrate corresponding with following situation in the diagram
Constitute, i.e. form hole portion 29 in the bottom surface of liquor box 28, with the semiconductor layer 11 that formed in the surface 10a base material in conveying
The mode that 10 contact site 35 is abutted with hole portion 29 arranges liquor box 28.It should be noted that the shape of liquor box 28 is not limited to
Shape shown in Fig. 4.
As shown in figure 4, to replace solution tank 18 by using liquor box 28, can keep pigment solution 12 hardly with outside
Air contact, thus for example can get following effect, i.e. the moisture absorption having in hygroscopic pigment solution 12 can be suppressed
Deng, suppression pigment solution 12 deterioration.
Although it should be noted that illustrate in Fig. 1～Fig. 4 using a solution tank 18 with respect to a base material 10
Or the corresponding composition of situation of liquor box 28 is but it is also possible to as desired using multiple solution tanks 18 or liquor box 28, example
As solution tank 18 or liquor box 28 can also be arranged to each contact site 35.Thereby, it is possible to cut down pigment solution 12 further
Usage amount.
As other variation of the colouring method of present embodiment, can include to making pigment solution 12 and semiconductor layer
The example that the method for 11 contacts is changed.In the dyeing process of present embodiment, make pigment solution 12 and semiconductor layer 11
The method on basis is not particularly limited, and in addition to aforesaid infusion process, can also be made using drip method, rubbing method, print process etc.
The conventional method that liquid is contacted with base material.
For example, as the method making pigment solution 12 contact with semiconductor layer 11 it is also possible to select to drip method.This situation
Under, as shown in figure 5, becoming the contact site 35 of base material 10 and the position P1 on the border of drying section 36, by using mechanism of dripping
14 drip pigment solution 12 to semiconductor layer 11, and pigment solution 12 can be made to contact with semiconductor layer 11.It should be noted that using
The position of dripping of the pigment solution 12 of mechanism 14 of dripping be not particularly limited or contact site 35 and side downstream dry
Boundary position between dry portion 36.Pigment solution 12 preferably considers the defeated of base material 10 from the amount of dripping of mechanism 14 of dripping and speed of dripping
Speed etc. is sent to set.
In addition, as the method making pigment solution 12 contact with semiconductor layer 11 it is also possible to select rubbing method.This situation
Under, by using coating mechanism, pigment solution 12 is coated semiconductor layer 11, so that pigment solution 12 is connect with semiconductor layer 11
Touch.As coating mechanism, though the gravure roll 21 shown in spray equipment 15 or Fig. 7 and Figure 10 or sponge roller shown in Fig. 6 can be enumerated
22nd, the mould 26 shown in transfer device, Fig. 9 such as die 24 shown in Fig. 8, but not limited to this.Spray equipment 15 is being used as to apply
In the case of cloth mechanism, the usage amount of pigment solution 12 significantly can be cut down to required Min..The color that coating mechanism is realized
The coating weight of plain solution 12 and coating speed preferably consider that transporting velocity of base material 10 etc. sets.
It should be noted that as make pigment solution 12 be impregnated in Fig. 7 and Figure 10 illustrate gravure roll 21 or sponge roller
The method on 22 surface, can enumerate as shown in Figure 7 to solution tank 18 dipping contact with the hole portion 29 of liquor box 28,
Drip the dripping of mechanism 14 realization, supply etc. that spray equipment 15 is realized, be not limited to these methods.
Select gravure roll 21 or sponge roller 22 as coating mechanism in the case of it is also possible to make the many places position of base material 10
Semiconductor layer 11 contact with a gravure roll 21 or sponge roller 22.The structure corresponding with following situation is illustrated in Figure 10
Become, i.e. so that a gravure roll 21 or sponge roller 22 is installed in along between the adjacent contact site in arrow D1 direction 35,35, make in the back of the body
The semiconductor layer 11 that face 10b is formed is abutted with the surface of gravure roll 21 or sponge roller 22 in adjacent each contact site 35,35.
And then, as the method making pigment solution 12 contact with semiconductor layer 11 it is also possible to make liquid and base by aforesaid
Two or more Combination of Methods in the conventional method of material contact.For example, though not shown, conduct makes pigment solution 12 and half
The method of conductor layer 11 contact is it is also possible to combine infusion process and method of dripping.Define half when surface 10a is incorporated in using this group
In the case of conductor layer 11, for example, dripped pigment solution 12 using the contact site 35 to the base material 10 in conveying for the mechanism 14 that drips,
And make the ormal weight that semiconductor layer 11 can be impregnated pigment solution 12 be stored in base material 10 sweep inner side.So
Afterwards, separate from the pigment solution 12 stored in base material 10, be conveyed direction and be set to upwardly-directed period, quasiconductor can be made
Layer 11 is dried.
