WO2012042264A2 - Composition imprimable, procédé et utilisations - Google Patents

Composition imprimable, procédé et utilisations Download PDF

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Publication number
WO2012042264A2
WO2012042264A2 PCT/GB2011/051842 GB2011051842W WO2012042264A2 WO 2012042264 A2 WO2012042264 A2 WO 2012042264A2 GB 2011051842 W GB2011051842 W GB 2011051842W WO 2012042264 A2 WO2012042264 A2 WO 2012042264A2
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Prior art keywords
composition
group
metal
printed
polymer binder
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PCT/GB2011/051842
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English (en)
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WO2012042264A3 (fr
Inventor
Dan Tonchev
Zlatka Stoeva
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Dzp Technologies Ltd
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Priority to EP11767290.7A priority Critical patent/EP2640788A2/fr
Publication of WO2012042264A2 publication Critical patent/WO2012042264A2/fr
Publication of WO2012042264A3 publication Critical patent/WO2012042264A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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 is concerned with the fabrication of electronic devices, particularly opto-electronic devices such as photocells, photodiodes, phototransistors and solar cells.
  • a photoconductor or photoresistor means a component whose resistance decreases with increasing the intensity of the incident light.
  • a photodiode is a component capable of converting light into either current or voltage, depending on the mode of operation.
  • Photovoltaics In photovoltaics (PV), electrical power is generated by converting solar radiation into direct current electricity using semiconductors that exhibit the photovoltaic effect.
  • Photovoltaic power generation employs solar panels composed of a number of solar cells containing a photovoltaic material.
  • Photoconductivity is an optical and electrical phenomenon in which a material becomes more electrically conductive due to the absorption of electromagnetic radiation such as visible light, ultraviolet light, infrared light, or gamma radiation.
  • electromagnetic radiation such as visible light, ultraviolet light, infrared light, or gamma radiation.
  • a material such as a semiconductor
  • the number of free electrons and electron holes changes and raises its electrical conductivity.
  • the light that strikes the semiconductor must have enough energy to raise electrons across the band gap, or to excite the impurities within the band gap.
  • a bias voltage and a load resistor are used in series with the semiconductor, a voltage drop across the load resistors can be measured when the change in electrical conductivity of the material varies the current flowing through the circuit.
  • Applications of photoconductive materials include xerography, infrared detection applications, and television or monitor displays.
  • solution-processing methods such as spin-casting are often used to fabricate prototype photocells, and especially photo-voltaic cells.
  • spin-casting is undesirable for large-scale industrial manufacture because it is a slow batch process which very often lacks reproducibility.
  • phthalocyanine films in the prior art are typically obtained by sublimation or vacuum deposition which ensure high purity and high macroscopic order of the phthalocyanine material (Chem. Commun. 2010, Vol. 46, 7090-7108).
  • the invention is concerned with printable compositions which are used to print semiconductive and photoconductive functional objects, devices containing such objects, and methods of producing such objects.
  • the printable compositions disclosed herein are suitable for the deposition of both photoconductors and photodiode components.
  • the compositions are also suitable for the deposition of components for other opto-electronic devices such as phototransistors, photo-detectors and photocells.
  • the functional object of the present invention is preferably a component of a functional electronic device, preferably selected from the group consisting of an opto-electronic device, including but not limited to photodiodes, photocells, phototransistors, photoresistor, optocoupler, and photo-voltaic cells.
  • a particularly preferred device is a photocell.
  • the photocell is suitable for use in solar panels.
  • a functional electronic device having printed thereon a composition comprising a charge transport organic or metalo-organic conjugated hetero-aromatic compound and a polymer binder.
  • the functional object of the present invention may be a component of a functional electronic device having two or more different photoconductor or semiconductor compositions applied to them, the details of the compositions being described in further detail below.
  • the photoconductor or semiconductor compositions are preferably in the form of a film, layer or coating.
  • the film, layer or coating is deposited in contact with another such film, layer or coating.
  • the charge transport organic or metalo-organic conjugated hetero- aromatic compound is a phthalocyanine or phthalocyanine derivative, hole- transport organic or metalo-organic compound.
  • the phthalocyanine macrocycle preferably has the following structure:
  • M represents a non-metal, metal, a metal oxide, or a metal halide.
  • Preferred metals are selected from the group consisting of iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.
  • Preferred metal oxides include oxotitanium and oxovanadium.
  • Preferred metal halides are selected from the group consisting of aluminum chloride, indium chloride, germanium chloride, tin (I I) chloride and tin(IV) chloride, and silicon chloride.
  • M is a metal or metal oxide.
  • M is copper or zinc, particularly zinc.
  • the phthalocyanine is a compound selected from the group consisting of copper phthalocyanine, zinc phthalocyanine, oxotitanium (IV) phthalocyanine, oxovanadium phthalocyanine.
  • the most preferred charge transport organic or metalo-organic conjugated hetero- aromatic compound used in the present invention is unfunctionalised phthalocyanine as shown in Figure 1.
  • phthalocyanine preferred derivatives of phthalocyanine are phthalocyanines where one or more carbon atoms of the macrocycle are exchanged for nitrogen atoms.
