US20100180944A1 - Polymers with low band gaps and high charge mobility - Google Patents

Polymers with low band gaps and high charge mobility Download PDF

Info

Publication number
US20100180944A1
US20100180944A1 US12724704 US72470410A US2010180944A1 US 20100180944 A1 US20100180944 A1 US 20100180944A1 US 12724704 US12724704 US 12724704 US 72470410 A US72470410 A US 72470410A US 2010180944 A1 US2010180944 A1 US 2010180944A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
moiety
alkoxy
embodiments
photovoltaic cell
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12724704
Inventor
Russell Gaudiana
Richard Kingsborough
Xiaobo Shi
David Waller
Zhengguo Zhu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Konarka Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0034Organic polymers or oligomers
    • H01L51/0043Copolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0034Organic polymers or oligomers
    • H01L51/0035Organic polymers or oligomers comprising aromatic, heteroaromatic, or arrylic chains, e.g. polyaniline, polyphenylene, polyphenylene vinylene
    • H01L51/0036Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4253Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture comprising bulk hetero-junctions, e.g. interpenetrating networks
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0045Carbon containing materials, e.g. carbon nanotubes, fullerenes
    • H01L51/0046Fullerenes, e.g. C60, C70
    • H01L51/0047Fullerenes, e.g. C60, C70 comprising substituents, e.g. PCBM
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/549Material technologies organic PV cells

