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WO2012073010A1 - Dispositif à hétérojonction solide - Google Patents

Dispositif à hétérojonction solide Download PDF

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WO2012073010A1
WO2012073010A1 PCT/GB2011/052347 GB2011052347W WO2012073010A1 WO 2012073010 A1 WO2012073010 A1 WO 2012073010A1 GB 2011052347 W GB2011052347 W GB 2011052347W WO 2012073010 A1 WO2012073010 A1 WO 2012073010A1
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type material
heterojunction
solid
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Henry Snaith
Agnese Abrusci
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Oxford University Innovation Ltd
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    • 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
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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 present invention relates to a solid-state p-n heterojunction and to its use in optoelectronic devices, in particular in solid-state solar cells (SSCs) and
  • the present invention relates to optoelectronic devices having a polymeric hole transporting material and methods by which this material can be introduced.
  • DSCs are composed of mesoporous Ti0 2 (electron transporter) sensitized with a light-absorbing molecular dye, which in turn is contacted by a redox-active hole-transporting medium (electrolyte).
  • a redox-active hole-transporting medium electro-active hole-transporting medium
  • Photo- excitation of the sensitizer leads to the transfer (injection) of electrons from the excited dye into the conduction band of the Ti0 2 .
  • These photo-generated electrons are subsequently transported to and collected at the anode.
  • the oxidized dye is regenerated via hole-transfer to the redox active medium with the holes being transported through this medium to the cathode.
  • the most efficient DSCs are composed of Ti0 2 in combination with a redox active liquid electrolyte, or a "gel" type semi-solid electrolyte .
  • a redox active liquid electrolyte or a "gel” type semi-solid electrolyte .
  • Those incorporating an iodide/triiodide redox couple in a volatile solvent can convert over 12% of the solar energy into electrical energy. However, this efficiency is far from optimum.
  • Even the most effective sensitizer/electrolyte combination which uses a ruthenium complex with an iodide/triiodide redox couple sacrifices approx. 600 mV in order to drive the dye regeneration/iodide oxidation reaction.
  • Solid phase organic hole-transporters are much more appealing for large scale processing and durability due to their lack of corrosive properties and saving in potential by avoiding the need to drive the redox couple.
  • Polymeric organic hole transporters offer the potential of high efficiency charge transfer but are considered to be of limited application because it is difficult to cause the polymer to penetrate and fill the porous network of the n-type material (such as mesoporous metal oxide).
  • n-type material such as mesoporous metal oxide.
  • various workarounds have been proposed, such as the use of monomers that can be polymerised within the device after incorporation and the use of a molecular hole-transporters which dissolve to provide low viscosity solutions and can be incorporated readily into the device.
  • PFF pore filling fraction
  • heterojunctions such as solar cells
  • solid-state heterojunction devices such as solid-state solar cells
  • the present inventors have taken the unusual step of questioning the long-held view in the art that polymeric p-type materials require specialised techniques and have attempted to make solid-state devices using a simple solution of polymer. Unexpectedly, they have now established that by doing this, heterojunction devices, such as solar cells can be constructed which function with good efficiency even when much thicker than expected (e.g. when 2 ⁇ or greater). Furthermore, the present inventors have now established that contrary to the previously held belief, a high pore filling fraction (PFF) is not necessary in order to achieve good
  • the present invention therefore provides a solid-state p-n heterojunction (e.g. in a solar cell) comprising an organic p-type material in contact with a porous layer of n-type material, characterised in that the thickness of the porous layer of n-type material is 2 ⁇ or greater.
  • the present invention also provides a solid-state p-n
  • heterojunction e.g. in a solar cell
  • a heterojunction comprising an organic p-type material in contact with a porous layer of n-type material, characterised in that the pore-filling-fraction of the porous layer of n-type material by the organic p-type material is no more than 50%.
  • the p-type material should form an electrically continuous layer over the internal surface of the pores of the n-type material. This will preferably be the case even when the overall PFF is no more than 50%.
  • the organic p-type material will preferably be an organic polymer, more preferably a conducting polymer or a semi-conducting polymer. The categories of polymer and individual polymers indicated herein are particularly suitable.
  • the present invention therefore provides an optoelectronic device comprising at least one solid state p-n heterojunction as indicated in any embodiment of the present invention and/or formable by any indicated method.
  • optoelectronic devices include all those indicated herein, such as photo-detectors, solid-state polymer-oxide solar cells, solid state dye sensitised solar cells and/or solid state polymer sensitised solar cells.
  • solutions of polymers have previously not been considered appropriate for the formation of heterojunctions (e.g. in solar cells) of 2 ⁇ or greater in thickness because the relatively low pore filling fraction was considered to render such devices useless.
  • the present invention provides, in a further aspect, the use of a solution of polymeric organic p-type material in the formation of a solid-state p-n heterojunction wherein said p-n heterojunction comprises a porous layer of n-type material having a thickness of 2 ⁇ or greater.
  • the present invention provides the use of a solution of polymeric organic p-type material in the formation of a solid-state p-n heterojunction wherein said p-n heterojunction comprises a porous layer of n-type material and wherein said polymerised organic p-type material fills the pores of said n-type material with a pore filling fraction of 50% or less.
  • a heterojunction e.g. in a solar cell
  • a heterojunction may be formed having at least one of the advantageous properties indicated herein.
  • the present invention therefore provides a method for the manufacture of a solid-state p-n heterojunction (such as in a solar cell) comprising an organic p-type material in contact with a porous layer of n-type material, said method characterised by; a) coating an anode, preferably a transparent anode (e.g.
