WO2010147428A2 - 신규한 유기염료 및 이의 제조방법 - Google Patents
신규한 유기염료 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2010147428A2 WO2010147428A2 PCT/KR2010/003950 KR2010003950W WO2010147428A2 WO 2010147428 A2 WO2010147428 A2 WO 2010147428A2 KR 2010003950 W KR2010003950 W KR 2010003950W WO 2010147428 A2 WO2010147428 A2 WO 2010147428A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- dye
- substituted
- unsubstituted
- independently
- Prior art date
Links
- 0 *c1ccc(*(c2ccc(C=C(C=C3N4)NC3=CC4=O)cc2)c2ccc(C=C(CC=C3N4)NC3=CC4=O)cc2)cc1 Chemical compound *c1ccc(*(c2ccc(C=C(C=C3N4)NC3=CC4=O)cc2)c2ccc(C=C(CC=C3N4)NC3=CC4=O)cc2)cc1 0.000 description 17
- VIPCQVJTVIFNEV-UHFFFAOYSA-N CC(C)(c(cccc1)c1C1=CC2)C1=CC2N(C(CC1)=CC(CC2)=C1C21CC#CCC1)c1ccc(C=C)cc1 Chemical compound CC(C)(c(cccc1)c1C1=CC2)C1=CC2N(C(CC1)=CC(CC2)=C1C21CC#CCC1)c1ccc(C=C)cc1 VIPCQVJTVIFNEV-UHFFFAOYSA-N 0.000 description 1
- VMMMNDGOMFEXEO-BTOFHOTMSA-N CCCCCCC(/C(/S1)=C/c(cc2)ccc2N(c2ccccc2)c2ccccc2)=C/C1=C(\C(CCCCCC)=C1)/S/C1=C(/C(O)=O)\C#N Chemical compound CCCCCCC(/C(/S1)=C/c(cc2)ccc2N(c2ccccc2)c2ccccc2)=C/C1=C(\C(CCCCCC)=C1)/S/C1=C(/C(O)=O)\C#N VMMMNDGOMFEXEO-BTOFHOTMSA-N 0.000 description 1
- QMTGLEDZNBTJCD-NXPSLKMHSA-N N#C/C(/C(O)=O)=C(/C=C1)\S/C1=C\c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound N#C/C(/C(O)=O)=C(/C=C1)\S/C1=C\c(cc1)ccc1N(c1ccccc1)c1ccccc1 QMTGLEDZNBTJCD-NXPSLKMHSA-N 0.000 description 1
- KDTRJTZKYWSUEF-CXBGVVRYSA-N O=C(C=C1SC2=C3)SC1=C2S/C3=C(\C=C1S2)/SC1=C/C2=C(/C1=C2OCCO1)\S/C2=C\Br Chemical compound O=C(C=C1SC2=C3)SC1=C2S/C3=C(\C=C1S2)/SC1=C/C2=C(/C1=C2OCCO1)\S/C2=C\Br KDTRJTZKYWSUEF-CXBGVVRYSA-N 0.000 description 1
- QECUHNUUHBDIFA-ONEGZZNKSA-N O=C(CC1S2)SC1=C/C2=C\Br Chemical compound O=C(CC1S2)SC1=C/C2=C\Br QECUHNUUHBDIFA-ONEGZZNKSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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
-
- 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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/611—Charge transfer complexes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- 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
- 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
- Y02E10/549—Organic PV 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
Definitions
- the present invention relates to a novel organic dye for dye-sensitized photovoltaic devices used in dye-sensitized solar cells (DSSC) and a method of manufacturing the same.
- DSSC dye-sensitized solar cells
- Dye-sensitized solar cells are expected to be able to replace conventional amorphous silicon solar cells because of their higher efficiency and lower manufacturing costs than conventional silicon-based solar cells.
- dye-sensitized solar cells are photoelectrochemical solar cells that consist mainly of dyes that absorb visible light to form electron-hole pairs, and transition metal oxides that transfer the generated electrons. .
- organic dyes containing no metals exhibiting excellent physical properties in terms of light absorption efficiency, redox reaction stability, and intermolecular charge-transfer (CT) absorption have replaced dyes by replacing expensive ruthenium metal complexes. It has been found that it can be used as a dye for solar cells, and research on organic dyes containing no metals has been focused on.
- Organic dyes generally have a structure of electron donor-electron acceptor residues linked by ⁇ -binding units.
- amine derivatives act as electron donors
- 2-cyanoacrylic acid or rhodanine residues act as electron acceptors
- these two sites are ⁇ -binding systems such as metaine units or thiophene chains. Is connected by.