Like that the method making pigment solution 12 be contacted with semiconductor layer 11 is changed by above-mentioned, except available
Outside the action effect of the colouring method of above-mentioned present embodiment, also can get reduction and the color of the usage amount of pigment solution 12
The such effect of reduction of the manufacturing cost of plain sensitized solar cell.
In addition, in the colouring method of present embodiment, as shown in figure 11, preferably in the transport road of position P2 and base material 10
Between position P1 near the downstream in footpath, drier is set, from base material 10 on from surface 10a towards the direction of back side 10b
Outer direction semiconductor layer 11 blow or heated.By this method, can remove moment and impregnated in semiconductor layer 11
Pigment solution 12 solvent.
As long as the mechanism that the solvent in pigment solution 12 can be removed by drier, it is not particularly limited.As
Drier, can enumerate the air that the width along base material 10 (that is, the arrow D3 direction representing in Figure 11 and Figure 12) extends
Knife 16, hot ply rolling roller 40 etc..Illustrate the structure corresponding with the colouring method that air knife 16 is used as drier in fig. 11
Become.Illustrate in Figure 12 and be used as drier with by hot ply rolling roller 40, and conduct makes pigment solution 12 connect with semiconductor layer 11
Tactile method and adopt rubbing method and mould 26 be used as the corresponding composition of colouring method of coating mechanism.Illustrated in Figure 12
Colouring method in, semiconductor layer 11 is previously formed at the relative back side 10b and surface 10a of two base materials 10A, 10B.It
Afterwards, rearwardly inject pigment solution 12 between 10b and surface 10a from mould 26, so that pigment solution 12 is contacted with semiconductor layer 11.
Surface 10a and base material 10B in the base material 10A of the contrary opposition side of the back side 10b contacting with pigment solution 12 and surface 10a
The resin film 34 of back side 10b cladding protection.Then, by hot ply rolling roller 40 across resin film 34 be attached to two base material 10A,
On 10B, thus semiconductor layer 11 can be made to be dried.
In addition, as other driers, can enumerate using installing the methods such as non-woven fabrics on the surface of conveying roller R makes
This surface has absorptive suction roll (omitting diagram).In the case of using suction roll, if make the surface of suction roll with
The semiconductor layer 11 contacting pigment solution 12 abuts.
In addition, as drier, moment solvent can be removed by above-mentioned headed by air knife or suction roll etc.
Method in two or more Combination of Methods.
Drier is set by above-mentioned, can get the action effect of the colouring method of above-mentioned present embodiment,
Particularly, by reliably eliminate after each dyeing process the pigment solution 12 in semiconductor layer 11 solvent state according to
Secondary carry out dyeing process, it is rapid and good to being impregnated with of semiconductor layer 11 to can get pigment solution 12, and can shorten dyeing
Time such effect.Further, since the drying time of semiconductor layer 11 is shortened, thus the size that also can get device is contracted
Little, there is the such effect of practicality.
And then as other variation, though not shown, can enumerate and not change solution tank 18 with respect to base material 10
The relative position of transfer position and example that the set location of drier is changed.For example, illustrate defeated in Figure 11
The drying section 36 of the base material 10 in sending, period above the conveying direction of base material 10 is set to, the situation of setting air knife 16.So
And, when carrying out the colouring method of present embodiment it is considered to device constitute etc. it is also possible to base material 10 drying section 36, will
The conveying direction of base material 10 arranges air knife 16 during being set to lower section.Should in the case of, from semiconductor layer 11 from the contact of base material 10
Portion 35 is moved to drying section 36 and is separated with pigment solution 12 and play the air dried time blown by air knife 16
Become longer, thus in addition to can get the action effect of colouring method of above-mentioned present embodiment, also can get can
The such effect of air output in suppression air knife 16.
It should be noted that the variation of the colouring method of above-mentioned present embodiment can also combine two or more examples
Son and use.The composition corresponding with following colouring method is illustrated, i.e. select to drip method as making pigment solution in Figure 13
12 methods being contacted with semiconductor layer 11, are dripped pigment solution 12 to semiconductor layer 11 from mechanism 14 of dripping in position P1, and
It is air knife 16 in position P2 using drier and so that semiconductor layer 11 is dried.So, by by the dyeing of present embodiment
Method and this variation are appropriately combined, are free to the characteristic to the material considering base material 10 and shape or pigment solution 12
Deng, the composition of device of colouring method or equipment for implementing present embodiment be designed, can achieve these devices or
The space saving of equipment.