Abstract

Polymers with low band gaps and high charge mobility, as well as related systems, methods and components are disclosed.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of U.S. Utility application Ser. No. 11/485,708, filed Jul. 13, 2006, which in turn is a continuation-in-part of U.S. Utility application Ser. No. 11/450,521, filed Jun. 9, 2006, which in turn is a continuation-in-part of U.S. Utility application Ser. No. 11/375,643, filed Mar. 14, 2006, which claims priority to U.S. Provisional Application Ser. No. 60/699,123, filed Jul. 14, 2005. The contents of all parent applications are hereby incorporated by reference.
  • TECHNICAL FIELD
  • This disclosure generally relates to the field of electron donor materials, as well as related photovoltaic cells.
  • BACKGROUND OF THE INVENTION
  • Photovoltaic cells are commonly used to transfer energy in the form of light into energy in the form of electricity. A typical photovoltaic cell includes a photoactive material disposed between two electrodes. Generally, light passes through one or both of the electrodes to interact with the photoactive material. As a result, the ability of one or both of the electrodes to transmit light (e.g., light at one or more wavelengths absorbed by a photoactive material) can limit the overall efficiency of a photovoltaic cell. In many photovoltaic cells, a film of semiconductive material (e.g., indium tin oxide) is used to form the electrode(s) through which light passes because, although the semiconductive material can have a lower electrical conductivity than electrically conductive materials, the semiconductive material can transmit more light than many electrically conductive materials.
  • SUMMARY
  • An aspect of the invention relates to a new combination of monomers that produce polymers, wherein the polymers have properties suitable for use as charge carriers in the active layer of a photovoltaic cell.
  • In one aspect, the invention features a class of co-polymers including at least two co-monomers, at least one of which is a cyclopentadithiophene.
  • In another aspect, this invention features a photovoltaic cell including a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first comonomer repeat unit and a second comonomer repeat unit. The first comonomer repeat unit includes a cyclopentadithiophene moiety. The second comonomer repeat unit includes a silole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, or a tetrahydroisoindole moiety.
  • In another aspect, this invention features a photovoltaic cell including a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first comonomer repeat unit and a second comonomer repeat unit different from the first comonomer repeat unit. The first comonomer repeat unit includes a cyclopentadithiophene moiety.
  • In another aspect, this invention features a polymer that includes a first comonomer repeat unit containing a cyclopentadithiophene moiety, and a second comonomer repeat unit containing a benzothiadiazole moiety, a thiadiazoloquinoxaline moiety, a cyclopentadithiophene oxide moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thiophene oxide moiety, a fluorene moiety, a thiophene moiety, a silole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, or a moiety containing at least three thiophene moieties.
  • In another aspect, this invention features a polymer that includes a first comonomer repeat unit and a second comonomer repeat unit different from the first comonomer repeat unit. The first comonomer repeat unit contains a cyclopentadithiophene moiety substituted with at least one substituent selected from the group consisting of hexyl, ethylhexyl, dimethyloctyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, and C3-C20 heterocycloalkyl.
  • In another aspect, this invention features a device (e.g., a photovoltaic cell) that includes a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first monomer repeat unit, which includes a benzothiadiazole moiety, a thiophene oxide moiety, a cyclopentadithiophene oxide moiety, a thiadiazoloquinoxaline moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, a fluorene moiety, a thiophene moiety, a silole moiety, or a fluorene moiety.
  • In another aspect, this invention features a device (e.g., a photovoltaic cell) that includes a first electrode, a second electrode, and a photoactive material disposed between the first and second electrodes. The photoactive material includes a polymer having a first monomer repeat unit, which includes a cyclopentadithiophene moiety substituted with at least one substituent selected from the group consisting of hexyl, ethylhexyl, dimethyloctyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
  • Embodiments can include one or more of the following features.
  • In some embodiments, the cyclopentadithiophene moiety is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. Examples of C1-C20 alkyl can be hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl.
  • In some embodiments, the cyclopentadithiophene moiety can be substituted at 4-position.
  • In some embodiments, the first monomer or comonomer repeat unit can include a cyclopentadithiophene moiety of formula (I):
  • Figure US20100180944A1-20100722-C00001
  • In formula (I), each of R1, R2, R3, and R4, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R1 and R2, independently, is hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl. In certain embodiments, each of R1 and R2, independently, is hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl. In some embodiments, one of R1 and R2 is hexyl, ethylhexyl, dimethyloctyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl, the other of R1 and R2 is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R1 and R2, independently, is C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). In certain embodiments, each of R1 and R2, independently, is C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo.
  • In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety, a thiadiazoloquinoxaline moiety, a cyclopentadithiophene oxide moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thiophene oxide moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, a fluorene moiety, a thiophene moiety, or a silole moiety, each of which is optionally substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, the second comonomer repeat unit can include a 3,4-benzo-1,2,5-thiadiazole moiety.
  • In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety of formula (II), a thiadiazoloquinoxaline moiety of formula (III), a cyclopentadithiophene dioxide moiety of formula (IV), a cyclopentadithiophene monoxide moiety of formula (V), a benzoisothiazole moiety of formula (VI), a benzothiazole moiety of formula (VII), a thiophene dioxide moiety of formula (VIII), a cyclopentadithiophene dioxide moiety of formula (IX), or a cyclopentadithiophene tetraoxide moiety of formula (X):
  • Figure US20100180944A1-20100722-C00002
    Figure US20100180944A1-20100722-C00003
  • in which each of R5, R6, and R7, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety of formula (II). In certain embodiments, R5 and R6 is H.
  • In some embodiments, the second comonomer repeat unit can include at least three thiophene moieties. In some embodiments, at least one of the thiophene moieties is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In certain embodiments, the second comonomer repeat unit includes five thiophene moieties.
  • In some embodiments, the second comonomer repeat unit can include a thienothiophene moiety of formula (XI), a thienothiophene tetraoxide moiety of formula (XII), a dithienothiophene moiety of formula (XIII), a dithienothiophene dioxide moiety of formula (XIV), a dithienothiophene tetraoxide moiety of formula (XV), a tetrahydroisoindole moiety of formula (XVI), a thienothiophene dioxide moiety of formula (XVII), or a dithienothiophene dioxide moiety of formula (XVIII):
  • Figure US20100180944A1-20100722-C00004
  • in which each of X and Y, independently, is CH2, O, or S; each of R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R, in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; and R7 is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
  • In some embodiments, the polymer can further include a third comonomer repeat unit that contains a thiophene moiety or a fluorene moiety. In some embodiments, the thiophene or fluorene moiety is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, and C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
  • In some embodiments, the first monomer or comonomer repeat unit can include a benzothiadiazole moiety of formula (II), a thiophene dioxide moiety of formula (VIII), a cyclopentadithiophene tetraoxide moiety of formula (X), or a fluorene moiety of formula (XIX):
  • Figure US20100180944A1-20100722-C00005
  • in which each of R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R. R can be C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R5 and R6 can be C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3).
  • In some embodiments, the polymer can include a second monomer repeat unit different from the first monomer repeat unit. The second monomer repeat unit can include a cyclopentadithiophene moiety, a benzothiadiazole moiety, a thiophene oxide moiety, a cyclopentadithiophene oxide moiety, a fluorene moiety, or a thiophene moiety.
  • In some embodiments, the first or second monomer repeat unit can include at least one substituent on a ring selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. The substituent can be hexyl, ethylhexyl, or C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3).
  • In some embodiments, the second monomer repeat unit can include a cyclopentadithiophene moiety of formula (I), a benzothiadiazole moiety of formula (II), a thiophene dioxide moiety of formula (VIII), a cyclopentadithiophene tetraoxide moiety of formula (X), a fluorene moiety of formula (XIX), a thiophene moiety of formula (XX), or a silole moiety of formula (XXI):
  • Figure US20100180944A1-20100722-C00006
  • in which each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R. R can be C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7, and R8, can be C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3).
  • In some embodiments, when the second comonomer contains a silole moiety of formula (XXI), at least one of R5, R6, R7 and R8 can be C1-C20 alkyl optionally substituted with halo, or aryl optionally substituted with C1-C20 alkyl. In certain embodiments, each of R5 and R6, independently can be aryl optionally substituted with C1-C20 alkyl, and each of R7 and R8, independently, can be C1-C20 alkyl optionally substituted with halo. An example of a silole moiety is
  • Figure US20100180944A1-20100722-C00007
  • In some embodiments, the polymer can be an electron donor material or an electron acceptor material.
  • In some embodiments, the polymer can be
  • Figure US20100180944A1-20100722-C00008
  • in which n can be an integer greater than 1.
  • In some embodiments, the photovoltaic cell can be a tandem photovoltaic cell.
  • In some embodiments, the photoactive material can include an electron acceptor material. In some embodiments, the electron acceptor material can be a fullerene (e.g., C61-phenyl-butyric acid methyl ester, PCBM).
  • In some embodiments, the polymer and the electron acceptor material each can have a LUMO energy level. The LUMO energy level of the polymer can be at least about 0.2 eV (e.g., at least about 0.3 eV) less negative than the LUMO energy level of the electron acceptor material.
  • In some embodiments, the device can be an organic semiconductive device. In certain embodiments, the device can be a member selected from the group consisting of field effect transistors, photodetectors, photovoltaic detectors, imaging devices, light emitting diodes, lasing devices, conversion layers, amplifiers and emitters, storage elements, and electrochromic devices.
  • Embodiments can provide one or more of the following advantages.
  • In some embodiments, using a polymer containing a cyclopentadithiophene moiety can be advantageous because the cyclopentadithiophene moiety can contribute to a shift in the maximum absorption wavelength toward the red or near IR region of the electromagnetic spectrum. When such a polymer is incorporated into a photovoltaic cell, the current and efficiency of the cell can increase.
  • In some embodiments, substituted fullerenes or polymers containing substituted monomer repeat units (e.g., substituted with long-chain alkoxy groups such as oligomeric ethylene oxides or fluorinated alkoxy groups) can have improved solubility in organic solvents and can form an photoactive layer with improved morphology.
  • In some embodiments, a polymer containing a silole moiety can absorb light at a relatively long wavelength and have improved solubility in organic solvents. In some embodiments, a polymer containing a silole moiety can be used to prepare an electron donor material with improved semiconductive properties.
  • In some embodiments, a polymer fullerene cell containing a polymer described above can have a band gap that is relatively ideal for its intended purposes.
  • In some embodiments, a photovoltaic cell having high cell voltage can be created, whereby the HOMO level of the polymer is at least about 0.2 electron volts more negative relative to the LUMO or conduction band of an electron acceptor material.
  • In some embodiments, a photovoltaic cell containing a polymer described above can have relatively fast and efficient transfer of an electron to an electron acceptor material, whereby the LUMO of the donor is at least about 0.2 electron volt (e.g., at least about 0.3 electron volt) less negative than the conduction band of the electron acceptor material.
  • In some embodiments, a photovoltaic cell containing a polymer described above can have relatively fast charge separation, whereby the charge mobility of the positive charge, or hole, is relatively high and falls within the range of 10−4 to 10−1 cm2/Vs.
  • In some embodiments, the polymer is soluble in an organic solvent and/or film forming.
  • In some embodiments, the polymer is optically non-scattering.
  • In some embodiments, the polymer can be used in organic field effect transistors and OLEDs.
  • Other features and advantages of the invention will be apparent from the description, drawings, and claims.
  • DESCRIPTION OF DRAWING
  • FIG. 1 is a cross-sectional view of an embodiment of a photovoltaic cell.
  • FIG. 2 is a schematic of a system containing one electrode between two photoactive layers.
  • Like reference symbols in the various drawings indicate like elements.
  • DETAILED DESCRIPTION
  • FIG. 1 shows a cross-sectional view of a photovoltaic cell 100 that includes a substrate 110, a cathode 120, a hole carrier layer 130, an active layer 140 (containing an electron acceptor material and an electron donor material), a hole blocking layer 150, an anode 160, and a substrate 170.
  • In general, during use, light impinges on the surface of substrate 110, and passes through substrate 110, cathode 120, and hole carrier layer 130. The light then interacts with active layer 140, causing electrons to be transferred from the electron donor material (e.g., a polymer described above) to the electron acceptor material (e.g., PCBM). The electron acceptor material then transmits the electrons through hole blocking layer 150 to anode 160, and the electron donor material transfers holes through hole carrier layer 130 to cathode 120. Anode 160 and cathode 120 are in electrical connection via an external load so that electrons pass from anode 160, through the load, and to cathode 120.
  • Electron acceptor materials of active layer 140 can include fullerenes. In some embodiments, active layer 140 can include one or more unsubstituted fullerenes and/or one or more substituted fullerenes. Examples of unsubstituted fullerenes include C60, C70, C76, C78, C82, C84, and C92. Examples of substituted fullerenes include PCBM or fullerenes substituted with C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). Without wishing to be bound by theory, it is believed that fullerenes substituted with long-chain alkoxy groups (e.g., oligomeric ethylene oxides) or fluorinated alkoxy groups have improved solubility in organic solvents and can form an photoactive layer with improved morphology.
  • In some embodiments, the electron acceptor materials can include polymers (e.g., homopolymers or copolymers). A polymers mentioned herein include at least two identical or different monomer repeat units (e.g., at least 5 monomer repeat units, at least 10 monomer repeat units, at least 50 monomer repeat units, at least 100 monomer repeat units, or at least 500 monomer repeat units). A copolymer mentioned herein refers to a polymer that includes at least two co-monomers of differing structures. In some embodiments, the polymers used as an electron acceptor material can include one or more monomer repeat units listed in Tables 1 and 2 below. Specifically, Table 1 lists examples of the monomers that can be used as an electron donating monomer and can serve as a conjugative link. Table 2 lists examples of the monomers that can be used as an electron withdrawing monomer. Note that depending on the substituents, monomers listed in Table 1 can also be used as electron withdrawing monomers and monomers listed in Table 2 can also be used as electron donating monomers. Preferably, the polymers used as an electron acceptor material include a high molar percentage (e.g., at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%) of an electron withdrawing monomer.
  • Electron donor materials of active layer 140 can include polymers (e.g., homopolymers or copolymers). In some embodiments, the polymers used as an electron donor material can include one or more monomer repeat units listed Tables 1 and 2. Preferably, the polymers used as an electron donor material include a high molar percentage (e.g., at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%) of an electron donating monomer. In some embodiments, the polymers include a monomer containing C1-C20 alkoxy on a ring, which is optionally further substituted with C1-C20 alkoxy or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). Without wishing to be bound by theory, it is believed that polymers containing monomers substituted with long-chain alkoxy groups (e.g., oligomeric ethylene oxides) or fluorinated alkoxy groups have improved solubility in organic solvents and can form an photoactive layer with improved morphology.
  • TABLE 1
    Figure US20100180944A1-20100722-C00009
    Figure US20100180944A1-20100722-C00010
    Figure US20100180944A1-20100722-C00011
  • TABLE 2
    Figure US20100180944A1-20100722-C00012
    Figure US20100180944A1-20100722-C00013
    Figure US20100180944A1-20100722-C00014
    Figure US20100180944A1-20100722-C00015
    Figure US20100180944A1-20100722-C00016
    Figure US20100180944A1-20100722-C00017
    Figure US20100180944A1-20100722-C00018
    Figure US20100180944A1-20100722-C00019
    Figure US20100180944A1-20100722-C00020
    Figure US20100180944A1-20100722-C00021
    Figure US20100180944A1-20100722-C00022
    Figure US20100180944A1-20100722-C00023
    Figure US20100180944A1-20100722-C00024
    Figure US20100180944A1-20100722-C00025
    Figure US20100180944A1-20100722-C00026
    Figure US20100180944A1-20100722-C00027
    Figure US20100180944A1-20100722-C00028
    Figure US20100180944A1-20100722-C00029
  • Referring to formulas listed in Tables 1 and 2 above, each of X and Y, independently, can be CH2, O, or S; each of R1, R2, R3, R4, R5, R6, R7, and R8, independently, can be H, C1-C20 alkyl, C1-C20 alkoxy, aryl (e.g., phenyl or substituted phenyl), heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, or SO2R; and R7 can be H, C1-C20 alkyl, C1-C20 alkoxy, aryl (e.g., phenyl or substituted phenyl), heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; in which R is C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. An alkyl can be saturated or unsaturated and branch or straight chained. A C1-C20 alkyl contains 1 to 20 carbon atoms (e.g., one, two, three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of alkyl moieties include —CH3, —CH2—, —CH2═CH2—, —CH2—CH═CH2, and branched —C3H7. An alkoxy can be branch or straight chained and saturated or unsaturated. An C1-C20 alkoxy contains an oxygen radical and 1 to 20 carbon atoms (e.g., one, two, three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of alkoxy moieties include —OCH3 and —OCH═C2H4. A cycloalkyl can be either saturated or unsaturated. A C3-C20 cycloalkyl contains 3 to 20 carbon atoms (e.g., three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of cycloalkyl moieties include cyclohexyl and cyclohexen-3-yl. A heterocycloalkyl can also be either saturated or unsaturated. A C3-C20 heterocycloalkyl contains at least one ring heteroatom (e.g., O, N, and S) and 3 to 20 carbon atoms (e.g., three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of heterocycloalkyl moieties include 4-tetrahydropyranyl and 4-pyranyl. An aryl can contain one or more aromatic rings. Examples of aryl moieties include phenyl, phenylene, naphthyl, naphthylene, pyrenyl, anthryl, and phenanthryl. A heteroaryl can contain one or more aromatic rings, at least one of which contains at least one ring heteroatom (e.g., O, N, and S). Examples of heteroaryl moieties include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.
  • Alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl mentioned herein include both substituted and unsubstituted moieties, unless specified otherwise. Examples of substituents on cycloalkyl, heterocycloalkyl, aryl, and heteroaryl include C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, amino, C1-C10 alkylamino, C1-C20 dialkylamino, arylamino, diarylamino, hydroxyl, halogen, thio, C1-C10 alkylthio, arylthio, C1-C10 alkylsulfonyl, arylsulfonyl, cyano, nitro, acyl, acyloxy, carboxyl, and carboxylic ester. Examples of substituents on alkyl include all of the above-recited substituents except C1-C20 alkyl. Cycloalkyl, heterocycloalkyl, aryl, and heteroaryl also include fused groups.
  • The copolymers described above can be prepared by methods known in the art. For example, a copolymer can be prepared by a cross-coupling reaction between one or more comonomers containing two alkylstannyl groups and one or more comonomers containing two halo groups in the presence of a transition metal catalyst. As another example, a copolymer can be prepared by a cross-coupling reaction between one or more comonomers containing two borate groups and one or more comonomers containing two halo groups in the presence of a transition metal catalyst. The comonomers can be prepared by the methods described herein or by the methods know in the art, such as those described in Coppo et al., Macromolecules 2003, 36, 2705-2711 and Kurt et al., J. Heterocycl. Chem. 1970, 6, 629, the contents of which are hereby incorporated by reference.
