WO2004008554A2 - Chelates metalliques - Google Patents

Chelates metalliques Download PDF

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WO2004008554A2
WO2004008554A2 PCT/GB2003/003035 GB0303035W WO2004008554A2 WO 2004008554 A2 WO2004008554 A2 WO 2004008554A2 GB 0303035 W GB0303035 W GB 0303035W WO 2004008554 A2 WO2004008554 A2 WO 2004008554A2
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metal
iii
rare earth
different
quinolate
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WO2004008554A3 (fr
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Poopathy Kathirgamanathan
Juan ANTIPÁN-LARA
Arumugam Partheepan
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Elam-Limited
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    • 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
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • 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
    • 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
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/351—Metal complexes comprising lanthanides or actinides, e.g. comprising europium
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
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    • 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
    • H10K30/57—Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • 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
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • 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

  • the present invention relates to photovoltaic devices and elements useful in such devices.
  • Photovoltaic devices i.e. solar cells
  • the energy conversion occurs as a result of what is well known in the solar cell field as the photovoltaic effect.
  • Solar radiation impinging on a solar cell and absorbed by an active region generates electrons and holes.
  • the electrons and holes are separated by a built-in electric field, for example a rectifying junction, in the solar cell.
  • This separation of electrons and holes results in the generation of an electrical current as explained below.
  • a built-in electric field can be generated in a solar cell by an active semiconductor layer with regions of P-type, intrinsic and N-type hydrogenated amorphous silicon.
  • a built-in electric field can also be generated in a solar cell by, for example, a Schottky barrier. The electrons generated at the metal (Schottky barrier) semiconductor body junction flow towards the semiconductor body.
  • a typical simple photovoltaic solar cell comprises an electrically conductive substrate layer; a semiconductor body deposited upon said substrate layer and a transparent conductive layer over at least a portion of said semiconductor body for facilitating collection of electrical current produced by the photovoltaic cell.
  • the electrons generated in the intrinsic region by absorption of solar radiation of the appropriate bandgap, produce electron-hole pairs.
  • the separation of the electron-hole pairs with the electrons flowing toward the region of N-type conductivity, and the holes flowing toward the region of P-type conductivity, creates the photovoltage and photocurrent of the cell.
  • the photocurrent output of a solar cell is maximized by increasing the total number of photons of differing energy and wavelength which are absorbed by the semiconductor material.
  • the solar spectrum roughly spans the region of wavelengths from about 300 nanometers to about 2200 nanometers, which corresponds to from about 4.2 eN to about 0.59 eN, respectively.
  • the portion of the solar spectrum which is absorbed by the solar cell is determined by the size of the bandgap energy of the semiconductor material, h the past, solar cells were fabricated from single crystal materials such as gallium arsenide, which has a bandgap energy of about 1.45 eN, or crystalline silicon, C-Si, which has a bandgap energy of about 1.1 eN.
  • Solar radiation having an energy less than the bandgap energy is not absorbed by the semiconductor material, and thus does not contribute to the generation of the photocurrent output of the cell.
  • Semiconductor materials such as GaAs and C-Si have been utilized together in solar cells to increase the overall conversion of solar energy into electrical energy.
  • problems are encountered when different semiconductor materials are used in the same solar cell.
  • One solution to the problem of fabricating a solar cell structure with different semiconductor materials was to use filters to reflect light of the appropriate wavelength onto a solar cell of the first material and transmit the non- absorbed light to a cell of the second semiconductor material.
  • a second solution used semiconductor materials of differing bandgaps which could be epitaxially grown on one another, such as aluminum gallium arsenide, gallium arsenide, and gallium phosphide structures. Both these systems have been loosely called tandem junction solar cells.
  • a third alternative was to stack individual solar cells of differing bandgap energies and connect the cells in series. These three alternatives are either cumbersome, expensive and/or bulky. A description of photovoltaic cells and their operation is disclosed in a paper by Jean-Michel ⁇ unzi in C.R.Physique 3 (2002) 523-542.
  • a photovoltaic device can be made using metal chelates such as a rare earth or non rare earth metal chelate or a mixture of rare earth metal chelates as the photovoltaic element in place of the prior art semi conductors.
  • metal chelates such as a rare earth or non rare earth metal chelate or a mixture of rare earth metal chelates as the photovoltaic element in place of the prior art semi conductors.