  • phthalocyanine particularly preferred derivatives of phthalocyanine are phthalocyanines where one or more hydrogen atoms of the phthalocyanine ring are substituted by functional groups selected from the group consisting of halogens (F, CI, Br, I), hydroxy, amino, C 1-12 alkyl, C ⁇ 12 alkylamino, COOH, C 5 . 24 aryl, thiol, C ⁇ 12 alkoxy, quaternary ammonium, sulphate, sulphonate, sulphamido and nitro groups.
  • halogens F, CI, Br, I
  • Particularly preferred derivatives of phthalocyanine are phthalocyanines having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12 hydrogen atoms of the phthalocyanine ring substituted by functional groups independently selected from the group consisting of halogens (F, CI, Br, I), hydroxy, amino, C 1-12 alkyl, C 12 alkylamino, COOH, C 5 . 24 aryl, thiol, C ⁇ alkoxy, quaternary ammonium, sulphate, sulphonate, sulphamido and nitro groups and mixtures thereof.
  • These derivatives can be used to increase the solubility and dispersability of the phthalocyanine compound, however they are preferably used in limited quantities as they can tend to reduce charge transport in the printed composition.
  • any of the above phthalocyanine derivatives contain copper, zinc, oxotitanium or oxovanadium cores.
  • Preferred derivatives of phthalocyanine are phthalocyanines where wherein M represents a non-metal, metal, a metal oxide, or a metal halide having any of the preferences set out above in respect of non-derivitised phthalocyanine molecules.
  • Phthalocyanines the structure of which is shown in Figure 1 above, are chromophore compounds which have a two-dimensional ⁇ -electron hetero- aromatic system isoelectronic with that of porphyrins, the compounds which are employed by nature in the photosynthesis process. Phthalocyanines and porphyrins have extensively conjugated hetero-aromatic ⁇ systems which are amenable to fast charge transfer to an acceptor. They absorb intensively in the visible region and are usually deeply coloured.
  • Phthalocyanines are well suited for industrial and technical use as photoconductors because they are thermally and chemically stable compounds which absorb intensively in the whole solar spectrum, with very high extinction coefficients and fluorescence quantum yields. This lends them to processing and deposition which are carried out at elevated temperatures, or subsequent curing or drying processes. Because phthalocyanines absorb over a wide spectral range, phthalocyanines absorb more photons and generate higher photocurrents compared to other porphyrins. Phthalocyanines are therefore one of the best organic molecule light- harvesting systems.
  • the phthalocyanines used in the present invention have some other important advantages over other members of the porphyrins group. They have longer exciton diffusion length because they usually stack closely, thus permitting ⁇ - ⁇ orbital overlap and a strong electronic coupling. This is possible because phthalocyanines are usually used without substituent groups whilst porphyrins structures typically have substituents which prevent their close packing, and electron coupling.
  • Phthalocyanines used in the present invention also have relatively high hole mobilities compared to other organic molecules. Different values of mobilities have been reported in the literature, ranging from 10 "7 to 10 2 cm 2 / (V c) (A. W. Hains et al, Chem. Rev, 2010, 1 10, 6689-6735). Mobility is found to depend on the purity of the material, exposure to oxygen, structural templating, etc.
  • the phthalocyanines have highly tunable electronic and optical properties which can be tailored in two ways. First, it is possible to replace the two protons usually found in the molecule cavity by a metal ion/atom, to obtain the metal phthalocyanines described above. Second, it is possible to add various functional or substituent groups to the molecule perimeter.
  • the phthalocyanine compounds are cheap and usually very low in toxicity.
  • the phthalocyanine pigments are usually not film-forming because of their poor solubility but they can be vacuum deposited. However, vacuum deposition is an expensive and time-consuming process.
  • new solvent processes were introduced in the field of electrophotography. These solution processes made use of solutions applied by means of a doctor blade, a bar coater, a roll coater or the like. An example of such solvent process is described in EP 0050464 B1 by Fujitsu Limited.
  • Water-based inkjet inks comprising phthalocyanine compounds are known in the prior art.
  • WO 98/14524 by Zeneca discloses ink composition comprising water, water-dissipative polyester, a disperse phthalocyanine dye and other additives. This composition is suitable for thermal inkjet printing, producing high colour strength and clear images.
  • WO 00/78876 by Avecia Ltd discloses a composition containing phthalocyanine compounds which is suitable for use in inkjet printers.
  • the compositions disclosed in '524 and '876 preferably contain functionalised phthalocyanines which are more soluble and facilitate the preparation and the shelf life of obtained inks.
  • the functionalised phthalocyanines tend to show reduced charge transport when printed, due to the lack or organisation and close stacking of the molecules which contain bulky substituents.
  • compositions disclosed in '524 and '876 further contain 40 to 90 parts of water and are suitable for application on paper, transparent plastics (e.g. overhead projector slides) and textiles which easily absorb water during drying. These compositions are not shown to be suitable for application on metal-coated or semiconductive substrates which are typical component of the electronic and optoelectronic devices.
  • the inkjet inks disclosed in '524 and '876 may comprise ethylene glycol waxes, beeswaxes and other additives which improve the appearance (e.g. gloss) and the scratch resistance of the prints. These additives, whilst desirable in conventional printing, are detrimental to the conductive properties of the obtained prints.
  • Flexographic inks containing phthalocyanine compounds are disclosed in EP 0933407 A1 by NCR International Inc. These inks preferably comprise functionalised phthalocyanines which improve the solubility and stability of the ink but are detrimental to the charge transport properties.
