WO2014015288A1 - Multijunction organic photovoltaics incorporating solution and vacuum deposited active layers - Google Patents

Multijunction organic photovoltaics incorporating solution and vacuum deposited active layers Download PDF

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Publication number
WO2014015288A1
WO2014015288A1 PCT/US2013/051354 US2013051354W WO2014015288A1 WO 2014015288 A1 WO2014015288 A1 WO 2014015288A1 US 2013051354 W US2013051354 W US 2013051354W WO 2014015288 A1 WO2014015288 A1 WO 2014015288A1
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Prior art keywords
photovoltaic device
organic photovoltaic
subcell
organic
weight material
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PCT/US2013/051354
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English (en)
French (fr)
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Stephen R. Forrest
Brian LASSITER
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Forrest Stephen R
Lassiter Brian
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Application filed by Forrest Stephen R, Lassiter Brian filed Critical Forrest Stephen R
Priority to IN516DEN2015 priority Critical patent/IN2015DN00516A/en
Priority to JP2015523291A priority patent/JP2015526901A/ja
Priority to CN201380043784.XA priority patent/CN104937736A/zh
Priority to CA2879573A priority patent/CA2879573A1/en
Priority to EP13750173.0A priority patent/EP2875534A1/en
Priority to KR20157002820A priority patent/KR20150037974A/ko
Priority to AU2013292306A priority patent/AU2013292306A1/en
Priority to US14/414,933 priority patent/US11744089B2/en
Publication of WO2014015288A1 publication Critical patent/WO2014015288A1/en
Priority to IL236765A priority patent/IL236765A0/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H10K30/211Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/16Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30Organic 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
    • H10K30/353Organic 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 blocking layers, e.g. exciton blocking layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50Photovoltaic [PV] devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50Photovoltaic [PV] devices
    • H10K30/57Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211Fullerenes, e.g. C60
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211Fullerenes, e.g. C60
    • H10K85/215Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/311Phthalocyanine
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/321Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/654Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Definitions

  • OCV organic photovoltaic device
  • Photosensitive optoelectronic devices rely on the optical and electronic properties of materials to either produce or detect electromagnetic radiation electronically or to generate electricity from ambient electromagnetic radiation.
  • Photosensitive optoelectronic devices convert electromagnetic radiation into electricity.
  • Solar cells also called photovoltaic (PV) devices, are a type of photosensitive optoelectronic device that is specifically used to generate electrical power.
  • PV devices which may generate electrical energy from light sources other than sunlight, can be used to drive power consuming loads to provide, for example, lighting, heating, or to power electronic circuitry or devices such as calculators, radios, computers or remote monitoring or communications equipment.
  • resistive load refers to any power consuming or storing circuit, device, equipment or system.
  • Another type of photosensitive optoelectronic device is a
  • signal detection circuitry monitors the resistance of the device to detect changes due to the absorption of light.
  • Another type of photosensitive optoelectronic device is a
  • a photodetector In operation, a photodetector is used in conjunction with a current detecting circuit which measures the current generated when the photodetector is exposed to electromagnetic radiation and may have an applied bias voltage.
  • a detecting circuit as described herein is capable of providing a bias voltage to a photodetector and measuring the electronic response of the photodetector to electromagnetic radiation.
  • These three classes of photosensitive optoelectronic devices may be characterized according to whether a rectifying junction as defined below is present and also according to whether the device is operated with an external applied voltage, also known as a bias or bias voltage.
  • a photoconductor cell does not have a rectifying junction and is normally operated with a bias.
  • a PV device has at least one rectifying junction and is operated with no bias.
  • a photodetector has at least one rectifying junction and is usually but not always operated with a bias.
  • a photovoltaic cell provides power to a circuit, device or equipment, but does not provide a signal or current to control detection circuitry, or the output of information from the detection circuitry.
  • photoconductor provides a signal or current to control detection circuitry, or the output of information from the detection circuitry but does not provide power to the circuitry, device or equipment.
