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WO2019137354A1 - Systèmes aromatiques fusionnés à base de thiophène - Google Patents

Systèmes aromatiques fusionnés à base de thiophène Download PDF

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WO2019137354A1
WO2019137354A1 PCT/CN2019/070780 CN2019070780W WO2019137354A1 WO 2019137354 A1 WO2019137354 A1 WO 2019137354A1 CN 2019070780 W CN2019070780 W CN 2019070780W WO 2019137354 A1 WO2019137354 A1 WO 2019137354A1
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alkyl
group
sma
ixic
hydrogen
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He Yan
Yuzhong Chen
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Hong Kong University of Science and Technology
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Hong Kong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • 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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • H10K30/57—Photovoltaic [PV] devices comprising multiple junctions, e.g. tandem PV cells
    • 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
    • H10K85/151—Copolymers
    • 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 disclosure generally relates to organic semiconductors, their methods of preparation, and formulations thereof useful for preparing photoactive layers in organic solar cells (OSCs) .
  • OSCs organic solar cells
  • OSC Organic solar cells
  • a typical OSC device consists of a pair of materials that function as electron donor and electron acceptor.
  • One of the most commonly used class of electron acceptors are fullerene-based electron acceptors.
  • Conventional fullerene-based OSCs have achieved great successes with power conversion efficiencies (PCEs) reaching beyond 10%.
  • PCEs power conversion efficiencies
  • fullerene derivatives as the electron-accepting material suffers have several drawbacks, which include low absorbance in the visible region, costly production and purification processes and morphological instability.
  • non-fullerene based OSCs which are expected to be the next generation of OSCs that will be more efficient and stable and lower in cost than conventional fullerene-based OSCs.
  • OSCs based on a polymer donor and a small molecular acceptor (SMA) have experienced rapid development in the past three years.
  • SMA OSCs intensive research efforts have been devoted to the design and synthesis of novel SMA materials.
  • SMAs based on a fused terthieno [3, 2-b] thiophene core.
  • the SMAs can exhibit an ultralow-band gap and can show a wide adsorption range extending to the near-infrared region.
  • SMA small molecular acceptor
  • each A is independently selected from the group consisting of:
  • each B is absent; or each B is independently selected from the group consisting of:
  • each V is independently selected from the group consisting of hydrogen, alkyl, Cl, Br, CN, OR 6 , and NHR 6 ;
  • each of X and Y is independently hydrogen, F, Cl, Br, CN, OR 6 , or NHR 6 ;
  • each of W is independently O, S, Se, or Te;
  • R 5 is alkyl or cycloalkyl
  • R 6 is alkyl or cycloalkyl
  • each of R 7 and R 8 is independently hydrogen or alkyl.
  • each of R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of C 2 -C 20 alkyl, C 2 -C 20 cycloalkyl, C 2 -C 20 alkyl phenyl, C 2 -C 20 alkyl aryl, and C 2 -C 20 alkyl thienyl.
  • each B is absent; and each A is independently selected from the group consisting of:
  • a third embodiment of the first aspect provided herein is the SMA of the second embodiment of the first aspect, wherein each of X and Y is independently hydrogen, Cl, or F.
  • each of R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of C 2 -C 20 alkyl, C 2 -C 20 cycloalkyl, C 2 -C 20 alkyl phenyl, C 2 -C 20 alkyl aryl, and C 2 -C 20 alkyl thienyl.
  • each of R 1 , R 2 , R 3 , and R 4 is a para-substituted C 3 -C 12 alkyl phenyl.
  • each B is independently selected from the group consisting of:
  • each A is independently selected from the group consisting of:
  • each W is independently O or S.
  • each of R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of C 2 -C 20 alkyl, C 2 -C 20 cycloalkyl, C 2 -C 20 alkyl phenyl, C 2 -C 20 alkyl aryl, and C 2 -C 20 alkyl thienyl.
  • A is:
  • V is hydrogen or alkyl
  • each of X and Y is independently hydrogen, F, Cl, or CN;
  • R 9 is C 2 -C 20 alkyl.
  • the SMA of the first aspect wherein the compound is selected from the group consisting of:
  • a photoactive layer comprising at least one donor material and at least one SMA of the first aspect.
  • the photoactive layer of the second aspect wherein the at least one donor material is a polymer comprising a repeat unit having the Formula III:
  • each R 10 is independently selected from the group consisting of C 2 -C 20 alkyl.
  • the photoactive layer of the first embodiment of the second aspect wherein the at least one donor material is a polymer comprising a repeat unit having Formula III; and the at least one SMA has the Formula II:
  • A is:
  • each of X and Y is independently hydrogen, F, Cl, or CN;
  • V is hydrogen or alkyl
  • R 9 is C 2 -C 20 alkyl.
  • each of X and Y is independently hydrogen or Cl; and R 9 is C 6 -C 12 alkyl.
  • the photoactive layer of the third embodiment of the second aspect wherein the at least one donor material is poly [ [4, 8-bis [5- (2-ethylhexyl) -2-thienyl] benzo [1, 2-b: 4, 5-b′] dithiophene-2, 6-diyl] -2, 5-thiophenediyl [5, 7-bis (2-ethylhexyl) -4, 8-dioxo-4H, 8H-benzo [1, 2-c: 4, 5-c′] dithiophene-1, 3-diyl] ] (PBDB-T) .
  • the at least one donor material is poly [ [4, 8-bis [5- (2-ethylhexyl) -2-thienyl] benzo [1, 2-b: 4, 5-b′] dithiophene-2, 6-diyl] -2, 5-thiophenediyl [5, 7-bis (2-ethylhexyl) -4, 8-dioxo-4H,
  • the photoactive layer of the second embodiment of the second aspect wherein the at least one donor material is a polymer comprising a repeat unit having the Formula IV; and the at least one SMA has the Formula II:
  • A is:
  • each of X and Y is independently hydrogen, F, Cl, or CN;
  • V is hydrogen or alkyl
  • R 9 is C 2 -C 20 alkyl.
  • each of X and Y is independently hydrogen or Cl; and R 9 is C 6 -C 12 alkyl.