  • phthalocyanine inks which are used to produce colour images by traditional printing methods are not suitable for printing photoconductive components.
  • the printed composition further contains a phthalocyanine coordination complex or compound comprising transition metals including heavy metals with 4d or 5d valence electrons in which mixing between the metal atom d orbitals and ⁇ orbitals from the phthalocyanine macrocycle can improve the carrier mobility.
  • the printed composition further contains an inorganic photoconductive material such as chemical elements (Se, Se-Te, polycrystalline silicon, amorphous silicon), binary oxides (ZnO, Ti0 2 ), binary sulphides (ZnS, CdS), binary tellurides, binary nitrides, or ternary or higher oxides, sulphides, tellurides, nitrides (e.g. transition metal doped ZnO or ZnS, copper indium selenide, etc). Many of these materials are also excitonic semiconductors, i.e. materials in which electrostatically bound excitons are formed upon light absorption.
  • an inorganic photoconductive material such as chemical elements (Se, Se-Te, polycrystalline silicon, amorphous silicon), binary oxides (ZnO, Ti0 2 ), binary sulphides (ZnS, CdS), binary tellurides, binary nitrides, or ternary or higher oxides, sulphides, tellurides, nitrides (e.
  • Preferred inorganic photoconductive materials include ZnO, Ti0 2 , Se, CdS, ZnS, ln 2 S 3 , ln(OH) x S y , CulnS 2 , CulnSe 2 , CdTe, ZnO-Ag, ZnO-Cu, ZnO-CdS, ZnO-Ti0 2 , ZnO-Si0 2 , ZnOTi0 2 , ZnS:Mn and CdSe, more preferably Ti0 2 , ZnO, ZnS, ZnSe, CdS, CdSe, copper indium selenide, copper indium sulphide or their transition metal or main-group metal doped derivates.
  • inorganic photoconductive materials are ZnO,, Se, polycrystalline Si and amorphous Si.
  • Said inorganic photoconductive material may be present in the printed composition in an amount of up to 90% by weight of the entire printed composition, more preferably between 0.5% and 80% by weight, for example between 1 % and 70% by weight, preferably between 5% and 60% by weight.
  • the printed composition may further contain other electron acceptor materials which increase the charge mobility in the printed objects.
  • electron acceptor materials include carbonaceous materials such as, carbon nanotubes, graphene and fullerenes.
  • the printed composition used in the invention may take the form of solid, a paste, or a gel, most preferably a solid.
  • the printed composition forms a thin film having a thickness of between 0.1 um and 1000pm, more preferably between 0.5 ⁇ and 500/im, more preferably between 1 ⁇ and 100/jm, more preferably between 1 /Jim and 10/um, for example, about 1 , 2, 3, 4, 5, 6, 7, 8 or 9 ⁇ .
  • Preferred polymer binder used in the present invention becomes water insoluble when printed.
  • the phthalocyanine compound or derivative is homogeneously dissolved or dispersed in the polymer binder when deposited on the functional object.
  • the polymer binder binds the charge-transport organic or metalo- organic compound to the surface of the printed object.
  • the polymer binder prior to printing is as described below in the following section.
  • the act of printing may cause the polymer binder to react.
  • the act of printing may cause the polymer binder to further polymerise, cross-link, condense, or a mixture thereof.
  • a process may be carried out after printing (such as heating, exposure to UV radiation, etc.) which causes the polymer binder to further polymerise, cross-link, condense, or a mixture thereof.
  • the printed polymer binder is obtainable from a dispersed and dissolved oligomer or polymer.
  • the printed polymer binder may be obtainable from a reactive oligomer or polymer, i.e., there are preferably greater than 1 % by weight, more preferably greater than 5% by weight of functional groups which are capable of reaction (e.g. cross-linking) during the printing/deposition process of the composition according to the present invention.
  • the printed polymer binder is obtainable from the printing of a polymer binder selected from the group consisting of cellulosic binders, polyacetals, polyamides, polyimides, polyesters, polycarbonates, polyamide-imides, polyamide- esters, polyamide ethers, polycarbonate-esters, polyamide-ethers, polyacrylates, polyacrylics, elastomers such as polybutadiene, copolymers of butadiene with one or more other monomers, polyalkylmethacrylates, polyethylene, polypropylene, polystyrene, polyvinyl acetate and polyvinylalcohol.
  • Such polymer binders may be functionalised with hydrophilic groups (such as carboxyl, hydroxyl, sulphonate, quaternary ammonium, and mixtures thereof etc.) in order to render them more water soluble.
  • the polymer binders are used in the form of a blend of two or more members, most preferably blends of low molecular weight and high molecular weight fractions of the same polymer.
  • the printed polymer binder itself, or a blend thereof with another polymer binder is substantially transparent to visible light and/or infra red light.
  • the polymer binder is obtainable from the printing of a polymer binder selected from the group consisting of poly-acrylic, poly-urethane, poly-styrene/poly- acrylic, poly-urethane/poly-acrylic or polyamide polymers, cellulosic binders or commercially formulated binders.
  • the polymer binder is not removed during drying or other post-treatment.
  • the polymer binder which remains in the printed object is crucial for achieving some very desirable properties such as flexibility, conformity and mechanical robustness. Additionally, the polymer binder promotes good adhesion to the printed object. This is particularly useful when the substrate serves as an electrode in a device, for example a metal electrode.