  • photosensitive optoelectronic devices have been constructed of a number of inorganic semiconductors, e.g., crystalline, polycrystalline and amorphous silicon, gallium arsenide, cadmium telluride and others.
  • semiconductor denotes materials which can conduct electricity when charge carriers are induced by thermal or electromagnetic excitation.
  • photoconductive generally relates to the process in which electromagnetic radiant energy is absorbed and thereby converted to excitation energy of electric charge carriers so that the carriers can conduct, i.e., transport, electric charge in a material.
  • photoconductor and “photoconductive material” are used herein to refer to semiconductor materials which are chosen for their property of absorbing electromagnetic radiation to generate electric charge carriers.
  • PV devices may be characterized by the efficiency with which they can convert incident solar power to useful electric power.
  • Devices utilizing crystalline or amorphous silicon dominate commercial applications, and some have achieved efficiencies of 23% or greater.
  • efficient crystalline-based devices, especially of large surface area are difficult and expensive to produce due to the problems inherent in producing large crystals without significant efficiency-degrading defects.
  • high efficiency amorphous silicon devices still suffer from problems with stability.
  • Present commercially available amorphous silicon cells have stabilized efficiencies between 4 and 8%. More recent efforts have focused on the use of organic photovoltaic cells to achieve acceptable photovoltaic conversion efficiencies with economical production costs.
  • PV devices may be optimized for maximum electrical power generation under standard illumination conditions (i.e., Standard Test Conditions which are 1000 W/m 2 , AM1 .5 spectral illumination), for the maximum product of photocurrent times photovoltage.
  • standard illumination conditions i.e., Standard Test Conditions which are 1000 W/m 2 , AM1 .5 spectral illumination
  • the power conversion efficiency of such a cell under standard illumination conditions depends on the following three parameters: (1 ) the current under zero bias, i.e., the short-circuit current Isc, in Amperes (2) the photovoltage under open circuit conditions, i.e., the open circuit voltage Voc, in Volts and (3) the fill factor, FF.
  • PV devices produce a photo-generated current when they are connected across a load and are irradiated by light.
  • a PV device When irradiated under infinite load, a PV device generates its maximum possible voltage, V open-circuit, or Voc- When irradiated with its electrical contacts shorted, a PV device generates its maximum possible current, I short-circuit, or Isc- When actually used to generate power, a PV device is connected to a finite resistive load and the power output is given by the product of the current and voltage, I * V.
  • the maximum total power generated by a PV device is inherently incapable of exceeding the product, Isc x Voc- When the load value is optimized for maximum power extraction, the current and voltage have the values, Lax and V max , respectively.
  • a figure of merit for PV devices is the fill factor, FF, defined as:
  • FF ⁇ l max V max ⁇ / ⁇ Isc Voc ⁇ (1 )
  • FF is always less than 1 , as Isc and Voc are never obtained simultaneously in actual use. Nonetheless, as FF approaches 1 , the device has less series or internal resistance and thus delivers a greater percentage of the product of Isc and V 0 c to the load under optimal conditions.
  • Pi nc is the power incident on a device
  • the power efficiency of the device, ⁇ ⁇ may be calculated by:
  • n-type denotes that the majority carrier type is the electron. This could be viewed as the material having many electrons in relatively free energy states.
  • p-type denotes that the majority carrier type is the hole. Such material has many holes in relatively free energy states.
  • the type of the background, i.e., not photo-generated, majority carrier concentration depends primarily on unintentional doping by defects or impurities.
  • the type and concentration of impurities determine the value of the Fermi energy, or level, within the gap between the conduction band minimum and valance band maximum energies, also known as the HOMO-LUMO gap.
  • the Fermi energy characterizes the statistical occupation of molecular quantum energy states denoted by the value of energy for which the probability of occupation is equal to 1 ⁇ 2.
  • a Fermi energy near the conduction band minimum (LUMO) energy indicates that electrons are the predominant carrier.
