EP2430679A1 - Couches minces de semi-conducteur - Google Patents

Couches minces de semi-conducteur

Info

Publication number
EP2430679A1
EP2430679A1 EP10721183A EP10721183A EP2430679A1 EP 2430679 A1 EP2430679 A1 EP 2430679A1 EP 10721183 A EP10721183 A EP 10721183A EP 10721183 A EP10721183 A EP 10721183A EP 2430679 A1 EP2430679 A1 EP 2430679A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
semiconductor material
organic
semiconductor
organic semiconductor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10721183A
Other languages
German (de)
English (en)
Inventor
Timothy Jones
Ross Hatton
Stefan Schumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Warwick
Original Assignee
University of Warwick
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Warwick filed Critical University of Warwick
Publication of EP2430679A1 publication Critical patent/EP2430679A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • 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
    • H10K85/10—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
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • 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

  • This invention relates to semiconductor thin films, particularly but not exclusively for use in the construction of photo-sensitive devices such as photovoltaic cells. More particularly the invention concerns a process for the production of a semiconductor thin film structure, and preferably one incorporating an organic semiconductor.
  • PV organic photovoltaic
  • one electrode In order to allow light into the cell, typically one electrode must be transparent and conductive, for example consisting of a thin film coating of indium tin oxide (ITO) or SnO 2 on a glass substrate.
  • ITO indium tin oxide
  • SnO 2 on a glass substrate.
  • organic PV devices operate by combining organic materials which have donor and acceptor properties and providing a heterojunction between two such organic layers, where one layer is an electron transporter (acceptor) and the other is a hole transporter (donor).
  • acceptor electron transporter
  • donor hole transporter
  • known organic solar cells are based on thin films of organic semiconducting materials, such as phthalocyanines and fullerenes, or conjugated polymers and fullerenes.
  • the donor-acceptor films are typically 100 nm in thickness.
  • an exciton i.e. a bound electron - hole pair
  • the electron and hole are bound together by electrostatic attraction and are strongly localised.
  • the exciton is able to migrate or diffuse to a lower energy state.
  • This exciton must reach a donor-acceptor interface in order to dissociate efficiently into free charge carriers.
  • This dissociation is essential in solar cells such that when an exciton reaches an interface between the donor material and acceptor material, the electron of the electron hole pair (exciton) may be transferred to the acceptor material.
  • the electron in the acceptor material is transported to the cathode, and the hole, remaining in the donor material, is transported to the anode.
  • the diffusion length of an exciton is of the order of 10 to 50 nm; for example in copper phthalocyanine (CuPc) it has been found experimentally to be about 30 nm. Beyond this length the probability of the electron and hole recombining increases. It may therefore appear desirable to reduce the film thickness to less than 30 nm in order that the exciton reaches a donor-acceptor interface and dissociates. However, in order to absorb light efficiently and hence create excitons, film thicknesses of typically 100 nm are required.
  • a typical example of such a mixed blend device has a transparent electrode and a conductor electrode situated on opposite sides of a mixed blend layer made up of donor material and acceptor material.
  • the donor and acceptor materials form a random distributed heteroj unction.
  • a further variation of such a mixed blend organic device has been developed, having multiple mixed blend layers.
  • the composite is arranged in planar layers which are composed of blended donor material and acceptor material.
  • the composition of the layers is graded, the composition of the layer nearest one electrode being made of 100 percent acceptor material, the proportion of acceptor materials then decreasing to zero percent acceptor material and 100 percent donor material in the layer adjacent to the second electrode.
  • This type of device is, however, extremely difficult to manufacture.
  • a 3D corrugated interface structure has been proposed.
  • Two electrodes are situated on opposite faces of an organic layer.
  • the organic layer is made up of corrugated "fingers" of acceptor material and donor material.
  • the maximum thickness of these fingers should be about two times the exciton diffusion length in that material. All excitons will thus be formed within the diffusion distance of the acceptor-donor material interface and charge transfer to the electrodes is efficient.
