WO2012157110A1 - フタロシアニンナノロッド、及び光電変換素子 - Google Patents
フタロシアニンナノロッド、及び光電変換素子 Download PDFInfo
- Publication number
- WO2012157110A1 WO2012157110A1 PCT/JP2011/061531 JP2011061531W WO2012157110A1 WO 2012157110 A1 WO2012157110 A1 WO 2012157110A1 JP 2011061531 W JP2011061531 W JP 2011061531W WO 2012157110 A1 WO2012157110 A1 WO 2012157110A1
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- WO
- WIPO (PCT)
- Prior art keywords
- phthalocyanine
- atom
- photoelectric conversion
- group
- conversion element
- Prior art date
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 229
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 22
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
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- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0673—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having alkyl radicals linked directly to the Pc skeleton; having carbocyclic groups linked directly to the skeleton
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- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
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- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton
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- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4
- C09B67/0019—Influencing the physical properties by treatment with an acid, H2SO4 of phthalocyanines
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- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
- H10K30/352—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles the inorganic nanostructures being nanotubes or nanowires, e.g. CdTe nanotubes in P3HT polymer
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- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Definitions
- the present invention includes a phthalocyanine nanorod, an ink composition containing the phthalocyanine nanorod, a transistor containing the phthalocyanine nanorod, a material for a photoelectric conversion element containing the phthalocyanine nanorod, and the phthalocyanine nanorod between a positive electrode and a negative electrode. It is related with the photoelectric conversion element characterized by these.
- An organic thin-film solar cell is a photoelectric conversion active layer (photoelectric conversion) consisting of an electron-donating material (donor) composed of an organic semiconductor material and an electron-accepting material (acceptor) composed of an organic semiconductor material.
- a photoelectric conversion element made of an organic semiconductor material.
- the electron-donating material include electron-donating ⁇ -conjugated polymers such as polythiophene and polyphenylene vinylene, and electron-donating low molecular weight materials such as phthalocyanines, and examples of the electron-accepting material include fullerenes. Etc.
- Patent Document 1 proposes a bulk heterojunction type in which the electron donating material and the electron accepting material are composited at the nano level to increase the junction interface (DA junction interface) of both materials contributing to photoelectric conversion. Actively performed (Patent Document 1).
- the principle of photoelectric conversion of organic thin film solar cells is (1) Exciton (hole-electron pair) is generated by light absorption of the organic semiconductor layer, (2) This diffuses and moves to the DA junction interface. (3) Charge separation into holes and electrons, (4) Each charge is transported to the positive electrode and the negative electrode through the electron donating material and the electron accepting material to generate electric power, and the photoelectric conversion efficiency is determined by integrating the efficiency of each process. .
- the exciton has a very short lifetime, and the distance that can be diffused and transferred is extremely short, from several nanometers to several tens of nanometers. Therefore, in order to increase the efficiency of photoelectric conversion, the DA junction interface in the organic semiconductor layer is excited by the excitation. It is preferable that it exists within a distance range that is about the same distance as the distance that exciton can move and diffuse (exciton diffusion length), and a charge transport path that can quickly move the charge after charge separation to each electrode is secured. It is preferable that
- the excitons generated in the step (1) are deactivated before reaching the DA junction interface, and the charge cannot be taken out.
- the organic semiconductor layer does not have a charge transport path by the electron donating material and the electron accepting material, each charge generated in the step (3) cannot reach the positive electrode and the negative electrode. There arises a problem that power cannot be obtained.
- the problem is how to secure the electron donating material and the electron accepting material in the organic semiconductor layer without isolating (forming a dead end) in the organic semiconductor layer.
- organic thin-film solar cell includes a ⁇ -conjugated polymer such as poly-3-hexylthiophene (hereinafter P3HT) as an electron-donating material, and fullerene as an electron-accepting material.
- P3HT poly-3-hexylthiophene
- PCBM a derivative, [6,6] -phenyl C61 butyric acid methyl ester
- a photoelectric conversion element composed of an electron donating ⁇ -conjugated polymer and PCBM can be easily formed by a wet process (printing or coating) from a solution in which both organic materials are dissolved, and therefore requires expensive manufacturing equipment. Therefore, it has the advantage that it can be produced at low cost.
- a ⁇ -conjugated polymer is susceptible to an oxidation reaction by oxygen in the atmosphere, and has a problem in durability such as deterioration due to strong light irradiation, and the photoelectric conversion element made of the material has a problem of low life. was there.
- P3HT which is an electron-donating ⁇ -conjugated polymer
- P3HT / Compared with the photoelectric conversion element in which the PCBM type photoelectric conversion element does not contain the nanowire, the photoelectric conversion efficiency is improved.
- polymer systems such as P3HT generally have low oxygen resistance and light resistance as described above. It is inferior in durability, and the problem from the practical viewpoint of the photoelectric conversion element cannot be solved.
- a photoelectric conversion element that can be formed by a coating method using benzoporphyrins as an electron-donating material and fullerenes such as PCBM as an electron-accepting material is a conventional electron-donating ⁇ -conjugated polymer. Compared to those used, it has the advantage of excellent durability, such as oxygen resistance and light resistance.
- Patent Document 3 discloses a photoelectric conversion element including an organic semiconductor layer in which fine particles derived from a phthalocyanine pigment (phthalocyanine pigment fine particles) are formed by a wet process.
- phthalocyanine pigment fine particles are not suitable for charge transport because the crystal orientation is not controlled inside the fine particles, and as a result, the arrangement direction of the phthalocyanine molecules is random.
- Patent Document 4 also describes a phthalocyanine nanowire obtained by one-dimensional crystal growth of phthalocyanine and an ink composition containing it and an organic solvent as essential components.
- JP 2006-245073 A JP2008-016834 JP2009-252768 WO / 2010 / 122921A1
- the present invention has been made in view of the above problems, and aims to provide an organic semiconductor material excellent in durability that provides a structure suitable for charge transport by a low-cost wet process. Furthermore, the present invention aims to provide a photoelectric conversion element that is hard to break, lightweight, inexpensive, and has high characteristics.
- an organic semiconductor material suitable for a wet process can be provided by converting phthalocyanines into nanorods, and the present invention has been completed. Furthermore, it has been found that by using the organic semiconductor material as an electron donating material, a photoelectric conversion element having excellent durability and excellent charge transportability can be provided at low cost, and the present invention has been completed.
- the present invention relates to a phthalocyanine nanorod having a minor axis of 100 nm or less as an electron-donating material and a ratio of the length to the minor axis (length / minor axis) of less than 10, and an ink composition containing the phthalocyanine nanorod And a transistor containing the phthalocyanine nanorod, a material for a photoelectric conversion element containing the phthalocyanine nanorod, and a photoelectric conversion element containing the phthalocyanine nanorod.
- the phthalocyanine nanorod according to the present invention is composed of phthalocyanines having excellent durability, a long-life photoelectric conversion element can be provided. Further, since the phthalocyanine nanorod according to the present invention is superior in solvent dispersibility than the phthalocyanine pigment fine particles, it is easy to form an ink composition, and thus can be formed by a wet process. Thus, it is possible to provide a light-weight and inexpensive photoelectric conversion element that is hard to break. Furthermore, since the phthalocyanine nanorod according to the present invention has higher controllability of arrangement of phthalocyanine molecules over the entire particle than phthalocyanine pigment fine particles, the charge transport efficiency can be improved.
- the phthalocyanine nanorod according to the present invention has an aspect ratio smaller than that of the phthalocyanine nanowire, so that the charge transport efficiency is improved.
- a photoelectric conversion element having improved photoelectric conversion characteristics particularly, fill factor (FF) can be provided.
- the phthalocyanine nanorod of the present invention As the phthalocyanine nanorods having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of less than 10, the present invention includes unsubstituted phthalocyanine and a substituted phthalocyanine (phthalocyanine derivative). And phthalocyanine nanorods.
- a phthalocyanine represented by the general formula (1) and a metal-free phthalocyanine represented by the formula (2) can be used.
- X is not limited as long as it constitutes phthalocyanine.
- Metal atoms such as palladium atoms, and metal oxides and metal halides such as titanyl (TiO), vanadyl (VO), and aluminum chloride (AlCl), among which copper atoms, zinc atoms, and iron atoms Particularly preferred.
- a phthalocyanine derivative represented by the following general formula (3) or (4) can be used as the phthalocyanine having a substituent constituting the phthalocyanine nanorod of the present invention.
- X is not particularly limited as long as it is known and commonly used as a central metal of metal phthalocyanine, but preferred are a copper atom, a zinc atom, a cobalt atom, a nickel atom, a tin atom, a lead atom, A magnesium atom, a silicon atom, an iron atom, a palladium atom, etc. can be mentioned. Further, as X, a metal oxide such as titanyl (TiO), vanadyl (VO), aluminum chloride (AlCl), or a metal halide can be used.
- a metal-free phthalocyanine derivative containing no central metal X can also be used as the phthalocyanine having the substituent.
- Y 1 to Y 4 represent a linking group for bonding the phthalocyanine skeleton and R 1 to R 4, and when Y 1 to Y 4 are not present as a linking group, R 1 1 to R 4 may have —SO 3 H, —CO 2 H, an alkyl group that may have a substituent, an (oligo) aryl group that may have a substituent, or a substituent ( Oligo) heteroaryl groups, phthalimide groups which may have a substituent, or fullerenes which may have a substituent.
- Y 1 to Y 4 can be used without particular limitation as long as they are a linking group that binds the phthalocyanine ring and R 1 to R 4 .
- linking groups include alkylene groups, arylene groups, heteroarylene groups, vinylene bonds, ethynylene, sulfide groups, ether groups, sulfoxide groups, sulfonyl groups, urea groups, urethane groups, amide groups, amino groups, imino groups. Groups, ketone groups, ester groups, and the like.
- R 1 to R 4 are functional groups that can be bonded to the phthalocyanine ring via the bonding groups Y 1 to Y 4 .
- such functional groups include, for example, alkyl groups, alkyloxy groups, amino groups, mercapto groups, carboxy groups, sulfonic acid groups, silyl groups, silanol groups, boronic acid groups, nitro groups, and phosphoric acids.
- aryl group such as, a heteroaryl group such as an indoyl group and a pyridinyl group, an alkyl group such as a methyl group, and the like.
- specifically preferred groups include —SO 3 H, —CO 2 H, an alkyl group which may have a substituent, an alkyl group having an ether group or an amino group, and a substituent ( (Oligo) aryl group, (oligo) heteroaryl group which may have a substituent, phthalimide group which may have a substituent, or fullerenes which may have a substituent.
- alkyl group examples include an alkyl group having 1 to 20 carbon atoms, and a lower alkyl group such as a methyl group, an ethyl group, or a propyl group is particularly preferable. Further, an alkyl group having an ether group or an amino group is also preferable.
- M is an integer of 1 to 20, and R and R ′ are each independently an alkyl or aryl group having 1 to 20 carbon atoms.
- the group represented by can also be used.
- the (oligo) aryl group which may have a substituent is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent.
- An oligophenylene group or an oligonaphthyl group which may have a substituent can be exemplified. Examples of the substituent include conventionally known substituents that can be substituted on the aryl group.
- the (oligo) heteroaryl group which may have a substituent is preferably a pyrrole group which may have a substituent, a thiophene group which may have a substituent, or a substituent. Examples thereof include a good oligopyrrole group and an oligothiophene group which may have a substituent. Examples of the substituent include conventionally known substituents that can be substituted on the heteroaryl group.
- fullerenes which may have a substituent include unsubstituted fullerenes and generally fullerenes having a known substituent. Examples thereof include C60 fullerene, C70 fullerene and [6,6] -phenyl. Examples thereof include C61 butyric acid methyl ester (PCBM).
- phthalimide group examples include:
- A, b, c and d each independently represents an integer of 0 to 4, and represents the number of substituents Y 1 R 1 to Y 4 R 4 substituted on the phthalocyanine ring. Note that at least one of the numbers a to d of the substituents substituted on the phthalocyanine ring is not zero.
- phthalocyanine having a substituent represented by the general formula (3) include, but are not limited to, the following.
- the numbers next to the parentheses in the formula of the substituted phthalocyanine represent the average number of substituents introduced into the phthalocyanine molecule. The reason why this number is a decimal number is that although the number of substituents introduced for each molecule is an integer, different numbers of substituents are introduced in actual use.
- X is a copper atom or zinc atom
- n is an integer of 1 to 20
- m is a numerical value of 0 to 4 representing the average number of substituents introduced.