  • the polymer binder by itself may not be semiconductive or photoconductive, the obtained printed objects display useful charge transport properties. This is an unexpected finding, because the prior art teaches that phthalocyanine films of very high purity are usually required to obtain good charge transport. It is also noteworthy that the polymer binders disclosed in this invention are common and cheap polymers, which is very favourable for large-scale manufacture.
  • the polymer binders used in this invention are different by chemical composition, physical properties and function from specialty polymers used in the prior art for the preparation of photo-active layers such as layers in photo-voltaic devices. Polymers which are used in the prior art for the fabrication of photo-active layers are typically conjugated specialty polymers, such as poly(thiophenes) and poly(phenylene vinylenes).
  • one or more of the above-described phthalocyanine compounds are preferably present at a concentration of at least 8 wt% based on a total weight of the composition, preferably between 10 and 80 wt%, more preferably between 15 and 70 wt%, more preferably between 20 and 60 wt%, more preferably between 30 and 50 wt%.
  • one or more of the above-described polymeric binders are preferably present at a concentration of at least 2 wt% based on a total weight of the composition, preferably between 5 and 60 wt%, more preferably between 10 and 50 wt%, more preferably between 15 and 40 wt %.
  • one or more organic solvents may be present in the printed compositions. Such solvents may be removed during or after the printing process. Alternatively, they may be retained in the printed composition, and may have important material properties such as acting as a plasticizer for the printed composition.
  • Suitable organic solvents include, but are not limited to, hydrocarbon solvents such as benzene and toluene; ether type solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; ketone type solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol type solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert- butyl alcohol; nitrile type solvents such as acetonitrile, propionitrile and benzonitrile; ester type solvents such as ethyl acetate and butyl acetate; carbonate type solvents such as ethylene carbonate and propylene carbonate; and the like. These may be used singly or two or
  • one or more additional compositional components may be present in the composition.
  • suitable additional composition components include, but are not limited to, a polymer additive, a rheological modifier, a surfactant, a semiconductor that is a complementary hole transfer partner for the phthalocyanine compound or a combination thereof.
  • the composition immediately (within 5 seconds) after deposition by printing on the object has an organic solvent content of less than 5% by weight of the composition, preferably less than 1% by weight, preferably less than 0.5% by weight of the composition.
  • the composition immediately (within 5 seconds) of deposition by printing on the object has a water content of less than 20% by weight of the deposited composition, preferably less than 10% by weight, preferably less than 5% by weight of the printed composition, preferably less than 1 % by weight of the printed composition.
  • the printed ZnO photoconductor object preferably contains the same polymer binders and solvents as disclosed herein, with all of the analogous preferences disclosed above.
  • ZnO is preferably present at a concentration of at least 10 wt% based on a total weight of the composition, preferably between 20 and 95 wt%, more preferably between 40 and 90 wt%.
  • the composition prior to printing contains the same charge-transport organic or metalo-organic compound as the printed composition, with all of the analogous preferences disclosed above. In this regard, there is preferably no chemical change to the charge-transport organic or metalo- organic compound as a consequence of the printing process.
  • the printable composition is preferably applied by a deposition method on a flexible or rigid substrate followed by removal of at least a portion of the solvent (which may be water, organic solvent or a mixture thereof) to obtain a semiconductive or photoconductive object.
  • the solvent which may be water, organic solvent or a mixture thereof
  • the polymer binder is dispersed or dissolved in water, organic solvent or mixture thereof and contains a low molecular weight and high-molecular weight fraction of the same polymer.
  • the low-molecular weight fraction has a molecular weight between 500 and 10,000 and is used to improve the solubility and stability of the printable composition.
  • the high molecular weight fraction has a molecular weight between 20,000 and 1 ,000,000, preferably between 50,000 and 200,000. This fraction is used to improve the adhesion of the printed object to the substrate and to improve the robustness and mechanical properties of the obtained printed object.
  • the polymer binder can be a reactive oligomer or polymer, i.e., there are preferably greater than 1 % by weight, more preferably greater than 5% by weight of functional groups which are capable of reaction (e.g. cross-linking) during the printing/deposition process of the composition according to the present invention.
  • the polymer binder is selected from the group consisting of cellulosic binders, polyacetals, polyamides, polyimides, polyesters, polycarbonates, polyamide-imides, polyamide-esters, polyamide ethers, polycarbonate-esters, polyamide-ethers, polyacrylates, polyacrylics, elastomers such as polybutadiene, copolymers of butadiene with one or more other monomers, polyalkylmethacrylat.es, polyethylene, polypropylene, polystyrene, polyvinylacetate and polyvinylalcohol.
  • Such polymer binders may be functionalised with one or more hydrophilic groups (such as carboxyl, hydroxyl, sulphonate, quaternary ammonium, and mixtures thereof etc.) in order to render them more water soluble.
  • the polymer binders are used in the form of a blend of two or more members, most preferably blends of low molecular weight and high molecular weight fractions of the same polymer.
  • the weight ratio of low molecular weight fraction to high molecular weight fraction is preferably in the range of 90:10 to 10:90, preferably, 60:40 to 40:60.
  • the polymer binder itself, or a blend thereof with another polymer binder is substantially transparent to visible light and/or infra red light.
  • the polymer binder is selected from the group consisting of poly-acrylic, poly-urethane, poly-styrene/poly-acrylic, poly-urethane/poly-acrylic or polyamide polymers, cellulosic binders, or commercially formulated binders.
