WO2014026244A1 - Dispositifs optoélectroniques photoactifs et à transistors - Google Patents

Dispositifs optoélectroniques photoactifs et à transistors Download PDF

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WO2014026244A1
WO2014026244A1 PCT/AU2013/000914 AU2013000914W WO2014026244A1 WO 2014026244 A1 WO2014026244 A1 WO 2014026244A1 AU 2013000914 W AU2013000914 W AU 2013000914W WO 2014026244 A1 WO2014026244 A1 WO 2014026244A1
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optionally substituted
independently selected
group
photoactive
formula
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Kevin Norman Winzenberg
Kimmo Petteri Kemppinen
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Commonwealth Scientific And Industrial Research Organisation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains three hetero rings
    • C07D513/14—Ortho-condensed systems

Definitions

  • the present invention relates to photoactive optoelectronic devices, such as organic photovoltaic devices, and transistor devices, and to organic compounds for use in the optoelectronic and transistor devices.
  • the present invention also relates to processes for preparing photoactive optoelectronic and transistor devices.
  • Photoactive optoelectronic devices include organic photovoltaic devices (OPVs), which are also referred to as organic solar cells, and photosensors where the device signals the detection of particular wavelengths of electromagnetic radiation.
  • Photovoltaic devices include heteroj unction and bilayer organic photovoltaic cells, and hybrid solar cells.
  • OPVs come with the promise of efficient conversion of sunlight into direct usable electrical energy at a much lower cost than the traditional silicon based solar cells.
  • OPVs contain a combination of electron acceptor materials (n-type
  • Dissociation of the bound electron-hole pair is facilitated by the interface between the electron donor and electron acceptor materials.
  • the separated holes and electrons travel towards respective electrodes and consequently generate a voltage potential at the electrodes.
  • OPVs are heteroj unction devices that involve the use of poly 3-hexylthiophene (P3HT) as an example of a polymeric organic material used as the electron donor material, together with a fullerene derivative as the electron acceptor material.
  • the two materials may be present as layers, forming a bilayer photovoltaic cell, or may be present as a blend, forming a bulk heterojunction photovoltaic cell.
  • P3HT poly 3-hexylthiophene
  • the two materials may be present as layers, forming a bilayer photovoltaic cell, or may be present as a blend, forming a bulk heterojunction photovoltaic cell.
  • the donor material (or p-type conductor) and acceptor material (n-type conductor) are presented in a blend in the active (specifically, photoactive) layer of a device, and the concentration of each component often gradually increases when approaching the corresponding electrode. This provides an increase in the total surface area of the junctions between the materials and facilitates dissoci
  • Fullerenes have been optimised for use in solar cells providing power conversion efficiencies in the range 3 to 10% when combined with selected commercial and experimental electron donor materials. Fullerenes tend to be poor at harvesting visible sunlight, and are difficult to synthesize and purify. In principle small molecule electron acceptor compounds are cheap, easy to synthesize and purify, but it has proven difficult to discover compounds of this type that can be used to fabricate OPV devices with efficient power conversion efficiencies.
  • Organic transistors are promising candidates for application in integrated circuits, sensors and displays. Practical exploitation of organic electronic circuitry requires the use of both p-channel transistors, which are fabricated from electron donor materials, and n-channel transistors, which are fabricated from electron acceptor materials, to produce complementary circuits, which show greater speed, reliability and stability than those of unipolar circuits. Whereas much progress has been made in the discovery of electron donor semiconductors for use in transistors, the development of high-performance, ambient-stable electron acceptor semiconductors has lagged far behind, particularly as far as solution-processable electron acceptor semiconductors are concerned (Advanced Materials, 2010, 22, 1331-1345).
  • organic compounds in particular electron acceptor or n-type semiconductor compounds, that can be used in photoactive optoelectronic devices, such as OPV heterojunction devices, or transistor devices.
  • a photoactive optoelectronic device comprising:
  • the light-absorbing electroactive layer comprises an electron donor material and an electron acceptor material, the electron acceptor material comprising a com stereoisomers thereof:
  • D is a conjugated group that provides at least one conjugated pathway between at least two terminal groups and which is selected from one or more optionally substituted, optionally fused, rings provided that at least one of the rings is aromatic; n is an integer of 2 to 20;
  • A is independently selected for each terminal group from an optionally substituted 5, 6 or 7 membered carbocyclic or heterocyclic ring, which is optionally fused with one or more aryl or heteroaryl rings;
  • X 1 is independently selected for each terminal group from O, S and CR 1 R 2 , wherein R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from optionally substituted d-Ci 0 alkyl, optionally substituted C 2 -Ci 0 alkenyl, optionally substituted C 2 -Ci 0 alkynyl, optionally substituted aryl and arylCi-Ci 0 alkyl.
  • the photoactive optoelectronic device generates an electrical current in response to electromagnetic radiation.
  • An example of this class of device is an organic photovoltaic device (OPV), which is also referred to as an organic solar cell.
  • OCV organic photovoltaic device
  • This type of device may be a heterojunction OPV, bilayer OPV or hybrid solar cell (OSC).
  • Another type of device is a photosensor where the device signals the detection of particular wavelengths of electromagnetic radiation.
  • the organic OPV device is a bulk heterojunction OPV device.
  • a transistor device comprising:
  • the gate electrode, the gate insulating layer, the source and drain electrodes, and the channel-forming region being disposed on a base, and wherein the channel- forming region comprises an electron acceptor material comprising a compound according to Formula 1 or stereoisomers thereof:
  • D is a conjugated group that provides at least one conjugated pathway between at least two terminal groups and which is selected from one or more optionally substituted, optionally fused, rings provided that at least one of the rings is aromatic; n is an integer of 2 to 20;
  • A is independently selected for each terminal group from an optionally substituted 5, 6 or 7 membered carbocyclic or heterocyclic ring, which is optionally fused with one or more aryl or heteroaryl rings;
  • X 1 is independently selected for each terminal group from O, S and CR 1 R 2 , wherein R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from optionally substituted d-Ci 0 alkyl, optionally substituted C 2 -Ci 0 alkenyl, optionally substituted C 2 -Ci 0 alkynyl, optionally substituted aryl and arylCi-Ci 0 alkyl.
  • the compounds of Formula 1 comprise at least two terminal groups separated by the conjugated group D.
  • the integer n may be any integer of 2 to 10. In one embodiment, n is an integer of 2 or 4.
  • a compound of Formula 1 is provided as follows:
  • A, X and D are as described in the first or second aspect above, or embodiments described herein.
  • A, X and D are as described in the first or second aspect above, or embodiments described herein.
  • an electron acceptor material comprising a compound according to Formula 1 described above or a stereoisomer thereof.
  • the electron acceptor material can be used as an n-type semiconductor material.
  • An electron donor material which can be used as a p-type semiconductor, can be associated with the electron acceptor material to provide an active material for a photoactive optoelectronic device.
  • an active material for use in a photoactive optoelectronic device wherein the active material comprises an electron donor material and an electron acceptor material comprising a compound according to Formula 1 as described herein.
  • the active material is photoactive, and may for example be suitable for use in an OPV device.
  • the association of the electron donor and electron acceptor material may be layered or mixed, for example provided as a bilayer or bulk heterojunction.
  • the electron donor material is P3HT.
  • n is an integer of 2 to 20;
  • X 1 is independently selected for each terminal group from O, S and CR 1 R 2 ;
  • n is an integer selected from 0, 1 and 2;
  • R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from optionally substituted d-Ci 0 alkyl, optionally substituted C 2 -Ci 0 alkenyl, optionally substituted C 2 -Ci 0 alkynyl, optionally substituted aryl and arylCi-Ci 0 alkyl; and
  • R 4 and R 5 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 haloalkyl, optionally substituted C C 20 alkylamino, optionally substituted C 3 -C 20 cycloalkyl, optionally substituted C 2 - C 20 alkenyl, optionally substituted C 3 -C 20 cycloalkenyl, optionally substituted C 2 - C 20 alkynyl, optionally substituted C 3 -C 20 cycloalkynyl, optionally substituted aryl and arylCrC 20 alkyl.
  • D is a conjugated group that provides at least one conjugated pathway between at least two terminal groups and which is selected from one or more optionally substituted, optionally fused, rings provided that at least one of the rings is aromatic, and which is selected from a grou ula 3
  • p is independently selected from an integer of 0 to 15;
  • Z 1 is independently selected from O, S, Se, S0 2 , NR 12 , CR 12 R 13 and
  • SiR 12 R Z 2 and Z 3 are each independently selected from N and CR 12 ;
  • Ar is selected from an optionally substituted, optionally fused, aryl or heteroaryl group
  • X 1 and X 2 are O or C(CN) 2
  • p is 0, and Ar is selected from optionally substituted, optionally fused, thiophene groups, then at least two thiophene groups are fused together;
  • X 1 and X 2 are O or C(CN) 2
  • p is at least 1
  • each Z 1 is S
  • each Z 2 and Z 3 are CH
  • Ar is selected from optionally substituted, optionally fused, thiophene groups, then at least two thiophene groups are fused together;
  • n may be any integer of 2 to 20, such as an integer of 2 to 10.
  • n may be any integer of 2 to 20, such as an integer of 2 to 10.
