AU2006311032B8 - Use of rylene derivatives as photosensitizers in solar cells - Google Patents

Use of rylene derivatives as photosensitizers in solar cells Download PDF

Info

Publication number
AU2006311032B8
AU2006311032B8 AU2006311032A AU2006311032A AU2006311032B8 AU 2006311032 B8 AU2006311032 B8 AU 2006311032B8 AU 2006311032 A AU2006311032 A AU 2006311032A AU 2006311032 A AU2006311032 A AU 2006311032A AU 2006311032 B8 AU2006311032 B8 AU 2006311032B8
Authority
AU
Australia
Prior art keywords
alkyl
radicals
mono
polysubstituted
aryl
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.)
Ceased
Application number
AU2006311032A
Other languages
English (en)
Other versions
AU2006311032A1 (en
AU2006311032B2 (en
AU2006311032A8 (en
Inventor
Tomas Edvinsson
Felix Eickemeyer
Peter Erk
Anders Hagfeldt
Andreas Herrmann
Martin Konemann
Alfred Kuhn
Chen Li
Klaus Mullen
Gero Nordmann
Neil Gregory Pschirer
Jianqiang Qu
Jan Schoneboom
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.)
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften
Original Assignee
Max Plank Der Wss E V Gesell zur Forderung
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften
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
Application filed by Max Plank Der Wss E V Gesell zur Forderung, BASF SE, Max Planck Gesellschaft zur Foerderung der Wissenschaften filed Critical Max Plank Der Wss E V Gesell zur Forderung
Publication of AU2006311032A1 publication Critical patent/AU2006311032A1/en
Application granted granted Critical
Publication of AU2006311032B2 publication Critical patent/AU2006311032B2/en
Publication of AU2006311032B8 publication Critical patent/AU2006311032B8/en
Publication of AU2006311032A8 publication Critical patent/AU2006311032A8/en
Ceased legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrane Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
AU2006311032A 2005-11-10 2006-11-06 Use of rylene derivatives as photosensitizers in solar cells Ceased AU2006311032B8 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005053995A DE102005053995A1 (de) 2005-11-10 2005-11-10 Verwendung von Rylenderivaten als Photosensibilisatoren in Solarzellen
DE102005053995.5 2005-11-10
PCT/EP2006/068102 WO2007054470A1 (de) 2005-11-10 2006-11-06 Verwendung von rylenderivaten als photosensibilisatoren in solarzellen

Publications (4)

Publication Number Publication Date
AU2006311032A1 AU2006311032A1 (en) 2007-05-18
AU2006311032B2 AU2006311032B2 (en) 2013-03-21
AU2006311032B8 true AU2006311032B8 (en) 2013-07-25
AU2006311032A8 AU2006311032A8 (en) 2013-07-25

Family

ID=37708221

Family Applications (1)

Application Number Title Priority Date Filing Date
AU2006311032A Ceased AU2006311032B8 (en) 2005-11-10 2006-11-06 Use of rylene derivatives as photosensitizers in solar cells

Country Status (9)

Country Link
US (2) US8231809B2 (enExample)
EP (1) EP1951842B1 (enExample)
JP (1) JP5393154B2 (enExample)
KR (1) KR101583382B1 (enExample)
CN (1) CN101351524B (enExample)
AU (1) AU2006311032B8 (enExample)
DE (1) DE102005053995A1 (enExample)
WO (1) WO2007054470A1 (enExample)
ZA (1) ZA200804950B (enExample)

