EP0000829B1 - Elément transducteur photo-électrique - Google Patents

Elément transducteur photo-électrique Download PDF

Info

Publication number
EP0000829B1
EP0000829B1 EP78300233A EP78300233A EP0000829B1 EP 0000829 B1 EP0000829 B1 EP 0000829B1 EP 78300233 A EP78300233 A EP 78300233A EP 78300233 A EP78300233 A EP 78300233A EP 0000829 B1 EP0000829 B1 EP 0000829B1
Authority
EP
European Patent Office
Prior art keywords
compound
electron acceptor
photovoltaic element
layer
layers
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.)
Expired
Application number
EP78300233A
Other languages
German (de)
English (en)
Other versions
EP0000829A1 (fr
Inventor
Ching Wan Tang
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
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 Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0000829A1 publication Critical patent/EP0000829A1/fr
Application granted granted Critical
Publication of EP0000829B1 publication Critical patent/EP0000829B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/652—Cyanine dyes
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • 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

Definitions

  • This invention relates to photovoltaic elements useful for converting light into electrical energy.
  • Schottky barrier and P-N junction photocells rely upon the fact that a built-in-potential exists at the metal/semiconductor interface as in the Schottky device or at the junction between the P-type and N-type semiconductors as in the P-N junction device.
  • Inorganic semiconductors have been used in the past for solar cells because of their fairly high conversion efficiencies which have been as high as 12 to 15 percent.
  • such cells have proven to be very expensive to construct because of the melt and other processing techniques necessary to fabricate the semiconductor layer.
  • Such cells have had extensive practical utility only in the field of space exploration, and not in terrestrial applications.
  • Phthalocyanine has been used in organic solar cells in the past in contact with a layer containing an electron acceptor such as oxidized tetramethyl p-phenylenediamine, A-carotene, dibrominated p-phenylenediamine and p-chloranil.
  • an electron acceptor such as oxidized tetramethyl p-phenylenediamine, A-carotene, dibrominated p-phenylenediamine and p-chloranil.
  • An example is described in U.S. Patent 3,057,947 in which a layer of compressed magnesium phthalocyanine 1 mm (1000 microns) thick is coated with a layer of air- oxidised tetramethyl-p-phenylene-diamine. It is assumed that there exists a rectifying junction between these layers. Electrodes, one of them transparent, are placed in contact with each layer. Such photovoltaic cells have thick layers, very high internal resistance and very low power outputs.
  • Multilayer photoelectric cells have been constructed from a layer comprising a phthalocyanine dispersed in an organic polymeric binder with or without an overcoat of malachite green, as reported, for example, in Topics in Current Chemistry, Springer-Verlag, Volume 61, 1976, page 124, and U.S. Patent 3,789,216, issued January 29, 1974.
  • the conversion efficiency of such cells was very low - less than 10- 4 percent, as reported in Springer-Verlag.
  • a layer of porphyrin has been used to improve certain inorganic photovoltaic cel!s e.g., selenium cells. Examples are disclosed in U.S. Patent 3,935,031. However, only expensive inorganic semiconductors which themselves are self-sufficient cell materials have been suggested for such use with porphyrin.
  • a photovoltaic element which comprises
  • each of said organic compounds has a molecule whose surface area is at least 0.4 nm 2 and a width of at least 0.5 nm.
  • the electron acceptor has a molecule containing a nucleus having at least 7 fused carbocyclic and/or heterocyclic rings and the electron donor has a molecule containing a nucleus having at least 8 fused carbocyclic and/or heterocyclic rings.
  • the surface area of the molecule is calculated by assuming the atoms are points connected by a bond of appropriate length, i.e. 0.139 nm in a benzene ring. Hence the surface area of benzene is 0.05 nm 2 .
  • the effective area is greater than the area as calculated above. In such a case, it is the effective area which should be taken and this will normally be some 30% greater than the calculated area.
