WO2010144472A2 - Compositions de porphyrine et de polymère conducteur destinées à être utilisées dans des dispositifs électroniques à semi-conducteurs - Google Patents

Compositions de porphyrine et de polymère conducteur destinées à être utilisées dans des dispositifs électroniques à semi-conducteurs Download PDF

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WO2010144472A2
WO2010144472A2 PCT/US2010/037805 US2010037805W WO2010144472A2 WO 2010144472 A2 WO2010144472 A2 WO 2010144472A2 US 2010037805 W US2010037805 W US 2010037805W WO 2010144472 A2 WO2010144472 A2 WO 2010144472A2
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copolymer
segment
porphyrinic
porphyrin
composition according
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WO2010144472A3 (fr
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Christopher T. Brown
Elena E. Sheina
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Plextronics, Inc.
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Definitions

  • Electronic and optical properties of inherently conductive or conjugated polymers can be tuned to improve the performance of polymer-based electronic devices, such as light emitting diodes, photovoltaic cells, and field effect transistors. These devices and materials are of interest in, for example, displays, off-grid power generation, and low weight, flexible, and printable circuitry. It is of great importance to improve the performance of currently existing devices including enhancing their efficiencies and tunability.
  • polythiophenes including regioregular polythiophenes, are particularly useful. See, for example, McCullough et al, US Patent Nos. 6,602,974 and 6,166,172, which are incorporated by reference in their entirety. See also Plextronics US Patent Publication 2006/0076050 to Williams et al., "Heteroatomic Regioregular Poly(3-Substitutedthiophenes) for Photovoltaic Cells.”
  • porphyrinic pigments e.g., porphyrins, chlorins, and bacteriochlorins
  • porphyrinic pigments which exhibit intense absorption in the blue, red, and near infrared (NIR, 700-900 nm) region.
  • NIR near infrared
  • the synthetic pigments exhibit spectral and photophysical attributes similar to those of the natural pigments, but have advantages over the natural materials in terms of stability and synthetic variability. The latter permits facile tuning of spectral features, photophysical properties, redox potentials, and self-assembly or building block attributes.
  • porphyrins are available that bear four distinct meso substituents.
  • Stable chlorins are now available wherein control of substituents can be exercised at all but one site, enabling tuning of absorption from 605-685 nm.
  • Stable bacteriochlorins are now available wherein distinct patterns of substituents can be introduced; the absorption spectrum can be tuned from 730-800 nm.
  • synthetic porphyrinic pigments can be used to address fundamental and commercial questions regarding solar-energy transduction in molecular materials whose design is inspired by natural photosynthetic assemblies. Synthetic porphyrinic pigments have been used as light harvesting arrays, as disclosed in, for example, Lindsey et al, U.S. Patent Nos. 6,420,648; 6,916,982; 6,596,935; 6,407,330; 6,603,070, herein incorporated by reference in their entirety.
  • Embodiments provided herein include compositions, devices, methods of making, and methods of using.
  • One embodiment provides, for example, a composition comprising a copolymer, said copolymer comprising at least one acceptor segment and at least one donor segment, wherein said copolymer comprises one or more porphyrinic macrocycles comprising porphyrin, chlorin, or bacteriochlorin.
  • At least one additional embodiment provides a composition prepared by: providing at least one first comonomer comprising at least one acceptor segment, providing at least one second comonomer comprsing at least one donor segment, forming a copolymer comprising said at least one acceptor segment and said at least one donor segment, wherein said copolymer comprises one or more porphyrinic macrocycles comprising porphyrin, chlorin, or bacteriochlorin.
  • Still other embodiments provide a solid state device comprising a first electrode, a second electrode, and an active layer disposed between said first electrode and said second electrode, wherein said active layer comprises a composition as described or claimed herein.
  • Another embodiment provides a method comprising: providing at least one first comonomer comprising at least one acceptor segment, providing at least one second comonomer comprising at least one donor segment, forming a copolymer comprising said at least one acceptor segment and said at least one donor segment, wherein said copolymer comprises one or more porphyrinic macrocycles comprising porphyrin, chlorin, or bacteriochlorin.
  • compositions comprising at least one copolymer, said copolymer comprising a polymer backbone comprising at least one acceptor segment, at least one donor segment, and at least one or more porphyrinic macrocycles comprising porphyrin, chlorin, or bacteriochlorin.