  • a compound of Formula 2 is provided as follows:
  • p 1 and p 2 are each independently selected from an integer of 0 to 15, and Ar, Z 1 , Z 2 and Z 3 , are each independently selected from the groups as described in the fourth aspect above, or embodiments described herein; and for each terminal group A, X 1 , L, E 1 , E 2 , G and m, are each independently selected from the groups as described in the fourth aspect above, or embodiments described herein.
  • p 1 , p 2 , p 3 and p 4 are each independently selected from an integer of 0 to 15, and Ar, Z 1 , Z 2 and Z 3 , are each independently selected from the groups as described in the fourth aspect above, or embodiments described herein; and for each terminal group A, X 1 , L, E 1 , E 2 , G and m, are each independently selected from the groups as described in the fourth aspect above, or embodiments described herein.
  • n is an integer of 2 to 20, and therefore the compounds of Formula 1 comprise at least two terminal groups A.
  • n is an integer of 2 to 10.
  • n is an integer of 2 to 4.
  • n is 2 or 4.
  • X is O.
  • A may be an optionally substituted, optionally fused, 5, 6 or 7 membered heterocyclic ring, wherein the heteroatoms of the heterocyclic ring may be selected from O, N and S.
  • A may be an optionally substituted, optionally fused, 5, 6 or 7 membered carbocyclic ring.
  • the A ring may be optionally fused, such as fused with a monocyclic aromatic group, for example benzene, or fused with a polycyclic aromatic group containing 2 to 4 aryl rings, for example naphthalene and anthracene, or fused with an aromatic heterocyclic ring system containing 1 to 4 rings, for example quinazoline and acridine.
  • the fused ring systems may each be optionally substituted.
  • the conjugated group D provides a conjugated ⁇ bond system that has at least one conjugated pathway between at least two terminal groups A.
  • the conjugated group D may be one or more optionally substituted, optionally fused, rings joined or fused together to provide the conjugated ⁇ bond system.
  • the D group may be selected from one or more optionally substituted, optionally fused, aryl and heteroaryl groups that are joined or fused together to provide the conjugated pathway.
  • the D group may have from 5 to 100 ring atoms, from 5 to 60 ring atoms, from 5 to 50 ring atoms, from 5 to 30 ring atoms, or from 5 to 20 ring atoms.
  • the D group may consist of at least 2 aromatic rings, at least 4 aromatic rings, or at least 6 aromatic rings.
  • the D group may consist of 20 aromatic rings or less, 15 aromatic rings or less, or 10 aromatic rings or less.
  • the D group may consist of any number or range of aromatic rings selected from the following: 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15.
  • the optionally substituted, optionally fused, aryl and heteroaryl groups may be formed from one or more 5, 6 or 7 membered rings.
  • the D group may include optionally substituted, optionally fused, carbocyclic or heterocyclic groups.
  • the D group is one or more optionally substituted, optionally fused, aryl groups.
  • the optionally substituted aryl groups may be monocyclic or polycyclic.
  • the optionally substituted monocyclic aryl groups may be a 6 membered ring, such as optionally substituted benzene.
  • the optionally substituted polycyclic aryl groups may be two or more 6-member rings fused together, such as naphthalene, anthracene, pyrene, tetracene, and pentacene, which may each be optionally substituted.
  • the optionally substituted polycyclic aryl groups may be two or more 6 member rings joined together, such as biphenyl, or two or more fused rings that are joined together, such as fluorene and perylene, and which may each be optionally substituted.
  • the D group is selected from one or more optionally substituted, optionally fused, heteroaryl groups.
  • the optionally substituted heteroaryl groups may be monocyclic or polycyclic.
  • the optionally substituted heteroaryl groups may be selected from 5-membered monocyclic rings, such as thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, or 6 membered rings, such as pyridine and triazine, which may each be optionally substituted.
  • the heteroaryl groups may be polycyclic rings, which may contain fused or joined aryl groups, such as benzothiadiazole and carbazole, and which may be each optionally substituted.
  • the D group may consist of optionally substituted aryl and heteroaryl groups as described above that may be joined or fused together to provide a conjugated ⁇ bond system. ln one particular embodiment, the D group has 5 to 100 ring atoms formed from one or more groups selected from benzene, naphthalene, thiophene, furan, biphenyl and fluorene, that are joined or fused together to provide the conjugated ⁇ bond system, and wherein each group may each be optionally substituted.
  • the D group, or any groups thereof, may be substituted as herein described with one or more optional substituents.
  • the optional substituents of the D group may be selected from halogen, cyano, CrC 20 alkyl, CrC 20 haloalkyl, d-C ⁇ oalkylamino, C 3 - C 2 ocycloalkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkynyl, C C 20 alkylsilyl, C 2 -C 20 alkenylsilyl, C 2 -C 20 alkynylsilyl, aryl, arylC r 2oalkyl, heteroaryl and i o heteroaryld-2oalkyl. and wherein alkyl, haloalkyl, alkylamino, cycloalkyl, alkenyl,
  • cycloalkenyl, alkynyl, cycloalkynyl, alkylsilyl, alkenylsilyl, alkynylsilyl, aryl, heteroaryl, arylalkyl and heteroarylalkyl, in each occurrence may be optionally substituted.
  • the substituents are selected from C 4 _i 2 alkyl and C 4 _i 2 cycloalkyl.
  • a process for preparing a thin film component 15 for a photoactive optoelectronic device comprising the steps of:
  • the depositing of the solution is by spin coating.
  • a process for preparing a thin film 25 component comprising an electron acceptor material selected from one or more of the compounds as described in the above aspects and embodiments thereof for a photoactive optoelectronic device, the process comprising the step of vapour deposition of one or more of the compounds onto a substrate.
  • a process for preparing a thin film 30 component for a transistor device comprising the steps of:
  • the depositing of the solution is by spin coating.
  • the organic solvent for the above aspects may be selected from chloroform, tetrachloroethane, tetrahydrofuran, toluene, tetrahydronaphthalene, anisole, xylene, mesitylene, ethyl acetate, methyl ethyl ketone, dimethyl formamide, chlorobenzene, dichlorobenzene, trichlorobenzene and propylene glycol monomethyl ether acetate (PGMEA).
  • a process for preparing a thin film component comprising an electron acceptor material selected from one or more of the compounds as described in the above aspects and embodiments thereof for a transistor device, the process comprising the step of vapour deposition of one or more of the compounds onto a transistor substrate.
  • a process for preparing the compounds as described herein according to any one of the synthetic schemes described herein comprising the step of reacting n terminal groups of:
  • conjugated group D selected from at least one of (Ar)-Ln and
  • X 1 , A, Ar, n, p, Z 1 , Z 2 and Z 3 are as defined herein, and L is a group selected from halo, aldehyde and dioxaborinane, to form a compound according of Formula 1.
  • Figure 1 shows a general configuration of a bilayer organic solar cell device according to one embodiment of the invention
  • Figure 2 shows a general configuration of a bulk heteroj unction organic solar cell device according to one embodiment of the invention
  • Figures 3, 4 & 5 show l-V curves from testing of solar cell devices according to embodiments on the invention
  • Figure 6 shows bottom gate/top contact transistor architecture with a surface treatment applied to the dielectric layer, according to one embodiment of the invention.
  • Figures 7 and 8 show the output and transfer curves respectively for transistor device Example 1.
  • the present invention is described in the following various non-limiting embodiments, which relate to investigations undertaken to identify organic compounds for advantageous use as semiconductor materials in photoactive optoelectronic devices. It was surprisingly found that a range of organic compounds are useful as semiconductors materials in photoactive optoelectronic and transistor devices, and in particular as n-type semiconductors, which may be provided by the electron acceptor materials as described herein. TERMS
  • conjugated refers to a molecule having two or more double and/or triple bonds in sequence, each double or triple bond being separated from the next consecutive double or triple bond by a single bond so that ⁇ orbitals overlap not only across the double or triple bond, but also across adjacent single bonds located between adjacent double and/or triple bonds.
  • an aromatic group means a cyclic group having 4 m+2 ⁇ electrons, where m is an integer equal to or greater than 1.
  • aromatic is used interchangeably with “aryl” to refer to an aromatic group, regardless of the valency of aromatic group.
  • aryl refers to monovalent aromatic groups, bivalent aromatic groups and higher multivalency aromatic groups.
  • joind refers to a ring, moiety or group that is joined to at least one other ring, moiety or group by a single covalent bond.
  • fused refers to one or more rings that share at least two common ring atoms with one or more other rings.
  • a heteroaromatic group is an aromatic group or ring containing one or more heteroatoms, such as N, O, S, Se, Si or P.
  • heteroaryl is used interchangeably with “heteroaryl”
  • a heteroaryl group refers to monovalent aromatic groups, bivalent aromatic groups and higher multivalency aromatic groups containing one or more heteroatoms.
  • substitution means that a functional group is either substituted or unsubstituted, at any available position. Substitution can be with one or more functional groups selected from, e.g., alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl, formyl, alkanoyl, cycloalkanoyl, aroyl, heteroaroyl, carboxyl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, heteroaryloxycarbonyl, alkylaminocarbonyl,
  • heteroarylaminocarbonyl cyano, alkoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, alkanoate, cycloalkanoate, aryloate, heterocyclyloate, heteroaryloate, alkylcarbonylamino, cycloalkylcarbonylamino, arylcarbonylamino,
  • haloheterocyclyl haloheteroaryl, haloalkoxy, haloalkylsulfonyl, silylalkyl, alkenylsilylalkyl, and alkynylsilylalkyl. It will be appreciated that other groups not specifically described may also be used.