  • WO 2008/029161 the contents of which are incorporated herein by reference, there is disclosed a thin film structure for use in photovoltaic cells, comprising first and second continuous interpenetrating lattices of semiconductor materials acting as respective electron donor and acceptor materials.
  • the creation of continuous interpenetrating lattices for each of the donor and acceptor materials is said to maximise the interfacial area between the materials and hence the exciton dissociation efficiency, minimising the exciton diffusion path.
  • a substrate such as an ITO coated transparent glass electrode is coated with a layer of a first phase material which is either donor or acceptor material.
  • the donor material can for example be a phthalocyanine, e.g. a metal phthalocyanine, such as copper phthalocyanine, and the acceptor material can for example be a fullerene or a perylene.
  • a phthalocyanine e.g. a metal phthalocyanine, such as copper phthalocyanine
  • the acceptor material can for example be a fullerene or a perylene.
  • colloidal spheres is then deposited on the layer of first phase material, for example by controlled self-assembly deposition from a colloid suspension. Typically, several layers of spheres are deposited, according to the device thickness required.
  • the particles may be of any monodisperse, removable material, which is able to produce an ordered, hexagonally or cubic or other geometry close-packed structure. As this structure is ordered or structured and not random, each particle will be in contact with all of its neighbours, and hence be interconnected.
  • the removable particles may for example be polystyrene spheres.
  • any carrier solvent is then removed, leaving the layers of spheres in contact with each other but with the interstitial spaces empty.
  • the interstitial spaces are then infiltrated by a further amount of the first phase material. This may be done for example by solution infiltration, by dipping or by deposition from the vapour phase.
  • the spheres are then removed from the structure by a suitable means so as to leave no residue, resulting in empty space where the spheres were.
  • a suitable means so as to leave no residue, resulting in empty space where the spheres were.
  • This may be by combustion, or by a low temperature process, preferably room temperature solution processing; for example the spheres may be removed by solvent extraction, or sonication.
  • the voids created by removal of the spheres are interconnected because the spheres were originally in contact with each other.
  • the voids form a continuous lattice that interpenetrates the skeleton of the first phase material.
  • the interconnected lattice comprising the empty space previously occupied by the spheres in the composite structure is then infiltrated by the second phase material which will be an acceptor material if the first phase material was a donor material, or vice versa.
  • a continuous layer of the second phase material is then formed at the upper face of the composite structure and a second electrode, which may be of any appropriate material, for example a metal such as aluminium, gold or copper, is then applied to the continuous layer of the second phase material.
  • McLachlan et al Journal of Materials Chemistry, 2007,17,3773-3776, the contents of which are incorporated herein by reference, discloses the fabrication of three- dimensionally ordered macroporous thin film structures using organic semiconductors but relatively large template particles were used with diameters of 250 -400 nm.
  • a large interface area combined with a high degree of open-cellular interconnectivity is required, necessitating the use of small template particles having dimensions of, for example, no more than about 100 nm.
  • the spheres may be between 10 and 500 nm in diameter and that a typical diameter would be 50 nm.
  • WO 2008/029161 discloses that in the process described there are three possibilities, namely: both the donor and acceptor materials are organic semiconductors; or one of the donor and acceptor materials is an organic semiconductor and the other is an inorganic semiconductor; or both of the donor and acceptor materials are inorganic semiconductors.
  • WO 2008/029161 a process for the production of a semiconductor thin film structure in which nanoparticles of a removable material are deposited on a substrate and by self assembly form a structure defining a network of interstitial spaces; the interstitial spaces are infiltrated by a first semiconductor material which will serve as a donor or acceptor material; and the nanoparticles are removed so as to leave a three dimensional structure of the first semiconductor material including a network of interconnected pores.
  • the present invention is characterised over this process in that the nanoparticles and the first semiconductor material are co-deposited so that the first semiconductor material infiltrates the interstitial spaces during nanoparticle self-assembly.
  • the mean diameters of the nanoparticles is no more than about 100 nm, or ' less than about 100 nm.
