WO2014025435A2 - Matériaux à base de dipyrrine pour photovoltaïque, composés aptes à subir un transfert de charge intermoléculaire à rupture symétrique dans un milieu polarisant et dispositifs photovoltaïques organiques les comprenant - Google Patents

Matériaux à base de dipyrrine pour photovoltaïque, composés aptes à subir un transfert de charge intermoléculaire à rupture symétrique dans un milieu polarisant et dispositifs photovoltaïques organiques les comprenant Download PDF

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WO2014025435A2
WO2014025435A2 PCT/US2013/041079 US2013041079W WO2014025435A2 WO 2014025435 A2 WO2014025435 A2 WO 2014025435A2 US 2013041079 W US2013041079 W US 2013041079W WO 2014025435 A2 WO2014025435 A2 WO 2014025435A2
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group
chosen
optionally substituted
donor
compound
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PCT/US2013/041079
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WO2014025435A3 (fr
WO2014025435A9 (fr
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Stephen R. Forrest
Mark E. Thompson
John J. Chen
Jonathan R. Sommer
Peter I. Djurovich
Kathryn R. ALLEN
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Forrest Stephen R
Thompson Mark E
Chen John J
Sommer Jonathan R
Djurovich Peter I
Allen Kathryn R
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Priority claimed from US13/564,953 external-priority patent/US20150303377A1/en
Application filed by Forrest Stephen R, Thompson Mark E, Chen John J, Sommer Jonathan R, Djurovich Peter I, Allen Kathryn R filed Critical Forrest Stephen R
Priority to CA2873468A priority Critical patent/CA2873468A1/fr
Priority to CN201380031559.4A priority patent/CN105409020A/zh
Priority to AU2013300142A priority patent/AU2013300142A1/en
Priority to JP2015512780A priority patent/JP6339561B2/ja
Priority to EP13802466.6A priority patent/EP2850670A2/fr
Priority to KR20147034571A priority patent/KR20150020297A/ko
Publication of WO2014025435A2 publication Critical patent/WO2014025435A2/fr
Publication of WO2014025435A9 publication Critical patent/WO2014025435A9/fr
Publication of WO2014025435A3 publication Critical patent/WO2014025435A3/fr
Priority to IL235713A priority patent/IL235713A0/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • 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 photosensitive optoelectronic devices comprising at least one boron dipyrrin compound.
  • the present disclosure relates to methods of making organic photosensitive optoelectronic devices comprising at least one boron dipyrrin compound.
  • the present disclosure also generally relates to chromophoric compounds, including boron dipyrrin compounds, that combine strong absorption of light at visible to near infrared wavelengths with the ability to undergo symmetry- breaking intramolecular charge transfer (ICT), and their use for the generation of free carriers in organic photovoltaic cells (OPVs) and electric-field-stabilized geminate polaron pairs.
  • ICT intramolecular charge transfer
  • OOVs organic photovoltaic cells
  • the present disclosure also relates to the synthesis of such compounds, methods of manufacture, and applications in photovoltaic systems and organic lasers.
  • 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
  • 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.
  • power generation applications also often involve the charging of batteries or other energy storage devices so that operation may continue when direct illumination from the sun or other light sources is not available, or to balance the power output of the PV device with a specific application's requirements.
  • the term "resistive load” refers to any power consuming or storing circuit, device, equipment or system.
  • Another type of photosensitive optoelectronic device is a
  • photoconductor cell In this function, signal detection circuitry monitors the resistance of the device to detect changes due to the absorption of light.
  • signal detection circuitry monitors the resistance of the device to detect changes due to the absorption of light.
  • 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%.
  • 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 c, 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 l S c x V 0 c- 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 ⁇ lmax V max ⁇ / ⁇ l SC 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.
  • 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.
  • 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 energy indicates that electrons are the predominant carrier.
  • a Fermi energy near the valence band maximum energy indicates that holes are the predominant carrier. Accordingly, the Fermi energy is a primary
  • 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.
  • the terms “donor” and “acceptor” refer to the relative positions of the HOMO and LUMO energy levels of two contacting but different organic materials. This is in contrast to the use of these terms in the inorganic context, where “donor” and “acceptor” may refer to types of dopants that may be used to create inorganic n- and p- types layers, respectively.
  • donor and “acceptor” may refer to types of dopants that may be used to create inorganic n- and p- types layers, respectively.
  • the LUMO energy level of one material in contact with another is lower, then that material is an acceptor. Otherwise it is a donor. It is energetically favorable, in the absence of an external bias, for electrons at a donor-acceptor junction to move into the acceptor material, and for holes to move into the donor material.
  • 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 is an ETL and a donor material is a HTL.
  • 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.
  • 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 donor-acceptor (D-A) interface.
  • D-A donor-acceptor
  • the donor material with a low ionization potential forms a heteroj unction 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 external quantum efficiency (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 (I_D) of an exciton is typically much less (I_D ⁇ 50 ⁇ ) than the optical absorption length (-500 ⁇ ), 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.
  • polymer organic PVs While favorable absorption and charge mobility characteristics make polymer organic PVs among the most highly efficient organic PV devices, polymer organic PVs may have several drawbacks. For example, polymers can be harder to synthesize, less predictable in terms of morphology, and not sublimable. Thus, there is a continuing need to develop new classes of compounds for photovoltaic applications.
  • BODIPY 4,4-difluoro-4-bora-3a,4a-diaza-s- indacene
  • R 1 is chosen from an optionally substituted monocyclic group, an optionally substituted C6- 24 multicyclic group, and an optionally substituted meso-linked BODIPY, or R 1 and R 2 and R 7 taken together with any intervening atoms comprise a substituted BODIPY, wherein R 1 is meso-linked and R 2 and R 7 are beta-linked;
  • R 2 is chosen from hydrogen, an alkyl group, and a cyano group, or R 2 and R 3 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group, or R 2 and R 1 and R 7 taken together with any intervening atoms comprise a substituted BODIPY, wherein R 1 is meso-linked and R 2 and R 7 are beta-linked;
  • R 3 is chosen from hydrogen, an alkyl group, and a cyano group, or R 3 and R 2 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group, or R 3 and R 4 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group;
  • R 4 is chosen from hydrogen, an alkyl group, and a cyano group, or R 4 and R 3 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group;
  • R 5 is chosen from hydrogen, an alkyl group, and a cyano group, or R 5 and R 6 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group;
  • R 6 is chosen from hydrogen, an alkyl group, and a cyano group, or R 6 and R 5 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group, or R 6 and R 7 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group; and
  • R 7 is chosen from hydrogen, an alkyl group, and a cyano group, or R 7 and R 6 taken together with any intervening atoms comprise a group chosen from an optionally substituted monocyclic group and an optionally substituted C 6 -2 4 multicyclic group, or R 7 and R 1 and R 2 taken together with any intervening atoms comprise a substituted BODIPY, wherein R 1 is meso-linked and R 2 and R 7 are beta-linked;
  • R 1 is chosen from optionally substituted benzene and optionally substituted fused benzene.
  • R 2 and R 7 are both chosen from hydrogen, an alkyl group, and a cyano group.
  • R 5 and R 4 are both chosen from hydrogen, an alkyl group, and a cyano group.
  • R 3 and R 6 are both chosen from hydrogen, an alkyl group, and a cyano group.
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are all chosen from hydrogen, an alkyl group, and a cyano group.
  • the present disclosure also provides methods for making the photosensitive optoelectronic devices of the present disclosure.
  • the method comprises depositing a photoactive region over a substrate, wherein the photoactive region comprises at least one compound of formula (I).
  • the photoactive region comprises a donor material and an acceptor material, wherein at least one of the donor and acceptor materials comprise at least one compound of formula (I).
  • candidate molecules must combine strong absorption of light at visible wavelengths with an ability to undergo symmetry-breaking ICT. There are few dimeric molecules that meet these criteria. To date, the best studied system of this sort is 9,9'-bianthryl. However, 9,9'-bianthryl predominantly absorbs ultraviolet light.