- An object of the present invention is to provide an organic dye for a dye-sensitized photoelectric conversion device that can improve the efficiency of the dye-sensitized solar cell by showing an improved molar absorption coefficient and photoelectric conversion efficiency than the conventional metal complex dye.
- Another object of the present invention is to provide a method for producing the organic dye.
- Still another object of the present invention is a dye-sensitized photoelectric conversion device including the organic dye exhibiting a markedly improved photoelectric conversion efficiency, excellent Jsc (short circuit photocurrent density) and a molar absorption coefficient, and efficiency including the same It is to provide this remarkably improved solar cell.
- the present invention provides an organic dye for dye-sensitized photoelectric conversion device represented by the following formula (1):
- o, p and q are each independently 0 or 1, provided that at least one of o, p and q is 1,
- An1 to An3 are each independently or And Ar1 to Ar3 are each independently a substituted or unsubstituted C6-C50 aryl group when o, p or q is 0, and each independently a substituted or unsubstituted C6-C50 arylene group when p or q is 1
- Ar 1 to Ar 3 may be connected to each other to form a ring together with N,
- Sp1 to Sp3 are each independently , , And At least one selected from the group consisting of wherein X is each independently selected from the group consisting of O, S, CR5R6, SiR7R8 and NR9, R1 to R4 are each independently hydrogen, substituted or unsubstituted C1-12 alkyl , Substituted or unsubstituted C6-30 aryl and substituted or unsubstituted C6-20 heteroaryl, or may be linked to each other to form a ring, R5 to R9 are each independently hydrogen or substituted or Unsubstituted C1-12 alkyl, n is an integer from 1 to 10.
- Sp is each independently , , And At least one selected from the group consisting of, wherein X is each independently selected from the group consisting of O, S, CR5R6, SiR7R8 and NR9, R1 to R4 are each independently hydrogen, substituted or unsubstituted C1-12 alkyl , Substituted or unsubstituted C6-30 aryl and substituted or unsubstituted C6-20 heteroaryl, or may be linked to each other to form a ring, R5 to R9 are each independently hydrogen or substituted or Unsubstituted C1-12 alkyl, n is an integer from 1 to 10, and Ar1-Ar3, o, p, and q are as defined above.
- the present invention is oxide semiconductor fine particles; And it provides a dye-sensitized photoelectric conversion device comprising the organic dye supported on the oxide semiconductor fine particles.
- the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion device.
- the dye compound of the present invention can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar absorption coefficient, Jsc (single-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of the solar cell.
- DSSC dye-sensitized solar cell
- alkyl means a linear or branched saturated C 1 to C 6 hydrocarbon radical chain. Specific examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl and hexyl.
- aryl means a ring system that can be formed by the optionally substituted benzene ring or by fusion of one or more optional substituents.
- the optional substituents include substituted C1-3 alkyl, substituted C2-3 alkenyl, substituted C2-3 alkynyl, heteroaryl, heterocycle, aryl, alkoxy with or without 1-3 fluorine substituents, Aryloxy, aralkoxy, acyl, aroyl, heteroaroyl, acyloxy and aroyloxy.
- the ring or ring system may be optionally fused to an aryl ring (including benzene ring), carbocycle ring or heterocycle ring with or without one or more substituents.
- aryl include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracyl, phenanthryl and substituted derivatives thereof.
- heteroaryl means a monocyclic 5-6 membered aromatic ring having one or more heteroatoms such as oxygen, sulfur and nitrogen in the ring, or a heteroaryl ring, aryl ring, heterocycle ring or carbocycle Aromatic rings (eg, bicyclic or tricyclic ring systems) fused to one or more rings, such as rings.
- heteroaryl examples include pyridinyl, pyrrolyl, oxazolyl, indolyl, isoindolyl, purinyl, furanyl, thienyl, benzofuranyl, benzothiophenyl, carbazolyl, imidazolyl, thiazolyl, isox Sazolyl, pyrazolyl, isothiazolyl, quinolyl, isoquinolyl, pyridazyl, pyrimidyl, pyrazil, which may be substituted or unsubstituted, and the like.
- substituted or “substituted” means that at least one hydrogen in the compound or functional group is halogen, alkyl, alkenyl, alkynyl, aryl, alkoxy, hydroxy, carboxy, carbamoyl, alkoxycarbonyl It means substituted with a substituent selected from the group consisting of, nitro, haloalkyl, amino, alkylcarbonylamino, cycloalkyl group, cyano and thiol.