  • the photoactive layer of the sixth embodiment of the second aspect wherein the donor material is poly ( [2, 6 ′-4, 8-di (5-ethylhexylthienyl) benzo [1, 2-b; 3, 3-b] dithiophene] ⁇ 3-fluoro-2 [ (2-ethylhexyl) carbonyl] thieno [3, 4-b] thiophenediyl ⁇ ) (PTB7-Th) .
  • a photovoltaic cell comprising at least one SMA of the first aspect.
  • a photovoltaic cell comprising a photoactive layer of the second aspect.
  • SMAs with the structures described herein were demonstrated to exhibit small bandgaps suitable for organic solar cell applications.
  • the present subject matter further relates to the use of a formulation as described above and below as a coating or printing interlayer, especially for the preparation of OE devices and rigid or flexible organic photovoltaic (OPV) cells and devices.
  • a formulation as described above and below as a coating or printing interlayer, especially for the preparation of OE devices and rigid or flexible organic photovoltaic (OPV) cells and devices.
  • OUV organic photovoltaic
  • the formulations, methods and devices of the present subject matter provide surprising improvements in the efficiency of the OE devices and the production thereof. Unexpectedly, the performance, the lifetime and the efficiency of the OE devices can be improved, if these devices are achieved by using a formulation of the present subject matter. Furthermore, the formulation of the present subject matter provides an astonishingly high level of film forming. Especially, the homogeneity and the quality of the films can be improved. In addition thereto, the present subject matter enables better solution printing of OE devices, especially OPV devices.
  • Figure 1 depicts the chemical structures of exemplary SMAs IXIC, IXIC-2Cl, and IXIC-4Cl and an exemplary donor material PBDB-T in accordance with certain embodiments as described herein.
  • Figure 2 depicts an energy-band diagram depicting the energy levels of exemplary SMAs: IXIC, IXIC-2Cl, and IXIC-4Cl and exemplary donor material PBDB-T in accordance with certain embodiments as described herein.
  • Figure 3 is an exemplary schematic of a single junction photovoltaic cell in accordance with certain embodiments as described herein.
  • Figure 4A depicts a current-density (J-V) curves for photoactive layers comprising PBDB-T: IXIC (annealed at RT) ; PBDB-T: IXIC (annealed at 100 °C) ; PBDB-T: IXIC-2Cl (annealed at RT) ; PBDB-T: IXIC-2Cl (annealed at 100 °C) ; PBDB-T: IXIC-4Cl (annealed at RT) ; and PBDB-T: IXIC-4Cl (annealed at 100 °C) in accordance with certain embodiments as described herein.
  • Figure 4B depicts external quantum efficiency (EQE) spectra for photoactive layers comprising PBDB-T: IXIC (annealed at RT) ; PBDB-T: IXIC (annealed at 100 °C) ; PBDB-T: IXIC-2Cl (annealed at RT) ; PBDB-T: IXIC-2Cl (annealed at 100 °C) ; PBDB-T: IXIC-4Cl (annealed at RT) ; and PBDB-T: IXIC-4Cl (annealed at 100 °C) in accordance with certain embodiments as described herein.
  • EQE external quantum efficiency
  • Figure 4C depicts photoluminescence quenching spectra of exemplary SMAs: IXIC, IXIC-2Cl, and IXIC-4Cl and photoactive layers comprising PBDB-T: IXIC (annealed at RT) ; PBDB-T: IXIC-2Cl (annealed at RT) ; and PBDB-T: IXIC-4Cl (annealed at RT) excited at 690 nm.
  • Figure 4D depicts photoluminescence quenching spectra of exemplary SMAs: IXIC, IXIC-2Cl, and IXIC-4Cl and photoactive layers comprising PBDB-T: IXIC (annealed at 100 °C) ; PBDB-T: IXIC-2Cl (annealed at 100 °C) ; and PBDB-T: IXIC-4Cl (annealed at 100 °C) excited at 690 nm.
  • Figure 4E depicts J ph versus V eff curves for photoactive layers comprising PBDB-T: IXIC (annealed at RT) ; PBDB-T: IXIC (annealed at 100 °C) ; PBDB-T: IXIC-2Cl (annealed at RT) ; PBDB-T: IXIC-2Cl (annealed at 100 °C) ; PBDB-T: IXIC-4Cl (annealed at RT) ; and PBDB-T: IXIC-4Cl (annealed at 100 °C) in accordance with certain embodiments as described herein.
  • Figure 4F depicts light intensity dependence of J sc for photoactive layers comprising PBDB-T: IXIC (annealed at RT) ; PBDB-T: IXIC (annealed at 100 °C) ; PBDB-T: IXIC-2Cl (annealed at RT) ; PBDB-T: IXIC-2Cl (annealed at 100 °C) ; PBDB-T: IXIC-4Cl (annealed at RT) ; and PBDB-T: IXIC-4Cl (annealed at 100 °C) in accordance with certain embodiments as described herein.
  • Figure 5 depicts the basic properties of exemplary SMAs IXIC, IXIC-2Cl, and IXIC-4Cl according to certain embodiments described herein.
  • Figure 6 depicts the basic photovoltaic parameters of PBDB-T: IXIC, PBDB-T: IXIC-2Cl, and PBDB-T: IXIC-4Cl according to certain embodiments described herein.
  • Figure 7 depicts morphological parameters obtained by RSoXS and grazing-incidence wide-angle X-ray scattering (GIWAXS) of PBDB-T: IXIC, PBDB-T: IXIC-2Cl, and PBDB-T: IXIC-4Cl based photoactive layers and IXIC, IXIC-2Cl, and IXIC-4Cl thin films.
  • GIWAXS grazing-incidence wide-angle X-ray scattering
  • OSCs comprising the SMAs described herein exhibit a number of advantageous properties including good near infrared adsorption, which enables the construction of semi-transparent optical photovoltaic (OPV) devices, high PCE, low voltage loss, and high fill rates, and can achieve exceptionally low voltage loss, e.g., 0.59 V (calculated as the difference between the bandgap of the SMA to the Voc of the cell) , even when the bandgap of the OSC is as small as 1.2 eV.
  • OOV optical photovoltaic
  • compositions of the present teachings can also consist essentially of, or consist of, the recited components, and that the processes of the present teachings can also consist essentially of, or consist of, the recited process steps.