  • the nanoparticles have no particular upper limit in terms of the ability to self assemble, and for example could have a diameter of up to at least about 500 nm, in the context of organic photovoltaic device in particular it is desirable to have diameters of no more than about 100 nm given the low exciton diffusion lengths of organic semiconductors. With typical exciton diffusion lengths for organic semiconductors being the range of about 10 nm to about 30 nm, that would be a goal for the nanoparticle / pore size.
  • the nanoparticle / pore diameters are preferably a few tens of nanometres.
  • the smaller the diameter of the nanoparticles the greater the disorder there is in, the self assembled structure. As more disorder is introduced, the connectivity of the different regions is disrupted and this may limit the performance of a device due to transport problems.
  • the mean diameters of the nanoparticles are in the range of about 50 nm to about 100 nm. In some embodiments of the invention the nanoparticles have a diameter in the range of about 60 nm to about 100 nm. In some embodiments of the invention the nanoparticles have a diameter in the range of about 70 nm to about 100 nm. In some embodiments of the invention the nanoparticles have a diameter in the range of about 80 nm to about 100 nm. In some embodiments of the invention the nanoparticles have a diameter in the range of about 90 nm to about 100 nm.
  • the mean diameters of the nanoparticles are in the range of about 10 nm to about 30 nm. In some embodiments of the invention, the mean diameters of the nanoparticles are in the range of about 10 nm to about 50 nm . In some embodiments of the invention, the mean diameters of the nanoparticles are in the range of about 30 nm to about 50 nm.
  • the nanoparticles may be of any suitable material that can form a structure by self assembly and can be removed afterwards by a method that will not also remove the first semiconductor material.
  • the nanoparticles are preferably able to produce an ordered, or pseudo or partially ordered structure.
  • a typical ordered structure would be a hexagonal or cubic or other geometry close-packed structure.
  • each sphere or at least. a substantial number of spheres will be in contact with all or a substantial number of its neighbours, so that there is an interconnected array of spheres.
  • the nanoparticles When the nanoparticles are removed, there will be defined a structure with interconnected pores.
  • a solid lattice of the first semiconductor material defining a lattice of interconnected spaces.
  • the nanoparticles are preferably substantially monodisperse, i.e. particles whose variation in size is small or extremely small.
  • the nanoparticles are removed using solvent vapour.
  • the solvent vapour is hot, i.e. substantially above ambient temperature.
  • the solvent may be boiled, preferably under reflux, to create the vapour.
  • THF tetrahydrofurane
  • THF has a boiling point of 66 0 C at standard pressure bur preferably nanoparticle extraction is carried out under pressure so this will change.
  • the nanoparticles may for example be of polystyrene but other nanoparticle materials may be used, for example another polymer such as polymethylmethacrylate.
  • preferred nanoparticles will be of a polymer that can be removed by exposure to an organic solvent, preferably in hot vapour form.
  • organic solvent preferably in hot vapour form.
  • THF tetrahydrofurane
  • the hot solvent provides deeper penetration into small spaces to remove the nanoparticles.
  • the hot solvent may also provide hot solvent annealing of the material, leading to higher or different material crystallinity.
  • WO 2008/029161 there is disclosed a process for the production of a semiconductor thin film structure in which nanoparticles of a removable material are deposited on a substrate and by self assembly form a structure defining a network of interstitial spaces; the interstitial spaces are infiltrated by a first semiconductor material which will serve as a donor or acceptor material; and the nanoparticles are removed so as to leave a three dimensional structure of the first semiconductor material including a network of interconnected pores.
  • the nanoparticles which may be polystyrene, may be removed by combustion or by a low temperature process, preferably room temperature solution processing.
  • the invention is characterised over WO 2008/029161 in that the nanoparticles are removed by the use of solvent in vapour form.
  • the vapour is hot, and thus the vapour is preferably obtained by increasing the temperature of the solvent beyond ambient temperature to its boiling point. This is preferably done under reflux.
  • nanoparticle removal is carried out under pressure.
  • the substrate may be exposed to a solution of the first semiconductor material which also contains the nanoparticles in colloidal form.
  • the first semiconductor material is water soluble.
  • the substrate is immersed in the solution and then there is controlled evaporation so that there is generated a thin film comprising the nanoparticles which have self-assembled, and the first semiconductor material occupying the interstitial spaces between the spheres.