- Organic dye organic dye for photoelectric conversion device has a structure of the following formula 1) improved molar absorption coefficient, Jsc (short circuit photocurrent density) and photoelectricity when used in dye-sensitized solar cells (DSSC) as a dye-sensitized photoelectric conversion device
- Jsc short circuit photocurrent density
- DSSC dye-sensitized solar cells
- o, p and q are each independently 0 or 1, provided that at least one of o, p and q is 1,
- An1 to An3 are each independently an anchoring group. or ego,
- Ar1 to Ar3 are each independently a substituted or unsubstituted C6-C50 aryl group when o, p or q is 0, and are each independently a substituted or unsubstituted C6-C50 arylene group when p or q is 1, Or Ar1 to Ar3 may be connected to each other to form a ring together with N,
- Sp1 to Sp3 are each independently a spacer group , , And At least one selected from the group consisting of, wherein X is each independently selected from the group consisting of O, S, CR5R6, SiR7R8 and NR9, R1 to R4 are each independently hydrogen, substituted or unsubstituted C1-12 alkyl , Substituted or unsubstituted C6-30 aryl and substituted or unsubstituted C6-20 heteroaryl, or may be linked to each other to form a ring, R5 to R9 are each independently hydrogen or substituted or Unsubstituted C1-12 alkyl, n is an integer from 1 to 10.
- Sp 1 to Sp 3 in Formula 1 are each independently a linking group having the following Formula SP 1-30:
- R1 to R8 are as defined above.
- the organic dyes according to the present invention may include compounds having a chemical formula represented by the following Chemical Formulas 5 to 54:
- It may be prepared by a manufacturing method comprising:
- Ar 1 -Ar 3 o, p, q, and Sp are as defined above.
- the coupling reaction is preferably carried out in an organic solvent such as dimethylformamide (DMF) in the presence of a catalyst such as Pd (PPh3) 4 and a base such as K2CO3.
- a catalyst such as Pd (PPh3) 4
- a base such as K2CO3.
- the compounds of formulas (2) and (3) used as starting materials can be prepared by conventional methods or obtained commercially.
- the compound of Chemical Formula 2 it is preferable to use one of the following Chemical Formulas 2-1 to 2-4.
- a compound of Chemical Formulas 3-1 to 3-5 may be used.
- the compound of Formula 3 is preferably used in 1 to 3 moles per 1 mole of the compound of Formula 2.
- the organic dye according to the present invention may be prepared by combining the prepared compound of Chemical Formula 4 with an anchoring group-providing compound such as cyanoacetic acid in the presence of piperidine in CH 3 CN.
- the compound of formula 4 is preferably used in 1.2 to 2.5 moles per mole of the anchoring group providing compound.
- organic dye according to the present invention may be prepared by the methods described in the following Schemes 1 to 9, but this is only an example and the present invention is not limited thereto.
- the organic dye according to the present invention prepared by the above manufacturing method is used in dye-sensitized solar cells (DSSC) as a dye-sensitized photoelectric conversion element, improved molar absorption coefficient, Jsc (short circuit photocurrent density) and The photoelectric conversion efficiency can be shown to greatly improve the efficiency of the solar cell.
- DSSC dye-sensitized solar cells
- the present invention provides a dye-sensitized photoelectric conversion device comprising the organic dye.
- the dye-sensitized photoelectric conversion device is characterized in that it comprises an oxide semiconductor microparticles, and the organic dye supported on the oxide semiconductor microparticles.
- a dye-sensitized photoelectric conversion device in addition to using the organic dye, methods for manufacturing dye-sensitized photoelectric conversion devices for solar cells using conventional dyes may be applied, and preferably, the dyes of the present invention.
- the sensitized photoelectric conversion device can be manufactured by producing a thin film of an oxide semiconductor on a substrate using oxide semiconductor fine particles, and then supporting the organic dye according to the present invention on the thin film.
- the substrate on which the thin film of the oxide semiconductor is formed is preferably conductive, and a commercially available one may be used.
- a thin film of conductive metal oxide such as tin oxide coated with indium, fluorine, or antimony on the surface of a transparent polymer material such as glass or polyethylene terephthalate or polyether sulfone, or a metal thin film such as copper, silver, or gold What formed this can be used.
- the conductivity is preferably 1000 ⁇ or less, particularly preferably 100 ⁇ or less.
- oxide semiconductor fine particles a metal oxide is preferable.
- oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum and vanadium can be used.
- oxides such as titanium, tin, zinc, niobium and indium are preferable, titanium oxide, zinc oxide and tin oxide are more preferable, and titanium oxide is most preferred.
- the oxide semiconductor may be used alone, or may be mixed or coated on the surface of the semiconductor.