- X is a copper atom or zinc atom
- n is an integer from 1 to 20
- m is a numerical value from 0 to 4 representing the average number of substituents introduced
- R 1 to R 4 are each independently a hydrogen atom. , Halogen, an alkyl group having 1 to 20 carbon atoms, an alkyloxy group, or an alkylthio group.
- X is a copper atom or zinc atom
- n is an integer from 1 to 20
- m is a numerical value from 0 to 4 representing the average number of substituents introduced
- R 1 to R 2 are each independently a hydrogen atom. , Halogen, an alkyl group having 1 to 20 carbon atoms, an alkyloxy group, or an alkylthio group.
- the phthalocyanine derivative in which a central metal does not exist in the said Formula (Chemical Formula 5)-(Chemical Formula 13) can be mentioned.
- the phthalocyanine (phthalocyanine derivative) having a substituent of the general formula (3) or (4) can be synthesized by introducing a side chain or a functional group into the phthalocyanine ring.
- the sulfonated copper phthalocyanine described in (Chemical Formula 5), (Chemical Formula 6), and (Chemical Formula 7) can be obtained by heating copper phthalocyanine in fuming sulfuric acid (sulfur trioxide concentration: 20%).
- the compound can be synthesized, for example, by the method disclosed in US Pat. No. 2,761,868.
- phthalocyanines having various substituents
- 4-phenoxy-phthalo Various phthalonitrile compounds such as nitrile, 4-phenylthio-phthalonitrile, 4- (1,3-benzothiazol-2-yl) -phthalonitrile, etc. are mixed in any ratio with orthophthalonitrile that has no substituent.
- a phthalocyanine derivative having the above-mentioned various functional groups in an arbitrary ratio can be synthesized.
- the number of the functional groups of the phthalocyanine derivative that can be synthesized using the phthalonitrile compound as one of the raw materials can be arbitrarily changed by changing the mixing ratio of the phthalonitrile compound and orthophthalonitrile,
- the mixture of the phthalonitrile derivative and orthophthalonitrile may be 1: 3, and an average of 1.5 is desired to be introduced.
- the compound can be synthesized at a ratio of 3: 5 using the method described in the patent document.
- a phthalocyanine derivative having a plurality of types of functional groups can be synthesized from two or more types of phthalonitrile compounds and orthophthalonitrile.
- the phthalonitrile derivative having a substituent includes various known and commonly used phthalonitrile derivatives other than those described above. Examples of the phthalonitrile derivative in JP-A-2007-519636, paragraph 0006 in JP-A-2007-526881
- phthalonitrile derivatives linked to oligothiophenes described in Chemical Formula 2 of Paragraph 0014 of JP-A-2006-143680, and Chemical Formula of Paragraph 0021 of JP-A-2009-135237 can be given.
- the phthalonitrile derivatives linked with the described fullerenes are also included as raw materials for synthesizing phthalocyanines having substituents that can be used in the present invention.
- the phthalocyanine derivative which is the following general formula (5) or (6) can be used for the phthalocyanine having a substituent constituting the phthalocyanine nanorod of the present invention.
- X is not particularly limited as long as it is known and commonly used as the central metal of metal phthalocyanine, but preferred are copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom. , Iron atoms, palladium atoms, etc. Further, as X, metal oxides and metal halides such as titanyl (TiO), vanadyl (VO), and aluminum chloride (AlCl) can also be used.
- TiO titanyl
- VO vanadyl
- AlCl aluminum chloride
- a metal-free phthalocyanine derivative that does not contain the central metal X such as the phthalocyanine derivative represented by the general formula (6), can also be used as the phthalocyanine having the substituent, and Z is represented by the following formula (a) or ( b), a, b, c and d each independently represents an integer of 0 to 4, of which at least one is 0 It has.)
- n is an integer of 4 to 100
- Q is each independently a hydrogen atom or a methyl group
- Q ' is an acyclic hydrocarbon group having 1 to 30 carbon atoms.
- the phthalocyanine (phthalocyanine derivative) having a substituent represented by the general formula (5) or (6) is a compound in which a phthalocyanine ring is substituted with at least one sulfamoyl group.
- the sulfamoyl group to be introduced can be used without particular limitation as long as it is at least one per phthalocyanine ring, but is preferably 1 or 2, more preferably 1.
- the position to be substituted is not particularly limited.
- polyalkylene oxide copolymers represented by the general formula (a) that is, any polyalkylene oxides such as ethylene oxide polymers and ethylene oxide / propylene oxide copolymers, which are block-polymerized.
- polyalkylene oxide copolymers represented by the general formula (a) any polyalkylene oxides such as ethylene oxide polymers and ethylene oxide / propylene oxide copolymers, which are block-polymerized.
- Q ′ may be a linear hydrocarbon group or a branched hydrocarbon group as an acyclic hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Either hydrogen group may be used.
- Examples of such acyclic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-octyl group, 2 Examples thereof include linear or branched saturated hydrocarbon groups such as -ethyl-hexyl group, n-dodecyl group, stearyl group, n-tetracosyl group and n-triacontyl group.
- the hydrocarbon group may have a double bond or a triple bond, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group.
- Linear or branched unsaturated hydrocarbon groups such as isoprene group, hexenyl group, heptenyl group, octenyl group, decenyl group, geranyl group, ethynyl group, 2-propynyl group, 2-pentene-4-ynyl group, etc. be able to.
- the repeating number n of the polyalkylene oxide moiety is not particularly limited, but is preferably 4 or more and 100 or less, more preferably 5 from the viewpoint of the affinity with the dispersion solvent, that is, the dispersion stability of the obtained nanorods. It is more than 80 and still more preferably 10 or more and 50 or less.
- Examples of the phthalocyanine derivative represented by the general formula (5) include, but are not limited to, compounds of the formula (17).
- N is a numerical value of 4 to 100.
- the number m of polyalkylene oxide chains bonded to the phthalocyanine via a sulfamoyl bond is included in the phthalocyanine. (It is a numerical value from 0 to 4 representing the average number of introductions for four benzene rings.)
- the phthalocyanine having a substituent represented by the general formula (5) may have a group represented by the general formula (b) as Z in addition to the phthalocyanine derivative.
- Preferred examples of R and R ′ include a lower alkyl group, particularly a methyl group, and m is preferably 1 to 6.
- Specific preferred phthalocyanine derivatives include the following.
- the numbers next to the parentheses in the formula of the substituted phthalocyanine represent the average number of substituents introduced into the phthalocyanine molecule. The reason why this number is a decimal number is that although the number of substituents introduced for each molecule is an integer, different numbers of substituents are introduced in actual use.
- the phthalocyanine (phthalocyanine derivative) having a substituent represented by the general formula (5) can be obtained by combining known and commonly used methods.
- copper phthalocyanine sulfonyl chloride and polyether amine having an amine at the end of the polyether main chain hereinafter abbreviated as polyether monoamine
- copper phthalocyanine sulfonyl chloride and an amine represented by the following formula may be reacted. .
- m is a numerical value of 1 to 20, and R and R ′ are each independently an alkyl group having 1 to 20 carbon atoms.
- Copper phthalocyanine sulfonyl chloride as a raw material can be obtained by reaction of copper phthalocyanine with chlorosulfonic acid or thionyl chloride.
- the polyether monoamine which is the other raw material can be obtained by a known and conventional method.
- the hydroxyl group at the end of the polyether skeleton can be obtained by reductive amination using a nickel / copper / chromium catalyst, and the hydroxyl group at the end of the polyether skeleton can be obtained by Mitsunobu reaction (reference: synthesis). (Synthesis) 1981, P.1) and then amination by hydrazine reduction (reference: Chemical Communications, 2003, P.2062).
- Polyether monoamines are also provided as commercial products, such as the JEFFAMINE M series (trade name, manufactured by Huntsman).
- Production methods (I) and (II) are methods for obtaining nanorods by producing phthalocyanine nanowires and then reducing the aspect ratio of the phthalocyanine nanowires.
- a method for producing the phthalocyanine nanowire for example, the method described in WO2010 / 122921 can be used.
- the production method (III) is a method in which phthalocyanines are one-dimensionally crystallized with a low aspect ratio.
- This manufacturing method (A) a step of dissolving an unsubstituted phthalocyanine and a phthalocyanine having a substituent (phthalocyanine derivative) in an acid and then precipitating it in a poor solvent to obtain a composite; (B) converting the composite into a nanowire; (C) a step of forming the nanowire into a nanorod.
- phthalocyanines are known to be soluble in an acid solvent such as sulfuric acid.
- an acid solvent such as sulfuric acid.
- the unsubstituted phthalocyanine and the phthalocyanine having the substituent are converted into an acid such as sulfuric acid, chlorosulfuric acid, methanesulfonic acid, or trifluoroacetic acid. Dissolve in solvent. Thereafter, it is poured into a poor solvent such as water to precipitate a complex of the unsubstituted phthalocyanine and the phthalocyanine derivative having the substituent.
- the mixing ratio of the substituted phthalocyanine derivative to the unsubstituted phthalocyanine is preferably in the range of 1 to 200% by mass, more preferably 1 to 120% by mass.
- the mixing ratio is 1% by mass or more, crystal growth (one-dimensional crystal) in the step (b) described later is caused by the action of the substituent (functional group or polymer side chain) of the phthalocyanine having the substituent.
- the functional groups and polymer side chains are not so large as to inhibit crystal growth. It does not become a plate, plate or particle.
- the amount of the unsubstituted phthalocyanine and the phthalocyanine having a substituent added to the acid solvent is not particularly limited as long as there is no undissolved content and the concentration can be completely dissolved, but the solution has sufficient fluidity. As a range which maintains the viscosity of a certain level, 20 mass% or less is preferable.
- the solution includes: The range of 0.01 to 50 mass% is preferable with respect to the poor solvent. If it is 0.01% by mass or more, the concentration of the complex to be precipitated is sufficiently high, so that solids can be easily recovered. If it is 50% by mass or less, all of the unsubstituted phthalocyanines and the substituents are contained. Phthalocyanine precipitates to form a solid composite, which has no dissolved components and can be easily recovered.
- the poor solvent is not particularly limited as long as the unsubstituted phthalocyanine and the substituted phthalocyanine are insoluble or hardly soluble liquid, but the homogeneity of the precipitated complex can be kept high, and will be described later.
- Water or an aqueous solution containing water as a main component which is suitable for a fine dispersion (miniaturization) step and has a small environmental load, can be mentioned as the most preferable poor solvent.
- the complex can be recovered by filtering with a filter paper and a Buchner funnel to remove acidic water, washing with water until the filtrate becomes neutral, and collecting water.
- the recovered complex may be dehydrated and dried to remove moisture, or may remain water-containing when water or a water-soluble organic solvent is used in the next step.
- the complex of the unsubstituted phthalocyanine and the substituted phthalocyanine obtained in the step (a) was confirmed to be amorphous from the observation result with a transmission electron microscope.
- the step (b) is a step of forming a nanowire by one-dimensional crystal growth of the composite obtained through the step (a).
- the width (minor axis) of the obtained nanowire is preferably 100 nm or less, and the width (minor axis) is preferably 50 nm or less from the viewpoint of improving photoelectric conversion efficiency.
- the method for forming the nanowire is not particularly limited as long as the composite can be formed into a nanowire, and examples thereof include a method of forming the composite into a nanowire in an organic solvent (in a liquid phase). it can. Specifically, the composite can be made into a nanowire by (heating) stirring or (heating) standing in an organic solvent (in a liquid phase).
- the solvent to be used is not particularly limited as long as it does not have low affinity with phthalocyanines.
- the solvent to be used has high affinity with phthalocyanines.
- Amide solvents and aromatic organic solvents are preferred, and specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene, which have particularly high affinity with phthalocyanine , Dichlorobenzene and the like can be mentioned as the most suitable organic solvent.
- the amide organic solvent and the aromatic organic solvent can be used alone, but the amide organic solvent and the aromatic organic solvent can be mixed and used in an arbitrary ratio, and other These organic solvents can also be used in combination.
- organic solvent that can be used in combination with an amide organic solvent and an aromatic organic solvent, it is possible to promote the formation of nanowires, so that ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Examples thereof include glycol esters such as acetate.
- organic solvents may be added after the composite is dispersed in an amide organic solvent or an aromatic organic solvent, or may be added and dispersed after mixing with the organic solvent in advance.
- the solid content concentration of the complex with respect to the organic solvent is in the range of 0.1 to 20% from the viewpoint of appropriate fluidity and prevention of aggregation. Preferably, it is 1 to 10%.