  • an organic photosensitive optoelectronic device comprising at least one higher order compound, such as dyads, triads and tetrads, that are capable of undergoing symmetry-breaking intramolecular charge transfer in a polarizing medium.
  • the intramolecular charge transfer occurs at a polarizing donor/acceptor interface.
  • the higher order compounds disclosed herein exhibit a high absorptivity of light in the visible and near infrared spectrum.
  • "high absorptivity of light” includes absorptivity of > 10 4 M “1 cm “1 at one or more visible to near infrared wavelengths ranging from 350 to 1500 nm.
  • the higher order compound forms at least one donor and/or acceptor region in a donor-acceptor heterojunction.
  • the donor-acceptor heterojunction absorbs photons to form excitons.
  • the device is an organic device, such as an organic photodetector, an organic solar cell, or an organic laser.
  • the photosensitive optoelectronic device comprising a higher order compound.
  • the device may be an organic photodetector, in another an organic solar cell.
  • Figure 1 depicts a scheme for synthesizing BenzoBODIPY.
  • Figure 2 depicts a scheme for synthesizing IndoBODIPY.
  • Figure 3 depicts a scheme for synthesizing CyanoBODIPY.
  • Figure 4 provides Nuclear Magnetic Resonance (NMR) data for BenzoBODIPY.
  • Figure 5 provides NMR data for IndoBODIPY.
  • Figure 6 provides NMR data for CyanoBODIPY.
  • Figure 7(a) shows absorption spectra for synthesized BenzoBODIPY in its solution and solid states.
  • Figure 7(c) shows excitation and emission spectra for BenzoBODIPY in its solution and solid states.
  • Figure 8(a) shows solution absorption and emission spectra for CyanoBODIPY.
  • Figure 8(b) shows film excitation, emission, and absorption spectra for CyanoBODIPY.
  • Figures 9(a), 9(b), and 9(c) show PV performance data of an organic PV using CuPc as the donor material and of organic PVs using BenzoBODIPY as the donor material at various thicknesses.
  • Fig. 9(a) shows current- voltage curves
  • Fig. 9(b) shows external quantum efficiencies (EQEs)
  • Fig. 9(c) shows dark current curves.
  • Figures 10(a) and 10(b) show additional PV performance data of organic PVs using BenzoBODIPY as the donor material at various thicknesses.
  • Fig. 10(a) shows current-voltage curves
  • Fig. 10(b) shows EQEs.
  • Figures 11 (a) and 11 (b) show PV performance data of organic PVs that were thermally annealed after deposition of the donor layer but prior to deposition of the acceptor material and that used BenzoBODIPY as the donor material at various thicknesses.
  • Fig. 1 1 (a) shows current-voltage curves
  • Fig. 11 (b) shows EQEs.
  • Figure 11 (c) shows absorption spectra for non-treated and thermally treated organic PVs.
  • Figures 12(a) and 12(b) show PV performance data of organic PVs that were thermally annealed after deposition of the donor and acceptor layers and that used BenzoBODIPY as the donor material at various thicknesses.
  • Fig. 12(a) shows current-voltage curves
  • Fig. 12(b) shows EQEs.
  • Figures 13(a) and 13(b) show PV performance data of an organic PV device using CuPc and C 6 o as donor and acceptor materials, respectively, and of an organic PV device using CuPc as the donor material and a 1 :1 ratio of
  • CyanoBODIPY and C60 as acceptor materials.
  • One CyanoBODIPY device was thermally annealed after deposition of the acceptor layer.
  • Fig. 13(a) shows current- voltage curves and Fig. 13(b) shows EQEs.
  • Figure 14 is a schematic representation of symmetry-breaking ICT to facilitate charge separation at a polarizing donor/acceptor interface.
  • Figure 15 shows examples of dyes that can be coupled into dimers, trimers, etc. for symmetry breaking ICT.
  • Figure 16 shows examples of dipyrrin chromophores synthesized for symmetry breaking ICT.
  • Figure 17 shows the synthetic scheme and displacement ellipsoid of BODIPY dyad 23 of Figure 16.
  • Figure 18 shows a synthetic scheme for BODIPY dyad 26.
  • Figure 19 represents the normalized absorption and emission spectra of dyad 23 and the absorption spectra of 3,5-Me 2 BODIPY-Ph in CH 2 CI 2 .
  • Figure 20 shows the cyclic voltammetry of dyad 23 in CH 2 CI 2 .
  • Figures 21 (a) and 21 (b) represent the ultrafast transient absorption spectra of dyad 23 after excitation at 508 nm, and time domain slices of transient absorptions at 507 and 550 nm with predicted traces based on kinetic parameters.
  • Figure 22 shows the transient absorption of dyad 23 in toluene.
  • Figure 23 shows the absorption spectra of dyad 26 in CH 2 CI 2 and emission spectra of 26 in solvents of varying polarity.
  • Figure 24 shows the normalized emission decays of dyad 26 in cyclohexane (564 nm) and CH 2 CI 2 (651 nm) following excitation at 405 nm.
  • Figure 25 represents the transient absorption of dyad 26 in CH 2 CI 2 .
  • Figure 26 represents the generation of stabilized intramolecular polaron pairs in the presence of an electric field.
  • Figure 27(a), 27(b), and 27(c) represent methods for structuring symmetry-breaking ICT dyads, triads, and tetrads ((a), (b) and (c) respectively) where R represents the linking molecule between the dyes.
  • Figure 28 represents methods for connecting two dyes to facilitate symmetry-breaking ICT.
  • Figure 29 shows the transient absorption of dyad 23 in acetonitrile with all transient spectral features completely relaxed within ca. 150 ps.
  • Figure 30 represents time domain slices of transient absorption of dyad 23 in toluene.
  • Figure 31 shows the normalized emission decay of dyad 23 in toluene (535 nm) following excitation at 435 nm.
  • Figure 32 represent time domain slices of transient absorptions at 475 and 575 nm with predicted traces based on kinetic parameters.
  • Figure 33 shows the X-ray structure of dyad 23.
  • Figure 34(a) shows device structures of organic PVs using compound 31 of Figure 16;
  • Figure 34(b) shows current-voltage characteristics of the organic PVs under AM1 .5G illumination;
  • Figure 34(c) shows EQEs.
  • Figure 35 shows a non-limiting example of a lamellar device structure of an organic PV using at least one compound of formula (I) as a donor material.
  • the organic photosensitive optoelectronic device is a solar cell. In other embodiments, the organic photosensitive optoelectronic device is a photodetector. In some embodiments, the organic photosensitive optoelectronic device is a photosensor. In other embodiments, the organic photosensitive optoelectronic device is a
  • the at least one compound of formula (I) exhibits an absorptivity of light greater than 10 4 M "1 cm “1 at one or more wavelengths ranging from 450 to 900 nm. In some embodiments, the at least one compound of formula (I) exhibits an absorptivity of light greater than 10 5 M "1 cm “1 at one or more wavelengths ranging from 450 to 900 nm.
  • the term "monocyclic” refers to a carbocyclic or heterocyclic group comprising only a single ring.
  • multicyclic refers to a carbocyclic or heterocyclic group comprising at least two rings. Some or all of the rings in the “multicyclic” group can be peri-fused, ortho-fused and/or bridged.
  • alkyl refers to a straight-chain or branched saturated hydrocarbyl group.
  • aryl refers to an aromatic hydrocarbyl group.
  • the “aryl” group is monocyclic or multicyclic.
  • heteroaryl refers to an aryl group having at least one N, O, or S ring atom, with C atom(s) as the remaining ring atom(s).
  • substituted means that the chemical group has at least one hydrogen atom replaced by a substituent.
  • the at least one compound of formula (I) is chosen from
  • R is chosen from an optionally substituted monocyclic group and an optionally substituted C6- 24 multicyclic group.
  • the optionally substituted monocyclic or multicyclic group of R is an aryl or a heteroaryl group.
  • R is chosen from
  • R' is chosen from H, alkyl, and aryl or heteroaryl groups.