  • the electron donor is a porphyrin or phthalocyanine and the electron acceptor is a photoconductive organic dye capable of absorbing radiation at wavelengths between 350 and 1000 nm.
  • photovoltaic element means a solid state device which converts radiation absorbed by the element directly to electric power.
  • the elements of this invention are suitable as terrestrial rooftop generators (solar cells) or as light-level measuring devices.
  • the element may be used both at high and low light levels.
  • the elements exhibit moderately high open circuit voltages of from 300-500 mV.
  • the element may also be used in the current mode.
  • the current generated in a diffuse room-light condition is about 20 fL A/cm 2 , a large enough current to be measured accurately.
  • the current can thus become a measure of the light intensity, and the cell can be used as an exposure meter.
  • the photovoltaic elements of the present invention are capable of working at conversion efficiencies of at least 0.02% and, for example, as high as 1%.
  • an electron donor has a relatively low electron affinity
  • an electron acceptor has a relatively high electron affinity.
  • an electron donor tends to act as a p-type semi- conductor whereas an electron acceptor tends to act as an n-type semi-conductor.
  • rectifying junction means a junction which provides a ratio of forward current to reverse current of at least 10 when a potential of at least 0.5 V is applied to the element.
  • Polycyclic is used in the present specification and claims to mean containing two or more rings which may be fused or not.
  • planar used in the present specification and claims we mean that the atoms of the nucleus lie in the same plane or that any atom of the nucleus or a resonance form thereof lies no more than 10° out of the plane
  • the photovoltaic elements made from coatings of the above compounds will be generally free from short circuits between the electrodes due to pinholes in the coatings.
  • the planar polycyclic nuclei of the compounds are highly conjugated, have pi-electrons and have a large surface area.
  • the larger the molecular surface area of such compounds the more likely it is that the compounds will provide an element with high conversion efficiencies. It is believed that this greater area provides greater assurance of molecular overlap hence less likelihood of pinhole shorts.
  • Examples of useful electron donor compounds with planar, fused polycyclic nuclei are the porphyrin and phthalocyanine compounds. Any such compound is operative, with or without a chelated metal atom.
  • the chelated metal if present, may be cobalt, magnesium, zinc, palladium, nickel, copper, lead, or platinum.
  • Such metal phthalocyanines are preferred for this invention because of the greater conversion efficiencies which they confer on the element.
  • Examples of preferred metal phthalocyanines include copper, lead and platinum phthalocyanine.
  • Lead phthalocyanine has been used to produce an efficient cell with a spectral response extending to almost 1000 nm. It is preferred that an electron donor layer containing a porphyrin be structureless or micro-crystalline, because large crystals in such a layer tend to provide a shorting path which can decrease the efficiency of the element.
  • porphyrin or phthalocyanine compound means any compound, natural or synthetic, which contains the basic porphyrin or phthalocyanine structure. Examples of such porphyrins are disclosed in the aforesaid U.S. Patent 3,935,031. A preferred class of such compounds are those having the formula: wherein
  • One further option is to use compounds of Formula IV, but in a nonmetallic form, wherein two of the four nitrogen atoms associated with M are hydrogenated.
  • two electron donor layers of the same or different electron donor compounds may be used. Only one of these layers contacts the electron acceptor layer, while the other is in ohmic contact with an electrode.
  • Other useful compounds for the electron donor layer are compounds which contain at least 8 carbocyclic and/or heterocyclic fused rings. Examples include ovalene, diindeno [1,2,3-cd-1'2'3'-Im]perylene. violanthrene, isoviolanthrene, and pyranthrene.