- the temperature at the time of stirring or standing when the composite is made into a nanowire is preferably in the range of 5 to 250 ° C, more preferably 20 to 200 ° C. If the temperature is 5 ° C. or higher, the crystal growth of phthalocyanines can be sufficiently induced, and can be grown into nanowires by the desired one-dimensional crystal growth. If the temperature is 250 ° C. or lower, nanowire aggregation Fusing is hardly observed, and the crystal grows in the width direction and does not become coarse.
- the stirring time or standing time for nanowire formation there is no particular limitation on the stirring time or standing time for nanowire formation, but it is preferable to stir or stand for at least 10 minutes until the length of the phthalocyanine nanowire grows to 100 nm or more.
- the composite is simply put into an organic solvent, and then (heated) or stirred (heated) to stand to form a nanowire; and A method of making nanowires by finely dispersing in an organic solvent and then (heating) stirring or (heating) standing can be mentioned, but when considering the ink formation described later, the process for inking is simplified. Therefore, after the composite is finely dispersed in an organic solvent, it is preferably converted to a nanowire by (heating) stirring or (heating) standing.
- the composite When the composite is finely dispersed in an organic solvent and then nanowired by (heating) stirring or (heating) standing, the composite is finely dispersed in the organic solvent.
- the composite There are a wet method for finely dispersing the composite in the liquid phase and a method for dispersing the composite in an organic solvent after making it fine in the gas phase, but the former can be simplified because the process can be simplified.
- the wet dispersion method is more preferable.
- Examples of the wet dispersion method include a method in which the composite obtained in the step (a) is treated with a dispersion solvent and a wet disperser using fine beads such as a bead mill and a paint conditioner.
- K A method using a medialess disperser typified by fillmix can be mentioned.
- processing by high-power ultrasonic irradiation using an ultrasonic homogenizer or the like is also applicable, and these methods can be performed in one kind or in combination.
- water, an organic solvent, a water-containing organic solvent, etc. are mentioned as a dispersion solvent used for a wet dispersion process.
- organic solvent examples include alcohols such as ethanol, glycols, and glycol esters in addition to the organic solvent used for forming the nanowire. These dispersion solvents can be used alone or in combination. More preferred are water, ethanol, methanol, chlorobenzene, dichlorobenzene, and N-methyl-2-pyrrolidone in terms of suppression of crystal growth and crystal transition.
- the mass ratio of the composite to the dispersion solvent is not particularly limited, but from the viewpoint of dispersion efficiency, it is preferable to carry out the dispersion treatment in a solid content concentration range of 1 to 30% by mass.
- the bead diameter is preferably in the range of 0.01 to 2 mm in view of the degree of fine dispersion of the composite.
- the amount of the minute media used is most preferably in the range of 100 to 1000% by mass with respect to the composite dispersion from the viewpoints of the efficiency of micronization and the recovery efficiency.
- the degree of fine dispersion is preferably such that the composite has a particle size of less than 1 ⁇ m, preferably from less than 500 nm from the viewpoint of promoting nanowire formation, and more preferably less than 300 nm.
- the particle size is due to dynamic light scattering.
- the solvent used in the wet dispersion treatment and the nanowire formation may be different. At that time, after carrying out the wet dispersion treatment, the solvent used for the wet dispersion is removed, and the miniaturized composite is redispersed in the nanowire-forming solvent.
- the method of re-dispersing in the nanowire-forming solvent is not particularly limited, but known and conventional heat treatment, stirring treatment, dispersion stirring treatment, dispersion uniform treatment, ultrasonic irradiation treatment, ultrasonic stirring treatment, ultrasonic uniform treatment
- a method such as ultrasonic dispersion treatment can be used alone or in combination.
- the nanowire obtained through the step (b) is shortened (reducing the aspect ratio) to form a nanorod.
- the nanowire in an organic solvent, stirring treatment, dispersion stirring treatment, dispersion uniform treatment, ultrasonic irradiation treatment, ultrasonic stirring treatment, ultrasonic uniform treatment Methods such as ultrasonic dispersion treatment and laser irradiation treatment can be used alone or in combination.
- phthalocyanine nanorods having a minor axis of 100 nm or less and a ratio of length to minor axis (length / minor axis) of less than 10 can be obtained.
- This production method comprises a step of reacting an isoindoline compound with a metal ion in the presence of a phthalocyanine having a substituent in a water-soluble polyhydric alcohol to obtain a nanowire, and a step of forming the nanowire into a nanorod. It is what.
- a phthalocyanine having a substituent, an isoindoline compound, and a metal ion are dissolved in a water-soluble polyhydric alcohol and sufficiently stirred to obtain a uniform mixed solution.
- a phthalocyanine having a substituent, an isoindoline compound, and a metal ion are dissolved in a water-soluble polyhydric alcohol and sufficiently stirred to obtain a uniform mixed solution.
- the temperature at the time of stirring is higher than 80 ° C.
- phthalocyanine crystals having a size larger than the nano level may be partially generated at a stage where mixing is insufficient, or the yield may be reduced. It is preferable to carry out at 80 degrees C or less.
- a polyhydric alcohol solution containing the substituted phthalocyanine, the isoindoline compound, and metal ions is mixed at a temperature of 80 ° C. or lower to obtain a mixed solution, and then the mixed solution is heated to 80 to 200 ° C. with stirring. By doing so, an isoindoline compound and a metal ion are reacted to obtain a nanowire.
- the stirring temperature is preferably 100 to 180 ° C.
- a nanowire can be obtained by reacting an isoindoline compound with a metal ion.
- the mixing ratio of the isoindoline compound and the metal ion is preferably adjusted so that the metal ion is 1 to 4 mol with respect to 4 mol of the raw isoindoline compound from the stoichiometric viewpoint.
- Water-soluble polyhydric alcohols that can be used in the present invention are ⁇ -glycols such as ethylene glycol, propylene glycol, 1,2-butanediol, and 2,3-butanediol, and glycerin. Those having adjacent carbon atoms to which one or three hydroxyl groups are bonded are preferred.
- Examples of the phthalocyanine having a substituent used in the present invention include a compound in which the phthalocyanine ring is substituted with at least one substituent and is soluble in a polyhydric alcohol. More specifically, And compounds represented by the general formula (5) or (6).
- Z in the general formula (5) or (6) in this production method is not particularly limited as long as it is a water-soluble polymer chain having a number average molecular weight of 1000 or more, but more preferably a water-soluble polymer having a number average molecular weight of 1000 to 10,000. It is done.
- any water-soluble polymer chain can be used without particular limitation as long as it is water-soluble and has an affinity for water-soluble polyhydric alcohols. Examples include polymer chains having partial structures, and more specifically, polymer chains having all polyalkylene oxides such as ethylene oxide polymers and ethylene oxide / propylene oxide copolymers as partial structures, which may be block-polymerized or randomly polymerized. be able to.
- Z is a polymer chain derived from an alkylene oxide copolymer which is a group represented by the general formula (15), and its hydrophilicity and lipophilicity are optimized according to the solubility in the polyhydric alcohol used. It is desirable to do.
- the isoindoline compound used in the present invention can be synthesized by a known and conventional method.
- 1,2-diazabicyclo (5.4.0) undecene-7 (hereinafter referred to as “DBU”) is obtained by dissolving a phthalonitrile compound such as orthophthalonitrile in a polyhydric alcohol such as ⁇ -glycol or glycerin while heating.
- a phthalonitrile compound soluble in a water-soluble polyhydric alcohol and the polyhydric alcohol reaction product (isoindoline compound) are synthesized by reacting in the presence or absence of an organic base such as the above or a metal alkoxide.
- the phthalonitrile compound that can be used in the present invention includes orthophthalonitrile and those having two —CN groups at the ortho position of the benzene ring or naphthalene ring.
- orthophthalonitrile and those having two —CN groups at the ortho position of the benzene ring or naphthalene ring.
- Ring A in the formula represents a benzene ring or a naphthalene ring which may have a substituent such as an alkyl group, an alkoxy group, an alkylthio group, or a halogen group.
- the reaction temperature of the phthalonitrile compound and the water-soluble polyhydric alcohol is 80 ° C. or higher when no organic base or metal alkoxide is added. However, since a metal-free phthalocyanine compound is formed at a high temperature, a process such as filtration is necessary. It is not preferable. In addition, since the reaction may take a long time when the temperature is low, the reaction is preferably carried out in the range of 100 to 130 ° C. for 15 minutes to 8 hours, more preferably 1 to 3 hours. It is preferable that the obtained solution containing the isoindoline compound is immediately cooled to 80 ° C. or lower immediately after the completion of the reaction to stop the further progress of the reaction. Moreover, it is preferable to avoid mixing of moisture in the air, for example, by placing it in a nitrogen atmosphere during the reaction, and it is preferable to dehydrate the water-soluble polyhydric alcohol in advance.
- the reaction can be performed at a lower temperature than when the organic base is not used, thereby suppressing the formation of a metal-free phthalocyanine compound. It is convenient to do. Specifically, the reaction may be performed in the range of 30 to 100 ° C. for 10 minutes to 2 hours.
- the mass ratio when the phthalonitrile compound and the water-soluble polyhydric alcohol are reacted when the concentration of the phthalonitrile compound is lower than 2%, the productivity when the metal phthalocyanine compound is synthesized later
- the viscosity is higher than 40%, the viscosity of the obtained solution becomes remarkably high, and the amount of metal-free phthalocyanine compound produced may increase, so that the concentration of the phthalonitrile compound is 2 to 40% by mass.
- the range of 5 to 20% by mass is preferable.
- metal ions examples include all metal ions that can be the central metal of metal phthalocyanine, specifically copper ions, zinc ions, cobalt ions, nickel ions, tin ions, lead ions, A magnesium ion, a silicon ion, an iron ion, a palladium ion etc. are mentioned. These metal ions are usually subjected to the reaction by dissolving a metal salt in a water-soluble polyhydric alcohol. Examples of the salt include halides and sulfates. For example, in the case of a copper salt, copper chloride (II) and copper sulfate (II) can be mentioned as preferable salts.
- a glycol solvent may be added to a water-soluble polyhydric alcohol solution containing these compound and metal ion.
- the glycol solvent is particularly preferably a glycol ester solvent in view of the affinity with the metal phthalocyanine nanowire to be generated and the heatable temperature.
- Specific examples of the solvent include, but are not limited to, propylene glycol monomethyl ether acetate.
- the reason why the glycol solvent is preferable is an effect of promoting unidirectional crystal growth for making the phthalocyanine of the present invention into a nanowire.
- the nanowire thus obtained is made into a nanorod in the same manner as in step (c) of production method (I).
- step (b) of the production method (I) by monitoring the one-dimensional crystal growth of the composite obtained in step (a) over time, before growing to an aspect ratio of 10 or more (wired) By stopping the treatment, nanorods having an aspect ratio of less than 10 can be obtained.
- the production method (I) is more preferred.
- the ink composition (or material for a photoelectric conversion element) of the present invention contains phthalocyanine nanorods having a minor axis of 100 nm or less and a ratio of the length to the minor axis (length / minor axis) of less than 10.
- the phthalocyanine nanorod is used as an ink composition (or a material for a photoelectric conversion element) suitable for a wet process (printing or coating) by being dispersed in an organic solvent.
- the type of the organic solvent is not particularly limited as long as it stably disperses phthalocyanine nanorods, and may be a single organic solvent or an organic solvent in which two or more types are mixed. From the viewpoint that nanorods can be dispersed satisfactorily and stably, amide solvents are preferred, and specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, N, N-diethyl Examples include formamide, and among them, N-methylpyrrolidone is particularly preferable.
- the solvent constituting the ink composition can be appropriately selected depending on the type of phthalocyanine having a substituent contained in the phthalocyanine nanorod.
- a derivative of (Chemical Formula 10) In addition to the amide solvent, an aromatic solvent, a halogenated aromatic organic solvent, a halogen organic solvent, and the like can be given as preferred organic solvents that can disperse the phthalocyanine nanorods contained in a favorable and stable manner.
- the aromatic solvent include toluene, xylene, ethylbenzene
- examples of the halogenated aromatic organic solvent include chlorobenzene and dichlorobenzene.
- the halogen organic solvent include chloroform, methylene chloride, dichloroethane and the like. Of these, dichlorobenzene is particularly preferred.
- the phthalocyanine nanorods in the composition The content is preferably 0.05 to 20% by mass, and particularly preferably 0.1 to 10% by mass.
- the ink composition (or photoelectric conversion element material) of the present invention may contain other electron donating materials and hole transporting materials in addition to the phthalocyanine nanorods.