  • the at least one compound of formula (I) does not include
  • the device comprises at least one donor material and at least one acceptor material, wherein at least one of the donor and acceptor materials comprises at least one compound of formula (I).
  • the at least one donor material comprises at least one compound of formula (I).
  • the at least one acceptor material comprises at least one compound of formula (I).
  • both the donor and acceptor materials comprise at least one compound of formula (I), wherein the at least one compound of formula (I) that comprises the donor material is different from the at least one compound of formula (I) that comprises the acceptor material.
  • the use of the BODIPY compounds disclosed herein as a donor and/or acceptor material depends upon the relationship of the HOMO and LUMO levels between two BODIPY compounds or between the BODIPY compound and a second organic semiconducting material used to complete a donor-acceptor pair.
  • the at least one donor material comprises at least one compound of formula (I), and the at least one acceptor material comprises a fullerene or a derivative thereof.
  • the at least one acceptor material comprises at least one of C 6 o, C 7 o and phenyl-C 7 i-butyric-acid-methyl ester (PCBM).
  • the at least one acceptor material comprises at least one compound of formula (I), and the at least one donor material comprises copper phthalocyanine (CuPc).
  • the at least one acceptor material comprises at least one compound of formula (I) and a second organic semiconducting material.
  • the second organic semiconducting material comprises Cm-
  • the at least one donor material and the at least one acceptor material form a donor-acceptor heterojunction.
  • the donor-acceptor heteroj unction may be planar or non-planar.
  • the donor and acceptor materials may form at least one of a mixed heterojunction, planar heterojunction, bulk heterojunction, and hybrid planar-mixed heterojunction.
  • the at least one donor material and the at least one acceptor material form a lamellar structure, wherein the at least one donor material comprises at least one compound of formula (I) and has a thickness ranging from about 1 - 150 nm, or about 10 - 150 nm, or about 10 - 100 nm, or about 20 - 80 nm.
  • a non-limiting example of a device comprising at least one donor material and at least one acceptor material forming a lamellar structure, wherein the at least one donor material comprises at least one compound of formula (I), is shown in Figure 35.
  • the organic photosensitive optoelectronic device of the present disclosure may further comprise two electrodes comprising an anode and a cathode.
  • a photoactive region can be located between the anode and the cathode, wherein the photoactive region comprises at least one compound of formula (I).
  • the photoactive region comprises at least one donor material and at least one acceptor material, wherein at least one of the donor and acceptor materials comprises the at least one compound of formula (I).
  • the donor and acceptor materials may form a donor-acceptor heterojunction as described herein.
  • the stacked device may comprise a plurality of photosensitive optoelectronic subcells, wherein at least one subcell comprises two electrodes comprising an anode and a cathode in superposed relation, and a photoactive region between the two electrodes, wherein the photoactive region comprises at least one compound of formula (I).
  • the photoactive region comprises at least one donor material and at least one acceptor material, wherein at least one of the donor and acceptor materials comprises at least one compound of formula (I).
  • the donor and acceptor materials may form a donor-acceptor heterojunction as described herein.
  • the donor and acceptor materials may form a lamellar structure as described herein.
  • optoelectronic device typically includes a complete set of electrodes, i.e., positive and negative. In some stacked configurations, it is possible for adjacent subcells to utilize common, i.e., shared, electrode, charge transfer region or charge
  • subcell is disclosed herein to encompass the subunit construction regardless of whether each subunit has its own distinct electrodes or shares electrodes or charge transfer regions with adjacent subunits.
  • the subcells may be electrically connected either in parallel or in series.
  • the organic photosensitive optoelectronic devices of the present disclosure may also comprise one or more blocking layers, such as exciton blocking layers (EBLs), between the two electrodes.
  • one or more blocking layers are located between the photoactive region and the anode, between the photoactive region and the cathode, or both. Examples of blocking layers are described in U.S. Patent Publication Nos. 2012/0235125 and 201 1/0012091 and in U.S. Patent Nos. 7,230,269 and 6,451 ,415, which are incorporated herein by reference for their disclosure of blocking layers.
  • the organic photosensitive devices of the present disclosure may be structured in various configurations with varying material combinations. Examples of device configurations and materials are described in U.S. Patent Application No. 13/666,664, U.S. Patent Publication Nos. 2012/0235125 and 2010/0102304, and U.S. Patent Nos. 6,657,378; 6,580,027, and 6,352,777, which are incorporated herein by reference for their disclosure of organic photosensitive optoelectronic device structures, particularly photovoltaic structures, and materials.
  • the method comprises depositing a photoactive region over a substrate, wherein the photoactive region comprises at least one compound of formula (I).
  • the photoactive region comprises at least one donor material and at least one acceptor material, wherein at least one of the donor and acceptor materials comprises at least one compound of formula (I).
  • the at least one donor material comprises the at least one compound of formula (I).
  • the at least one acceptor material comprises the at least one compound of formula (I).
  • both the donor and acceptor materials comprise at least one compound of formula (I), wherein the at least one compound of formula (I) that comprises the donor material is different from the at least one compound of formula (I) that comprises the acceptor material.
  • the deposition of the photoactive region comprises depositing at least one compound of formula (I) over the substrate.
  • the deposition of the photoactive region comprises codepositing an organic semiconducting material and at least one compound of formula (I) over the substrate.
  • the deposition of the photoactive region may form at least one of a donor-acceptor mixed heterojunction, planar heterojunction, bulk heterojunction, and hybrid planar-mixed heterojunction.
  • the deposition of the photoactive region forms a lamellar device structure.
  • the deposition of the photoactive region comprises depositing at least one donor material over a substrate, thermally annealing the substrate and the at least one donor material, and depositing at least one acceptor material over the at least one donor material.
  • the at least one donor material comprises at least one compound of formula (I).
  • the at least one donor material comprises at least one compound of formula (I)
  • the at least one acceptor material comprises Cm- In other embodiments, the at least one acceptor material comprises at least one compound of formula (I).
  • the deposition of the photoactive region comprises depositing at least one donor material over a substrate, depositing at least one acceptor material over the at least one donor material, and thermally annealing the substrate, the at least one donor material, and the at least one acceptor material.
  • the at least one donor material comprises at least one compound of formula (I).
  • the at least one donor material comprises at least one compound of formula (I)
  • the at least one acceptor material comprises Cm-
  • the at least one acceptor material comprises at least one compound of formula (I).
  • the at least one acceptor material comprises at least one compound of formula (I), and the at least one donor material comprises CuPc.
  • annealing is performed between 90 °C and 150 °C from 0 to 30 minutes. Suitable times and temperatures for annealing may be chosen based on the particular materials used.
  • Organic layers may be deposited using methods known in the art.
  • One advantage of the BODIPY dyes disclosed herein is that they are solution- processable and sublimable.
  • the at least one compound of formula (I) is deposited over a substrate using a technique chosen from spin casting and vapor deposition.
  • Another aspect of the present disclosure relates to compounds that exhibit the light absorption and symmetry breaking properties required for applications in OPVs. By extension, these compounds of the present disclosure mimic features seen in the photosynthetic reaction center.
  • Compounds that exhibit the light absorption and symmetry breaking properties required for applications in OPVs include, for example, higher order compounds, such as symmetrical dyads, triads, tetrads, etc. These compounds may populate intramolecular charge-transfer states in a polarizing medium by symmetry breaking, but cannot do so in the absence of a polarizing medium because of their symmetry.
  • the higher order compounds may have at least C 2 symmetry and should have a luminescent lifetime of at least 1 ps to allow charge transfer to take place prior to other radiative or non-radiative decay processes.
  • the higher order compounds may comprise, for example, dye compounds chosen from perylenes, malachites, xanthenes, cyanines, bipyridines, dipyrrins, coumarins, acridines, phthalocyanines, subphthalocyanines, porphyrins, and acenes. These dyes may be substituted with alkyl, H, electron donating or electron withdrawing groups at any position other than the linking site to control the physical and electronic properties of the dye.