  • Rare earth chelates are known which fluoresce in ultra violet radiation and A. P. Sinha (Spectroscopy of Inorganic Chemistry Vol. 2 Academic Press 1971) describes several classes of rare earth chelates with various monodentate and bidentate ligands.
  • Group III A metals and lanthanides and actinides with aromatic complexing agents have been described by G. Kallistratos (Chimica Chronika, New Series, 11, 249-266 (1982)). This reference specifically discloses the Eu(III), Tb(III), U(III) and U(IN) complexes of diphenyl-phosponamidotriphenyl-phosphoran.
  • EP 0556005A and 0744451 A also disclose fluorescent chelates of transition or lanthanide or actinide metals.
  • Patent application WO98/58037 describes a range of lanthanide complexes which can be used in electroluminescent devices which have improved properties and give better results.
  • Patent Applications PCT/GB98/01773, PCT/GB99/03619, PCT/GB99/04030, PCT/GB99/04024, PCT/GB99/04028, PCT/GBOO/00268 describe electroluminescent complexes, structures and devices using rare earth chelates.
  • a photovoltaic device comprising a metal chelate as the photovoltaic element.
  • the invention also provides a photovoltaic device which comprises sequentially (i) a first electrode comprising a metal, (ii) the photovoltaic element and (iii) a second electrode in which the photovoltaic element comprises a metal chelate.
  • photovoltaic element is meant a compound which will generate electrons and holes when exposed to light.
  • the metal chelates can absorb light of a specific wavelength or wavelengths depending on the metal and ligands used and, as the photocurrent output of a solar cell is maximized by increasing the total number of photons of differing energy and wavelength which are absorbed by the semiconductor material, by having a plurality of layers of different metal chelates which absorb light at different wavelengths, a wide range of the visible spectrum can be used.
  • Metal chelates can also absorb light in the infra-red, ultra-violet or shorter wavelengths so improving the utilisation of sunlight and increasing the power achievable by a solar cell. Alternatively there can be several layers of metal chelates which absorb light in different parts of the spectrum.
  • the preferred metal chelates useful in the present invention have the formula
  • L ⁇ and Lp are organic ligands
  • M is a metal
  • n is the valence state of the metal M and in which the ligands L ⁇ are the same or different.
  • ligands Lp There can be a plurality of ligands Lp which can be the same or different.
  • (L 1 )(L 2 )(L )(L..)M (Lp) where M is a metal e.g. rare earth, transition metal, lanthanide or an actinide and (Li)(L 2 )(L 3 )(L(7) are the same or different organic complexes and (Lp) is a neutral ligand.
  • the total charge of the ligands (L (L 2 )(L 3 )(L..) is equal to the valence state of the metal M.
  • L ⁇ which corresponds to the III valence state of M
  • the complex has the formula (L ⁇ )(L 2 )(L 3 )M (Lp) and the different groups (L (L 2 )(L 3 ) may be the same or different.
  • Lp can be monodentate, bidentate or polydentate and there can be one or more ligands Lp.
  • M is a metal ion having an unfilled inner shell and the preferred metals are selected from Sm(III), Eu(II), Eu(III), Tb(III), Dy(III), Yb(II ⁇ ), Lu(III), Gd (III), Gd(III) U(III), Tm(III), Ce (III), Pr(H ⁇ ), Nd(IH), Pm(III), Dy(III), Ho(III), Er(III) and more preferably Eu(IH), Tb(III), Dy(III), Gd (III).
  • the metal M 2 can be any metal which is not a rare earth, transition metal, lanthanide or an actinide; examples of metals which can be used include lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper (I), copper (II), silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin (II), tin (IV), antimony
  • transition metals in different valence states e.g. manganese, iron, ruthenium, osmium, cobalt, nickel, palladium(II), palladium(IV), platinum(IT), platinum(IN), cadmium, chromium, titanium, vanadium, zirconium, tantulum, molybdenum, rhodium, iridium, titanium, niobium, scandium, yttrium.
  • organometallic complexes which can be used in the present invention are binuclear, trinuclear and polynuclear organometallic complexes e.g. of formula ( Lm M, L M 2 (i_n )
  • L is a bridging ligand and where Mi is a rare earth metal and M 2 is Mi or a non rare earth metal, Lm and Ln are the same or different organic ligands L ⁇ as defined above, x is the valence state of Mi and y is the valence state of M 2 .