  • Perylene derivatives which are particularly useful as electron acceptor compounds have the formula: wherein
  • Examples of compounds of formula II are: and, preferably
  • the electron acceptor compound may comprise 7-14 fused carbocyclic and/or heterocyclic rings which may be substituted with one or more electron withdrawing groups such as keto; cyano; halogen, e.g. chlorine or bromine; sulphonyl; carboxy, nitro; imino; alkyl or alkoxy containing from 1 to 5 carbon atoms, for example, methyl, ethyl, propyl; hydroxyl; amino; aryl containing from 6 to 10 carbon ring atoms which may be substituted e.g., phenyl, naphthyl or halo-, alkyl- or alkoxyphenyl; provided that the compound contains at least one electron-withdrawing group.
  • electron withdrawing groups such as keto; cyano; halogen, e.g. chlorine or bromine; sulphonyl; carboxy, nitro; imino; alkyl or alkoxy containing from 1 to 5 carbon atoms, for example, methyl, e
  • fused polycyclic compounds of this type are anthraquinone-derived vat dyes such as flavanthrone and derivatives of perylene, coronone-imide, ovalene and compounds of the structure: where E is 0 or S.
  • polycyclic compounds which may be used in electron acceptor layers include those in which the polycyclic rings are not fused.
  • Particularly useful examples are photoconductive organic dyes such as pyrylium-type dye salts which include pyrylium, thiapyrylium and selenapyrylium dye salts, and also salts of the aforementioned pyrylium-type dye salts containing condensed ring systems such as salts of benzopyrylium and naphthopyrylium dyes.
  • Highly preferred examples have a molecule having a surface area of at least 0.4 nm 2 and a width in the plane of the compound of at least 0.5 nm.
  • pyrylium-type dyes which may be used are those with the formula: wherein
  • Examples of anions Z- are perchlorate and fluoroborate.
  • R l , R 2 , R 3 or R 4 are substituted phenyl, it is preferred that thesubstituents be located in the para position and be selected from those which shift the blue absorption peak of the dye salt to a longer wavelength.
  • substituents include alkyl having from 1 to 3 carbon atoms and halogens e.g. chlorine or fluorine.
  • Another class of useful polycyclic compounds of the unfused type includes 2,4,6-trisubstituted pyrylium, thiapyrylium and selenapyrylium dye salts of the general structure: in which
  • pyrylium-type dyes which may be employed as the electron acceptor include:
  • the electron acceptor layer may comprise a mixture of different dye salts of formula (I), or one or more dye salts of formula (I) with one or more dye salts of formula (V). In some instances synergism has been demonstrated, in that the conversion efficiency of the mixture exceeds that obtainable from using either of the dye salts alone.
  • More than one electron acceptor layer may be employed. They may comprise different compounds or the same compound as used in the first electron acceptor layer.
  • the thickness of the combined electron donor and acceptor layers is an important aspect of the photovoltaic elements of the invention. It has been found that efficiencies begin to decrease drastically for a thickness in excess of 0.5 micron. This decrease in efficiency is believed to be caused by decreased penetration of light to the region adjacent the rectifying junction, or by increased electrical resistance within the layers. Minimum thickness for the individual layers appears to be dictated by coating techniques and the minimum that can be used without shorting out. Useful devices of good efficiency have been constructed with thicknesses for each of the two layers as low as 10 nm.
  • Preferred thicknesses for each of the two layers, for optimum photovoltaic element results, are from 30 to 50 nm. If unequal thicknesses are to be used, it is preferred that the thinner layer be adjacent the transparent electrode to permit the best exposure of the rectifying junction to radiation.
  • the electrodes are in operative ohmic contact, one to the electron donor layer and the other to the electron acceptor layer.
  • the preferred construction is one in which the electrodes are in actual physical contact with their respective donor or acceptor layers, this need not alway be the case.
  • the electron donor layer which contributes to the formation of the rectifying junction can be spaced away from its electrode by a second electron donor layer, as indicated above.