  • the relevant physical properties include solubility as well as sublimation and melting temperatures.
  • the relevant electronic properties include the absorption and emission energies, as well as the oxidation and reduction potentials.
  • the higher order compounds are chosen from the following dipyrrin chromophores:
  • Another embodiment of the present disclosure provides for symmetry- breaking ICT compounds and their use as chromophores for the generation of electric-field-stabilized geminate polaron pairs. These polaron pairs collapse in the absence of an electric field, generating a high concentration of excitons and may be useful for the construction of organic lasers. In this process a large electric field is applied to drive the charge separation of excitons formed on light absorption and stabilize the geminate polaron pairs toward recombination. This was accomplished with a lightly doped matrix, where the dopant absorbs light and acts as one of the polarons (cation or anion), with the other polaron on the matrix material.
  • BODIPY dyads and related compounds described herein have donor and acceptor present in the same molecule (though in the absence of an electric field there is no driving force for excited-state charge separation), such that charge separation to form the geminate pairs can be efficiently achieved within the chromophore itself.
  • This allows the chromophore to be doped into nonconductive host materials, preventing carrier leakage.
  • the inherent C2 symmetry of the substituted porphryins ensure that nearly every molecule is present in an orientation that will promote charge separation (Figure 26).
  • An orientation that cannot be efficiently coupled with the electric field is one in which the plane of the dyad is perpendicular to the applied electric field. By using a randomly doped film, only a low percentage of the dopant is present in the nonproductive orientation.
  • the constituent higher order dye compounds must exhibit high absorptivity ( ⁇ > 10 "4 M "1 cm “1 ) of light at some visible to near infrared wavelengths (350-1500 nm), for example, dyads of xanthenes dyes (e.g., fluorescein, eosins, and rhoadmines), coumarins, acridines, phthalocyanines, subphthalocyanines, porphyrins, acenes such as tetracene or pentacene, perylenes, malachites, cyanines, bipyridines, and dipyrrins, among others.
  • xanthenes dyes e.g., fluorescein, eosins, and rhoadmines
  • coumarins e.g., acridines, phthalocyanines, subphthalocyanines, porphyrins, acenes such as tetracene or pentacen
  • the higher order dye compounds may exhibit high absorptivity of light at some visible to near infrared wavelengths between 350 to 950 nm.
  • the higher order dye compounds may exhibit high absorptivity of light at some visible to near infrared wavelengths between 350 nm to at least 1200 nm.
  • the higher order dye compounds may exhibit high absorptivity of light at some visible to near infrared wavelengths between 350 nm to at least 1500 nm.
  • the dyad (or triad, tetrad, etc.) must also possess an intramolecular charge-transfer (ICT) state that is energetically accessible from the photogenerated Si state in a polarizing medium. It is known that the energy of an ICT state can be approximated as:
  • E(ICT) IP(D) - EA(A) +C + ⁇ 80 ⁇ ⁇ (1)
  • IP(D) is the ionization potential of the donor
  • EA(A) is the electron affinity of the acceptor
  • C is the Coulombic stabilization of a neighboring cation and anion in the system
  • ⁇ 80 ⁇ ⁇ is the stabilization of the ion pair by a surrounding polar environment (due to solvent or otherwise).
  • the donor and acceptor are the same moiety, so a crude approximation of the energy of a symmetry-breaking ICT state can come from the energy required to pass one electron through the potential difference between the one-electron oxidation and reduction events, as determined by cyclic voltammetry or other electrochemical method. Since C and ⁇ 80 ⁇ ⁇ only serve to stabilize the ICT state, this method will always lead to an overestimate of the energy. Thus, for example, if the difference in oxidation and reduction events for a dye is 2.50 V, then the energy of an ICT state for a dyad constructed from that dye will be less than 2.50 eV.
  • dimers (and higher order structures) of dyes with a first singlet excited state (S-i) energy greater than E / cr- 0.260 eV may be able to undergo symmetry-breaking intramolecular charge transfer at a polarizing donor/acceptor interface to facilitate charge separation in photovoltaics.
  • S-i first singlet excited state
  • E,cr as determined by this method minus 10kT
  • the absorption profiles of the chromophores in Figure 16 are generally similar to the monomer units of their respective dyes, indicating minimal excitonic coupling between the two (or three or more) dye units on the chromophore molecule. They are also generally invariant across different solvent polarities, since accessing any ICT state should first excite directly to the Si state.
  • the absorption of the chromophores from Figure 16 are listed in Table 2 for different solvents.
  • the dyes In order to undergo such symmetry-breaking charge transfer, the dyes must be able to communicate electronically (though there need not be any ground- state interaction). Thus, the manner in which they are connected is important.
  • Three examples are illustrated in Figure 27 for bringing two, three, or four dyes together.
  • the two constituent dyes may be connected directly or through a linker that places them in linear or cofacial arrangements (Figure 28).
  • the linker must have higher energy optical transitions than the dyes to prevent direct energy transfer from the dye to the linker.
  • Numerous linkers can be utilized, including saturated and unsaturated hydrocarbon linkers, with the most important requirement being that the linker must have ground state oxidation and reduction potentials, such that the linker is neither reduced nor oxidized by the photoexcited dye.
  • Figure 27(a) contemplates a wide range of effectively divalent linkers.
  • the linker could be a single atom, as illustrated for the Zinc based materials in compounds 31-34 of Figure 16.
  • This divalent group can also be a disubstituted arene, as illustrated in compounds 23-25 or a single bond as illustrated in
  • Figure 27(b) illustrates three dyes disposed around a linker. This effectively trivalent linkage is demonstrated for 1 ,3,5-benzene in compound 30 of Figure 16. This linkage could also be a trivalent metal atom such as Al or Ga, or a transition metal. These complexes are analogous to compounds 31-34 of Figure 16, except the central metal atom would be surrounded by three bidentate ligands.
  • One of skill in the art can envision a range of similar trivalent linkers using trivalent atoms or effective trivalent linkers constructed from aryl, fused aryl, such as naphthyl, anthryl, etc., alkyl, alkenyl, a heterocycle, or organosilane moiety.
  • Figure 27(c) illustrates four dyes bound to a central linker.
  • This linkage could be a tetravalent metal atom such as Ti, Zr or Hf.
  • These complexes are analogous to compounds 31-34 of Figure 16, except the central metal atom would be surrounded by four bidentate ligands.
  • One of skill in the art can envision a range of similar tetravalent linkers using trivalent atoms or effective tetravalent linkers constructed from aryl, fused aryl, such as naphthyl, anthryl, etc., alkyl, alkenyl, a heterocycle, or organosilane moiety.
  • a number of other geometries can be envisioned for higher-order structures, with the requirement that they be symmetric or pseudosymmetric in the ground state so that there is no driving force for ICT in the absence of a polarizing medium. Moreover, any interaction of the two molecules in the ground or excited state should not lead to the formation of an excited state lower in energy than the ICT, such as a triplet or excimeric excited state. These alternate excited states can exist, but they must be higher in energy than the ICT.
  • the symmetry-breaking charge transfer compounds has at least C 2 symmetry, and this symmetry is maintained upon linkage in the dyad, triad, tetrad, etc..
  • the symmetry can be maintained by having the atom linking the dye to the linker lying on the C 2 axis, as in cynines, malachites, xanthenes and perylenes.
  • the dye can be bound in such a way that the C 2 symmetry is retained in the bound structure— no atom bonded to the linkage center is on the C 2 axis.
  • one aspect of the disclosure provides for the synthesis and unusual symmetry- breaking ICT properties of symmetrical BODIPY dyads, wherein the units are connected through the meso position either indirectly by an intervening phenylene or directly through a C-C bond. Further investigation found the directly linked dyad to have excited-state properties that mimic behavior found in 9,9'-bianthryl.
  • Phenylene-bridged BODIPY dyad 23 of Figure 16 was initially targeted due to its structural semblance to BODIPY-porphyrin hybrids.