  • a small molecular organic compound is defined as an organic molecule with molecular weight lower than 2,000 g/mol.
  • a "P-type semiconductor material” or a “donor” material refers to a semiconductor material, for example, an organic semiconductor material, having holes as the majority current or charge carriers.
  • a p-type semiconductor material when deposited on a substrate, it can provide a hole mobility in excess of about 10 -5 cm 2 /Vs.
  • a p-type semiconductor In the case of field-effect devices, a p-type semiconductor also can exhibit a current on/off ratio of greater than about 10.
  • an "N-type semiconductor material” or an “acceptor” material refers to a semiconductor material, for example, an organic semiconductor material, having electrons as the majority current or charge carriers.
  • an n-type semiconductor material when deposited on a substrate, it can provide an electron mobility in excess of about 10 -5 cm 2 /Vs. In the case of field-effect devices, an n-type semiconductor also can exhibit a current on/off ratio of greater than about 10.
  • mobility refers to a measure of the velocity with which charge carriers, for example, holes (or units of positive charge) in the case of a p-type semiconductor material and electrons (or units of negative charge) in the case of an n-type semiconductor material, move through the material under the influence of an electric field.
  • charge carriers for example, holes (or units of positive charge) in the case of a p-type semiconductor material and electrons (or units of negative charge) in the case of an n-type semiconductor material
  • homo-tandem refers to the tandem solar cells constructed from the photoactive layers with identical optical absorptions.
  • hybrid tandem refers to the tandem solar cells constructed from the photoactive layers with optical absorptions.
  • sub-cell refers to the photoactive layers that can convert light into electricity in tandem solar cells.
  • a compound can be considered “ambient stable” or “stable at ambient conditions” when a transistor incorporating the compound as its semiconducting material exhibits a carrier mobility that is maintained at about its initial measurement when the compound is exposed to ambient conditions, for example, air, ambient temperature, and humidity, over a period of time.
  • ambient stable if a transistor incorporating the compound shows a carrier mobility that does not vary more than 20%or more than 10%from its initial value after exposure to ambient conditions, including, air, humidity and temperature, over a 3 day, 5 day, or 10 day period.
  • fill factor is the ratio (given as a percentage) of the actual maximum obtainable power, (Pm or Vmp*Jmp) , to the theoretical (not actually obtainable) power, (Jsc*Voc) . Accordingly, FF can be determined using the equation:
  • Jmp and Vmp represent the current density and voltage at the maximum power point (Pm) , respectively, this point being obtained by varying the resistance in the circuit until J*V is at its greatest value; and Jsc and Voc represent the short circuit current and the open circuit voltage, respectively.
  • Fill factor is a key parameter in evaluating the performance of solar cells. Commercial solar cells typically have a fill factor of about 0.60%or greater.
  • the open-circuit voltage is the difference in the electrical potentials between the anode and the cathode of a device when there is no external load connected.
  • the power conversion efficiency (PCE) of a solar cell is the percentage of power converted from absorbed light to electrical energy.
  • the PCE of a solar cell can be calculated by dividing the maximum power point (Pm) by the input light irradiance (E, in W/m2) under standard test conditions (STC) and the surface area of the solar cell (Ac in m2) .
  • STC typically refers to a temperature of 25°C and an irradiance of 1000 W/m2 with an air mass 1.5 (AM 1.5) spectrum.
  • a component such as a thin film layer
  • a component can be considered "photoactive" if it contains one or more compounds that can absorb photons to produce excitons for the generation of a photocurrent.
  • solution-processable refers to compounds (e.g., polymers) , materials, or compositions that can be used in various solution-phase processes including spin-coating, printing (e.g., inkjet printing, gravure printing, offset printing and the like) , spray coating, electrospray coating, drop casting, dip coating, blade coating, and the like.
  • a "semicrystalline polymer” refers to a polymer that has an inherent tendency to crystallize at least partially either when cooled from a melted state or deposited from solution, when subjected to kinetically favorable conditions such as slow cooling, or low solvent evaporation rate and so forth.
  • the crystallization or lack thereof can be readily identified by using several analytical methods, for example, differential scanning calorimetry (DSC) and/or X-ray diffraction (XRD) .
  • annealing refers to a post-deposition heat treatment to the semicrystalline polymer film in ambient or under reduced/increased pressure for a time duration of more than 100 seconds
  • annealing temperature refers to the maximum temperature that the polymer film is exposed to for at least 60 seconds during this process of annealing.
  • DSC differential scanning calorimetry
  • XRD X-ray diffraction
  • polymeric compound refers to a molecule including a plurality of one or more repeating units connected by covalent chemical bonds.
  • a polymeric compound can be represented by General Formula I:
  • each Ma and Mb is a repeating unit or monomer.
  • the polymeric compound can have only one type of repeating unit as well as two or more types of different repeating units. When a polymeric compound has only one type of repeating unit, it can be referred to as a homopolymer. When a polymeric compound has two or more types of different repeating units, the term "copolymer” or “copolymeric compound” can be used instead.
  • a copolymeric compound can include repeating units where Ma and Mb represent two different repeating units. Unless specified otherwise, the assembly of the repeating units in the copolymer can be head-to-tail, head-to-head, or tail-to-tail.
  • the copolymer can be a random copolymer, an alternating copolymer, or a block copolymer.
  • General Formula I can be used to represent a copolymer of Ma and Mb having x mole fraction of Ma and y mole fraction of Mb in the copolymer, where the manner in which comonomers Ma and Mb is repeated can be alternating, random, regiorandom, regioregular, or in blocks, with up to z comonomers present.
  • a polymeric compound in addition to its composition, can be further characterized by its degree of polymerization (n) and molar mass (e.g., number average molecular weight (M) and/or weight average molecular weight (Mw) depending on the measuring technique (s) ) .
  • halo or halogen refers to fluoro, chloro, bromo, and iodo.
  • alkyl refers to a straight-chain or branched saturated hydrocarbon group.