  • trinuclear there are three rare earth metals joined by a metal to metal bond i.e. of formula
  • Mi, M 2 and M 3 are the same or different rare earth metals and Lm, Ln and Lp are organic ligands, L ⁇ and x is the valence state of Mi, y is the valence state of M 2 and z is the valence state of M 3 .
  • Lp can be the same as Lm and Ln or different.
  • the rare earth metals and the non rare earth metals can be joined together by a metal to metal bond and/or via an intermediate bridging atom, ligand or molecular group.
  • the metals can be linked by bridging ligands e.g.
  • polynuclear there are more than three metals joined by metal to metal bonds and/or via intermediate ligands
  • Mi, M 2 , M 3 and are rare earth metals and L is a bridging ligand.
  • the metal M 2 can be any metal which is not a rare earth, transition metal, lanthanide or an actinide examples of metals which can be used include lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper, silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin, antimony, lead, and metals of the first, second and third groups of transition metals e.g.
  • L ⁇ is selected from ⁇ diketones such as those of formulae
  • Ri , R 2 and R 3 can be the same or different and are selected from hydrogen, and substituted and unsubstituted hydrocarbyl groups such as substituted and unsubstituted aliphatic groups, substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups; R 1; R 2 and R 3 can also form substituted and unsubstituted fused aromatic, heterocyclic and polycyclic ring structures and can be copolymerisable with a monomer e.g. styrene.
  • a monomer e.g. styrene.
  • X is Se, S or O
  • Y can be hydrogen, substituted or unsubstituted hydrocarbyl groups, such as substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorine, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups or nitrile.
  • Examples of ⁇ and/or R 2 and/or R 3 include aliphatic, aromatic and heterocyclic alkoxy, aryloxy and carboxy groups, substituted and substituted phenyl, fluorophenyl, biphenyl, phenanthrene, anthracene, naphthyl and fluorene groups alkyl groups such as t-butyl, heterocyclic groups such as carbazole.
  • Some of the different groups L ⁇ may also be the same or different charged groups such as carboxylate groups so that the group Li can be as defined above and the groups L 2 , L 3 . .. can be charged groups such as
  • Ri R 2 and R 3 can also be
  • X is O, S, Se or H.
  • a preferred moiety Ri is trifluoromethyl CF and examples of such diketones are, banzoyltrifluoroacetone, p-chlorobenzoyltrifluoroacetone, p-bromotrifluoroacetone, p-phenyltrifluoroacetone, 1 -naphthoyltrifluoroacetone, 2-naphthoyltrifluoroacetone, 2-phenathoyltrifluoroacetone, 3-phenanthoyltrifluoroacetone, 9- anthroyltrifluoroacetonetrifluoroacetone, cinnamoyltrifluoroacetone, and 2- thenoyltrifluoroacetone.
  • the different groups L ⁇ may be the same or different ligands of formulae
  • R 5 is a substituted or unsubstituted aromatic, polycyclic or heterocyclic ring a polypyridyl group
  • R 5 can also be a 2-ethyl hexyl group so L n is 2-ethylhexanoate or R 5 can be a chair structure so that L n is 2-acetyl cyclohexanoate or L ⁇ can be
  • R is as above e.g. alkyl, allenyl, amino or a fused ring such as a cyclic or polycyclic ring.
  • the different groups L ⁇ may also be
  • the groups L P can be selected from Ph Ph
  • each Ph which can be the same or different and can be a phenyl (OPNP) or a substituted phenyl group, other substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic or polycyclic group, a substituted or unsubstituted fused aromatic group such as a naphthyl, anthracene, phenanthrene or pyrene group.
  • the substituents can be for example an alkyl, aralkyl, alkoxy, aromatic, heterocyclic, polycyclic group, halogen such as fluorine, cyano, amino. Substituted amino etc. Examples are given in figs.
  • R, R 1; R 2; R 3 and j can also be unsaturated alkylene groups such as vinyl groups or groups
  • L p can also be compounds of formulae
  • L p can also be
  • L p chelates are as shown in figs. 4 and fluorene and fluorene derivatives e.g. a shown in figs. 5 and compounds of formulae as shown as shown in figs. 6 to 8.
