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• • 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
  • 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
  • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • 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
  • H10F71/00—Manufacture or treatment of devices covered by this subclass
• • 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
  • H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
  • H10F77/147—Shapes of bodies
• • 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
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• • 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
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/114—Poly-phenylenevinylene; Derivatives thereof
• • 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
  • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
  • H10K85/211—Fullerenes, e.g. C60
  • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K99/00—Subject matter not provided for in other groups of this subclass
• • 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
• • 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
  • Y02E10/541—CuInSe2 material PV 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to a method for producing a layer containing inorganic semiconductor particles and to components comprising this layer.
• Em component of the aforementioned type is known from WO-Al-00/33396, which has inorganic semiconductor particles in colloidally dissolved form.
• Solar cells for example, which convert sunlight into electrical energy, pay for these components.
• the energy is generated by a solar cell system, which consists of a hybrid layer.
• hybrid solar cells also called nanocomposite solar cells are made of inorganic semiconductors such as CdSe 11 "" 1, CdS 151, CdTe I6), ZnO 1? 1, TiO 2 18 '91, CuInS 2 110 "131 or CuInSe 2 1141 or fullerenes 115 "201 and an electroactive polymer.
• the preparation of the inorganic semiconductor nanoparticles for such solar cells can be carried out using a variety of methods.
• the most common methods are the colloidal ones
• the invention further relates to components comprising the erfmdungsgebound prepared inorganic semiconductor particles containing layer.
• these inventive components are solar cells, in particular hybrid solar cells.
• the erfmdungsgebound produced inorganic semiconductor particles containing layer include pay more photodetectors.
• a solar cell is to be produced as a component according to the present invention, then inorganic particles are directly converted into semiconductors within the photoactive layer of the solar cell in situ in a semiconductive organic matrix consisting of, for example, low molecular weight electroactive molecules, semiconducting polymers and / or oligomers.
• a semiconductive organic matrix consisting of, for example, low molecular weight electroactive molecules, semiconducting polymers and / or oligomers.
• Capper consist mainly of organic surfactants, which are mostly insulators. These insulators make it difficult to dissociate excitons (electron-hole pairs) at the p / n boundary layer as well as the charge transport to the electrode and thus reduce the efficiency of the solar cells.
• insulators make it difficult to dissociate excitons (electron-hole pairs) at the p / n boundary layer as well as the charge transport to the electrode and thus reduce the efficiency of the solar cells.
• the respective inorganic and organic starting compounds are applied as a film and then converted into semiconductors.
• Another, equally advantageous manufacturing method for the erfmdungsgesellen components are that the semiconductive layers are generated by applying the organic and inorganic starting compounds with simultaneous conversion m semiconductor.
• the conversion of the starting compounds in semiconductors within the organic matrix is preferably carried out by thermal treatment of the starting compounds at temperatures between 50 ° and at most 400 0 C.
• temperatures substantially below 400 0 C are used, as too high temperatures to undesirable Reactions of the starting compounds, or decomposition products can lead.
• the photoactive semiconductor layers are made at low temperatures, the use of ITO (indium tin oxide) coated plastic substrates and thus the production of flexible solar cells is possible.
• the transition temperature can also be below 100 ° C.
• the conversion of the starting compounds into semiconductors can be carried out in the presence of an acid.
• the conversion of the starting compounds into semiconductors can likewise advantageously be carried out in the presence of a base.
• photons with an energy greater than 1 (eV) eV can also be used for the conversion of the semiconductors.
• the conversion of the layers in the semiconductor can take place in an inert gas atmosphere or in air.
• the starting compounds can be present both as a dispersion or suspension, as a solution, as a paste or as a slurry (slurry sludge).
• the starting compounds may also be in complexed form.
• the Metallverbmdung which serves as a starting compound, it can also be a salt-like compound.
• the metal compound may be an organometallic compound or an organometallic complex.
• the metal compound used can have both basic and acidic properties that allow for conversion to a semiconductor at low temperatures or catalytically affect that conversion.
• the preparation according to the invention also comprises reactions in the presence of an oxidizing or reducing agent.
• a high current efficiency of the components according to the invention in the form of solar cells is achieved in that the inorganic semiconductor materials are particles whose grain size is between 0.5 nm and 500 nm.
• the big one of these Particles depend strongly on the concentration ratios of the starting compounds and the polymer matrix.
• the inorganic semiconductor particles also include
• Nanoparticles may have particular properties, such as Impact ionization own, in the third
• the physical properties of the semiconductors may be different from macroscopic analogs.
• the inorganic semiconductor material may also be in the form of agglomerates of particles as well as of a network with or without appreciable grain boundaries.
• Charge carriers can flow in the material via the network, for example in one
• organic semiconductor particles includes organic semiconductor particles
• the inorganic semiconductor particles obtained can take on the role of both an electron donor and an electron acceptor in solar cells. It is expedient that the production of the inorganic semiconductor particles takes place in a semiconducting organic matrix.