  • Table 3 below lists three exemplary polymers (i.e., polymers 1-3) described in the Summary section above. These polymers can have unique properties, which make them particularly suitable as charge carriers in the active layer of a photovoltaic cell. Polymers 1 and 2 can be obtained by the methods described in Examples 4 and 7 below.
  • TABLE 3
    Figure US20100180944A1-20100722-C00030
    Figure US20100180944A1-20100722-C00031
    Figure US20100180944A1-20100722-C00032
  • Generally, one co-monomer in the polymers described in the Summary section above is a cyclopentadithiophene. An advantage of a co-polymer containing a cyclopentadithiophene moiety is that its absorption wavelength can shift toward the red and near IR portion (e.g., 650-800 nm) of the electromagnetic spectrum, which is not accessible by most other polymers. When such a co-polymer is incorporated into a photovoltaic cell, it enables the cell to absorb the light in this region of the spectrum, thereby increasing the current and efficiency of the cell.
  • The polymers described above can be useful in solar power technology because the band gap is close to ideal for a photovoltaic cell (e.g., a polymer-fullerene cell). The HOMO level of the polymers can be positioned correctly relative to the LUMO of an electron acceptor (e.g., PCBM) in a photovoltaic cell (e.g., a polymer-fullerene cell), allowing for high cell voltage. The LUMO of the polymers can be positioned correctly relative to the conduction band of the electron acceptor in a photovoltaic cell, thereby creating efficient transfer of an electron to the electron acceptor. For example, using a polymer having a band gap of about 1.4-1.6 eV can significantly enhance cell voltage. Cell performance, specifically efficiency, cam benefit from both an increase in photocurrent and an increase in cell voltage, and can approach and even exceed 15% efficiency. The positive charge mobility of the polymers can be relatively high and approximately in the range of 10−4 to 10−1 cm−2/Vs. In general, the relatively high positive charge mobility allows for relatively fast charge separation. The polymers can also be soluble in an organic solvent and/or film forming. Further, the polymers can be optically non-scattering.
  • Components in photovoltaic cell other than the electro acceptor materials and the electron donor materials are known in the art, such as those described in U.S. patent application Ser. No. 10/723,554, the contents of which are incorporated herein by references.
  • In some embodiments, the polymer described above can be used as an electron donor material or an electro acceptor material in a system in which two photovoltaic cells share a common electrode. Such a system is also known as tandem photovoltaic cell. Examples of tandem photovoltaic cells are discussed in U.S. patent application Ser. No. 10/558,878, filed Nov. 29, 2005, the contents of which are hereby incorporated by reference.
  • As an example, FIG. 2 is a schematic of a tandem photovoltaic cell 200 having a substrate 210, three electrodes 220, 240, and 260, and two photoactive layers 230 and 250. Electrode 240 is shared between photoactive layers 230 and 250, and is electrically connected with electrodes 220 and 260. In general, electrodes 220, 240, and 260 can be formed of an electrically conductive material, such as those described in U.S. patent application Ser. No. 10/723,554. In some embodiments, one or more (i.e., one, two, or three) electrodes 220, 240, and 260 is a mesh electrode. In some embodiments, one or more electrodes 220, 240, and 260 is formed of a semiconductive material. Examples of semiconductive materials include titanium oxides, indium tin oxides, fluorinated tin oxides, tin oxides, and zinc oxides. In certain embodiments, one or more (i.e., one, two, or three) electrodes 220, 240, and 260 are formed of titanium dioxide. Titanium dioxide used to prepare an electrode can be in any suitable forms. For example, titanium dioxide can be in the form of interconnected nanoparticles. Examples of interconnected titanium dioxide nanoparticles are described, for example, in U.S. Pat. No. 7,022,910, the contents of which are incorporated herein by reference. In some embodiments, at least one (e.g., one, two, or three) of electrodes 220, 240, and 260 is a transparent electrode. As referred to herein, a transparent electrode is formed of a material which, at the thickness used in a photovoltaic cell, transmits at least about 60% (e.g., at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%) of incident light at a wavelength or a range of wavelengths used during operation of the photovoltaic cell. In certain embodiments, both electrodes 220 and 260 are transparent electrodes.
  • Each of photoactive layers 230 and 250 can contain at least one semiconductive material. In some embodiments, the semiconductive material in photoactive layer 230 has the same band gap as the semiconductive material in photoactive layer 250. In certain embodiments, the semiconductive material in photoactive layer 230 has a band gap different from that of the semiconductive material in photoactive layer 250. Without wishing to be bound by theory, it is believed that incident light not absorbed by one photoactive layer can be absorbed by the other photoactive layer, thereby maximizing the absorption of the incident light.
  • In some embodiments, at least one of photoactive layers 230 and 250 can contain an electron acceptor material (e.g., PCBM or a polymer described above) and an electron donor material (e.g., a polymer described above). In general, suitable electron acceptor materials and electron donor materials can be those described above. In certain embodiments, each of photoactive layers 230 and 250 contains an electron acceptor material and an electron donor material.
  • Substrate 210 can be formed of one or more suitable polymers, such as those described in U.S. patent application Ser. No. 10/723,554. In some embodiments, an additional substrate (not shown in FIG. 2) can be disposed on electrode 260.
  • Photovoltaic cell 200 can further contain a hole carrier layer (not shown in FIG. 2) and a hole blocking layer (not shown in FIG. 2), such as those described in U.S. patent application Ser. No. 10/723,554.
  • While photovoltaic cells have been described above, in some embodiments, the polymers described herein can be used in other devices and systems. For example, the polymers can be used in suitable organic semiconductive devices, such as field effect transistors, photodetectors (e.g., IR detectors), photovoltaic detectors, imaging devices (e.g., RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (e.g., organic LEDs or IR or near IR LEDs), lasing devices, conversion layers (e.g., layers that convert visible emission into IR emission), amplifiers and emitters for telecommunication (e.g., dopants for fibers), storage elements (e.g., holographic storage elements), and electrochromic devices (e.g., electrochromic displays).
  • The following examples are illustrative and not intended to be limiting.
  • Example 1 Synthesis of 4,4-Dihexyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene
  • Figure US20100180944A1-20100722-C00033
  • 4H-Cyclopenta[2,1-b;3,4-b′]dithiophene was synthesized according to literature procedure illustrated in Coppo et al., Macromolecules 2003, 36, 2705-2711. All other starting materials were purchased from Sigma-Aldrich and used as received.
  • 4H-Cyclopenta[2,1-b;3,4-b′]dithiophene (1.5 g, 0.00843 mol) was dissolved in DMSO (50 mL). The solution was purged with nitrogen, and grounded KOH (1.89 g, 0.0337 mol) and sodium iodide (50 mg) were added, followed by hexyl bromide (3.02 g, 0.0169 mol). The reaction was stirred for 17 h under nitrogen at room temperature. Water was added and the reaction was extracted with t-butyl-methyl ether. The organic layer was separated and dried over magnesium sulfate. Solvent was removed under vacuum and the residue was purified by chromatography using hexanes as eluent. Fractions containing pure 4,4-dixeyl-4H-cyclopenta[2,1-b;3,4-b]dithiophene product were combined and the solvents evaporated. The product was obtained as a colorless oil. Yield: 2.36 g (81%).
  • Example 2 The Synthesis of 4,4-Dihexyl-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene
  • Figure US20100180944A1-20100722-C00034
  • Starting material 4,4-dihexyl-4H-cyclopenta[2,1-b;3,4-b]dithiophene (1.5 g, 0.00433 mol) was dissolved in dry THF (30 mL). The solution was cooled to −78° C. and butyl lithium (6.1 mL, 0.0130 mol) was added drop wise. The reaction was stirred at this temperature for 2 h and warmed to room temperature, stirred for 3 h. Again reaction was cooled to −78° C. and trimethyltin chloride (1 M in hexanes, 16.0 mL, 16.0 mmol) was added dropwise. The reaction was allowed to warm to rt and stirred for 17 h. Water was added and the reaction was extracted with toluene. The organic layer was washed with water and dried over sodium sulfate. Solvent was removed under vacuum and the residue was dissolved in toluene, and quickly passed through a plug of silica gel pretreated with triethyl amine. Solvent was removed and the residue dried under vacuum to afford 2.65 g of the bis(trimethyltin) monomer. 1H NMR (CDCl3, 200 MHz): 6.97 (m, 2H), 1.84 (m, 4H), 1.20 (m, 16H), 0.88 (m, 6H), 0.42 (m, 18H).
  • Example 3 The Synthesis of bis-(tributylstannyl)-4,4-dihexyl-cyclopenta[2,1-b:3,4-b′]dithiophene
  • Figure US20100180944A1-20100722-C00035
  • 4,4-Dihexyl-4H-cyclopenta[2,1-b;3,4-b]dithiophene (2.2 g, 0.0065 mol) was dissolved in dry THF (20 mL). The solution was cooled to −78° C. BuLi (7.62, 2.5 M in hexanes, 0.019 mol) was then added to the solution. The reaction mixture was allowed to warm to room temperature and was stirred for 5 hours. The mixture was then cooled again to −78° C. and Bu3SnCl (7.44 g, 0.0229 mol) was added. The reaction mixture was allowed to warm to room temperature and was stirred for another 48 hours. Water was then added and the mixture was extracted with dihicholomethane. Organic layer was collected, dried over anhydrous Na2SO4, and concentrated. The residue thus obtained was dissolved in hexane and quickly passed through a plug of silica gel pretreated with triethylamine. The solvent was removed and the residue was dried under vacuum to afford bis-(tributylstannyl)-4,4-dihexyl-cyclopenta[2,1-b:3,4-b′]dithiophene (5.7 g).
  • Example 4 Polymerization of bis-(tributylstannyl)-4,4-dihexyl-cyclopenta[2,1-b:3,4-b′]dithiophene and 4,7-dibromo-2,1,3-benzothiadiazole
  • Figure US20100180944A1-20100722-C00036
  • Bis-(tributylstannyl)-4,4-dihexyl-cyclopenta[2,1-b:3,4-b′]dithiophene (0.775 g, 0.000816 mol) and 4,7-dibromo-2,1,3-benzothiadiazole (0.24 g, 0.000816 mol) were first dissolved in toluene. After the reaction was purged with nitrogen, palladium tretakistriphenylphosphine (15 mg, 0.0065 mmol) was added. The reaction mixture was heated at 100° C. for 24 hour. After the solvent was removed, the residue was washed with acetone and extracted in a Soxlet extractor for 8 hours to afford the product as an insoluble blue solid.
  • Example 5 Synthesis of 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene
  • Figure US20100180944A1-20100722-C00037
  • 4H-Cyclopenta[2,1-b;3,4-b]dithiophene (1.5 g, 0.00843 mol) was dissolved in DMSO (50 mL). After the solution was purged with nitrogen, and grounded KOH (1.89 g, 0.0337 mol), sodium iodide (50 mg), and 2-ethylhexyl bromide (3.25 g, 0.0169 mol) were sequentially added. The reaction mixture was stirred overnight under nitrogen (c.a. 16 hours). Water was added and the reaction was extracted with t-butylmethyl ether. The organic layer was collected, dried over magnesium sulfate, and concentrated. The residue was purified by chromatography using hexanes as eluent. Fractions containing pure 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene product were combined and concentrated. The product was obtained as a colorless oil after drying under vacuum. Yield: 2.68 g (79%). 1H NMR (CDCl3, 250 MHz): 7.13 (m, 2H), 6.94 (m, 2H), 1.88 (m, 4H), 0.94 (m, 16H), 0.78 (t, 6.4 Hz, 6H), 0.61 (t, 7.3 Hz, 6H).
  • Example 6 Synthesis of 4,4-Bis-(2-ethyl-hexyl)-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene
  • Figure US20100180944A1-20100722-C00038
  • Starting material 4,4-Bis-(2-ethyl-hexyl)-4H-cyclopenta[2,1-b;3,4-b]dithiophene (1.5 g, 0.00372 mol) was dissolved in dry THF (20 mL). After the solution was cooled to −78° C., butyl lithium (5.21 mL, 0.0130 mol) was added dropwise. The reaction mixture was stirred at this temperature for 1 hour. It was then warmed to room temperature and stirred for another 3 hours. The mixture was again cooled to −78° C. and trimethyltin chloride (1 M in hexane, 15.6 mL, 15.6 mmol) was added dropwise. The reaction mixture was allowed to warm to room temperature and stirred overnight (c.a. 16 hours).
  • Water was added and the reaction was extracted with toluene. The organic layer was washed with water, dried over sodium sulfate, and concentrated. The residue was dissolved in toluene, and quickly passed through a small plug of silica gel pretreated with triethylamine. The solvent was removed and the residue was dried under vacuum. 1.25 g of the product was obtained. 1H NMR (CDCl3, 250 MHz): 6.96 (m, 2H), 1.85 (m, 4H), 1.29 (m, 2H), 0.92 (m, 16H), 0.78 (t, 6.8 Hz, 6H), 0.61 (t, 7.3 Hz, 6H), 0.38 (m, 18H).
  • Example 7 Polymerization of Bis-(trimethylstannyl)-4,4-Di(2-ethylhexyl)-cyclopenta[2,1-b:3,4-b′]dithiophen and 4,7-dibromo-2,1,3-benzothiadiazole
  • Figure US20100180944A1-20100722-C00039
  • Bis-(trimethylstannyl)-4,4-di(2-ethylhexyl)-cyclopenta[2,1-b:3,4-b]dithiophene (0.686 g, 0.000943 mol) and 4,7-dibromo-2,1,3-benzothiadiazole (0.269 g, 0.000915 mol) were dissolved in toluene (20 mL). After the reaction was purged with nitrogen, tris(dibenzylideneacetone)dipalladium(0) (25.1 mg, 0.0275 mmol) and triphenylphosphine (57.6 mg, 0.220 mmol) were added. The reaction was further purged with nitrogen for 10 minutes and heated to 120° C. under nitrogen for 24 hours. The solvent was removed under vacuum and the residue was dissolved in chloroform. After the mixture was poured into methanol (500 mL), the blue precipitate thus obtained was collected by filtration, washed with methanol, and dried. The precipitate was dissolved in chloroform (30 mL) under heating, and filtered through a 0.45 μm membrane. The solution was loaded on to recycling HPLC (2H+2.5H column on a Dychrome recycling HPLC, 5 cycles for each injection), in 3 mL portions for purification. Higher-molecular-weight fractions were combined to give 120 mg pure polymer (Mn=35 kDa).
  • Example 8 Copolymerization of 4,4-Dihexyl-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene, 4,4-Bis-(2-ethyl-hexyl)-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b′]dithiophene, and 4,7-Dibromo-benzo[1,2,5]thiadiazole
  • Figure US20100180944A1-20100722-C00040
  • 4,4-Dihexyl-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b]dithiophene (0.0863 g, 0.000128 mol), 4,4-bis-(2-ethyl-hexyl)-2,6-bis-trimethylstannanyl-4H-cyclopenta[2,1-b;3,4-b]dithiophene (0.187 g, 0.000257 mol), and 4,7-Dibromo-benzo[1,2,5]thiadiazole (0.111 g, 0.000378 g) were dissolved in toluene (15 mL) and the solution was degassed and purged with N2. Tris(dibenzylideneacetone)dipalladium(0) (6.78 mg, 0.0074 mmol) and triphenylphosphine (15.5 mg, 0.0 593 mmol) were then added. The reaction was purged again with nitrogen for 30 minutes and heated at 120° C. under nitrogen. The solvent was then removed under vacuum. The residue was dissolved in chloroform and the solution was added into methanol. The precipitates were collected and extracted with hexane for 24 hours and then extracted with chloroform for 8 hours. The resultant blue solution was concentrated and added to methanol. The precipitates were collected to afford a first fraction of the polymer (70 mg). The remaining materials on the thimble was further extracted with chloroform for 20 hours. 20 mg additional polymer was collected.
  • Example 9 Preparation of 4H-4,4-bis(2′-ethylhexyl)cyclopenta[2,1-b:3,4-b′]thiophene-2,6-bis(pinacolborate) ester
  • Figure US20100180944A1-20100722-C00041
  • 100 mL oven dried Schlenk flask was charged with 1.097 g (2.72 mmol) of 4H-4,4-bis(2′-ethylhexyl)cyclopenta[2,1-b:3,4-b′]dithiophene. The flask was evacuated and purged with argon three times. To this flask was then added 20 mL of dry, distilled THF. The resulting solution was cooled to −78° C. and 4.35 mL (10.88 mmol, 4 equiv.) of 2.5M BuLi was added dropwise. The reaction was stirred for 1 hour at −78° C. and then warmed to room temperature and stirred for an additional 3 hours. The solution was cooled again to −78° C. and 2.77 mL (13.6 mmol, 5 equiv.) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added in one portion via syringe. The reaction was stirred at −78° C. for 1 hour and then allowed to warm to room temperature overnight. The solution was poured into water and extracted with 4×150 mL of methyl tert-butyl ether. The organic layers were combined and washed with 2×150 mL of brine, dried with anhydrous MgSO4, and filtered. The solvent was removed under vacuum to yield and orange oil, which was purified by column chromatography (5% EtOAc in hexanes) to yield a colorless, viscous oil, 1.34 g (75% yield).
  • Example 10 Preparation of a Pentathienyl-Cyclopentadithiophene Copolymer
  • Figure US20100180944A1-20100722-C00042
  • A 50 mL Schlenk flask was charged with 0.309 g (0.472 mmol) of 4H-4,4-bis(2′-ethylhexyl)cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-bis(pinacolborate) ester prepared in Example 9, 0.367 g (0.510 mmol) of 5,5′-dibromo-3″,4″-dihexyl-a-pentathiophene (its synthesis was described in WO 2005/092947, which is incorporated herein by reference) 0.0013 g (0.00185 mmol) of PdCl2(PPh3)2, and 0.057 g (0.142 mmol) of trioctylmethylammonium chloride (Aliquot 336, Aldrich, St. Louis, Mo.). The flask was fitted with a reflux condenser and the flask was evacuated and refilled with nitrogen three times. The solids were dissolved in 6 mL of toluene and then 0.88 mL of 2M Na2CO3 were added via syringe. The reaction was then heated to 95° C. with stiffing for 5 hours. Phenylboronic acid (0.031 g, 0.250 mmol) and 0.0016 g (0.00228 mmol) of PdCl2(PPh3)2 were dissolved in 1 mL of THF and added to the reaction mixture, and stiffing was continued for 16 h at 95° C. The reaction mixture was diluted with toluene (50 mL) and the organic layer was separated and washed with warm water (3×50 mL). The solution was then treated with an aqueous solution of diethyldithiocarbamic acid sodium salt trihydrate (7.5%, DDC, 5 mL) and heated at 80° C. overnight. The aqueous layer was separated and discarded and the organic layer was washed with warm water (3×50 mL) and the polymer precipitated into methanol (500 mL). The polymer was collected by filtration, washed with methanol (50 mL) and redissolved in hot toluene (200 mL). The hot polymer solution was passed through a tightly packed column of celite (1×8 cm), silica get (3×8 cm), and basic alumina (3×8 cm) (previously rinsed with 200 mL of hot toluene). The polymer solution was collected and the volume concentrated to approximately 50 mL. The polymer was precipitated into methanol (500 mL), washed with methanol (100 mL), acetone (100 mL) and again with methanol (100 mL). The polymer was then dried in vacuo overnight to yield a brick red material. Yield: 0.327 g.
  • Example 11 Fabrication of Solar Cell
  • The polymer solar cells were fabricated by doctor-blading a blend of the polymer prepared in Example 7 (PCPDTBT) and PC61BM or PC71BM (purchased from Nano-C, Westwood, Mass.) in a 1:3 w/w ratio sandwiched between a transparent anode and an evaporated metal cathode. The transparent anode was an indium tin oxide (ITO)-covered glass substrate (Merck, Whitehouse Station, N.J.) which was coated with a ˜60 nm thick PEDOT:PSS layer (Baytron PH from H. C. Starck) applied by doctorblading. The ITO-glass-substrate was cleaned by ultrasonification subsequently in acetone, isopropyl alcohol and deionized water. The cathode, a bilayer of a thin (1 nm) LiF layer covered with 80 nm Al, was prepared by thermal evaporation. PCPDTBT and PC61BM or PC71BM were dissolved together in o-dichlorobenzene (ODCB) to give an overall 40 mg/ml solution and was stirred overnight at 60-70° C. inside a glovebox. The active layer thickness, as determined by AFM, was between 150-250 nm. Device characterization was done under AM 1.5G irradiation (100 mW/cm2) on an Oriel Xenon solar simulator with a well calibrated spectral mismatch of 0.98 jV-characteristics were recorded with a Keithley 2400. Active areas were in the range of 15 to 20 mm2. EQE was detected with a lock-in amplifier under monochromatic illumination. Calibration of the incident light was done with a monocrystalline silicon diode. Mobility measurements were done using an Agilent 4155C parameter analyzer. Absorption measurements were done inside the glovebox with an Avantes fiberoptic spectrometer or outside with a HP spectrometer.
  • The interaction with PCBM and the photoinduced charge transfer was investigated by PL quenching. The PL of pristine PCPDTBT versus PCPDTBT/PCBM composites was measured at liquid N2 temperatures in a cryostat, excitation was provided by an Ar laser at 488 nm.
  • Electrochemical experiments were carried out on dropcast polymer films at room temperature in a glovebox. The supporting electrolyte was tetrabutylammonium-hexafluorophosphate (TBAPF6, electrochemical grade, Aldrich) ˜0.1 M in acetonitrile anhydrous (Aldrich). The working electrode (WE), as well as the counter electrode (CE), was a platinum foil. A silver wire coated with AgCl was used as a reference electrode (RE). After each measurement, the RE was calibrated with ferrocene (E0=400 mV vs. NHE) and the potential axis was corrected to NHE (using −4.75 eV for NHE24,25) according to the difference of E0 (ferrocene) and the measured E1/2 (ferrocene). λmax (CHCl3)=710 nm, λband edge (CHCl3)=780 nm, band gap (CHCl3)=1.59 eV, λmax (film)=700-760 nm, λband edge (film)=855 nm, band gap (film)=1.45 eV, HOMO=−5.3 eV, −5.7 eV (electrochem), LUMO=−3.85 eV, −4.25 eV, μ+=2×10−2 cm2/Vs (TOF), 1×10−3 cm2/Vs (FET).
  • Other embodiments are in the claims.