  • At least one advantage for at least one embodiment is the ability to formulate the active layer ink to include lower absorptivity materials because of the good absorption provided by the dye.
  • At least one additional advantage for at least one embodiment comprises relatively good efficiency for a porphyrin polymer.
  • At least one additional advantage for at least one embodiment comprises good synthetic versatility.
  • Figure 1 shows an example of a photovoltaic or solar cell.
  • Figure 2 shows schematic representations of porphyrinic macrocycle -polymer conjugates.
  • Figure 3 shows compounds used to prepare porphyrinic macrocycle -polymer conjugates of preferred embodiments and different points of attachment of porphyrinic macrocycle with polymer.
  • Figure 4 shows the SEC trace of the crude reaction mixture upon Sonogashira coupling of H-Br terminated P3HT (P2) and a diethynylporphyrin (upper panel), and the mixture of starting materials (lower panel).
  • the wavelength of detection was 520 nm.
  • the absorption spectrum of each component eluting in advance of the P3HT polymer (upper panel) showed the characteristic absorption peaks of both the porphyrin and the polymer.
  • Figure 5 shows absorption spectrum of the crude reaction mixture upon Sonogashira coupling of H-Br terminated P3HT (P2) and a diethynylporphyrin in C ⁇ CVethanol (3:1) at room temperature.
  • the absorption spectrum of the product obtained upon preparative SEC is identical with that displayed here.
  • the characteristic band of the porphyrin (422 nm) and those of the P3HT polymer (500-600 nm region) are clearly visible. These data pertain to reaction VII.
  • Figure 1 illustrates some components of a conventional solar cell. See also for example Dennler et al., "Flexible Conjugated Polymer-Based Plastic Solar Cells: From Basics to Applications," Proceedings of the IEEE, vol. 93, no. 8, August 2005, 1429- 1439, including Figures 4 and 5.
  • Various architectures for the solar cell can be used.
  • Important elements include the active layer, an anode, a cathode, and a substrate to support the larger structure.
  • a hole injection layer and/or hole transport layer can be used, and a conditioning layer can be used.
  • the active layer can comprise a P/N composite including for example a P/N bulk heterojunction.
  • US Patent Application serial number 12/124,972 filed on May 21, 2008 and published as US 2002/9023842 discloses the use of porphyrins in combination with certain polymers to act as an antenna to collect light in the UV -visible spectrum not otherwise absorbed in OPV devices containing active layer polymer compositions that do not use prophyrins.
  • Porphyrin compositions are described in, for example, US patent application published 2009/0023842. See also, for example, Huang et al., Macromolecules, 2008, 41, 6895; and Wrobel et al., Solar Energy Materials and Solar Cells, 94, 492, 2010.
  • Inherently conductive polymers or conjugated polymers are organic polymers that, due to their conjugated backbone structure, show relatively high electrical conductivities under some conditions (relative to those of traditional polymeric materials). Performance of a conjugated polymer as an organic conductor can also be dependant upon the morphology of the polymer in the solid state. Electronic properties can be dependent upon the electrical connectivity and inter-chain charge transport between polymer chains. Pathways for charge transport can be along a polymer chain or between adjacent chains. Transport along a chain can be facilitated by a planar backbone conformation due to the dependence of the charge carrying moiety on the amount of double-bond character between the rings, an indicator of ring planarity.
  • This conduction mechanism between chains can involve either a stacking of planar, polymer segment, called pi-stacking, or an inter-chain hopping mechanism in which excitons or electrons can tunnel or "hop" through space or other matrix to another chain that is in proximity to the one that it is leaving. Therefore, a process that can drive ordering of polymer chains in the solid state can help to improve the performance of the conducting polymer. It is known that the absorbance characteristics of thin films of inherently conductive polymers reflect the increased re- stacking which occurs in the solid state.
  • the conjugated polymer comprises a homopolymer, a copolymer, a terpolymer, a random copolymer, a block copolymer, or an alternating copolymer.
  • Suitable inherently conductive polymers include, but are not limited to, poly(thiophene), poly(thiophene) derivatives, poly(pyrrole), poly(pyrrole) derivatives, poly(aniline), poly(aniline) derivatives, poly(phenylene vinylene), poly(phenylene vinylene) derivatives, poly(thienylene vinylene), poly(thienylene vinylene) derivatives, poly(bis- thienylene vinylene), poly(bis-thienylene vinylene) derivatives, poly(acetylene), poly(acetylene) derivatives, poly(fluorene), poly(fluorene) derivatives, poly(arylene), poly(arylene) derivatives, poly(isothianaphthalene), poly(isothianaphthalene) derivatives, and mixtures thereof.