  • Alkyl whether used alone, or in compound words such as alkoxy, alkylthio, alkylamino, dialkylamino or haloalkyl, represents straight or branched chain
  • alkyl moieties include, unless explicitly limited to smaller groups, moieties ranging in size, for example, from one to about 6 carbon atoms or greater, such as, methyl, ethyl, n- propyl, iso-propyl and/or butyl, pentyl, hexyl, and higher isomers, including, e.g., those straight or branched chain hydrocarbons ranging in size from about 6 to about 20 carbon atoms, or greater.
  • Alkenyl whether used alone, or in compound words such as alkenyloxy or haloalkenyl, represents straight or branched chain hydrocarbons containing at least one carbon-carbon double bond, including, unless explicitly limited to smaller groups, moieties ranging in size from two to about 6 carbon atoms or greater, such as, methylene, ethylene, 1-propenyl, 2-propenyl, and/or butenyl, pentenyl, hexenyl, and higher isomers, including, e.g., those straight or branched chain hydrocarbons ranging in size, for example, from about 6 to about 20 carbon atoms, or greater.
  • Alkynyl represents straight or branched chain hydrocarbons containing at least one carbon- carbon triple bond, including, unless explicitly limited to smaller groups, moieties ranging in size from, e.g., two to about 6 carbon atoms or greater, such as, ethynyl, 1- propynyl, 2-propynyl, and/or butynyl, pentynyl, hexynyl, and higher isomers, including, e.g., those straight or branched chain hydrocarbons ranging in size from, e.g., about 6 to about 20 carbon atoms, or greater.
  • Cycloalkyl represents a mono- or polycarbocyclic ring system of varying sizes, e.g., from about 3 to about 20 carbon atoms, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
  • the term cycloalkyloxy represents the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • cycloalkylthio represents the same groups linked through a sulfur atom such as cyclopentylthio and cyclohexylthio.
  • Cycloalkenyl represents a non-aromatic mono- or polycarbocyclic ring system, e.g., of about 3 to about 20 carbon atoms containing at least one carbon-carbon double bond, e.g., cyclopentenyl, cyclohexenyl or cycloheptenyl.
  • cycloalkenyloxy represents the same groups linked through an oxygen atom such as cyclopentenyloxy and cyclohexenyloxy.
  • cycloalkenylthio represents the same groups linked through a sulfur atom such as cyclopentenylthio and cyclohexenylthio.
  • Carbocyclic and “carbocyclyl” represent a ring system wherein the ring atoms are all carbon atoms, e.g., of about 3 to about 20 carbon atoms, and which may be aromatic, non-aromatic, saturated, or unsaturated, and may be substituted and/or carry fused rings. Examples of such groups include benzene, cyclopentyl, cyclohexyl, or fully or partially hydrogenated phenyl, naphthyl and fluorenyl.
  • Aryl whether used alone, or in compound words such as arylalkyl, aryloxy or arylthio, represents: (i) an optionally substituted mono- or polycyclic aromatic carbocyclic moiety, e.g., of about 6 to about 100 carbon atoms, such as phenyl, naphthyl or fluorenyl; or, (ii) an optionally substituted partially saturated polycyclic carbocyclic aromatic ring system in which an aryl and a cycloalkyl or cycloalkenyl group are fused together to form a cyclic structure such as a tetrahydronaphthyl, indenyl jndanyl or fluorene ring.
  • Heterocyclyl or “heterocyclic” whether used alone, or in compound words such as heterocyclyloxy represents: (i) an optionally substituted cycloalkyl or cycloalkenyl group, e.g., of about 3 to about 100 ring members, which may contain one or more heteroatoms such as nitrogen, oxygen, or sulfur (examples include pyrrolidinyl, morpholino, thiomorpholino, or fully or partially hydrogenated thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, oxazinyl, thiazinyl, pyridyl and azepinyl); (ii) an optionally substituted partially saturated polycyclic ring system in which an aryl (or heteroaryl) ring and a heterocyclic group are fused together to form a cyclic structure (examples include chromanyl, dihydrobenzofuryl and indolinyl);
  • Heteroaryl or “hetaryl” whether used alone, or in compound words such as heteroaryloxy represents: (i) an optionally substituted mono- or polycyclic aromatic organic moiety, e.g., of about 5 to about 20 ring members in which one or more of the ring members is/are element(s) other than carbon, for example nitrogen, oxygen, sulfur or silicon; the heteroatom(s) interrupting a carbocyclic ring structure and having a sufficient number of delocalized pi electrons to provide aromatic character, provided that the rings do not contain adjacent oxygen and/or sulfur atoms.
  • Typical 6-membered heteroaryl groups are pyrazinyl, pyridazinyl, pyrazolyl, pyridyl and pyrimidinyl. All regioisomers are contemplated, e.g., 2-pyridyl, 3-pyridyl and 4-pyridyl.
  • Typical 5- membered heteroaryl rings are furyl, imidazolyl, oxazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, pyrrolyl, 1 ,3,4-thiadiazolyl, thiazolyl, thienyl, triazolyl, and silole.
  • Bicyclic groups typically are benzo-fused ring systems derived from the heteroaryl groups named above, e.g., benzofuryl, benzimidazolyl, benzthiazolyl, indolyl, indolizinyl, isoquinolyl, quinazolinyl, quinolyl and benzothienyl; or, (ii) an optionally substituted partially saturated polycyclic heteroaryl ring system in which a heteroaryl and a cycloalkyi or cycloalkenyl group are fused together to form a cyclic structure such as a tetrahydroquinolyl or pyrindinyl ring.
  • Forml represents a -CHO moiety.
  • One example is acyl.
  • Examples include benzoyl and 1-naphthoyl and 2-naphthoyl.
  • a heteroaroyl ranges in size from about C6"C 2 o.
  • An example is pyridylcarbonyl.
  • Carboxyl represents a -C0 2 H moiety.
  • Oxycarbonyl represents a carboxylic acid ester group -C0 2 R which is linked to the rest of the molecule through a carbon atom.
  • Alkoxycarbonyl represents an -C0 2 -alkyl group in which the alkyl group is as defined supra. In a particular embodiment, an alkoxycarbonyl ranges in size from about C 2 -C 20 . Examples include methoxycarbonyl and ethoxycarbonyl.
  • Aryloxycarbonyl represents an -C0 2 -aryl group in which the aryl group is as defined supra. Examples include phenoxycarbonyl and naphthoxycarbonyl.
  • Heterocyclyloxycarbonyl represents a -C0 2 -heterocyclyl group in which the heterocyclic group is as defined supra.
  • Heteroaryloxycarbonyl represents a -CO-heteroaryl group in which the heteroaryl group is as defined supra.
  • NR 2 is a heterocyclic ring, which is optionally substituted.
  • NR 2 is a heteroaryl ring, which is optionally substituted.
  • Cyano represents a -CN moiety.
  • Alkoxy represents an -O-alkyl group in which the alkyl group is as defined supra. Examples include methoxy, ethoxy, n-propoxy, iso-propoxy, and the different butoxy, pentoxy, hexyloxy and higher isomers.
  • Aryloxy represents an -O-aryl group in which the aryl group is as defined supra. Examples include, without limitation, phenoxy and naphthoxy.
  • Alkenyloxy represents an -O-alkenyl group in which the alkenyl group is as defined supra.
  • An example is allyloxy.
  • Heterocyclyloxy represents an -O-heterocyclyl group in which the heterocyclic group is as defined supra.
  • Heteroaryloxy represents an -O-heteroaryl group in which the heteroaryl group is as defined supra.
  • An example is pyridyloxy.
  • Amino represents an -NH 2 moiety.
  • Alkylamino represents an -NHR or -NR 2 group in which R is an alkyl group as defined supra. Examples include, without limitation, methylamino, ethylamino, n- propylamino, isopropylamino, and the different butylamino, pentylamino, hexylamino and higher isomers.
  • Arylamino represents an -NHR or -NR 2 group in which R is an aryl group as defined supra.
  • An example is phenylamino.
  • Heterocyclylamino represents an -NHR or -NR 2 group in which R is a heterocyclic group as defined supra.
  • NR 2 is a heterocyclic ring, which is optionally substituted.
  • Heteroarylamino represents a -NHR or ⁇ NR 2 group in which R is a heteroaryl group as defined supra.
  • NR 2 is a heteroaryl ring, which is optionally substituted.
  • Niro represents a -N0 2 moiety.
  • Alkylthio represents an -S-alkyl group in which the alkyl group is as defined supra. Examples include, without limitation, methylthio, ethylthio, n-propylthio, iso propylthio, and the different butylthio, pentylthio, hexylthio and higher isomers.
  • Arylthio represents an -S-aryl group in which the aryl group is as defined supra. Examples include phenylthio and naphthylthio.
  • Heterocyclylthio represents an -S-heterocyclyl group in which the heterocyclic group is as defined supra.
  • Heteroarylthio represents an -S-heteroaryl group in which the heteroaryl group is as defined supra.
  • Sulfonyl represents an -S0 2 R group that is linked to the rest of the molecule through a sulfur atom.