  • alkyl groups include methyl (Me) , ethyl (Et) , propyl (e.g., n-propyl and z'-propyl) , butyl (e.g., n-butyl, z'-butyl, sec-butyl, tert-butyl) , pentyl groups (e.g., n-pentyl, z'-pentyl, -pentyl) , hexyl groups, and the like.
  • an alkyl group can have 1 to 40 carbon atoms (i.e., C1-40 alkyl group) , for example, 1-30 carbon atoms (i.e., C1-30 alkyl group) .
  • an alkyl group can have 1 to 6 carbon atoms, and can be referred to as a "lower alkyl group. " Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and z'-propyl) , and butyl groups (e.g., n-butyl, z'-butyl, sec-butyl, tert-butyl) .
  • alkyl groups can be substituted as described herein.
  • An alkyl group is generally not substituted with another alkyl group, an alkenyl group, or an alkynyl group.
  • alkenyl refers to a straight-chain or branched alkyl group having one or more carbon-carbon double bonds.
  • alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl groups, and the like.
  • the one or more carbon-carbon double bonds can be internal (such as in 2-butene) or terminal (such as in 1-butene) .
  • an alkenyl group can have 2 to 40 carbon atoms (i.e., C2-40 alkenyl group) , for example, 2 to 20 carbon atoms (i.e., C2-20 alkenyl group) .
  • alkenyl groups can be substituted as described herein.
  • An alkenyl group is generally not substituted with another alkenyl group, an alkyl group, or an alkynyl group.
  • cycloalkyl by itself or as part of another substituent means, unless otherwise stated, a monocyclic hydrocarbon having between 3-12 carbon atoms in the ring system and includes hydrogen, straight chain, branched chain, and/or cyclic substituents.
  • exemplary cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • a "fused ring” or a “fused ring moiety” refers to a polycyclic ring system having at least two rings where at least one of the rings is aromatic and such aromatic ring (carbocyclic or heterocyclic) has a bond in common with at least one other ring that can be aromatic or non-aromatic, and carbocyclic or heterocyclic.
  • aromatic ring or heterocyclic
  • These polycyclic ring systems can be highly p-conjugated and optionally substituted as described herein.
  • heteroatom refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium.
  • aryl refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (i.e., having a bond in common with) together or at least one aromatic monocyclic hydrocarbon ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings.
  • An aryl group can have 6 to 24 carbon atoms in its ring system (e.g., C6-24 aryl group) , which can include multiple fused rings.
  • a polycyclic aryl group can have 8 to 24 carbon atoms. Any suitable ring position of the aryl group can be covalently linked to the defined chemical structure.
  • aryl groups having only aromatic carbocyclic ring include phenyl, 1-naphthyl (bicyclic) , 2-naphthyl (bicyclic) , anthracenyl (tricyclic) , phenanthrenyl (tricyclic) , pentacenyl (pentacyclic) , and like groups.
  • polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings include, among others, benzo derivatives of cyclopentane (i.e., an indanyl group, which is a 5, 6-bicyclic cycloalkyl/aromatic ring system) , cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6, 6-bicyclic cycloalkyl/aromatic ring system) , imidazoline (i.e., a benzimidazolinyl group, which is a 5, 6-bicyclic cycloheteroalkyl/aromatic ring system) , and pyran (i.e., a chromenyl group, which is a 6, 6-bicyclic cycloheteroalkyl/aromatic ring system) .
  • aryl groups include benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, and the like.
  • aryl groups can be substituted as described herein.
  • an aryl group can have one or more halogen substituents, and can be referred to as a "haloaryl” group.
  • Perhaloaryl groups i.e., aryl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., -C6F5) , are included within the definition of "haloaryl.
  • an aryl group is substituted with another aryl group and can be referred to as a biaryl group. Each of the aryl groups in the biaryl group can be substituted as disclosed herein.
  • heteroaryl refers to an aromatic monocyclic ring system containing at least one ring heteroatom selected from oxygen (O) , nitrogen (N) , sulfur (S) , silicon (Si) , and selenium (Se) or a polycyclic ring system where at least one of the rings present in the ring system is aromatic and contains at least one ring heteroatom.
  • Polycyclic heteroaryl groups include those having two or more heteroaryl rings fused together, as well as those having at least one monocyclic heteroaryl ring fused to one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings, and/or non-aromatic cycloheteroalkyl rings.
  • a heteroaryl group as a whole, can have, for example, 5 to 24 ring atoms and contain 1-5 ring heteroatoms (i.e., 5-20 membered heteroaryl group) .
  • the heteroaryl group can be attached to the defined chemical structure at any heteroatom or carbon atom that results in a stable structure. Generally, heteroaryl rings do not contain O-O, S-S, or S-0 bonds. However, one or more N or S atoms in a heteroaryl group can be oxidized (e.g., pyridine Noxide thiophene S-oxide, thiophene S, S-dioxide) .
  • heteroaryl groups include, for example, the 5-or 6-membered monocyclic and 5-6 bicyclic ring systems shown below: where T is O, S, NH, N-alkyl, N-aryl, N- (arylalkyl) (e.g., N-benzyl) , SiH2, SiH (alkyl) , Si (alkyl) 2, SiH (arylalkyl) , Si (arylalkyl) 2, or Si(alkyl) (arylalkyl) .
  • T is O, S, NH, N-alkyl, N-aryl, N- (arylalkyl) (e.g., N-benzyl) , SiH2, SiH (alkyl) , Si (alkyl) 2, SiH (arylalkyl) , Si (arylalkyl) 2, or Si(alkyl) (arylalkyl) .
  • heteroaryl rings examples include pyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuryl, benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl, lH-indazolyl, 2H-indazo
  • heteroaryl groups include 4, 5, 6, 7-tetrahydroindolyl, tetrahydroquinolinyl, benzothienopyridinyl, benzofuropyridinyl groups, and the like.
  • heteroaryl groups can be substituted as described herein.
  • the compounds described herein may include one or more groups that can exist as stereoisomers. All such stereoisomer isomers are contemplated by the present disclosure. In instances in which stereochemistry is indicated (for example E/Z double bond isomers) , it is understood that for the sake of simplicity that only one stereoisomer is depicted. However, all stereoisomers and mixtures thereof are contemplated by the present disclosure.