- the particle diameter of the oxide semiconductor fine particles is preferably 1 to 500 nm, more preferably 1 to 100 nm as the average particle diameter.
- the fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.
- the oxide semiconductor thin film is a method of forming oxide semiconductor fine particles into a thin film directly on the substrate through spray spraying, a method of electrically depositing a semiconductor fine particle thin film using the substrate as an electrode, a slurry of semiconductor fine particles, or a semiconductor such as a semiconductor alkoxide.
- the paste containing the fine particles prepared by hydrolyzing the precursor of the fine particles can be applied onto a substrate, and then produced by drying, curing or baking. Among these, a method of applying the paste onto the substrate is preferable.
- the said slurry can be obtained by disperse
- a dispersion medium which disperses a slurry as long as it can disperse semiconductor fine particles, it can use without a restriction
- a dispersion stabilizer can be used for the purpose of stabilizing the dispersion state of oxide semiconductor microparticles
- coated the slurry is 100 degreeC or more, Preferably it is 200 degreeC or more, and the upper limit is generally below melting
- the firing time is not particularly limited, but is generally within 4 hours.
- the thickness of the oxide semiconductor fine particles formed on the substrate is preferably 1 to 200 m, more preferably 1 to 50 m.
- a part of the thin film of the oxide semiconductor fine particles may be deposited during firing, but such deposition does not particularly affect the present invention.
- Secondary processing may be performed on the oxide semiconductor thin film.
- the performance of a semiconductor thin film may be improved by directly depositing a thin film for each substrate and drying or refiring it in a solution such as alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor.
- a solution such as alkoxide, chloride, nitride or sulfide of the same metal as the semiconductor.
- the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyl tin, and the like.
- the solvent may be used as an alcohol solution using alcohol.
- the chloride examples include titanium tetrachloride, tin tetrachloride, and zinc chloride, and the like can be used as an aqueous solution using water as a solvent.
- the oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.
- a method of supporting the dye on the oxide semiconductor fine particles formed in the thin film phase is not particularly limited, and as a specific example, a solution prepared by dissolving an organic dye represented by the formula (I) in a solvent that can dissolve, or The method of immersing the board
- the concentration of the organic dye in the solution or dispersion can be appropriately determined depending on the dye.
- the dye concentration is preferably 1 ⁇ 10 ⁇ 6 M to 1 M, more preferably 1 ⁇ 10 ⁇ 5 M to 1 ⁇ 10 ⁇ 1 M.
- the temperature during deposition is usually from room temperature to the boiling point of the solvent, and the deposition time is about 1 minute to 48 hours.
- the organic dye to be supported may be one kind or may be mixed in several kinds.
- other organic dyes or metal complex dyes may be mixed with the organic dyes according to the present invention.
- the metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes and quaternary salts thereof, phthalocyanine, porphyrin and the like are preferable, and other organic dyes include metal-free phthalocyanine, porphyrin or cyanine, merocyanine, oxo.
- Methine dyes such as knol, triphenylmethane, and acrylic acid dyes described in WO2002 / 011213, and dyes such as xanthene, azo, anthraquinone, and perylene-based dyes (MK Nazeeruddin, A.). Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzel, J. Am. Chem. Soc., Vol. 115, p . 6382 (1993). . In the case of using two or more kinds of dyes, the dyes may be adsorbed onto the semiconductor thin film in order, or may be mixed and dissolved and adsorbed.
- the dye when the dye is supported on the thin film of the oxide semiconductor fine particles, it is preferable to support the dye in the presence of the inclusion compound in order to prevent the dyes from bonding.
- the inclusion compound include cholic acids such as deoxycholic acid, dehydrodeoxycholic acid, kenodeoxycholic acid, cholate methyl ester and sodium cholate; Steroid compounds such as polyethylene oxide and cholic acid; Crown ethers; Cyclodextrins; Callix arene; Polyethylene oxide and the like can be used.
- the substrate on which the semiconductor fine particle thin film is installed can be treated with an amine compound such as 4-t-butyl pyridine or a compound having an acidic group such as acetic acid or propionic acid.
- an amine compound such as 4-t-butyl pyridine
- a compound having an acidic group such as acetic acid or propionic acid.
- a treatment method for example, a method of dipping a substrate provided with a thin film of semiconductor fine particles in which a dye is supported in an amine ethanol solution may be used.
- the present invention provides a dye-sensitized solar cell comprising the dye-sensitized photoelectric conversion element.
- the dye-sensitized solar cell may be composed of a photoelectric conversion element electrode (cathode), a counter electrode (anode), a redox electrolyte, a hole transport material, or a p-type semiconductor, in which an organic dye is supported on oxide semiconductor fine particles.