  • Alkylsulfonyl represents an -S0 2 -alkyl group in which the alkyl group is as defined supra.
  • Arylsulfonyl represents an -S0 2 -aryl group in which the aryl group is as defined supra.
  • Heterocyclylsulfonyl represents an -S0 2 -heterocyclyl group in which the heterocyclic group is as defined supra.
  • Heteoarylsulfonyl presents an -S0 2 -heteroaryl group in which the heteroaryl group is as defined supra.
  • Alkylsilyl presents an alkyl group that is linked to the rest of the molecule through the silicon atom, which may be substituted with up to three independently selected alkyl groups in which each alkyl group is as defined supra.
  • Alkenylsilyl presents an alkenyl group that is linked to the rest of the molecule through the silicon atom, which may be substituted with up to three independently selected alkenyl groups in which each alkenyl group is as defined supra.
  • Alkynylsilyl presents an alkynyl group that is linked to the rest of the molecule through the silicon atom, which may be substituted with up to three independently selected alkynyl groups in which each alkenyl group is as defined supra.
  • halo or "halogen” whether employed alone or in compound words such as haloalkyl, haloalkoxy or haloalkylsulfonyl, represents fluorine, chlorine, bromine or iodine. Further, when used in compound words such as haloalkyl, haloalkoxy or haloalkylsulfonyl, the alkyl may be partially halogenated or fully substituted with halogen atoms which may be independently the same or different. Examples of haloalkyl include, without limitation, -CH 2 CH 2 F, -CF 2 CF 3 and -CH 2 CHFCI. Examples of haloalkoxy include, without limitation, -OCHF 2 , -OCF 3 , -OCH 2 CCI 3 , -
  • haloalkylsulfonyl examples include, without limitation, -S0 2 CF 3 , -S0 2 CCI 3 , -S0 2 CH 2 CF 3 and -S0 2 CF 2 CF 3 .
  • Photoactive optoelectronic devices such as a photovoltaic device, generally comprise an active material in electrical connection with a first and second electrode, wherein the active material comprises an electron donor material and an electron acceptor material.
  • the electron acceptor material can be provided by a compound according to Formula 1 or Formula 2 as defined herein.
  • the invention is generally described below with reference to a photovoltaic device, although it will be appreciated that other types of photoactive optoelectronic devices may apply.
  • a photovoltaic device generates an electrical current upon the absorption of photons.
  • the active material is arranged such that the device generates an electrical current upon the absorption of the photons.
  • the compounds of Formula 1 or Formula 2 can act as an electron acceptor material in the device, for example as an n-type semiconductor.
  • the electron donor material can donate an electron to the electron acceptor material in the device upon the absorption of photons, for example act as a p-type semiconductor.
  • the electron donor material may be selected from any electron donor materials known in the art.
  • the electron donor materials are generally organic electron donors, such as conductive polymers including polythiophenes (including P3HT) and the like.
  • the device may be in the form of an organic solar cell, such as a bulk heteroj unction organic solar cell or a bilayer organic solar cell.
  • the electron acceptor material and electron donor material can be provided in the device as discrete layers.
  • the electron donor material (p-type conductor) and electron acceptor material (n-type conductor) can be provided as a mixed blend in an active material layer of the device.
  • the concentration of each of the electron acceptor material and electron donor material in the active material gradually increases when approaching its respective electrode.
  • the first electrode may be an anode. Any suitable anode materials can be used.
  • the anode material is suitably a transparent anode material.
  • the anode is a metal oxide anode, including doped metal oxides, such as fluorine tin oxide (FTO), indium tin oxide (ITO), conductive polymer layers or graphene or single-walled carbon nanotubes (SWCNT) or grids or meshes of metals such as gold or silver, and the like.
  • FTO fluorine tin oxide
  • ITO indium tin oxide
  • SWCNT single-walled carbon nanotubes
  • the anode may be supported on a suitable support.
  • Supports include transparent supports, such as glass or polymer plates.
  • the second electrode may be a cathode.
  • Any suitable cathode material can be used.
  • the cathode is a metal or metal alloy, or graphene or single-walled carbon nanotubes (SWCNT).
  • Suitable metals and alloys are well known in the art and include aluminium, gold, silver, indium, ytterbium, a calcium:silver alloy, an aluminum:lithium alloy, or a magnesium:silver alloy.
  • the device may further comprise any additional features known in the art.
  • Some photovoltaic devices contain interfacial layers between one or both of the anodes and the active material, and such features may be incorporated into the photovoltaic devices of the present application.
  • the devices may be constructed by any techniques known in the art.
  • the compounds of the invention described herein can be suitably used in transistors.
  • the transistors comprise a gate electrode, a gate insulating layer, source and drain electrodes and a channel-forming region, the gate electrode, the gate insulating layer, the source/drain electrodes, and the channel-forming region being disposed on a base, wherein the channel-forming region comprises an electron acceptor material comprising a compound according to Formula 1 or Formula 2.
  • a surface treatment may optionally be applied to the gate dielectric layer.
  • the transistors can be fabricated by methods well known in the art.
  • the compounds of Formula 1 which may be suitable for use as an electron acceptor material, generally comprise two or more terminal groups linked together by a conjugated group (D), as follows:
  • Conjugated group D is selected from one or more optionally substituted, optionally fused, aromatic rings that provide a conjugated pathway between the terminal groups.
  • n may be any integer of 2 to 20, such as any integer of from 2 to 10.
  • n is an integer of 2 to 4.
  • the compound of Formula 1 would consist of two terminal groups linked together by a bivalent conjugated group D as follows:
  • the terminal groups comprise a strong electron withdrawing group to enable for example a LUMO suitable for use with a chosen electron donor material in a photoactive optoelectronic device or fabrication of a transistor.
  • the electron deficient properties of the compounds of Formula 1 together with strong absorption capabilities in the visible range, make them advantageous candidates as acceptor materials in organic electronic devices.
  • Each terminal group of Formula 1 is generally provided as follows:
  • A is independently selected for each terminal group from an optionally substituted 5, 6 or 7 membered carbocyclic or heterocyclic ring, which is optionally fused with one or more aryl or heteroaryl rings;
  • X 1 is independently selected for each terminal group from O, S and CR 1 R 2 , wherein R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from optionally substituted C C 10 alkyl, optionally substituted C 2 -C 10 alkenyl, optionally substituted C 2 -C 10 alkynyl, optionally substituted aryl and arylCrC 10 alkyl.
  • X 1 is independently selected from O, S and C(CN) 2 . In another embodiment, X 1 is O.
  • the core ring A of the terminal group may be fully or partially saturated.
  • ring A may contain one or more double bonds between ring atoms.
  • Ring A may also contain one or more optional substituents and optional fused groups.
  • Optional substituents of the terminal group A ring may be selected from halo, cyano, carbamoyl, CrC 20 alkyloxycarbonyl, CrC 20 alkyl, CrC 20 haloalkyl, d- C 20 alkylamino, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 - C 20 cycloalkynyl, aryl and arylCrC 20 alkyl, heteroaryl and heteroarylCrC 20 alkyl, C C 20 alkyloxy, C 3 -C 20 cycloalkyloxy and wherein alkyloxycarbonyl, alkyl, haloalkyl, alkylamino, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, ary
  • Optionally fused groups of the terminal group A ring may be optionally substituted aryl or heteroaryl groups.
  • the optionally substituted aryl groups may be monocyclic or polycyclic.
  • the monocyclic aryl groups may be an optionally substituted 6 membered ring, such as benzene.
  • the polycyclic aryl groups may be two or more optionally substituted 6-member rings fused together, such as naphthalene, anthracene, pyrene, tetracene, and pentacene.
  • the heteroaryl groups may be monocyclic or polycyclic.
  • the heteroaryl groups may be selected from 5-membered monocyclic rings, such as thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, or 6 membered rings, such as pyridine and triazine, wherein each ring may be optionally substituted.
  • 5-membered monocyclic rings such as thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, or 6 membered rings, such as pyridine and triazine, wherein each ring may be optionally substituted.
  • the terminal group may be independently selected from an optionally substituted, optionally fused, 5, 6 or 7 membered carbocyclic or heterocyclic ring according to Formula 2:
  • D, X 1 and n are defined according to Formula 1 as described above;
  • n is an integer selected from 0, 1 and 2;
  • CR 4 and CR 4 R 5 when m is 0 are optionally joined together to form one or more optionally substituted aryl or heteroaryl ring fused to the A ring, and when m is 1 or 2 each of E 1 and E 2 are optionally independently joined with G to form one or more optionally substituted aryl or heteroaryl ring fused to the A ring;
  • R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from optionally substituted d-Ci 0 alkyl, optionally substituted C 2 -Ci 0 alkenyl, optionally substituted C 2 -Ci 0 alkynyl, optionally substituted aryl and arylCi-Ci 0 alkyl; and
  • R 4 and R 5 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 haloalkyl, optionally substituted C C 20 alkylamino, optionally substituted C 3 -C 20 cycloalkyl, optionally substituted C 2 - C 2 oalkenyl, optionally substituted C 3 -C 2 ocycloalkenyl, optionally substituted C 2 - C 2 oalkynyl, optionally substituted C 3 -C 20 cycloalkynyl, optionally substituted aryl and arylCrC 20 alkyl.