Families Citing this family (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005021362A1 (de) * 2005-05-04 2006-11-09 Basf Ag Terrylen- und Quaterrylenderivate
JP5151192B2 (ja) * 2007-03-09 2013-02-27 Ｊｎｃ株式会社 ペリレン誘導体およびそれを用いた光電変換素子
CN101772492A (zh) * 2007-06-22 2010-07-07 巴斯夫欧洲公司 N,n’-双(1,1-二氢全氟-c3-c5烷基)苝-3,4:9,10-四羧酸二酰亚胺的用途
US8563855B2 (en) 2007-07-23 2013-10-22 Basf Se Tandem photovoltaic cell
EP2181096A1 (de) * 2007-07-23 2010-05-05 Basf Se Verwendung von rylenderivaten als aktive komponenten in solarzellen und photodetektoren
WO2009024512A1 (de) * 2007-08-17 2009-02-26 Basf Se Halogenhaltige perylentetracarbonsäurederivate und deren verwendung
AU2008320815B2 (en) * 2007-10-31 2014-07-03 Basf Se Use of halogenated phthalocyanines
CN102066374A (zh) * 2008-04-22 2011-05-18 巴斯夫欧洲公司 三取代和四取代的五并苯四羧酸二酰亚胺
WO2009141387A1 (de) * 2008-05-23 2009-11-26 Basf Se Chinoide rylendicarboximide als ir-absorber
US8618297B2 (en) 2008-07-25 2013-12-31 Basf Se Azide substituted naphthylene or rylene imide derivatives and their use as reagents in click-reactions
DE102009049696A1 (de) 2008-10-16 2010-04-22 Basf Se Verbindung mit einer Salzgruppe und einer p-Halbleitergruppe und deren Verwendung in Solarzellen
US20110297235A1 (en) 2009-02-23 2011-12-08 Basf Se Use of triarylamine derivatives as hole-conducting materials in organic solar cells and organic solar cells containing said triarylamine derivatives
KR101538133B1 (ko) 2009-03-10 2015-07-22 주식회사 동진쎄미켐 염료감응 태양전지 흡착 염료용액의 모니터링 장치 및 염료용액의 조절 장치
US9595678B2 (en) 2010-07-23 2017-03-14 Basf Se Dye solar cell with improved stability
US9087991B2 (en) 2011-02-01 2015-07-21 Basf Se Photovoltaic element
US9001029B2 (en) 2011-02-15 2015-04-07 Basf Se Detector for optically detecting at least one object
EP2676102B1 (en) 2011-02-15 2016-04-20 Basf Se Detector for optically detecting at least one object
AR086509A1 (es) * 2011-05-25 2013-12-18 Sicpa Holding Sa Tintes de quaterrileno y/o terrileno unidos a polimeros y composiciones que los contienen
DE102012211788A1 (de) 2011-07-11 2013-01-17 Basf Se Verfahren zur photokatalytischen Reduktion von Kohlendioxid unter Einwirkung von Sonnenlicht
MX2014006028A (es) 2011-11-23 2014-07-09 Sicpa Holding Sa Compuestos aromaticos policiclicos que contienen un atomo de s o un grupo s(=o)2 y su uso como tintes.
EP2812412A4 (en) * 2012-02-09 2015-10-14 Basf Se RYLENE MUNOIMID DERIVATIVES AND USE THEREOF AS PHOTOSENSITIZER IN SOLAR CELLS AND PHOTODETECTORS
US9054325B2 (en) 2012-02-09 2015-06-09 03;Basf Se Rylene monoimide derivatives and use thereof as photosensitizers in solar cells and photodetectors
US9343686B2 (en) * 2012-07-09 2016-05-17 Sharp Kabushiki Kaisha Compound, solar cell module, and solar power generation device
US8816081B2 (en) 2012-08-06 2014-08-26 Basf Se Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells
CN104603112B (zh) * 2012-08-30 2017-06-16 巴斯夫欧洲公司 经由多功能结构单元双给体官能化苝和萘单酰亚胺的迫位
AU2013365772B2 (en) 2012-12-19 2017-08-10 Basf Se Detector for optically detecting at least one object
WO2014111365A1 (en) * 2013-01-15 2014-07-24 Basf Se Triangulene oligomers and polymers and their use as hole conducting material
US9428518B2 (en) 2013-03-18 2016-08-30 Basf Se Perylenemonoimide and naphthalenemonoimide derivatives and their use in dye-sensitized solar cells
US9989623B2 (en) 2013-06-13 2018-06-05 Basf Se Detector for determining a longitudinal coordinate of an object via an intensity distribution of illuminated pixels
CN105452808A (zh) 2013-06-13 2016-03-30 巴斯夫欧洲公司 用于光学检测至少一个对象的取向的检测器
US9741954B2 (en) 2013-06-13 2017-08-22 Basf Se Optical detector and method for manufacturing the same
EP3036503B1 (en) 2013-08-19 2019-08-07 Basf Se Optical detector
WO2015024870A1 (en) 2013-08-19 2015-02-26 Basf Se Detector for determining a position of at least one object