  • a Fluorine doped Tin Oxide - FTO cathode with a compact layer of an n-type semiconductor material (such as any of those described herein); b) forming a porous (preferably mesoporous) layer of an n-type semiconductor material (such as any of those described herein) on said compact layer, c) optionally surface sensitizing said compact layer and/or said porous layer of n-type material with at least one sensitizing agent;
  • a cathode preferably a metal cathode (e.g. a silver or gold cathode) on said porous barrier layer, in contact with said p-type semiconductor material.
  • a metal cathode e.g. a silver or gold cathode
  • step d) an ionic material, such as a lithium salt at step d) enhances the generation of an electrically continuous layer of p-type material over the pore-surface within the n-type material. It is therefore preferable that step d) is included. It is more preferable that the ionic material in step d) be a lithium salt and still more preferable that this be Li-TFSI or an analogue or derivative thereof (including any indicated in any section of this application). Devices formed or formable from any of the heterojunctions of the invention or by any of the methods, uses or process of the invention evidently also form additional aspects of the invention in themselves.
  • step d) comprises treating said compact layer and/or said porous layer of n-type material with a mixture of at least two ionic materials.
  • Suitable ionic materials preferably include metal salts
  • lithium salts such as lithium bis(trifluoromethylsulfonyl)imide lithium salt
  • ionic liquids such as, 1-Ethyl-3-methylimidazolium
  • the term "ionic liquid" is used to indicate an ionic species with a melting point sufficiently low for convenient processing in the formation of the heterejunctions and devices of the invention.
  • ionic liquid is used to indicate an ionic species with a melting point sufficiently low for convenient processing in the formation of the heterejunctions and devices of the invention.
  • suitable low melting-point salts are known and in one embodiment, salts having a melting point of 100°C or lower are preferable. Salts having a melting point of below 50°C or even below room temperature may be preferably used.
  • bis(trifluoromethylsulfonyl)imide have a melting point below 0°C.
  • Highly preferable ionic liquids include those selected from 1-Ethyl-3-methylimidazolium
  • a polymer oxide solar cell relies initially on the collection of solar light energy in the form of capture of solar photons by the polymer and/or by an additional sensitizer (typically a molecular, metal complex, or polymer dye).
  • an additional sensitizer typically a molecular, metal complex, or polymer dye.
  • the effect of the light absorption is to raise an electron into a higher energy level in the polymer and/or sensitizer.
  • This excited electron will eventually decay back to its ground state, but in a solar cell, the n-type material in close proximity to the excited material provides an alternative (faster) route for the electron to leave its excited state, viz. by "injection" into the n-type semiconductor material.
  • This injection can be direct or via an intermediate material but in all cases results in a charge separation, whereby the n-type semiconductor has gained a net negative charge and the polymer has gained a net positive charge. Where a sensitizer or injecting material is present this may initially take the positive charge but it will rapidly be passed to the polymer charge carrier. This serves to "regenerate” the dye or portion of the polymer close to the heterojunction by passing the positive charge ("hole") on through the p-type semiconductor material of the junction (the "hole transporter"). In a solid state polymer oxide device, this hole transporter is in direct contact with the n-type material and/or sensitizer material, while in the more common electrolytic dye sensitised photocells, a redox couple (typically
  • iodide/triiodide serves to regenerate a dye and transports the "hole species" (triiodide) to the counter electrode. Once the electron is passed into the n-type material, it must then be transported away, with its charge contributing to the current generated by the solar cell.
  • each of these competing pathways results in the loss of potentially useful current and thus a reduction in cell energy-conversion efficiency. It is therefore essential that each of the desired steps occurs at a rate which is considerably faster than the competing undesirable processes to avoid wasting potentially useful energy. It is also important that there is not too much of a disparity in the speeds of the various steps since a fast step followed by a slow step can lead to a build-up of a short-lived intermediate material which may then follow an energy-wasteful path. Thus it is particularly critical that the polymer hole- transporter is capable of effectively carrying charge away from the site of generation.
  • a schematic diagram indicating a typical structure of the solid-state DSC is given in attached Figure 1 a and a diagram indicating some of the key steps in electrical power generation from a polymer oxide solar cell is given in attached Figure 1 b .
  • Polymer-oxide solar cells composed of mesoporous metal oxide electrodes infiltrated with (optionally light absorbing) semiconducting polymers and optionally also dye materials, have the potential to deliver high power conversion efficiencies while being compatible with low cost large area chemical processing.
  • solar-to-electrical power conversion efficiencies have remained below 1 %.
  • a suitable fraction of sun light needs to be absorbed in the photoactive layer, excitons formed in the dye and/or polymer need to be ionised at the polymer-oxide heterojunction, and the photo-generated charges need to be separated and carried out of the solar cell to their respective electrodes. The latter requires effective percolation for both charge carriers, electrons and holes, in the oxide and polymer phases respectively.
  • the present inventors have provided cells in which the polymer appears to form a "wetting film" over the entire internal surface of the dye-sensitized mesoporous electrode.
  • this wetting layer of only a few nm thick, is sufficiently capable of transporting the holes out of the device to make efficient solar cells.
  • Charge collection efficiencies by the polymer film at the pore surface can be up to 98%, as estimated from transient electronic measurements.
  • the inventors have found evidence to suggest that even in the thickest devices of over 7 ⁇ thick, the charge collection is limited by electron transport through the mesoporous n-type material, even though the polymer "shell" may only have an average thickness of around 0.2 to 10 nm (e.g. around 1 nm).