  • a second semiconductor material infiltrates the pores left by the nanoparticles.
  • One of the two semiconductor materials is a donor material and the other is an acceptor material.
  • Infiltration of the second semiconductor material results in there being a solid lattice of the first semiconductor material, interpenetrated by a lattice of the second semiconductor material.
  • the first semiconductor material is an organic semiconductor material.
  • the organic semiconductor material could be, for example, an organic semiconducting polymer, such as sodium poly[2-(3- thienyl)ethoxy-4-butylsulfonate] (PTEBS), or a molecular semiconductor such as copper(ll) phthalocyanine-tetrasulfonic acid tetrasodium salt (TS-CuPc).
  • the second semiconductor material is also an organic semiconductor material.
  • the second semiconductor material may be an inorganic material.
  • the substrate is an electrode and after infiltration by a second semiconductor material, a second electrode is placed on the other side of the structure.
  • a second electrode is placed on the other side of the structure.
  • at least one of the electrodes will be transparent.
  • the nanoparticles are removed and a second semiconductor material is infiltrated into the structure.
  • co-deposition is applicable to other arrangements also, such as other arrangements as disclosed in WO 2008/029161.
  • non- sacrificial nanoparticles of a first semiconductor material may be co-deposited with a second semiconductor material which infiltrates the interstitial spaces during self assembly of the nanoparticles.
  • the nanoparticles are left in place and are used as either the donor or acceptor material. This can be used in inorganic-organic hybrid devices, wherein one of either the donor or the acceptor material is an inorganic material.
  • the deposited nanoparticles could for example be of titanium oxide or zinc oxide, which are able to act as semiconductors. These are co-deposited with a second semi-conducting material which infiltrates the interstitial spaces. These may act as an acceptor and the co-deposited donor material could be, for example, P3HT (poly-3(hexylthiophene). Alternatively the deposited nanoparticles could be an organic material, examples of which are given above, which would not be removed.
  • the invention provides a process for the production of a semiconductor thin film structure in which nanoparticles of a first semiconductor material are deposited on a substrate and by self assembly form a structure defining a network of interstitial spaces; and the interstitial spaces are infiltrated by a second semiconductor material so as to provide a three dimensional structure of interpenetrating regions of the first and second semiconductor materials; one of the first and second semiconductor materials serving as a donor and the other serving as an acceptor, material; characterised in that the nanoparticles and the second semiconductor material are co-deposited so that the second semiconductor material infiltrates the interstitial spaces during nanoparticle self-assembly.
  • this further aspect of the invention such as the nature a of the nanoparticles, and the selection of the second semiconductor material, such as an organic semiconductor material, are as discussed above in respect of the first aspect of the invention.
  • nanoparticles covers a range of particles, some of which may be referred to as nanospheres or nanocapsules. Whilst it may be that in many cases, the particles will be generally spherical, the nanoparticles may have other shapes. Where the expression diameter is used, this does not imply that there is a sphere, and the expression can for example encompass the maximum or mean dimension across a particle. As set out in WO 2008/029161 , the particles may be any geometric shape which is capable of packing to form a continuous interpenetrable lattice, for example non-tessellating shapes or tessellating shapes laid out in a non-tessellating orientation, and any packing geometry may be adopted.
  • Figures 1 (a), (b), (c) and (d) are images from field emission scanning electron microscopy (FE-SEM);
  • Figures 2 (a) and (b) are images from field emission scanning electron microscopy (FE-SEM);
  • Figure 3 is a diagram showing ultra violet / visible absorption spectra;
  • Figure 4 is a second diagram showing ultra violet / visible absorption spectra
  • FIG. 5 illustrates diagrammatically steps in a process in accordance with the invention.
  • Figure 6 is a diagram illustrating a co-deposition process.
  • Synthesis of 3D ordered macroporous (3DOM) structures in this embodiment of the invention can be broken down into two main fabrication steps: (1 ) vertical or convective self-assembly, followed by (2) nanoparticle removal.