  • a Fermi energy near the valence band maximum (HOMO) energy indicates that holes are the predominant carrier. Accordingly, the Fermi energy is a primary characterizing property of traditional semiconductors and the prototypical PV junction has traditionally been the p-n interface.
  • rectifying denotes, inter alia, that an interface has an asymmetric conduction characteristic, i.e., the interface supports electronic charge transport preferably in one direction. Rectification is associated normally with a built- in electric field which occurs at the junction between appropriately selected materials.
  • a significant property in organic semiconductors is carrier mobility. Mobility measures the ease with which a charge carrier can move through a conducting material in response to an electric field.
  • a layer including a material that conducts preferentially by electrons due to a high electron mobility may be referred to as an electron transport layer, or ETL.
  • a layer including a material that conducts preferentially by holes due to a high hole mobility may be referred to as a hole transport layer, or HTL.
  • an acceptor material may be an ETL and a donor material may be an HTL.
  • Conventional inorganic semiconductor PV cells may employ a p-n junction to establish an internal field. However, it is now recognized that in addition to the establishment of a p-n type junction, the energy level offset of the
  • heterojunction may also play an important role.
  • the energy level offset at the organic donor-acceptor (D-A) heterojunction is believed to be important to the operation of organic PV devices due to the fundamental nature of the photogeneration process in organic materials.
  • D-A organic donor-acceptor
  • Upon optical excitation of an organic material localized Frenkel or charge-transfer excitons are generated.
  • the bound excitons must be dissociated into their constituent electrons and holes.
  • Such a process can be induced by the built-in electric field, but the efficiency at the electric fields typically found in organic devices (F ⁇ 10 6 V/cm) is low.
  • the most efficient exciton dissociation in organic materials occurs at a D-A interface.
  • the donor material with a low ionization potential forms a heterojunction with an acceptor material with a high electron affinity.
  • the dissociation of the exciton can become energetically favorable at such an interface, leading to a free electron polaron in the acceptor material and a free hole polaron in the donor material.
  • Organic PV cells have many potential advantages when compared to traditional silicon-based devices.
  • Organic PV cells are light weight, economical in materials use, and can be deposited on low cost substrates, such as flexible plastic foils.
  • organic PV devices typically have relatively low quantum yield (the ratio of photons absorbed to carrier pairs generated, or electromagnetic radiation to electricity conversion efficiency), being on the order of 1 % or less. This is, in part, thought to be due to the second order nature of the intrinsic photoconductive process. That is, carrier generation requires exciton generation, diffusion, and ionization or collection. There is an efficiency ⁇ associated with each of these processes.
  • the diffusion length (L D ) of an exciton is typically much less (L D ⁇ 50 A) than the optical absorption length (-500 A), requiring a tradeoff between using a thick, and therefore resistive, cell with multiple or highly folded interfaces, or a thin cell with a low optical absorption efficiency.
  • an organic photovoltaic device comprising at least one first subcell comprising at least one first small molecular weight material deposited by solution processing; and at least one second subcell comprising a weight at least one second small molecular material deposited by vacuum evaporation.
  • Also disclosed herein is a method of preparing an organic photovoltaic device comprising at least one first subcell comprising at least one first small molecular weight material and at least one second subcell comprising at least one second small molecular weight material comprising depositing at least one first small molecular weight material by solution processing; and depositing at least one second small molecular weight material by vacuum evaporation.
  • the OPV comprises two or more subcells. In one embodiment, the OPV comprises two subcells. In one embodiment, the OPV comprises three subcells. In another embodiment, the OPV comprises four subcells. In yet another experiment, the OPV comprises more than four subcells.
  • each subcell comprises at least one donor- acceptor heterojunction.
  • the solution processing is spin-coating, doctor- blading, or spray-coating process.
  • the vacuum evaporation is vacuum thermal evaporation or organic vapor phase deposition.