  • L ⁇ and Lp are tripyridyl and TMHD, and TMHD complexes, ⁇ , ⁇ , ⁇ " tripyridyl, crown ethers, cyclans, cryptans phthalocyanans, porphoryins ethylene diamine tetramine (EDTA), DCTA, DTPA and TTHA, where TMHD is 2,2,6,6-tetramethyl-3,5-heptanedionato and OPNP is diphenylphosphonimide triphenyl phosphorane.
  • TMHD 2,2,6,6-tetramethyl-3,5-heptanedionato
  • OPNP diphenylphosphonimide triphenyl phosphorane.
  • the formulae of the polyamines are shown in fig. 9.
  • electroluminescent materials which can be used include metal quinolates such as lithium quinolate, aluminium quinolate, scandium quinolate zirconium quinolate, hafnium quinolate vanadium quinolate etc.
  • the quinolates can be doped e.g. with a dye such as diphenylquinacridine, diphenylquinacridone, coumarins, perylene and their derivatives.
  • electroluminescent materials which can be used include organic complexes of non rare earth metals such as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper, silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin, antimony, lead, and metals of the first, second and third groups of transition metals e.g.
  • non rare earth metals such as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, copper, silver, gold, zinc, cadmium, boron, aluminium, gallium, indium, germanium, tin, antimony, lead, and metals of the first, second and third groups of transition metals e.g.
  • the complexes can be formed with the ligands of formula (I) to (XNII) above, optionally with a neutral ligand of formula L p as defined above.
  • Such complexes are complexes of ⁇ -diketones e.g. tris -(l,3-diphenyl-l-3- propanedione) (DBM) and suitable metal complexes are A1(DBM) 3; Zn(DBM) 2 and Mg(DBM) 2 ., Sc(DBM) 3 etc.
  • Further complexes which can be used as the photovoltaic element are borate complexes of formula
  • M is a rare earth, lanthanide or an actinide and R ⁇ ; R 2 and R 3 are as defined above.
  • a photovoltaic device can be made in the conventional way for example by forming a layer of the metal chelate on a metal so the metal forms a first electrode and preferably the other, second electrode, comprises a transparent conductive layer.
  • This electrode is preferably a transparent substrate which is a conductive glass or plastic material which acts as the cathode; preferred substrates are conductive glasses such as indium tin oxide coated glass, but any glass which is conductive or has a conductive layer can be used, so that, when light falls on the metal chelate an electric field is generated between the electrodes.
  • the metal chelates can be used as the photovoltaic element in such devices.
  • the metal chelate material can be deposited on the metal or conductive transparent material substrate directly by evaporation from a solution of the material in an organic solvent.
  • the solvent which is used will depend on the material, but chlorinated hydrocarbons such as dichloromethane, n-methyl pyrrolidone, dimethyl sulphoxide, tetra hydrofuran dimethylformamide etc. are suitable in many cases.
  • the material can be deposited by spin coating from solution or by vacuum deposition from the solid state e.g. by sputtering or any other conventional method can be used.
  • the electrons by absorption of solar radiation of the appropriate bandgap, produce electron-hole pairs.
  • a layer of a hole transmitting material i.e. a p-type transmitter between the cathode and the metal chelate and/or a layer of an electron transmitting material between the metal chelate and the anode, increased mobility of the holes and the electrons can be achieved increasing the effectiveness of the photovoltaic cell.
  • Hole transmitting layers are used in polymer electroluminescent devices and any of the known hole transmitting materials in film form can be used.
  • the hole transporting material can be an amine complex such as poly (vinylcarbazole), N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1' -biphenyl -4,4'- diamine (TPD), an unsubstituted or substituted polymer of an amino substituted aromatic compound, a polyaniline, substituted polyanilines, polythiophenes, substituted polythiophenes, polysilanes etc.
  • polyanilines are polymers of
  • R is in the ortho - or meta-position and is hydrogen, Cl-18 alkyl, Cl-6 alkoxy, amino, chloro, bromo, hydroxy or the group
  • R is alky or aryl and R' is hydrogen, Cl-6 alkyl or aryl with at least one other monomer of formula I above.
  • the hole transporting material can be a polyaniline.
  • Polyanilines which can be used in the present invention have the general formula
  • XXVII where p is from 1 to 10 and n is from 1 to 20, R is as defined above and X is an anion, preferably selected from Cl, Br, SO 4 , BF 4 , PF 6 , H 2 PO 3 , H 2 PO 4 , arylsulphonate, arenedicarboxylate, polystyrenesulphonate, polyacrylate alkysulphonate, vinylsulphonate, vinylbenzene sulphonate, cellulose sulphonate, camphor sulphonates, cellulose sulphate or a perfluorinated polyanion.