  • Polystyrene nanoparticles i.e. nanospheres, were synthesised by radical initiated soap-free emulsion polymerisation with either cationic or anionic initiator and dialysed against water prior to use. See K. Tauer et al, Colloid and Polymer Science, 2008, 246, 499 - 515. Size and polydispersity were determined by dynamic light scattering and transmission electron microscopy. In this example, colloids of mean diameters between 50-100 nm were used with a polydispersity index range of 0.034-0.010.
  • the structures were grown on either plain glass slides or indium-tin oxide (ITO) coated glass substrates pre-cleaned by sonicating in appropriate solvents followed by ultraviolet/ozone or oxygen plasma treatment. After immersing the substrate in a mixture of colloidal dispersion and organic semiconductor solution, the structures were grown in a temperature-stable incubator at 60 ° C ⁇ 0.4 ° C and a relative humidity ⁇ 15 %.
  • ITO indium-tin oxide
  • the nanoparticles were selectively removed from the composite structure by exposure of the sample to vapour from hot solvent boiling under reflux, in this case tetrahydrofurane. Purified, fresh vapour deeply penetrates the composite structure, dissolving any remaining polystyrene and results in the formation of well defined 3DOM organic thin films.
  • the resulting 3D0M structures were analysed by field emission scanning electron microscopy (FE-SEM) and ultraviolet/visible (UV/vis).
  • FE-SEM field emission scanning electron microscopy
  • UV/vis ultraviolet/visible
  • polystyrene nanospheres were synthesised by radical initiated soap- free emulsion polymerisation using either a cationic or anionic initiator and dialysed against water prior to use.
  • the average particle size and polydispersity was determined by dynamic light scattering and transmission electron microscopy.
  • Polystyrene sphere latexes with two distinct mean particle diameters (100 nm and 60 nm) were prepared with polydispersities of 0.02 and 0.06 respectively.
  • 0.10-0.15 mL of latex was added to 20 ml_ of water containing 0.02-0.15 mg ml_-1 of the water-soluble polymeric semiconductor, PTEBS, or the molecular semiconductor, TS-CuPc.
  • Figure 1 (a) shows an FE-SEM image of a film from co-deposition of PTEBS with 100 nm polystyrene latex nanoparticles, showing a crack free film covering a large substrate area.
  • Figures 1 (b) and 1 (c) are larger scale images.
  • Figure 1 (d) is a larger scale image, but in this case for a film made from co-deposition of TS-CuPc with the 100 nm polystyrene nanoparticles.
  • the soluble filling material acts as a surfactant, modifying the inter-sphere interactions and capillary forces which drive nanoparticle self-assembly.
  • the presence of the filling material may destabilise the latex leading to random clustering and agglomeration of the nanoparticles, although this is not observed to any significant extent when using 100 nm diameter spheres.
  • the use of co-deposition creates a strong composite film which helps to release built up tension in the film during the drying process which otherwise might result in film cracking.
  • Figure 2 (a) is an FE-SEM image of a film from co-deposition of PTEBS with 60 nm polystyrene latex nanoparticles.
  • Figure 2 (b) is an FE-SEM image of a film from co-deposition of TS-CuPc with 60 nm polystyrene latex nanoparticles.
  • the self-assembly driving capillary attraction energy decreases to a level comparable to the thermal energy of the, particles, thus counteracting particle ordering. Since the latter operates to disrupt regular array formation, the level of disorder in the films fabricated using 50 nm or 60 nm diameter spheres is to be expected.
  • Useful structures can be obtained with with sphere (nanoparticle) diameters of no more than 60nm or no more than 50 nm. It is also believed that viable structures can be obtained with smaller nanoparticle diameters, i.e. diameters of no more than about 40 nm, or no more than about 30 nm, or no more than about 20 nm or no more than about 10 nm.
  • Figure 3 shows UV/vis electronic absorption spectra of the composite (nanoparticle/organic semiconductor) films and the resulting 3DOM films formed after sphere removal, for (a) PTEBS and (b) TS-CuPc.
  • For reference spectra are also shown for the polystyrene colloidal particles and a two-dimensional (2D) film of each organic semiconductor formed by spin coating. Whilst the lowest energy electronic transition in polystyrene is in the UV region of the spectrum, the polystyrene sphere assemblies (and cavities formed after sphere removal) appear to absorb light due to scattering, the efficiency of which increases as the wavelength of the light approaches that of the polystyrene sphere (or cavity).
  • the 2D PTEBS film made via spin coating shows the expected behaviour with an absoption peak at -430 nm. This peak is preserved in the composite PTEBS/polystyrene sphere film, before and after removal of the polystyrene template.
  • the composite spectrum correlates relatively well as a linear combination of the 2D PTEBS film and the polystyrene sphere assembly.
  • the absorption spectrum of the final 3DOM structure is not the same as that of the solid film of PTEBS due to scattering of light, especially at low wavelengths.