  • X 1 is independently selected from O, S and C(CN) 2 . In another embodiment, X 1 is O.
  • E 1 and E 2 may each be independently selected from NH and NCi-i 0 alkyl.
  • E 1 and E 2 may be joined together to form an optionally substituted aryl or heteroaryl ring fused to the A ring, for example an optionally substituted benzene ring fused to the A ring at E 1 and E 2 .
  • each of E 1 and E 2 may be independently joined with G to form an aryl or heteroaryl ring fused to the A ring, for example a naphthalene group fused to the A ring at E 1 , E 2 and G.
  • the aryl ring may be an optionally substituted monocyclic or polycyclic ring.
  • the monocyclic aryl ring may be an optionally substituted 6 membered ring, such as benzene.
  • the polycyclic aryl ring may be two or more optionally substituted 6-member rings fused together, such as naphthalene, anthracene, pyrene, tetracene, and pentacene, which may each be optionally substituted.
  • the heteroaryl ring may be monocyclic or polycyclic.
  • the optionally substituted heteroaryl ring may be selected from optionally substituted 5-membered monocyclic rings, such as thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, or 6 membered rings, such as pyridine and triazine, which may each be optionally substituted.
  • the terminal group may be independently selected from an optionally substituted 5 membered carbocyclic or heterocyclic ring according to Formula 2a:
  • D, n, X 1 , L, R 4 and R 5 are defined according to Formula 2 as described above.
  • the J ring is an optionally substituted aryl ring.
  • E 1 and E 2 may be optionally joined together to form an optionally substituted monocyclic or polycyclic aryl ring J that is fused to the A ring.
  • the optionally substituted monocyclic aryl ring may be a 6 membered ring, such as an optionally substituted benzene.
  • the optionally substituted polycyclic aryl ring may be two or more 6-member rings fused together, such as naphthalene, anthracene, pyrene, tetracene, and pentacene, which may each be optionally substituted.
  • the aryl ring J is selected from an optionally substituted benzene, napthalene and anthracene.
  • the optional substitution is selected from halo, such as F and CI, cyano, d-C 20 alkyl, C 3 -C 2 ocycloalkyl, CrC 20 haloalkyl, C
  • the J ring is an optionally substituted heteroaryl ring.
  • E 1 and E 2 may be optionally joined together to form an optionally substituted monocyclic or polycyclic heteroaryl ring J that is fused to the A ring.
  • the optionally substituted heteroaryl ring may be selected from 5-membered monocyclic rings, such as thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4- oxadiazole, 1 ,3,4-thiadiazole, or 6 membered rings, such as pyridine and triazine, which may each be optionally substituted.
  • the optionally substituted, optionally fused, 5 membered carbocyclic or heterocyclic ring of the terminal group A may be selected from one of the following groups:
  • D and n are as described above for Formula 2 or embodiments thereof;
  • X 1 and X 2 are each independently selected from O, S and CR 1 R 2 ; wherein R 1 and R 2 are each independently selected from CN and C0 2 R 3 , wherein R 3 is selected from CrC 20 alkyl, C 3 -C 2 ocycloalkyl, C 2 -C 2 oalkenyl, C 3 - C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkynyl, aryl and arylCrC 20 alkyl, and wherein alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and arylalkyl in each occurrence may be optionally substituted;
  • R 7 represents one or more optional substituents selected from halo, cyano, carbamoyl, CrC 20 alkyloxycarbonyl, CrC 20 alkyl, CrC 20 haloalkyl, C
  • R 7 represents one or more optional substituents selected from halo, cyano, carbamoyl, CrC 20 alkyloxycarbonyl, C C 20 alkyl, CrC 20 haloalkyl, C C 20 alkylamino, benzene, naphthalene, anthracene, pyrene, tetracene, pentacene, thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4-oxadiazole, 1 ,3,4- thiadiazole, pyridine and triazine, which may each be optionally substituted and/or provided as a fused substituent.
  • R 7 represents one or more optional substituents selected from benzene, naphthalene and anthracene, which may be provided as a fused substituent.
  • a terminal group A may be an optionally substituted, optionally fused, 5 membered carbocyclic group according to Formula 2a(i) as follows:
  • R 1 , R 2 , R 3 , R 4 and R 5 are defined according to Formula 2a as described above or embodiments thereof;
  • X 1 and X 2 are each independently selected from O, S and CR 1 R 2 ; and R 7 represents one or more optional substituents selected from halo, cyano, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 haloalkyl, optionally substituted CrC 20 alkylamino and optionally substituted phenyl; and M represents an optionally substituted aryl or heteroaryl ring that is fused to the benzene ring of the terminal group.
  • the optionally substituted aryl or heteroaryl ring M that is fused to the benzene ring of the terminal group may be selected from benzene and naphthalene.
  • X 1 and X 2 may each be independently selected from O and C(CN) 2 .
  • 5 membered carbocyclic or heterocyclic rings of the terminal group according to Formula 2a which may be further optionally substituted, optionally fused, are provided as follows:
  • the terminal group may be an optionally substituted, optionally fused, 6 membered carbocyclic or heterocyclic ring according to Formula 2b:
  • X 3 is selected from O, S and CR 1 R 2 ;
  • the optionally substituted, optionally fused, 6 membered carbocyclic or heterocyclic ring of the terminal group may be selected from one of the following groups:
  • X 1 , X 2 and X 3 are each independently selected from O, S and CR 1 R 2 ;
  • E 2 and E 3 are each independently selected from N, NR 4 , O, S, S0 2 , CR 4 and CR 4 R 5 ;
  • R 1 and R 2 are each independently selected from CN and C0 2 R 3 ;
  • R 3 is selected from CrC 20 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkynyl, aryl and arylCrC 20 alkyl, and wherein alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and arylalkyi in each occurrence may be optionally substituted;
  • R 4 and R 5 are each independently selected from hydrogen, halo, cyano, CrC 2 oalkyl, CrC 2 ohaloalkyl, Ci-C 2 oalkylamino, C 3 -C 2 ocycloalkyl, C 2 -C 20 alkeny
  • R 7 represents one or more optional substituents selected from halo, cyano, C C 20 alkyl, d-C 20 haloalkyl, CrC 20 alkylamino, benzene, naphthalene and anthracene, and wherein each of benzene, naphthalene and anthracene may be optionally fused.
  • the terminal group may be an optionally substituted, optionally fused, 7 membered carbocyclic or heterocyclic ring according to Formula 2c as follows:
  • X 1 and X 2 are each independently selected from O, S and CR 1 R 2 ;
  • E 2 and E 3 are each independently selected from N, NR 4 , O, S, S0 2 , CR 4 and CR 4 R 5 ;
  • R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from d-C 20 alkyl, C 3 -C 2 ocycloalkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkynyl, aryl and arylCrC 20 alkyl, and wherein alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and arylalkyl in each occurrence may be optionally substituted;
  • R 4 and R 5 are each independently selected from H, halo, cyano, C C 20 alkyl, CrC 20 haloalkyl, d-C ⁇ alkylamino, C 3 -C 20 cycloalkyl, C 2 -C 20 alkenyl, C 3 - C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkynyl, aryl and arylCrC 20 alkyl, and wherein alkyl, haloalkyl, alkylamino, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl and arylalkyl in each occurrence may be optionally substituted; and
  • R 7 represents one or more optional substituents selected from halo, cyano, CrC 20 alkyl, CrC 20 haloalkyl, CrC 20 alkylamino, benzene, naphthalene and anthracene, and wherein each of benzene, naphthalene and anthracene may be optionally fused.
  • the conjugated group D provides a conjugated ⁇ bond system that has at least one conjugated pathway between at least two terminal groups.
  • the exocyclic methylene group of the terminal A group provides a conjugation link to the conjugated system in the D group.
  • the conjugated group D may be one or more optionally substituted, optionally fused, unsaturated rings joined or fused together to provide the conjugated ⁇ bond system.
  • the unsaturated rings of the D group may be selected from one or more aryl and heteroaryl groups.
  • the conjugated systems for the D group are selected to provide advantageous properties including solubility and crystallinity properties as well as suitable and preferred HOMO/LUMO energy levels of the compounds.
  • the HOMO/LUMO energy levels can be modified by selecting particular functional groups that provide advantageous electronic properties for a semiconductor material, for example enabling the electron accepting semiconductor material to more efficiently absorb sunlight and transport electrons.
  • the D group may have from 5 to 100 ring atoms, from 5 to 60 ring atoms, from 5 to 50 ring atoms, from 5 to 30 ring atoms, or from 5 to 20 ring atoms.
  • the D group may consist of one or more aromatic rings, for example at least 2 aromatic rings, at least 4 aromatic rings, at least 6 aromatic rings, or at least 8 aromatic rings.
  • the D group may consist of 20 aromatic rings or less, 15 aromatic rings or less, or 10 aromatic rings or less.
  • the D group may consist of any number or range of rings selected from the following: 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, wherein at least 1 of the rings is aromatic and there is provided at least one conjugated pathway connecting the terminal groups.
  • the conjugated group D contains 1 to 15 rings wherein at least 1 of the rings is aromatic and there is provided at least one conjugated pathway connecting the terminal groups. In another embodiment, the conjugated group D contains 1 to 10 rings wherein at least 1 of the rings is aromatic and there is provided at least one conjugated pathway connecting the terminal groups.
  • the D group may be substituted.