  • the conductive polymer has molecular weight of from, for example, about 1,000 to about 40,000 g/mol. In certain cases, the conductive polymers have a molecular weight of, for example, from about 1000; 10,000; or 20,000 to about 30,000 or 40,000 g/mol.
  • the polymer can have a number average molecular weight of at least about 2,000 g/mol, or at least about 5,000 g/mol, or at least about 20,000 g/mol.
  • Molecular weight can be measured by, for example, gel permeation chromatography using, for example, chloroform as eluent and applying calibration based on molecular weight standards such as for example polystyrene standards for determination of molecular weight.
  • Conductive polymers including methods of making, are described in for example T. A. Skotheim, Handbook of Conducting Polymers, 3 rd Ed. (two vol), 2007; Meijer et al, Materials Science and Engineering, 32 (2001), 1-40; and Kim, Pure Appl. Chem., 74, 11, 2031-2044, 2002, and references cited in each of these references.
  • p-type materials can be found in WO 2007/011739 (Gaudiana et al.) which describes polymers having monomers which are substituted cyclopentadithiophene moieties, and which is hereby incorporated by reference in its entirety.
  • porphyrinic macrocycle refers to a porphyrin or porphyrin derivative.
  • Such derivatives include porphyrins with extra rings ortho-fused, or ortho-perifused, to the porphyrin nucleus, porphyrins having a replacement of one or more carbon atoms of the porphyrin ring by an atom of another element (skeletal replacement), derivatives having a replacement of a nitrogen atom of the porphyrin ring by an atom of another element (skeletal replacement of nitrogen), derivatives having substituents other than hydrogen located at the peripheral (meso-, beta-) or core atoms of the porphyrin, derivatives with saturation of one or more bonds of the porphyrin (hydroporphyrins, e.g., chlorins, bacteriochlorins, isobacteriochlorins, decahydroporphyrins, corphins, pyrrocorphins, etc.), derivatives obtained by coordination of one or more metals to one or
  • porphyrin refers to a cyclic structure typically composed of four pyrrole rings together with four nitrogen atoms and two replaceable hydrogens for which various metal atoms can readily be substituted.
  • a typical porphyrin is hemin.
  • chlorin is essentially the same as a porphyrin, but differs from a porphyrin in having one partially saturated pyrrole ring.
  • the basic chromophore of chlorophyll, the green pigment of plant photosynthesis, is a chlorin.
  • a "bacteriochlorin” is essentially the same as a porphyrin, but differs from a porphyrin in having two partially saturated non-adjacent (i.e., trans) pyrrole rings.
  • An “isobacteriochlorin” is essentially the same as a porphyrin, but differs from a porphyrin in having two partially saturated adjacent (i.e., cis) pyrrole rings.
  • porphyrinic pigments into solid-state arrays can afford improvements in solar absorptivity, excitonic energy transduction, charge separation, and electron transfer in organic photovoltaic (OPV) devices.
  • the porphyrinic macrocycle compounds e.g., porphyrins, chlorins, bacteriochlorins
  • NIR near-infrared
  • Advances in synthetic capabilities can enable tunability of electronic structure (including, for instance, control of molecular orbital energy levels and energy gap), incorporation of reactive groups for macroscale organization, and control over solubility to enable low-cost device fabrication procedures.
  • Porphyrinic macrocycles for starting materials in preferred embodiments can be synthesized by methods presented in, for example, U.S. Patent Nos. 6,849,730; 6,603,070; 6,916,982; 6,559,374; 6,765,092; and 6,946,552, herein incorporated by reference in their entirety. Additional references include, for example:
  • Alkylthio Unit as an a-Pyrrole Protecting Group for use in Dipyrromethane Synthesis Thamyongkit, P.; Bhise, A. D.; Taniguchi, M.; Lindsey, J. S. J. Org. Chem. 2006, 71, 903-910.
  • “Investigation of Streamlined Syntheses of Porphyrins Bearing Distinct Meso Substituents Zaidi, S. H. H.; Fico, R., Jr.; Lindsey, J. S. Org. Process Res. Dev. 2006, 10, 118-134.