  • Dyad 23 was prepared by acid-catalyzed condensation of
  • Dyad 26 was prepared in low yield ( ⁇ 3%) from 1 ,1 ,2,2-tetrakis(5-methyl-1 H-pyrrol-2yl)ethene, which in turn was synthesized by a McMurry reaction, using standard oxidation and difluoroborylation conditions (Eq I). Although X-ray quality single crystals of dyad 26 have not been obtained, structure minimization using DFT (B3LYP/63lg*) methods indicated that the planar BODIPY units of dyad 26 have local geometries similar to those of dyad 23, and are canted at a dihedral angle of 71 ° with respect to each other.
  • dyad 26 represents the first example of a dyad that combines symmetry- breaking formation of an emissive ICT state with intense absorption in the visible region of the spectrum. While porphyrins are in many respects related to dipyrrins, the meso-linked porphyrin analogues of dyad 26 do not undergo symmetry-breaking ICT because formation of such an excited state is endothermic with respect to the Si state. BODIPY dyads directly linked at the a- or ⁇ positions also do not exhibit this sort of emissive behavior. However, Benniston et al.
  • BODIPY dyads 23 and 26 lead to formation of ICT states in polar media by solvent-induced symmetry breaking. The further presence of strong absorption at visible wavelengths enables these molecules to mimic features seen in the photosynthetic reaction center. Model systems that possess both these characteristics are rare. Differing degrees of rotational freedom in the dyads significantly alter the behavior of the ICT state. Whereas dyad 23 undergoes rapid non-radiative decay to the ground state, the more hindered dyad 26 has a long-lived ICT state with moderate-to-high fluorescence quantum efficiency.
  • Femtosecond transient absorption measurements were performed using a Tksapphire regenerative amplifier (Coherent Legend, 3.5 mJ, 35 fs, 1 kHz repetition rate). Approximately 10% of the amplifier output was used to pump a type II OPA (Spectra Physics OPA-80OC) resulting in the generation of excitation pulses centered at 508 nm with 1 1 .5 nm of bandwidth. At the sample position, the pump was lightly focused to a spot size of 0.29 mm (FWHM) using a 50 cm CaF 2 lens. Probe pulses were generated by focusing a small amount of the amplifier output into a rotating CaF 2 plate, yielding a supercontinuum spanning the range of 320-950 nm. A pair of off-axis aluminum parabolic mirrors collimated the supercontinuum probe and focused it into the sample.
  • the measured transient spectra indicate that in dyad 23, the initially excited population evolves over time to form an ICT state that non-radiatively returns to the ground state while in dyad 26 the ICT state persists for nanosecond or longer time scales.
  • the transient spectra can be described using a three-state model governed by a series of sequential first order rate processes:
  • Csi ⁇ and Cicr(t) denote their time-dependent populations of the Si and ICT states of a given dyad
  • ⁇ $ ⁇ ( ⁇ ) and ⁇ / ⁇ ) represent the time-independent characteristic transient absorption spectrum that results from the population of either state.
  • the present disclosure provides for an organic photosensitive optoelectronic device comprising: at least one compound chosen from a higher order structure, wherein said compound's absorptivity of light at some visible wavelength is about > 10 4 M "1 cm "1 , and wherein said compound is capable of undergoing symmetry-breaking intramolecular charge transfer in the excited state.
  • the organic photosensitive devices disclosed herein can be, for example, an organic
  • the at least one compound is chosen from dyads of xanthenes dyes, coumarins, acridines, phthalocyanines,
  • the compound is chosen from even higher order structures such as triads and tetrads.
  • the intramolecular charge transfer occurs in a polarizing medium.
  • the intramolecular charge transfer in the excited state is energetically accessible from a photogenerated Si state in a polarizing medium.
  • the dyads may be connected either directly or through a linker (such as saturated or unsaturated linear or branched hydrocarbons, or aromatic rings, e.g., phenylene, or constructed from aryl, fused aryl, such as naphthyl, anthryl, etc., alkyl, alkynyl, alkenyl, a heterocycle, a diazo or organosilane moiety), such that the dyads are arranged in linear or cofacial fashion.
  • a linker such as saturated or unsaturated linear or branched hydrocarbons, or aromatic rings, e.g., phenylene, or constructed from aryl, fused aryl, such as naphthyl, anthryl, etc., alkyl, alkynyl, alkenyl, a heterocycle, a diazo or organosilane moiety
  • the higher order compound is 1 ,4-Bis(4,4- difluoro-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene-8-yl)benzene or a salt or hydrate thereof.
  • the higher order compound is Bis(4,4- difluoro-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene-8-yl), or a salt or hydrate thereof.
  • a further embodiment is directed to a process for preparing 1 ,4- Bis(4,4-difluoro-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene-8-yl)benzene, or a salt or hydrate thereof, comprising treating a mixture comprising terephthalaldehyde and 2-methylpyrrole with a halogenated carboxylic acid, an oxidizing agent, and Lewis acid to form 1 ,4-Bis(4,4-difluoro-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene-8- yl)benzene.
  • the halogenated carboxylic acid can be trifluoroacetic acid
  • the oxidant can be DDQ
  • the Lewis acid can be boron trifluoride diethyl etherate.
  • An additional embodiment is directed to a process for preparing Bis(4,4-difluoro-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene-8-yl), or a salt or hydrate thereof, comprising treating a mixture comprising a first Lewis acid and a transition metal with a mixture comprising bis(5-methyl-1 H-pyrrol-2-yl)methanone to form 1 , 1 ,2,2-tetrakis(5-methyl-1 H-pyrrol-2-yl)ethene; and treating a mixture comprising 1 ,1 ,2,2-tetrakis(5-methyl-1 H-pyrrol-2-yl)ethene and a base with an oxidant and second Lewis acid to form Bis(4,4-difluoro-3,5-dimethyl-4-bora-3a,4a- diaza-s-indacene-8-yl).
  • the first Lewis acid can be TiCI4, the transition metal can be zinc, the base can be triethylamine, the oxidant can be DDQ, and the second Lewis acid can be boron trifluoride diethyl etherate.
  • the present disclosure also provides for methods of making an organic photosensitive device comprising an organic photosensitive optoelectronic device, wherein said organic photosensitive optoelectronic device comprises: at least one compound chosen from a dyad or higher order structure, wherein said compounds absorptivity of light at some visible wavelength is about > 10 4 M "1 cm "1 , and wherein said compound is capable of undergoing symmetry-breaking
  • BenzoBODIPY was prepared in two steps from the corresponding pyrrole and aldehyde followed by retro-Diels-Alder deprotection.
  • the required pyrrole was prepared via Barton-Zard synthesis from the necessary precursors with yields generally >80 %.
  • the pyrrole carboxylate ester was converted to the methyl pyrrole moiety using lithium aluminum hydride and used without further purification due to its sensitivity to air.
  • a yield of about 40 % was obtained for the masked BenzoBODIPY.
  • the masked BenzoBODIPY was quantitatively converted to BenzoBODIPY. The materials were then recrystallized into copper-colored crystals and sublimed.
  • IndoBODIPY was prepared by first isolating its corresponding diindolyl-methane precursor. The precursor was isolated using known literature techniques. The boron complex was prepared using conditions identical to those of BenzoBODIPY, though only a yield of 7 % was achieved. The materials were recrystallized to give a purple solid.
  • CyanoBODIPY was prepared using the synthetic scheme shown in Figure 3.
  • Example 2 Optical Properties of BenzoBODIPY, IndoBODIPY, and CvanoBODIPY
  • IndoBODIPY broadened significantly, deviating from the narrow bandwidth that is usually observed for this class of materials as exhibited by BenzoBODIPY in Figure 7(a).
  • Figure 7 also shows that the film excitation of BenzoBODIPY was much wider and more red shifted than the solution absorption due to strong intermolecular interactions. A larger Stokes shift was also observed when comparing solution and solid-state.
  • Photovoltaic devices using BenzoBODIPY as a donor material and a device using CuPc as a donor material were fabricated on ITO-glass substrates cleaned with Tergitol, alcohols, acetone, followed by UV-ozone treatment.