Claims (7)

  1. 1. A photovoltaic cell, comprising:
    a first electrode,
    a second electrode, and
    a photoactive material disposed between the first and second electrodes, the photoactive material comprising an electron donor material and an electron acceptor material, the electron donor material comprises a copolymer including a first monomer repeat unit, and the first monomer repeat unit comprises a thienothiophene moiety.
  2. 2. The photovoltaic cell of claim 1, wherein the thienothiophene moiety is optionally substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, halo, CN, NO2, and SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl.
  3. 3. The photovoltaic cell of claim 1, wherein the thienothiophene moiety is optionally substituted with halo.
  4. 4. The photovoltaic cell of claim 1, wherein the thienothiophene moiety is optionally substituted with fluoro.
  5. 5. The photovoltaic cell of claim 1, wherein the electron acceptor material comprises a fullerene.
  6. 6. The photovoltaic cell of claim 1, wherein the electron acceptor material comprises a substituted fullerene.
  7. 7. The photovoltaic cell of claim 1, wherein the electron acceptor material comprises a PCBM.
US12724704 2005-07-14 2010-03-16 Polymers with low band gaps and high charge mobility Abandoned US20100180944A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US69912305 true 2005-07-14 2005-07-14
US11375643 US7772485B2 (en) 2005-07-14 2006-03-14 Polymers with low band gaps and high charge mobility
US11450521 US7781673B2 (en) 2005-07-14 2006-06-09 Polymers with low band gaps and high charge mobility
US11485708 US8058550B2 (en) 2005-07-14 2006-07-13 Polymers with low band gaps and high charge mobility
US12724704 US20100180944A1 (en) 2005-07-14 2010-03-16 Polymers with low band gaps and high charge mobility

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12724704 US20100180944A1 (en) 2005-07-14 2010-03-16 Polymers with low band gaps and high charge mobility
US14256613 US20140224331A1 (en) 2005-07-14 2014-04-18 Polymers with Low Band Gaps and High Charge Mobility

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11485708 Continuation US8058550B2 (en) 2005-07-14 2006-07-13 Polymers with low band gaps and high charge mobility

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14256613 Continuation US20140224331A1 (en) 2005-07-14 2014-04-18 Polymers with Low Band Gaps and High Charge Mobility

Publications (1)

Publication Number Publication Date
US20100180944A1 true true US20100180944A1 (en) 2010-07-22

Family

ID=37669399

Family Applications (5)