  • the substituents may be provided to modify the solid state structure or crystallinity of the material. It will be appreciated that aromatic groups are essentially planar and provide good stacking arrangement of individual compounds in a solid material, which provides an advantage by enabling electrons to be conducted through the stacked ⁇ system of the material. However, it may be advantageous to restrict a high degree of crystallinity in the material to facilitate processing, for example to provide the material with a certain degree of solubility in relation to fabrication by solution processing, such as spin coating of thin films of the material.
  • the D group may contain one or more vinyl groups in linear sequence with a aryl or heteroaryl group, which may provide the conjugated pathway between at least two terminal groups.
  • the one or more vinyl groups may be provided in a carbocyclic or heterocyclic group, such as an unsaturated ring.
  • the carbocyclic or heterocyclic group may be a 5 or 6 membered ring.
  • the D group may be provided by one or more optionally substituted, optionally fused, aryl and/or heteroaryl groups that are joined or fused together to provide the conjugated pathway.
  • the optionally substituted, optionally fused, aryl and/or heteroaryl groups may be formed from one or more 5, 6 or 7 membered rings.
  • the D group may include optionally substituted, optionally fused, carbocyclic or heterocyclic groups.
  • the D group is one or more optionally substituted, optionally fused, aryl groups.
  • the optionally substituted aryl groups may be monocyclic or polycyclic.
  • the optionally substituted monocyclic aryl groups may be a 6 membered ring, such as optionally substituted benzene.
  • the optionally substituted polycyclic aryl groups may be two or more 6-member rings fused together, such as naphthalene, anthracene, pyrene, tetracene, and pentacene, which may each be optionally substituted.
  • the polycyclic aryl groups may be two or more 6 member rings joined together, such as biphenyl, or two or more fused rings that are joined together, such as fluorene and perylene, which may each be optionally substituted.
  • the D group is selected from one or more optionally substituted, optionally fused, heteroaryl groups.
  • the optionally substituted heteroaryl groups may be monocyclic or polycyclic.
  • the optionally substituted heteroaryl groups may be selected from 5-membered monocyclic rings, such as thiophene, furan, pyrrole, silole, imidazole, 1 ,3-thiazole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, or 6 membered rings, such as pyrazine, pyridine and triazine, which may each be optionally substituted.
  • the heteroaryl groups may be polycyclic rings, which may contain fused or joined aryl groups, such as benzothiadiazole and carbazole, which may each be optionally substituted.
  • the D group has 5 to 80 ring atoms formed from one or more groups selected from benzene, naphthalene, thiophene, furan, biphenyl and fluorene, that are joined or fused together to provide the conjugated ⁇ bond system.
  • the D group, or aromatic rings or groups thereof, may be substituted as herein described with one or more optional substituents.
  • the optional substituents may be selected from halo, cyano, CrC 20 alkyl, CrC 2 ohaloalkyl, CrC 20 alkylamino, C 3 - C 2 ocycloalkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkynyl, C C 20 alkylsilyl, C 2 -C 20 alkenylsilyl, C 2 -C 20 alkynylsilyl, aryl, arylCi_C 20 alkyl, heteroaryl and heteroarylCi-C 2 oalkyl, and wherein alkyl, haloakyl, alkylamino, cycloalkyl, alkenyl, cycloalkenyl, al
  • the substituents are selected from Ci_ 20 alkyl, Ci- 20 alkylamino and d. 20 alkylsilyl, wherein each may be optionally with halo, OH, CN, NH 2 and COOH.
  • the substituents are selected from C 4 . 12 alkyl, C ⁇ oalkylamino and C 4 . 12 alkylsilyl.
  • the substituents are selected from C 4 . 12 alkyl.
  • the D group may be provided by a conjugated group that is linked to each of the terminal groups via an unsaturated 5-membered cyclic group, such as one or more thiophene groups.
  • the rings or aromatic rings are provided by monocyclic or polycyclic 6 membered aryl or heteroaryl rings. In another embodiment, at least one of the rings or aromatic rings is carbocyclic. In another embodiment, the rings or aromatic rings are provided by a heterocyclic ring containing heteroatoms selected from at least one of N and Si.
  • the aromatic rings for the conjugated group D may be provided by one or more optionally substituted, optionally fused, carbocyclic and/or heterocyclic aromatic rings that are joined together, fused together, or a combination thereof, to provide the conjugated pathway.
  • the aromatic rings for the conjugated group D comprise at least one optionally substituted, optionally fused, heterocyclic aromatic ring, and wherein the rings are joined together, fused together, or a combination thereof, to provide the conjugated pathway.
  • At least one optionally substituted, optionally fused, heterocyclic aromatic ring is joined to each terminal group.
  • the conjugated group D may be provided by a single optionally substituted, optionally fused, heterocyclic aromatic ring.
  • the conjugated group D may be provided by two optionally substituted heterocyclic aromatic rings joined together by a bond.
  • the conjugated group D may be provided by three optionally substituted heterocyclic aromatic rings, one of which is a fused heterocyclic ring that is independently joined to each of the two other
  • the aromatic rings for the conjugated group D are provided by at least one optionally substituted, optionally fused, carbocyclic aromatic ring and at least one optionally substituted, optionally fused, heterocyclic aromatic ring, wherein the rings are joined together, fused together, or a combination thereof, to provide the conjugated pathway.
  • the carbocyclic aromatic rings of the D group may be independently selected from benzene, naphthalene, biphenyl and fluorene
  • the heterocyclic aromatic rings may be independently selected from thiophene and furan, and wherein each ring is optionally substituted.
  • the carbocyclic aromatic rings may be selected from fluorene
  • the heterocyclic aromatic rings may be selected from thiophene, and wherein each group is optionally substituted.
  • the conjugated group D is a group according to
  • p is independently selected from an integer of 0 to 15;
  • Z 1 is selected from O, S, Se, S0 2 , NR 12 and CR 12 R 13 ;
  • Z 2 and Z 3 are each independently selected from N and CR 12 ;
  • R 12 and R 13 are each independently selected from hydrogen, halo, cyano, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 2 oalkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 -C 20 alkynylsilyl; and Ar is selected from one or more optionally substituted, optionally fused, carbocyclic or heterocyclic group that provides at least one conjugated pathway between at least two terminal groups.
  • the unsaturated 5-membered cyclic group defined in Formula 3 by p, Z 1 , Z 2 and Z 3 is an optional group, which provides a link between a terminal group and the Ar group.
  • the conjugated D group is provided by the Ar group, and the Ar group may be defined according to any of the embodiments described herein for the D group.
  • Z 1 is selected from O and S.
  • Z 2 and Z 3 are each independently selected from N and CCrC 20 alkyl. / ' .
  • the D group or Ar group may be one or more optionally substituted bivalent linking groups selected from the following groups:
  • Q 1 and Q 2 are each independently selected from CR 14 , N and SiR 15 ;
  • R 14 and R 15 are each independently selected from hydrogen, halo, cyano, optionally substituted d-C 20 alkyl, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 -C 20 alkynylsilyl; and
  • R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 alkylamino, optionally substituted C 2 -C 2 oalkenyl, optionally substituted C 2 -C 2 oalkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 - C 20 alkynylsilyl.
  • R 8 and R 9 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 alkylamino, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted d-C 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 - C 20 alkynylsilyl.
  • R 8 and R 9 are each independently selected from hydrogen, halo, CN, optionally substituted C C 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl.
  • R 14 and R 15 are each independently selected from hydrogen, halo, cyano, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 2 oalkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 -C 20 alkynylsilyl; and
  • R 8 and R 9 are each independently selected from hydrogen, halo, CN, optionally substituted C C 20 alkyl, optionally substituted d-C ⁇ alkylamino, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted C
  • Q 3 is selected from CR 14 R 15 , NR 14 and SiR 14 R 15 .
  • Q 3 is selected from CR 14 R 15 , wherein R 14 and R 15 are defined as above.
  • R 14 and R 15 are each independently selected from C 4 . 12 alkyl and C 4 . 12 cycloalkyl; and R 8 and R 9 are each independently selected from H and CrC 20 alkyl.
  • R 14 , R 15 , R 8 and R 9 are each independently selected from hydrogen, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl.
  • R 14 and R 15 are each independently selected from hydrogen, optionally substituted d-C 20 alkyl, optionally substituted C 2 -C 2 oalkenyl and optionally substituted C 2 -C 20 alkynyl.
  • R 8 , R 9 , R 10 , R 11 , R 14 and R 15 are each independently selected from hydrogen, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl.
  • R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 alkylamino, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 2 oalkylsilyl, optionally substituted C 2 -C 2 oalkenylsilyl and optionally substituted C 2 -C 2 oalkynylsilyl.
  • Q 1 and Q 2 are each independently selected from CR 14 , N and SiR 14 ;
  • Q 6 and Q 9 are each independently selected from CR 14 , N, SiR 14 ;
  • R 14 and R 15 are each independently selected from hydrogen, halo, CN, optionally substituted C C 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl.
  • Q 6 and Q 9 are each selected from CH.
  • Q 7 and Q 8 are each selected from S.
  • Q 1 and Q 2 are each independently selected from CR 14 , NR 14 and SiR 14 , wherein R 14 is defined as above.
  • Q 2 is selected from CH
  • Q 1 is selected from CR 14 , NR 14 and SiR 14 , wherein R 14 is defined as above.