(second embodiment)
Hereinafter, with reference to Figure 14, second embodiment of the present invention is illustrated.
Figure 14 is the skeleton diagram of the colouring method for present embodiment is described.It should be noted that in fig. 14, to
Element identical element for Fig. 1～Figure 13 of the colouring method of first embodiment is described marks same labelling
And the description thereof will be omitted.
In the colouring method of present embodiment, as shown in figure 14, the conveying direction of base material 10 is set to helical form.Specifically
Ground, helically conveys base material 10 using conveying roller R (not shown) etc..
Base material 10 from conveying start along Figure 14 represent arrow D1 direction and arrow D3 direction rightabout (that is, from
Towards direction on hand in paper) traveling of this both direction.
In addition, the transport path of the base material 10 helically conveying along in the solution tank 18 in storage pigment solution 12,
Setting pigment solution 12.Then, the side of pigment solution 12 is impregnated in the semiconductor layer 11 being transported to the contact site 35 of spiral
Solution tank 18 is arranged on relatively suitable position with respect to the transport path of base material 10 by formula.By this configuration, when to arrow
When D1 direction helically conveys base material 10, before and after the conveying direction of base material 10 switches from below upward, with pigment
The position P1 that the upper surface of solution 12 connects, base material 10 impregnated in pigment solution 12, and pigment solution 12 is connect with semiconductor layer 11
Touch.
According to above-mentioned colouring method, based on the colouring method identical principle with first embodiment, by being sensitized
Pigment is carried out repeatedly to the dyeing of semiconductor layer 11, makes the sensitization pigment in pigment solution 12 reliably reach semiconductor layer 11
Inside, when the manufacture of the dye-sensitized solar cell that RtoR mode is realized, even if at high speed convey base material 10,
Sensitization pigment can be efficiently made to support in semiconductor layer 11 at short notice.
In addition, the conveying direction of base material 10, in the colouring method of present embodiment, is helically set, so base material 10
Alternately repeatedly move forward and backward.Thus, even if the length of base material 10 is expanded it is also possible to suppress the reality of colouring method further
Apply the increase of required distance.Therefore, in the same manner as the colouring method of first embodiment, it is capable of for implementing this enforcement
The device of the colouring method of mode, the space saving of equipment, it is possible to increase employ the sensitization dyeing to semiconductor layer 11 for the pigment
The manufacture efficiency of the dye-sensitized solar cell of the colouring method of operation and present embodiment.
But, in the colouring method of present embodiment, as previously described, because base material 10 starts not only along arrow from conveying
Advancing in D1 direction, also advances along the rightabout in arrow D3 direction, so preferably coupling can arrange device or equipment etc. simultaneously
The length and width in space and set the size of the transport path of spiral helicine base material 10.
In the colouring method of present embodiment, if not producing unfavorable condition when implementing, it is contemplated that implementing with first
The variation identical variation of the colouring method of mode.
(the 3rd embodiment)
Hereinafter, with reference to Figure 15, third embodiment of the present invention is illustrated.
Figure 15 is the skeleton diagram of the colouring method for present embodiment is described.It should be noted that in fig .15, to
Element identical element for Fig. 1～Figure 13 of the colouring method of first embodiment is described marks same labelling
And the description thereof will be omitted.
In the colouring method of present embodiment, there is the colouring method identical dyeing process with first embodiment,
As shown in figure 15, the center of the width (the arrow D3 direction representing in Figure 15) of base material 10 is set to axis A, by base material
The 10 arrow D5 directions representing along along Figure 15 are reversed, and rotation edge arrow D1 direction in side is conveyed.
In addition, being arranged on relatively suitable position by being stored with the solution tank 18 of pigment solution 12 transport path along base material 10
Put.The composition corresponding with following situation is illustrated, i.e. with the lower half under the axis A of the base material 10 being twisted in Figure 15
Part can impregnated in the mode of pigment solution 12, is arranged as opposed to solution tank 18 with respect to the transport path of base material 10.By this
Kind of configuration, when being reversed base material 10 centered on axis A to arrow D1 direction, and when being conveyed in rotation, in axis A
The semiconductor layer 11 being previously formed on the base material 10 of lower section is contacted with pigment solution 12, on the axis a on the base material 10 of side in advance
The semiconductor layer 11 being formed is exposed in the air.