- examples of such a material include a ⁇ -conjugated polymer, a non- ⁇ -conjugated polymer exhibiting semiconducting properties, and a low molecular organic semiconductor compound.
- the ⁇ -conjugated polymer polythiophenes, poly-p-phenylene vinylenes, poly-p-phenylenes, polyfluorenes, polypyrroles, polyanilines, polyacetylenes, polythienylene vinylenes, etc.
- Examples of the non- ⁇ conjugated polymer exhibiting a physical property include polyvinyl carbazole, and examples of the low molecular organic semiconductor compound include a soluble or solvent dispersible phthalocyanine derivative, a soluble or solvent dispersible porphyrin derivative, and the like.
- the polymer material is given wet process (printing or coating) suitability and film forming property (film quality after printing or coating) to the ink composition (or photoelectric conversion element material). There is also an effect.
- the ink composition (or material for a photoelectric conversion element) of the present invention may contain an electron-accepting material typified by fullerenes.
- the photoelectric conversion layer can be formed by a single film formation.
- the electron-accepting material include naphthalene derivatives, perylene derivatives, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerenes, carbon nanotubes (CNT), modified graphenes, poly- Derivatives (CN-PPV) in which a cyano group is introduced into p-phenylene vinylene, Boramer (trade name, manufactured by TDA Research), known low-molecular organic semiconductor materials or polymeric organic semiconductor materials in which a CF3 group or F group is introduced, etc.
- naphthalene derivative 1,4,5,8-naphthalene tetracarboxyl diimide (NTCDI), N, N′-dialkyl-1,4,5,8-naphthalene tetracarboxyl diimide (NTCDI-R) (R is an alkyl group having 1 to 20 carbon atoms), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) and the like
- perylene derivatives include 3,4,9,10-perylenetetracarboxylic dian Hydride (PTCDA), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), N, N′-dialkyl-3, 4,9,10-perylenetetracarboxylic diimide ( Examples of oxazole derivatives such as TCDI-R) (
- fullerenes are preferably used because of their high charge separation rate and electron transfer rate.
- PCBM and C70 derivatives are more preferable because they are particularly excellent in charge separation speed and electron transfer speed and can provide higher photoelectric conversion efficiency.
- the electron-accepting materials include polymer-based materials (electron-accepting polymers) such as a derivative in which a cyano group is introduced into poly-p-phenylene vinylene (CN-PPV), Boramer (trade name, manufactured by TDA Research)
- the ink composition or photoelectric conversion element material
- the ink composition has wet process (printing or coating) suitability and film forming properties (film quality after printing or coating). Since there exists an effect to provide, it is preferable.
- Phthalocyanine nanorod / electron-accepting material is preferably in the range of 1/99 to 99/1, more preferably in the range of 1/9 to 9/1, and even more preferably in the range of 2/8 to 8/2. It is.
- the total content of the phthalocyanine nanorods and the electron-accepting material is 0.05 to 20 with respect to the solvent. It is preferable to set it as the mass%, and it is preferable to set it as 0.1 to 10 mass% especially.
- the resin component is adjusted to rheology. Or as a binder component.
- the resin is not particularly limited as long as it is a publicly known one, and it may be a single resin or two or more resins may be used in combination. Polymethyl methacrylate, polystyrene, polycarbonate, etc. may be used. preferable.
- the content of these resins is preferably 20% by mass or less, and more preferably 10% by mass or less.
- the ink composition (or material for the photoelectric conversion element) of the present invention is mainly composed of an improvement in wet process (printing or coating) suitability and film-forming property (film quality after printing or coating), and constitutional components and various types.
- a surfactant or the like can be added and used as necessary.
- a known and commonly used fine particle powder alone a dispersion obtained by dispersing these fine particle powder alone in a dispersant or an organic solvent can be used alone or in combination. Two or more types may be used in combination.
- Aerosil series (trade name, manufactured by Evonik), Cylicia, Silo Hovic, Silo Pute, Silo Page, Silo Pure, Thylosphere, Silo Mask, Silwell, Fuji Balloon (above, trade name, manufactured by Fuji Silicia),
- PMA-ST There are PMA-ST, IPA-ST (above, trade name, manufactured by Nissan Chemical Co., Ltd.), NANOBIC 3600 series, NANOBIC 3800 series (above, trade name, manufactured by BYK Chemie), etc., but there is no particular limitation. These may be used alone or in combination of two or more.
- the photoelectric conversion element transports electric charges in the film thickness direction, the surface smoothness of the film is required.
- the average particle size of the constitutional component added to the ink is preferably 1 to 150 nm, more preferably 5 to 50 nm, and PMA-ST and IPA-ST which are fine particle silica and alumina dispersions (product) Name, manufactured by Nissan Chemical Co., Ltd.) and NANOBIC 3600 series (trade name, manufactured by Big Chemie) are preferable.
- the average particle diameter can be easily measured by, for example, a dynamic light scattering method.
- these constitutional components are electrically inactive, the concentration of the electron-donating material and the electron-accepting material becomes relatively thin when the content is too high. The developed photoelectric conversion characteristics will be reduced. Therefore, the content rate of the constitutional component in the ink composition (or photoelectric conversion element material) is 90% by mass or less, preferably 70% by mass or less, based on the total solid content.
- the surfactant examples include hydrocarbons, silicons, and fluorines, and these can be used alone or in combination of two or more.
- a preferred fluorosurfactant is a nonionic fluorosurfactant having a linear perfluoroalkyl group and having a chain length of C6 or more, more preferably C8 or more.
- Specific examples include, for example, Megafuck F-482, Megafuck F-470 (R-08), Megafuck F-472SF, Megafuck R-30, Megafuck F-484, Megafuck F-486, Mega There are Facque F-172D, MegaFuck F178RM (the trade name, manufactured by DIC), etc., but there is no particular limitation. These may be used alone or in combination of two or more.
- These surfactants are contained in the ink composition (or photoelectric conversion element material) in an active ingredient of 5.0% by mass or less, and preferably in an active ingredient of 1.0% by mass or less.
- the materials described above are mixed and used.
- the mixing method is not particularly limited, but after adding the above-described materials to the solvent in a desired ratio, a known and commonly used method, that is, heat treatment, stirring treatment, dispersion stirring treatment, dispersion homogenization treatment, Examples thereof include a method in which one or a plurality of methods such as ultrasonic irradiation treatment, ultrasonic stirring treatment, ultrasonic homogenization, ultrasonic dispersion treatment, and laser irradiation treatment are combined and dispersed in a solvent.
- the photoelectric conversion element of the present invention has at least a pair of electrodes, that is, a positive electrode and a negative electrode, and includes the phthalocyanine nanorod of the present invention between these electrodes.
- FIG. 1 is a schematic view showing an example of the photoelectric conversion element of the present invention.
- reference numeral 1 is a substrate
- reference numeral 2 is an electrode a
- reference numeral 3 is a photoelectric conversion layer (organic semiconductor layer) including the phthalocyanine nanorod of the present invention
- reference numeral 4 is an electrode b.
- the organic semiconductor layer 3 is a film containing the phthalocyanine nanorod of the present invention. Moreover, the organic-semiconductor layer 3 is a film
- the phthalocyanine nanorod of the present invention and the electron accepting material may be mixed or laminated.
- An example in the case of being laminated is shown in FIG. It is preferable that the layer having the phthalocyanine nanorod of the present invention as the electron donating material is on the positive electrode side and the layer having the electron accepting material is on the negative electrode side. Therefore, when reference numeral 5 in FIG. 2 is a layer having the phthalocyanine nanorod of the present invention, and reference numeral 6 is a layer containing an electron-accepting material, the electrode a with reference numeral 2 is a positive electrode and the electrode b with reference numeral 4 is a negative electrode.
- an electron donating material other than the above-described phthalocyanine nanorods may be contained in the layer (reference numeral 5) containing the phthalocyanine nanorod of the present invention, or an electron accepting material. It may be contained in a layer (reference numeral 6) containing.
- the thickness of the organic semiconductor layer is not particularly limited as long as the thickness can sufficiently absorb light and does not cause charge deactivation. Is preferably in the range of 10 to 500 nm, more preferably 20 to 300 nm.
- the layer having phthalocyanine nanorods of the present invention preferably has a thickness of 1 to 500 nm, more preferably 5 to 300 nm.
- the organic semiconductor layer can be obtained by forming a film of the ink composition (or material for a photoelectric conversion element) of the present invention by a wet process (printing or coating) and drying it.
- a film forming method of the ink composition (or photoelectric conversion element material) of the present invention a known and commonly used method can be employed without any particular limitation, and specifically, an inkjet method, a gravure printing method, a gravure offset printing.
- the electron-accepting material is the same as the buffer layer formation described later.
- the layers may be laminated by a known and conventional method. It should be noted that since the phthalocyanine nanorods of the present invention have improved solvent resistance after film formation, an electron-accepting material can be laminated by a wet process.
- silicon, glass, various resin materials, or the like can be used.
- Various resin materials include, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC). , Cellulose triacetate (TAC), cellulose acetate propionate (CAP), acrylic resin, and the like.
- a material having good light transmittance is preferable, and examples of such a material include glass, PET, PC, polyimide, PES, acrylic resin, and the like.
- a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode it is preferable to use a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode.
- An electrode using a conductive material having a large work function is a positive electrode.
- the conductive material used for the positive electrode is preferably one that is in ohmic contact with the organic semiconductor layer 3. Furthermore, when the buffer layer 1 described later is used, it is preferable that the conductive material used for the positive electrode is in ohmic contact with the buffer layer 1.
- An electrode using a conductive material having a small work function is a negative electrode, and as the conductive material having a small work function, alkali metal or alkaline earth metal, specifically lithium, magnesium, calcium, or the like is used. . Further, tin, silver, aluminum and the like are also preferably used. Furthermore, an electrode made of an alloy made of the metal or a laminate of the metal is also preferably used.
- the conductive material used for the negative electrode is preferably one that is in ohmic contact with the organic semiconductor layer 3. Furthermore, when the buffer layer 2 described later is used, it is preferable that the conductive material used for the negative electrode is in ohmic contact with the buffer layer 2.
- the electrode a or the electrode b has a light transmittance.
- the light transmittance of the electrode is not particularly limited as long as incident light reaches the organic semiconductor layer 3 and an electromotive force is generated.
- a conductive material for example, among the conductive materials, ITO (indium oxide-tin oxide composite), FTO (fluorine-doped tin oxide), (laminated) graphene, (laminated) modified graphene, conductive by doping
- a commonly known conductive polymer conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene (PEDOT), etc.
- these materials can be used in combination with a mesh made of a metal material having high conductivity.
- the thickness of the electrode may be in a range having light transmittance and conductivity, and varies depending on the electrode material, but is preferably 5 to 10,000 nm, preferably 10 to 5000 nm, and more preferably 20 to 300 nm.
- the other electrode is not necessarily light-transmitting as long as it has conductivity, and the thickness is not particularly limited.
- the above materials are used as raw materials, such as a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, and an atmospheric pressure plasma method.
- Dry process inkjet method, gravure printing method, gravure offset printing method, offset printing method, relief printing method, relief printing method, screen printing method, micro contact printing method, reverse coater method, air doctor coater method, blade coater method , Air knife coater method, roll coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, electrostatic coater method, ultrasonic spray coater method, die coater method, Pinkota method, a bar coater method, a slit coater method, include wet process drop casting, it may be appropriately used depending on the material.
- a method of forming an electrode through a pattern mask or the like using a dry process such as vapor deposition or sputtering, a conductive solid film formed by a dry process such as vapor deposition or sputtering, and a known conventional photolithographic method-etching method Electrode forming method, electrodeposition method combining dry process such as vapor deposition and sputtering and photolithographic method-lift-off method, conductive solid film formed using dry process such as vapor deposition and sputtering, resist by inkjet etc. And a method of etching using the above.
- the conductive fine particle dispersion or the conductive polymer solution or dispersion may be directly patterned by a wet process such as an ink jet method, a screen printing method, a gravure offset printing method, a letterpress reverse printing method, or a micro contact printing method. Then, after forming a solid film by coating film formation, patterning may be performed by a well-known and commonly used photolithography-etching method or laser ablation method, or a combination of a wet process and a photolithography method-lift-off method. You may do it.
- a wet process such as an ink jet method, a screen printing method, a gravure offset printing method, a letterpress reverse printing method, or a micro contact printing method.