  • R 14 is selected from C 4 _i 2 alkyl and C 4 _i 2 cycloalkyl.
  • R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 alkylamino, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted d-C 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 -C 20 alkynylsilyl.
  • Q 1 and Q 2 are each independently selected from CR 14 , N and SiR 14 ;
  • Q 6 and Q 8 are each independently selected from CR 14 , N, SiR 14 ;
  • R 14 and R 15 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl.
  • Q 6 and Q 8 are each selected from CH.
  • Q 7 and Q 9 are each selected from S.
  • Q 1 and Q 2 are each independently selected from CR 14 , N and SiR 14 , wherein R 14 is defined as above.
  • Q 2 is selected from CH
  • Q 1 is selected from CR 14 , N and SiR 14 , wherein R 14 is defined as above.
  • R 14 is selected from C 4 . 12 alkyl and C 4 . 12 cycloalkyl.
  • R and R are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 2 oalkylamino, optionally substituted C 2 -C 2 oalkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 - C 20 alkynylsilyl.
  • the D group or Ar group may be an optionally substituted bivalent linking group selected from any of the following groups:
  • R 14 and R 15 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 2 oalkynyl;
  • R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted CrC 20 alkylamino, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 - C 20 alkynylsilyl.
  • the D group may be provided by a conjugated group that is linked to each of the terminal groups via an unsaturated 5-membered cyclic group, such as one or more thiophene groups.
  • the conjugated group D is a group according to
  • p is independently selected from an integer of 0 to 15;
  • Z 1 is selected from O, S, Se, S0 2 , NR 12 and CR 12 R 13 ;
  • Z 2 and Z 3 are each independently selected from N and CR 12 ;
  • R 12 and R 13 are each independently selected from hydrogen, halo, cyano, optionally substituted C C 20 alkyl, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 -C 20 alkynylsilyl; and
  • Ar is selected from one or more optionally substituted, optionally fused, carbocyclic or heterocyclic group that provides at least one conjugated pathway between at least two terminal groups.
  • the unsaturated 5-membered cyclic group defined in Formula 3 by p, Z 1 , Z 2 and Z 3 is an optional group, which provides a link between a terminal group and the Ar group.
  • the conjugated D group is provided by the Ar group, and the Ar group may be defined according to any of the embodiments described herein for the D group.
  • Z 1 is selected from O and S.
  • Z 2 and Z 3 are each independently selected from N and CCi-C 2 oalkyl.
  • the Ar group in Formula 3 may be linked to each terminal group by one or more of the unsaturated 5-membered rings defined by p, Z 1 , Z 2 and Z 3 .
  • the D group may be provided by a bivalent linking group according to Formula 19 as follows:
  • p 1 and p 2 are each independently selected from an integer of 0 to 15; and Z 1 , Z 2 , Z 3 and Ar, are defined herein as for Formula 3.
  • the integer p which includes integers for p 1 , p 2 , p 3 etc, may each be
  • p is an integer between 1 and 10.
  • p is 1 , 2 or 3.
  • p is 1.
  • Z 1 is S or O and Z 2 and Z 3 are both CH.
  • Formula 3 provides a group selected from an optionally substituted thiophene and furan group.
  • the Ar group according to Formula 3 may be provided by any of the
  • the Ar group may be provided by a group according to any of Formulae 4 to 14, including any embodiments thereof described above.
  • p 1 and p 2 are each independently selected from an integer of 0 to 10;
  • R 14 and R 15 are each independently selected from hydrogen, halo, CN, optionally substituted d-C 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl;
  • R 8 , R 9 , R 10 and R 11 are each independently selected from hydrogen, halo, CN, optionally substituted C C 20 alkyl, optionally substituted d-C ⁇ alkylamino, optionally substituted C 2 -C 20 alkenyl, optionally substituted C 2 -C 20 alkynyl, optionally substituted CrC 20 alkylsilyl, optionally substituted C 2 -C 20 alkenylsilyl and optionally substituted C 2 - C 20 alkynylsilyl.
  • Q 4 and Q 5 are S, and Q 3 is selected from CR 14 R 15 , NR 14 and SiR 14 R 15 , wherein R 14 and R 15 are defined as above. In one particular embodiment, Q 3 is selected from CR 14 R 15 , wherein R 14 and R 15 are defined as above. In a further embodiment, R 14 and R 15 are each independently selected from C 4 _i 2 alkyl and C 4 _i 2 cycloalkyl. In a further embodiment, p 1 and p 2 are each independently selected from an integer of 1 to 5.
  • R 14 and R 15 are each independently selected from hydrogen, halo, CN, optionally substituted C C 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl. In one particular embodiment R 14 and R 15 are each independently selected from C 4 -C 12 alkyl.
  • R 14 and R 15 are each independently selected from hydrogen, halo, CN, optionally substituted CrC 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 2 oalkynyl.
  • the D group may be provided by a tetravalent linking group according to Formula 20 as follows:
  • p 1 , p 2 , p 3 and p 4 are each independently selected from an integer of 0 to 15; and Z 1 , Z 2 , Z 3 and Ar, are defined herein as for Formula 3.
  • Ar is a conjugated group according to Formula 19 as described above
  • an example of a tetravalent linked conjugated group also in accordance with Formula 20 may be provided as follows:
  • the D group may be a group according to Formula 24:
  • p is independently selected from an integer of 0 to 15;
  • Z 1 is selected from O, S, Se, S0 2 , NR 12 and CR 12 R 13 ;
  • Z 2 and Z 3 are each independently selected from N and CR 12 ;
  • R 12 and R 13 are each independently selected from hydrogen, halo, cyano, C C 20 alkyl, C 3 -C 2 ocycloalkyl, C 2 -C 2 oalkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 - C 20 cycloalkynyl, CrC 20 alkylsilyl, C 2 -C 20 alkenylsilyl and C 2 -C 20 alkynylsilyl, and wherein alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylsilyl, alkenylsilyl and alkynylsilyl, in each occurrence may be optionally substituted.
  • Z 1 is selected from O and S.
  • Z 2 and Z 3 are each independently selected from N and CCrC 20 alkyl.
  • the D group of Formula 24 may be provided by a group according to Formula 24a:
  • Each Z 1 is independently selected from O, S, Se, S0 2 , NR 12 and
  • Each Z 2 and Z 3 are independently selected from N and CR 12 ;
  • R 12 and R 13 are each independently selected from hydrogen, halo, cyano, C C 20 alkyl, C 3 -C 2 ocycloalkyl, C 2 -C 2 oalkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 - C 20 cycloalkynyl, CrC 20 alkylsilyl, C 2 -C 20 alkenylsilyl and C 2 -C 20 alkynylsilyl, and wherein alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylsilyl, alkenylsilyl and alkynylsilyl, in each occurrence may be optionally substituted.
  • the compounds of Formula 1 can exist as one or more stereoisomers.
  • the various stereoisomers can include enantiomers, diastereomers and geometric isomers. Those skilled in the art will appreciate that one stereoisomer may be more active than the other(s). In addition, the skilled person would know how to separate such
  • the present invention comprises mixtures, individual stereoisomers, and optically active mixtures of the compounds described herein.
  • Formula 1 has been drawn as the (E)-isomer, it should be understood that the compounds of the present invention may also exist as (Z)- isomers, or mixtures thereof, and therefore, such isomers or mixtures thereof are clearly included within the present invention.
  • n is an integer of 2 to 20;
  • X 1 is independently selected for each terminal group from O, S and CR 1 R 2 ;
  • n is an integer selected from 0, 1 and 2;
  • R 1 and R 2 are each independently selected from CN and C0 2 R 3 , R 3 is selected from optionally substituted C C 10 alkyl, optionally substituted C 2 -C 10 alkenyl, optionally substituted C 2 -C 10 alkynyl, optionally substituted aryl and aryld-C 10 alkyl; and
  • R 4 and R 5 are each independently selected from hydrogen, halo, CN, optionally substituted C C 20 alkyl, optionally substituted CrC 20 haloalkyl, optionally substituted C C 20 alkylamino, optionally substituted C 3 -C 20 cycloalkyl, optionally substituted C 2 - C 20 alkenyl, optionally substituted C 3 -C 20 cycloalkenyl, optionally substituted C 2 - C 20 alkynyl, optionally substituted C 3 -C 20 cycloalkynyl, optionally substituted aryl and arylCrC 20 alkyl.
  • D is a conjugated group that provides at least one conjugated pathway between at least two terminal groups and which is selected from one or more optionally substituted, optionally fused, rings provided that at least one of the rings is aromatic, and which is selected from a grou ula 3
  • p is independently selected from an integer of 0 to 15;
  • Z 1 is independently selected from O, S, Se, S0 2 , NR 12 , CR 12 R 13 and SiR 12 R 13 ;
  • Z 2 and Z 3 are each independently selected from N and CR 12 ;
  • Ar is selected from an optionally substituted, optionally fused, aryl or heteroaryl group.
  • X 1 and X 2 are O or C(CN) 2
  • p is 0, and Ar is selected from optionally substituted, optionally fused, thiophene groups, then at least two thiophene groups are fused together; or
  • X 1 and X 2 are O or C(CN) 2
  • p is at least 1
  • each Z 1 is S
  • each Z 2 and Z 3 are CH
  • Ar is selected from optionally substituted, optionally fused, thiophene groups, then at least two thiophene groups are fused together; or
  • p may be selected from 1 to 15, preferably 1 to 5.