  • the printable composition preferably contains the same inorganic photoconductive material as the printed composition, with all of the analogous preferences disclosed above.
  • the printable composition preferably contains the same electron (n-type) conductive materials as the printed composition, with all of the analogous preferences disclosed above.
  • the printable composition used in the invention may take the form of a liquid, paste, gel or thixotropic liquid.
  • the polymer binder is used to bind the charge transport organic or metalo-organic conjugated hetero-aromatic compound when deposited on the surface of the printed object.
  • the charge transport organic or metalo- organic conjugated hetero-aromatic compound is homogeneously dispersed or dissolved in the printable compositions along with the polymer binder.
  • the charge transport organic or metalo-organic conjugated hetero-aromatic compound and the polymer binder are preferably homogeneously dispersed or dissolved in water, organic solvent, or mixture thereof.
  • the printed polymer binder may be obtainable from a reactive oligomer or polymer, i.e., there are preferably greater than 1 % by weight, more preferably greater than 5% by weight of functional groups which are capable of reaction (e.g. cross-linking) during the printing/deposition process of the composition according to the present invention.
  • the polymer binder may be a cellulose polymer, such as ethyl cellulose, for example an ethyl cellulose extender of in an amount of 5-15% by weight.
  • one or more of the above-described phthalocyanine compounds are preferably present at a concentration of at least 1 wt% based on a total weight of the composition.
  • the upper limit of the concentration of the phthalocyanine compound in the composition is often near the solubility limit, or the limit of phase stability of the dispersion of that compound in the particular solvent at the temperature of the composition during its application to a substrate such as in the fabrication of a functional electronic device.
  • one or more of the above-described phthalocyanine compounds are preferably present in a concentration ranging from about 1 wt% to about 60 wt% based on a total weight of the composition, more preferably, from about 5 wt% to about 50 wt%, more preferably 10 to 40 wt%.
  • one or more of the above-described polymeric binders are preferably present in a concentration of at least 2 wt% based on a total weight of the composition, preferably between 2 and 80 wt%, more preferably between 5 and 70 wt%, more preferably between 5 and 60 wt%.
  • the polymer binder which is a polyacrylic, polyurethane, polystyrene/polyacrylic, polystyrene/polyurethene or polyamide polymer, which is preferably present in an amount of 5-15% by weight.
  • the printable composition preferably further comprises water as a solvent in the range 30% to 60% by weight of the total composition.
  • the binder is cellulose based polymer binder. Preferably, it is present in an amount of 5-15% by weight.
  • the printable composition further comprises a non-aqueous solvent in an amount of 30 to 60% by weight of the total composition.
  • the printable composition further contains an inorganic photoconductive material such as chemical elements (Se, Se-Te, polycrystalline silicon, amorphous silicon), binary oxides, binary sulphides, binary tellurides, binary nitrides (ZnO, Ti0 2 , ZnS, CdS), or ternary or higher oxides, sulphides, tellurides, nitrides (e.g. transition metal doped ZnO or ZnS, copper indium selenide, etc). Many of these materials are also excitonic semiconductors, i.e. materials in which electrostatically bound excitons are formed upon light absorption.
  • chemical elements Se, Se-Te, polycrystalline silicon, amorphous silicon
  • binary oxides binary sulphides, binary tellurides, binary nitrides (ZnO, Ti0 2 , ZnS, CdS), or ternary or higher oxides, sulphides, tellurides, nitrides (e.g. transition metal doped ZnO or Z
  • Preferred inorganic photoconductive materials include ZnO, Ti0 2 , Se, CdS, ZnS, in 2 S 3 , ln(OH) x S y , CulnS 2 , CulnSe 2 , CdTe, ZnO-Ag, ZnO-Cu, ZnO-CdS, ZnO-Ti0 2 , ZnO- Si0 2 , ZnOTi0 2 , ZnS:Mn and CdSe, more preferably Ti0 2 , ZnO, ZnS, ZnSe, CdS, CdSe, copper indium selenide, copper indium sulphide or their transition metal or main-group metal doped derivates.
  • inorganic photoconductive materials are ZnO, Se, polycrystalline Si and amorphous Si.
  • Said inorganic photoconductive material may be present in the printable composition in an amount of up to 80% by weight of the entire composition, more preferably between 0.5% and 70% by weight, for example between 1 % and 60% by weight, preferably between 2% and 50% by weight.
  • the printable composition contains one or more organic solvents.
  • Suitable organic solvents include, but are not limited to, hydrocarbon solvents such as benzene and toluene; ether type solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; ketone type solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohol type solvents such as methanol, ethanol, propanol, isopropanol, n- butyl alcohol and tert-butyl alcohol; nitrile type solvents such as acetonitrile, propionitrile and benzonitrile; ester type solvents such as ethyl acetate and butyl acetate; carbonate type solvents such as ethylene carbonate and propylene
  • compositions preferably contain a suitable organic solvent in an amount of up to 80 wt% based on a total weight of the composition, preferably up to 50 wt% based on a total weight of the composition, preferably greater than 5 wt%, preferably in the range of 5 wt% to 40 wt%.
  • one or more additional compositional components may be present in the composition.
  • Suitable additional composition components include, but are not limited to, a polymer additive, a rheological modifier, a surfactant or a combination thereof.