- the dye-sensitized solar cell may be applied to conventional methods of manufacturing a solar cell using a conventional photoelectric conversion element, in addition to using a dye-sensitized photoelectric conversion element using the oxide semiconductor fine particles carrying the organic dye.
- the dye-sensitized solar cell according to the present invention comprises the steps of coating a titanium oxide paste on a conductive transparent substrate; Baking the paste-coated substrate to form a titanium oxide thin film; Impregnating the substrate on which the titanium oxide thin film is formed into a mixed solution in which an organic dye is dissolved to form a titanium oxide film electrode to which dye is adsorbed; Providing a second glass substrate having a counter electrode formed thereon; Forming a hole penetrating the second glass substrate and the counter electrode; Bonding the counter electrode to the titanium oxide film electrode by placing a thermoplastic polymer film between the counter electrode and the titanium oxide film electrode to which the dye is adsorbed, and performing a heat compression process; Injecting an electrolyte into the thermoplastic polymer film
- the redox electrolyte, hole transport material, p-type semiconductor, and the like may be used in the form of a liquid, a solid (gel and gel), a solid, and the like.
- redox electrolyte, dissolved salt, hole transport material, p-type semiconductor, etc. are dissolved in a solvent, or room temperature dissolved salts, etc., respectively, in the case of coagulated bodies (gel and gel form), these are polymer matrix or low molecular gel.
- a solid phase redox electrolyte, a dissolved salt, a hole transport material, a p-type semiconductor, or the like can be used.
- the hole transport material examples include conductive polymers such as amine derivatives, polyacetylene, polyaniline, and polythiophene; Or an object using a discotech liquid crystal phase such as a triphenylene compound.
- conductive polymers such as amine derivatives, polyacetylene, polyaniline, and polythiophene; Or an object using a discotech liquid crystal phase such as a triphenylene compound.
- CuI, CuSCN, etc. can be used as a p-type semiconductor.
- the counter electrode has conductivity and catalyzes the reduction reaction of the redox electrolyte.
- platinum, carbon, rhodium, ruthenium, or the like deposited on glass or a polymer film, or coated with conductive fine particles can be used.
- the redox electrolyte examples include a halogen redox electrolyte composed of a halogen compound-halogen molecule having halogen ions as a counter ion; Metal redox-based electrolytes such as metal complexes such as ferrocyanate-ferrocyanate, ferrocene-ferricinium ions and cobalt complexes; Organic redox-based electrolytes such as alkylthiol-alkyldisulfide, viologen dye, hydroquinone-quinone and the like can be used, and a halogen redox-based electrolyte is preferable.
- a halogen redox electrolyte composed of a halogen compound-halogen molecule having halogen ions as a counter ion
- Metal redox-based electrolytes such as metal complexes such as ferrocyanate-ferrocyanate, ferrocene-ferricinium ions and cobalt complexes
- halogen molecule in a halogen redox electrolyte composed of halogen compound-halogen molecules an iodine molecule is preferable.
- a halogen compound having a halogen ion as a large ion halogenated metal salts such as LiI, NaI, KI, CaI2, MgI2 and CuI, or organic ammonium salts of halogen such as tetraalkylammonium iodine, imidazolium iodine and pyridium iodine, or I2 Can be used.
- an electrochemically inert one may be used as the solvent.
- an electrochemically inert one may be used as the solvent.
- Specific examples include acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, methoxy acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butyrolactone, dimethoxyethane, dimethyl carbonate, 1,3-dioxolane, methylformate, 2-methyltetrahydrofuran, 3-methoxy-oxazolidin-2-one, sulfolane, tetrahydrofuran, water, and the like, in particular acetonitrile, Propylene carbonate, ethylene carbonate, 3-methoxy propionitrile, ethylene glycol, 3-methoxy-oxazolidin-2-one, butyrolactone and the like are preferable.
- the solvents may be used alone or in combination.
- the gel electrolyte one containing an electrolyte or an electrolyte solution in a matrix such as an oligomer and a polymer, or one containing an electrolyte or an electrolyte solution in the same manner as a starch gelling agent can be used.
- the concentration of the redox electrolyte is preferably 0.01 to 99% by weight, more preferably 0.1 to 30% by weight.
- a counter electrode anode
- a photoelectric conversion element cathode
- a solution containing a redox electrolyte is filled therebetween.
- Example (E) -5- (Bromomethylene) thieno [3,2-b] thiophene-2 (5H) -one except for using the intermediate (36a) in Example 7 above The same procedure as in (4) was carried out sequentially to obtain the compound of formula (46).
- a dye-sensitized solar cell was prepared using a 13 + 10 ⁇ m TiO 2 transparent layer.