- patterning may be performed by a well-known and commonly used photolithography-etching method or laser ablation method, or a combination of a wet process and a photolithography method-lift-off method. You may do it.
- the buffer layer 1 may be provided between the positive electrode and the organic semiconductor layer.
- the buffer layer 1 is used as necessary to enable efficient charge extraction.
- Examples of the material for forming the buffer layer 1 include graphene oxide, modified graphene, polythiophenes, poly-p-phenylene vinylenes, polyfluorenes, polyvinyl carbazoles, phthalocyanine derivatives (H2Pc, CuPc, ZnPc, etc.), porphyrin derivatives, and the like. Preferably used. These materials may have improved conductivity (hole transportability) by doping.
- PEDOT polyethylenedioxythiophene
- PSS polystyrene sulfonate
- the thickness of the buffer layer 1 is preferably 5 to 600 nm, more preferably 10 to 200 nm.
- the buffer layer 2 may be provided between the organic semiconductor layer and the negative electrode.
- the buffer layer 2 is used as necessary to enable efficient charge extraction.
- the above-described electron accepting materials naphthalene derivatives, perylene derivatives, oxazole derivatives, triazole derivatives, phenanthroline derivatives, phosphine oxide derivatives, fullerenes, carbon nanotubes (CNT), modified graphenes, poly -Derivatives (CN-PPV) in which a cyano group is introduced into p-phenylene vinylene, Boramer (trade name, manufactured by TDA Research), known low-molecular organic semiconductor materials or polymeric organic semiconductors in which a CF3 group or an F group is introduced Materials), perfluoro compounds such as octaazaporphyrin, perfluoropentacene and perfluorophthalocyanine, electron donating compounds such as tetrathiofulvalene and te
- Transfer complexes composed of electron-accepting compounds such as titanium and tetracyanoethylene, n-type inorganic oxide semiconductors such as titanium oxide, zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride and cesium fluoride Etc. can be used.
- the thickness of the buffer layer 2 is preferably 0.5 to 600 nm, more preferably 1 to 200 nm.
- Buffer layer formation methods include vacuum deposition, molecular beam epitaxial growth, ion cluster beam method, low energy ion beam method, ion plating method, CVD method, sputtering method, atmospheric pressure plasma method and other dry processes, inkjet Method, gravure printing method, gravure offset printing method, offset printing method, relief printing method, relief printing method, screen printing method, micro contact printing method, reverse coater method, air doctor coater method, blade coater method, air knife coater method, Roll coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, electrostatic coater method, ultrasonic spray coater method, die coater method, spin coater , A bar coater method, a slit coater method, include wet process drop casting, it may be appropriately used depending on the material.
- an inorganic oxide for the buffer layer when using an inorganic oxide for the buffer layer, as a wet process, a liquid in which fine particles of the inorganic oxide are dispersed in any organic solvent or water using a dispersion aid such as a surfactant as required is applied. Further, a drying method or a so-called sol-gel method in which a solution of an oxide precursor, for example, an alkoxide body is applied and dried can be used.
- These buffer layers may be a single layer or may be a laminate of different materials.
- the photoelectric conversion element by this invention can comprise a solar cell module by integration.
- the photoelectric conversion element of this invention can also be set as the structure which interrupts
- the photoelectric conversion element according to the present invention is integrated in series by bringing the electrode a of the photoelectric conversion element according to the present invention into contact with the electrode b of another photoelectric conversion element according to the present invention adjacent thereto.
- the solar cell module characterized by having been made into can be mentioned.
- the electrodes a of adjacent photoelectric conversion elements according to the present invention are brought into contact with each other, and the electrodes b of adjacent photoelectric conversion elements according to the present invention are brought into contact with each other, whereby the photoelectric conversion elements according to the present invention are connected in parallel and integrated.
- It may be a solar cell module characterized in that
- Example 1 ⁇ Production of ink composition (material for photoelectric conversion element)> ⁇ Process (a) Copper phthalocyanine (Fastogen Blue 5380E (trade name, manufactured by DIC)) 1.6 g as unsubstituted phthalocyanine and 1.2 g of a phthalocyanine derivative represented by (Chemical Formula 10) as a substituted phthalocyanine (concentrated sulfuric acid) The solution was poured into 81 g and completely dissolved to prepare a concentrated sulfuric acid solution.
- ethylene glycol monomethyl ether acetate manufactured by Wako Pure Chemical Industries, Ltd.
- ethylene glycol monomethyl ether acetate manufactured by Wako Pure Chemical Industries, Ltd.
- the dispersion was filtered using a membrane filter (pore size: 0.1 ⁇ m), and the residue was thoroughly washed with orthodichlorobenzene.
- the filter residue was put into orthodichlorobenzene so that the solid concentration would be 2%, and shaken well to obtain a dispersion using orthodichlorobenzene as a dispersion solvent.
- a wire-like solid having a minor axis of about 50 nm or less and a ratio of the length to the minor axis of 10 or more was confirmed (FIG. 3).
- An ITO transparent conductive layer serving as a positive electrode was deposited to a thickness of 100 nm on a glass substrate by sputtering, and this was patterned into a 2 mm-wide strip by photolithography-etching.
- the obtained glass substrate with pattern ITO was subjected to ultrasonic cleaning three times for 15 minutes each in the order of neutral detergent, distilled water, acetone and ethanol, and then UV / ozone treatment for 30 minutes, and PEDOT: PSS on this.
- a buffer layer 1 made of PEDOT: PSS was formed to a thickness of 60 nm on the ITO transparent electrode layer by spin coating an aqueous dispersion (AI4083 (trade name, manufactured by HC Starck)).
- the photoelectric conversion layer material (1) was spin-coated on the PEDOT: PSS layer and derived from the photoelectric conversion layer material (1) having a film thickness of 100 nm.
- An organic semiconductor layer was formed.
- the “substrate on which the organic semiconductor layer is formed” and a metal mask for vapor deposition (for forming a 2 mm strip pattern) are placed in a vacuum vapor deposition apparatus, and the degree of vacuum in the apparatus is reduced to 5 ⁇ 10 ⁇ 4 Pa.
- aluminum serving as a negative electrode was deposited by vapor deposition so as to form a strip pattern having a width of 2 mm by a resistance heating method (film thickness: 80 nm).
- the photoelectric conversion element (1) having an area of 2 mm ⁇ 2 mm (a portion where the strip-like ITO layer and the aluminum layer intersect) was manufactured.
- the positive and negative electrodes of the photoelectric conversion element (1) are connected to a digital multimeter (6241A, product name (manufactured by ADC)), and the spectrum shape is AM1.5 and the irradiation intensity is 100 mW / cm 2 simulated sunlight (simple Under the irradiation (irradiation from the ITO layer side) of a type solar simulator XES151S (product name, manufactured by Mitsunaga Electric Manufacturing Co., Ltd.), the voltage was swept from ⁇ 0.1 V to +0.8 V in the atmosphere, and the current value was measured. At this time, the short-circuit current density (the value of the current density when the applied voltage is 0 V.
- J sc is 4.47 mA / cm 2
- the open end voltage (the value of the applied voltage when the current density is 0. , V oc ) was 0.56 V
- the fill factor (FF) was 0.40
- the photoelectric conversion efficiency (PCE) calculated from these values was 1.02%.
- FF and PCE were calculated by the following formula.
- JV max is the value of the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage is maximum between the applied voltage of 0 V and the open-circuit voltage value.
- PCE [(J sc ⁇ V oc ⁇ FF) / pseudo sunlight intensity (100 mW / cm 2 )] ⁇ 100 (%)
- Example 2 ⁇ Production of photoelectric conversion element> 180 mg of orthodichlorobenzene was added to 180 mg of the dispersion liquid (1) obtained in Example (1) to obtain an ink composition (2) (photoelectric conversion element material (2)).
- a photoelectric conversion element (2) was produced in the same manner as in Example (1) except that 2 wt% PCBM-orthodichlorobenzene was spin-coated thereon and an electron-accepting material layer was laminated thereon. .
- Example 3 Manufacture of Transistor> An n-type silicon substrate was prepared and used as a gate electrode, and the surface layer was thermally oxidized to form a gate insulating film made of silicon oxide.
- the ink composition (2) obtained in Example (2) was spin-coated to form a semiconductor film (channel portion).
- a source / drain electrode made of a gold thin film was patterned by vapor deposition to produce a transistor (3).
- the channel length L (source electrode-drain electrode interval) was 75 ⁇ m, and the channel width W was 5.0 mm.
- the transistor characteristics were evaluated using a digital multimeter (SMU237, manufactured by Keithley), sweeping from 0 to -80V voltage (Vg) to the gate electrode, and the current (Id) between the source and drain electrodes to which -80V was applied. This was done by measuring. As a result, the mobility was 10 ⁇ 4 and the ON / OFF ratio was 10 4 . The mobility was obtained from the slope of ⁇ Id ⁇ Vg by a known method. The unit is cm 2 / V ⁇ s. The ON / OFF ratio was determined by (maximum value of absolute value of Id) / (minimum value of absolute value of Id).
- Q represents a hydrogen atom or a methyl group
- propylene oxide / ethylene oxide 29/6 (molar ratio)
- the average value of n 35.
- the phthalocyanine derivative represented by (Chemical Formula 10) is converted into orthodichlorobenzene as a dispersion solvent in the step (b).
- a phthalocyanine nanorod dispersion (4) was obtained in the same manner as in Example (1) except that NMP was used instead.
- a photoelectric conversion element (4) was produced in the same manner as in Example (2) except that the photoelectric conversion element material (4) was used instead of the photoelectric conversion element material (2).
- a transistor (4) was produced in the same manner as in Example (3) except that the ink composition (4) was used instead of the ink composition (2).
- the transistor (4) was evaluated for transistor characteristics. As a result, the mobility was 10 ⁇ 4 and the ON / OFF ratio was 10 3 .
- Example 5 ⁇ Production of ink composition (material for photoelectric conversion element)>
- the phthalocyanine derivative represented by (Chemical Formula 6) is changed to the phthalocyanine derivative represented by (Chemical Formula 6), and orthodichlorobenzene is changed to Ndichlorobenzene as a dispersion solvent in the step (b).
- a phthalocyanine nanorod dispersion (5) was obtained in the same manner as in Example (1) except that was used.
- 180 mg of NMP was added to 180 mg of the phthalocyanine nanorod dispersion (5) to obtain an ink composition (5) (photoelectric conversion element material (5)).
- a photoelectric conversion element (5) was produced in the same manner as in Example (2) except that the photoelectric conversion element material (5) was used instead of the photoelectric conversion element material (2).
- a transistor (5) was produced in the same manner as in Example (3) except that the ink composition (5) was used instead of the ink composition (2).
- Example 6 ⁇ Production of ink composition (material for photoelectric conversion element)>
- the phthalocyanine derivative represented by (Chemical Formula 8) is changed to the phthalocyanine derivative represented by (Chemical Formula 10), and orthodichlorobenzene is changed to Ndichlorobenzene as the dispersion solvent in the step (b).
- a phthalocyanine nanorod dispersion (6) was obtained in the same manner as in Example (1) except that was used.
- 180 mg of NMP was added to 180 mg of the phthalocyanine nanorod dispersion (6) to obtain an ink composition (6) (photoelectric conversion element material (6)).
- a photoelectric conversion element (6) was produced in the same manner as in Example (2) except that the photoelectric conversion element material (6) was used instead of the photoelectric conversion element material (2).
- a transistor (6) was produced in the same manner as in Example (3) except that the ink composition (6) was used instead of the ink composition (2).
- Example 7 Example 7 to (Example 31) Thereafter, the following Examples (7) to (31) are carried out in the same manner as in the above Examples to produce phthalocyanine nanorods containing various unsubstituted phthalocyanines and substituted phthalocyanines, and photoelectric conversion containing the phthalocyanine nanorods The characteristics of the device were evaluated. The results are shown in Table 1. (In the table, examples to be referred to in the production of phthalocyanine nanorods are described.)
- sulfonic acid represents the substituent described in (Chemical Formula 6
- imide represents the substituent described in (Chemical Formula 10)
- sulfamoyl represents the substituent described in (Chemical Formula 21).
- the phthalocyanine nanorod according to the present invention is superior in solvent dispersibility than the phthalocyanine pigment fine particles, so that it is easy to form an ink composition, and thus a photoelectric conversion element can be produced by a wet process. Furthermore, the photoelectric conversion element using the phthalocyanine nanorod according to the present invention has a higher fill factor (FF) than the photoelectric conversion element using the phthalocyanine nanowire, and as a result, the photoelectric conversion efficiency is improved.