  • the present invention may be applied to devices wherein the porous layer of n-type material is any thickness (e.g. 0.1 to 50 ⁇ ) but it is a particularly unexpected development that heterojunctions having a layer of porous n-type material (as described herein) of significant thickness can be formed into an efficient solar cell with a polymeric p-type material, using the techniques described herein.
  • the thickness of the porous layer of n-type material in all aspects of the invention may be 0.1 to 50 ⁇ , but is typically greater than 1 ⁇ , preferably 2 ⁇ or greater (e.g. 2 to 20 ⁇ ) and more preferably 2.5 ⁇ or greater (e.g. 2.5 to 10 ⁇ ).
  • Devices of at least 7 ⁇ have been shown to have efficient hole-conduction through the polymer material in the present invention.
  • the present invention is not limited to thin devices (e.g. 1 ⁇ or less) as has previously been thought for polymer oxide solar cells absent special techniques such as in situ polymerisation.
  • the present invention may therefore be applied to devices having any degree of pore filling fraction (PFF) (e.g. 0.1 % to substantially 100%, such as 1 % to 99.9%).
  • PFF degree of pore filling fraction
  • heterojunctions and corresponding devices e.g. polymer oxide solar cells
  • a pore filling fraction of significantly less than 100% This may be, for example, no more than 75% (e.g. 1 to 75%), or no more than 50% (e.g. 2 to 50%).
  • a pore filling fraction of less than 50% e.g.
  • the heterojunctions and devices are both effective and can have a PFF in this range an below (e.g. 0.5 to 30% or 1 to 20%).
  • the present inventors have now established that in fact the pore filling fraction of a heterojunction or device is not an effective measure of the amount of functional p- type material present in the pores of the n-type oxide layer.
  • CCE Charge collection efficiency
  • the CCE of the heterojunctions or devices of the present invention may be at least 50% (e.g. 50 to 99%), preferably at least 60% (e.g. 60 to 98%) and more preferably at least 70% (e.g. 70 to 98%).
  • the p-n heterojunctions of the invention are light sensitive and as such include at least one light sensitizing agent (sensitizer).
  • this material may be the (or one of the) polymer p-type material(s) itself, and/or may be one or more dyes, salts, films, particles, or any material which generates an electronic excitation as a result of photon absorption and which is capable of direct or indirect injection of the excited electron into the n-type material.
  • At least a part of the light absorbing capacity of the heterojunction or device is provided by the polymeric p- type material (or where that material is a mixture, by at least one component thereof).
  • Polymeric p-type materials can be highly effective in absorbing certain frequencies in the electromagnetic spectrum useful for photovoltage generation and/or photo-detection. Thus, where possible, it is desirable to take advantage of this property.
  • the term "sensitizer" may indicate, where context allows, a property of the polymeric p-type material (or at least one component thereof).
  • one or more further sensitizers may be used in the devices of the present invention. These may be chosen, for example, in order to enhance the absorption of light at wavelengths not effectively absorbed by the p-type material of the polymer(s) and/or to act as one or more intermediaries serving to aid in transferring the excitation energy from the polymer and complete the charge separation and "injection". Where a "cascade" of sensitizers of this type is used then it is desirable that there be at least some overlap between the emission spectrum of a first dye and the absorption spectrum of a second so that a "resonance energy transfer" type effect may occur.
  • indolene based dyes of which D102, D131 and D149 (shown below) are particular examples.
  • the general structure of indolene dyes is that of Formula si below:
  • R1 and R2 are independently optionally substituted alkyl, alkenyl, alkoxy, heterocyclic and/or aromatic groups, preferably with molecular weight less than around 360 amu.
  • R1 will comprise aralkyl, alkoxy, alkoxy aryl and/ or aralkenyl groups (especially groups of formula C x H y O z where x, y and z are each 0 or a positive integer, x+z is between 1 and 16 and y is between 1 and 2x +1 ) including any of those indicated below for R1
  • R2 will comprise optionally substituted carbocyclic, heterocyclic (especially S and/or N-containing heterocyclic) cycloalkyl, cycloalkenyl and/or aromatic groups, particularly those including a carboxylic acid group.
  • R2 All of the groups indicated below for R2 are highly suitable examples.
  • One preferred embodiment of R2 adheres to the formula C x H y O z N v S w where x, y, z, v and w are each 0 or a positive integer, x+z+w+v is between 1 and 22 and y is between 1 and 2x+v+1 .
  • z ⁇ 2 and in particular, it is preferable that R2 comprises a carboxylic acid group.
  • R1 and R2 groups and especially those indicated below may be used in any combination, but highly preferred combinations include those indicated below:
  • Indolene dyes are discussed, for example, in Horiuchi et al. J Am. Chem. Soc. 126 12218-12219 (2004), which is hereby incorporated by reference.
  • sensitizers are ruthenium metal complexes, particularly those having two bipyridyl coordinating moieties. These are typically of formula sll below
  • each R1 group is independently a straight or branched chain alkyl or oligo alkoxy chain such as C n H 2 n + i where n is 1 to 20, preferably 5 to 15, most preferably 9, 10 or 1 1 , or such as C-(-XCnH2n-)m-XCpH 2 p + i , where n is 1 , 2, 3 or 4, preferably 2, m is 0 to 10, preferably 2, 3 or 4, p is an integer from 1 to 15, preferably 1 to 10, most preferably 1 or 7, and each X is independently O, S or NH, preferably O; and wherein each R2 group is independently a carboxylic acid or alkyl carboxylic acid, or the salt of any such acid (e.g. the sodium, potassium salt etc) such as a
  • R1 moieties of formula sll may also be of formula sill below:
  • Ruthenium dyes are discussed in many published documents including, for example, Kuang et al. Nano Letters 6 769-773 (2006), Snaith et al. Angew. Chem. Int. Ed. 44 6413-6417 (2005), Wang et al. Nature Materials 2, 402-498 (2003), Kuang et al. Inorganica Chemica Acta 361 699-706 (2008), and Snaith et al. J Phys, Chem. Lett. 112 7562-7566 (2008), the disclosures of which are hereby incorporated herein by reference, as are the disclosures of all material cited herein.