  • Porphyrinic macrocycle compounds can be bonded or linked covalently to inherently conductive polymers to provide advantages. Since overall photovoltaic efficiency of inherently conductive polymers is limited by insufficient solar absorptivity, the absorptivity of the polymeric system can be enhanced by covalently linking porphyrin macrocyclic units onto the polymer backbone, side groups, or end groups.
  • An additional molecular chromophore can increase the total absorption and afford a direct increase in external quantum efficiency of OPV cells versus control cells lacking the additional chromophore.
  • Molecular architectures with well-defined absorption and hole transport properties can improve the bulk heterojunction between the n- and p-type materials resulting in improved photovoltaic efficiencies.
  • the bandgap of the polymer can be less than that of the excited-state energy of the porphyrinic photosensitizer to facilitate energy transfer will occur. This criterion can be satisfied with porphyrinic macrocycles.
  • Representative molecular design considerations are that (1) energy transfer occurs from photoexcited porphyrinic macrocycle to the polymer, either intramolecularly to the attached polymer, or intermolecularly to polymer in close proximity, without competing electron-transfer quenching, (2) the porphyrinic macrocycle does not serve as a hole trap (i.e., is not readily oxidized), and (3) the appropriate phase segregation of the resulting porphyrin macrocycle-polymer and and n-type component, such as fullerene, still occurs.
  • the oxidation potential of the porphyrinic macrocycle can be tuned by nearly IV by appropriate choice of substituents and metal on the porphyrinic macrocycle.
  • the substituents described herein can provide a combination of variation in oxidation potential and steric encumbrance. Steric encumbrance can be tuned to tailor solubility and distance of approach of neighboring polymer chains.
  • the substituents on the porphyrinic macrocycle can be chosen to tailor energetics and solubility.
  • the electrochemical potential of a given porphyrin can be tuned over quite a wide range by incorporation of electron-withdrawing or electron-releasing substituents (Yang, S. I. et al., J. Porphyrins Phthalocyanines 1999, 3, 117-147).
  • substituents include aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxy, alkylthio, perfluoroalkyl, perfluoroaryl, pyridyl, cyano, thiocyanato, nitro, amino, N-alkylamino, acyl, sulfoxyl, sulfonyl, imido, amido, and carbamoyl.
  • the metal is present. In another embodiment, the metal is not present (metal-free).
  • the central metal of the porphyrinic macrocycle can also be chosen to tailor energetics. With monomeric porphyrinic macrocycle, variation in electrochemical potential can be obtained with different central metals (Fuhrhop, J. -H.; Mauzerall, D. J. Am. Chem. Soc. 1969, 91, 4174-4181).
  • a wide variety of metals can be incorporated in porphyrinic macrocycles. Those metals that are photochemically active include, but are not limited to, Zn, Mg, Al, Sn, Cd, Au, Pd, and Pt. Counterions can be present. Porphyrins generally form very stable radical cations (Felton, R. H. In The Porphyrins; Dolphin, D., Ed.; Academic Press: New York, 1978; Vol. V, pp 53-126).
  • One approach for preparing the conjugates entails reaction of a suitably substituted-porphyrin and a suitably substituted-conductive polymer.
  • One embodiment provides a composition comprising at least one conjugated polymer, at least one porphyrinic macrocycle, wherein the conjugated polymer and porphyrinic macrocycle are bonded or covalently linked to each other. Bonding can be covalent, ionic, dative in character.
  • the conjugated polymer and porphyrinic macrocycle may be bonded directly to one another or they may be bonded through a linker or spacer group.
  • the attachment can be carried out on intact polymers which are singly or doubly end-capped.
  • the attachment can be through covalent bonding including use of linker groups to link together the porphyrinic macrocycle and conjugated polymer.
  • the porphyrinic macrocycle can be bonded to an end group of the conducting polymer or a side group of the conducting polymer.
  • Porphyrinic macrocycles can be attached to one, two, three, four, or more polymer chains. In certain cases, the porphyrinic macrocycles can be attached to one or two polymer chains.
  • the conductive polymer can have from about 1 to about 200 bonds to porphyrinic macrocycles. In certain cases, the conductive polymer has from about 2 to about 100 bonds to porphyrinic macrocycles. In certain cases, the conductive polymer has from about 10 to about 50 bonds to porphyrinic macrocycles.
  • a suitably-substituted porphyrinic macrocycle and a conductive polymer whose backbone comprises a functional group that is able to react with the suitably-substituted porphyrinic macrocycle can be combined.