- FF fill factor
- a long-lived photoelectric conversion element derived from the high durability of phthalocyanine can be provided at a low cost by a wet process, and further, by using the photoelectric conversion element, Due to the characteristics of the photoelectric conversion element, it is possible to construct a long-life solar cell module at low cost.
- Electrode b 5 A layer containing the phthalocyanine nanorod of the present invention (when the electrode a is a positive electrode) or a layer containing an electron accepting material (when the electrode a is a negative electrode) 6 Layer containing electron-accepting material (when electrode b is negative electrode) or layer containing phthalocyanine nanorod of the present invention (when electrode b is positive electrode)
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Abstract
Description
(1)環境負荷が少ない
(2)製造コストが安い
(3)軽量で壊れにくい
等の点でポテンシャルが高く、近年注目を集めている。有機薄膜太陽電池とは、有機半導体材料で構成される電子供与性材料(ドナー)と有機半導体材料で構成される電子受容性材料(アクセプター)からなる有機半導体層を光電変換の活性層(光電変換層)とした、有機半導体材料で構成される光電変換素子のことである。ここで、電子供与性材料としては、ポリチオフェン系やポリフェニレンビニレン系等の電子供与性π共役系ポリマーや、フタロシアニン類等の電子供与性低分子材料が挙げられ、電子受容性材料としては、フラーレン類等が挙げられる。最近は、特に、該電子供与性材料と該電子受容性材料とをナノレベルでコンポジット化して、光電変換に寄与する両材料の接合界面(DA接合界面)を増大させたバルクヘテロ接合型の開発が活発に行われている(特許文献1)。
(1)有機半導体層の光吸収により励起子(正孔・電子の対)が生じ、
(2)これがDA接合界面に拡散移動し、
(3)正孔及び電子に電荷分離し、
(4)それぞれの電荷が電子供与性材料及び電子受容性材料を通じて、正極及び負極に電荷輸送されて電力を発生するものであり、前記各過程の効率の積算でその光電変換効率が決定される。ここで励起子の寿命は極めて短く、拡散移動できる距離はせいぜい数ナノメートルから十数ナノメートルと極めて短いため、光電変換の効率を高めるためには、有機半導体層中のDA接合界面が前記励起子の拡散移動可能な距離(励起子拡散長)と同程度の距離範囲内に存在していることが好ましく、且つ、電荷分離後の電荷がそれぞれの電極へ速やかに移動できる電荷輸送経路が確保されていることが好ましい。
一方、近年、前記「光電変換の原理」における過程(4)の電荷輸送効率を上げるために、ナノワイヤ状の電子供与性材料を用いた光電変換素子が提案されている(非特許文献1)。これは、電子供与性π共役系ポリマーであるP3HTをナノワイヤ化、すなわち、幅が数十nm程度の細線に形態制御することにより、電荷輸送効率が増大し、その結果、P3HTナノワイヤを含むP3HT/PCBM系光電変換素子が該ナノワイヤを含まない該光電変換素子に比べて、光電変換効率が向上するというものである。
このように、ポリマー系ナノワイヤを含む光電変換素子は光電変換効率の向上に有用であることが確認されているが、一般にP3HT等のポリマー系は前記のごとく、耐酸素性や耐光性が低いために耐久性に劣り、光電変換素子の実用的観点からの問題は解決できていない。
以下、本発明のフタロシアニンナノロッドについて説明する。
本発明の短径が100nm以下であってその短径に対する長さの比率(長さ/短径)が10未満であるフタロシアニンナノロッドとしては、無置換フタロシアニンと置換基を有するフタロシアニン(フタロシアニン誘導体)からなる、フタロシアニンナノロッドを挙げることができる。
一般式(3)又は(4)において、R1からR4は、前記結合基Y1からY4を介してフタロシアニン環と結合しえる官能基である。
で表される基も用いることができる。
で表される基を挙げることができる。置換基としては、フタルイミド基に置換が可能な通常公知の置換基を挙げることができる。
一般式(3)又は(4)の置換基を有するフタロシアニン(フタロシアニン誘導体)は、フタロシアニン環に側鎖又は官能基を導入することにより、合成することができる。(化5)、(化6)、(化7)記載のスルホン酸化銅フタロシアニンは銅フタロシアニンを発煙硫酸(三酸化硫黄濃度:20%)中で加熱することにより得ることができ、(化10)の化合物の合成は、例えば、米国特許2761868号に開示の方法で合成することができる。
一般式(5)又は(6)で表される置換基を有するフタロシアニン(フタロシアニン誘導体)は、フタロシアニン環が少なくとも1個以上のスルファモイル基で置換された化合物である。導入されるスルファモイル基は、フタロシアニン環1個あたり少なくとも1個であれば特に限定なく用いることができるが、好ましくは1又は2個、より好ましくは1個である。置換される位置は、特に限定はない。
好ましいR及びR’として、低級アルキル基、特にメチル基を挙げることができ、mとしては、1から6であるものが好ましい。具体的に好ましいフタロシアニン誘導体として以下が挙げられる。なお、ここで、置換基を有するフタロシアニンの式の括弧の横の数字はフタロシアニン分子に対する置換基の平均導入数を表している。この数が小数である理由は、個々の分子についての置換基導入数は整数であるが、実際の使用に当たっては、置換基導入数の異なるものが混在しているためである。
ポリエーテルモノアミンは市販品としても提供されており、例えばJEFFAMINE Mシリーズ(商品名、Huntsman製)がある。
次に、本発明に使用されるフタロシアニンナノロッドの製造方法(I)から(III)について説明する。
本製造方法は、
(a)無置換フタロシアニンと置換基を有するフタロシアニン(フタロシアニン誘導体)とを酸に溶解させた後に、貧溶媒に析出させて複合体を得る工程、
(b)前記複合体をナノワイヤ化する工程、
(c)前記ナノワイヤをナノロッド化する工程
とを有するものである。
一般にフタロシアニン類は硫酸等の酸溶媒に可溶であることが知られており、まず前記無置換フタロシアニンと前記置換基を有するフタロシアニンとを硫酸、クロロ硫酸、メタンスルホン酸、トリフルオロ酢酸等の酸溶媒に溶解させる。その後に水等の貧溶媒に投入して該無置換フタロシアニンと該置換基を有するフタロシアニン誘導体の複合体を析出させる。
該複合体は、濾紙及びブフナーロートを用いて濾過し、酸性水を除去するともに、濾液が中性になるまで水洗して、含水した状態で回収することができる。回収した複合体は、脱水・乾燥して水分を除去するか、又は次工程において水又は水溶性有機溶媒を用いる場合には、含水状態のままであってもよい。
工程(b)は、前記工程(a)を経て得られた複合体を、一次元結晶成長させることでナノワイヤ化する工程である。ナノワイヤ化の程度は、得られるナノワイヤの形状が、幅(短径)が100nm以下であることが好ましく、光電変換効率向上の観点からは幅(短径)が50nm以下であることが好ましい。
ナノワイヤ化の方法は、該複合体をナノワイヤ化することができれば、その方法は特に限定されるものではないが、該複合体を有機溶媒中(液相中)でナノワイヤ化する方法を挙げることができる。具体的には、該複合体を、有機溶媒中(液相中)にて、(加熱)攪拌又は(加熱)静置することで、該複合体をナノワイヤ化せしめることが出来る。
該複合体をナノワイヤ化する場合の攪拌又は静置時の温度は、5から250℃の範囲が好ましく、さらに好ましくは20から200℃である。温度が5℃以上であれば、十分にフタロシアニン類の結晶成長を誘発することができ、目的とする一次元結晶成長により、ナノワイヤへ成長可能であり、又、250℃以下であればナノワイヤの凝集、融着がほとんど見られず、又、幅方向に結晶成長して粗大化することもない。
該複合体を液相中でナノワイヤ化する場合、該複合体を有機溶媒に単純に投入した後、(加熱)攪拌又は(加熱)静置することにより、ナノワイヤ化する方法と、該複合体を有機溶媒中に微分散させてから、(加熱)攪拌又は(加熱)静置することにより、ナノワイヤ化する方法が挙げられるが、後述するインキ化を考慮した場合、インキ化のための工程を簡略化することが出来ることから、該複合体を有機溶媒中に微分散させてから、(加熱)攪拌又は(加熱)静置することにより、ナノワイヤ化する方法が好ましい。
ここで、湿式分散処理に用いる分散溶媒としては、水、有機溶媒、含水有機溶媒等が挙げられる。有機溶媒としては、前記ナノワイヤ化に用いる有機溶媒に加え、エタノールなどのアルコール類、グリコール類、グリコールエステル類を挙げることができ、これらの分散溶媒を1種又は複数種組み合わせて行なう事もできるが、結晶成長や結晶転移の抑制の点でより好ましくは、水、エタノール、メタノール、クロロベンゼン、ジクロロベンゼン、N-メチル-2-ピロリドンである。
湿式分散処理を実施するに当たり、微分散化の程度は、該複合体が粒径1μm未満になることが好ましく、ナノワイヤ化促進という観点から、500nm未満となることが好ましく、さらには、300nm未満となることが好ましい(粒径は動的光散乱による)。
ここで、前記湿式分散処理と前記ナノワイヤ化において、用いる溶媒が異なっていてもかまわない。その際、湿式分散処理を実施した後、湿式分散に用いた溶媒を除去し、微細化された複合体を、ナノワイヤ化溶媒に再分散させる。湿式分散に用いた溶媒を除去する方法としては特に制限はないが、ろ過、遠心分離、ロータリーエバポレーター等による蒸発処理等を挙げることができる。さらに、これらの処理の後、真空乾燥機などを用いて溶媒分を完全に除去するまで乾燥してもよい。ナノワイヤ化溶媒に再分散させる方法は特に限定されるものではないが、公知慣用の、加熱処理、撹拌処理、分散攪拌処理、分散均一処理、超音波照射処理、超音波攪拌処理、超音波均一処理、超音波分散処理等の方法を1種又は複数種組み合わせて行なう事ができる。
最後に、工程(b)を経て得られたナノワイヤを短尺化する(アスペクト比を下げる)ことでナノロッド化する。ナノロッド化の方法としては特に限定されるものではないが、前記ナノワイヤを有機溶媒中にて、撹拌処理、分散攪拌処理、分散均一処理、超音波照射処理、超音波攪拌処理、超音波均一処理、超音波分散処理、レーザー照射処理等の方法を1種又は複数種組み合わせて行なう事ができる。これらの処理により、短径が100nm以下であってその短径に対する長さの比率(長さ/短径)が10未満であるフタロシアニンナノロッドを得ることが出来る。
本製造方法は、水溶性多価アルコール中において、置換基を有するフタロシアニンの存在下、イソインドリン化合物と金属イオンとを反応させナノワイヤを得る工程と該ナノワイヤをナノロッド化する工程とを有することを特徴とするものである。
が挙げられる。
このようにして得られたナノワイヤを製造方法(I)の工程(c)と同様にして、ナノロッド化する。
前記製造方法(I)の工程(b)において、工程(a)で得られた複合体の一次元結晶成長を経時的にモニタリングすることで、アスペクト比10以上に成長する(ワイヤ化)前に該処理を止め、これにより、アスペクト比が10未満のナノロッドを得ることが出来る。
前記で挙げた本発明に使用されるフタロシアニンナノロッドの製造方法(I)から(III)のうち、(I)の製造方法がより好ましい。
本発明のインキ組成物(又は光電変換素子用材料)は、短径が100nm以下であってその短径に対する長さの比率(長さ/短径)が10未満であるフタロシアニンナノロッドを含有する。
前記フタロシアニンナノロッドは、有機溶媒に分散させることにより、ウエットプロセス(印刷又は塗布)に適したインキ組成物(又は光電変換素子用材料)として使用される。
又、ハロゲン系有機溶媒として、クロロホルム、塩化メチレン、ジクロロエタン等の有機溶媒を挙げることができる。この中で、特に好ましいものはジクロロベンゼンである。
次に、本発明の光電変換素子について説明する。本発明の光電変換素子は、少なくとも一対の電極、すなわち正極と負極を有し、これら電極間に本発明のフタロシアニンナノロッドを含む。図1は本発明の光電変換素子の一例を示す模式図である。図1において符号1は基板、符号2は電極a、符号3は本発明のフタロシアニンナノロッドを含む光電変換層(有機半導体層)、符号4は電極bである。
これらバッファー層は、単層であってもよく、又、異なる材料を積層したものであってもよい。
・工程(a)
無置換フタロシアニンとして銅フタロシアニン(Fastogen Blue 5380E(商品名、DIC製))1.6gと、置換基を有するフタロシアニンとして(化10)で表されるフタロシアニン誘導体1.2gを濃硫酸(関東化学製)81gに投入して完全に溶解させ、濃硫酸溶液を調製した。続いて、蒸留水730gを1000mLのビーカーに投入し、これを氷水で十分冷却した後、該蒸留水を撹拌しながら、先に調製した濃硫酸溶液を投入し、無置換銅フタロシアニンと(化10)で表される銅フタロシアニン誘導体とからなる複合体を析出させた。
続いて得られた該複合体を、濾紙を用いてろ過し、蒸留水を用いて十分に洗浄し、含水した該複合体を回収した。
工程(a)で得られた含水複合体12gを容量50mLのポリプロピレン製容器に投入し、さらに蒸留水を加えて、該複合体(固形分)の水に対する重量比を15%とし、次いでφ0.5mmのジルコニアビーズ60gを加えて、ペイントシェイカーを用いて2時間、微分散処理した。続いて該微分散処理により微粒子化した複合体の分散液をジルコニアビーズから分離回収し、さらに蒸留水を加えて重量50gの微粒子化複合体水分散液(固形物濃度5%)を得た。