  • sensitizers which will be known to those of skill in the art include Metal- Phalocianine complexes such as zinc phalocianine PCH001 , the synthesis and structure of which is described by Reddy et al. (Angew. Chem. Int. Ed. 46 373-376 (2007)), the complete disclosure of which (particularly with reference to Scheme 1 ), is hereby incorporated by reference.
  • metal phthalocianine dyes suitable for use in the invention include those having a structure as shown in formula sIV below: Formula sIV
  • M is a metal ion, such as a transition metal ion, and may be an ion of Co, Fe, Ru, Zn or a mixture thereof.
  • Zinc ions are preferred.
  • Each of R1 to R4, which may be the same or different is preferably straight or branched chain alkyl, alkoxy, carboxylic acid or ester groups such as C n H 2n+ i where n is 1 to 15, preferably 2 to 10, most preferably 3, 4 or 5, with butyl, such as tertiary butyl, groups being particularly preferred, or such as OX or C0 2 X wherein X is H or a straight or branched chain alkyl group of those just described.
  • each of R1 to R3 is an alkyl group as described and R4 is a carboxylic acid C0 2 H or ester C0 2 X, where X is for example methyl, ethyl, iso- or n-propyl or tert-, iso-, sec-or n- butyl.
  • dye TT1 takes the structure of formula sIV, wherein R1 to R3 are t-butyl and R4 is C0 2 H.
  • suitable categories of dyes include Metal-Porphyrin
  • Metal porphyrin complexes include, for example, those of formula sV and related structures, where each of M and R1 to R4 can be any appropriate group, such as those specified above for the related phthalocyanine dyes: Formula sV
  • Squaraine dyes form a preferred category of dye for use in the present invention.
  • the above Burke citation provides information on Squaraine dyes, but briefly, these may be, for example, of the following formula sVI
  • any of R1 to R8 may independently be a straight or branched chain alkyl group or any of R1 to R5 may independently be a straight or branched chain alkyloxy group such as C n H 2n +i or C n H 2n +iO respectively where n is 1 to 20, preferably 1 to 12, more preferably 1 to 9.
  • each R1 to R5 will be H, C n H 2n +i or C n H 2n +iO wherein n is 1 to 8 preferably 1 to 3 more preferably 1 or two.
  • R1 is H and each R5 is methyl.
  • each R6 to R8 group is H or C n H 2n+ i wherein n is 1 to 20, such as 1 to 12.
  • n with preferably be 1 to 5 more preferably 1 to 3 and most preferably ethyl.
  • R7 n will preferably be 4 to 12, more preferably 6 to 10, most preferably 8, and for R8, preferred groups are H, methyl or ethyl, preferably H.
  • One preferred squaraine dye referred to herein is SQ02, which is of formula sVI wherein R1 and R8 are H, each of R2 to R5 is methyl, R6 is ethyl, and R7 is octyl (e.g. n-octyl).
  • a further example category of valuable sensitizers are polythiophene
  • x is an integer between 0 and 10, preferably 1 , 2, 3, 4 or 5, more preferably 1
  • any of R1 to R10 may independently be hydrogen, a straight or branched chain alkyl group or any of R1 to R9 may independently be a straight or branched chain alkyloxy group such as C n H 2n+ i or C n H 2n+ iO respectively where n is 1 to 20, preferably 1 to 12, more preferably 1 to 5.
  • each if R1 to R10 will independently be a hydrogen or C n H 2n+ i group where n is 1 to 5, preferably methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or t-butyl. Most preferably, each of R2 to R4 will be methyl or ethyl and each of R1 and R6 to R10 will be hydrogen.
  • the group R1 1 may be any small organic group (e.g. molecular weight less than 100) but will preferably be unsaturated and may be conjugated to the extended pi-system of the dithiophene groups.
  • R1 1 groups include alkenyl or alkynyl groups (such as C n H 2n -i and C n H 2n- 3 groups respectively, e.g. where n is 2 to 10, preferably 2 to 7), cyclic, including aromatic groups, such as substituted or unsubstituted phenyl, piridyl, pyrimidyly, pyrrolyl or imidazyl groups, and unsaturated hetero-groups such as oxo, nitrile and cyano groups.
  • a most preferred R1 1 group is cyano.
  • One preferred dithiophene based dye is 2-cyanoacrylic acid-4- (bis-dimethylfluorene aniline)dithiophene, known as JK2.
  • dye sensitizer is necessary for the functioning of the present invention since light may be absorbed either by the polymeric p-type material and/or by sensitizers of other types, such as inorganic films or nanoparticles. Where present, in one embodiment, only a single dye sensitizer will be employed in the p-n
  • heterojunctions herein described may serve to absorb over a broad range of wavelengths and/or may act to increase absorption in regions of the spectrum where the absorption of the polymer material is relatively low.
  • two or more dye sensitizers may nevertheless be used.