  • Many reactions are available to perform coupling between a porphyrinic macrocycle and a conductive polymer.
  • the porphyrinic macrocycle and the conductive polymer proper substituents on the compounds facilitate the coupling.
  • a suitable coupling reaction to combine a porphyrinic macrocycle with a conductive polymer can be nucleophilic substitution.
  • reactants for a nucleophilic substitution include compounds with leaving groups such as halo, mesylate, tosylate, haloalkyl, and compounds with nucleophilic groups such as hydroxyl, amino, thiol, hydroxylalkyl, aminoalkyl, and thioalkyl.
  • the halo can be for example bromo.
  • a porphyrinic macrocycle can comprise a leaving group and a conductive polymer can comprise a nucleophilic group.
  • a porphyrinic macrocycle comprises a leaving group
  • at least one of S 1 , S 2 , S 3 , S 4 , S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , S 14 , S 15 , and S 16 of a compound of formula Ia, Ib, and Ic is a leaving group or comprises a leaving group.
  • a porphyrinic macrocycle can comprise a nucleophilic group and a conductive polymer can comprise a leaving group.
  • a porphyrinic macrocycle comprises a leaving group
  • at least one of S 1 , S 2 , S 3 , S 4 , S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , S 14 , S 15 , and S 16 of a compound of formula Ia, Ib, and Ic is a nucleophilic group or comprises a leaving group.
  • the inherently conductive polymer has bonds to the porphyrinic macrocycle derived from or through a functional group on the conductive polymer backbone selected from halo, hydroxyl, amino, thiol, boronic acid, boronate, acyl, formyl, acetyl, carboxylic acid, carboxylate ester, haloalkyl, hydroxylalkyl, aminoalkyl, and thioalkyl.
  • Non-covalent linkages can encompass a variety of molecular interactions including van der Waals forces, hydrogen bonding, and electrostatic forces. The latter include salt formation between ionizable groups.
  • Typical hydrogen-bonding groups include amides, imides, sulfonamides, alcohols with ketones, and the like.
  • FIG 3 which is merely illustrative, shows an example of a coupling reaction of a porphyrinic macrocycle and polymer utilizing nucleophilic substitution.
  • a bromomethyl-substituted porphyrinic macrocycle and a hydroxyalkylthiophene are used to prepare a porphyrinic macrocycle-polymer conjugate.
  • Alteration of the number of bromomethyl groups on the porphyrinic macrocycle results in corresponding designs with attachment to variable number of polymer chains.
  • suitable coupling reactions include organometallic-mediated coupling reactions (e.g., Suzuki coupling, Stille coupling, Heck coupling, Hartwig-Buchwald coupling, Kumada coupling) and more traditional coupling procedures (e.g., Wittig reaction, Williamson ether synthesis), and the like.
  • organometallic-mediated coupling reactions e.g., Suzuki coupling, Stille coupling, Heck coupling, Hartwig-Buchwald coupling, Kumada coupling
  • more traditional coupling procedures e.g., Wittig reaction, Williamson ether synthesis
  • Embodiments provide for a composition
  • a composition comprising a soluble, inherently conductive polymer with at least one bond to a porphyrinic macrocycle through L, wherein the porphyrinic macrocycle comprising a chemical entity selected from Formula Ia, Ib, Ic,
  • K 1 , K 2 , K 3 and K 4 are each independently selected from Se, NH, CH 2 , O, and S; S 1 , S 2 , S 3 , S 4 , S 5 , S 6 , S 7 , S 8 , S 9 , S 10 , S 11 , S 12 , S 13 , S 14 , S 15 , and S 16 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, heterocyclo, heterocycloalkyl, heterocycloalkenyl, heterocycloalkynyl, aryl, aryloxy, arylalkyl, arylalkenyl, arylalkynyl, heteroaryl
  • the metal M can be removed as appropriate.
  • Synthesis can be also carried out so that a spacer group is used to link the porphyrinic macrocycle to the polymer.
  • the spacer group can be based on a carbon chain or a carbon chain also comprising one or more heteroatoms.
  • One or more repeat units can be present. Mixtures of repeat units can be present.
  • spacer group can comprise alkylene or alkyleneoxy units, or propyl eneoxy units, including for example spacer groups with two to 50 carbon atoms, or three to 25 carbon atoms.
  • the porphyrinic macrocycle may be incorporated into a monomer or comonomer prior to polymerization by, for example, organometallic mediated coupling reactions.