  • Cm MRR Limited
  • BCP 2,9-dimethyl-4,7-diphenyl-1 ,10-phenanthroline
  • BenzoBODIPY were purified by sublimation prior to use.
  • Aluminum Alfa Aesar
  • All devices were fabricated as lamellar devices in a vacuum deposition chamber with a fixed deposition rate for each layer.
  • Three BenzoBODIPY devices were fabricated each with a different donor layer thickness— 10 nm, 20 nm, and 30 nm.
  • Device performance (Current- Voltage curve and external quantum efficiency (EQE)) was measured under simulated AM 1 .5G solar illumination (Oriel Instruments) using a Keithley 2420 3A Source Meter. The device structures and performance of each device are summarized below and in Figure 9.
  • CuPc Device Glass/ITO/CuPc(40 nm)/C 60 (40 nm)/BCP(10nm)/AI
  • BenzoBODIPY Device Glass/ITO/BDPY(30-10 nm)/C 60 (40 nm)/BCP(10 nm)/AI.
  • CyanoBODIPY purified by sublimation was used in preparing the devices.
  • the devices were prepared and tested under the conditions described above in Example 3.
  • Unannealed and annealed CyanoBODIPY devices employed copper phthalocyanine (CuPc) as an electron donor material and a 1 : 1 ratio codeposited layer of CyanoBODIPY and Cm as an electron acceptor.
  • the annealed device the device was heated at 1 10 °C under nitrogen for 10 minutes after deposition of the acceptor layer.
  • the device structures are summarized as follows:
  • 2-M ethyl pyrrole was obtained by a Wolff-Kishner reduction of pyrrole- 2-carboxaldehyde as previously described.
  • 1 -Methyl-4,7-dihydro-2/-/-4,7- ethanoisoindole was prepared by lithium aluminum hydride reduction of the corresponding ester according to literature procedure. All other reagents were purchased from commercial vendors and used without further purification. All air- sensitive manipulations were performed using standard Schlenk techniques as needed, following the procedures indicated below for each preparation. NMR spectra were recorded at ambient temperature on Varian Mercury 400 MHz and 600 MHz spectrometers. 1 H chemical shifts were referenced to residual solvent.
  • UV-vis spectra were recorded on a Hewlett-Packard 4853 diode array spectrophotometer. Steady-state emission experiments were performed using a Photon Technology International QuantaMaster Model C-60SE spectrofluorimeter. Fluorescence lifetime measurements were performed by a time-correlated single-photon counting method using an IBH Fluorocube lifetime instrument by equipped with a 405 nm or 435 nm LED excitation source. Quantum efficiency measurements were carried out using a Hamamatsu C9920 system equipped with a xenon lamp, calibrated integrating sphere and model C10027 photonic multichannel analyzer.
  • Phenylene Bridged Dyad 23 Terephthalaldehyde (762 mg, 5.68 mmol) and 2-methylpyrrole (2.03 g, 23.3 mmol) were dissolved in dry, degassed CH 2 CI 2 (40 mL) under N 2 . The resulting solution was further degassed for 10 min, and trifluoroacetic acid (64 ⁇ _, 0.84 mmol) was added in two portions, causing the solution to darken immediately, and the reaction was allowed to proceed with stirring for 2 h. DDQ (2.58 g, 1 1 .4 mmol) was added in one portion, causing an immediate color change to dark red-orange, and the resulting mixture was stirred for 13 h.
  • N,N- Diisopropylethylamine (8.0 mL, 46 mmol) was added at once, causing a color change to dark brown, and stirring was continued for 15 min.
  • Boron trifluoride diethyl etherate (8.0 mL, 64 mmol) was added slowly over the course of 1 min, causing the mixture to warm slightly. After 45 min, the mixture was quenched with NaHC0 3 (5% aq, 200 mL) and stirred vigorously for 2 h. Organics were removed and washed with Na 2 S0 3 (10% aq, 2 100 mL), HCI (5% aq, 1 ⁇ 100 mL), and brine (2 100 mL).
  • Phenylene Bridged Dyad 24 Terephthalaldehyde (1 g, 7.55 mmol) and 2,4-dimethylpyrrole (2.98 g, 31 .3 mmol) were dissolved in dry, degassed CH 2 CI 2 (30 mL) under N 2 . The resulting solution was further degassed for 10 min, and trifluoroacetic acid (1 drop) was added and the reaction was allowed to proceed with stirring for 5 h. DDQ (3.38 g, 14.9 mmol) was added in one portion, and the resulting mixture was stirred overnight.
  • Phenylene Bridged Dyad 25 Terephthalaldehyde (1 g, 7.46 mmol) and 2,4-dimethyl-3-ethylpyrrole (3.67 g, 29.8 mmol) were dissolved in dry, degassed CH 2 CI 2 (40 mL) under N 2 . The resulting solution was further degassed for 10 min, and trifluoroacetic acid (1 drop) was added and the reaction was allowed to proceed with stirring for 2 h. DDQ (3.39 g, 14.9 mmol) was added in one portion, causing an immediate color change to dark red-orange, and the resulting mixture was stirred for 13 h.
  • Example 6 General Reaction Scheme for Directly Linked Dyads 26, 27, 28, and 29 of Figure 16.
  • ⁇ /,/V-Diisopropylethylamine (8.58 mL, 49.3 mmol) was added at room temperature, causing a color change to clear orange, and stirring was continued for 30 min followed by dropwise addition of BF 3 »OEt 2 (6.18 mL, 49.3 mmol). During addition of BF 3 »OEt 2 the color changed to dark red.
  • ⁇ /,/V-Diisopropylethylamine (0.10 mL, 0.58 mmol) was added in one portion, followed after 15 min by dropwise addition of BF 3 »OEt 2 (0.07 mL, 0.6 mmol).
  • the reaction was left stirring for 15 min and then was quenched with saturated Na 2 S 2 0 3 (25 mL), washed with saturated NaHC0 3 (2 ⁇ 50 mL) and the organic layer was removed.
  • Step 1 1 .1 .2.2-tetrakis(5-methyl-IH-pyrrol-2-yl)ethene.
  • Titanium tetrachloride (87 uL, 0.80 mmol) was added dropwise to a solution of dry THF (15 mL) at 0 °C under nitrogen. The solution was stirred for 10 min, after which a suspension of zinc powder (98 mg, 1 .5 mmol) in 3 mL of dry THF was added via cannula. The resulting blue slurry was heated at reflux for 3 h and cooled to room temperature. Dry pyridine (55 uL, 0.68 mmol) was added and the solution set to reflux for 30 min.
  • Step 2 Bis(4,4-ditluoro-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene-8-yl). 1 , 1 ,2,2- tetrakis(5-methyl-1 H-pyrrol-2-yl)ethene (90 mg, 0.26 mmol) was dissolved in dry, degassed CH 2 CI 2 (15 mL) under N 2 . The solution was degassed for an additional 5 min, and Et 3 N (0.29 mL, 2.0 mmol) added by syringe. The resulting solution was stirred for 30 min at room temperature and DDQ (68 mg, 0.30 mmol) added.
  • Triad 30. 1 ,3,5-Benzenetricarbonyl trichloride (1 g, 3.76 mmol) was dissolved in dry dichloromethane (80 ml) under N 2 .
  • 2,4-Dimethyl-3-ethylpyrrole (2.78 g, 22.6 mmol) was added and the flask was fitted with a condenser and refluxed overnight.
  • ⁇ /Jv-Diisopropylethylamine (7.85 ml, 45.12 mmol) was added at reflux. After 15 minutes, the mixture was cooled to room temperature and boron trifluoride etherate (5.66 mL, 45.12 mmol) was added in one portion.
  • Example 8 General Reaction Scheme for Zinc Compounds 31 -34 of Figure 16.