  • the primary absorption in TS-CuPc is located at -610 nm where the effects of light scattering by 100 nm transparent particles/cavities is less significant (Fig 3b).
  • the embodiments of the invention allow for the fabrication of continuous, large area 3DOM structures of organic semiconductors using vertical co-deposition of templating polystyrene spheres of 100 nm and sub - 100 nm diameter in conjuction with water soluble small molecule (i.e. TS-CuPc) or polymeric (i.e. PTEBS) organic semiconductors.
  • TS-CuPc water soluble small molecule
  • PTEBS polymeric organic semiconductors.
  • Subsequent post-deposition treatment with hot solvent vapour is an efficient means of sphere removal, generating 3DOM organic semiconductor films of tunable pore size between about 50 to about 100 nm depending on the size of the polystyrene latex spheres used.
  • the resulting interconnected cellular networks of organic semiconductor provide a suitable platform for subsequent infiltration of a variety of materials to form interpenetrating network nanocomposites with broad application potential.
  • Figure 4 is a diagrammatic view of a process in accordance with the invention.
  • a 1 substrate in the form of an indium-tin oxide (ITO) coated glass electrode is immersed in a mixture 2 of a colloidal dispersion of polystyrene nanoparticles, and organic semiconductor solution.
  • the structures are grown in a temperature-stable incubator to produce self assembled layers 3 of the polystyrene spheres, with the organic semiconductor 4 in the interstitial spaces.
  • the nanoparticles are selectively removed from the composite structure by exposure of the sample to vapour from a source 5 of hot solvent boiling under reflux, in this case tetrahydrofurane.
  • the vapour penetrates the composite structure, dissolving the polystyrene and resulting in the formation of a thin film of the organic semiconductor 4 with well defined pores 6 as shown at step D.
  • a second organic semiconductor material 7 is infiltrated into the interconnected spaces defined by the lattice of organic semiconductor material 4. This provides a lattice of the semiconductor material 7, with the two lattices interpenetrating.
  • a second indium-tin oxide (ITO) coated glass electrode 8 is then placed on the structure at step F.
  • the semiconductor device could be, for example, a photo-sensitive device, such as a photovoltaic cell or a photo detection device.
  • the first organic semiconductor material such as TS-CuPc or PTEBS may act as a donor, with the second semiconductor material being an acceptor material such as fullerene or fullerene derivative such as PCBM ([6, 6]-phenyl-C61 -butyric acid methyl ester).
  • Figure 6 shows a preferred co-deposition process.
  • a substrate 9 is directed upwardly, at an inclination.
  • Evaportation of the liquid takes place from the meniscus 13, as indicated by arrows 14, this leading to self assembly of the nanoparticles into an array 15, with the organic semiconductor infiltrated into the interstitial spaces .
  • Nanoparticles of a removable material such as polystyrene are co-deposited with an organic semiconductor on an electrode substrate from a mixture of a colloidal suspension of the nanoparticles and a solution of the organic semiconductor.
  • the nanoparticles form an ordered structure defining a network of interstitial spaces which are infiltrated by the organic semiconductor material.
  • the nanoparticles are removed by hot solvent vapour so as to leave a three dimensional ordered macroporous structure of the organic semiconductor material.
  • a second semiconductor material can then be infiltrated into the pores left by removal of the nanoparticles and a second electrode added, to create a photo-sensitive device.
  • a process which comprises vertical co-deposition of a water soluble organic semiconductor with polystyrene nanospheres as a template, followed by solvent vapour nanosphere removal, so as to generate a macroporous large area thin film of the organic semiconductor having a network of pores of pore size less than 100 nm.
  • the film has low number crack and defect disorder and is of broad application in different fields.
  • the invention provides a process for producing a multiphase thin film structure in which there is co-deposition on a substrate of (i) a first phase material in the form of nanoparticles which self assemble such that nanoparticles are in contact with neighbouring nanoparticles, so as to define a first lattice of first phase material and a second lattice of interconnected interstitial spaces between the nanoparticles and (ii) a second phase material which infiltrates interstitial spaces between the nanoparticles during self assembly of the nanoparticles, so as to occupy at least partially the second lattice.
  • the nanoparticles may be removed subsequently so as to vacate the first lattice, which can then occupied by a third phase material.
  • the first and third phase materials may be semiconductors, one acting as a donor and the other as an acceptor.