EP2937399A1 (en) 2014-04-22 2015-10-28 Basf Se Hole-transport materials for organic solar cells or organic optical sensors
US10340082B2 (en) 2015-05-12 2019-07-02 Capacitor Sciences Incorporated Capacitor and method of production thereof
US10347423B2 (en) 2014-05-12 2019-07-09 Capacitor Sciences Incorporated Solid multilayer structure as semiproduct for meta-capacitor
US20170301477A1 (en) 2016-04-04 2017-10-19 Capacitor Sciences Incorporated Electro-polarizable compound and capacitor
JP6953306B2 (ja) 2014-05-12 2021-10-27 キャパシター サイエンシズ インコーポレイテッドＣａｐａｃｉｔｏｒ Ｓｃｉｅｎｃｅｓ Ｉｎｃｏｒｐｏｒａｔｅｄ エネルギー蓄積装置及びその製造方法
KR102397527B1 (ko) 2014-07-08 2022-05-13 바스프 에스이 하나 이상의 물체의 위치를 결정하기 위한 검출기
WO2016051323A1 (en) 2014-09-29 2016-04-07 Basf Se Detector for optically determining a position of at least one object
SG11201703441YA (en) 2014-11-04 2017-05-30 Capacitor Sciences Inc Energy storage devices and methods of production thereof
CN104672140A (zh) * 2014-11-21 2015-06-03 华中科技大学 一种多取代苝类衍生物及其制备方法
EP3230841B1 (en) 2014-12-09 2019-07-03 Basf Se Optical detector
CN107438775B (zh) 2015-01-30 2022-01-21 特里纳米克斯股份有限公司 用于至少一个对象的光学检测的检测器
US9852846B2 (en) 2015-02-26 2017-12-26 Capacitor Sciences Incorporated Self-healing capacitor and methods of production thereof
US9932358B2 (en) 2015-05-21 2018-04-03 Capacitor Science Incorporated Energy storage molecular material, crystal dielectric layer and capacitor
US9941051B2 (en) 2015-06-26 2018-04-10 Capactor Sciences Incorporated Coiled capacitor
WO2017012986A1 (en) 2015-07-17 2017-01-26 Trinamix Gmbh Detector for optically detecting at least one object
TWI565700B (zh) * 2015-08-24 2017-01-11 臺灣塑膠工業股份有限公司 具有苝酸酐骨架的光敏染料、包含其的光敏染料混合物及染料敏化太陽能電池
CN108141579B (zh) 2015-09-14 2020-06-12 特里纳米克斯股份有限公司 3d相机
US10026553B2 (en) 2015-10-21 2018-07-17 Capacitor Sciences Incorporated Organic compound, crystal dielectric layer and capacitor
US20170233528A1 (en) * 2016-02-12 2017-08-17 Capacitor Sciences Incorporated Sharp polymer and capacitor
US10305295B2 (en) 2016-02-12 2019-05-28 Capacitor Sciences Incorporated Energy storage cell, capacitive energy storage module, and capacitive energy storage system
US10153087B2 (en) 2016-04-04 2018-12-11 Capacitor Sciences Incorporated Electro-polarizable compound and capacitor
US9978517B2 (en) 2016-04-04 2018-05-22 Capacitor Sciences Incorporated Electro-polarizable compound and capacitor
CN109564927B (zh) 2016-07-29 2023-06-20 特里纳米克斯股份有限公司 光学传感器和用于光学检测的检测器
JP7114578B2 (ja) 2016-10-06 2022-08-08 ビーエーエスエフ ソシエタス・ヨーロピア ２－フェニルフェノキシ置換ペリレンビスイミド化合物およびそれらの使用
JP7241684B2 (ja) 2016-10-25 2023-03-17 トリナミクス ゲゼルシャフト ミット ベシュレンクテル ハフツング 少なくとも１個の対象物の光学的な検出のための検出器
JP2019532517A (ja) 2016-10-25 2019-11-07 トリナミクス ゲゼルシャフト ミット ベシュレンクテル ハフツング 光学的に検出するための光検出器
EP3571522B1 (en) 2016-11-17 2023-05-10 trinamiX GmbH Detector for optically detecting at least one object
US11860292B2 (en) 2016-11-17 2024-01-02 Trinamix Gmbh Detector and methods for authenticating at least one object
US10395841B2 (en) 2016-12-02 2019-08-27 Capacitor Sciences Incorporated Multilayered electrode and film energy storage device
US11060922B2 (en) 2017-04-20 2021-07-13 Trinamix Gmbh Optical detector
US11067692B2 (en) 2017-06-26 2021-07-20 Trinamix Gmbh Detector for determining a position of at least one object
CN113024568B (zh) * 2021-03-03 2022-08-23 宁德新能源科技有限公司 正极材料、电化学装置和电子装置
CN114843406B (zh) * 2022-04-02 2024-05-24 湖北文理学院 有机无机杂化钙钛矿薄膜的制备方法及半透明太阳能电池的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599408A (en) * 1980-05-05 1986-07-08 Hoechst Aktiengesellschaft Perylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimides
WO2002066438A1 (de) * 2001-02-20 2002-08-29 Basf Aktiengesellschaft Rylenderivate und deren verwendung als farbstoffe