  • Zinc Compound 31 5-Mesityldipyrromethane (2 g, 7.57 mmol) was dissolved in 200 ml of freshly distilled THF under Nitrogen. 2,3-Dichloro-5,6- dicyano-1 ,4-benzoquinone (DDQ) (1 .72 g, 7.57 mmol) in 15 ml of freshly distilled THF was added slowly to the solution. Reaction mixture turned to dark red color. Reaction mixture was stirred under nitrogen for 1 hour. The reaction was quenched by adding 5 ml of Triethylamine, stirred for another 5 min. Solvent was then removed under reduced pressure.
  • DDQ 2,3-Dichloro-5,6- dicyano-1 ,4-benzoquinone
  • the product mixture was dissolved in 200 ml of dichloromethane, and was washed with saturated NaHC0 3 solution in water (150 ml, 3 times) and brine (150 ml, 1 time). The solution was then dried over anhydrous Na 2 S0 4 and filtered. This solution of 5-mesityldipyrromethene was used without further purification.
  • the obtained solid was passed through short neutral alumina plug using hexanes/dichloromethane (50/50) mixture as eluent, the portion in orange color was collected. Solvent was then removed under reduced pressure to obtain 1 g of orange solid (14% yield).
  • the obtained 10 was further purified by gradient sublimation under ultra high vacuum (10 " 5 torr) at 180°C - 140°C - 100°C gradient temperature zones.
  • 1 H NMR 400 MHz, CDCI 3
  • Zinc Compound 32 A mixture of mesitaldehyde (4.6 g, 30.9 mmol) and 2-methylpyrrole (5 g, 61 .7 mmol) was dissolved in 200 ml dichloromethane in a 500-mL single-neck round-bottomed flask was degassed with a stream of nitrogen for 10 min. Then 5 drops of trifluoroacetic acid (TFA) was added to the reaction mixture, the solution turned to dark red color. Reaction mixture was stirred under nitrogen for 6 hours until the starting materials were completely consumed. The reaction was quenched with 3 ml of triethylamine.
  • TFA trifluoroacetic acid
  • Reaction mixture was then washed with saturated Na 2 CC>3 solution in water (100 ml, 3 times) and brine (100, 1 time). Solution was dried over anhydrous Na 2 S0 4 . Solvent was then removed under reduced pressure to obtain the viscous pale yellow liquid (it turns to solid upon standing at room temperature).
  • This product was dissolved in 250 ml of freshly distilled THF under Nitrogen. 2,3-Dichloro-5,6-dicyano-1 ,4-benzoquinone (DDQ) (7.02 g, 30.9 mmol) in 35 ml of freshly distilled THF was added slowly to the solution. Reaction mixture turned to dark red color. Reaction mixture was stirred under nitrogen for 1 hour.
  • DDQ 2,3-Dichloro-5,6-dicyano-1 ,4-benzoquinone
  • Zinc Compound 33 A mixture of mesitaldehyde (5 g, 33.5 mmol) and 2,4dimethylpyrrole (6.4 g, 67 mmol) was dissolved in 250 ml dichloromethane in a 500-mL single-neck round-bottomed flask was degassed with a stream of nitrogen for 10 min. Then 5 drops of trifluoroaceticacid (TFA) was added to the reaction mixture, the solution turned to dark red color. Reaction mixture was stirred under Nitrogen for 7 hours until the starting materials were completely consumed. The reaction was quenched with 3 ml of triethylamine.
  • TFA trifluoroaceticacid
  • Reaction mixture was then washed with saturated Na 2 CC>3 solution in water (100 ml, 3 times) and brine (100, 1 time). Solution was dried over anhydrous Na 2 S0 4 . Solvent was then removed under reduced pressure to obtain the viscous pale yellow liquid (it turns to solid upon standing at room temperature).
  • the crude product obtained was dissolved in 250 ml of freshly distilled THF under nitrogen.
  • DDQ (7.61 g, 30.9 mmol) in 40 ml of freshly distilled THF was added slowly to the solution. Reaction mixture turned to dark red color. Reaction mixture was stirred under nitrogen for 1 hour. The reaction was quenched by adding 10 ml of Triethylamine, stirred for another 5 min. Solvent was then removed under reduced pressure.
  • the product mixture was dissolved in 500 ml of dichloromethane, and was washed with saturated NaHCC solution in water (250 ml, 3 times) and brine (250 ml, 1 time). The solution was then dried over anhydrous Na 2 S0 4 and filtered. This solution of 1 ,3, 7,9-tetramethyl-5-Mesityldipyrromethene was used without further purification.
  • reaction mixture was filter using filter paper. Solvent was then removed under reduced pressure. The obtained solid was passed through short neutral alumina plug using hexanes/dichloromethane (70/30) mixture as eluent, the portion in orange-red color was collected. Solvent was then removed under reduced pressure to obtain 3.0 g of orange-red solid (13 % total yield).
  • the obtained 33 was further purified by gradient sublimation under ultra high vacuum (10 "5 torr) at 230°C - 160°C - 120°C gradient temperature zones.
  • Zinc Compound 34 2,8diethyl1 ,3,7,9-tetramethyl-5- Mesityldipyrromethane.
  • a mixture of mesitylaldehyde (2 g, 13.4 mmol) and 3- ethyl2,4dimethylpyrrole (3.3 g, 26.8 mmol) was dissolved in 150 ml dichloromethane in a 500-mL single-neck round-bottomed flask was degassed with a stream of nitrogen for 10 min. Then 3 drops of trifluoroaceticacid (TFA) was added to the reaction mixture, the solution turned to dark red color. Reaction mixture was stirred under Nitrogen for 7 hours until the starting materials were completely consumed.
  • TFA trifluoroaceticacid
  • reaction was quenched with 3 ml of triethylamine. Reaction mixture was then washed with saturated Na 2 CC>3 solution in water (100 ml, 3 times) and brine (100, 1 time). Solution was dried over anhydrous Na 2 S0 4 . Solvent was then removed under reduced pressure. This product was dissolved in 150 ml of freshly distilled THF under nitrogen. DDQ (3.3 g, 13.4 mmol) in 15 ml of freshly distilled THF was added slowly to the solution. Reaction mixture turned to dark red color. Reaction mixture was stirred under nitrogen for 1 hour. The reaction was quenched by adding 10 ml of Triethylamine, stirred for another 5 min. Solvent was then removed under reduced pressure.
  • the obtained 34 was further purified by gradient sublimation under ultra high vacuum (10 "5 torr) at 240°C - 160°C - 120°C gradient temperature zones.
  • Example 9 An Organic Photosensitive Optoelectronic Device Using
  • OPVs using compound 31 of Figure 16 as a donor material and fullerene Cm as an acceptor material have been fabricated using vacuum deposition technique on glass coated with Indium doped Tin Oxide (ITO) substrate.
  • ITO Indium doped Tin Oxide
  • the OPV device with Mo03 as hole conducting/electron blocking layer was also fabricated.
  • the device structures and characteristics are shown in the table below and in Figure 34. Both devices have significant photocurrents (3.06 and 3.49 mA/cm2).
  • External Quantum Efficiency measurements (Figure 34(c)) confirm the contribution of compound 31 to the photocurrent (up to 30% EQE at 500 nm).
  • the Mo03 hole conducting/electron blocking layer increases the open circuit voltage (VOC) from 0.60 to 0.82 V, while the short circuit current (JSC) and the fill factor (FF) decreases slightly compared to the device without Mo03. Thus, both devices (D1 and D2) have comparable power conversion efficiency (0.9%).
  • VOC open circuit voltage
  • JSC short circuit current
  • FF fill factor
  • D1 ITO/Mo03 (8 nm)/31 (10 nm)/C60 (40 nm)/BCP (10 nm)/AI
  • D2 ITO/31 (10 nm)/C60 (40 nm)/BCP (10 nm) /AI.