  • the amount of these additives is preferably kept to a minimum as they are detrimental to the photoconductive properties of the obtained printed objects.
  • the composition may contain water as a solvent.
  • the water is preferably present in up to 80% by weight, more preferably up to 60% by weight, more preferably in the range of 20% to 50% by weight of the entire composition.
  • the composition contains more than 5% by weight of water.
  • the water is deionized.
  • the composition comprises a solvent which consists essentially of water.
  • the composition may contain a mixture of water and organic solvent as a solvent.
  • the solvent is preferably present in up to 80% by weight, more preferably up to 60% by weight, more preferably in the range of 20% to 50% by weight of the entire composition.
  • the water is deionized.
  • the present invention discloses a cheap and reproducible printable composition, a method of using the said composition to obtain photoconductive and photodiode objects, and uses of the obtained objects. More specifically, the invention discloses a printable composition comprising charge transport organic or metalo- organic compound or compounds which are semiconductive or photoconductive.
  • the said composition can be applied by a printing method such as flexography, gravure, screen and other printing and coating methods known in the art.
  • the composition may also contain an inorganic photoconductor or semiconductor which enhances the photoconductive and charge transport properties.
  • a ZnO printable composition comprising:
  • Zinc Oxide Zinc Oxide (ZnO);
  • the disclosed ZnO printable composition is used to fabricate printed ZnO photoconductor object.
  • the ZnO printable composition preferably contains the same polymer binders and solvents as disclosed herein, with all of the analogous preferences disclosed above.
  • ZnO is preferably present at a concentration of at least 10 wt% based on a total weight of the composition, preferably between 15 and 90 wt%, more preferably between 20 and 80 wt%, more preferably between 30 and 80 wt%.
  • water can be used as a solvent in the composition prior to printing. This makes the manufacturing process extremely beneficial in terms of environmental protection, human health and safety. More specifically, water can be used as a solvent when the polymer binder is water-soluble which is the case with poly-acrylic, poly-urethane, poly-styrene/poly-acrylic, poly-urethane/poly-acrylic or polyamide polymer binders.
  • the printable composition is formulated with organic solvents, for example ethyl acetate solvent.
  • the printable composition disclosed in this invention is applied using any coating or printing methods, including flexography, gravure, screen, inkjet printing, offset and lithographic printing.
  • the printable composition is preferably printed onto a suitable substrate.
  • substrates may be semiconductor substrates, paper, metal, metal-laminated paper, glass, quartz, textiles, polymers, metal-laminated polymers and the like.
  • the functional electronic device may be formed from this printed substrate, for example, by the application of electronic connections and other components thereto.
  • the functional electronic device may be pre-formed (i.e., including, for example, electronic connections and other components) from an unprinted substrate, and subsequently printed with the printable composition to form the functional electronic device.
  • the solvent (either water or organic solvent or both) is preferably removed after deposition by air drying, elevated temperature or UV treatment to obtain a printed photoconductive or semiconductive object.
  • the present invention also provides a method of producing a semiconductive or photoconductive electronic device, comprising:
  • composition comprising:
  • the printing is preferably applied using flexography, gravure, screen, inkjet printing, offset or lithographic printing, or mixtures thereof.
  • the printable composition used in the method may comprise any of the features described above, including the preferred features described.
  • the method may include roll-to-roll fabrication techniques.
  • composition used in the method may be printed onto a substrate selected from the group consisting of semiconductor substrates, paper, metal, metal-laminated paper, glass, quartz, textiles, polymers, metal-laminated polymers and metal- laminated textiles.
  • the substrate can be a partially assembled photonic or electronic device.
  • the semiconductive or photoconductive electronic device is preferably selected from the group consisting of photodiodes, photocells, phototransistors, photoresistor, optocoupler, and photo-voltaic cells, preferably a photocell.
  • a method of producing a semiconductive or photoconductive electronic device comprising: printing or coating a composition comprising:
  • solvent selected from the group consisting of water, organic solvent, and mixtures thereof;
  • the device, compositions and method may further comprise any of the features disclosed in respect of previous aspects of the invention.
  • preferred features according to previous aspects of the invention apply (particularly in relation to the polymer binder, water, solvents, and their preferred quantities, ratios and specific embodiments).
  • the substrate (1 ) can be paper, polymer, fabric or other flexible or rigid material.
  • Electrically conductive layer (2) serving as an electrode is attached to the substrate.
  • the electrode can be applied by lamination, for example by aluminium lamination.
  • the electrode can also be applied by printing, vacuum deposition (e.g. argon plasma sputtering), or other suitable method.
  • the photoconductive composition (3) is printed on the electrode.
  • a top electrode (4) for example gold electrode, is printed or deposited using printing, vacuum deposition or other suitable method.
  • the photocell can be used as a component of a printed planar photovoltaic cell as shown in Figure 3 where two different photoconductors (2) and (5) are deposited successively to form a cell.
  • the photocells illustrated in Figure 2 and Figure 3 can be produced in an "invert" geometry where the top electrode (4) is a transparent substrate such as glass, on which components (3), (5) and (2) are subsequently deposited.
  • a “charge transport compound” means a chemical compound which has charge transport functionality, i.e. it can transport charge carriers such as electrons or holes.
  • Organic compounds which have ⁇ -bonds, ⁇ -conjugated systems, polycyclic or macrocyclic aromatic hydrocarbons are charge transport compounds.