  • the device comprises a two terminal series architecture. In another embodiment, the device comprises a three-terminal parallel architecture. In yet another embodiment, the device comprises a four-terminal architecture.
  • the device comprises two heterojunctions with a two terminal series architecture.
  • the power conversion efficiency (PCE) of the device is improved compared to the first subcell or the second subcell, or the first and second subcells combined.
  • the at least one first small molecular weight material or the at least one second small molecular weight material comprises at least one donor material.
  • the at least one donor material is chosen from boron subphthalocyanine (SubPc), copper phthalocyanine(CuPc), chloroaluminium phthalocyanine (CIAIPc), tin phthalocyanine (SnPc), pentacene, tetracene, diindenoperylene (DIP), and squaraine (SQ).
  • the donor is chosen from 2,4-bis[4-(N,N-diphenylamino)-2,6-dihydroxyphenyl] squaraine (DPSQ) and SubPc.
  • the at least first subcell further comprises a material deposited by vacuum evaporation.
  • the material deposited by vacuum evaporation comprises an acceptor layer.
  • the at least second subcell further comprises a material deposited by solution processing.
  • the at least one first small molecular weight material and/or the at least one second small molecular weight material further comprises at least one acceptor material.
  • the at least one acceptor is chosen from fullerene, 3,4,9,10-perylenetetracarboxylicbis-benzimidazole (PTCBI), phenyl-C 6 r butyric-acid-methyl ester ([60]PCBM), phenyl-C 7 i-butyhc-acid-methyl ester
  • Fullerene includes, for example, C 6 o and C 7 o.
  • Fullerene includes, for example, Qso and C 7 o.
  • the at least one second material comprises a small molecule:fullerene layer.
  • the at least one heterojunction comprises a SubPc:fullerene layer.
  • the heterojunction comprises SubPc:C 70 layer.
  • the first subcell and/or the second subcell further comprises an electron blocking layer.
  • the electron blocking layer comprises BCP, BPhen, PTCBI, TPBi, Ru(acac) 3 , and Alq 2 OPH.
  • the first subcell and/or the second subcell further comprises an buffer layer.
  • the buffer layer comprises M0O3.
  • the photovoltaic device further comprises a charge recombination or a charge transfer layer between the at least one first subcell and the at least one second subcell.
  • the charge recombination layer, or charge transfer layer comprises a material chosen from Al, Ag, Au, M0O 3 ,
  • OCV organic photovoltaic device
  • the at least one first subcell is closer to the substrate of the device and is referred to as the front subcell, and the at least one second subcell, further away from the substrate, is referred to as a back subcell.
  • the at least one first subcell is a back subcell, and the at least one second subcell is a front subcell.
  • Figure 1 Schematic diagram of the structure of three devices: a) front-only, b) back-only, and c) tandem. The illustrations are not to scale.
  • an organic photovoltaic device comprising at least one first subcell comprising at least one first small molecular weight material deposited by solution processing, and at least one second subcell comprising a weight, and at least one second small molecular material deposited by vacuum evaporation.
  • Also disclosed herein is a method for preparing an organic photovoltaic device comprising at least one first subcell comprising at least one first small weight material and at least one second subcell comprising at least one second small weight material, the method comprising depositing at least one first small weight material by solution processing; and depositing at least one second small weight material by vacuum evaporation.
  • Organic photosensitive optoelectronic devices of the embodiments described herein may function as a PV device, photodetector or photoconductor.
  • the OPV comprises two or more heterojunctions.
  • the OPV comprises two heterojunctions.
  • the OPV comprises three heterojunctions.
  • the OPV comprises four or more heterojunctions.
  • Each subcell comprises at least one heterojunction.
  • a two-terminal series device is known as a tandem device.
  • the organic PV device may exist as a tandem device comprising one or more donor-acceptor heterojunctions.
  • a tandem device may comprise charge transfer material, electrodes, or charge recombination material between the tandem donor- acceptor heterojunctions.