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Abstract

La présente invention concerne généralement des dispositifs optoélectroniques photosensibles organiques comprenant au moins un composé de dipyrrine de bore. De plus, la présente invention concerne les procédés de fabrication de dispositifs optoélectroniques photosensibles organiques comprenant au moins un composé de dipyrrine de bore. La présente invention concerne également généralement des composés chromophores qui combinent une forte absorption de lumière à des longueurs d'onde visibles avec la capacité de subir un transfert de charge intermoléculaire (ICT) à rupture symétrique, et leur utilisation pour la génération de porteurs libres dans des cellules photovoltaïques organiques (OPV) et des paires de polarons géminés stabilisés par champ électrique. La présente invention concerne également la synthèse de tels composés, des procédés de fabrication, et des applications dans des systèmes photovoltaïques et des lasers organiques.
PCT/US2013/041079 2012-05-15 2013-05-15 Matériaux à base de dipyrrine pour photovoltaïque, composés aptes à subir un transfert de charge intermoléculaire à rupture symétrique dans un milieu polarisant et dispositifs photovoltaïques organiques les comprenant WO2014025435A2 (fr)

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CA2873468A CA2873468A1 (fr) 2012-05-15 2013-05-15 Materiaux a base de dipyrrine pour photovoltaique, composes aptes a subir un transfert de charge intermoleculaire a rupture symetrique dans un milieu polarisant et dispositifs photovoltaiques organiques les comprenant
CN201380031559.4A CN105409020A (zh) 2012-05-15 2013-05-15 用于光伏的基于次甲基二吡咯的材料、能够在极化介质中经历对称性破缺分子内电荷转移的化合物以及包含它们的有机光伏器件
AU2013300142A AU2013300142A1 (en) 2012-05-15 2013-05-15 Dipyrrin based materials for photovoltaics, compounds capable of undergoing symmetry breaking intramolecular charge transfer in a polarizing medium and organic photovoltaic devices comprising the same
JP2015512780A JP6339561B2 (ja) 2012-05-15 2013-05-15 光起電力のためのジピリン系材料、極性媒体中で対称性破壊性分子内電荷移動が可能な化合物およびこれを含む有機光起電力デバイス
EP13802466.6A EP2850670A2 (fr) 2012-05-15 2013-05-15 Matériaux à base de dipyrrine pour photovoltaïque
KR20147034571A KR20150020297A (ko) 2012-05-15 2013-05-15 광전지용 디피린계 물질, 편광 매체에서 대칭성 깨짐 분자내 전하 이동을 진행할 수 있는 화합물 및 이를 포함하는 유기 광전지 디바이스
IL235713A IL235713A0 (en) 2012-05-15 2014-11-13 Diphyrin-based materials for photovoltaic compounds capable of undergoing intramolecular charge transfer from symmetric refraction by means of polarization and organic photovoltaic devices containing them

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013106639A1 (de) * 2013-06-25 2015-01-08 Heliatek Gmbh Organisches, halbleitendes Bauelement
WO2015077427A1 (fr) 2013-11-20 2015-05-28 The University Of Akron Chromophores de pyrrole-bf2 hautement fluorescents
KR20150120243A (ko) * 2014-04-17 2015-10-27 삼성전자주식회사 화합물, 유기 광전 소자 및 이미지 센서
WO2016072119A1 (fr) * 2014-11-07 2016-05-12 ソニー株式会社 Dispositif d'imagerie à semi-conducteurs, et dispositif électronique
CN105914297A (zh) * 2016-04-27 2016-08-31 扬州鑫晶光伏科技有限公司 一种有机光伏电池及其制备方法
WO2019243286A1 (fr) 2018-06-22 2019-12-26 Basf Se Colorant de bore-dipyrrométhène photostable substitué par un groupe cyano comme émetteur vert pour les applications d'affichage et d'éclairage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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TWI638822B (zh) 2016-07-29 2018-10-21 南韓商Ｌｇ化學股份有限公司 含氮之環狀化合物，含彼之變色膜，及含彼之背光元件和顯示裝置

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6352777B1 (en) 1998-08-19 2002-03-05 The Trustees Of Princeton University Organic photosensitive optoelectronic devices with transparent electrodes
US6451415B1 (en) 1998-08-19 2002-09-17 The Trustees Of Princeton University Organic photosensitive optoelectronic device with an exciton blocking layer
US6580027B2 (en) 2001-06-11 2003-06-17 Trustees Of Princeton University Solar cells using fullerenes
US6657378B2 (en) 2001-09-06 2003-12-02 The Trustees Of Princeton University Organic photovoltaic devices
US7230269B2 (en) 2005-06-13 2007-06-12 The Trustees Of Princeton University Organic photosensitive cells having a reciprocal-carrier exciton blocking layer
US20100102304A1 (en) 2008-10-27 2010-04-29 The Regents Of The University Of Michigan Inverted organic photosensitive devices
US20110012091A1 (en) 2009-01-12 2011-01-20 The Regents Of The University Of Michigan Enhancement of organic photovoltaic cell open circuit voltage using electron/hole blocking exciton blocking layers
US20120235125A1 (en) 2011-02-21 2012-09-20 Forrest Stephen R Organic photovoltaic cell incorporating electron conducting exciton blocking layers

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6407330B1 (en) * 2000-07-21 2002-06-18 North Carolina State University Solar cells incorporating light harvesting arrays
WO2010075512A1 (fr) * 2008-12-23 2010-07-01 Michigan Technological University Polymères avec squelette à base de bodipy pour des cellules solaires
CN107039591A (zh) * 2011-08-02 2017-08-11 南加利福尼亚大学 能够在极化介质中经历对称破裂分子内电荷转移的化合物和包含其的有机光伏器件

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6352777B1 (en) 1998-08-19 2002-03-05 The Trustees Of Princeton University Organic photosensitive optoelectronic devices with transparent electrodes
US6451415B1 (en) 1998-08-19 2002-09-17 The Trustees Of Princeton University Organic photosensitive optoelectronic device with an exciton blocking layer
US6580027B2 (en) 2001-06-11 2003-06-17 Trustees Of Princeton University Solar cells using fullerenes
US6657378B2 (en) 2001-09-06 2003-12-02 The Trustees Of Princeton University Organic photovoltaic devices
US7230269B2 (en) 2005-06-13 2007-06-12 The Trustees Of Princeton University Organic photosensitive cells having a reciprocal-carrier exciton blocking layer
US20100102304A1 (en) 2008-10-27 2010-04-29 The Regents Of The University Of Michigan Inverted organic photosensitive devices
US20110012091A1 (en) 2009-01-12 2011-01-20 The Regents Of The University Of Michigan Enhancement of organic photovoltaic cell open circuit voltage using electron/hole blocking exciton blocking layers
US20120235125A1 (en) 2011-02-21 2012-09-20 Forrest Stephen R Organic photovoltaic cell incorporating electron conducting exciton blocking layers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TANG, APPL. PHYS LETT., vol. 48, 1986, pages 183

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013106639A1 (de) * 2013-06-25 2015-01-08 Heliatek Gmbh Organisches, halbleitendes Bauelement
US9685616B2 (en) 2013-06-25 2017-06-20 Heliatek Gmbh Organic semiconductive component
WO2015077427A1 (fr) 2013-11-20 2015-05-28 The University Of Akron Chromophores de pyrrole-bf2 hautement fluorescents
KR20150120243A (ko) * 2014-04-17 2015-10-27 삼성전자주식회사 화합물, 유기 광전 소자 및 이미지 센서
KR102204111B1 (ko) * 2014-04-17 2021-01-15 삼성전자주식회사 화합물, 유기 광전 소자 및 이미지 센서
WO2016072119A1 (fr) * 2014-11-07 2016-05-12 ソニー株式会社 Dispositif d'imagerie à semi-conducteurs, et dispositif électronique
CN105914297A (zh) * 2016-04-27 2016-08-31 扬州鑫晶光伏科技有限公司 一种有机光伏电池及其制备方法
WO2019243286A1 (fr) 2018-06-22 2019-12-26 Basf Se Colorant de bore-dipyrrométhène photostable substitué par un groupe cyano comme émetteur vert pour les applications d'affichage et d'éclairage

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