Application Number Title Priority Date Filing Date
US11450521 Active 2027-10-13 US7781673B2 (en) 2005-07-14 2006-06-09 Polymers with low band gaps and high charge mobility
US11485708 Active 2028-05-05 US8058550B2 (en) 2005-07-14 2006-07-13 Polymers with low band gaps and high charge mobility
US11486536 Abandoned US20070020526A1 (en) 2005-07-14 2006-07-14 Polymers with low band gaps and high charge mobility
US12724704 Abandoned US20100180944A1 (en) 2005-07-14 2010-03-16 Polymers with low band gaps and high charge mobility
US14256613 Abandoned US20140224331A1 (en) 2005-07-14 2014-04-18 Polymers with Low Band Gaps and High Charge Mobility

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US11450521 Active 2027-10-13 US7781673B2 (en) 2005-07-14 2006-06-09 Polymers with low band gaps and high charge mobility
US11485708 Active 2028-05-05 US8058550B2 (en) 2005-07-14 2006-07-13 Polymers with low band gaps and high charge mobility
US11486536 Abandoned US20070020526A1 (en) 2005-07-14 2006-07-14 Polymers with low band gaps and high charge mobility

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14256613 Abandoned US20140224331A1 (en) 2005-07-14 2014-04-18 Polymers with Low Band Gaps and High Charge Mobility

Country Status (5)

Country Link
US (5) US7781673B2 (en)
EP (2) EP2716677A1 (en)
JP (1) JP2009506519A (en)
CA (1) CA2614958A1 (en)
WO (1) WO2007011739A3 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090139558A1 (en) * 2007-11-29 2009-06-04 Shunpei Yamazaki Photoelectric conversion device and manufacturing method thereof
US20090165854A1 (en) * 2007-12-28 2009-07-02 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion device and manufacturing method thereof
WO2012174561A3 (en) * 2011-06-17 2013-06-20 The Regents Of The University Of California REGIOREGULAR PYRIDAL[2,1,3]THIADIAZOLE π-CONJUGATED COPOLYMERS FOR ORGANIC SEMICONDUCTORS
US8772763B2 (en) 2009-10-29 2014-07-08 Sumitomo Chemical Company, Limited Photovoltaic cell
DE102013206586A1 (en) 2013-04-12 2014-10-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. A semiconductive copolymer, and method for its manufacture, composition of matter, electrical or electronic component and method for its production
US8994009B2 (en) 2011-09-07 2015-03-31 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion device
US9006714B2 (en) 2009-10-29 2015-04-14 Sumitomo Chemical Company, Limited Photovoltaic device
US9209404B2 (en) 2009-10-29 2015-12-08 Sumitomo Chemical Company, Limited Macromolecular compound
US20160260900A1 (en) * 2015-03-02 2016-09-08 The Regents Of The University Of California Blade coating on nanogrooved substrates yielding aligned thin films of high mobility semiconducting polymers
US9472763B2 (en) 2009-10-29 2016-10-18 Sumitomo Chemical Company, Limited Macromolecular compound

Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7838623B2 (en) * 2004-09-14 2010-11-23 Corning Incorporated Fused thiophenes, methods for making fused thiophenes, and uses thereof
US20080006324A1 (en) * 2005-07-14 2008-01-10 Konarka Technologies, Inc. Tandem Photovoltaic Cells
US7781673B2 (en) * 2005-07-14 2010-08-24 Konarka Technologies, Inc. Polymers with low band gaps and high charge mobility
US8158881B2 (en) * 2005-07-14 2012-04-17 Konarka Technologies, Inc. Tandem photovoltaic cells
US20070181179A1 (en) * 2005-12-21 2007-08-09 Konarka Technologies, Inc. Tandem photovoltaic cells
JP5324425B2 (en) * 2006-04-11 2013-10-23 メルク パテント ゲーエムベーハー Tandem photovoltaic cell
KR101477703B1 (en) 2006-06-13 2015-01-02 솔베이 유에스에이 인크. Organic photovoltaic devices comprising fullerenes and derivatives thereof
US20090126779A1 (en) * 2006-09-14 2009-05-21 The Regents Of The University Of California Photovoltaic devices in tandem architecture
KR100796643B1 (en) * 2006-10-02 2008-01-22 삼성전자주식회사 Polymer memory device and method for forming thereof
US8008424B2 (en) * 2006-10-11 2011-08-30 Konarka Technologies, Inc. Photovoltaic cell with thiazole-containing polymer
US8008421B2 (en) * 2006-10-11 2011-08-30 Konarka Technologies, Inc. Photovoltaic cell with silole-containing polymer
GB2444993B (en) * 2007-03-01 2011-09-07 Kenneth Stanley Jones Plastic digital video codec circuit
KR101597373B1 (en) 2007-12-21 2016-02-24 솔베이 유에스에이 인크. Organic photovoltaic devices comprising fullerenes and derivatives thereof and improved methodes of making fullerene derivatives
US20090221740A1 (en) * 2008-02-15 2009-09-03 Plextronics, Inc. Novel compositions, methods, and polymers
JP2011513951A (en) * 2008-02-21 2011-04-28 コナルカ テクノロジーズ インコーポレイテッドKonarka Technologies,Inc. Tandem photovoltaic cell
CA2729714A1 (en) 2008-07-02 2010-01-07 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. High performance solution processable semiconducting polymers based on alternating donor acceptor copolymers
US8455606B2 (en) * 2008-08-07 2013-06-04 Merck Patent Gmbh Photoactive polymers
JP5580976B2 (en) * 2008-10-30 2014-08-27 出光興産株式会社 Organic thin-film solar cells
CA2744544A1 (en) * 2008-11-26 2010-06-03 University Of Florida Research Foundation, Inc. Black soluble conjugated polymers with high charge carrier mobilities
WO2010083161A1 (en) 2009-01-13 2010-07-22 Konarka Technologies, Inc. Photovoltaic module
US20100224252A1 (en) * 2009-03-05 2010-09-09 Konarka Technologies, Inc. Photovoltaic Cell Having Multiple Electron Donors
WO2010138414A1 (en) 2009-05-27 2010-12-02 Konarka Technologies, Inc. Reflective multilayer electrode
WO2010144469A3 (en) 2009-06-08 2011-07-07 Plextronics, Inc. Dye and conductive polymer compositions for use in solid-state electronic devices
WO2010144472A3 (en) 2009-06-08 2011-07-07 Plextronics, Inc. Porphyrin and conductive polymer compositions for use in solid-state electronic devices
JP5763632B2 (en) 2009-06-30 2015-08-12 ソルベイ ユーエスエイ インコーポレイテッド Polymer comprising at least one bithiophene repeating units, a method of synthesizing the polymer, and compositions comprising the same
US20110006287A1 (en) * 2009-07-10 2011-01-13 Wei You Polymers with tunable band gaps for photonic and electronic applications
WO2011052702A1 (en) * 2009-10-29 2011-05-05 住友化学株式会社 Polymeric compound and electronic element
JP5782703B2 (en) * 2009-10-29 2015-09-24 住友化学株式会社 Polymeric compounds and electronic device using the same
KR101113007B1 (en) 2010-02-19 2012-03-13 한국과학기술원 Tandem type solar cell comprising organic photoelectric converstion material
CN102191037A (en) * 2010-03-09 2011-09-21 海洋王照明科技股份有限公司 Organic photoelectric material containing condensed ring thiophene, manufacturing method and application thereof
WO2011112701A1 (en) 2010-03-09 2011-09-15 Konarka Technologies, Inc. Photovoltaic module containing buffer layer
WO2011113194A1 (en) * 2010-03-15 2011-09-22 海洋王照明科技股份有限公司 Cyclopentadienedithiophene-quinoxaline conjugated polymer and preparation method and uses thereof
US8772443B2 (en) 2010-03-26 2014-07-08 Hitachi Chemical Co., Ltd. Water soluble near infrared sensing polymers with low band gaps
JP5288640B2 (en) 2010-03-31 2013-09-11 富士フイルム株式会社 The imaging device and manufacturing method thereof
WO2011127131A1 (en) 2010-04-06 2011-10-13 Konarka Technologies, Inc. Novel electrode
DE102011006686A1 (en) 2010-04-16 2011-12-29 Basf Se Preparing optically active hydroxylamine comprises reacting an optically active amine with a hydrocarbon in a solvent and dissolving resulting aminonitrile in alcohol, oxidizing, cooling and drying the precipitate or oil
CN105439976A (en) 2010-04-28 2016-03-30 住友化学株式会社 Polymer compound
WO2011160021A3 (en) 2010-06-17 2012-06-21 Konarka Technologies, Inc. Fullerene derivatives and photovoltaic cell containing them
US8895693B2 (en) 2010-06-25 2014-11-25 Samsung Electronics Co., Ltd. Electron-donating polymers and organic solar cells including the same
JP5947795B2 (en) 2010-09-10 2016-07-06 日立化成株式会社 Method of producing individually addressable band electrode array and it
WO2012078517A1 (en) 2010-12-06 2012-06-14 Plextronics, Inc. Inks for solar cell inverted structures
CN103270076B (en) 2010-12-21 2016-11-23 住友化学株式会社 And a polymer compound using the same device structure of the organic carbon clusters
WO2012116017A3 (en) * 2011-02-24 2014-05-01 Rieke Metals Inc. Polythiophene–fullerene conjugates for photovoltaic cells
US20140017762A1 (en) * 2011-03-28 2014-01-16 Hitachi Chemical Research Center, Inc. Network conjugated polymers with enhanced solubility
JP5779233B2 (en) * 2011-03-31 2015-09-16 株式会社クラレ Block copolymer and a photoelectric conversion element
EP2692761A4 (en) * 2011-03-31 2014-09-17 Kuraray Co Block copolymer and photoelectric conversion element
WO2012149189A3 (en) 2011-04-28 2013-03-28 Merck Patent Gmbh Novel photoactive polymers
JP2014513443A (en) 2011-05-09 2014-05-29 メルク パテント ゲーエムベーハー Multi-junction photovoltaic cell
KR101853395B1 (en) 2011-05-23 2018-04-30 삼성전자주식회사 Electron donating polymer and solar cell including the same
JP5742494B2 (en) 2011-06-10 2015-07-01 住友化学株式会社 Polymeric compounds and electronic device using the same
JP5834682B2 (en) * 2011-09-21 2015-12-24 住友化学株式会社 Polymeric compounds and electronic device using the same
KR101777326B1 (en) 2011-10-05 2017-09-12 삼성전자주식회사 Electron donating polymer and organic solar cell including the same
JPWO2013065621A1 (en) * 2011-11-04 2015-04-02 株式会社クラレ The photoelectric conversion device and a manufacturing method thereof
JP5884423B2 (en) * 2011-11-15 2016-03-15 住友化学株式会社 Polymer compound and an organic photoelectric conversion device using the same
WO2013099926A1 (en) * 2011-12-28 2013-07-04 株式会社クラレ Photoelectric conversion element and method of fabricating same
JP5874463B2 (en) * 2012-03-16 2016-03-02 住友化学株式会社 Compounds and polymer compounds, and organic thin film and organic semiconductor device comprising a polymeric compound
US20130263925A1 (en) 2012-04-05 2013-10-10 Merck Patent Gmbh Hole Carrier Layer For Organic Photovoltaic Device
US9679672B2 (en) * 2012-04-13 2017-06-13 Wake Forest University Low band gap conjugated polymeric compositions and applications thereof
JP6070701B2 (en) * 2012-05-31 2017-02-01 三菱化学株式会社 Copolymers, organic semiconductor material, an organic electronic device and a solar cell module
US9359470B2 (en) * 2012-07-23 2016-06-07 Basf Se Dithienobenzofuran polymers and small molecules for electronic application
KR20150085523A (en) 2012-11-15 2015-07-23 솔베이(소시에떼아노님) Film forming composition comprising graphene material and conducting polymer
CN103833975B (en) * 2012-11-27 2016-04-20 海洋王照明科技股份有限公司 And containing dithiophene - silolo bis (benzothiadiazole) copolymers and their preparation and use
DE112014000493T5 (en) 2013-01-21 2015-11-19 Sumitomo Chemical Co., Ltd. Reactive Compound