  • a small molecular weight material means a material with molecular weight no more than 5000 Daltons, for example, no more than 4500 Daltons, no more than 4000 Daltons, no more than 3500 Daltons, no more than 3000 Daltons, no more than 2500 Daltons, no more than 2000 Daltons, no more than 1500 Daltons, or no more than 1000 Daltons, as opposed to a polymeric material.
  • small molecular weight material is used interchangeably with "small molecule.”
  • material and “layer” are used interchangeably, referring to a member or component of a photosensitive device whose primary dimension is X-Y, i.e., along its length and width.
  • layer is not necessarily limited to single layers or sheets of materials.
  • the surfaces of certain layers, including the interface(s) of such layers with other material(s) or layers(s) may be imperfect, wherein said surfaces represent an interpenetrating, entangled or convoluted network with other material(s) or layer(s).
  • a layer may be discontinuous, such that the continuity of said layer along the X-Y dimension may be disturbed or otherwise interrupted by other layer(s) or material(s).
  • Subcell means a component of the photovoltaic device which comprises at least one a donor-acceptor heterojunction.
  • Donor- acceptor heterojunction means a component of the photovoltaic device which comprises at least one a donor-acceptor heterojunction.
  • Donor- acceptor heterojunction means a component of the photovoltaic device which comprises at least one a donor-acceptor heterojunction.
  • heterojunction may be formed by a planar, bulk, mixed, hybrid-planar-mixed, or nanocrystalline bulk heterojunction.
  • the heterojunction may comprise mixtures of two or more materials chosen from: boron subphthalocyanine (SubPc), C 6 o, C 70 , squaraine, copper phthalocyanine(CuPc), tin phthalocyanine (SnPc), chloroaluminum phthalocyanine (CIAIPc), and
  • DIP diindenoperylene
  • front or front subcell means the subcell closest to the substrate structure, while “back” or “back subcell” refers to the subcell furthest away from the substrate structure.
  • the organic materials or organic layers, or organic thin films can be applied via solution processing, such as by one or more techniques chosen from spin-coating, spin-casting, spray coating, dip coating, doctor-blading, inkjet printing, or transfer printing.
  • solution-processing technique can be used to achieve uniform, high-quality thin films for electronic purposes.
  • the organic materials may be deposited using vacuum evaporation, such as vacuum thermal evaporation, organic vapor phase deposition, or organic vapor-jet printing.
  • donor materials that may be used in the present disclosure, non-limiting mention is made to those chosen from boron subphthalocyanine (SubPc), copper phthalocyanine(CuPc), chloroaluminium phthalocyanine (CIAIPc), tin phthalocyanine (SnPc), pentacene, tetracene, diindenoperylene (DIP), and squaraine (SQ).
  • SubPc boron subphthalocyanine
  • CuPc copper phthalocyanine
  • CIAIPc chloroaluminium phthalocyanine
  • SnPc tin phthalocyanine
  • pentacene tetracene
  • DIP diindenoperylene
  • SQL squaraine
  • Non-limiting embodiments of the squaraine compound that may be used are those chosen from 2,4-bis [4-(N,N-dipropylamino)-2,6-dihydroxyphenyl] squaraine, 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine, 2,4- bis[4-(N,N-diphenylamino)-2,6-dihydroxyphenyl] squaraine (DPSQ) and salts thereof.
  • the donor materials may be doped with a high mobility material, such as one that comprises pentacene or metal nanoparticles.
  • the acceptor materials that may be used in the present disclosure include polymeric or non-polymeric perylenes, polymeric or non- polymeric naphthalenes, and polymeric or non-polymeric fullerenes.
  • At least one subcell may further comprise a exciton blocking layer (EBL). In some embodiments, at least one subcell may further comprise a charge transfer layer or charge recombination layer. In some other embodiments, at least one subcell may optionally comprises a buffer layer.
  • EBL exciton blocking layer
  • at least one subcell may further comprise a charge transfer layer or charge recombination layer. In some other embodiments, at least one subcell may optionally comprises a buffer layer.