  • SMAs provided herein can generally be represented by the Formula I:
  • each A is independently selected from the group consisting of:
  • each B is absent; or each B is independently selected from the group consisting of:
  • each V is independently selected from the group consisting of hydrogen, alkyl, Cl, Br, CN, OR 6 , and NHR 6 ;
  • each of X and Y is independently hydrogen, F, Cl, Br, CN, OR 6 , or NHR 6 ;
  • each of W is independently O, S, Se, or Te;
  • R 5 is alkyl or cycloalkyl
  • R 6 is alkyl or cycloalkyl
  • each of R 7 and R 8 is independently hydrogen or alkyl.
  • each B is independently selected from the group consisting of:
  • each D is independently sulfur or N-R 5 .
  • A can independently be selected from the group consisting of:
  • each W is independently O or S; and R 5 is C 1 -C 20 alkyl or C 3 -C 7 cycloalkyl.
  • R 5 is C 1 -C 20 alkyl; C 1 -C 16 alkyl; C 1 -C 12 alkyl; C 1 -C 10 alkyl; C 1 -C 8 alkyl; or C 1 -C 6 alkyl.
  • V is independently selected from the group consisting of hydrogen, alkyl, Cl, Br, CN, OR 6 , and NHR 6 , wherein R 6 is C 1 -C 14 alkyl; C 1 -C 12 alkyl; C 1 -C 14 alkyl; C 1 -C 12 alkyl; C 1 -C 10 ; C 1 -C 8 alkyl; C 1 -C 8 alkyl; C 1 -C 6 alkyl; C 1 -C 4 alkyl; C 3 -C 10 cycloalkyl; C 3 -C 8 cycloalkyl; C 3 -C 6 cycloalkyl; or C 5 -C 8 cycloalkyl.
  • V is hydrogen, Cl, Br, CN, or alkyl.
  • V is hydrogen or alkyl.
  • V is hydrogen or n-C 6 H 13 .
  • R 1 , R 2 , R 3 , and R 4 is independently selected from the group consisting of C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkyl phenyl, C 1 -C 20 alkyl aryl, and C 1 -C 20 alkyl thienyl.
  • R 1 , R 2 , R 3 , and R 4 is independently C 1 -C 20 alkyl thienyl
  • the C 1 -C 20 alkyl thienyl can represented by:
  • m is a whole number selected between 1-3; and each R is independently C 1 -C 20 alkyl. In certain embodiments, m is 1 and R is C 2 -C 14 alkyl. In certain embodiments, the thiophene is a 2, 5-disubstituted thiophene.
  • R 1 , R 2 , R 3 , and R 4 is independently C 1 -C 20 alkyl phenyl
  • the C 1 -C 20 alkyl phenyl can represented by:
  • n is a whole number selected between 1-5; and each R is independently C 1 -C 20 alkyl. In certain embodiments, n is 1 and R is C 2 -C 14 alkyl.
  • the benzene is a 1, 4-disubstituted benzene as shown below:
  • the benzene is a 1, 4-disubstituted benzene and R 9 is C 2 -C 20 alkyl; C 2 -C 18 alkyl; C 2 -C 16 alkyl; C 2 -C 14 alkyl; C 3 -C 12 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 4 -C 10 ; C 4 -C 8 alkyl; or C 2 -C 8 alkyl.
  • R 1 , R 2 , R 3 , and R 4 is independently C 1 -C 20 alkyl
  • the C 1 -C 20 alkyl can be a C 4 -C 20 moiety as shown below:
  • each R 11 is independently C 1 -C 16 alkyl. In certain embodiments, each R 11 is independently C 2 -C 14 alkyl; C 2 -C 12 alkyl; C 2 -C 10 alkyl; C 2 -C 8 alkyl; or C 2 -C 6 alkyl.
  • the C 1 -C 20 alkyl aryl can be a mono-, di-, tri-, or tetra-substituted C 1 -C 20 alkyl furan, C 1 -C 20 alkyl oxazole, C 1 -C 20 alkyl pyrrole, C 1 -C 20 alkyl imidazole, C 1 -C 20 alkyl isoimidazole, C 1 -C 20 alkyl triazole, C 1 -C 20 alkyl thiazole, C 1 -C 20 pyridine, or C 1 -C 20 alkyl pyrazine (e.g., 1, 2; 1, 3; or 1, 4 pyrazine) .
  • the C 1 -C 20 alkyl aryl can be a mono-, di-, tri-, or tetra-substituted C 1 -C 20 alkyl furan, C 1 -C 20 alkyl oxazole, C 1 -C
  • the C 1 -C 20 alkyl aryl can comprise a C 2 -C 20 alkyl; C 2 -C 18 alkyl; C 2 -C 16 alkyl; C 2 -C 14 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 4 -C 10 ; C 4 -C 8 alkyl; or C 2 -C 8 alkyl.
  • each of R 5 and R 6 is independently C 1 -C 14 alkyl; C 1 -C 12 alkyl; C 1 -C 14 alkyl; C 1 -C 12 alkyl; C 1 -C 10 ; C 1 -C 8 alkyl; C 1 -C 8 alkyl; C 1 -C 6 alkyl; C 1 -C 4 alkyl; C 3 -C 10 cycloalkyl; C 3 -C 8 cycloalkyl; C 3 -C 6 cycloalkyl; or C 5 -C 8 cycloalkyl.
  • A is independently selected from the group consisting of:
  • X and Y is independently hydrogen, F, Cl, Br, CN, OR 6 , or NHR 6 .
  • X and Y is independently hydrogen, F, Cl, Br, CN, O (C 1 -C 8 alkyl) , or NH (C 1 -C 8 alkyl) .
  • X and Y is independently hydrogen, F, Cl, Br, or CN.
  • X is hydrogen and Y is F; X is hydrogen and Y is Cl; X is hydrogen and Y is Br; X is hydrogen and Y is CN; X is F and Y is H; X is Cl and Y is H; X is Br and Y is H; X is CN and Y is H; X and Y are F; X and Y are Cl; X and Y are Br; or X and Y are CN.
  • each A is independently selected from the group consisting of:
  • each A is the same moiety.