  • a “polymer” means a material formed by polymerising and/or crosslinking one or more monomers, macromers and/or oligomers and having two or more repeat units.
  • a semiconducting material, composition or layer is one which has an electrical conductivity in the range of 10 3 to 1 CT 8 Siemens per centimetre, more preferably between 500 to 10 "7 , more preferably between 300 to 10 ⁇ 6 , more preferably between 250 to 10 ⁇ 5 , more preferably between 10 to 10 ⁇ 5 Siemens per centimetre, more preferably greater than 10 " "* or 10 "3 Siemens per centimetre.
  • the conductivity of the material or composition is measured according to ASTM D4308 - 10.
  • alkyl group refers to a straight or branched saturated monovalent hydrocarbon radical, having the number of carbon atoms as indicated.
  • suitable alkyl groups include, methyl, ethyl, propyl, n-butyl, t-butyl, iso-butyl and dodecanyl.
  • alkoxy group include without limitation, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy, etc.
  • amino group includes, without limitation, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.
  • Example 1 Printable composition containing copper phthaiocyanine (CuPc)
  • a composition comprising copper phthaiocyanine was formulated and prepared.
  • the composition contained copper phthaiocyanine (CuPc) which was dispersed in commercial cellulose-based polymer binder in organic solvent, (ethyl acetate and alcohol).
  • the composition was mixed and shaken at room temperature using a laboratory mixer.
  • the amount of the CuPc pigment varied from 8 to 20%..
  • the exact content was adjusted to obtain the typical viscosity required for flexographic printing.
  • the composition was applied onto an aluminium-laminated paper of size 7cm x 10cm at room temperature using flexographic hand proofer.
  • the obtained prints were air-dried at room temperature to remove the solvent.
  • a top gold contact was deposited using argon cold plasma deposition.
  • the electron transport properties of the obtained printed photoconductors were measured using time-of-flight measurements.
  • the data can be summarised as follows:
  • Printed film thickness was 1 -3 microns
  • Electrons mobility ⁇ 4.3x1 Oe-7 (cm 2 fs/.s)
  • Electrons lifetime ⁇ 400 microseconds
  • the hole mobility of the films is surprisingly high, given that the films do not consist of pure copper phthalocyanine. This suggests that other factors could be at play, such as self- organisation of the Cu-phthalocyanine molecules during the printing process, which leads to their alignment parallel to the substrate/electrode. Such self-organisation facilitates anisotropic charge transport along the ⁇ orbitals, i.e. perpendicular to the electrode, which explains the high hole mobility in the printed films.
  • prior art teaches that charge mobility in phthalocyanine films occurs along the stacking axis due to the strong ⁇ - coupling between neighbouring molecules.
  • phthalocyanine films of such good quality are obtained using a simple deposition method such as printing.
  • films of phthalocyanine compounds are typically obtained by vacuum deposition or sublimation which are expensive methods requiring special controlled environment and specialised equipment.
  • vacuum deposited films of phthalocyanines align in such a way that the stacking direction is perpendicular to the optimal direction of charge transport, i.e. perpendicular to the substrate (Chem Commun. 2010, 46, 7090- 7108).
  • Sullivan et al Appl. Phys.
  • PTCDA perylenetetracarboxylic acid
  • Example 2 Printable composition containing copper phthalocyanine (CuPc) and a-Se
  • This example demonstrates the use of a hybrid printable composition which comprises a charge transport compound copper phthalocyanine (CuPc) and an inorganic photoconductor to enhance the properties of the printed photoconductor.
  • the inorganic photoconductor in this example is Se.
  • a composition comprising copper phthalocyanine and Se was formulated and prepared. The composition contained, copper phthalocyanine (CuPc) and Se powder dispersed in commercial cellulose-based polymer binder in organic solvent (ethyl acetate and alcohol). The Se powder was 20% by weight of the total solids in the composition.
  • the composition was thoroughly mixed in a laboratory mixer until reaching viscosity of about 50s measured by Zahn 2 cup.
  • the composition was applied onto an aluminium-laminated paper (size 7cm x 10cm) at room temperature using flexographic hand proofer. A top gold contact was deposited using argon cold plasma deposition.
  • Example 1 illustrates, there is surprisingly good compatibility of the semiconductive organic and inorganic compounds with polymer binders and solvents typically used in for flexographic inks. Also, the hole mobility is significantly increased compared to pure copper phthalocyanine printed films in Example 1. This shows the potential for improving the properties of the printed photoconductive objects and the opportunity to prepare purely semiconductive inks which can replace expensive vacuum deposition with printing.
  • Example 3 Printable composition containing zinc phthalocyanine (ZnPc) and ZnO
  • This example demonstrates the use of a hybrid printable composition which comprises an organic charge transport compound, zinc phthalocyanine (ZnPc), and an inorganic photoconductor (ZnO).
  • This composition is used to obtain a photodiode working in a photo-voltaic (PV) mode.
  • the composition is also used to obtain a printed photoconductor.
  • a composition comprising zinc phthalocyanine (ZnPc) pigment of purity 99.5% and ZnO powder in ratio 1 :1 was formulated and prepared.
  • the composition contained solids of 12% by weight dispersed in acrylic binder using deionised water as a solvent.
  • the composition was thoroughly mixed using a laboratory mixer until reaching viscosity of about 20s measured by Zahn 2 cup.