  • an electrode which is operative is one which is connected in a manner that does not short circuit the element.
  • the electrode adjacent to the electron donor layer preferably has a high work function, while the one adjacent to the electron acceptor layer preferably has a low work function.
  • a preferred electrode adjacent to the electron donor layer is a glass or a transparent film such as poly(ethylene terephthalate) coated with a transparent layer of indium tin oxide, tin oxide or nickel.
  • This electrode not only has a high work function, but is transparent.
  • Examples of such electrodes having a glass support are Nesa and Nesatron glass electrodes manufactured by PPG Industries and having a surface resistivity of about 10 to 50 ohms/square and an optical transmittance of about 80 percent, for visible light. Nesa and Nesatron are trademarks of PPG Industries.
  • the opposite electrode is preferably a metal with a low work function, such as indium, silver, tin or. aluminium and can be transparent or opaque. Silver is a preferred electrode for minimum loss in conversion efficiency upon aging.
  • a photovoltaic element according to the present invention is shown in enlarged cross-section in the accompanying drawing and comprises a laminar array 10 of a window electrode 12 comprising a transparent support 14 and a transparent electrically conductive layer 16; an electron donor layer 18, an electron acceptor layer 20 and an electrode 22 of a metal in ohmic contact with layer 20.
  • a laminar array 10 of a window electrode 12 comprising a transparent support 14 and a transparent electrically conductive layer 16; an electron donor layer 18, an electron acceptor layer 20 and an electrode 22 of a metal in ohmic contact with layer 20.
  • Preferred thicknesses for the layers comprise, for layer 16, 0.5 micron to 5 microns; for layer 18, 10 to 250 nm; for layer 20, 10 to 250 nm; and for electrode 22, 10 to 200 nm.
  • the combined thicknesses of layers 18 and 20 do not exceed 0.5 micron.
  • Wires 24 represent leads contacting the electrodes to connect the element to a load circuit.
  • a preferred technique for making the present photovoltaic elements involves forming the electron donor layer and the electron acceptor layer (forming the rectifying junction) by coating them from two different solvents, one upon the other, the solvent for one being a poor solvent for the other. In this manner, a well-defined interface between the two layers will be maintained.
  • An alternative and highly preferred method is to vapor deposit a porphyrin or phthalocyanine electron donor layer on a clean, i.e. polished, window electrode (using electron donor compounds which are reasonably free of decomposable impurities) and thereafter solvent coat a dye salt electron acceptor layer, for example, by spin coating it at between 1,000 and 10,000 rpm from the solvents 1,2-dichloroethane, dichloromethane or mixtures of the two.
  • a particularly useful solvent mixture has been, 49 weight percent 1,2-dichloroethane, 49 weight percent dichloromethane, and 2 weight percent 1,1,1,3,3,3-hexafluoroisopropyl alcohol.
  • This solvent mixture is employed for spin-coating throughout the Examples below.
  • a currently preferred process for polishing the Nesatron glass comprises rubbing the Nesatron glass surface with a cotton flannel wetted with a suspension of an alumina or other abrasive.
  • the polished Nesatron glass is then cleaned in an ultrasonic cleaner containing 1:1 H 2 0/isopropyl alcohol for about a half an hour to remove the abrasive particles. It can then be rinsed thoroughly with distilled water.
  • the electrode for the electron acceptor containing the dye salt layer is preferably applied by conventional vapor deposition techniques.
  • the voltage across the element and the current through it were measured by a multimeter and were simultaneously plotted usiung an x-y recorder.
  • Fill Factor (as defined by Hovel supra) is the fraction of the product of the short circuit current and open circuit voltage which is available as power output.
  • the element Under the simulated sunlight illumination described above (75 mW/cm 2 ), the element developed an open-circuit voltage of 0.36 volt, a short-circuit current of 2 mA/cm 2 , and a fill factor of 0.47. The power conversion efficiency was 0.45 percent.