  • each V is hydrogen
  • the SMA is represented by the Formula II:
  • A is:
  • V is hydrogen or alkyl
  • each of X and Y is independently hydrogen, F, Cl, or CN; and R 9 is C 2 -C 20 alkyl. In certain embodiments, each A is the same group.
  • each A is:
  • X is hydrogen and Y is F; X is hydrogen and Y is Cl; X is hydrogen and Y is Br; X is hydrogen and Y is CN; X is F and Y is H; X is Cl and Y is H; X is Br and Y is H; X is CN and Y is H; X and Y are F; X and Y are Cl; X and Y are Br; or X and Y are CN.
  • V is C 2 -C 18 alkyl; C 2 -C 16 alkyl; C 2 -C 14 alkyl; C 3 -C 12 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 4 -C 10 ; C 4 -C 8 alkyl; or C 2 -C 8 alkyl.
  • V is hydrogen.
  • R 9 is C 2 -C 18 alkyl; C 2 -C 16 alkyl; C 2 -C 14 alkyl; C 3 -C 12 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 4 -C 10 ; C 4 -C 8 alkyl; or C 2 -C 8 alkyl.
  • X and Y are H; X and Y are F; X and Y are Cl; X is hydrogen and Y is F; or X is F and Y is H; and R 9 is C 2 -C 18 alkyl; C 2 -C 16 alkyl; C 2 -C 14 alkyl; C 3 -C 12 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 4 -C 10 ; C 4 -C 8 alkyl; or C 2 -C 8 alkyl.
  • the SMA of Formula I is selected from the group consisting of:
  • the SMA comprises the following aromatic core structure:
  • the SMA has a general structure of:
  • A is selected from:
  • X and Y are independently selected from hydrogen, Cl, Br, CN, OR 5 , and NHR 5 , wherein R 5 is independently a straight-chain, branched, or cyclic alkyl group.
  • the SMA has a general structure:
  • PI is selected from:
  • X and Y are independently selected from hydrogen, Cl, Br, CN, OR 5 , or NHR 5 , wherein R 5 is independently a straight-chain, branched, or cyclic alkyl group; R 6 is independently a straight-chain, branched, or cyclic alkyl group; and
  • A is selected from
  • Z and W are independently selected from O, S, Se, or Te;
  • R 7 is independently a straight-chain, branched, or cyclic alkyl group.
  • the SMA is selected from the group consisting of IXIC, IXIC-2Cl, and IXIC-4Cl, which are depicted in Figure 1.
  • the basic properties of IXIC, IXIC-2Cl, and IXIC-4Cl are all presented in Figures 5 and 6.
  • a photoactive layer comprising at least one donor material and at least one SMA as described herein.
  • the photoactive layer can comprise a bulk heterojunction comprising at least one donor material and at least one SMA as described herein.
  • the bulk heterojunction may be an interpenetrating network of the at least one donor material and at least one SMA.
  • the absorption of a photon may occur near the donor-acceptor interface, increasing the probability of charge dissociation.
  • a mixed donor-acceptor molecular film can be deposited on a substrate and annealed, to induce phase-separation.
  • two polymers may be spin-cast and allowed to phase-segregate, producing an interpenetrating structure.
  • Suitable donor materials include conducting polymers (e.g., a conjugated organic polymer) , which generally have a conjugated portion. Conjugated polymers are characterized in that they have overlapping ⁇ orbitals, which contribute to the conductive properties of the material. Conjugated polymers may also be characterized in that they can assume two or more resonance structures.
  • the conjugated organic polymer may be, e.g., linear or branched, so long as the polymer retains its conjugated nature.
  • the donor material can be any donor material known in the art. The selection of a suitable donor material is well within the skill of a person of ordinary skill in the art.
  • Suitable donor materials include one or more of polyacetylene, polyaniline, polyphenylene, poly (p-phenylene vinylene) , polythienylvinylene, polythiophene, polyporphyrins, porphyrinic macrocycles, polymetallocenes, polyisothianaphthalene, polyphthalocyanine, a discotic liquid crystal polymer, and a derivative or a combination thereof.
  • exemplary derivatives of the electron donor materials include derivatives having pendant groups, e.g., a cyclic ether, such as epoxy, oxetane, furan, or cyclohexene oxide. Derivatives of these materials may alternatively or additionally include other substituents.
  • thiophene components of electron donor may include a phenyl group, such as at the 3 position of each thiophene moiety.
  • alkyl, alkoxy, cyano, amino, and/or hydroxy substituent groups may be present in any of the polyphenylacetylene, polydiphenylacetylene, polythiophene, and poly (p-phenylene vinylene) conjugated polymers.
  • Exemplary conjugated organic polymer donor materials include poly [ [4, 8-bis [5- (2-ethylhexyl) -2-thienyl] benzo [1, 2-b: 4, 5-b′] dithiophene-2, 6-diyl] -2, 5-thiophenediyl [5, 7-bis (2-ethylhexyl) -4, 8-dioxo-4H, 8H-benzo [1, 2-c: 4, 5-c′] dithiophene-1, 3-diyl] ] (PBDB-T) ; poly [ (5, 6-dihydro-5-octyl-4, 6-dioxo-4H-thieno [3, 4-C] pyrrole-1, 3-diyl) ⁇ 4, 8-bis [ (2-butyloctyl) oxy] benzo [1, 2-b: 4, 5-b′] dithiophene-2, 6-diyl ⁇ ] (PBDTBO- TPDO) ; poly [ (5, 6-dihydro
  • the at least one donor material is a polymer comprising a repeat unit having the Formula III:
  • each R 10 is independently C 2 -C 20 alkyl.
  • R 10 is C 4 -C 20 alkyl; C 4 -C 18 alkyl; C 4 -C 16 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 6 -C 12 alkyl; or C 6 -C 10 alkyl.
  • R 10 is 2-ethylhexyl.
  • R 10 can be represented by a moiety as shown below:
  • each R 12 is independently C 1 -C 16 alkyl. In certain embodiments, each R 12 is independently C 2 -C 14 alkyl; C 2 -C 12 alkyl; C 2 -C 10 alkyl; C 2 -C 8 alkyl; or C 2 -C 6 alkyl.