Citations (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292092A (en) * 1980-06-02 1981-09-29 Rca Corporation Laser processing technique for fabricating series-connected and tandem junction series-connected solar cells into a solar battery
US4416959A (en) * 1980-11-18 1983-11-22 Terje Skotheim Photoelectrochemical cells for conversion of solar energy to electricity
US4574160A (en) * 1984-09-28 1986-03-04 The Standard Oil Company Flexible, rollable photovoltaic cell module
US4639328A (en) * 1983-11-25 1987-01-27 Merck Patent Gesellschaft Mit Beschrankter Haftung Thienothiophene derivatives
US4686323A (en) * 1986-06-30 1987-08-11 The Standard Oil Company Multiple cell, two terminal photovoltaic device employing conductively adhered cells
US4746618A (en) * 1987-08-31 1988-05-24 Energy Conversion Devices, Inc. Method of continuously forming an array of photovoltaic cells electrically connected in series
US4795687A (en) * 1986-09-12 1989-01-03 Mitsubishi Kasei Corp. Electrically conductive material and a process for the preparation of same and secondary battery using the electrically conductive material
US4913744A (en) * 1987-01-13 1990-04-03 Helmut Hoegl Solar cell arrangement
US4948436A (en) * 1988-02-05 1990-08-14 Siemens Aktiengesellschaft Thin-film solar cell arrangement
US5071490A (en) * 1988-03-18 1991-12-10 Sharp Kabushiki Kaisha Tandem stacked amorphous solar cell device
US5221363A (en) * 1991-02-28 1993-06-22 Lockheed Missiles & Space Company, Inc. Solar cell window fitting
US5274058A (en) * 1991-09-12 1993-12-28 Board Of Regents, The University Of Texas System Low bandgap polymers rf fused bithiophenes
US5536808A (en) * 1994-10-05 1996-07-16 The Regents Of The University Of Michigan Thiazole polymers and method of producing same
US5708130A (en) * 1995-07-28 1998-01-13 The Dow Chemical Company 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
US6109330A (en) * 1996-10-09 2000-08-29 Peter Butz Gmbh & Co. Verwaltungs-Kg Blind for motor-vehicle rear window
US6132585A (en) * 1992-07-01 2000-10-17 Canon Kabushiki Kaisha Semiconductor element and method and apparatus for fabricating the same
US6188175B1 (en) * 1995-04-18 2001-02-13 Cambridge Display Technology Limited Electroluminescent device
US6198091B1 (en) * 1998-08-19 2001-03-06 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with a mixed electrical configuration
US6198092B1 (en) * 1998-08-19 2001-03-06 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with an electrically parallel configuration
US6239355B1 (en) * 1998-10-09 2001-05-29 The Trustees Of Columbia University In The City Of New York Solid-state photoelectric device
US6278055B1 (en) * 1998-08-19 2001-08-21 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with an electrically series configuration
US6297495B1 (en) * 1998-08-19 2001-10-02 The Trustees Of Princeton University Organic photosensitive optoelectronic devices with a top transparent electrode
US6333458B1 (en) * 1999-11-26 2001-12-25 The Trustees Of Princeton University Highly efficient multiple reflection photosensitive optoelectronic device with optical concentrator
US6353083B1 (en) * 1999-02-04 2002-03-05 The Dow Chemical Company Fluorene copolymers and devices made therefrom
US6352777B1 (en) * 1998-08-19 2002-03-05 The Trustees Of Princeton University Organic photosensitive optoelectronic devices with transparent electrodes
US20020040728A1 (en) * 2000-08-15 2002-04-11 Masaru Yoshikawa Photoelectric conversion device and method for producing same
US20020050289A1 (en) * 2000-10-31 2002-05-02 Kenji Wada Solar cell substrate, thin-film solar cell, and multi-junction thin-film solar cell
US6399224B1 (en) * 2000-02-29 2002-06-04 Canon Kabushiki Kaisha Conjugated polymers with tunable charge injection ability
US20020105005A1 (en) * 2001-02-08 2002-08-08 Satoshi Seo Light emitting device
US6440769B2 (en) * 1999-11-26 2002-08-27 The Trustees Of Princeton University Photovoltaic device with optical concentrator and method of making the same
US6451415B1 (en) * 1998-08-19 2002-09-17 The Trustees Of Princeton University Organic photosensitive optoelectronic device with an exciton blocking layer
US6464762B1 (en) * 1997-10-15 2002-10-15 Canon Kabushiki Kaisha Aqueous solution for the formation of an indium oxide film by electroless deposition
US20030008172A1 (en) * 2001-04-10 2003-01-09 Mario Leclerc Conjugated polycarbazole derivatives in Organic Light Emitting Diodes
US20030023029A1 (en) * 2000-04-11 2003-01-30 Hailiang Wang Soluble poly(aryl-oxadiazole) conjugated polymers
US20030036612A1 (en) * 1999-12-28 2003-02-20 Ilya E. Nifant'ev Hetero cyclic metallocene compounds and use thereof in catalyst system for producing olefin polymers
US20030042471A1 (en) * 2001-08-17 2003-03-06 Merck Patent Gmbh Conjugated copolymers of dithienothiophene with vinylene or acetylene
US20030102024A1 (en) * 2001-12-05 2003-06-05 Zeira Eitan C. Photovoltaic solar cell
US6580027B2 (en) * 2001-06-11 2003-06-17 Trustees Of Princeton University Solar cells using fullerenes
US20030127967A1 (en) * 2001-12-05 2003-07-10 Semiconductor Energy Laboratory Co., Ltd. Organic semiconductor element
US20030159729A1 (en) * 2000-04-27 2003-08-28 Sean Shaheen Photovoltaic cell
US20030175411A1 (en) * 2001-10-05 2003-09-18 Kodas Toivo T. Precursor compositions and methods for the deposition of passive electrical components on a substrate
US20030188777A1 (en) * 2002-01-25 2003-10-09 Konarka Technologies, Inc. Co-sensitizers for dye sensitized solar cells
US20030189402A1 (en) * 2002-01-25 2003-10-09 Konarka Technologies, Inc. Displays with integrated photovoltaic cells
US6657378B2 (en) * 2001-09-06 2003-12-02 The Trustees Of Princeton University Organic photovoltaic devices
US20030230225A1 (en) * 2002-06-18 2003-12-18 Hatfield Robert Lee Planting device having adjustable handle
US20030230335A1 (en) * 2002-06-17 2003-12-18 Fuji Photo Film Co., Ltd. Methods for producing titanium oxide sol and fine titanium oxide particles, and photoelectric conversion device
US20040118448A1 (en) * 2002-09-05 2004-06-24 Nanosys, Inc. Nanostructure and nanocomposite based compositions and photovoltaic devices
US6772817B2 (en) * 2000-12-11 2004-08-10 Tony Lai Adjustable window blind cord stopper
US20040187911A1 (en) * 2003-03-24 2004-09-30 Russell Gaudiana Photovoltaic cell with mesh electrode
US20040192871A1 (en) * 2003-02-12 2004-09-30 Hailiang Wang Monomers, conjugated polymers and electronic devices using such polymers
US20040201018A1 (en) * 2001-09-05 2004-10-14 Motohiro Yamahara Polymer structure and functional element having the same, and transistor and display using the same
US20040214036A1 (en) * 2003-04-15 2004-10-28 3M Innovative Properties Company Electron transport agents for organic electronic devices
US6818260B2 (en) * 2001-07-09 2004-11-16 Merck Patent Gmbh Thienothiophene derivatives
US6830832B2 (en) * 2001-11-09 2004-12-14 Sumitomo Chemical Company, Limited Polymer compound and polymer light-emitting device using the same
US20040256615A1 (en) * 2001-07-09 2004-12-23 Henning Sirringhaus Lamellar polymer architecture
US20050022865A1 (en) * 2003-07-29 2005-02-03 Robeson Lloyd Mahlon Photovoltaic devices comprising layer(s) of photoactive organics dissolved in high Tg polymers
US6864333B2 (en) * 1999-12-28 2005-03-08 Basel Polyolefine Gmbh Process for the preparation of ethylene polymers
US20050124784A1 (en) * 2003-10-01 2005-06-09 Sotzing Gregory A. Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof
US20050145972A1 (en) * 2002-01-28 2005-07-07 Susumu Fukuda Tandem thin-film photoelectric transducer and its manufacturing method
US20050194038A1 (en) * 2002-06-13 2005-09-08 Christoph Brabec Electrodes for optoelectronic components and the use thereof
US20050224905A1 (en) * 2004-04-13 2005-10-13 Forrest Stephen R High efficiency organic photovoltaic cells employing hybridized mixed-planar heterojunctions
US6962766B2 (en) * 2001-03-30 2005-11-08 Fuji Photo Film Co., Ltd. Positive photoresist composition
US20060022192A1 (en) * 2004-07-29 2006-02-02 Christoph Brabec Inexpensive organic solar cell and method of producing same
US20060027834A1 (en) * 2004-08-05 2006-02-09 Stephen Forrest Stacked organic photosensitive devices
US20060076050A1 (en) * 2004-09-24 2006-04-13 Plextronics, Inc. Heteroatomic regioregular poly(3-substitutedthiophenes) for photovoltaic cells
US20060141662A1 (en) * 2002-11-29 2006-06-29 Christoph Brabec Photovoltaic component and production method therefor
US20060155106A1 (en) * 2002-09-25 2006-07-13 3M Innovative Properties Company Electroactive polymers
US7095044B2 (en) * 2000-11-28 2006-08-22 Merck Patent Gmbh Field effect transistors and materials and methods for their manufacture
US20070014939A1 (en) * 2005-07-14 2007-01-18 Russell Gaudiana Polymers with low band gaps and high charge mobility
US20070020526A1 (en) * 2005-07-14 2007-01-25 Russell Gaudiana Polymers with low band gaps and high charge mobility
US20070120045A1 (en) * 2005-08-31 2007-05-31 Fuji Photo Film Co., Ltd. Organic photoelectric conversion device and stack type photoelectric conversion device
US20070131270A1 (en) * 2005-07-14 2007-06-14 Russell Gaudiana Window with photovoltaic cell
US20070181179A1 (en) * 2005-12-21 2007-08-09 Konarka Technologies, Inc. Tandem photovoltaic cells
US20070193621A1 (en) * 2005-12-21 2007-08-23 Konarka Technologies, Inc. Photovoltaic cells
US20070267055A1 (en) * 2005-07-14 2007-11-22 Konarka Technologies, Inc. Tandem Photovoltaic Cells
US20080053518A1 (en) * 2006-09-05 2008-03-06 Pen-Hsiu Chang Transparent solar cell system
US20080087324A1 (en) * 2006-10-11 2008-04-17 Konarka Technologies, Inc. Photovoltaic Cell With Silole-Containing Polymer
US7368510B2 (en) * 2004-07-08 2008-05-06 Samsung Electronics Co., Ltd. Organic semiconductor copolymers containing oligothiophene and n-type heteroaromatic units
US20080121281A1 (en) * 2006-10-11 2008-05-29 Konarka Technologies, Inc. Photovoltaic Cell With Thiazole-Containing Polymer
US7405775B2 (en) * 2003-01-17 2008-07-29 Cbrite Inc. Display employing organic material
US20080264488A1 (en) * 2007-04-27 2008-10-30 Srini Balasubramanian Organic Photovoltaic Cells