  • Dye salts having the formula: wherein the R 30 and R 31 substituents are para and as identified in Table II below were tested as electron acceptor compounds in photovoltaic elements as described in Example 1. Table II lists the output of these elements.
  • Metal-free phthalocyanine and a number of metal-phthalocyanines were tested as electron donor compounds in photovoltaic elements as described in Example 1. Phthalocyanine layers of thickness ranging from 30 to 50 nm were deposited on clean Nesatron glass electrode. Then a 40 to 50 nm thick electron acceptor layer consisted of 4-[(2,6-diphenyl-4H-thiapyran-4-ylidene)methyl]-2,6-diphenyl- thiapyrylium perchlorate. Table III lists the output of these elements.
  • a 40 to 50 nm thick Cu-phthalocyanine electron donor layer was deposited on a clean Nesatron glass electrode by vapor deposition. Then a 40 to 50 nm thick layer containing a 1:1 by weight mixture of 4-[(2,6-diphenyl-4H-pyran-4-ylidene)methyl]-2,6-diphenylpyrylium perchlorate and 4-[(2,6-diphenyl-4H-thiapyran-4-ylidene)methyl]-2,6-diphenylthiapyrylium perchlorate, was spin-coated on top of the Cu-phthalocyanine layer to form an electron acceptor layer. Indium was the other electrode. Under artifical illumination, as described in Example 1, the element developed an open-circuit voltage of 0.43 volt, a short-circuit current of 2 mA/cm 2 , and a fill factor of 0.44, giving an efficiency of 0.5 percent.
  • Example 20 was repeated, except that a 1:1 mixture of 4-[(2,6-diphenyl-4H-thiapyran-4-ylidene)-methyl]-2,6-diphenylthiapyrylium perchlorate and 2,6-diphenyl-4-(4-dimethylaminophenyl)thiapyrylium perchlorate was used to form the electron acceptor layer.
  • the conversion efficiency was found to be about 0.5 percent.
  • the element was quite stable under prolonged illumination. After subjecting the element to a 90-hour exposure to the 75 mW/cm 2 illumination described above, the element reached an efficiency of 0.23 to 0.25 percent, with no evidence of further degradation.
  • step (c) An element was fabricated as described in Example 1, but the dye salt used in step (c) was the following:
  • the element had an open-circuit voltage of 0.5 V, a short-circuit current of 0.2 mA/cm 2 , a fill factor of 0.28, and an efficiency of 0.05 percent.
  • Example 1 was repeated, except that the dye salt used was the following:
  • the element had an open-circuit voltage of 0.5 V, a short-circuit current of 0.24 mA/cm 2 , a fill factor of 0.34, and a conversion efficiency of 0.05 percent.
  • Table IV lists the output of these elements for various substitutions at Q, X, and R.
  • a photovoltaic element was prepared and tested as described in Example 1, except that the electron acceptor layer, at a thickness of 40 nm, was:
  • This element was found to have an open-circuit voltage of about 0.52 V, a short-circuit current of about 1 mA/cm 2 , and a fill factor of 0.40, producing a conversion efficiency of about 0.27 percent.
  • a photovoltaic element was prepared and tested as described in Example 1, except that as the electron acceptor layer a compound of the structure: wherein R 14 and R 15 are as designated in Table V, was used in place of the photoconductive dye salt of Example 1, and a silver electrode was used in place of indium. Table V sets forth the resulting element properties.
  • Photovoltaic elements were prepared and illuminated as described in Examples 29-36, except for the electron acceptor.
  • the identity of each electron acceptor compound dyes and the results are given in Table VI.
  • Example 2 an element was prepared and tested, as described in Example 1, except that in place of copper-phthalocyanine, ovalene was used, silver Was used in place of indium, and each of the electron donor and electron acceptor layers was 50 nm thick. The resulting element had a conversion efficiency of about 0.1 percent.
  • An element was prepared and illuminated as described in Example 1, except that the electron donor was diindeno[1,2,3-cd-1'2'3'-Im]perylene and the electron acceptor was flavanthrone.
  • the resulting element had an open-circuit voltage of 825 mV, a short-circuit current of 0.8 mA/cm 2 , a fill factor of 0.51, and a conversion efficiency of 0.46 percent.