  • arylsulphonates are p-toluenesulphonate, benzenesulphonate, 9,10- anthraquinone-sulphonate and anthracenesulphonate; an example of an arenedicarboxylate is phthalate and an example of arenecarboxylate is benzoate.
  • evaporable deprotonated polymers of unsubstituted or substituted polymer of an amino substituted aromatic compound are used.
  • the de-protonated unsubstituted or substituted polymer of an amino substituted aromatic compound can be formed by deprotonating the polymer by treatment with an alkali such as ammonium hydroxide or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.
  • the degree of protonation can be controlled by forming a protonated polyaniline and de-protonating.
  • Methods of preparing polyanilines are described in the article by A. G. MacDiarmid and A. F. Epstein, Faraday Discussions, Chem Soc.88 P319 1989.
  • the conductivity of the polyaniline is dependant on the degree of protonation with the maximum conductivity being when the degree of protonation is between 40 and 60% e.g. about 50%.
  • the polymer is substantially fully deprotonated.
  • a polyaniline can be formed of octamer units i.e. p is four e.g.
  • the polyanilines can have conductivities of the order of 1 x 10 "1 Siemen cm "1 or higher.
  • the aromatic rings can be unsubstituted or substituted e.g. by a Cl to 20 alkyl group such as ethyl.
  • the polyaniline can be a copolymer of aniline and preferred copolymers are the copolymers of aniline with o-anisidine, m-sulphanilic acid or o-aminophenol, or o- toluidine with o-aminophenol, o-ethylaniline, o-phenylene diamine or with amino anthracenes.
  • polymers of an amino substituted aromatic compound which can be used include substituted or unsubstituted polyaminonapthalenes, polyaminoanthracenes, polyaminophenanthrenes, etc. and polymers of any other condensed polyaromatic compound.
  • Polyaminoanthracenes and methods of making them are disclosed in US Patent 6,153,726.
  • the aromatic rings can be unsubstituted or substituted e.g. by a group R as defined above.
  • conjugated polymer and the conjugated polymers which can be used can be any of the conjugated polymers disclosed or referred to in US 5807627, PCT/WO90/13148 and PCT/WO92/03490.
  • the preferred conjugated polymers are poly (p-phenylenevinylene)-PPV and copolymers including PPV.
  • Other preferred polymers are poly(2,5 dialkoxyphenylene vinylene) such as poly (2-methoxy-5-(2-methoxypentyloxy-l,4-phenylene vinylene), poly(2-methoxypentyloxy)-l,4-phenylenevinylene), poly(2-methoxy-5-(2- dodecyloxy-l,4-phenylenevinylene) and other poly(2,5 dialkoxyphenylenevinylenes) with at least one of the alkoxy groups being a long chain solubilising alkoxy group, polyfluorenes and oligofluorenes, polyphenylenes and ohgophenylenes, polyanthracenes and oligo anthracenes, ploythiophenes and oligothiophenes.
  • the phenylene ring may optionally carry one or more substituents e.g. each independently selected from alkyl, preferably methyl, alkoxy, preferably methoxy or ethoxy.
  • Any poly(arylenevinylene) including substituted derivatives thereof can be used and the phenylene ring in poly(p-phenylenevinylene) may be replaced by a fused ring system such as anthracene or naphthlyene ring and the number of vinylene groups in each polyphenylenevinylene moiety can be increased e.g. up to 7 or higher.
  • the conjugated polymers can be made by the methods disclosed in US 5807627, PCT/WO90/13148 and PCT/WO92/03490.
  • the thickness of the hole transporting layer is preferably 20nm to 200nm.
  • polymers of an amino substituted aromatic compound such as polyanilines referred to above can also be used as buffer layers with or in conjunction with other hole transporting materials.
  • Ri, R 2 and R 3 can be the same or different and are selected from hydrogen, and substituted and unsubstituted hydrocarbyl groups such as substituted and unsubstituted aliphatic groups, substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups; Ri , R 2 and R 3 can also form substituted and unsubstituted fused aromatic, heterocyclic and polycyclic ring structures and can be copolymerisable with a monomer e.g.