  • the at least one donor material is a polymer comprising a repeat unit having the Formula IV:
  • each R 10 is independently C 2 -C 20 alkyl.
  • R 10 is C 4 -C 20 alkyl; C 4 -C 18 alkyl; C 4 -C 16 alkyl; C 4 -C 14 alkyl; C 4 -C 12 alkyl; C 6 -C 12 alkyl; or C 6 -C 10 alkyl.
  • R 10 is 2-ethylhexyl.
  • R 10 can be represented by a moiety as shown below:
  • each R 12 is independently C 1 -C 16 alkyl. In certain embodiments, each R 12 is independently C 2 -C 14 alkyl; C 2 -C 12 alkyl; C 2 -C 10 alkyl; C 2 -C 8 alkyl; or C 2 -C 6 alkyl.
  • the conjugated organic polymer donor materials can have an average molecular weight of 5,000-250,000 amu. In certain embodiments, the conjugated organic polymer donor materials can have an average molecular weight of 5,000-10,000; 5,000-20,000; 10,000-50,000; 50,000-100,000; or 100,000-150,000; 150,000-200,000; or 100,000-200,000 amu.
  • the donor material is PBDB-T.
  • the PBDB-T can have an average molecular weight of 40,000 to 100,000; 40,000 to 80,000; 40,000 to 60,000, or greater than 50,000 amu.
  • the donor material is PTB7-TH.
  • the PTB7-TH can have an average molecular weight of 150,000 to 200,000; 170,000 to 200,000; 190,000 to 200,000; or greater than 190,000 amu.
  • the absorption range of the SMAs described can be in the infrared region, ⁇ 800-1,000 nm. Consequently, photoactive layers comprising the SMAs described herein can transmit a large portion of the light in the visible region.
  • a photoactive layer that is capable of transmitting a substantial portion of light in the visible region can be prepared.
  • Such photoactive layers may be particularly useful in the preparation of semitransparent organic solar cells for window and outer wall applications.
  • the photoactive layer transmits up to 30%, 40%, 50%, 60%, 70%, 80%, 85%, or 90%of light in the visible range.
  • the photovoltaic cell comprising the photoactive layer described herein.
  • the photovoltaic cell can be a single junction, double junction, or multi-junction cell.
  • the photovoltaic cell can comprise a transparent cathode 150, an electron transport layer 140, the photoactive layer described herein 130, an anode interlayer 120, and an anode 110.
  • the transparent cathode 150 may generally include any transparent or semi-transparent conductive material.
  • Indium tin oxide (ITO) can be used for this purpose, because it is substantially transparent to light transmission and thus facilitates light transmission through the ITO cathode layer to the photoactive layer without being significantly attenuated.
  • transparent means allowing at least 50 percent, commonly at least 80 percent, and more commonly at least 90 percent, of light in the wavelength range between 350-750 nm to be transmitted.
  • the electron transport layer 150 comprises at least one material selected from the group consisting of zinc oxide (ZnO) , tin oxide (SnO 2 ) , lithium fluoride (LiF) , zinc indium tin oxide (ZITO) , poly [ (9, 9-bis (3′- (N, N-dimethylamino) propyl) -2, 7-fluorene) -alt-2, 7- (9, 9–dioctylfluorene) ] (PFN) , poly [ (9, 9-bis (3'- ( (N, N -dimethyl) -N -ethylammonium) -propyl) -2, 7-fluorene) -alt-2, 7- (9, 9-dioctylfluorene) ] (PFN-Br) , and poly [9, 9-bis (6’- (N, N-diethylamino) propyl) -fluorene-alt
  • the anode interlayer 120 can comprises at least one material selected from the group consisting of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT: PSS) , polyanaline (PANI) , vanadium (V) oxide (V 2 O 5 ) , molybdenum oxide (MoO 3 ) , and Tungsten oxide (WO 3 ) .
  • the anode interlayer is vanadium (V) oxide (V 2 O 5 ) , molybdenum oxide (MoO 3 ) .
  • the anode 110 can comprise any anodic material known to those of skill in the art.
  • the anode comprises aluminum, gold, copper, silver, or a combination thereof.
  • the anode comprises aluminum.
  • the electron transport layer 150 can be made using any method known in the art, such as by sequential physical vapor deposition, chemical vapor deposition, sputtering, and the like.
  • the electron transport layer 150 comprises ZnO
  • it can be prepared by depositing a solution comprising an electron transport layer precursor.
  • the electron transport layer is prepared by the deposition of a solution comprising an organic zinc compound in an organic solvent on the surface of the transparent cathode and annealing the deposited organic zinc compound solution at a temperature of 60 to 120; 70 to 120; 80 to 120; 80 to 110 or 80 to 100 °C thereby forming the electron transport layer 150.
  • Suitable organic zinc compounds include any aryl, alkyl, cycloalkyl, alkenyl, and alkynyl zinc species.
  • the organic zinc compound is a dialkyl zinc compound, such as dimethyl or diethyl zinc.
  • the organic zinc compound Due to the reactivity of the organic zinc compound, it is typically deposited from an anhydrous solvent, such as an ether, alkane, and/or aromatic solvent.
  • anhydrous solvent such as an ether, alkane, and/or aromatic solvent.
  • diethyl zinc in tetrahydrofuran is deposited on the ITO layer by spin coating.
  • the deposited thin layer of diethyl zinc is then annealed at a temperature of 60 to 120; 70 to 120; 80 to 120; 80 to 110 or 80 to 100 °C.
  • the photoactive layer comprising the at least one SMA and at least one donor material can be prepared by forming a photoactive layer solution comprising the at least one SMA and at least one donor material and depositing the photoactive layer solution onto the electron transport layer 150 and optionally annealing the applied photoactive layer solution thereby forming the photoactive layer.
  • the solvent used to prepare the photoactive layer solution can be a solvent in which the at least one SMA and at least one donor material are substantially soluble in when solvent is heated above room temperature.
  • the solvent can be 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 2, 4-trichlorobenzene, chlorobenzene, 1, 2, 4-trimethylbenzene, chloroform and combinations thereof.
  • the photoactive layer solution further comprises one or more solvent additives, such as 1-chloronaphthalene and 1, 8-octanedithiol, 1, 8-diiodooctane, and combinations thereof.