工程(b)で得られたフタロシアニンナノワイヤの分散液を、超音波ホモジナイザー(商品名:US300、日本精機製作所製)を用いて、氷冷下、7φのホーンを使用し、出力10で30分間処理した。このようにして得られた分散液を回収し、その固形分を走査型電子顕微鏡で観察したところ、短径が約20nm以下、短径に対する長さの比率が5以下であるロッド状固形物が確認された(図4参照)。以上より、該処理にて、フタロシアニンナノワイヤのナノロッド化(フタロシアニンナノロッドの形成)が確認された。
かくして、本工程において、固形分濃度2%のフタロシアニンナノロッド分散液(1)が製造された。
ガラス基板にスパッタリング法により正極となるITO透明導電層を100nm堆積させ、これをフォトリソグラフィー-エッチング法により2mm幅の短冊状にパターニングした。得られたパターンITO付きガラス基板を、中性洗剤、蒸留水、アセトン、エタノールの順にそれぞれにつき15分間超音波洗浄を3回実施した後、30分間UV/オゾン処理し、この上にPEDOT:PSS水分散液(AI4083(商品名、HCStarck製))をスピンコートすることで、PEDOT:PSSよりなるバッファー層1を60nmの厚さでITO透明電極層上に形成した。これを100℃に加熱したホットプレート上で5分間乾燥した後、該PEDOT:PSS層上に光電変換層用材料(1)をスピンコートし、膜厚100nmの光電変換層用材料(1)由来の有機半導体層を形成した。その後、前記「有機半導体層が形成された基板」と蒸着用メタルマスク(2mm幅の短冊パターン形成用)を真空蒸着装置内に設置して、装置内の真空度を5×10-4Paまで高めた後、抵抗加熱法によって、負極となるアルミニウムを2mm幅の短冊パターンになるように蒸着堆積した(膜厚:80nm)。以上のようにして、面積が2mm×2mm(短冊状のITO層とアルミニウム層が交差する部分)である光電変換素子(1)を製造した。
前記光電変換素子(1)の正極と負極をデジタルマルチメーター(6241A、製品名(ADC製))に接続して、スペクトル形状:AM1.5、照射強度:100mW/cm2の擬似太陽光(簡易型ソーラシミュレータ XES151S(製品名、三永電機製作所製))の照射下(ITO層側から照射)、大気中で電圧を-0.1Vから+0.8Vまで掃引し、電流値を測定した。この時の短絡電流密度(印加電圧が0Vのときの電流密度の値。以下、Jsc)は4.47mA/cm2、開放端電圧(電流密度が0になるときの印加電圧の値。以下、Voc)は0.56V、フィルファクター(FF)は0.40であり、これらの値から算出した光電変換効率(PCE)は1.02%であった。なお、FFとPCEは次式により算出した。
FF=JVmax/(Jsc×Voc)
(ここで、JVmaxは、印加電圧が0Vから開放端電圧値の間で電流密度と印加電圧の積が最大となる点における電流密度と印加電圧の積の値である。)
PCE=[(Jsc×Voc×FF)/擬似太陽光強度(100mW/cm2)]×100(%)
実施例(1)で得た分散液(1)180mgにオルトジクロロベンゼン180mgを加えインキ組成物(2)(光電変換素子用材料(2))を得た。
光電変換素子用材料(1)の変わりに光電変換素子用材料(2)を使用し実施例(1)と同様に光電変換素子用材料(2)由来の有機半導体層(電子供与性材料層)を形成した後、この上に、2重量%のPCBM-オルトジクロロベンゼンをスピンコートし電子受容性材料層を積層した以外は実施例(1)と同様にして光電変換素子(2)を製造した。
光電変換素子(1)の替わりに光電変換素子(2)を用いる他は、実施例1と同様にして光電変換素子の評価を行った。結果は、Jscが4.25mA/cm2、Vocが0.53V、FFが0.44であり、これらの値から算出したPCEは0.99%であった。
n型のシリコン基板を用意してこれをゲート電極とし、この表面層を熱酸化処理して酸化シリコンからなるゲート絶縁膜を形成した。ここに、実施例(2)で得たインキ組成物(2)をスピンコートし、半導体膜(チャネル部)を形成した。次に、蒸着成膜によって、金薄膜からなるソース・ドレイン電極をパターン形成し、トランジスタ(3)を製造した。なお、チャネル長L(ソース電極-ドレイン電極間隔)を75μm、チャネル幅Wを5.0mmとした。
<トランジスタの評価>
上記トランジスタ(3)について、トランジスタ特性を評価した。トランジスタ特性の評価は、デジタルマルチメーター(SMU237、ケースレー製)を用いて、ゲート電極に0から-80V電圧(Vg)をスイープ印加し、-80V印加したソース・ドレイン電極間の電流(Id)を測定することで行なった。結果は、移動度が10-4、ON/OFF比が104であった。なお、移動度は√Id-Vgの傾きから、周知の方法により求めた。単位はcm2/V・sである。また、ON/OFF比は(Idの絶対値の最大値)/(Idの絶対値の最小値)で求めた。
数平均分子量約2,000の第一アミン-末端ポリ(エチレンオキシド/プロピレンオキシド)コポリマー(Surfonamine B-200(商品名、Huntsman Corporation製))692質量部と炭酸ナトリウム66質量部と水150質量部の混合物に、銅フタロシアニンスルホニルクロリド(スルホン化度=1)210質量部を投入し、5℃~室温で6時間反応させた。得られた反応混合物を真空下で90℃に加熱して水を除去し、下記(化21)で表される銅フタロシアニンスルファモイル化合物を得た。
オキシド=29/6(モル比)、nの平均値=35である。
光電変換素子用材料に光電変換素子用材料(2)に変えて光電変換素子用材料(4)を用いた以外は実施例(2)と同様にして、光電変換素子(4)を製造した。
光電変換素子(1)に変えて光電変換素子(4)を用いた以外は実施例(1)と同様にして、光電変換素子の評価を行なったところ、Jscは4.54mA/cm2、Vocは0.58V、FFは0.44であり、これらの値から算出したPCEは1.15%であった。
インキ組成物(2)に変えてインキ組成物(4)を用いた以外は実施例(3)と同様にして、トランジスタ(4)を製造した。
前記トランジスタ(4)について、トランジスタ特性を評価した。結果は、移動度が10-4、ON/OFF比が103であった。
置換基を有するフタロシアニン(フタロシアニン誘導体)として(化10)で表されるフタロシアニン誘導体に変えて(化6)で表されるフタロシアニン誘導体を、工程(b)における分散溶媒としてオルトジクロロベンゼンに変えてNMPを用いた以外は実施例(1)と同様にして、フタロシアニンナノロッド分散液(5)を得た。
次に、前記フタロシアニンナノロッド分散液(5)180mgにNMP180mgを加えインキ組成物(5)(光電変換素子用材料(5))を得た。
光電変換素子用材料(2)に変えて光電変換素子用材料(5)を用いた以外は実施例(2)と同様にして、光電変換素子(5)を製造した。
光電変換素子(1)に変えて光電変換素子(5)を用いた以外は実施例(1)と同様にして、光電変換素子の評価を行なったところ、Jscは5.20mA/cm2、Vocは0.56V、FFは0.39であり、これらの値から算出したPCEは1.15%であった。
インキ組成物(2)に変えてインキ組成物(5)を用いた以外は実施例(3)と同様にして、トランジスタ(5)を製造した。
トランジスタ(3)に変えて前記トランジスタ(5)を用いた以外は実施例(3)と同様にして、トランジスタ特性を評価した。結果は、移動度が10-4、ON/OFF比が104であった。
置換基を有するフタロシアニン(フタロシアニン誘導体)として(化10)で表されるフタロシアニン誘導体に変えて(化8)で表されるフタロシアニン誘導体を、工程(b)における分散溶媒としてオルトジクロロベンゼンに変えてNMPを用いた以外は実施例(1)と同様にして、フタロシアニンナノロッド分散液(6)を得た。
次に、前記フタロシアニンナノロッド分散液(6)180mgにNMP180mgを加えインキ組成物(6)(光電変換素子用材料(6))を得た。
光電変換素子用材料(2)に変えて光電変換素子用材料(6)を用いた以外は実施例(2)と同様にして、光電変換素子(6)を作製した。
光電変換素子(1)に変えて光電変換素子(6)を用いた以外は実施例(1)と同様にして、光電変換素子の評価を行なったところ、Jscは4.32mA/cm2、Vocは0.54V、FFは0.40であり、これらの値から算出したPCEは0.92%であった。
インキ組成物(2)に変えてインキ組成物(6)を用いた以外は実施例(3)と同様にして、トランジスタ(6)を製造した。
トランジスタ(3)に変えて前記トランジスタ(6)を用いた以外は実施例(3)と同様にして、トランジスタ特性を評価した。結果は、移動度が10-4、ON/OFF比が103であった。
以下、上記実施例と同様にして、下記実施例(7)~(31)を行い、各種無置換フタロシアニン及び置換基を有するフタロシアニンを含有するフタロシアニンナノロッドを作製し、該フタロシアニンナノロッドを含有する光電変換素子の特性を評価した。その結果を表1に示す。(表中、フタロシアニンナノロッドの作製上参照すべき実施例を記載した。)
光電変換素子用材料(1)のフタロシアニンナノロッドのかわりに銅フタロシアニン顔料微粒子を用いた以外は実施例(1)と同様にして光電変換素子の製造を行なったが、銅フタロシアニン顔料微粒子の溶媒分散性が低いため、製膜性に問題があり、該分散液を用いて光電変換素子を製造することが出来なかった。
<光電変換素子の製造>
実施例(1)で製造したフタロシアニンナノロッドのかわりに、実施例(1)工程(b)で製造したフタロシアニンナノワイヤを用いた以外は実施例(1)と同様にして光電変換素子(2)’を製造した。
<光電変換素子の評価>
光電変換素子(1)の替わりに光電変換素子(2)’を用いる他は、実施例1と同様にして光電変換特性の評価を行った。結果は、Jscが4.17mA/cm2、Vocが0.56V、FFが0.28であり、これらの値から算出したPCEは0.66%であった。
2 電極a
3 光電変換層
4 電極b
5 本発明のフタロシアニンナノロッドを含有する層(電極aが正極の場合)、又は電子受容性材料を含有する層(電極aが負極の場合)
6 電子受容性材料を含有する層(電極bが負極の場合)、又は本発明のフタロシアニンナノロッドを含有する層(電極bが正極の場合)
Claims (25)
- 無置換フタロシアニン及び置換基を有するフタロシアニンを含有するフタロシアニンナノロッドであって、
短径が100nm以下であり、その短径に対する長さの比率(長さ/短径)が10未満であることを特徴とするフタロシアニンナノロッド。 - 置換基を有するフタロシアニンが、一般式(3)又は(4)で表されるものである請求項1に記載のフタロシアニンナノロッド。
Y1からY4が結合基として存在しない場合には、R1~R4は、-SO3H、-CO2H、置換基を有してもよいアルキル基、置換基を有してもよい(オリゴ)アリール基、置換基を有してもよい(オリゴ)へテロアリール基、置換基を有してもよいフタルイミド基又は置換基を有してもよいフラーレン類であり、
Y1からY4が、-(CH2)n-(nは1~10の整数を表す)、-CH=CH-、-C≡C-、-O-、-NH-、-S-、-S(O)-、又は-S(O)2-で表される結合基である場合には、R1~R4は、置換基を有してもよいアルキル基、置換基を有してもよい(オリゴ)アリール基、置換基を有してもよい(オリゴ)へテロアリール基、置換基を有してもよいフタルイミド基又は置換基を有してもよいフラーレン類であり、a、b、c及びdは各々独立に0~4の整数を表すが、そのうち少なくとも一つは0ではない。) - 置換基を有するフタロシアニンが、一般式(5)又は(6)で表されるものである請求項1に記載のフタロシアニンナノロッド。
- 請求項1~4の何れかに記載のフタロシアニンナノロッドと有機溶媒とを必須成分とするインキ組成物。
- フタロシアニンナノロッドの含有率が0.05~20質量%の範囲である請求項5に記載のインキ組成物。
- 前記有機溶媒が、アミド系有機溶媒、芳香族系有機溶媒又はハロゲン系有機溶媒である請求項5に記載のインキ組成物。
- 前記アミド系有機溶媒が、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド又はN,N-ジメチルアセトアミドである請求項7に記載のインキ組成物。
- 前記芳香族系有機溶媒が、トルエン、キシレン、エチルベンゼン、クロロベンゼン又はジクロロベンゼンである請求項7に記載のインキ組成物。
- 前記ハロゲン系有機溶媒が、クロロホルム、塩化メチレン又はジクロロエタンである請求項7に記載のインキ組成物。
- 更に造膜性材料を含有してなる請求項5~10の何れかに記載のインキ組成物。
- 造膜性材料がポリメチルメタクリレート、ポリチオフェン、ポリフェニレンビニレン、ポリスチレン、ポリカーボネート又はポリビニルカルバゾールである請求項11に記載のインキ組成物。
- 請求項1~4の何れかに記載のフタロシアニンナノロッドをチャネル部に含有するトランジスタ。
- 請求項13に記載のトランジスタの製造方法において、
請求項5~12の何れかに記載のインキ組成物を製膜することによりチャネル部を作製することを特徴とするトランジスタの製造方法。 - 請求項1~4の何れかに記載のフタロシアニンナノロッドを含有する光電変換素子用材料。
- 請求項15に記載の光電変換素子用材料が、更に電子受容性材料を含む光電変換素子用材料。
- 前記電子受容性材料がフラーレン類、電子受容性ポリマー又はペリレン類である請求項16に記載の光電変換素子用材料。
- 少なくとも正極と負極を有する光電変換素子であって、
正極と負極の間に請求項1~4の何れかに記載のフタロシアニンナノロッドを含む膜を有することを特徴とする光電変換素子。 - 請求項18に記載の光電変換素子の製造方法において、
正極と負極の間に請求項15~17の何れかに記載の光電変換素子用材料を製膜する工程を有することを特徴とする光電変換素子の製造方法。 - 請求項1~4に記載のフタロシアニンナノロッドの製造方法において、
(1)無置換フタロシアニンと置換基を有するフタロシアニンとを酸に溶解させた後に、貧溶媒に析出させて複合体を得る工程、