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3149620A1 (de) * 1981-12-15 1983-07-21 Bayer Ag, 5090 Leverkusen Lichtsammelsysteme unter verwendung von halogenierten perylenderivaten als lichtwandler
DE3703513A1 (de) * 1987-02-05 1988-08-18 Langhals Heinz Wasserloesliche perylen-fluoreszenzfarbstoffe
CH674596A5 (enExample) 1988-02-12 1990-06-15 Sulzer Ag
US5530644A (en) 1992-05-20 1996-06-25 Fuji Xerox Co., Ltd. Data processing device
DE59407520D1 (de) * 1993-08-13 1999-02-04 Ciba Geigy Ag Perylenamidinimid-Farbstoffe, ein Verfahren zu deren Herstellung und deren Verwendung
DE19809840A1 (de) * 1996-09-28 1999-09-02 Forschungszentrum Juelich Gmbh Langzeitstabile, farbstoffsensibilisierte Solarzelle
DE19757312A1 (de) * 1996-09-28 1999-06-24 Forschungszentrum Juelich Gmbh Langzeitstabile, farbstoffsensibilisierte Solarzelle
JP3968809B2 (ja) 1996-12-19 2007-08-29 富士ゼロックス株式会社 湿式太陽電池用光半導体電極、湿式太陽電池及び光電変換方法
JP3968819B2 (ja) 1997-06-02 2007-08-29 富士ゼロックス株式会社 湿式太陽電池用光半導体電極、湿式太陽電池及び光電変換方法
JP2000100484A (ja) 1998-09-24 2000-04-07 Fuji Xerox Co Ltd 光半導体電極、光電変換装置及び光電変換方法
DE19848555A1 (de) * 1998-10-21 2000-04-27 Heinz Langhals Neue Fluoreszenzfarbstoffe durch Kern-Erweiterung von Perylen-3,4:9,10-tetracarbonsäurebisimiden
TW473400B (en) * 1998-11-20 2002-01-21 Asahi Chemical Ind Modified photocatalyst sol
DE19900063A1 (de) * 1999-01-04 2000-07-27 Heinz Langhals Naphthalin- und Perylenhydrazamimide - eine neue Klasse von Farbstoffen
JP4211120B2 (ja) 1999-02-19 2009-01-21 富士ゼロックス株式会社 光半導体電極、光電変換装置及び光電変換方法
US6359211B1 (en) 1999-06-17 2002-03-19 Chemmotif, Inc. Spectral sensitization of nanocrystalline solar cells
JP2001093589A (ja) * 1999-09-21 2001-04-06 Fuji Xerox Co Ltd 光半導体電極、光電変換装置及び光電変換方法
EP1176646A1 (en) 2000-07-28 2002-01-30 Ecole Polytechnique Féderale de Lausanne (EPFL) Solid state heterojunction and solid state sensitized photovoltaic cell
DE10039232A1 (de) * 2000-08-11 2002-02-21 Basf Ag Flüssigkristalline Perylen-3,4:9,10-tetracarbonsäurediimide
DE10308940A1 (de) * 2003-02-28 2004-09-23 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Wasserlösliche, fluoreszierende Perylentetracarbonsäurebisimide
WO2005089094A2 (en) * 2003-11-21 2005-09-29 The Board Of Regents Of The University And Community College System Of Nevada Materials and methods for the preparation of anisotropically-ordered solids
US7763727B2 (en) * 2004-03-29 2010-07-27 Mitsui Chemicals, Inc. Compound and organic electronic device using the same
DE102005021362A1 (de) * 2005-05-04 2006-11-09 Basf Ag Terrylen- und Quaterrylenderivate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599408A (en) * 1980-05-05 1986-07-08 Hoechst Aktiengesellschaft Perylene-3,4,9,10-tetracarboxylic acid monoanhydride monoimides
WO2002066438A1 (de) * 2001-02-20 2002-08-29 Basf Aktiengesellschaft Rylenderivate und deren verwendung als farbstoffe