  • styrene X is Se, S or O
  • Y can be hydrogen, substituted or unsubstituted hydrocarbyl groups, such as substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures, fluorine, fluorocarbons such as trifluoryl methyl groups, halogens such as fluorine or thiophenyl groups or nitrile.
  • Ri and/or R and/or R include aliphatic, aromatic and heterocyclic alkoxy, aryloxy and carboxy groups, substituted and substituted phenyl, fluorophenyl, biphenyl, phenanthrene, anthracene, naphthyl and fluorene groups alkyl groups such as t-butyl, heterocyclic groups such as carbazole.
  • an electron injecting material between the anode and the electroluminescent material layer;
  • the electron injecting material is a material which will transport electrons when an electric current is passed through it;
  • electron injecting materials include a metal complex such as a metal quinolate e.g. an aluminium quinolate, lithium quinolate, a cyano anthracene such as 9,10 dicyano anthracene, cyano substituted aromatic compounds, tetracyanoquinidodimethane a polystyrene sulphonate or a compound with the structural formulae shown in figures 9 or 10 of the drawings in which the phenyl rings can be substituted with substituents R as defined above.
  • a metal complex such as a metal quinolate e.g. an aluminium quinolate, lithium quinolate, a cyano anthracene such as 9,10 dicyano anthracene, cyano substituted aromatic compounds, tetracyanoquinidodimethan
  • the cathode is preferably a transparent substrate such as a conductive glass or plastic material which acts as the anode.
  • Preferred substrates are conductive glasses such as indium tin oxide coated glass, but any glass which is conductive or has a conductive layer such as a metal or conductive polymer can be used. Conductive polymers and conductive polymer coated glass or plastics materials can also be used as the substrate.
  • the anode is preferably a low work function metal e.g. aluminium, calcium, lithium, silver/magnesium alloys, rare earth metal alloys etc., aluminium is a preferred metal.
  • a metal fluoride such as an alkali metal, rare earth metal or their alloys can be used as the second electrode for example by having a metal fluoride layer formed on a metal.
  • the photocurrent output of a solar cell is maximized by increasing the total number of photons of differing energy and wavelength which are absorbed by the semiconductor material and it is a feature of the present invention that the rare earth metal chelates can absorb light of a specific wavelength depending on the metal and ligands used so, by having a plurality of layers of different metal chelates of differing bandgaps which absorb light at different wavelengths, a wide range of the visible spectrum can be used.
  • Metal chelates can be also used which will absorb light in the infra-red, ultra-violet or shorter wavelengths so improving the utilisation of sunlight and increasing the power achievable by a solar cell.
  • the photocurrent output of a solar cell is maximized by increasing the total number of photons of differing energy and wavelength which are absorbed by the semiconductor material and it is a feature of the present invention that the rare earth metal chelates can absorb light of a specific wavelength depending on the metal and ligands used so, by having a plurality of layers of different metal chelates of differing bandgaps which absorb light at different wavelengths, a wide range of the visible spectrum can be used.
  • Metal chelates can be also used which will absorb light in the infra-red, ultra-violet or shorter wavelengths so improving the utilisation of sunlight and increasing the power achievable by a solar cell.
  • individual solar cells of differing bandgap energies i.e. using different metal chelates of differing bandgaps which absorb light at different wavelengths can be connected in series.
  • Fig. 17 shows a simple photovoltaic cell
  • Figs. 18 and 19 show other cells
  • Fig. 20 shows a tandem cell
  • a simple cell comprises a metal anode e.g. made of aluminium (1) a layer of an electroluminescent material (2) as described herein and a cathode comprising an indium titanium oxide (ITO) coated glass (3).
  • ITO indium titanium oxide
  • this shows a tandem solar cell in which there are a plurality of cells in series of fig. 17 formed of a cathode (11), an electroluminescent layer (13) and anode (12) so that a larger field is generated between the end anode and cathode, in order for there to be a transmission of light through the cells the anodes and cathodes of the intermediate cells are transparent. At least some of the photovoltaic elements (13) in each of the cells are different to adsorb light at a range of wavelengths.