Landscapes

  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Bipolar Transistors (AREA)

Claims (9)

1. Elément photovoltaïque qui comprend:
1) un première couche contenant un composé organique donneur d'électrons en contact avec
2) une deuxième couche contenant un composé organique accepteur d'électrons,

ces couches formant entre elles une jonction redresseuse et au moins l'une de ces couches pouvant absorber des radiations de longueurs d'onde comprises entre 350 nm et 1000 nm et
3) une électrode en contact ohmique effectif avec chacune de ces couches, au moins l'une de ces électrodes étant transparente au rayonnement électromagnétique auquel est sensible l'élélement photovoltaïque,

caractérisé en ce que le composé organique de chacune des couches (1) et (2) a une molécule comprenant un noyau polycyclique plan et en ce que l'épaisseur totale de la couche ou des couches contenant le composé donneur d'électrons et de la couche ou des couches contenant le composé accepteur d'électrons est au plus égale à 0,5 µm.
2. Elément photovoltaïque conforme à la revendication 1, caractérisé en ce que les composés donneur et accepteur d'électrons ont une molécule dont la surface est d'au moins 0,4 nm2 et dont la largeur est d'au moins 0,5 nm.
3. Elément photovoltaïque conforme à l'une des revendications 1 ou 2, caractérisé en ce que le composé accepteur d'électrons a une molécule contenant un noyau ayant au moins 7 cycles carbocycliques et/ou hétérocycliques accolés et le composé donneur d'électrons a une molécule contenant un noyau ayant au moins 8 cycles carbocycliques et/ou hétérocyclique accolés.
4. Elément photovoltaïque conforme à l'une des revendications 1 ou 2, caractérisé en ce que le composé donneur d'électrons est une porphyrine ou une phtalocyanine et le composé accepteur d'électrons est un colorant organique photoconducteur capable d'absorber des radiations de longueurs d'onde comprises entre 350 nm et 1000 nm.
5. Elément photovoltaïque conforme à l'une des revendications 1, 2, ou 4, caractérisé en ce que le composé accepteur d'électrons est un sel de pyrylium, de thiapyrylium ou de sélénapyrylium.
6. Elément photovoltaïque conforme à la revendication 5, caractérisé en ce que le composé accepteur d'électrons est un composé de formule:
Figure imgb0031
où
J est le groupe CR10 ou un atome d'azote
Q et X représentent chacun un atome d'oxygène, de soufre ou de sélénium,
R8, R9 et R10 représentent chacun un atome d'hydrogène, un radical alkyle de 1 à 3 atomes de carbone, un radical aryle, aryle substitué, cyano ou nitro,
R1, R2, R3 et R4 représentent chacun un radical phényle, phényle substitué ou un radical alkyle ou alkoxy de 1 à 5 atomes de carbone, au moins deux des symboles RI, R2, R3 et R4 étant des radicaux phényle substitué ou non,
m est égal à 1 ou 0 et m est égal à 0 si J est un atome d'azote, et
Z- est un anion.
7. Elément photovoltaïque conforme à l'une quelconque des revendications 1 à 4, caractérisé en ce que le composé accepteur d'électrons est un composé de formule:
Figure imgb0032
où
R14 et R15 représentent chacun un atome d'hydrogène ou un radical alkyle de 1 à 5 atomes de carbone qui peut être substitué, ou un groupe phényle, phényle substitué ou quinolyle, et
R16, R17, R18 et R19 représentent chacun un atome d'oxygène, ou bien R14 et un des symboles R16 et R17 et/ou R15 et un des symboles R18 et R19 forment ensemble un groupe hétérocyclique à un ou deux cycles et, dans ce cas, l'autre des symboles R16 et R17 et/ou l'autre des symboles R18 et R19 représente un atome d'oxygène.
8. Elément photovoltaïque conforme à la revendication 7, caractérisé en ce que le composé accepteur d'électrons est un composé de formule:
Figure imgb0033
9. Elément photovoltaïque conforme à l'une quelconque des revendications 1 à 8, caractérisé en ce que le composé donneur d'électrons est un composé de formule:
Figure imgb0034
où
L est le groupe CH ou un atome d'azote,
M est un métal,
T1 et T2 sont tous deux des atomes de soufre ou tous deux un groupe CH, ou bien l'un des symboles T1 et T2 est un atome d'azote, et l'autre le groupe CH,
X1 et X2 sont identiques ou différents et représentent chacun un atome d'halogène ou d'hydrogène,
Z1 représente les atomes nécessaires pour compléter un cycle non saturé de 6 atomes.
EP78300233A 1977-08-02 1978-08-02 Elément transducteur photo-électrique Expired EP0000829B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US82111577A 1977-08-02 1977-08-02
US821115 1977-08-02

Publications (2)

Publication Number Publication Date
EP0000829A1 EP0000829A1 (fr) 1979-02-21
EP0000829B1 true EP0000829B1 (fr) 1982-01-06

Family

ID=25232560

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300233A Expired EP0000829B1 (fr) 1977-08-02 1978-08-02 Elément transducteur photo-électrique