- the washed FTO (Pilkington, 8 ⁇ sq-1) glass substrate was impregnated in a 40 mM TiCl 4 aqueous solution.
- a TiO2 paste (Solaronix, 13 nm anatase) was screen printed to produce a 13 ⁇ m thick first TiO2 layer, and another light paste (CCIC, HWP-400) was used to prepare a 10 ⁇ m thick second TiO2 scattering layer.
- the TiO 2 electrode prepared was impregnated with a solution of the dye according to the present invention (dissolved 0.3 mM each of the compound prepared in Example 1-8 above in 10 mM 3a, 7a-dihydroxy-5b-cholic acid containing ethanol).
- the counter electrode was prepared by coating a solution of H 2 PtCl 6 (containing 2 mg of Pt in 1 mL of ethanol) on an FTO substrate. Then, an electrolyte in which 0.6 M 3-hexyl-1,2-dimethylimidazolium iodine, 0.04 M I2, 0.025 M LiI, 0.05 M guanidium thiocyanate and 0.28 M tert -butylpyridine was dissolved in acetonitrile was obtained.
- the dye compound of the present invention can be used in a dye-sensitized solar cell (DSSC) to exhibit an improved molar absorption coefficient, Jsc (single-circuit photocurrent density) and photoelectric conversion efficiency than conventional dyes, thereby greatly improving the efficiency of the solar cell.
- DSSC dye-sensitized solar cell
Abstract
Description
구분 | 효율(η)(%) | 구분 | 효율(η)(%) |
실시예 1 | 5.5 | 실시예 5 | 4.2 |
실시예 2 | 5.8 | 실시예 6 | 4.4 |
실시예 3 | 5.7 | 실시예 7 | 6.1 |
실시예 4 | 5.9 | 실시예 8 | 5.9 |
Claims (9)
- 하기 화학식 1로 표시되는 염료증감 광전변환소자용 유기염료:[화학식 1]상기 식에서,o, p 및 q는 각각 독립적으로 0 또는 1이고, 단 o, p 및 q 중 적어도 하나는 1이며,Ar1 내지 Ar3은 o, p 또는 q가 0일 때 각각 독립적으로 치환 또는 비치환된 C6-C50 아릴기이고, p 또는 q가 1일 때 각각 독립적으로 치환 또는 비치환된 C6-C50 아릴렌기이며, 또는 Ar1 내지 Ar3은 서로 연결되어 N과 함께 환을 형성할 수도 있고,Sp1 내지 Sp3은 각각 독립적으로 , , 및 으로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, CR5R6, SiR7R8 및 NR9로 이루어진 군으로부터 선택되고, R1 내지 R4는 각각 독립적으로 수소, 치환 또는 비치환된 C1-12 알킬, 치환 또는 비치환된 C6-30 아릴 및 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R5 내지 R9는 각각 독립적으로 수소 또는 치환 또는 비치환된 C1-12 알킬이고, n은 1 내지 10의 정수이다.
- 제1항에 있어서,상기 Sp1 내지 Sp3은 각각 독립적으로 하기 화학식으로 표시되는 연결기인 것을 특징으로 하는 유기염료:[SP1][SP2][SP3][SP4][SP5][SP6][SP7][SP8][SP9][SP10][SP11][SP12][SP13][SP14][SP15][SP16][SP17][SP18][SP19][SP20][SP21][SP22][SP23][SP24][SP25][SP26][SP27][SP28][SP29][SP30]상기 식에서 R1 내지 R8은 제1항에서 정의한 바와 같다.