Also Published As

Publication number Publication date
KR101583382B1 (ko) 2016-01-07
US20080269482A1 (en) 2008-10-30
EP1951842B1 (de) 2016-07-27
AU2006311032A1 (en) 2007-05-18
KR20080075864A (ko) 2008-08-19
JP5393154B2 (ja) 2014-01-22
DE102005053995A1 (de) 2007-05-24
WO2007054470A1 (de) 2007-05-18
US8231809B2 (en) 2012-07-31
CN101351524A (zh) 2009-01-21
AU2006311032B2 (en) 2013-03-21
US8501046B2 (en) 2013-08-06
JP2009515846A (ja) 2009-04-16
EP1951842A1 (de) 2008-08-06
AU2006311032A8 (en) 2013-07-25
CN101351524B (zh) 2015-01-21
ZA200804950B (en) 2010-02-24
US20120283432A1 (en) 2012-11-08

Similar Documents

Publication Publication Date Title
AU2006311032B2 (en) Use of rylene derivatives as photosensitizers in solar cells
US9385326B2 (en) Triangulene oligomers and polymers and their use as hole conducting material
JP2009528277A (ja) フッ素化されたリレンテトラカルボン酸誘導体及びそれらの使用
EP2181172A1 (de) Halogenhaltige perylentetracarbonsäurederivate und deren verwendung
WO2008132103A1 (de) Pentaphenylenderivate als photosensibilisatoren in solarzellen
AU2011216899B2 (en) Use of indanthrene compounds in organic photovoltaics
US8202994B2 (en) Pentarylene- and hexarylenetetracarboximides and preparation thereof
US9624375B2 (en) Boron containing perylene monoimides, a process for their production, their use as building blocks for the production of perylene monoimide derivatives, monoimide derivatives and their use in dye-sensitized solar cells
US8083971B2 (en) Use of rylene derivatives as active components in solar cells and photodetectors
CN101384655A (zh) 氟化萘嵌苯四甲酸衍生物及其用途
WO2008119797A1 (de) Dinaphthoquaterrylen als photosensibilisatoren in solarzellen
KR20150041069A (ko) 붕소 함유 페릴렌 모노이미드, 이의 제조 방법, 페릴렌 모노이미드 유도체의 제조를 위한 구성 블록으로서의 이의 용도, 모노이미드 유도체 및 염료-감응형 태양 전지에서의 이의 용도

Legal Events

Date Code Title Description
TH Corrigenda

Free format text: IN VOL 27 , NO 11 , PAGE(S) 1515 UNDER THE HEADING APPLICATIONS ACCEPTED - NAME INDEX UNDER THE NAME MAX-PLANCK-GESELLSCHAFT ZUR FORDERUNG DER WISSENSCHAFTEN E.V, APPLICATION NO. 2006311032, UNDER INID (71) CORRECT THE APPLICANT NAME TO MAX-PLANCK-GESELLSCHAFT ZUR FORDERUNG DER WISSENSCHAFT E.V.

Free format text: IN VOL 22 , NO 21 , PAGE(S) 2535 UNDER THE HEADING PCT APPLICATIONS THAT HAVE ENTERED THE NATIONAL PHASE - NAME INDEX UNDER THE NAME MAX-PLANCK-GESELLSCHAFT ZUR FORDERUNG DER WISSENSCHAFTEN E.V, APPLICATION NO. 2006311032, UNDER INID (71) CORRECT THE APPLICANT NAME TO MAX-PLANCK-GESELLSCHAFT ZUR FORDERUNG DER WISSENSCHAFT E.V.

FGA Letters patent sealed or granted (standard patent)
MK14 Patent ceased section 143(a) (annual fees not paid) or expired