  • the porphornic macrocycle may be incorporated into the backbone of the polymer or copolymer chain. Alternatively, it may be attached to the backbone of the chain, optionally through a spacer group. The attachment can be through covalent bonding of suitably substituted porphyrinic macrocycle and the remainder of the monomer or comonomer, which is also suitably substituted.
  • suitably substituted thiophene may be reacted with a suitably substituted porphyrinic macrocycle P and subsequently brominated to produce a comonomer:
  • R is a spacer group with two to 50 carbons, or three to 25 carbons.
  • a copolymer may comprise alternating donor and acceptor segments. Porphyrinic macrocycles may be incorporated into either or both types of segments. Such copolymers may be constructed using a variety of polymerization methods. For example, in some embodiments, such copolymers may be polymerized using organometallic mediated coupling reactions, sometimes referred to as Ullmann reactions. For example, each donor segment might be functionalized with two active groups (AGs), such as Sn(R) 3 , ZnX 2 , MgX 2 , B(OR) 2 , X, or silyl, where R represents an alkyl moiety and X represents a halogen or pseudohalogen moiety, and each acceptor segment functionalized with two halide groups.
  • AGs active groups
  • Suitable halogen or pseudohalogen moieties may comprise I, F, Br, Cl, or triflate. Subjecting these segments to such coupling reactions as Stille, Negishi, Suzuki, or the like, results in a copolymer comprising alternating donor and acceptor segments. Such reactions are described in the following references, each of which is incorporated by reference in its entirety: Cross-Coupling Reactions: A Practical Guide, Ed. Miyaura, 2002; Handbook of Organopalladium Chemistry for Organic Synthesis, Ed. Negishi, 2002; Kuwano, R, Utsunomiya, M., Hartwig, J. F., J. Org. Chem., 2002, 67, 6479-6486; Yu et al, J. Am. Chem.
  • a porphyrinic macrocycle may itself be an acceptor segment, if it is first suitably functionalized. Examples include dibromophenylporphyrin, mesodibromoporhyrin, ⁇ -dibromopophyrin, and the like.
  • additional sidegroups may be added to a porphyrinic macrocycle to improve solubility or to provide steric shielding to aid in subsequent processing. Examples of such side groups include alkyl or branched alkyl moieties. Such steric shielding may be beneficial in devices and compositions incorporating fullerene compositions. See, e.g., P.D. Boyd and CA. Reed, Ace. Chem. Res., 2005, 38, 235, which is incorporated by reference in its entirety.
  • a porphyrinic macrocycle may be a portion of a larger segment.
  • the porphyrinic macrocycle may be located so that it will be in the backbone of a copolymer incorporating its segment. Alternatively, it may be located so that it will be pendant to the backbone of the chain. Use of both types of segments can result in a copolymer with porphyrinic macrocycles both in the backbone and pendant to the backbone of the chain.
  • Still another embodiment is a segment comprising more than one porphyrinic macrocycle, so at least one is located so that it will be in the backbone and at least one will be located so that it will be pendant to the backbone of the chain.
  • Steric shielding of the porphyrinic macrocycle may be provided by substituents on neighboring portions of the copolymer chain, preferably within the same segment as the macrocycle.
  • Non- limiting examples of segments comprising porphyrinic macrocycles follow.
  • a box enclosing the letter "P" represents a porphyrinic macrocycle.
  • R and R' may be alkyl or branched alkyl moieties. Where alkyl or branched alkyl substituents are depicted, the length of such side chains may vary from about two to about 50 carbons. Similarly the number of branches on such a subsituent may vary from none to about five. Unlabeled bonds represent connections to adjacent segments or copolymer endgroups.
  • porphyrinic building blocks and various multicomponent architectures can be performed on the porphyrinic building blocks and various multicomponent architectures, including the porphyrinic macrocycle- polymer conjugated materials.
  • Studies include, for example: (1) static absorption and emission spectroscopies; (2) resonance Raman spectroscopy; (3) electron paramagnetic resonance (EPR) spectroscopy (of paramagnetic species); (4) x-ray photoelectron (XPS) and infrared (IR) spectroscopy of surface-bound species; (5) electrochemical measurements; and (6) density functional theory (DFT) calculations.