• This semiconducting organic matrix may consist of low molecular weight organic compounds, such as perylenes, phthalocyanines, or their derivatives, as well as semiconducting polycyclic compounds.
• Another, likewise preferred semiconductor matrix may consist of semiconducting oligomers. These are, for example, oligothiophenes, oligophenylenes, oligophenylenevinylenes and derivatives thereof.
• the semiconductor matrix may consist of electroactive polymers.
• Possible polymers and copolymers which can find their application in the inventive construction elements, such as solar cells, are, for example, polyphenylenes, Polyphenylenevinylenes, polythiophenes, polyanilines, polypyrroles, polyfluorenes and derivatives thereof.
• the conductivity of the organic semiconductor matrix can be improved by doping.
• the organic semiconductor matrix can take over the task of both an electron donor and an electron acceptor in the solar cells.
• the geometry of the erfmdungsgedorfen components in the form of solar cells comprises bulk heterojunction solar cells.
• bulk heterojunction solar cells are meant solar cells whose photoactive layer consists of a three-dimensional network of an electron donor and an electron acceptor.
• the geometry in the solar cells may correspond to that of a gradient solar cell.
• gradient solar cell includes solar cell geometries having a gradient of the organic or inorganic semiconductor material.
• the solar cells according to the invention may include a layer of the semiconductor matrix or of the inorganic semiconductors, which may function as an intermediate layer.
• the stoichiometry of the inorganic semiconductor materials produced according to the invention can be varied by varying the ratio of the metal compound used in relation to the respective reaction partner and to further metal compounds in the starting mixture. This variation allows the controlled adjustment of optical, structural and electronic properties. This also allows the targeted introduction of defects and doping Mate ⁇ alien in the Halbleitermate ⁇ alien to allow a wider range of applications.
• Fig. 3 shows the TEM (Transmission Electron Microscope) images of the photoactive layer.
• the TEM images show nearly spherical particles embedded in the polymer matrix.
• FIG. 4 current / voltage characteristics are shown showing a V or (open terminal voltage) of 700 mV and an I sc (short-circuit current) of 3.022 mA / cm 2 at an exposure of 70 mW / cm 2 .
• the full factor is 32% and an efficiency of 1% has been achieved.
• Copper indium disulfide can be made either as a p or n conductor. Therefore, the Cu / In / S ratio plays an essential role in the solar cells. Several of the copper indium sulfide solar cells were identified
• Example 2 Zinc sulfide-copper indium disulfide polyphenylene vinylene solar cells
• the active layers were prepared by zinc acetate, CuI, InCIj and thioacetamide and a poly (p-xylen tetrahydrothiophemumchlorid) precursor in a
• Solvent mixture of pyridine, water and ethanol were dissolved or complexed and from this solution a layer was produced.
• zinc sulfide-copper-indium sulfide mixed crystals were prepared in a PPV polymer matrix.
• Nanocomposite layer see Fig. 5, shows that uniformly large particles with an approximate diameter of 50-60 nm are formed. No larger particles could be found in the sample.
• the current / voltage characteristic of such a solar cell is shown in Fig. 7 and shows both a high photovoltage of 900 mV and a photocurrent of 8 mA / cm 2 .
• Example 3 As an alternative to the PPV precursor mentioned, other polymers, such as P3HT (poly-3-hexylthiophene), MEH-PPV (poly [2-methoxy-5- (2'-ethyl-hexyl) -1, 4-phenylenevinylene] ), MDMO-PPV (poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1,4-phenylenevinylene]) or copolymers.
• P3HT poly-3-hexylthiophene
• MEH-PPV poly [2-methoxy-5- (2'-ethyl-hexyl) -1, 4-phenylenevinylene]
• MDMO-PPV poly [2-methoxy-5- (3, 7-dimethyloctyloxy) -1,4-phenylenevinylene]
• Example 3 shows CuInS 2 / MEH-PPV solar cells.
• the active layers of these solar cells were prepared from a solution of CuI / InCl 3 / thioacetamide (1/5/16) and MEH-PPV (4/1 CIS / MEH-PPV).
• Solar cells with MEH-PPV as the electroactive polymer achieved a short-circuit current of 4 mA / cm 2 , an open terminal voltage of 0.93 V, a FF of 25%.
• the efficiency of these solar cells was 1.3%.
• S-compounds 1) in addition to the elements Cu, In, Zn and the elements Ag, Cd, Ga, Al, Pb, Hg, S, Se, Te can be used; 2) besides thioacetamide, the following S-compounds can also be used: elemental sulfur, elemental sulfur with a vulcanization accelerator, thiourea, thiuram, hydrogen sulfide, metal sulfides, hydrogen sulfides, CS 2 , P 2 S 5 ;
• semiconducting nanoparticles are produced directly on the active layer of the solar cell by thermal decomposition in the presence of organic electroactive polymers.
• this has the advantage that it is possible to dispense with the colloidal synthesis step and the associated, very expensive work-up steps.
• This provides a much simpler and cheaper manufacturing process for photovoltaic elements, such as solar cells and photodetectors.

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• 2006
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