According to above-mentioned colouring method, after base material 10 starts to be transported to the initial position P1 in upstream side from conveying,
From the position P2 near position P1 to side downstream, the semiconductor layer 11 being formed on the base material 10 below axis A impregnates
In pigment solution 12, support sensitization pigment.From position P1 to position P2, semiconductor layer 11 impregnated in pigment solution 12, and pigment is molten
The surface of the semiconductor layer 11 from pigment solution 12 side for the liquid 12 is towards internal immersion.Now, based on the dyeing with first embodiment
Method identical principle, the solvent in pigment solution 12 is impregnated with to the more internal of semiconductor layer 11 than sensitization pigment.
Then, when being reversed conveying direction centered on axis A, when conveying base material 10 in rotation, above-mentioned in be located at axle
The semiconductor layer 11 being formed on base material 10 below line A, is located near the position P1 in downstream from substrate location P2
It is exposed in the air above axis A.
Thus, the solvent only in pigment solution 12 evaporates rapidly.Meanwhile, shape on the base material 10 reaching below axis A
The semiconductor layer 11 becoming impregnated in pigment solution 12 first.Now, along with the power of impregnation of the solvent in pigment solution 12, pigment
Sensitization pigment in solution 12 is impregnated with to the inside of semiconductor layer 11, supports in quasiconductor.
Like that sensitization pigment is carried out repeatedly, making quick in pigment solution 12 to the dyeing of semiconductor layer 11 by above-mentioned
Change pigment and reliably reach the inside of semiconductor layer 11, during the manufacture of the dye-sensitized solar cell realized as RtoR mode
Like that, even if conveying base material 10 is it is also possible to efficiently make sensitization pigment support in semiconductor layer 11 at short notice at high speed.
In addition, in the colouring method of present embodiment, in dyeing process, because side is with the arrow D3 direction of base material 10
Center for axis A, base material 10 is reversed edge arrow D1 direction and is conveyed, even if so the length of base material 10 is expanded,
That can suppress colouring method implements the required increase of distance and the increase of height simultaneously.Therefore, with first embodiment
Colouring method similarly, can get following effect, i.e. can achieve the device of colouring method for implementing present embodiment,
The space saving of equipment.As a result, can improve sensitization pigment is employed to the dyeing process of semiconductor layer 11 and this embodiment party
The manufacture efficiency of the dye-sensitized solar cell of the colouring method of formula.
In the colouring method of present embodiment, if not producing unfavorable condition when implementing, it is contemplated that implementing with first
The variation identical variation of the colouring method of mode.
Then, illustrate to employ the optoelectronic pole of the present invention.
The optoelectronic pole being suitable for the present invention is the optoelectronic pole being made using the colouring method being suitable for the present invention.For example,
When with reference to Fig. 1～Figure 15 when understand, the optoelectronic pole of present embodiment be only base material 10 is placed in transport path so that it may with respect to
The optoelectronic pole layer being formed so that the semiconductor layer 11 that arbitrary graphic pattern is formed supports enough sensitization pigments in the plate face of base material 10
13.
By above-mentioned, can obtain being suitable to continuously produce, and there is the optoelectronic pole of high-photoelectric transformation efficiency.
Then, illustrate to be suitable for the optical-electric module of the present invention.
The optical-electric module being suitable for the present invention is the optical-electric module of the optoelectronic pole possessing described above.
As this optical-electric module, above-mentioned dye-sensitized solar cell can be enumerated, but as long as being to exist from irradiation light
Optoelectronic pole generation electric current, and the module of this electric current can be applied flexibly, it is not particularly limited.
In the case of photronic using the colouring method manufacture dye-sensitized solar being suitable for the present invention, carrying out
Before dyeing process, in the plate face of base material 10, conductive layer and semiconductor layer are formed with the pattern that specifies successively lamination.In addition, carry out
After dyeing process, by the comparative electrode making optoelectronic pole layer 11 be formed separately separate predetermined distance relative in the way of configure base material 10
With comparative electrode base material.Afterwards, filling electrolyte between optoelectronic pole layer 11 and comparative electrode.It should be noted that
In each operation carrying out before and after dyeing process, generally well-known step or material can be used.
By above-mentioned, can obtain being suitable to continuously produce, and there is the optical-electric module of high-photoelectric transformation efficiency.
More than, the optimal way of the present invention is described in detail, but the invention is not restricted to certain specific embodiment, at this
Various modifications, change can be carried out in the range of bright claimed invention purport.
For example, the transport path of base material 10 can not be path that is linear or having multiple kinks or tool
There is the path of bending section, may be designed to arbitrary shape.