  • materials that may be used as an exciton blocking layer include those chosen from bathocuproine (BCP), bathophenanthroline (BPhen), 3,4,9, 10-perylenetetracarboxylicbis-benzimidazole (PTCBI), 1 ,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBi), tris(acetylacetonato) ruthenium(lll) (Ru(acac) 3 ), and aluminum(lll)phenolate (Alq 2 OPH), N,N'-diphenyl- ⁇ , ⁇ '-bis-alpha-naphthylbenzidine (NPD), aluminum tris(8-hydroxyquinoline) (Alq 3 ), and carbazole biphenyl (CBP).
  • BCP bathocuproine
  • BPhen bathophenanthroline
  • PTCBI 3,4,9, 10-perylenetetracarboxylicbis-benzimidazole
  • the charge transfer layer or charge recombination layer may be chosen from Al, Ag, Au, M0O 3 , Li, LiF, Sn, Ti, WO 3 , indium tin oxide (ITO), tin oxide (TO), gallium indium tin oxide (GITO), zinc oxide (ZO), or zinc indium tin oxide (ZITO).
  • the charge transfer layer or charge recombination layer may be comprised of metal nanoclusters, nanoparticles, or nanorods.
  • the OPVs described herein further comprises a buffer layer, such as W0 3 , V 2 0 5 , M0O 3 , and other oxides.
  • first layer there may be other layers between a first and a second layer, unless it is specified that the first layer is "in physical contact with” the second layer.
  • a cathode may be described as “disposed over” or “on top of an anode, even though there are various organic layers in between.
  • the organic photovoltaic device may comprise at least one electrode.
  • An electrode may be reflective or transparent.
  • the electrode can be transparent conducting oxides, such as indium tin oxide (ITO), tin oxide (TO), gallium indium tin oxide (GITO), zinc oxide (ZO), and zinc indium tin oxide (ZITO), or transparent conductive polymers, such as polyanaline (PAN I).
  • ITO indium tin oxide
  • TO tin oxide
  • GITO gallium indium tin oxide
  • ZO zinc oxide
  • ZITO zinc indium tin oxide
  • PAN I polyanaline
  • the electrodes may be composed of metals such as Ag, Au, Ti, Sn, and Al.
  • at least one electrode is an anode that comprises indium tin oxide (ITO).
  • the electrode is a cathode that comprises a material chosen from Ag, Au, and Al.
  • the organic photovoltaic device further comprises a substrate.
  • Substrate, onto which the device may be grown or placed may be any suitable material that provides the desired structural properties.
  • the substrate may be flexible or rigid, planar or non-planar.
  • the substrate may be transparent, translucent or opaque. Plastic, glass, and quartz are examples of rigid substrate materials. Plastic and metal foils are examples of flexible substrate materials.
  • substrate is stainless steel, such as a stainless steel foil (SUS).
  • SUS substrates are relatively low cost compared to conventional materials, and provide better heat sinks during growth of layers.
  • Organic photosensitive optoelectronic devices of the embodiments described herein may function as a PV device, photodetector, or photoconductor. Whenever the organic photosensitive optoelectronic devices described herein function as a PV device, the materials used in the photoconductive organic layers and the thicknesses thereof may be selected, for example, to optimize the external quantum efficiency of the device. Whenever the organic photosensitive optoelectronic devices described herein function as a PV device, the materials used in the photoconductive organic layers and the thicknesses thereof may be selected, for example, to optimize the external quantum efficiency of the device. Whenever the organic photosensitive
  • the materials used in the photoconductive organic layers and the thicknesses thereof may be selected, for example, to maximize the sensitivity of the device to desired spectral regions.
  • a tandem organic photovoltaic device may be prepared by first growing a front subcell on to an electrode pre-coated on a substrate, for example, an anode, such as ITO, on a glass substrate.