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US740575A (en) * 1902-11-03 1903-10-06 Emil M Kramer Grain-separator.
JPH04192376A (en) 1990-11-22 1992-07-10 Sekisui Chem Co Ltd Tandem organic solar battery
JPH0511841A (en) 1991-07-05 1993-01-22 Toshiba Corp Conveyance control method
US5298086A (en) 1992-05-15 1994-03-29 United Solar Systems Corporation Method for the manufacture of improved efficiency tandem photovoltaic device and device manufactured thereby
US5412105A (en) * 1992-06-29 1995-05-02 Shin-Etsu Chemical Co., Ltd. Thiophene-silole copolymer and its method of manufacture
JP2862753B2 (en) * 1992-06-29 1999-03-03 信越化学工業株式会社 Thiophene - white - alcohol copolymer and a method of manufacturing
WO1997005184A1 (en) 1995-07-28 1997-02-13 The Dow Chemical Company 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
JP2001060707A (en) 1999-06-18 2001-03-06 Nippon Sheet Glass Co Ltd Photoelectric transfer device
JP4193961B2 (en) 2000-10-31 2008-12-10 シャープ株式会社 Multijunction thin film solar cell
JP4404550B2 (en) * 2001-01-24 2010-01-27 ケンブリッジ ディスプレイ テクノロジー リミテッド Monomers for use in preparing the polymer to be used in optical devices
JP2003264085A (en) 2001-12-05 2003-09-19 Semiconductor Energy Lab Co Ltd Organic semiconductor element, organic electroluminescence element and organic solar cell
US7071407B2 (en) 2002-10-31 2006-07-04 Emcore Corporation Method and apparatus of multiplejunction solar cell structure with high band gap heterojunction middle cell
DE10326547A1 (en) 2003-06-12 2005-01-05 Siemens Ag Tandem solar cell with a common organic electrode
JP2005011841A (en) 2003-06-16 2005-01-13 Japan Science & Technology Agency Vertical junction organic photovoltaic device and its manufacturing method
EP1507298A1 (en) 2003-08-14 2005-02-16 Sony International (Europe) GmbH Carbon nanotubes based solar cells
US7803885B2 (en) 2004-03-17 2010-09-28 Dow Global Technologies Inc. Pentathienyl-fluorene copolymer
WO2005111045A1 (en) * 2004-05-18 2005-11-24 Merck Patent Gmbh MONO-, OLIGO- AND POLYTHIENO[3,2-b]THIOPHENES
JP5046492B2 (en) * 2005-03-29 2012-10-10 Jsr株式会社 A photoelectric conversion element and a solar cell
DE602006016861D1 (en) 2005-12-21 2010-10-21 Konarka Technologies Inc Photovoltaic tandem cell
JP5324425B2 (en) 2006-04-11 2013-10-23 メルク パテント ゲーエムベーハー Tandem photovoltaic cell
WO2007133705A3 (en) 2006-05-11 2008-01-24 Univ Northwestern Silole-based polymers and semiconductor materials prepared from the same
KR100890145B1 (en) 2006-06-15 2009-03-20 주식회사 엘지화학 Thiazolothiazole derivatives and organic electronic devices using the same
KR101422054B1 (en) 2006-06-30 2014-07-23 시바 홀딩 인크 Diketopyrrolopyrrole polymers as organic semiconductors
EP2307483B1 (en) 2008-07-18 2015-04-22 University Of Chicago Semiconducting polymers

Patent Citations (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4292092A (en) * 1980-06-02 1981-09-29 Rca Corporation Laser processing technique for fabricating series-connected and tandem junction series-connected solar cells into a solar battery
US4416959A (en) * 1980-11-18 1983-11-22 Terje Skotheim Photoelectrochemical cells for conversion of solar energy to electricity
US4639328A (en) * 1983-11-25 1987-01-27 Merck Patent Gesellschaft Mit Beschrankter Haftung Thienothiophene derivatives
US4574160A (en) * 1984-09-28 1986-03-04 The Standard Oil Company Flexible, rollable photovoltaic cell module
US4686323A (en) * 1986-06-30 1987-08-11 The Standard Oil Company Multiple cell, two terminal photovoltaic device employing conductively adhered cells
US4795687A (en) * 1986-09-12 1989-01-03 Mitsubishi Kasei Corp. Electrically conductive material and a process for the preparation of same and secondary battery using the electrically conductive material
US4913744A (en) * 1987-01-13 1990-04-03 Helmut Hoegl Solar cell arrangement
US4746618A (en) * 1987-08-31 1988-05-24 Energy Conversion Devices, Inc. Method of continuously forming an array of photovoltaic cells electrically connected in series
US4948436A (en) * 1988-02-05 1990-08-14 Siemens Aktiengesellschaft Thin-film solar cell arrangement
US5071490A (en) * 1988-03-18 1991-12-10 Sharp Kabushiki Kaisha Tandem stacked amorphous solar cell device
US5221363A (en) * 1991-02-28 1993-06-22 Lockheed Missiles & Space Company, Inc. Solar cell window fitting
US5274058A (en) * 1991-09-12 1993-12-28 Board Of Regents, The University Of Texas System Low bandgap polymers rf fused bithiophenes
US5510438A (en) * 1991-09-12 1996-04-23 Board Of Regents, The University Of Texas System Low bandgap polymers from fused dithiophene diester
US6132585A (en) * 1992-07-01 2000-10-17 Canon Kabushiki Kaisha Semiconductor element and method and apparatus for fabricating the same
US5536808A (en) * 1994-10-05 1996-07-16 The Regents Of The University Of Michigan Thiazole polymers and method of producing same
US6188175B1 (en) * 1995-04-18 2001-02-13 Cambridge Display Technology Limited Electroluminescent device
US5708130A (en) * 1995-07-28 1998-01-13 The Dow Chemical Company 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers
US6109330A (en) * 1996-10-09 2000-08-29 Peter Butz Gmbh & Co. Verwaltungs-Kg Blind for motor-vehicle rear window
US6464762B1 (en) * 1997-10-15 2002-10-15 Canon Kabushiki Kaisha Aqueous solution for the formation of an indium oxide film by electroless deposition
US6352777B1 (en) * 1998-08-19 2002-03-05 The Trustees Of Princeton University Organic photosensitive optoelectronic devices with transparent electrodes
US6198092B1 (en) * 1998-08-19 2001-03-06 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with an electrically parallel configuration
US6198091B1 (en) * 1998-08-19 2001-03-06 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with a mixed electrical configuration
US6297495B1 (en) * 1998-08-19 2001-10-02 The Trustees Of Princeton University Organic photosensitive optoelectronic devices with a top transparent electrode
US6451415B1 (en) * 1998-08-19 2002-09-17 The Trustees Of Princeton University Organic photosensitive optoelectronic device with an exciton blocking layer
US6278055B1 (en) * 1998-08-19 2001-08-21 The Trustees Of Princeton University Stacked organic photosensitive optoelectronic devices with an electrically series configuration
US6239355B1 (en) * 1998-10-09 2001-05-29 The Trustees Of Columbia University In The City Of New York Solid-state photoelectric device
US6353083B1 (en) * 1999-02-04 2002-03-05 The Dow Chemical Company Fluorene copolymers and devices made therefrom
US6440769B2 (en) * 1999-11-26 2002-08-27 The Trustees Of Princeton University Photovoltaic device with optical concentrator and method of making the same
US6333458B1 (en) * 1999-11-26 2001-12-25 The Trustees Of Princeton University Highly efficient multiple reflection photosensitive optoelectronic device with optical concentrator
US6864333B2 (en) * 1999-12-28 2005-03-08 Basel Polyolefine Gmbh Process for the preparation of ethylene polymers
US20030036612A1 (en) * 1999-12-28 2003-02-20 Ilya E. Nifant'ev Hetero cyclic metallocene compounds and use thereof in catalyst system for producing olefin polymers
US6399224B1 (en) * 2000-02-29 2002-06-04 Canon Kabushiki Kaisha Conjugated polymers with tunable charge injection ability
US20030023029A1 (en) * 2000-04-11 2003-01-30 Hailiang Wang Soluble poly(aryl-oxadiazole) conjugated polymers
US20030159729A1 (en) * 2000-04-27 2003-08-28 Sean Shaheen Photovoltaic cell
US20020040728A1 (en) * 2000-08-15 2002-04-11 Masaru Yoshikawa Photoelectric conversion device and method for producing same
US20020050289A1 (en) * 2000-10-31 2002-05-02 Kenji Wada Solar cell substrate, thin-film solar cell, and multi-junction thin-film solar cell
US7095044B2 (en) * 2000-11-28 2006-08-22 Merck Patent Gmbh Field effect transistors and materials and methods for their manufacture
US6772817B2 (en) * 2000-12-11 2004-08-10 Tony Lai Adjustable window blind cord stopper
US20020105005A1 (en) * 2001-02-08 2002-08-08 Satoshi Seo Light emitting device
US6962766B2 (en) * 2001-03-30 2005-11-08 Fuji Photo Film Co., Ltd. Positive photoresist composition
US20030008172A1 (en) * 2001-04-10 2003-01-09 Mario Leclerc Conjugated polycarbazole derivatives in Organic Light Emitting Diodes
US6580027B2 (en) * 2001-06-11 2003-06-17 Trustees Of Princeton University Solar cells using fullerenes
US20040256615A1 (en) * 2001-07-09 2004-12-23 Henning Sirringhaus Lamellar polymer architecture
US6818260B2 (en) * 2001-07-09 2004-11-16 Merck Patent Gmbh Thienothiophene derivatives
US20030042471A1 (en) * 2001-08-17 2003-03-06 Merck Patent Gmbh Conjugated copolymers of dithienothiophene with vinylene or acetylene
US20040201018A1 (en) * 2001-09-05 2004-10-14 Motohiro Yamahara Polymer structure and functional element having the same, and transistor and display using the same
US6657378B2 (en) * 2001-09-06 2003-12-02 The Trustees Of Princeton University Organic photovoltaic devices
US20030175411A1 (en) * 2001-10-05 2003-09-18 Kodas Toivo T. Precursor compositions and methods for the deposition of passive electrical components on a substrate
US6830832B2 (en) * 2001-11-09 2004-12-14 Sumitomo Chemical Company, Limited Polymer compound and polymer light-emitting device using the same
US20030102024A1 (en) * 2001-12-05 2003-06-05 Zeira Eitan C. Photovoltaic solar cell
US20030127967A1 (en) * 2001-12-05 2003-07-10 Semiconductor Energy Laboratory Co., Ltd. Organic semiconductor element
US20030188777A1 (en) * 2002-01-25 2003-10-09 Konarka Technologies, Inc. Co-sensitizers for dye sensitized solar cells
US20030189402A1 (en) * 2002-01-25 2003-10-09 Konarka Technologies, Inc. Displays with integrated photovoltaic cells
US20050145972A1 (en) * 2002-01-28 2005-07-07 Susumu Fukuda Tandem thin-film photoelectric transducer and its manufacturing method
US20050194038A1 (en) * 2002-06-13 2005-09-08 Christoph Brabec Electrodes for optoelectronic components and the use thereof
US20030230335A1 (en) * 2002-06-17 2003-12-18 Fuji Photo Film Co., Ltd. Methods for producing titanium oxide sol and fine titanium oxide particles, and photoelectric conversion device
US20030230225A1 (en) * 2002-06-18 2003-12-18 Hatfield Robert Lee Planting device having adjustable handle
US20040118448A1 (en) * 2002-09-05 2004-06-24 Nanosys, Inc. Nanostructure and nanocomposite based compositions and photovoltaic devices
US20060155106A1 (en) * 2002-09-25 2006-07-13 3M Innovative Properties Company Electroactive polymers
US20060141662A1 (en) * 2002-11-29 2006-06-29 Christoph Brabec Photovoltaic component and production method therefor
US7405775B2 (en) * 2003-01-17 2008-07-29 Cbrite Inc. Display employing organic material
US20040192871A1 (en) * 2003-02-12 2004-09-30 Hailiang Wang Monomers, conjugated polymers and electronic devices using such polymers
US20040187911A1 (en) * 2003-03-24 2004-09-30 Russell Gaudiana Photovoltaic cell with mesh electrode
US20040214036A1 (en) * 2003-04-15 2004-10-28 3M Innovative Properties Company Electron transport agents for organic electronic devices
US7309833B2 (en) * 2003-07-29 2007-12-18 Air Products And Chemicals, Inc. Photovoltaic devices comprising layer(s) of photoactive organics dissolved in high Tg polymers
US20050022865A1 (en) * 2003-07-29 2005-02-03 Robeson Lloyd Mahlon Photovoltaic devices comprising layer(s) of photoactive organics dissolved in high Tg polymers
US7105237B2 (en) * 2003-10-01 2006-09-12 The University Of Connecticut Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof
US20050124784A1 (en) * 2003-10-01 2005-06-09 Sotzing Gregory A. Substituted thieno[3,4-B]thiophene polymers, method of making, and use thereof
US20050224905A1 (en) * 2004-04-13 2005-10-13 Forrest Stephen R High efficiency organic photovoltaic cells employing hybridized mixed-planar heterojunctions
US7368510B2 (en) * 2004-07-08 2008-05-06 Samsung Electronics Co., Ltd. Organic semiconductor copolymers containing oligothiophene and n-type heteroaromatic units
US20060022192A1 (en) * 2004-07-29 2006-02-02 Christoph Brabec Inexpensive organic solar cell and method of producing same
US20060027834A1 (en) * 2004-08-05 2006-02-09 Stephen Forrest Stacked organic photosensitive devices
US7196366B2 (en) * 2004-08-05 2007-03-27 The Trustees Of Princeton University Stacked organic photosensitive devices
US20060076050A1 (en) * 2004-09-24 2006-04-13 Plextronics, Inc. Heteroatomic regioregular poly(3-substitutedthiophenes) for photovoltaic cells
US20070267055A1 (en) * 2005-07-14 2007-11-22 Konarka Technologies, Inc. Tandem Photovoltaic Cells
US20070131270A1 (en) * 2005-07-14 2007-06-14 Russell Gaudiana Window with photovoltaic cell
US20070014939A1 (en) * 2005-07-14 2007-01-18 Russell Gaudiana Polymers with low band gaps and high charge mobility
US20070020526A1 (en) * 2005-07-14 2007-01-25 Russell Gaudiana Polymers with low band gaps and high charge mobility
US20070017571A1 (en) * 2005-07-14 2007-01-25 Russell Gaudiana Polymers with low band gaps and high charge mobility
US20070158620A1 (en) * 2005-07-14 2007-07-12 Russell Gaudiana Polymers with low band gaps and high charge mobility
US20070120045A1 (en) * 2005-08-31 2007-05-31 Fuji Photo Film Co., Ltd. Organic photoelectric conversion device and stack type photoelectric conversion device
US20070181179A1 (en) * 2005-12-21 2007-08-09 Konarka Technologies, Inc. Tandem photovoltaic cells
US20070193621A1 (en) * 2005-12-21 2007-08-23 Konarka Technologies, Inc. Photovoltaic cells
US20080053518A1 (en) * 2006-09-05 2008-03-06 Pen-Hsiu Chang Transparent solar cell system
US20080087324A1 (en) * 2006-10-11 2008-04-17 Konarka Technologies, Inc. Photovoltaic Cell With Silole-Containing Polymer
US20080121281A1 (en) * 2006-10-11 2008-05-29 Konarka Technologies, Inc. Photovoltaic Cell With Thiazole-Containing Polymer
US20080264488A1 (en) * 2007-04-27 2008-10-30 Srini Balasubramanian Organic Photovoltaic Cells