Claims (6)
1. a kind of colouring method of porous plastid, makes the porous plastid being formed and the solution containing pigment on the surface of base material connect
Touch, so that described porous plastid is dried afterwards it is characterised in that
There is following operation：While conveying described base material, make described porous plastid and the transport road along described base material
The described solution contact of footpath setting, making described porous plastid be dried downstream,
Described operation is carried out repeatedly.
2. porous plastid as claimed in claim 1 colouring method it is characterised in that
In described operation, the conveying direction of described base material is made continuously to bend along the vertical direction.
3. porous plastid as claimed in claim 1 colouring method it is characterised in that
The conveying direction of described base material, in described operation, is helically set.
4. porous plastid as claimed in claim 1 colouring method it is characterised in that
For axis, described base material is reversed with the width center of described base material, and conveyed in rotation.
5. a kind of optoelectronic pole it is characterised in that usage right require 1～4 described in the colouring method of porous plastid and make.
6. a kind of optical-electric module is it is characterised in that possess the optoelectronic pole described in claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-166630 | 2014-08-19 | ||
| JP2014166630 | 2014-08-19 | ||
| PCT/JP2015/073211 WO2016027826A1 (en) | 2014-08-19 | 2015-08-19 | Porous body dyeing method, photoelectrode and photoelectric module |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106471594A true CN106471594A (en) | 2017-03-01 |
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| CN201580036635.XA Pending CN106471594A (en) | 2014-08-19 | 2015-08-19 | The colouring method of porous plastid, optoelectronic pole and optical-electric module |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2016027826A1 (en) |
| KR (1) | KR20170044082A (en) |
| CN (1) | CN106471594A (en) |
| TW (1) | TW201613126A (en) |
| WO (1) | WO2016027826A1 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080078498A1 (en) * | 2006-10-03 | 2008-04-03 | Zeik Douglas B | Articles and methods for applying color on surfaces |
| JP2008093576A (en) * | 2006-10-12 | 2008-04-24 | Lintec Corp | Manufacturing method of multilayer film and film forming device |
| US20110159628A1 (en) * | 2009-07-02 | 2011-06-30 | Kee-Hyun Shin | System and method for producing flexible dye-sensitized solar cells by a roll-to-roll printing process |
| JP2012113954A (en) * | 2010-11-24 | 2012-06-14 | Sekisui Chem Co Ltd | Method for dyeing porous body |
| CN102859786A (en) * | 2010-04-22 | 2013-01-02 | 日立造船株式会社 | Method for producing electrode for photoelectric conversion element |
| CN102873971A (en) * | 2012-09-18 | 2013-01-16 | 四川汇利实业有限公司 | Novel processing and coating dryer for polrvinyl chloride/polyvinylidene chloride medicinal composite sheet and use method thereof |
-
2015
- 2015-08-19 CN CN201580036635.XA patent/CN106471594A/en active Pending
- 2015-08-19 JP JP2016544227A patent/JPWO2016027826A1/en active Pending
- 2015-08-19 KR KR1020177000315A patent/KR20170044082A/en unknown
- 2015-08-19 WO PCT/JP2015/073211 patent/WO2016027826A1/en active Application Filing
- 2015-08-19 TW TW104126927A patent/TW201613126A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080078498A1 (en) * | 2006-10-03 | 2008-04-03 | Zeik Douglas B | Articles and methods for applying color on surfaces |
| JP2008093576A (en) * | 2006-10-12 | 2008-04-24 | Lintec Corp | Manufacturing method of multilayer film and film forming device |
| US20110159628A1 (en) * | 2009-07-02 | 2011-06-30 | Kee-Hyun Shin | System and method for producing flexible dye-sensitized solar cells by a roll-to-roll printing process |
| CN102859786A (en) * | 2010-04-22 | 2013-01-02 | 日立造船株式会社 | Method for producing electrode for photoelectric conversion element |
| JP2012113954A (en) * | 2010-11-24 | 2012-06-14 | Sekisui Chem Co Ltd | Method for dyeing porous body |
| CN102873971A (en) * | 2012-09-18 | 2013-01-16 | 四川汇利实业有限公司 | Novel processing and coating dryer for polrvinyl chloride/polyvinylidene chloride medicinal composite sheet and use method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016027826A1 (en) | 2016-02-25 |
| TW201613126A (en) | 2016-04-01 |
| JPWO2016027826A1 (en) | 2017-06-01 |
| KR20170044082A (en) | 2017-04-24 |
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