  • the solvent is at least one of 1, 2-dichlorobenzene and chlorobenzene and optionally contains the solvent additive 1, 8-diiodooctane.
  • the solvent additive can be present between about 0.1%to about 8% (v/v) ; about 0.1%to about 6% (v/v) ; about 0.1%to about 4% (v/v) ; or about 0.1%to about 2% (v/v) in the solvent.
  • the photoactive layer solution can be deposited on the substrate using any method known to those of skill in the art including, but not limited to, spin coating, printing, print screening, spraying, painting, doctor-blading, slot-die coating, and dip coating.
  • the solvent can be removed (e.g., at atmospheric pressure and temperature or under reduced pressure and/or elevated temperature) thereby forming the thin film comprising the donor material and optionally be annealed.
  • the step of annealing can occur at 80 to 150 °C; 80 to 120 °C; or 90 to 110 °C.
  • the anode interlayer 140 comprises vanadium (V) oxide (V 2 O 5 ) , molybdenum oxide (MoO 3 )
  • the anode interlayer can be deposited by sequential thermal evaporation of the e.g., vanadium (V) oxide (V 2 O 5 ) , molybdenum oxide (MoO 3 ) onto photoactive layer 130.
  • the anode 110 can be deposited on the anode interlayer 140 using any method known in the art, such as by physical vapor deposition, chemical vapor deposition, or sputtering. In the examples below, an aluminum anode is deposited using thermal vaporization.
  • Photovoltaic cells comprising the photoactive layers described herein exhibit amongst some of the highest PCEs of photovoltaic devices based ultra-low bandgap acceptors.
  • Figure 5 presents photovoltaic properties of exemplary photovoltaic cells comprising IXIC, IXIC-2Cl, and IXIC-4Cl.
  • the hole and electron mobility of IXIC, IXIC-2Cl, and IXIC-4Cl neat and blend films were measured by space charge limited current (SCLC) method. As shown in Figure 6, the electron mobilities of IXIC, IXIC-2Cl, and IXIC-4Cl neat film are increased gradually with addition of chlorine atoms.
  • the hole and electron mobilities of IXIC, IXIC-2Cl, and IXIC-4Cl blend films are summarized in Figure 6. Annealing not only increases the hole and electron mobility of PBDB-T: IXIC, PBDB-T: IXIC-2Cl, and PBDBT: IXIC-4Cl based blend films but also decreases the ratio between hole mobility and electron mobility, which explains the enhancement of FF after annealing.
  • PBDB-T IXIC-2Cl based blend film has the highest electron mobility and most balanced carrier mobility among all blend films, contributing to high FF of PBDB-T: IXIC-2Cl based photovoltaic cells. Besides, due to highest hole mobility, PBDB-T: IXIC-4Cl based photovoltaic cells can gain highest FF of 71.2%.
  • the PBDB-T: IXIC, PBDB-T: IXIC-2Cl, and PBDBT: IXIC-4Cl based active layers all show smooth morphology with small root-mean-square (RMS) roughness (0.835–1.14 nm) . Annealing reduced the RMS roughness to achieve a more even surface, which is beneficial for contact between active layer and top electrode.
  • RMS root-mean-square
  • the curve of RSoXS results shown in Figure 4j shows reasonable domain size and domain purity and indicates that annealing treatment not only reduces the domain size of PBDB-T: IXIC, PBDB-T: IXIC-2Cl, and PBDB-T: IXIC-4Cl blend films, but also enhances the domain purity of three blends (Table 2) , which is beneficial to promote J sc and FF.
  • the largest domain size (31.96 nm) and lowest domain purity (0.93) of PBDB-T: IXIC based photoactive layer among the three blends does not benefit to form nanofiber structure and continuous interpenetrating networks, which lead to relatively low Jsc and FF of the corresponding OSCs.
  • Pre-patterned ITO-coated glass with a sheet resistance of ⁇ 15 ⁇ /square was used as the substrate. It was cleaned by sequential sonications in soap DI water, DI water, acetone, and isopropanol. After UV/ozone treatment for 60 min, a ZnO electron transport layer was prepared by spin-coating at 5000 rpm from a ZnO precursor solution (diethyl zinc) . Active layer solutions were prepared in CB/DCB or CB/DCB/DIO with various ratios (polymer concentration: 7-12 mg/mL) . To completely dissolve the polymer, the active layer solution should be stirred on hotplate at 100-120°C for at least 3 hours.
  • Active layers were spin-coated from warm solutions in a N 2 glovebox at 600-850 rpm to obtain thicknesses of ⁇ 100 nm.
  • the polymer/small molecular acceptor films were then annealed at 100 °C for 5 min before being transferred to the vacuum chamber of a thermal evaporator inside the same glovebox.
  • a thin layer (20 nm) of MoO 3 or V 2 O 5 was deposited as the anode interlayer, followed by deposition of 100 nm of Al as the top electrode. All cells were encapsulated using epoxy inside the glovebox.
  • Device J-V characteristics was measured under AM1.5G (100 mW/cm 2 ) using a Newport solar simulator.
  • the light intensity was calibrated using a standard Si diode (with KG5 filter, purchased from PV Measurement) to bring spectral mismatch to unity.
  • J-V characteristics were recorded using a Keithley 236 source meter unit. Typical cells have devices area of about 5.9 mm 2 , which is defined by a metal mask with an aperture aligned with the device area.
  • EQEs were characterized using a Newport EQE system equipped with a standard Si diode. Monochromatic light was generated from a Newport 300W lamp source. The EQE of the device in the present teaching are shown in Figure 3.
  • the V OC , J SC , FF and PCE of OPV devices in the present teaching are summarized in the following table.
  • Example 12b Photovoltaic parameters of solar cell devices

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Abstract

L'invention concerne des accepteurs à petites molécules à base de thiophène, leurs procédés de préparation, et des formulations associées utiles pour préparer des couches photoactives dans des cellules solaires organiques (OSC).
PCT/CN2019/070780 2018-01-10 2019-01-08 Systèmes aromatiques fusionnés à base de thiophène Ceased WO2019137354A1 (fr)

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