Abstract

La présente invention a trait à un processus permettant de produire une structure à couche mince de semi-conducteur organique. Des nanoparticules (11) d'une substance amovible telle que le polystyrène sont co-déposées avec un semi-conducteur organique sur une électrode de substrat (9) à partir d'un mélange (10) d'une suspension colloïdale des nanoparticules et d'une solution du semi-conducteur organique. Par autoassemblage, les nanoparticules forment une structure ordonnée (15) définissant un réseau d'espaces interstitiels qui sont infiltrés par la substance de semi-conducteur organique. Les nanoparticules sont supprimées par vapeur de solvant chaud de manière à obtenir une structure macroporeuse ordonnée tridimensionnelle de la substance de semi-conducteur organique. Une seconde substance de semi-conducteur peut alors être infiltrée dans les pores laissés par la suppression des nanoparticules et une seconde électrode ajoutée afin d'obtenir une cellule photosensible.
EP10721183A 2009-05-14 2010-05-14 Couches minces de semi-conducteur Withdrawn EP2430679A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0908240.5A GB0908240D0 (en) 2009-05-14 2009-05-14 Templating films
PCT/GB2010/000972 WO2010131011A1 (fr) 2009-05-14 2010-05-14 Couches minces de semi-conducteur

Publications (1)

Publication Number Publication Date
EP2430679A1 true EP2430679A1 (fr) 2012-03-21

Family

ID=40833940

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10721183A Withdrawn EP2430679A1 (fr) 2009-05-14 2010-05-14 Couches minces de semi-conducteur

Country Status (3)

Country Link
EP (1) EP2430679A1 (fr)
GB (1) GB0908240D0 (fr)
WO (1) WO2010131011A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125024A1 (fr) * 2010-04-05 2011-10-13 Ecole Polytechnique Federale De Lausanne (Epfl) Électrode améliorée
CN102515086B (zh) * 2011-11-21 2015-08-19 台州学院 具有形态相关磁性的Co纳米结构阵列材料的制备方法
CN104183703A (zh) * 2013-05-28 2014-12-03 中国科学院大连化学物理研究所 纳米结构的全聚合物太阳电池及其制备方法
CN104525197B (zh) * 2014-12-18 2017-05-17 北京工业大学 一种热稳定的负载型三维有序大孔三效催化剂的制备方法
CN107925000A (zh) * 2015-08-06 2018-04-17 默克专利股份有限公司 有机半导体组合物及其于制造有机电子器件的用途
RU2623717C1 (ru) * 2016-03-17 2017-06-28 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) Способ приготовления полимерных пленок для солнечных батарей (варианты)
CN107840304A (zh) * 2017-10-31 2018-03-27 北京信息科技大学 制备柔性电化学器件的方法、柔性电化学器件