  • all aspects of the present invention are suitable for use with co-sensitisation using a plurality of (e.g. at least 2, such as 2, 3, 4 or 5) different sensitizing agents, including dye sensitizing agents. If two or more dye sensitizers are used, these may be chosen such that their respective emission and absorption spectra overlap.
  • RET resonance energy transfer
  • the emission and absorption spectra of the individual dyes do not overlap to any significant extent. This ensures that all dye sensitizers are effective in the injection of electrons into the n-type material.
  • these dye sensitizers will preferably have complimentary absorption characteristics.
  • Some complimentary parings include, for example, the near-infra red absorbing zinc phalocianine dyes referred to above in combination with indoline or ruthenuim-based sensitizers to absorb the bulk of the visible radiation.
  • a polymeric or molecular visible light absorbing material may be used in conjunction with a near IR absorbing dye, such as a visible light absorbing polyfluorene polymer with a near IR absorbing zinc phlaocianine or squaraine dye.
  • a near IR absorbing dye such as a visible light absorbing polyfluorene polymer with a near IR absorbing zinc phlaocianine or squaraine dye.
  • sensitizers may also be used in the various aspects of the present invention and in each case may form all or the bulk of the light-absorbing material or may be used in conjunction with absorption from the polymeric p-type material and/or in combination with other sensitizers of the same or different types.
  • Preferred sensitizing agents include at least one inorganic light absorbing thin film or semiconductor nanoparticle layer, where the film or layer is formed from materials selected from, for example, PbS, PbSe, SnS, SnSe SbS, SbSe, CdSe, Ge, Si.
  • plasmonic nanoparticles allow injection of electrons which result from excitation of surface plasmon modes by lower energy solar photons including those of near infra-red frequencies. These are therefore advantageously combined with suitable dye sensitizers.
  • a p-type polymer is a material which exhibits good hole-transport characteristics and functions as a hole-transporter in the operating heterojunction (especially solar cell). Its function is to 1 . Transfer an electron from the highest occupied molecular orbital (HOMO) level of the p-type polymer to the HOMO level of the photo-oxidized dye or other sensitizer (where present - also known as dye regeneration). 2. Transfer an electron from HOMO level of the p-type polymer to the HOMO level of the photo-oxidized dye or other sensitizer (where present - also known as dye regeneration). 2. Transfer an electron from
  • a polymerised material is used as the p-type material of the heterojunction or device.
  • the polymeric p-type material is an organic polymer selected from poly thiophenes, poly p-phenylene vinylenes and mixtures, copolymers and derivatives thereof.
  • P3HT poly(3-hexylthiophene)
  • the n-type semiconductor material for use in the solid state heterojunctions (e.g. DSCs) relating to the present invention may be any of those which are well known in the art.
  • Oxides of Ti, Al, Sn, Mg and mixtures thereof are among those suitable.
  • Ti0 2 and Al 2 0 3 are common examples, as are MgO and Sn0 2 .
  • the n-type material is used in the form of a layer and will typically be mesoporous providing a relatively thick layer of around 0.05 - 100 ⁇ over which the second sensitizing agent may be absorbed at the surface.
  • a thin surface coating of a high band-gap / high band gap edge (insulating) material may be deposited on the surface of a lower band gap n-type semiconductor such as Sn0 2 .
  • n-type material of the solid state heterojunctions relating to all aspects of the present invention is generally a metal compound such as a metal oxide, compound metal oxide, doped metal oxide, selenide, teluride, and/or multicompound semiconductor, any of which may be coated as described above.
  • Suitable materials include single metal oxides such as Al 2 0 3 , ZrO, ZnO, Ti0 2 , Sn0 2 , Ta 2 0 5 , Nb 2 0 5 , W0 3 , W 2 0 5 , ln 2 0 3 , Ga 2 0 3 , Nd 2 0 3 , Sm 2 0 3 , La 2 0 3 , Sc 2 0 3 , Y 2 0 3 , NiO, Mo0 3 , PbO, CdO and/or MnO; compound metal oxides such as Zn x Ti y O z , ZrTi0 4 , ZrW 2 0 8 , SiAI0 3i 5, Si 2 AI0 5 ,5, SiTi0 4 and/or AITi0 5; doped metal oxides such as any of the single or compound metal oxides indicated above doped with at least one of Al, F, Ge, S, N, In, Mg, Si, C, Pb and/or Sb;
  • this mesoporous layer may be conveniently generated by sintering of appropriate semiconductor particles using methods well known in the art and described, for example in Green et al. (J. Phys. Chem. B 109 12525-12533 (2005)) and Kay et al. (Chem. Mater. 17 2930-2835 (2002)), which are both hereby incorporated by reference.
  • these may be applied before the particles are sintered into a film, after sintering, or two or more layers may be applied at different stages.
  • Typical particle diameters for the semiconductors will be dependent upon the application of the device, but might typically be in the range of 5 to 10OOnm, preferably 10 to 100 nm, more preferably still 10 to 30 nm, such as around 20 nm.
  • Surface areas of 1 -1000 m 2 g "1 are preferable in the finished film, more preferably 30-200 m 2 g "1 , such as 40 - 100 m 2 g "1 .
  • the film will preferably be electrically continuous (or at least substantially so) in order to allow the injected charge to be conducted out of the device.
  • the thickness of the film will be dependent upon factors such as the photon-capture efficiency of the photo-sensitizer, but may be in the range 0.05 - 100 ⁇ , preferably 0.5 to 20 ⁇ , more preferably 0.5 -10 ⁇ , e.g. 1 to 5 ⁇ .
  • the film is planar or substantially planar rather than highly porous, and for example has a surface area of 1 to 20 m 2 g "1 preferably 1 to 10 m 2 g "1 .