  • the composition was applied onto an aluminium-laminated paper of size 7cm x 10cm at room temperature using flexographic hand proofer.
  • a top gold contact was deposited using argon plasma sputtering.
  • the hole transport and electron transport properties of the prepared printed films were measured using time-of-flight measurements and the following data were obtained:
  • This example demonstrates the possibility to fabricate a printed photoconductor using a hybrid inorganic-organic composition.
  • ZnO is a cheap commercially available material.
  • the charge transport properties of the films show that mobility of both holes and electrons is significantly improved, compared to purely phthalocyanine films described in Example 1 .
  • the printable composition described in this example can be used to fabricate printed photocells, or to fabricate components of photovoltaic cells where both hole and electron mobilities are required.
  • the latter components are obtained using polymer or hybrid blends which are typically spin-cast to fabricate bulk hetero-junction photovoltaic layers.
  • the prior art also teaches that the two components can be co-evaporated or co-deposited using specialised equipment.
  • This example demonstrates a printable composition which can be used to fabricate printed films which display both hole and electron transport. Further, the composition is suitable for large-scale, cost-effective industrial printing and coating.
  • the printable compositions disclosed herein can be used to obtain such bi-layer or multi-layer structures.
  • Such a structure is presented in Figure 2, where electron-transport photoconductor ZnO (5) is first deposited by printing on aluminium coated paper.
  • the ZnO composition contained 15% by solids ZnO dispersed in acrylic binder using deionised water as a solvent. The composition was thoroughly mixed before printing, using a laboratory mixer.
  • a hole-transport layer, copper phthlocyanine (2) is then deposited by printing on the ZnO layer using the procedure described in Example 1. Finally, a gold contact is deposited by sputtering.
  • the printed cell represents a photodiode operating in photovoltaic mode.
  • the photo-voltaic effect can be observed by exposing the cell to the sunlight or other light source, which leads to the generation of voltage across the cell.
  • open circuit voltage (V oc ) of up to 0.5 V was observed for printed cells with area of the photoactive layer 3 x 3 cm, under illumination with sunlight.

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  • Life Sciences & Earth Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Cette invention concerne un dispositif électronique semi-conducteur ou photoconducteur portant une composition imprimée sur sa surface, ladite composition comprenant : un composé hétéro-aromatique de transport de charge de type organique ou métallo-organique conjugué ; et un liant polymère. Cette invention concerne, en outre, des compositions imprimables, et des procédés d'utilisation et de fabrication se rapportant audit dispositif.
PCT/GB2011/051842 2010-09-29 2011-09-29 Composition imprimable, procédé et utilisations WO2012042264A2 (fr)

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CN103242695A (zh) * 2013-05-05 2013-08-14 浙江师范大学 一种ZnO半导体纳米材料墨水的制备方法
US20150267108A1 (en) * 2014-03-19 2015-09-24 Li-Cor, Inc. Phthalocyanine formulation and uses thereof
EP2903049A4 (fr) * 2012-09-28 2016-06-01 Oceans King Lighting Science Dispositif électroluminescent organique et son procédé de préparation
WO2016139464A3 (fr) * 2015-03-03 2016-11-03 Dst Innovations Limited Matériaux fonctionnels imprimables pour applications électroniques en plastique
WO2020009911A1 (fr) * 2018-07-02 2020-01-09 Nanotek Instruments, Inc. Films composites polymères de couleur foncée
US11186704B2 (en) 2018-07-02 2021-11-30 Global Graphene Group, Inc. Manufacturing process for dark-color polymer composite films
US11242443B2 (en) 2018-07-02 2022-02-08 Global Graphene Group, Inc. Dark-color polymer composite films

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EP2549487A4 (fr) * 2010-03-15 2014-06-25 Masayuki Kanehara Composition de nano-encre
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EP2549487A1 (fr) * 2010-03-15 2013-01-23 Masayuki Kanehara Composition de nano-encre
EP2903049A4 (fr) * 2012-09-28 2016-06-01 Oceans King Lighting Science Dispositif électroluminescent organique et son procédé de préparation
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CN103242695A (zh) * 2013-05-05 2013-08-14 浙江师范大学 一种ZnO半导体纳米材料墨水的制备方法
US10988687B2 (en) 2014-03-19 2021-04-27 Li-Cor, Inc. Phthalocyanine formulation and uses thereof
US20150267108A1 (en) * 2014-03-19 2015-09-24 Li-Cor, Inc. Phthalocyanine formulation and uses thereof
US9845430B2 (en) * 2014-03-19 2017-12-19 Li-Cor, Inc. Phthalocyanine formulation and uses thereof
WO2016139464A3 (fr) * 2015-03-03 2016-11-03 Dst Innovations Limited Matériaux fonctionnels imprimables pour applications électroniques en plastique
WO2020009911A1 (fr) * 2018-07-02 2020-01-09 Nanotek Instruments, Inc. Films composites polymères de couleur foncée
US11186704B2 (en) 2018-07-02 2021-11-30 Global Graphene Group, Inc. Manufacturing process for dark-color polymer composite films
US11242443B2 (en) 2018-07-02 2022-02-08 Global Graphene Group, Inc. Dark-color polymer composite films
US11767412B2 (en) 2018-07-02 2023-09-26 Global Graphene Group, Inc. Manufacturing process for dark-color polymer composite films

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