Country Status (5)

Country Link
EP (1) EP0000829B1 (fr)
JP (1) JPS5427787A (fr)
AU (1) AU521118B2 (fr)
CA (1) CA1085947A (fr)
DE (1) DE2861508D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2222847C1 (ru) * 2002-10-21 2004-01-27 Государственное предприятие "Центр технологий микроэлектроники" Наносенсорная система

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2947797A1 (de) * 1979-11-28 1981-07-30 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung elektrisch leitfaehiger polyene und deren verwendung in der elektrotechnik und zur antistatischen ausruestung von kunststoffen
EP0047027A1 (fr) * 1980-08-22 1982-03-10 BBC Aktiengesellschaft Brown, Boveri & Cie. Mélange de cristaux liquides
JPS5940647A (ja) * 1982-05-05 1984-03-06 カナデイアン・パテンツ・アンド・デイベロツプメント・リミテツド 感光性分子
US4717673A (en) * 1984-11-23 1988-01-05 Massachusetts Institute Of Technology Microelectrochemical devices
JPS61200996A (ja) * 1985-03-04 1986-09-05 Agency Of Ind Science & Technol 有機導電体結晶の製造方法
JPH0719925B2 (ja) * 1985-03-05 1995-03-06 株式会社東芝 導電性薄膜
JPH02294257A (ja) * 1989-05-08 1990-12-05 Japan Servo Co Ltd 回転子
JP2001518078A (ja) * 1997-03-05 2001-10-09 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド クラウンエーテル誘導化ペリレン
US20070290195A1 (en) * 2005-08-22 2007-12-20 Stephen Forrest Increased open-circuit-voltage organic photosensitive devices
JP2008135540A (ja) * 2006-11-28 2008-06-12 Sanyo Electric Co Ltd 有機光電変換素子
DE102009051142B4 (de) 2009-06-05 2019-06-27 Heliatek Gmbh Photoaktives Bauelement mit invertierter Schichtfolge und Verfahren zu seiner Herstellung
DE102009038633B4 (de) 2009-06-05 2019-07-04 Heliatek Gmbh Photoaktives Bauelement mit organischen Doppel- bzw. Mehrfachmischschichten
DE102009024956A1 (de) * 2009-06-05 2010-12-09 Technische Universität Dresden Invertierte oder transparente organische Solarzelle oder Photodetektor mit verbesserter Absorption
WO2011015550A1 (fr) 2009-08-03 2011-02-10 Heliatek Gmbh Système évaporateur pour des couches et composants organiques
DE102010028945A1 (de) 2009-10-29 2010-12-09 Heliatek Gmbh Anwendungen für organische Photovoltaik
WO2011064330A1 (fr) 2009-11-27 2011-06-03 Heliatek Gmbh Composant photoactif organique à système de couche(s) à cavité
ES2587082T3 (es) 2009-12-16 2016-10-20 Heliatek Gmbh Elemento de construcción fotoactivo con capas orgánicas
DE102010007403A1 (de) 2010-02-09 2011-08-11 heliatek GmbH, 01139 Aufdampfparameter für organische Solarzellen
EP2385556B1 (fr) 2010-05-04 2021-01-20 Heliatek GmbH Composant photo-actif doté de couches organiques
EP2398056B1 (fr) 2010-06-21 2016-03-02 Heliatek GmbH Cellule solaire organique dotée de plusieurs systèmes de couches de transport
DE102012103448B4 (de) 2012-04-19 2018-01-04 Heliatek Gmbh Verfahren zur Optimierung von in Reihe geschalteten, photoaktiven Bauelementen auf gekrümmten Oberflächen
DE102012105812A1 (de) 2012-07-02 2014-01-02 Heliatek Gmbh Elektrodenanordnung für optoelektronische Bauelemente
DE102012105809B4 (de) 2012-07-02 2017-12-07 Heliatek Gmbh Organisches optoelektronisches Bauelement mit transparenter Gegenelektrode und transparenter Elektrodenvorrichtung
JP6449766B2 (ja) 2012-07-02 2019-01-09 ヘリアテク ゲゼルシャフト ミット ベシュレンクテル ハフツングＨｅｌｉａｔｅｋ Ｇｍｂｈ 光電子デバイス用透明電極
DE102012105810B4 (de) 2012-07-02 2020-12-24 Heliatek Gmbh Transparente Elektrode für optoelektronische Bauelemente
JP6995596B2 (ja) * 2017-12-08 2022-01-14 住友化学株式会社 光電変換素子