- [규칙 제91조에 의한 정정 24.08.2010]
제1항에 있어서, 상기 유기염료가 하기 화학식 5 내지 54로 표시되는 화합물들로 이루어진 군에서 선택되는 것을 특징으로 하는 유기염료: [화학식5] [화학식6] [화학식7] [화학식8] [화학식9] [화학식10] [화학식11] [화학식12] [화학식13] [화학식14] [화학식15] [화학식16] [화학식17] [화학식18] [화학식19] [화학식20] [화학식21] [화학식22] [화학식23] [화학식24] [화학식25] [화학식26] [화학식27] [화학식28] [화학식29] [화학식30] [화학식31] [화학식32] [화학식33] [화학식34] [화학식35] [화학식36] [화학식37] [화학식38] [화학식39] [화학식40] [화학식41] [화학식42] [화학식43] [화학식44] [화학식45] [화학식46] [화학식47] [화학식48] [화학식49] [화학식50] [화학식51] [화학식52] [화학식53] [화학식54] - (1) 하기 화학식 2의 화합물을 하기 화학식 3의 화합물과 커플링 반응시켜 하기 화학식 4의 화합물을 제조하는 단계; 및(2) 상기 제조된 화학식 4의 화합물을 CH3CN 중에서 피페리딘 존재 하에서 앵커링기 제공 화합물과 결합 반응시키는 단계를 포함하는 제1항에 따른 유기염료의 제조방법:[화학식 2][화학식 3][화학식 4]상기 식에서,Sp는 각각 독립적으로 , , 및 로 이루어진 군에서 1종 이상 선택되며, 이때 X는 각각 독립적으로 O, S, CR5R6, SiR7R8 및 NR9로 이루어진 군으로부터 선택되고, R1 내지 R4는 각각 독립적으로 수소, 치환 또는 비치환된 C1-12 알킬, 치환 또는 비치환된 C6-30 아릴 및 치환 또는 비치환된 C6-20 헤테로아릴로 이루어진 군에서 선택되거나, 또는 서로 연결되어 환을 형성할 수 있으며, R5 내지 R9는 각각 독립적으로 수소 또는 치환 또는 비치환된 C1-12 알킬이고, n은 1 내지 10의 정수이며, Ar1-Ar3, o, p, 및 q는 제1항에서 정의한 바와 같다.
- 산화물 반도체 미립자; 및상기 산화물 반도체 미립자에 담지된 제1항 기재의 유기염료를 포함하는 염료증감 광전변환소자.
- 제5항에 있어서,상기 유기염료가 포섭화합물의 존재 하에서 산화물 반도체 미립자에 담지된 것을 특징으로 하는 염료증감 광전변환소자.
- 제5항에 있어서,상기 산화물 반도체 미립자가 이산화티탄을 포함하는 것을 특징으로 하는 염료증감 광전변환소자.
- 제5항에 있어서,상기 산화물 반도체 미립자가 1 내지 500 nm의 평균 입경을 갖는 것을 특징으로 하는 염료증감 광전변환소자.
- 제5항 기재의 염료증감 광전변환소자를 전극으로서 포함하는 것을 특징으로 하는 염료감응태양전지.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080027067.4A CN102498176B (zh) | 2009-06-19 | 2010-06-18 | 有机染料及其制造方法 |
JP2012515991A JP5815514B2 (ja) | 2009-06-19 | 2010-06-18 | 新規の有機色素およびその製造方法 |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2009-0055103 | 2009-06-19 | ||
KR20090055103 | 2009-06-19 | ||
KR10-2009-0055218 | 2009-06-19 | ||
KR20090055218 | 2009-06-19 | ||
KR1020100057782A KR101827546B1 (ko) | 2009-06-19 | 2010-06-17 | 신규한 유기염료 및 이의 제조방법 |
KR10-2010-0057782 | 2010-06-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
WO2010147428A2 true WO2010147428A2 (ko) | 2010-12-23 |
WO2010147428A9 WO2010147428A9 (ko) | 2011-02-03 |
WO2010147428A3 WO2010147428A3 (ko) | 2011-04-28 |
Family
ID=43356943
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2010/003950 WO2010147428A2 (ko) | 2009-06-19 | 2010-06-18 | 신규한 유기염료 및 이의 제조방법 |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2010147428A2 (ko) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20110184A1 (it) * | 2011-02-08 | 2012-08-09 | Consiglio Nazionale Ricerche | Composti fotosensibilizzanti "metal free" |
WO2013042414A1 (ja) * | 2011-09-22 | 2013-03-28 | 日本電気株式会社 | ジチエノピロール系化合物、光電変換素子用色素、これを用いた光電変換素子用半導体電極、および光電変換素子 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007149570A (ja) * | 2005-11-30 | 2007-06-14 | Nippon Kayaku Co Ltd | 色素増感光電変換素子 |
KR20070102821A (ko) * | 2006-04-17 | 2007-10-22 | 삼성에스디아이 주식회사 | 염료 감응 태양 전지용 염료 및 이로부터 제조된 염료 감응태양 전지 |
KR20080104136A (ko) * | 2006-03-02 | 2008-12-01 | 니폰 가야꾸 가부시끼가이샤 | 색소 증감 광전변환소자 |
JP2009048925A (ja) * | 2007-08-22 | 2009-03-05 | Nippon Kayaku Co Ltd | 色素増感光電変換素子 |
-
2010
- 2010-06-18 WO PCT/KR2010/003950 patent/WO2010147428A2/ko active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007149570A (ja) * | 2005-11-30 | 2007-06-14 | Nippon Kayaku Co Ltd | 色素増感光電変換素子 |