  • a photovoltaic device was fabricated on a clean and dried ITO coated glass piece (1 x 1cm 2 ) by sequentially forming layers by vacuum evaporation to form a structure ITO/CuPc(20mn)/TPD(50nm)/ Eu (DBM) 3 (OPNP)/(85nm)Alq 3 /LiF(0.4nm)/Al
  • CuPc copper phthalocyanine
  • TPD is N, N'-diphenyl-N, N'-bis (3- methylphenyl) -1,1' -biphenyl -4,4'-diamine
  • Alq 3 is aluminium quinolate
  • LiF is lithium fluoride
  • Al is aluminium.
  • the organic coating on the portion which had been etched with the concentrated hydrochloric acid was wiped with a cotton bud.
  • the coated electrodes were stored in a vacuum desiccator over a molecular sieve and phosphorous pentoxide until they were loaded into a vacuum coater (Edwards, 10 " torr) and aluminium top contacts made.
  • the active area of the photovoltaic device wwaass 00..0088 ccmm bbyy 00..11 ccmm tthhee ddeevviicceess were then kept m a vacuum desiccator until the photovoltaic studies were performed.
  • the device was connected in an electric circuit and exposed to light of various wavelengths ⁇ and the voltage and current measured the results are shown graphically in fig. 21 where the open circuit voltage Voc and short circuit current Jsc (as described in the Jean-Michel Nunzi Article referred to above) were obtained.
  • the white light was obtained from a simulated daylight fluorescent bulb.
  • Example 1 was repeated using a structure comprising
  • DPQA is diphenylquinacridone.
  • the Zrq 4 is zirconium quinolate and the Zrq 4 :DPQA layer was formed by concurrent vacuum deposition to form a zirconium quinolate layer doped with DPQA.
  • the weight ratio of the Zrq and DPQA is conveniently shown by a relative thickness measurement.
  • the device was connected in an electric circuit and exposed to light of various wavelengths ⁇ and the voltage and current measured the results are shown graphically in fig. 22 where the open circuit voltage Voc and short circuit current Jsc (as described in the Jean-Michel Nunzi Article referred to above) were obtained.
  • the white light was obtained from a simulated daylight fluorescent bulb.
  • Example 1 was repeated using a structure comprising
  • the device was connected in an electric circuit and exposed to light of various wavelengths ⁇ and the voltage and current measured the results are shown graphically in fig. 23 where the open circuit voltage Voc and short circuit current Jsc (as described in the Jean-Michel Nunzi Article referred to above) were obtained.
  • the white light was obtained from a simulated daylight fluorescent bulb.
  • Example 1 was repeated using a structure comprising ITO/CuPc(20mn)/ ⁇ -NPB(75nm)/Liq(65nm)LiF(0.4nm/Al.
  • the device was connected in an electric circuit and exposed to light of various wavelengths ⁇ and the voltage and current measured the results are shown graphically in fig. 24 where the open circuit voltage Voc and short circuit current Jsc (as described in the Jean-Michel Nunzi Article referred to above) were obtained.
  • the white light was obtained from a simulated daylight fluorescent bulb.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention porte sur un dispositif photovoltaïque qui utilise un chélate métallique comme élément photovoltaïque
PCT/GB2003/003035 2002-07-12 2003-07-14 Chelates metalliques WO2004008554A2 (fr)

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AU2003281003A AU2003281003A1 (en) 2002-07-12 2003-07-14 Photovoltaic device comprising a metal chelate

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GBGB0216154.5A GB0216154D0 (en) 2002-07-12 2002-07-12 Metal chelates
GB0216154.5 2002-07-12

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WO2005086251A3 (fr) * 2004-03-03 2006-02-16 Novaled Gmbh Utilisation d'un complexe metallique comme dopant n d'un materiau matrice semi-conducteur organique et composant electronique, ainsi que dopant et ligand, et son procede de production
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WO2006087521A1 (fr) * 2005-02-18 2006-08-24 Oled-T Limited Matériaux et dispositifs électroluminescents