  • static absorption and emission spectroscopies include, for example: (1) static absorption and emission spectroscopies; (2) resonance Raman spectroscopy; (3) electron paramagnetic resonance (EPR) spectroscopy (of paramagnetic species); (4) x-ray photoelectron (XPS) and infrared (IR) spectroscopy of surface-bound species; (5) electrochemical measurements; and (6)
  • One structure to utilize directed energy flow is active layers based on porphyrinic macrocycle/polymer conjugates. These materials can be characterized in sandwich cells where the active layer comprises: (1) the active porphyrinic macrocycle/polymer conjugate; and (2) mixed nanoscale morphologies including phase segregated polymer/fullerene blends.
  • This cell takes advantage of the high molecular absorptivity of the porphyrinic macrocycle, and enables excitons produced upon light absorption from the porphyrinic macrocycle to be directed to the polymer.
  • An energy diagram of this system can be described. The absorptivity of a wider gap porphyrinic macrocycle is larger than the polymer at the same energy, increasing the net absorbance.
  • the wider gap material is shown behind the polymer to indicate that it serves primarily as a pathway for photon capture and exciton delivery to the polymer, which then makes contacts to the electron acceptor and anode electrodes (as in a typical bilayer cell).
  • Combining high absorptivity porphyrinic monomers with lower gap polymers to achieve broader solar spectral coverage can be used for future low cost polymer cells.
  • ITO indium tin oxide
  • Other anode materials can include for example metals, such as Au, carbon nanotubes, single or multiwalled, and other transparent conducting oxides.
  • the resistivity of the anode can be maintained below for example 15 ⁇ /sq or less, 25 or less, 50 or less, or 100 or less.
  • the substrate can be for example glass, plastics (PTFE, polysiloxanes, thermoplastics, PET, PEN and the like), metals (Al, Au, Ag), metal foils, metal oxides, (TiOx, ZnOx) and semiconductors, such as Si.
  • the ITO on the substrate can be cleaned using techniques known in the art prior to device layer deposition.
  • An optional hole injection layer (HIL) and/or hole transport layer (HTL) can be added using for example spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method.
  • the HIL can be for example poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4- ethylenedioxythiophene)poly(styrenesulfonate) PEDOT/PSS or N,N'-diphenyl-N,N'- bis(3-methylphenyl)-l,l '-biphenyl-4,4'-diamine (TBD), or N,N'-diphenyl-N,N'-bis(l- napthylphenyl)-l,l '-biphenyl-4,4' -diamine (NPB), or Plexcore HIL (Plextronics, Pittsburgh, PA).
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • PEDOT/PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) PEDOT/PSS or N,N'-diphenyl-N,N'- bis(3
  • the thickness of the HIL layer can be for example from 10 nm to 300 nm thick, or from 30 nm to 60 nm, or 60 nm to 100 nm, or 100 nm to 200 nm.
  • the film then can be optionally dried/annealed at 110 to 200 0 C for 1 min to an hour, optionally in an inert atmosphere.
  • the active layer can be formulated from a mixture of n-type and p-type materials.
  • the n- and p-type materials can be mixed in a ratio of for example from about 0.1 to 4.0 (p-type) to about 1 (n-type) based on a weight, or from about 1.1 to about 3.0 (p-type) to about 1 (n-type) or from about 1.1 to about 1.5 (p-type) to about 1 (n-type).
  • the amount of each type of material or the ratio between the two types of components can be varied for the particular application.
  • the n- and p-type materials can be mixed in a solvent at for example from about 0.01 to about 0.1% volume solids.
  • the solvents useful for the presently claimed inventions can include, for example, halogenated benzenes, alkyl benzenes, halogenated methane, and thiophenes derivatives, and the like. More specifically, solvent can be for example chlorobenzene, dichlorobenzene, xylenes, toluene, chloroform, and mixtures thereof.
  • the active layer can be then deposited by spin casting, ink jetting, doctor blading, spray casting, dip coating, vapor depositing, or any other known deposition method, on top of the HIL film.
  • the film is then optionally annealed at for example about 40 to about 250 0 C, or from about 150 to 180 0 C, for about 10 min to an hour in an inert atmosphere.
  • a cathode layer can be added to the device, generally using for example thermal evaporation of one or more metals. For example, a 1 to 15 nm Ca layer is thermally evaporated onto the active layer through a shadow mask, followed by deposition of a 10 to 300 nm Al layer.
  • an optional interlayer may be included between the active layer and the cathode, and/or between the HTL and the active layer .
  • This interlayer can be for example from 0.5 nm to about 100 nm, or from about 1 to 3 nm, thick.