(2)前記(1)工程で得られる複合体を、溶媒中にて、ナノワイヤ化する工程、
(3)前記(2)工程で得られるナノワイヤをナノロッド化する工程、
を有することを特徴とするフタロシアニンナノロッドの製造方法。 - 請求項20に記載のフタロシアニンナノロッドの製造方法において、
(2)工程で得られるナノワイヤが、短径が100nm以下であって、その短径に対する長さの比率(長さ/短径)が10以上であるフタロシアニンナノロッドの製造方法。 - 請求項20に記載のフタロシアニンナノロッドの製造方法において、
前記複合体を、溶媒中にて、ナノワイヤ化する工程が、前記複合体を、溶媒中に分散させた後、ナノワイヤ化する工程であるフタロシアニンナノロッドの製造方法。 - 請求項20に記載のフタロシアニンナノロッドの製造方法において、
前記溶媒が、アミド系有機溶媒又は芳香族系有機溶媒であるフタロシアニンナノロッドの製造方法。 - 前記アミド系有機溶媒が、N-メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド又はN,N-ジメチルアセトアミドである請求項23に記載のフタロシアニンナノロッドの製造方法。
- 前記芳香族系有機溶媒が、トルエン、キシレン、エチルベンゼン、クロロベンゼン又はジクロロベンゼンである請求項23に記載のフタロシアニンナノロッドの製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018078242A (ja) * | 2016-11-11 | 2018-05-17 | キヤノン株式会社 | 光電変換素子、それを有する撮像素子及び撮像装置 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9318719B2 (en) * | 2012-06-07 | 2016-04-19 | Sumitomo Chemical Company, Limited | Method of producing organic photoelectric conversion device |
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CA2999744A1 (en) * | 2015-10-01 | 2017-04-06 | Phillips 66 Company | Formation of films for organic photovoltaics |
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US11205753B2 (en) * | 2017-04-25 | 2021-12-21 | The Hong Kong University Of Science And Technology | Use of sequential processing for highly efficient organic solar cells based on conjugated polymers with temperature dependent aggregation |
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CN113773493B (zh) * | 2021-09-23 | 2022-05-17 | 北京科技大学 | 一种酞菁基二维有机框架材料超薄纳米带的制备方法 |
CN114890412A (zh) * | 2022-02-16 | 2022-08-12 | 陕西化工研究院有限公司 | 制备金铂-聚苯胺-还原氧化石墨烯纳米复合物方法 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2761868A (en) | 1953-05-13 | 1956-09-04 | American Cyanamid Co | Sulfonated and unsulfonated imidomethyl, carboxyamidomethyl and aminomethyl phthalocyanines |
JP2005145896A (ja) | 2003-11-17 | 2005-06-09 | Dainippon Ink & Chem Inc | 金属フタロシアニンの製造方法 |
JP2006143680A (ja) | 2004-11-22 | 2006-06-08 | Hiroshima Univ | 新規化合物及びその製造方法並びにその利用 |
JP2006245073A (ja) | 2005-02-28 | 2006-09-14 | Dainippon Printing Co Ltd | 有機薄膜太陽電池 |
JP2007039561A (ja) | 2005-08-03 | 2007-02-15 | Fujifilm Holdings Corp | フタロシアニン類の製造方法 |
JP2007519636A (ja) | 2004-01-08 | 2007-07-19 | ビーエーエスエフ アクチェンゲゼルシャフト | フタロシアニンの製造方法 |
JP2007526881A (ja) | 2003-07-02 | 2007-09-20 | ランクセス・ドイチュランド・ゲーエムベーハー | アルコキシ置換フタロシアニンの製造方法 |
JP2008016834A (ja) | 2006-06-09 | 2008-01-24 | Mitsubishi Chemicals Corp | 有機光電変換素子の製造方法及び有機光電変換素子 |
JP2009135237A (ja) | 2007-11-29 | 2009-06-18 | Nagoya Institute Of Technology | 溶解性フラーレン誘導体 |
JP2009252768A (ja) | 2008-04-01 | 2009-10-29 | Fuji Electric Holdings Co Ltd | 有機太陽電池、およびその製造方法 |
WO2010122921A1 (ja) | 2009-04-23 | 2010-10-28 | Dic株式会社 | フタロシアニンナノワイヤー、それを含有するインキ組成物及び電子素子、並びにフタロシアニンナノワイヤーの製造方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1068029C (zh) * | 1995-11-01 | 2001-07-04 | 中国科学院化学研究所 | 纳米级酞菁类有机光导材料及其制备方法和用途 |
JP2003071799A (ja) * | 2001-09-04 | 2003-03-12 | Mitsubishi Chemicals Corp | ナノワイヤ及びその製造方法 |
US7341944B2 (en) * | 2005-09-15 | 2008-03-11 | Honda Motor Co., Ltd | Methods for synthesis of metal nanowires |
US8809523B2 (en) * | 2008-03-10 | 2014-08-19 | Xerox Corporation | Method of making nanosized particles of phthalocyanine pigments |
JP5444634B2 (ja) * | 2008-05-23 | 2014-03-19 | Dic株式会社 | 金属フタロシアニンナノワイヤー及びその製造方法 |
-
2011
- 2011-05-19 KR KR20127015517A patent/KR101364221B1/ko not_active IP Right Cessation
- 2011-05-19 WO PCT/JP2011/061531 patent/WO2012157110A1/ja active Application Filing
- 2011-05-19 EP EP11865506.7A patent/EP2711400B1/en not_active Not-in-force
- 2011-05-19 JP JP2011537755A patent/JP4998645B1/ja not_active Expired - Fee Related
- 2011-05-19 US US13/979,999 patent/US8895850B2/en not_active Expired - Fee Related
- 2011-05-19 CN CN201180067485.0A patent/CN103429668B/zh not_active Expired - Fee Related
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2761868A (en) | 1953-05-13 | 1956-09-04 | American Cyanamid Co | Sulfonated and unsulfonated imidomethyl, carboxyamidomethyl and aminomethyl phthalocyanines |
JP2007526881A (ja) | 2003-07-02 | 2007-09-20 | ランクセス・ドイチュランド・ゲーエムベーハー | アルコキシ置換フタロシアニンの製造方法 |
JP2005145896A (ja) | 2003-11-17 | 2005-06-09 | Dainippon Ink & Chem Inc | 金属フタロシアニンの製造方法 |
JP2007519636A (ja) | 2004-01-08 | 2007-07-19 | ビーエーエスエフ アクチェンゲゼルシャフト | フタロシアニンの製造方法 |
JP2006143680A (ja) | 2004-11-22 | 2006-06-08 | Hiroshima Univ | 新規化合物及びその製造方法並びにその利用 |
JP2006245073A (ja) | 2005-02-28 | 2006-09-14 | Dainippon Printing Co Ltd | 有機薄膜太陽電池 |
JP2007039561A (ja) | 2005-08-03 | 2007-02-15 | Fujifilm Holdings Corp | フタロシアニン類の製造方法 |
JP2008016834A (ja) | 2006-06-09 | 2008-01-24 | Mitsubishi Chemicals Corp | 有機光電変換素子の製造方法及び有機光電変換素子 |
JP2009135237A (ja) | 2007-11-29 | 2009-06-18 | Nagoya Institute Of Technology | 溶解性フラーレン誘導体 |
JP2009252768A (ja) | 2008-04-01 | 2009-10-29 | Fuji Electric Holdings Co Ltd | 有機太陽電池、およびその製造方法 |
WO2010122921A1 (ja) | 2009-04-23 | 2010-10-28 | Dic株式会社 | フタロシアニンナノワイヤー、それを含有するインキ組成物及び電子素子、並びにフタロシアニンナノワイヤーの製造方法 |
Non-Patent Citations (6)
Title |
---|
CHEMICAL COMMUNICATIONS, 2003, pages 2062 |
JOURNAL OF MATERIALS CHEMISTRY, vol. 18, 2008, pages 1984 - 1990 |
KHARISOV I. BORIS ET AL.: "Nonsubstituted Phthalocyanine Nanostructures Obtained Using Activated Metals and Unstable Complexes at Ambient Temperature", JOURNAL OF COMPOSITE MATERIALS, vol. 44, no. 17, 2010, pages 2145 - 2155, XP008171530 * |
See also references of EP2711400A4 |
SYNTHESIS, 1981, pages 1 |
WANG CHIA-YU ET AL.: "Study of structural and optical properties of Ge doped ZnO films", THIN SOLID FILMS, vol. 518, 2010, pages 6720 - 6728, XP026735942 * |
Cited By (2)
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JP2018078242A (ja) * | 2016-11-11 | 2018-05-17 | キヤノン株式会社 | 光電変換素子、それを有する撮像素子及び撮像装置 |
WO2018088313A1 (ja) * | 2016-11-11 | 2018-05-17 | キヤノン株式会社 | 光電変換素子、それを有する撮像素子及び撮像装置 |
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KR20130014490A (ko) | 2013-02-07 |
CN103429668B (zh) | 2014-11-26 |
CN103429668A (zh) | 2013-12-04 |
US20140158203A1 (en) | 2014-06-12 |
KR101364221B1 (ko) | 2014-02-17 |
EP2711400A4 (en) | 2014-12-17 |
EP2711400B1 (en) | 2016-04-06 |
JP4998645B1 (ja) | 2012-08-15 |
US8895850B2 (en) | 2014-11-25 |
EP2711400A1 (en) | 2014-03-26 |
JPWO2012157110A1 (ja) | 2014-07-31 |
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