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Dibbs et al., "Fluorene Arylene Copolymers for Organic Photovoltaic Devices", SPIE proceedings, 2004 *
Lim et al., "Improved EL Efficiency of Fluorene-Thieno[3,2-b]thiophene-Based Conjugated Copolymers with Hole-Transporting or Electron-Transporting Units in the Main Chain", Journal of Polymer Science A, 11 November 2005 *
Lim et al., "Thin-Film Morphologies and Solution Processable Field Effect Transistor Behavior of a Fluorene-Theino[3,2-b]thiophene Based conjugated copolymer", Macromolecules, 2005 *
McCulloch et al., "Liquid-crystalline semiconducting polymers with high charge-carrier mobility" Nature Articles, 19 March 2006 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090139558A1 (en) * 2007-11-29 2009-06-04 Shunpei Yamazaki Photoelectric conversion device and manufacturing method thereof
US20090165854A1 (en) * 2007-12-28 2009-07-02 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion device and manufacturing method thereof
US9209404B2 (en) 2009-10-29 2015-12-08 Sumitomo Chemical Company, Limited Macromolecular compound
US8772763B2 (en) 2009-10-29 2014-07-08 Sumitomo Chemical Company, Limited Photovoltaic cell
US9472763B2 (en) 2009-10-29 2016-10-18 Sumitomo Chemical Company, Limited Macromolecular compound
US9006714B2 (en) 2009-10-29 2015-04-14 Sumitomo Chemical Company, Limited Photovoltaic device
WO2012174561A3 (en) * 2011-06-17 2013-06-20 The Regents Of The University Of California REGIOREGULAR PYRIDAL[2,1,3]THIADIAZOLE π-CONJUGATED COPOLYMERS FOR ORGANIC SEMICONDUCTORS
US9293708B2 (en) 2011-06-17 2016-03-22 The Regents Of The University Of California Regioregular pyridal[2,1,3]thiadiazole π-conjugated copolymers for organic semiconductors
US8994009B2 (en) 2011-09-07 2015-03-31 Semiconductor Energy Laboratory Co., Ltd. Photoelectric conversion device
DE102013206586A1 (en) 2013-04-12 2014-10-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. A semiconductive copolymer, and method for its manufacture, composition of matter, electrical or electronic component and method for its production
EP2824158A1 (en) 2013-04-12 2015-01-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Semiconducting copolymer and method for the production thereof, mixture of substances, electric or electronic component and method for producing the same
US20160260900A1 (en) * 2015-03-02 2016-09-08 The Regents Of The University Of California Blade coating on nanogrooved substrates yielding aligned thin films of high mobility semiconducting polymers

Also Published As

Publication number Publication date Type
EP1902439B1 (en) 2014-01-08 grant
EP2716677A1 (en) 2014-04-09 application
US20070017571A1 (en) 2007-01-25 application
US20140224331A1 (en) 2014-08-14 application
JP2009506519A (en) 2009-02-12 application
US7781673B2 (en) 2010-08-24 grant
EP1902439A4 (en) 2011-04-06 application
WO2007011739A2 (en) 2007-01-25 application
US20070158620A1 (en) 2007-07-12 application
WO2007011739A3 (en) 2009-04-23 application
US8058550B2 (en) 2011-11-15 grant
CA2614958A1 (en) 2007-01-25 application
US20070020526A1 (en) 2007-01-25 application
EP1902439A2 (en) 2008-03-26 application

Similar Documents

Publication Publication Date Title
Cui et al. Improvement of open-circuit voltage and photovoltaic properties of 2D-conjugated polymers by alkylthio substitution
Cho et al. Saturated and efficient red light-emitting fluorene-based alternating polymers containing phenothiazine derivatives
US6414104B1 (en) Arylamine-substituted poly (arylene vinylenes) and associated methods of preparation and use
Lee et al. Low band-gap polymers based on quinoxaline derivatives and fused thiophene as donor materials for high efficiency bulk-heterojunction photovoltaic cells
US20100326525A1 (en) Molecular semiconductors containing diketopyrrolopyrrole and dithioketopyrrolopyrrole chromophores for small molecule or vapor processed solar cells
US20110006287A1 (en) Polymers with tunable band gaps for photonic and electronic applications
EP2075274A1 (en) Soluble polythiophene derivatives
US20070246094A1 (en) Tandem photovoltaic cells
US20080006324A1 (en) Tandem Photovoltaic Cells
US20070267055A1 (en) Tandem Photovoltaic Cells
Chen et al. Synthesis and characterization of a narrow‐bandgap polymer containing alternating cyclopentadithiophene and diketo‐pyrrolo‐pyrrole units for solar cell applications
WO2011085004A2 (en) Photovoltaic cell with benzodithiophene-containing polymer
WO2012030942A1 (en) Photovoltaic cell containing novel photoactive polymer
Jung et al. Recent progress in high efficiency polymer solar cells by rational design and energy level tuning of low bandgap copolymers with various electron-withdrawing units
WO2007121252A2 (en) Tandem photovoltaic cells
US20100032018A1 (en) Novel Photoactive Polymers
US20080087324A1 (en) Photovoltaic Cell With Silole-Containing Polymer
US20080121281A1 (en) Photovoltaic Cell With Thiazole-Containing Polymer
CN101501862A (en) Polymers with low band gaps and high charge mobility
Hou et al. Synthesis and photovoltaic properties of the copolymers of 2-methoxy-5-(2′-ethylhexyloxy)-1, 4-phenylene vinylene and 2, 5-thienylene-vinylene
Xiang et al. Synthesis and characterization of porphyrin-terthiophene and oligothiophene π-conjugated copolymers for polymer solar cells
WO2010075512A1 (en) Polymers with bodipy-based backbone for solar cells
US20090299029A1 (en) Soluble polythiophene derivatives
Song et al. A low-bandgap alternating copolymer containing the dimethylbenzimidazole moiety
US20070131270A1 (en) Window with photovoltaic cell

Legal Events

Date Code Title Description
AS Assignment

Owner name: KONARKA TECHNOLOGIES, INC., MASSACHUSETTS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GAUDIANA, RUSSELL;KINGSBOROUGH, RICHARD;SHI, XIAOBO;AND OTHERS;REEL/FRAME:024117/0816

Effective date: 20060821

AS Assignment

Owner name: TOTAL GAS & POWER USA (SAS), FRANCE

Free format text: SECURITY AGREEMENT;ASSIGNOR:KONARKA TECHNOLOGIES, INC.;REEL/FRAME:027465/0192

Effective date: 20111005

AS Assignment

Owner name: MERCK PATENT GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MERCK KGAA;REEL/FRAME:029717/0065

Effective date: 20121120

Owner name: MERCK KGAA, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KONARKA TECHNOLOGIES, INC.;REEL/FRAME:029717/0048

Effective date: 20121102