  • Such a substantially planar film may also or alternatively have a thickness of 0.005 to 5 ⁇ , preferably 0.025 to 0.2 ⁇ , and more preferably 0.05 to 0.1 ⁇ .
  • the n-type material is surface coated
  • materials which are suitable as the coating material may have a conduction band edge closer to or further from the vacuum level (vacuum energy) than that of the principal n-type semiconductor material, depending upon how the property of the material is to be tuned. They may have a conduction band edge relative to vacuum level of at around -4.8 eV, or higher (less negative) for example -4.8 or -4.7 to -1 eV, such as - 4.7 to -2.5 eV, or -4.5 to -3 eV
  • Suitable coating materials include single metal oxides such as MgO, Al 2 0 3 , ZrO, ZnO, Hf0 2 , Ti0 2 , Ta 2 0 5 , Nb 2 0 5 , W0 3 , W 2 0 5 , ln 2 0 3 , Ga 2 0 3 , Nd 2 0 3 , Sm 2 0 3 , La 2 0 3 , Sc 2 0 3 , Y 2 0 3 , NiO, Mo0 3 , PbO, CdO and/or MnO; compound metal oxides such as Zn x Ti y O z , ZrTi0 4 , ZrW 2 0 8 , SiAI0 3 5 , Si 2 AI0 5 , 5 , SiTi0 4 and/or AITi0 5; doped metal oxides such as any of the single or compound metal oxides indicated above doped with at least one of Al, F, Ge, S, N, In, Mg, Si
  • carbonates such as Cs 2 C 5 ; sulphides such as PbS, CdS, CuS; selenides such as PbSe, CdSe; telurides such as CdTe; nitrides such as TiN; and/or multicompound semiconductors such as CIGaS 2 .
  • sulphides such as PbS, CdS, CuS
  • selenides such as PbSe, CdSe
  • telurides such as CdTe
  • nitrides such as TiN
  • multicompound semiconductors such as CIGaS 2 .
  • the coating on the n-type material will typically be formed by the deposition of a thin coating of material on the surface of the n-type semiconductor film or the particles which are to generate such a film. In most cases, however, the material will be fired or sintered prior to use, and this may result in the complete or partial integration of the surface coating material into the bulk semiconductor.
  • the surface coating may be a fully discrete layer at the surface of the semiconductor film, the coating may equally be a surface region in which the semiconductor is merged, integrated, or co-dispersed with the coating material. Since any coating on the n-type material may not be a fully discrete layer of material, it is difficult to indicate the exact thickness of an appropriate layer.
  • the appropriate thickness will in any case be evident to the skilled worker from routine testing, since a sufficiently thick layer will retard electron-hole recombination without undue loss of charge injection into the n-type material. Coatings from a monolayer to a few nm in thickness are appropriate in most cases (e.g. 0.1 to 100 nm, preferably 1 to 5 nm).
  • the bulk or "core" of the n-type material in all embodiments of the present invention may be essentially pure semiconductor material, e.g. having only unavoidable impurities, or may alternatively be doped in order to optimise the function of the p-n- heterojunction device, for example by increasing or reducing the conductivity of the n-type semiconductor material or by matching the conduction band in the n-type semiconductor material to the excited state of the chosen sensitizer.
  • n-type semiconductor and oxides such as Ti0 2 , ZnO, Sn0 2 and W0 3 referred to herein (where context allows) may be essentially pure semiconductor (e.g. having only unavoidable impurities). Alternatively they may be doped throughout with at least one dopant material of greater valency than the bulk (to provide n-type doping) and/or may be doped with at least one dopant material of lower valency than the bulk (to give p-type doping), n-type doping will tend to increase the n-type character of the semiconductor material while p-type doping will tend to reduce the degree of the natural n-type state (e.g. due to defects).
  • Such doping may be made with any suitable element including F, Sb, N, Ge, Si, C, In, InO and/or Al. Suitable dopants and doping levels will be evident to those of skill in the art. Doping levels may range from 0.01 to 49% such as 0.5 to 20%, preferably in the range of 5 to 15%. All percentages indicated herein are by weight where context allows, unless indicated otherwise.
  • an optional by preferable ionic material such as a lithium salt may also be included in all aspects of the present invention.
  • this ionic additive will be present.
  • this ionic additive will be present and will comprise a lithium salt or compound.
  • Particularly preferable ionic additives are lithium salts such as lithium perchlorate or ionic liquids, such as 1 -Ethyl-3- methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-Butyl-3-methylimidazolium
  • Figure 1 shows a schematic illustration of a cross section of a solid-state dye- sensitized solar cell using Sn0 2 as the n-type metal oxide.
  • Figure 1 b Shows an illustrative energy level diagram for a conventional solid-state dye sensitized solar cell.
  • Figure 2a shows a cross-section scanning electron microscopy (SEM) image of a 1 ⁇ thick dye-sensitized polymer-oxide solar cell.
  • Figure 2b shows the XPS depth profiling for a 1 ⁇ Ti0 2 thick D131 +P3HT device, showing the signals for the carbon, oxygen, titanium and tin.
  • Figure 2c Shows the depth profile for the P3HT in bare Ti0 2 device.
  • Figure 3 shows the UV-Vis absorption spectra for dye-sensitized Ti0 2 coated with P3HT with and without pre-coating with Li-TFSI.
  • Figure 4 shows the current voltage curves for complete devices with the addition of Li-TFSI and tBP with thicknesses of 1 , 2.5 and 4 ⁇ measured under AM 1 .5 simulated sun light of 100 mWcm "2 .