KR20080104136A (ko) * | 2006-03-02 | 2008-12-01 | 니폰 가야꾸 가부시끼가이샤 | 색소 증감 광전변환소자 |
KR20070102821A (ko) * | 2006-04-17 | 2007-10-22 | 삼성에스디아이 주식회사 | 염료 감응 태양 전지용 염료 및 이로부터 제조된 염료 감응태양 전지 |
JP2009048925A (ja) * | 2007-08-22 | 2009-03-05 | Nippon Kayaku Co Ltd | 色素増感光電変換素子 |
Non-Patent Citations (5)
Title |
---|
HAGBERG D.P. ET AL. J. AM. CHEM. SOC. vol. 130, 2008, pages 6259 - 6266 * |
KIM, S. ET AL. J. AM. CHEM. SOC. vol. 128, 2006, pages 16701 - 16707 * |
KIM, S. ET AL. TETRAHEDRON vol. 63, 2007, pages 11436 - 11443 * |
KIM, S. ET AL. TETRAHEDRON vol. 63, 2007, pages 9206 - 9212 * |
QIN, H. ET AL. J. AM. CHEM. SOC. vol. 130, 2008, pages 9202 - 9203 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20110184A1 (it) * | 2011-02-08 | 2012-08-09 | Consiglio Nazionale Ricerche | Composti fotosensibilizzanti "metal free" |
WO2012107488A3 (en) * | 2011-02-08 | 2013-01-10 | Universita' Degli Studi Di Milano | Metal-free photosensitizers |
WO2013042414A1 (ja) * | 2011-09-22 | 2013-03-28 | 日本電気株式会社 | ジチエノピロール系化合物、光電変換素子用色素、これを用いた光電変換素子用半導体電極、および光電変換素子 |
Also Published As
Publication number | Publication date |
---|---|
WO2010147428A9 (ko) | 2011-02-03 |
WO2010147428A3 (ko) | 2011-04-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2010147425A2 (ko) | 신규한 유기염료 및 이의 제조방법 | |
WO2012102544A2 (ko) | 신규한 유기염료 및 이의 제조방법 | |
WO2010002154A2 (ko) | 신규한 유기염료 및 이의 제조방법 | |
WO2013100538A1 (ko) | 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치 | |
WO2012134203A2 (ko) | 화합물 및 이를 이용한 유기전기소자, 그 전자장치 | |
WO2014171755A1 (ko) | 플러렌 유도체, 이를 이용한 유기 태양 전지 및 이의 제조 방법 | |
WO2020166875A1 (ko) | 신규한 화합물 및 이를 이용한 유기발광 소자 | |
WO2011102586A4 (ko) | 유기광전소자용 화합물 및 이를 포함하는 유기광전소자 | |
WO2013100539A1 (ko) | 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치 | |
WO2017057976A1 (ko) | 스피로형 화합물 및 이를 포함하는 유기 발광 소자 | |
WO2012039534A1 (ko) | 유기광전소자용 화합물 및 이를 포함하는 유기광전소자 | |
WO2013095039A1 (ko) | 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치 | |
WO2014058123A1 (ko) | 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치 | |
WO2019221545A1 (ko) | 유기발광소자 | |
WO2013100465A1 (ko) | 유기광전자소자용 화합물, 이를 포함하는 유기발광소자 및 상기 유기발광소자를 포함하는 표시장치 | |
WO2020166873A1 (ko) | 신규한 화합물 및 이를 이용한 유기발광 소자 | |
WO2019066305A1 (ko) | 중합체 및 이를 포함하는 유기 태양 전지 | |
WO2022211594A1 (ko) | 유기 광전자 소자용 조성물, 유기 광전자 소자 및 표시 장치 | |
WO2014119895A1 (ko) | 신규한 화합물, 이를 포함하는 발광 소자 및 전자 장치 | |
WO2023282617A2 (ko) | 유기 광전자 소자용 조성물, 유기 광전자 소자 및 표시 장치 | |
WO2022080715A1 (ko) | 신규한 화합물 및 이를 포함한 유기 발광 소자 | |
WO2010147427A2 (ko) | 신규한 유기염료 및 이의 제조방법 | |
WO2009096702A2 (ko) | 신규한 유기 염료 및 이의 제조방법 | |
WO2010147428A2 (ko) | 신규한 유기염료 및 이의 제조방법 | |
WO2022203276A1 (ko) | 핵생성 억제 형성용 물질 및 이를 포함하는 유기전계발광소자 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080027067.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10789755 Country of ref document: EP Kind code of ref document: A2 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012515991 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10789755 Country of ref document: EP Kind code of ref document: A2 |