  • a front subcell may be prepared by loading a substrate pre-coated with ITO into a high vacuum chamber to be deposited on an optional buffer layer, such as Mo0 3 , by vacuum thermal evaporation process.
  • the substrate can then be deposited with DPSQ films from a solution by spin-coating processing.
  • the substrate may then be deposited with organic material by vacuum evaporation. It may then be exposed to saturated solvent vapor, such as chloroform, to create a favorable film morphology.
  • a charge recombination layer such as Ag, and/or an electron transport layer, such as Mo0 3 , may be deposited on to the substrate by vacuum process.
  • the back subcell may be prepared by evaporating a mixed film of SubPc and C 7 o.
  • a film of electron blocking layer, such as BCP may be deposited by vacuum evaporation.
  • a second electrode such as a cathode, such as Ag, may be deposited in the same way.
  • the simple layered structure illustrated in Figure 1 is provided by way of non-limiting example, and it is understood that embodiments described herein may be used in connection with a wide variety of other structures.
  • the specific materials and structures described are exemplary in nature, and other materials and structures may be used.
  • Functional organic photosensitive optoelectronic devices may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used.
  • the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers.
  • Non-photoactive layers Organic layers that are not a part of the photoactive region, i.e., organic layers that generally do not absorb photons that make a significant contribution to photocurrent, may be referred to as "non-photoactive layers.” Examples of non-photoactive layers include EBLs and anode-smoothing layers. Other types of non-photoactive layers may also be used.
  • a tandem organic photovoltaic device having a solution-processed small molecule donor layer and evaporated fullerene acceptor layer for the front subcell and an evaporated small molecule:fullerene back subcell was prepared.
  • the work also applies to other types of architecture.
  • the tandem organic photovoltaic devices were grown on 150 nm thick layers of indium tin oxide (ITO) pre-coated onto glass substrates. Prior to deposition, the ITO surface was cleaned in a surfactant and a series of solvents and then exposed to ultraviolet-ozone for 1 0 min before loading into a high vacuum chamber (base pressure ⁇ 10 "7 Torr) where M0O 3 was thermally evaporated at -0.1 nm/s.
  • ITO indium tin oxide
  • Substrates were once again transferred into the high vacuum chamber for deposition of purified organics at 0.1 nm/s, followed by transfer back into the glovebox and exposure to saturated chloroform vapors for 10 min to create a favorable film morphology.
  • a 0.1 nm Ag silver nanocluster recombination layer and a M0O 3 transport layer were deposited.
  • a mixed film of boron subphthalocyanine chloride (SubPc) and C70 was evaporated where the rate of SubPc deposition was 0.012 nm/s while the rate of C70 deposition was varied from 0.02 to 0.08 nm/s.
  • the power conversion efficiency (PCE) for a tandem OPV is compared with individual subcells.
  • the subcell closest to the transparent substrate is referred to as the "front subcell,” and the other is referred to as the "back subcell.
  • the "front- only” cell consisted of glass/150 nm ITO/20 nm Mo0 3 /13 nm DPSQ/10 nm C 70 /5 nm PTCBI/0.1 nm Ag/30 nm M0O 3 /I OO nm Ag, while the "back-only” cell consisted of glass/150 nm ITO/5 nm Mo0 3 /29 nm SubPc:C 70 /3 nm C 70 /7 nm BCP/100 nm Ag.
  • the structures are also shown schematically in Figure 1.
  • the open-circuit voltage ⁇ V 0 c) of the tandem device is 1 .96 V, which is nearly the sum of the back-only and front-only devices (1 .04 and 0.94 V, respectively). This indicates that each heterojunction is functioning similarly in the tandem device as in the single heterojunction device, and that there is efficient recombination at the Ag recombination zone. Additionally, the short-circuit current (Jsc) of the tandem device is nearly identical to the smaller of the subcell Jsc (5.8 and 6.1 mA/cm 2 , respectively), indicating that there are few optical losses in the device.

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