  • Figure 5 Shows that with P3HT employed as a hole transporter, specifically when used in combination with Li-TFSI, the conductivity increases to the range of 10 "2 Scm "1
  • Figure 6 shows the spectral response for the 2.5 ⁇ thick device, along with the UV-Vis absorption spectra for a 1 ⁇ thick Ti0 2 film coated with dye (+ Li-TFSI), infiltrated with P3HT and both coated with dye (+ Li-TFSI) and P3HT.
  • Figure 7 shows the transport rate (left y-axis) and the charge collection efficiency (right y-axis) measured under conditions equivalent to full sun illumination at lOOmWcm " as a function of film thickness.
  • Figure 8 shows a cartoon to aid an intuitive explanation for ambipolar diffusion for P3HT (represented by the red phase) and Ti0 2 (white pillar).
  • Fluorine doped tin oxide (FTO) coated glass sheets (15 ⁇ ,/ ⁇ Pilkington) were etched with zinc powder and HC1 (2 Molar) to obtain the required electrode pattern. The sheets were then washed with soap (2% Hellmanex in water), de-ionized water, acetone, methanol and finally treated under an oxygen plasma for 10 minutes to remove the last traces of organic residues.
  • the FTO sheets were subsequently coated with a compact layer of Ti0 2 (100 nm) by aerosol spray pyro lysis deposition at 450 °C, using air as the carrier gas.
  • the standard Dyesol Ti0 2 paste was previously diluted down 1 :2 and 1 :3.5 in anhydrous ethanol and stirred and ultrasonicated until complete mixing has occurred.
  • the paste was then doctor-bladed by hand using 2 and 1 layer of scotch tape and a pipette on the Ti0 2 compact layer coated FTO sheets to get a Ti0 2 average thickness from 1 to 6 ⁇ .
  • the sheets were then slowly heated to 550 °C (ramped over 1 1 ⁇ 2 hours) and baked at this temperature for 30 minutes in air. After cooling, slides were cut down to size and soaked in a 15 mM of TiCl 4 in water bath and oven-baked for 1 hour at 70 °C. After rinsing with subsequently in water, ethanol and drying in air, they were subsequently baked once more at 550 °C for 45 min in air, then cooled down to 70 °C and finally introduced in a dye solution for 1 hour
  • a yellow indolene dye was used (D131) at 0.3 mM in a 1 : 1 volume ratio of tert- butanol and acetonitrile.
  • P3HT was synthesised by according to the published route (ref: Loewe, R. S.; Ewbank, P. C; Liu, J.; Zhai, L.; McCullough, R. D. Macromolecules 2001, 34, 4324-4333.). Briefly, to a 0.2M THF solution of 2,5- dibromo-3-hexylthiophene at 0°C was added 0.98 equivalents of a 0.98M solution of n-Butylmagnesium chloride in THF.
  • the polymer was dried, dissolved in hot chlorobenzene, filtered and precipitated into acetone (twice).
  • Number-average (M n ) and weight-average (M w ) were 27,500 g/mol and 35,000 g/mol respectively, as determined by Agilent Technologies 1200 series GPC running in chlorobenzene at 80 °C, using two PL mixed B columns in series, and calibrated against narrow polydispersity polystyrene standards.
  • Regioregularity was determined to be greater than 97% by NMR integration of the methylene protons.
  • P3HT was dissolved in chlorobenzene at 3,5,7 wt% concentration and heated at 70 °C for 1 hour.
  • Li-TFSI Lithium bis(trifluoromethylsulfonyl)imide salt
  • tBP 4-tert-butyl pyridine
  • the films were dried in air and then placed in a thermal evaporator where 150 nm thick silver electrodes were deposited through a shadow mask under high vacuum (10 "6 mbar).
  • the active areas of the devices were defined by metal optical masks with a round aperture of 2.5 mm giving an area of 0.0491 cm .
  • the masks used were single aperture and all light was excluded from entering the sides of devices by measuring them in a black box sample holder.
  • XPS spectra were acquired with a PHI 5000 Versaprobe system using a microfocused (100 ⁇ , 25 W) Al Kdon X-ray beam with a photoelectron takeoff angle of 45°.
  • a dual-beam charge neutralizer (10-V Ar + and 30-V electron beam) was used to compensate the charge-up effect.
  • Ar + ion source was operated at 1 ⁇ and 5 kV, with rastering on an area of 1 mm x 1 mm.
  • the film thicknesses were measured with a cross-section SEM image. The sputter rate was around 25 nm min "1 for all P3HT-infiltrated mesoporous Ti0 2 films.
  • the carbon signal comes from both the dye and P3HT.
  • a Ti0 2 film with only the dye and no polymer was first measured in XPS to quantify the carbon concentration. This concentration is subtracted from the other samples that contain both the dye and polymer
  • Figure 2a shows a cross-section scanning electron microscopy (SEM) image of a 1 ⁇ thick dye-sensitized polymer-oxide solar cell.
  • the layers from left to right are the silver electrode (bright), over-standing or capping layer of P3HT (dark), mesoporous Ti0 2 infiltrated with P3HT, and fluorine doped tin oxide (FTO) transparent conducting electrode.
  • the sulphur signal unique to P3HT, was too weak to use reliably. The carbon signal arises from both the dye and the P3HT.
  • Example 5 - pore filling by UV-Vis absorption Since XPS depth profiling cannot give a quantitative estimation of the pore filling fraction, we have employed UV-Vis absorption measurements, in combination with capping layer thickness measurements to estimate the pore filling fraction (PFF) in these films.