EP1723213A2 (fr) * 2004-02-14 2006-11-22 Oled-T Limited Matieres electroluminescentes et dispositifs associes
WO2008058525A2 (fr) * 2006-11-13 2008-05-22 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
WO2009049273A2 (fr) * 2007-10-12 2009-04-16 University Of Southern California Dispositifs optoélectroniques photosensibles organiques contenant des tétra-azaporphyrines
CN101803056B (zh) * 2007-08-13 2011-11-16 南加利福尼亚大学 具有三重态捕获的有机光敏光电器件
WO2012131257A1 (fr) * 2011-03-30 2012-10-04 Centre National De La Recherche Scientifique Utilisation de complexes de cobalt pour la préparation d'une couche active dans une cellule photovoltaïque, et cellule photovoltaïque correspondante

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US8012604B2 (en) * 2004-02-14 2011-09-06 Merck Patent Gmbh Electroluminescent materials and devices
EP1723213A2 (fr) * 2004-02-14 2006-11-22 Oled-T Limited Matieres electroluminescentes et dispositifs associes
WO2005086251A3 (fr) * 2004-03-03 2006-02-16 Novaled Gmbh Utilisation d'un complexe metallique comme dopant n d'un materiau matrice semi-conducteur organique et composant electronique, ainsi que dopant et ligand, et son procede de production
CN1914747B (zh) * 2004-03-03 2014-12-10 诺瓦莱德公开股份有限公司 金属络合物作为 n- 掺杂物用于有机半导体基质材料中的用途，以及含有掺杂该金属络合物的有机半导体材料的电子元件
KR100867028B1 (ko) * 2004-03-03 2008-11-04 노발레드 아게 금속 착물의 유기 반도체 매트릭스 물질용 ｎ-도판트로서의용도, 유기 반도체 물질 및 전자 소자, 및 도판트 및리간드 및 이들의 제조 방법
US8258501B2 (en) 2004-03-03 2012-09-04 Novaled Ag Use of a metal complex as an n-Dopant for an organic semiconducting matrix material, organic of semiconducting material and electronic component, and also a dopant and ligand and process for producing same
WO2005098990A1 (fr) * 2004-03-26 2005-10-20 The University Of Southern California Dispositifs photosensibles organiques
WO2006040593A1 (fr) * 2004-10-15 2006-04-20 Oled-T Limited Dispositifs electroluminescents
WO2006087521A1 (fr) * 2005-02-18 2006-08-24 Oled-T Limited Matériaux et dispositifs électroluminescents
WO2008058525A2 (fr) * 2006-11-13 2008-05-22 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
WO2008058525A3 (fr) * 2006-11-13 2008-09-12 Novaled Ag Utilisation d'une liaison de coordination pour doper des semiconducteurs organiques
AU2008286909B2 (en) * 2007-08-13 2014-07-10 University Of Southern California Organic photosensitive optoelectronic devices with triplet harvesting
CN101803056B (zh) * 2007-08-13 2011-11-16 南加利福尼亚大学 具有三重态捕获的有机光敏光电器件
US9391284B2 (en) 2007-08-13 2016-07-12 University Of Southern California Organic photosensitive optoelectronic devices with triplet harvesting
WO2009049273A2 (fr) * 2007-10-12 2009-04-16 University Of Southern California Dispositifs optoélectroniques photosensibles organiques contenant des tétra-azaporphyrines
CN102007615B (zh) * 2007-10-12 2013-05-01 南加利福尼亚大学 含有四氮杂卟啉的有机光敏光电子装置
WO2009049273A3 (fr) * 2007-10-12 2009-06-25 Univ Southern California Dispositifs optoélectroniques photosensibles organiques contenant des tétra-azaporphyrines
TWI510494B (zh) * 2007-10-12 2015-12-01 Univ Southern California 含有四一氮雜卟啉之有機光敏光電裝置
US8158972B2 (en) 2007-10-12 2012-04-17 The University Of Southern California Organic photosensitive optoelectronic devices containing tetra-azaporphyrins
FR2973574A1 (fr) * 2011-03-30 2012-10-05 Centre Nat Rech Scient Utilisation de complexes de cobalt pour la préparation d'une couche active dans une cellule photovoltaïque, et cellule photovoltaïque correspondante
CN103635482A (zh) * 2011-03-30 2014-03-12 国立科学研究中心 钴配合物在制备光伏电池中的活性层中的用途以及相应的光伏电池
WO2012131257A1 (fr) * 2011-03-30 2012-10-04 Centre National De La Recherche Scientifique Utilisation de complexes de cobalt pour la préparation d'une couche active dans une cellule photovoltaïque, et cellule photovoltaïque correspondante
CN103635482B (zh) * 2011-03-30 2016-11-09 国立科学研究中心 钴配合物在制备光伏电池中的活性层中的用途以及相应的光伏电池

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AU2003281003A8 (en) 2004-02-02

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