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3057947A (en) * 1959-10-01 1962-10-09 Calvin Melvin Photoelectric cell using organic materials
US3403165A (en) * 1963-11-19 1968-09-24 American Cyanamid Co Tetrathiotetracene ion-radical salts
US3379742A (en) * 1965-06-18 1968-04-23 American Cyanamid Co Process for preparing transformed 1:1 complex of 1, 6-diaminopyrene-p-chloranil
US3814600A (en) * 1970-06-30 1974-06-04 Eastman Kodak Co Electrophotographic element
JPS50942A (fr) * 1973-05-07 1975-01-08
NL7310500A (nl) * 1973-07-30 1975-02-03 Oce Van Der Grinten Nv Elektrofotografisch, donor-acceptor complex bevattend reproduktie-element, beelddrager, werkwijze ter bereiding van een preparaat, genitreerde 11h-pyrido (2,1-b) chinazolin-11-on verbindingen alsmede een werkwijze ter bereiding daarvan.
DE2353639C2 (de) * 1973-10-26 1983-08-04 Hoechst Ag, 6230 Frankfurt Elektrophotographisches Aufzeichnungsmaterial
GB1572181A (en) * 1975-08-18 1980-07-23 Ici Ltd Device comprising a thin film of organic materila

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2222847C1 (ru) * 2002-10-21 2004-01-27 Государственное предприятие "Центр технологий микроэлектроники" Наносенсорная система

Also Published As

Publication number Publication date
AU521118B2 (en) 1982-03-18
EP0000829A1 (fr) 1979-02-21
AU3854378A (en) 1980-02-07
CA1085947A (fr) 1980-09-16
JPS624871B2 (fr) 1987-02-02
DE2861508D1 (en) 1982-02-25
JPS5427787A (en) 1979-03-02

Similar Documents

Publication Publication Date Title
EP0000829A1 (fr) Elément transducteur photo-électrique
US4164431A (en) Multilayer organic photovoltaic elements
US4281053A (en) Multilayer organic photovoltaic elements
CA1096022A (fr) Cellule photovoltaique
Whitlock et al. Investigations of materials and device structures for organic semiconductor solar cells
CA1089065A (fr) Pile photovoltaique
US4125414A (en) Organic photovoltaic elements
US4127738A (en) Photovoltaic device containing an organic layer
JP3505414B2 (ja) 光化学電池およびその製造法
AU2003252477B2 (en) Solar cell
JPH08236166A (ja) 電荷輸送媒体および該媒体を含有する電気化学的電池
Shichiri et al. Three-Layer Organic Solar Cell.
JPS6028278A (ja) 光電変換素子
Antohe et al. Three-layered photovoltaic cell with an enlarged photoactive region of codeposited dyes
Antohe Electrical and photoelectrical properties of the single-, and multilayer organic photovoltaic cells
EP0000830B1 (fr) Elément transducteur photo-électrique
King et al. Measurement precautions for high-resistivity silicon solar cells
JPH01208873A (ja) 光電変換素子
JPH01154571A (ja) 光電変換素子
JP2947593B2 (ja) 積層型有機太陽電池
JPH05129643A (ja) 有機光起電力素子
Zhang Enhancing the open-circuit voltage of dye-sensitized solar cells: coadsorbents and alternative redox couples
Di Marco et al. Organic Photoconductors and Photovoltaics
JPH05259493A (ja) 有機光起電力素子
JPH01165177A (ja) 光電変換素子

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 2861508

Country of ref document: DE

Date of ref document: 19820225

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840808

Year of fee payment: 7

Ref country code: DE

Payment date: 19840808

Year of fee payment: 7

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19860430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19860501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT