WO2004024629A1 - Nanoparticules composites de chalcogenure metallique et couches formees de ces nanoparticules - Google Patents

Nanoparticules composites de chalcogenure metallique et couches formees de ces nanoparticules Download PDF

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Publication number
WO2004024629A1
WO2004024629A1 PCT/EP2002/010268 EP0210268W WO2004024629A1 WO 2004024629 A1 WO2004024629 A1 WO 2004024629A1 EP 0210268 W EP0210268 W EP 0210268W WO 2004024629 A1 WO2004024629 A1 WO 2004024629A1
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Prior art keywords
metal
nano
particle
chalcogenide
particles
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PCT/EP2002/010268
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English (en)
Inventor
Hieronymus Andriessen
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Agfa-Gevaert
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Application filed by Agfa-Gevaert filed Critical Agfa-Gevaert
Priority to PCT/EP2002/010268 priority Critical patent/WO2004024629A1/fr
Priority to AU2002340902A priority patent/AU2002340902A1/en
Priority to EP02774614A priority patent/EP1551767A1/fr
Priority to JP2004535035A priority patent/JP2005538518A/ja
Priority to US10/659,926 priority patent/US7468146B2/en
Publication of WO2004024629A1 publication Critical patent/WO2004024629A1/fr

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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/21—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to metal chalcogenide composite nano-particles, layers comprising same and photovoltaic devices comprising the layers.
  • a photovoltaic (PV) process basically consists of four steps: (1) absorption of a photon, (2) charge separation, (3) charge transport and (4) charge collection.
  • Today crystalline silicon is the dominant PV-material on the market (ca 85%) . Due to its high price much research has been focussed on thin-film technologies which have low cost potential, the most of which are given in the table below together with the compounds used for each step of the above mentioned photovoltaic process.
  • the construction of these devices is far more complicated than a one-step coating of a photovoltaic layer.
  • GB 1119372 discloses a photovoltaic device based on Cu 2 S-powder which is pressed at 700-1000°C and 100-1000 kg/cm 2 to form a plate
  • a CdS plate is prepared by pressing CdS powder into pellets, sintering at 800 °C in a nitrogen atmosphere, and grinding to a powder. The product is then pressed 2 as above to form a plate 0.75 cm in area and 0.35 mm thick. After etching and polishing the surfaces, both disks were placed in an alloy die, enveloped in powder graphite, and pressed at 400 °C and 200 kg/cm .
  • This photovoltaic device can be described as a two- dimensional p-n hetero unction device. ZnSe or ZnS could be also used instead of CdS, but with reduced light absorption due to the larger bandgaps .
  • Powder XRD spectra included new peaks which could not be attributed to copper (II) sulphide, nickel (II) sulphide or other known species suggesting the formation of new intermediate phases.
  • the powders exhibited broad particle size distributions with mean particle sizes of 5 to 11 ⁇ m.
  • EP-A 1 231 250 discloses a method for manufacturing a thin film inorganic light emitting diode device, said method comprising following steps: (1) preparing a nano-particle dispersion comprising together ZnS doped with a luminescence centre (n-type semiconductor) and Cu x S (p-type semiconductor) by precipitation from appropriate aqueous solutions of the respective ions, or, (1') preparing a first separate nano-particle dispersion of ZnS doped with a luminescent centre (n-type semiconductor) and a second separate nano-particle dispersion of Cu x S (p-type semiconductor) , both by precipitation from appropriate aqueous solutions of the respective ions, (2) washing the dispersion prepared according to (1) or both dispersions according to (1') to remove non- precipitated ions, (3) coating onto a first conductive electrode the dispersion resulting from steps (1) and (2), or a mixture of the dispersions resulting from steps (1') and (2) in one and the same layer, or the separate dis
  • metal chalcogenide composite nano-particles with a n-type semiconducting metal chalcogenide phase and a p-type semiconducting metal chalcogenide phase which at concentrations of the p-type semiconducting phase of 1 or 2 mole% exhibit electroluminescence, exhibit a photovoltaic effect at p-type semiconducting phases of 5 to 50 mole %.
  • This effect can be increased by incorporating a binder and a spectral sensitizer such as a metal chalcogenide spectral sensitizer either by admixture or by incorporation in the metal chalcogenide composite nano-particle itself.
  • a metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano- particles, wherein at least one of the metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of the metal capable of forming p-type semiconducting chalcogenide nano- particles is at least 5 atomic percent of the metal and is less than 50 atomic percent of the metal.
  • aspects of the present invention are also realized by a dispersion comprising the above-mentioned metal chalcogenide composite nano-particle.
  • aspects of the present invention are also realized by a process for preparing the above-mentioned dispersion comprising the steps of preparing a composite metal chalcogenide nano-particle containing an n-type semiconducting chalcogenide and a p-type semiconducting p-type semiconducting chalcogenide, wherein at least one of the metal chalcogenides has a band-gap between 1.5 and 2.9 eV.
  • aspects of the present invention are also realized by a layer comprising the above-mentioned metal chalcogenide composite nano- particles.
  • aspects of the present invention are also provided by the use of the above-mentioned metal chalcogenide composite nano-particle in a photovoltaic device.
  • Figure 1 represents the dependences of transmission, T, in % upon wavelength, ⁇ , in nm for ca. 100 nm thick layers prepared with coating dispersions F, G, H, I, J, K and L (see the INVENTION EXAMPLES for the compositions of these coating dispersions) .
  • metal chalcogenide composite nano-particle refers to the primary particle formed in the preparation process and not to agglomerates thereof.
  • metal chalcogenide means a binary compound containing a chalcogen and a more electropositive element or radical.
  • a chalcogen is an element from group IV of the periodic table including oxygen, sulphur, selenium, tellurium and polonium.
  • nano-particle for the purposes of the present invention means a number mean particle size of less than 50 nm.
  • support means a “self-supporting material” so as to distinguish it from a “layer” which may be coated on a support, but which is itself not self-supporting. It also 'includes any treatment necessary for, or layer applied to aid, adhesion to the support.
  • continuous layer refers to a layer in a single plane covering the whole area of the support and not necessarily in direct contact with the support.
  • non-continuous layer refers to a layer in a single plane not covering the whole area of the support and not necessarily in direct contact with the support.
  • coating is used as a generic term including all means of applying a layer including all techniques for producing continuous layers, such as curtain coating, doctor-blade coating etc., and all techniques for producing non-continuous layers such as screen printing, ink jet printing, flexographic printing, and techniques for producing continuous layers.
  • a metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano- particles, wherein at least one of the metal chalcogenides has a band-gap between 1.5 and 2.9 eV and the concentration of the metal capable of forming p-type semiconducting chalcogenide nano- particles is at least 5 atomic percent of the metal and is less than 50 atomic percent of the metal.
  • the metal chalcogenide composite particle comprises a p-type semiconducting metal chalcogenide phase and a n-type semiconducting chalcogenide phase, at least one of the metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of the p-type semiconducting metal chalcogenide in the metal chalcogenide composite nano-particle is at least 5 mole percent and is less than 50 mole percent.
  • the metal chalcogenide composite particle is a coprecipitated particle, being a particle prepared by a coprecipitation technique.
  • the metal chalcogenide composite particle is a metal sulphide composite particle.
  • the metal capable of forming n-type semiconducting chalcogenide nano- particles is selected from the group consisting of of zinc, bismuth, cadmium, mercury, indium, tin, tantalum and titanium.
  • the metal capable of forming p-type semiconducting chalcogenide nano- particles is selected from the group consisting of copper, chromium, iron, lead and nickel.
  • the metal chalcogenide composite particle further contains a metal capable of forming spectrally sensitizing chalcogenide nano- particles with a band-gap between 1.0 and 2.9 eV.
  • the metal chalcogenide composite particle further contains a metal capable of forming spectrally sensitizing chalcogenide nano- particles with a band-gap between 1.0 and 2.9 eV which is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.
  • the metal chalcogenide composite nano-particle is a coprecipitated metal sulphide composite nano-particle containing zinc and copper.
  • the metal chalcogenide composite nano-particle is a coprecipitated metal sulphide composite nano-particle containing zinc, copper and silver.
  • the metal chalcogenide composite nano-particle is a coprecipitated metal sulphide composite nano-particle containing zinc, copper and silver, wherein the metal is between 40 and 80 atomic percent zinc.
  • the metal chalcogenide composite nano-particle is a coprecipitated metal sulphide composite nano-particle containing zinc, copper and silver, wherein the metal is between 5 and 25 atomic percent silver.
  • the metal chalcogenide composite nano-particle is a coprecipitated metal sulphide composite nano-particle containing zinc, copper and silver, wherein the metal is between 15 and 50 atomic percent copper.
  • the stoichiometry of the metal chalcogenide composite nano- particle may be stoichiometric, may have a deficit in chalcogenide or may have a deficit in metal.
  • Photoluminescence which reduces any photovoltaic effect observed, is known to be quenched by a zinc deficiency in the case of zinc sulphide.
  • a stoichiometric deficit of the chalcogenide in the metal chalcogenide composite nano-particle is present in the nano- particle.
  • a fourteenth embodiment of the metal chalcogenide composite nano-particle according to the present invention, a stoichiometric deficit of the chalcogenide between 1 and 30 atomic percent is present in the nano-particle.
  • a stoichiometric deficit of the chalcogenide between 1.5 and 25 atomic percent is present in the nano-particle.
  • a stoichiometric deficit of the metal is present in the nano- particle.
  • X-ray diffraction spectra carried out on the metal chalcogenide composite nano-particles, according to the present invention were found to be substantially amorphous, although it was possible to determine the particle size from the peak-width of the X-ray diffraction peaks using the Debye-Scherrer equation, values of 1.5 to 5 nm depending upon the precipitation conditions being obtained.
  • the maximum crystallinity was estimated to be 10% and the primary particle size was estimated from the peak width to be substantially less than lOnm.
  • the metal chalcogenide composite nano-particle has a crystallinity of 10 percent or less.
  • the metal chalcogenide composite nano-particle comprising at least two metals can be prepared by coprecipitation, conversion with metal ions, encapsulation, co-chemical vapour deposition or simple mixing followed by a coagulation step such as heat and/or pressure sintering.
  • n-type semiconducting and p- type semiconducting phases form an n-p heterojunction and that this heterojunction provides for charge separation.
  • Spectrophotometric measurements carried out on layers of the metal chalcogenide composite nano-particles, according to the present invention showed transmissions between 55 and 85% in the visible region of the spectrum which is only weakly dependent upon wavelength (see Figure 1) .
  • aspects of the present invention are realized by a process for preparing a dispersion, according to the present invention, comprising the steps of preparing a composite metal chalcogenide nano-particle containing an n-type semiconducting chalcogenide and a p-type semiconducting p-type semiconducting chalcogenide, wherein at least one of the metal chalcogenides has a band-gap between 1.0 and 2.9 eV.
  • the process includes a coprecipitation step, a metal ion conversion step and/or a sintering step.
  • the sintering step may require the application of heat or pressure alone or the combined application of heating and pressure.
  • the process includes a coprecipitation step carried out in a medium containing at least one compound selected from the group of thiols, triazole compounds and diazole compounds.
  • Thiols such as 1-thioglycerol (3-mercapto-l, 2-propanediol)
  • triazole compounds and diazole compounds prevent agglomeration of the metal chalcogenide composite nano-particles.
  • the process includes the step of mixing the metal chalcogenide composite nano-particles with spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV.
  • the process includes the step of mixing the metal chalcogenide composite nano-particles with spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.5 and 2.8 eV.
  • the process includes the step of mixing the metal chalcogenide composite nano-particles with spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.7 and 2.7 eV.
  • the process further comprises the step of converting the metal chalcogenide composite nano-particles with metal ions .
  • the process further includes a diafiltration step.
  • the metal chalcogenide composite nano-particles are prepared using solutions of salts of the respective ions, the metal chalcogenide composite nano-particles produced are preferably washed, diafiltered and then concentrated.
  • the washing media may also contain ingredients such as phosphoric acid, phosphates or thiols, such as 1-thioglycerol, to stabilize or otherwise improve the properties of the metal chalcogenide composite nano-particles.
  • the process comprises a double jet coprecipitation step.
  • double jet coprecipitation a first and a second aqueous solution are added simultaneously to a third solution under controlled conditions of temperature and flow rate.
  • aspects of the present invention are also realized by a layer comprising the metal chalcogenide composite nano-particles according to the present invention.
  • the layer has a thickness of less than 500 nm.
  • the layer has a thickness of less than 200 nm.
  • the layer has a thickness of greater than 20 nm.
  • the layer further contains at least one spectral sensitizer for the metal chalcogenide composite nano- particles .
  • the layer further contains at least one spectral sensitizer for the metal chalcogenide composite nano-particles selected from the group consisting of metal chalcogenide nano- particles with a band-gap between 1.0 and 2.9 eV, organic dyes, and metallo-organic dyes.
  • the layer further contains at least one spectral sensitizer for the metal chalcogenide composite nano-particles selected from the group consisting of metal chalcogenide nano- particles with a band-gap between 1.5 and 2.8 eV, organic dyes, and etallo-organic dyes .
  • the layer further contains at least one spectral sensitizer for the metal chalcogenide composite nano- particles selected from the group consisting of metal chalcogenide nano-particles with a band-gap between 1.7 and 2.7 eV, organic - dyes, and metallo-organic dyes.
  • the layer further contains at least one spectral sensitizer for the metal chalcogenide composite nano- particles selected from the group consisting of metal oxides, metal sulphides and metal selenides.
  • the layer further contains at least one spectral sensitizer for the metal chalcogenide composite nano-particles selected from the group consisting of lead sulphide, bismuth sulphide, cadmium sulphide, silver sulphide, antimony sulphide, indium sulphide, copper sulphide, cadmium selenide, copper selenide, indium selenide and cadmium telluride.
  • Suitable spectrally sensitizing organic dyes (SSOD) include cyanine, merocyanine and anionic dyes, such as:
  • Suitable spectrally sensitizing metallo-organic dyes allowing for broad absorption of the solar spectrum include:
  • Ruthenium 505 a ruthenium cis-bis (isocyanato) (2,2'bipyridyl-4, 4' dye from Solaronix dicarbox 1ato) ruthenium (II)
  • Ruthenium 535 previously cis-bis (isothiocyanato)bis (2,2'-bipyridyl- known as SRS-HQ, N3), a 4,4' -dicarboxylato) -ruthenium (II) ruthenium dye from Solaronix
  • Ruthenium 620 Black Dye, (anion only) tris (isothiocyanato) - a ruthenium dye from ruthenium (II) -2 , 2 ' : 6 ' , 2 " -terpyridine-4 , 4 ' , 4 ' Solaronix tricarboxylic acid
  • the process further comprises a precipitation step carried out in a medium containing at least one of a triazole compound and a diazole compound.
  • the process further comprises a precipitation step carried out in a medium containing a tetraazaindene, a triazole compound.
  • the process further comprises a precipitation step carried out in a medium containing a triazole compound selected from the group consisting of
  • Suitable triazole or diazole compounds include:
  • the process further includes a diafiltration process in which the washing medium in the diafiltration process contains a phosphoric acid or a phosphoric acid salt.
  • the process further includes a diafiltration process in which the washing medium in the diafiltration process contains a phosphoric acid selected from the group consisting of, orthophosphoric acid, phosphorous acid, hypophosphorous acid and polyphosphoric acids.
  • Polyphosphoric acids include diphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, metaphosphoric acid and "polyphosphoric acid” .
  • the phosphate is selected from the group consisting of orthophosphates, phosphates, phosphites, hypophosphites and polyphosphates.
  • Polyphosphates are linear polyphosphates, cyclic polyphosphates or mixtures thereof.
  • Linear polyphosphates contain 2 to 15 phosphorus atoms and include pyrophosphates, dipolyphosphates, tripolyphosphates and tetrapolyphosphates .
  • Cyclic polyphosphates contain 3 to 8 phosphorus atoms and include trimetaphosphates and tetrametaphosphates and metaphosphates .
  • Polyphosphoric acid may be prepared by heating H 3 PO 4 with sufficient P 4 O 10 (phosphoric anhydride) or by heating H 3 PO 4 to remove water.
  • a P 4 O 10 /H 2 O mixture containing 72.74% P 4 O 10 corresponds to pure H 3 P0 4 , but the usual commercial grades of the acid contain more water.
  • P 4 O 10 content H 4 P 2 O 7 pyrophosphoric acid, forms along with P 3 through Ps polyphosphoric acids.
  • Triphosphoric acid appears at 71.7% P 2 O 5 (H 5 P 3 O 10 ) and tetraphosphoric acid (HsP 4 ⁇ 3 )at about 75.5% P 2 O 5 .
  • Such linear polyphosphoric acids have 2 to 15 phosphorus atoms, which each bear a strongly acidic OH group.
  • the two terminal P atoms are each bonded to a weakly acidic OH group.
  • High linear and cyclic polyphosphoric acids are present only at acid concentrations above 82% P 2 O 5 .
  • Commercial phosphoric acid has a 82 to 85% by weight P 2 O5 content. It consists of about 55% tripolyphosphoric acid, the remainder being H 3 PO 4 and other polyphosphoric acids.
  • a polyphosphoric acid suitable for use according to the present invention is a 84% (as P 2 O 5 ) polyphosphoric acid supplied by ACROS (Cat. No. 19695-0025). Binder
  • the layer further contains a binder. According to an eleventh embodiment of the layer, according to the present invention, the layer further contains polyvinylpyrrolidone) .
  • Adding a binder to the dispersion improves the layer quality and photovoltaic properties of layers, according to the present invention, and up to a weight ratio of 10% binder to metal chalcogenide composite nano-particles. Too much binder, e.g. a weight ratio of 50% binder to metal chalcogenide composite nano- particles, adversely affects the photovoltaic properties. This is probably due to adversely affecting the percolation threshold of the n- and p-type semi-conducting particles thereby reducing the short circuit current.
  • Suitable binders include: polyvinylpyrrolidone) ; cellulose and cellulose derivatives, such as carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methyl cellulose, ethyl cellulose, quaternary ammonium cellulose derivatives (e.g. CelquatTM) ; polyacrylic acid, polymethacrylic acid, poly (styrenesulphonic acid) ; polyallylamine; copolymers of methylvinylether and maleic anhydride; gelatine and polyvinylalcohol .
  • polyvinylpyrrolidone polyvinylpyrrolidone
  • cellulose and cellulose derivatives such as carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methyl cellulose, ethyl cellulose, quaternary ammonium cellulose derivatives (e.g. CelquatTM)
  • polyacrylic acid polymethacrylic acid, poly (styrenesulphonic acid
  • Supports for use according to the present invention include polymeric films, silicon, ceramics, oxides, glass, polymeric film reinforced glass, glass/plastic laminates, metal/plastic laminates, paper and laminated paper, optionally treated, provided with a subbing layer or other adhesion promoting means to aid adhesion to the layer configuration, according to the present invention.
  • Suitable polymeric films are poly (ethylene terephthalate) , poly (ethylene naphthalate) , polystyrene, polyethersulphone, polycarbonate, polyacrylate, polyamide, polyimides, cellulosetriacetate, polyolefins and poly (vinylchloride) , optionally treated by corona discharge or glow discharge or provided with a subbing layer.
  • the photovoltaic device comprises two electrodes at least one of which is transparent.
  • Suitable transparent electrodes are inorganic transparent electrodes, such as indium tin oxide, Sn ⁇ 2 :F, tin antimony oxide, zinc oxide, vanadium pentoxide and copper iodide, and organic transparent electrodes, such as polyaniline, poly(3,4- ethylenedioxythiophene) etc.
  • Photovoltaic devices comprising a layer, according to the present invention, can be of two types: the regenerative type which converts light into electrical power leaving no net chemical change behind in which current-carrying electrons are transported to the anode and the external circuit and the holes are transported to the cathode where they are oxidized by the electrons from the external circuit and the photosynthetic type in which there are two redox systems one reacting with the holes at the surface of the semiconductor electrode and one reacting with the electrons entering the counter-electrode, for example, water is oxidized to oxygen at the semiconductor photoanode and reduced to hydrogen at the cathode.
  • the charge transporting process can be ionic or electronic.
  • Such regenerative photovoltaic devices can have a variety of internal structures in conformity with the end use. Conceivable forms are roughly divided into two types: structures which receive light from both sides and those which receive light from one side.
  • An example of the former is a structure made up of a transparently conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer and a transparent counter electrode electrically conductive layer e.g. an ITO-layer or a PEDOT/PSS-containing layer having interposed therebetween a photosensitive layer and a charge transporting layer.
  • Such devices preferably have their sides sealed with a polymer, an adhesive etc. to prevent deterioration or volatilization of the inside substances.
  • the external circuit connected to the electrically-conductive substrate and the counter electrode via the respective leads is well-known. Industrial application
  • Layers can be used in both regenerative and photosynthetic photovoltaic devices.
  • the ZnS dispersion 20% substoichiometric in zinc was prepared as follows: first solutions 1 and 2 were added simultaneously at 25°C at a flow rate of 500 mL/min to 1000 mL of deionized water maintained at 25°C and stirred at 1500 rpm. To 1000 mL of the resulting dispersion, 1000 mL of a 5% thioglycerol solution in water were added and the dispersion concentrated to 1000 mL by means of a Fresenius F60 cartridge. This dispersion was subsequently diafiltered by using 5000 mL of a 5% solution of thioglycerol in water. This dispersion was then further diafiltered using 2000 mL of deionized water.
  • the dispersion was further concentrated to a volume of about 570 mL (0.382M in ZnS x ).
  • a concentration of 25 g/L of Zn was determined by ICP.
  • Absorption measurements showed a bandgap of around 295 nm, indicating particle sizes below 4 nm, according to the Brus ' s equation [L. E. Brus , J. Chem. Phys. 80(9), 4403-4409 (1984)].
  • the Cu x S dispersion 4.5% substoichiometric in sulphur was prepared as follows: solutions 3 and 4 were added simultaneously at 25°C and a flow rate of 500 mL/min to solution 5 maintained at 25°C and stirred at 1500 rpm. 1000 mL of the resulting dispersion was diafiltered using 5000 mL of a 5% solution of thioglycerol in water. This dispersion was then further diafiltered using 2000 mL of deionized water. Finally the dispersion was further concentrated to a volume of about 200 mL. A concentration of 25 g/L (0.393M) of Cu was determined by ICP.
  • dispersion 1 35.1 mL of dispersion 1 (0.382M) was mixed with 3.9 mL of dispersion 2 (0.393M) and to this 1 mL of a 1% solution in water of ZONYL FSN 100 (Dupont) was added to produce coating dispersion A with 90 mole % ZnS x and 10 mole % CuS x .
  • the Zn(99at%) Cu(lat%) metal sulphide nano-particle dispersion 1% substoichiometric in sulphur was prepared as follows: 0.5 mL of solution 7 was first added to solution 8 maintained at 25°C and stirred at 1500 rpm and then solutions 6 and 7 were added simultaneously at 25°C and at a flow rate of 500 mL/min. To 1000 mL of the resulting dispersion, 1000 mL of a 2% sodium polyphosphate solution was added to stabilize the nano-particle dispersion and this dispersion concentrated to 1000 mL by means of a Fresenius F60 cartridge.
  • This dispersion was then diafiltered using 6000 mL of a 2% solution of sodium polyphosphate in deionized water. The dispersion was further concentrated to a concentration of about 35 g ZnS/L (0.36M). This is dispersion 3.
  • the Zn (91.8at%) Cu(8.2at%) metal sulphide nano-particle dispersion substoichiometric in sulphur was prepared as follows: 0.5 mL of solution 9 was added to solution 11 maintained at 25°C and stirred at 1500 rpm and then solutions 9 and 10 were added simultaneously at 25°C and at a flow rate of 500 mL/min. To 1000 mL of the resulting dispersion, 1000 mL of a 2% polyphosphoric acid solution was added to stabilize the nano-particle dispersion and the dispersion concentrated to 1000 mL by means of a Fresenius F60 cartridge. This dispersion was then diafiltered using 6000 mL of a 2% solution of polyphosphoric acid in water.
  • the dispersion was further concentrated to a volume of about 570 mL (0.36M) to produce dispersion 4.
  • a volume of about 570 mL (0.36M) On average 20 to 30% by weight of the dispersion is lost during the washing and concentration processes through ion exchange, loss of small particles in the pores of the Fresenius cartridge etc.
  • the Zn(83.3at%) Cu(16.7at%) metal sulphide nano-particle dispersion substoichiometric in sulphur was prepared as follows: 0.5 mL of solution 12 was added to solution 11 maintained at 25°C and stirred at 1500 rpm and then solutions 10 and 12 were added simultaneously at 25°C and at a flow rate of 500 mL/min. To 1000 mL of the resulting dispersion, 1000 mL of a 2% polyphosphoric acid solution was added and the dispersion concentrated to 1000 mL using a Fresenius F60 cartridge. This dispersion was then diafiltered using 6000 mL of a 2% solution of polyphosphoric acid in water. The dispersion was further concentrated to a volume of about 570 mL (0.36M) to produce dispersion 5.
  • the Ag 2 S nano-dispersion 2.1% superstoichiometric in sulphur was prepared as follows: to solution 15, held at 4°C and stirred at 5 1500 rpm, solutions 13 and 14 were added, simultaneously both at 4°C at a flow rate of 500 mL/min. This is dispersion 6 which contained approximately 5 g/L (0.00403M) Ag 2 S nano-particles.
  • dispersion 7 33.2 mL of dispersion 7 was ultrasonically treated for 6 minutes of ultrasound treatment, followed by the addition of 2.5 mL of a 5 % solution of polyvinylpyrrolidone (LUVISKOL K-90; BASF) in water and 1 mL of a 1% solution of ZONYLTM FSN 100 (Dupont) in water to produce coating dispersion H.
  • polyvinylpyrrolidone LUVKOL K-90; BASF
  • ZONYLTM FSN 100 Dupont
  • the Zn(75at%)Cu(20at%)Ag(5at%) metal sulphide nano-particle dispersion 24% substoichiometric in sulphur was prepared as follows: solutions 17 and 18 were added simultaneously at 25°C and at a flow rate of 500 mL/min to solution 19 maintained at 25°C and stirred at 1500 rpm. To 1000 mL of the resulting dispersion, 1000 mL of a 2% polyphosphoric acid solution was added and the dispersion concentrated to 1000 mL using a Fresenius F60 cartridge. This dispersion was then diafiltered using 6000 mL of a 2% solution of polyphosphoric acid in water. The dispersion was then further concentrated to a volume of about 570 mL. Coating dispersion I:
  • the Zn(65at%) Cu(20at%)Ag(5at%) metal sulphide nano-particle dispersion 24% substoichiometric in sulphur was prepared as follows: solutions 20 and 18 were added simultaneously at 25°C and at a flow rate of 500 mL/min to solution 19 maintained at 25°C and stirred at 1500 rpm. To 1000 mL of the resulting dispersion, 1000 L of a 2% polyphosphoric acid solution was added and the dispersion concentrated to 1000 mL by means of a Fresenius F60 cartridge. This dispersion was then diafiltered by using 6000 mL of a 2% solution of polyphosphoric acid in water. The dispersion was then further concentrated to a volume of about 570 mL. Coating dispersion K:
  • the Zn(45at%) Cu(40at%) Ag(15at%) metal sulphide nano-particle dispersion 24% substoichiometric in sulphur was prepared as follows: solutions 21 and 18 were added simultaneously at 25°C and at a flow rate of 500 mL/min to solution 19 maintained at 25°C and stirred at 1500 rpm. To 1000 mL of the resulting dispersion, 1000 mL of a 2% polyphosphoric acid solution was added and the dispersion concentrated to 1000 mL by means of a Fresenius F60 cartridge. This dispersion was then diafiltered using 6000 mL of a 2% solution of polyphosphoric acid in water. The dispersion was then further concentrated to a volume of about 570 mL.
  • Photovoltaic devices 90; BASF) in water and 0.5 mL of a 1% solution of ZONYLTM FSN 100 (Dupont) in water was added to 18.15 mL of dispersion 10 to produce coating dispersion L with a weight ratio of binder/metal sulphide particles of 1:10.
  • Photovoltaic devices 90; BASF) in water and 0.5 mL of a 1% solution of ZONYLTM FSN 100 (Dupont) in water was added to 18.15 mL of dispersion 10 to produce coating dispersion L with a weight ratio of binder/metal sulphide particles of 1:10.
  • Photovoltaic devices was built up on an ITO layer on a PET
  • Spectrophotometric measurements were carried out on the ca. 100 nm thick layers prepared with coating dispersions F, G, H, I, J, K and L.
  • the absorption spectra obtained are shown in Figure 1.
  • the absorption spectra for 100 nm thick layers prepared with coating dispersions F, G, H, I, J, K and L are shown in Figure 1.
  • the high absorption with the layer prepared with coating dispersion H resulted from opacity, which was due to a very high haze probably due to larger agglomerates .
  • the active area was 25 mm2
  • V oc open circuit voltage
  • l sc short circuit current density
  • Adding a binder to the dispersion improved the layer quality and the photovoltaic properties up to a weight ratio of 10% binder to metal chalcogenide composite nano-particles. Too much binder, e.g. a weight ratio of 50% binder to metal chalcogenide composite nano-particles (Dispersion J) had an adverse effect on the photovoltaic properties.
  • Photovoltaic devices incorporating a layer coated with Dispersion L exhibited the highest photocurrent, which was probably due to the fact that the n-type (ZnS) and p-type (Cu x S) semiconducting material was present in similar concentrations.
  • the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention.

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Abstract

L'invention concerne une nanoparticule composite de chalcogénure métallique comportant un métal capable de former des nanoparticules de chalcogénure semi-conducteur de type p et un métal capable de former des nanoparticules de chalcogénure semi-conducteur de type n. Au moins un des chalcogénures métalliques a une bande interdite comprise entre 1.0 et 2.9 eV. La concentration du métal capable de former des nanoparticules de chalcogénure semi-conducteur de type p est au moins égale à 5 % et inférieure à 50 % du métal en pourcentage atomique. La présente invention porte également sur une dispersion et sur une couche comportant ces nanoparticules et sur un dispositif photovoltaïque doté de cette couche.
PCT/EP2002/010268 2002-09-12 2002-09-12 Nanoparticules composites de chalcogenure metallique et couches formees de ces nanoparticules WO2004024629A1 (fr)

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PCT/EP2002/010268 WO2004024629A1 (fr) 2002-09-12 2002-09-12 Nanoparticules composites de chalcogenure metallique et couches formees de ces nanoparticules
AU2002340902A AU2002340902A1 (en) 2002-09-12 2002-09-12 Metal chalcogenide composite nano-particles and layers therewith
EP02774614A EP1551767A1 (fr) 2002-09-12 2002-09-12 Nanoparticules composites de chalcogenure metallique et couches formees de ces nanoparticules
JP2004535035A JP2005538518A (ja) 2002-09-12 2002-09-12 金属カルコゲニド複合材料ナノ−粒子及びそれを有する層
US10/659,926 US7468146B2 (en) 2002-09-12 2003-09-11 Metal chalcogenide composite nano-particles and layers therewith

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WO2014091398A1 (fr) * 2012-12-14 2014-06-19 Commissariat A L'energie Atomique Et Aux Energies Alternatives Suspension d'agregats monodisperses de sulfure de metal, son procede de fabrication et ses utilisations
US8921688B2 (en) 2007-09-12 2014-12-30 Mitsubishi Materials Corporation Composite film for superstrate solar cell having conductive film and electroconductive reflective film formed by applying composition containing metal nanoparticles and comprising air pores of preset diameter in contact surface

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JP5538695B2 (ja) * 2007-09-12 2014-07-02 三菱マテリアル株式会社 スーパーストレート型薄膜太陽電池用の複合膜
JP5583060B2 (ja) * 2011-03-09 2014-09-03 大阪瓦斯株式会社 量産に適した方法で製造可能な亜鉛含有光電変換素子
ES2772177T3 (es) * 2013-08-01 2020-07-07 Lg Chemical Ltd Nanopartículas de calcogenuro metálico para preparar una capa de absorción de luz de una célula solar, y método de preparación para esto

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CN100441509C (zh) * 2005-12-20 2008-12-10 中国科学院兰州化学物理研究所 硫化铜纳米颗粒的制备方法
US8921688B2 (en) 2007-09-12 2014-12-30 Mitsubishi Materials Corporation Composite film for superstrate solar cell having conductive film and electroconductive reflective film formed by applying composition containing metal nanoparticles and comprising air pores of preset diameter in contact surface
WO2014091398A1 (fr) * 2012-12-14 2014-06-19 Commissariat A L'energie Atomique Et Aux Energies Alternatives Suspension d'agregats monodisperses de sulfure de metal, son procede de fabrication et ses utilisations
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