  • the interlayer can comprise an electron conditioning, a hole blocking, or an extraction material such as LiF, BCP, bathocuprine, fullerenes or fullerene derivatives, such as C60 and other fullerenes and fullerene derivatives discussed herein.
  • the devices can be then encapsulated using a glass cover slip sealed with a curable glue, or in other epoxy or plastic coatings. Cavity glass with a getter/desiccant may also be used.
  • the active layer can comprise additional ingredients including for example surfactants, dispersants, and oxygen and water scavengers.
  • the active layer can comprise multiple layers or be multi-layered.
  • the active layer composition can comprise a mixture in the form of a film.
  • Electrodes including anodes and cathodes, are known in the art for photovoltaic devices. Known electrode materials can be used. Transparent conductive oxides can be used. Transparency can be adapted for a particular application.
  • the anode can be indium tin oxide, including ITO supported on a substrate. Substrates can be rigid or flexible.
  • the active layer can form a P/N composite including nanoscale phase separated structures and bulk heterojunction. See for example discussion of nanoscale phase separation in bulk heteroj unctions in Dennler et al, "Flexible Conjugated Polymer-Based Plastic Solar Cells: From Basics to Applications," Proceedings of the IEEE, vol. 93, no. 8, August 2005, 1429-1439. Conditions and materials can be selected to provide for good film formation, low roughness (e.g., 1 nm RMS), and discrete, observable, phase separation characteristics can be achieved.
  • the present invention can have phase separated domains on a scale of about 5 to 50 nm as measured by AFM. AFM analysis can be used to measure surface roughness and phase behavior. In general, phase separated domains are not desirable so that both donor and acceptor are uniformly and continuously distributed in the active layer.
  • Known solar cell parameters can be measured including for example Jsc (mA/cm ) and Voc (V) and fill factor and efficiency (%) by methods known in the art.
  • the efficiency can be, for example, at least 1.0%, or at least 1.5%, or at least 2.0%, or at least 2.5%, or at least 3.0%, or at least 3.5%, or at least 4%, or at least 4.5%, or at least 5.0%, or at least 5.5%, or at least 6.0%.
  • the fill factor can be, for example, at least about 0.3, or at least about 0.4, or at least about 0.5, or at least about 0.60, or at least about 0.63, or at least about 0.67.
  • the Voc (V) can be at least about 0.56, or at least about 0.63, or at least about 0.82.
  • the Jsc (mA/cm ) can be at least about 4, or at least about 5, or at least about 6, or at least about 7, or at least about 8, or at least about 8.92, or at least about 9.20, or at least about 9.48.
  • An example of device structure is:
  • Examples of performance which can be achieved under unoptimized conditions include, for example:
  • the efficiency can be measured for a device comprising an active layer comprising a fullerene adduct and the efficiency compared to efficiency for a control including a substantially analogous device but wherein the active layer comprises poly(3- hexylthiophene)-PCBM.
  • An increase in efficiency can be determined and measured to be at least about 5%, or at least about 10%, or at least about 15%, or at least about 20%, or at least about 25%, or at least about 30%, or at least about 35%, or at least about 40%, or at least about 45%, or at least about 50%.
  • Methods are also providing for making the devices and using the devices.
  • Known methods for printing, depositing, and patterning layers can be used including solution or vacuum based methods.
  • Ink compositions can be formulated comprising a carrier or solvent system for the polymer and when present the n-acceptor.

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Abstract

La présente invention concerne des compositions comprenant des macrocycles porphyriniques et des polymères conjugués destinées à être utilisées dans des dispositifs électroniques organiques y compris des cellules solaires. La liaison covalente d'un macrocycle porphyrinique à un polymère ou l'incorporation d'un macrocycle porphyrinique dans un polymère permet d'ajuster les propriétés électroniques et spectroscopiques des polymères conjugués et peut améliorer la stabilité thermique du système comparativement à un système mixte. La présente invention porte également sur des compositions, des dispositifs et des procédés.
PCT/US2010/037805 2009-06-08 2010-06-08 Compositions de porphyrine et de polymère conducteur destinées à être utilisées dans des dispositifs électroniques à semi-conducteurs WO2010144472A2 (fr)

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EP2682996A1 (fr) * 2011-03-03 2014-01-08 Kinki University Photopile en couches minces
EP2682996A4 (fr) * 2011-03-03 2014-08-06 Univ Kinki Photopile en couches minces

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