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002117984A (ja) * 2000-10-12 2002-04-19 Auto Network Gijutsu Kenkyusho:Kk 有機ｅｌ表示装置及びその製造方法
US7253017B1 (en) * 2002-06-22 2007-08-07 Nanosolar, Inc. Molding technique for fabrication of optoelectronic devices
GB2421353A (en) * 2004-12-14 2006-06-21 Cambridge Display Tech Ltd Method of preparing opto-electronic device
GB0617727D0 (en) * 2006-09-08 2006-10-18 Imp College Innovations Ltd Photovoltaic devices

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010131011A1 *

Also Published As

Publication number Publication date
GB0908240D0 (en) 2009-06-24
WO2010131011A1 (fr) 2010-11-18

Similar Documents

Publication Publication Date Title
Docampo et al. Control of Solid‐State Dye‐Sensitized Solar Cell Performance by Block‐Copolymer‐Directed TiO2 Synthesis
Mao et al. Flexible silver grid/PEDOT: PSS hybrid electrodes for large area inverted polymer solar cells
Ahn et al. Hierarchical Double‐Shell Nanostructures of TiO2 Nanosheets on SnO2 Hollow Spheres for High‐Efficiency, Solid‐State, Dye‐Sensitized Solar Cells
KR101564390B1 (ko) 태양광 발전 장치용 고신뢰성 나노 구조체와 어레이 및 이의 제조 방법
US8319098B2 (en) Porous semiconductor film on a substrate
EP2430679A1 (fr) Couches minces de semi-conducteur
Tian et al. Design, fabrication and modification of metal oxide semiconductor for improving conversion efficiency of excitonic solar cells
US9214590B2 (en) High fidelity nano-structures and arrays for photovoltaics and methods of making the same
US8859423B2 (en) Nanostructured electrodes and active polymer layers
WO2010036805A2 (fr) Traitement photonique avec des matériaux à nanomotifs
Huang et al. Efficient and hysteresis-less pseudo-planar heterojunction perovskite solar cells fabricated by a facile and solution-saving one-step dip-coating method
DE102005003846A1 (de) Photovoltaikanlagen, die aus einem isolierenden, nanostrukturierten Templat hergestellt werden
WO2004001926A2 (fr) Pile electrique solaire nanostructuree/assemblee
JP2009088045A (ja) 光電変換素子およびその製造方法
Kim et al. Enhancing the optical properties using hemisphere TiO2 photonic crystal as the electron acceptor for perovskite solar cell
Hu et al. Template method for fabricating interdigitate pn heterojunction for organic solar cell
Bae et al. All-self-metered solution-coating process in ambient air for the fabrication of efficient, large-area, and semitransparent perovskite solar cells
US20170179198A1 (en) Tandem organic photovoltaic devices that include a metallic nanostructure recombination layer
EP2067189A2 (fr) Dispositifs photovoltaïques
Chen et al. Fabrication of silver sulfide thin films for efficient organic solar cells with high short-circuit currents based on double heterojunctions
Zhang et al. A comparative study on the morphology of P3HT: PCBM solar cells with the addition of Fe 3 O 4 nanoparticles by spin and rod coating methods
Lancelle‐Beltran et al. Solid‐State Organic/Inorganic Hybrid Solar Cells Based on Poly (octylthiophene) and Dye‐Sensitized Nanobrookite and Nanoanatase TiO2 Electrodes
Alishah et al. Investigation of various commercial PEDOT: PSS (poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate) as a hole transport layer in lead iodide-based inverted planar perovskite solar cells
Her et al. Hybrid photovoltaic cell with well-ordered nanoporous titania–P3HT by nanoimprinting lithography
Dai et al. Inverted Planar Perovskite Solar Cells Based on NiOx Nano Film with Enhanced Efficiency and Stability

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20111214

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20141202