  • the total equivalent thickness of P3HT in the film idtot pmi) is estimated by measuring the UV-Vis transmission spectra and comparing this to a solid-film of known thickness.
  • the capping, or over standing layer thickness idos is estimated from cross-section SEM images, and subtracted from the total P3HT thickness to give the equivalent thickness of P3HT within the porous titania film.
  • the pore filling fraction (PFF) is then calculated by dividing the product of the Ti0 2 film thickness ⁇ djioi) times the Ti0 2 porosity (pno 2 ⁇ 0.6) by the equivalent thickness of P3HT within the pores (d pores ), obtained by subtracting from the total P3HT equivalent thickness d to t_p3m), the polymer overlayer thickness (d os ).
  • the films Prior to P3HT coating the films were optionally coated with Li-TFSI (19 mg/ml in acetonitirile, coated at 1000 rpm), or tBP and Li-TFSI (17.5 ⁇ /ml and 19 mg/ml in acetonitirile, coated at 1000 rpm).
  • the thickness of a P3HT film spin-coated upon a microscope slide at 1000 rpm from a 30 mg/ml and 50 mg/ml solution is also shown (respectively 263 nm and 485 nm).
  • the pore filling fraction appears to be enhanced by the pre-deposition of the Li-TFSI solution (Table 2).
  • AOD is the difference in absorbance at 980 nm between a D131 film coated with 3% P3HT solution with and without pre-treatment with the Li-TFSI and ⁇ is the extinction coefficient at that wavelength (4 ⁇ 10 4 M ⁇ crrf ) as estimated by Durrant et al.
  • Table 2 we show the estimated pore filling fraction for the devices with a range of thicknesses, with and without dye and with and without the additives (Li-TFSI and tBP).
  • the pore filling fraction is in qualitative agreement with the XPS depth profiling, in as much as there is little drop in the pore filling fraction with increasing Ti02 thickness, and increasing the P3HT concentration from 30 to 50 mg/ml does not show any improvement on the pore filling.
  • the pore filling fraction is only between 6 to 23% for all the D131+P3HT films and it consistently increases with pre-treatment of the film with Li-TFSI.
  • Dye-sensitized polymer-oxide solar cells operate most effectively when ionic salts (typically Li-TFSl) and a base (typically 4-tert-butyl pyridine, fBP) are added to the system.
  • ionic salts typically Li-TFSl
  • a base typically 4-tert-butyl pyridine, fBP
  • Li-TFSl and fBP acetonitrile solution of the additives
  • XPS depth profiling [9] XPS is sensitive to the surface composition of the film with depth sensitivity on the order of 5 nm.
  • n is the free electron density
  • p is the free hole density
  • D n and D p are the diffusion coefficients for electrons and holes respectively.
  • the weighting for charge density is such that the ambipolar diffusion coefficient can still closely match D n even if D n > D p .
  • a cartoon to aid an intuitive explanation for ambipolar diffusion for P3HT (represented by the red phase) and Ti0 2 (white pillar) is shown in Figure 8: considering the requirement for current continuity, all the holes represented in the red region (P3HT) can collectively move a small distance to have one hole leaving the system at the top.
  • the lone electron illustrated in the gray region (Ti0 2 ) has to move the entire length of the cylinder within the same timeframe to exit the system at the bottom.
  • a balanced flux of electrons at the bottom and holes at the top can be achieved with the holes diffusing much slower than the electrons.
  • the ability to employ a heavily doped hole- transporter within this system implies that the required mobility of the hole- transporter could be very low, and significantly lower than the mobility of the Ti0 2 ,

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Abstract

La présente invention concerne une hétérojonction p-n solide, par exemple dans une photopile, comprenant un matériau organique de type p en contact avec une couche poreuse d'un matériau de type n, caractérisée en ce que l'épaisseur de la couche poreuse constituée du matériau de type n est supérieure ou égale à 2 µm. L'invention concerne également une hétérojonction p-n solide, par exemple dans une photopile, comprenant un matériau organique de type p en contact avec une couche poreuse d'un matériau de type n, caractérisée en ce que la fraction des pores de la couche poreuse constituée du matériau de type n remplis par le matériau organique de type p ne dépasse pas 50 %. L'invention concerne, en outre, des dispositifs tels que des photopiles ou des dispositifs photodétecteurs utilisant lesdites hétérojonctions, des procédés de fabrication desdits dispositifs et l'utilisation d'un matériau polymère de type p dans un tel dispositif ou un tel procédé.
PCT/GB2011/052347 2010-11-29 2011-11-28 Dispositif à hétérojonction solide Ceased WO2012073010A1 (fr)

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TWI776106B (zh) * 2018-12-12 2022-09-01 日商杰富意鋼鐵股份有限公司 積層體之製造方法及染料敏化太陽電池之製造方法
JPWO2020122019A1 (ja) * 2018-12-12 2021-02-15 Ｊｆｅスチール株式会社 積層体の製造方法および色素増感太陽電池の製造方法
US11594381B2 (en) 2018-12-12 2023-02-28 Jfe Steel Corporation Laminate production method, and dye-sensitized solar cell production method
WO2020122019A1 (fr) * 2018-12-12 2020-06-18 Ｊｆｅスチール株式会社 Procédé de production de stratifié et procédé de production de cellule solaire à colorant
CN111799381A (zh) * 2020-09-10 2020-10-20 江西省科学院能源研究所 一种基于含磷空穴掺杂剂的钙钛矿太阳能电池制备方法

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