  • Ar may be selected from optionally substituted, optionally fused, aryl groups.
  • the Ar group is provided by monocyclic or polycyclic 6 membered aryl or heteroaryl rings.
  • the Ar group may comprise at least one carbocyclic ring.
  • the aromatic rings for the conjugated group Ar are provided by at least one optionally substituted, optionally fused, carbocyclic aromatic ring and at least one optionally substituted, optionally fused, heterocyclic aromatic ring, wherein the rings are joined together, fused together, or a combination thereof, to provide the conjugated pathway.
  • the carbocyclic aromatic rings of the Ar group may be independently selected from benzene, naphthalene, biphenyl and fluorene, and the heterocyclic aromatic rings may be independently selected from thiophene and furan, and wherein each ring is optionally substituted.
  • the carbocyclic aromatic rings may be selected from fluorene, and the heterocyclic aromatic rings may be selected from thiophene, and wherein each group is optionally substituted.
  • Z 1 is selected from O, Se, S0 2 , NR 12 , CR 12 R 13 and SiR 12 R 13 . In a further embodiment, Z 1 is selected from N and Si.
  • p 1 and p 2 are each independently selected from an integer of 0 to 15, and Ar, Z 1 , Z 2 and Z 3 , are each independently selected from any of the groups or embodiments as previously described herein including
  • A, X 1 , L, E 1 , E 2 , G and m, for each terminal group are independently selected from any of the groups or embodiments as previously described herein including embodiments of the forth aspect.
  • p 1 , p 2 , p 3 and p 4 are each independently selected from an integer of 0 to 15, and Ar, Z 1 , Z 2 and Z 3 , are each independently selected from any of the groups or embodiments as previously described herein including embodiments of the forth aspect; and A, X 1 , L, E 1 , E 2 , G and m, for each terminal group are independently selected from any of the groups or embodiments as previously described herein including embodiments of the forth aspect.
  • p 1 and p 2 are each independently selected from an integer of 0 to 10;
  • R 14 and R 15 are each independently selected from hydrogen, halo, cyano, C C 2 oalkyl, C 3 -C 2 ocycloalkyl, C 2 -C 2 oalkenyl, C 3 -C 20 cycloalkenyl, C 2 -C 20 alkynyl, C 3 - C 20 cycloalkynyl, d-C 20 alkylsilyl, C 2 -C 20 alkenylsilyl and C 2 -C 20 alkynylsilyl, and wherein alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, alkylsilyl, alkenylsilyl and alkynylsilyl, in each occurrence may be optionally substituted; and R 8 and R 9 each represent one or more optional substituents independently selected from hydrogen, halo, cyano, CrC 20 alkyl, CrC 2
  • Q 3 is selected from CR 14 R 15 , S, S0 2 , O, NR 14 and
  • R 8 , R 9 , R 14 and R 15 are each independently selected from hydrogen, optionally substituted C C 20 alkyl, optionally substituted C 2 -C 20 alkenyl and optionally substituted C 2 -C 20 alkynyl.
  • the electron donor material may comprise polymers such as regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT), regioregular poly(3-ocylthiophene-2,5-diyl) (P30T), regioregular poly(quarterthiophene) (PQT), a-poly(phenylene ethynylene)- poly(phenylene vinylene) (A-PPE-PPV), poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1 ,4- phenylene vinylene] (MEH-PPV), or poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1 ,4- phenylenevinylene] (MDMO-PPV), or short oligomers of these polymers.
  • P3HT regioregular poly(3-hexylthiophene-2,5-d
  • Small molecules such as 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2- ethylhexyl)pyrrolo[3,4-c]pyrrole-1 ,4(2H,5H)-dione (EH-DPP), 6, 13- bis((triisopropylsilyl)ethynyl)pentacene (TIPS-PEN) or 2-(2,6-bis((E)-4- (diphenylamino)styryl)-4H-pyran-4-ylidene)malononitrile (DPAPM) may also be used as donor materials.
  • EH-DPP 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2- ethylhexyl)pyrrolo[3,4-c]pyrrole-1 ,4(2H,5H)-dione
  • TIPS-PEN 6, 13
  • the electron donor material is P3HT.
  • the thin film or layer comprising the compound of Formula 1 may further comprise one or more additives, such as additional film components, which may include additives beneficial to film formation or film morphology. These additives may be removed from the formed film or layer by evaporation or they may be permanently incorporated into the thin film or layer.
  • additives are hexadecane, 1 ,8- diiodooctane (DIO), 1 ,8-octanedithiol (ODT), 1-chloronaphthalene, /V-methyl-2- pyrrolidone, diethylene glycol dibutyl ether, polystyrene, or polysiloxanes, or mixtures of the aforesaid additives.
  • Optoelectronic photoactive devices such as organic solar cells, may be prepared in the form of a bilayer device, bulk heterojunction device or blend or hybrid device.
  • a bilayer organic solar cell (1) may generally comprise an anode (2), for example as a transparent layer of indium tin oxide on a transparent thin film support (3), and a cathode (4), for example in the form of an adjacent metal cathode. Between the anode and cathode are layers of an electron donor material (or p-conductor) (5), for example P3HT, and an electron acceptor material (6) (or n-conductor), for example a compound of Formula 1.
  • the device may contain multiple layers, and the term "bilayer" should be interpreted as encompassing 2 or more layered devices.
  • the device may be in the form of a single cell, or multiple cells connected in parallel and/or series.
  • the device typically further comprises positive and negative terminals (not illustrated) for connection to an energy storage device or other electrical component(s) or circuit(s).
  • a bulk heterojunction organic solar cell (7) may generally comprise an anode (2), for example a transparent layer of indium tin oxide supported on a transparent thin film support (3), and a cathode (4), for example in the form of an adjacent metal cathode. Between the anode and cathode is an active material comprising a blend of electron acceptor material (6) (or n-conductor), for example a compound of Formula 1 , and an electron donor (or p-conductor) material (5), for example P3HT. In one embodiment, the concentration of each component (5) and (6) gradually increases when approaching to the corresponding electrode.
  • the device may be in the form of a single cell, or multiple cells connected in parallel and/or series. The device typically further comprises positive and negative terminals (not illustrated) for connection to an energy storage device or other electrical component(s) or circuit(s).
  • one configuration comprises providing a thin layer (e.g. about 40 nm layer) of PEDOT/PSS solution on a substrate, for example by spin coating and annealing.
  • a thin layer e.g. about 40 nm layer
  • solutions of the organic blends can be deposited onto the PEDOT/PSS layer by spin coating.
  • Advantageous spinning conditions and film thicknesses can be identified for various blends.
  • Single layers of the organic materials can also be deposited sequentially, for example by thermal evaporation at reduced pressures (e.g. below 2 ⁇ ⁇ 0 ⁇ 6 mbar).
  • Organic layers may be dissolved in a solvent, such as an organic solvent for example chlorobenezene and 1 ,2-dichlorobenezene. Solutions can be spin coated, for example by using a Laurell WS-650SZ-23NPP Lite single wafer spin processor. Preferred spin parameters may range from 2000-3000 RPM with an acceleration of 6000 RPM. Thin films can be further thermally annealed, for example at 120°C for 10 minutes.
  • a solvent such as an organic solvent for example chlorobenezene and 1 ,2-dichlorobenezene. Solutions can be spin coated, for example by using a Laurell WS-650SZ-23NPP Lite single wafer spin processor. Preferred spin parameters may range from 2000-3000 RPM with an acceleration of 6000 RPM. Thin films can be further thermally annealed, for example at 120°C for 10 minutes.
  • a layer of Ca can also be deposited by thermal evaporation at reduced pressures, for example below 2* 10 ⁇ 7 mbar.
  • a metal layer such as an Al layer, can be deposited, for example by Angstrom Engineering evaporator at pressures below 2x 10 " 7 mbar.
  • the devices can be annealed, for example on a hotplate in a glovebox.
  • a small amount of silver paint (Silver Print II , GC electronics, Part no. : 22-023) can also be deposited onto the connection points of the electrodes.
  • Completed devices can be encapsulated with glass and a UV-cured epoxy, for example by using Lens Bond type J-91 and exposing to 254nm UV-light inside a glovebox (H 2 0 and 0 2 levels both ⁇ 1 ppm) for 10 minutes.
  • the structure of the entire device can be inverted and the device fabrication process can commence with a cathode and be completed by the addition of a top anode.
  • either or both electrodes may be transparent to the electromagnetic radiation, for example light, that is being detected.
  • a thin film component for a photoactive optoelectronic device may be prepared by a spin coating process.
  • an active material comprising an electron acceptor material according to the compound of Formula 1 defined above may be spin coated onto a substrate.
  • a coating process may comprise the steps of: providing a solution comprising a compound of Formula 1 and at least a solvent, optionally an additive and optionally an electron donor material; depositing the solution onto an optionally coated anode or cathode material; and optionally evaporating the solvent from the deposited solution.
  • the optionally coated anode or cathode material may be provided on a support, such as a glass support.
  • the anode is any material able to conduct holes and inject them into organic layers.
  • the anode may comprise of layers such as poly(ethylene dioxythiophene): polystyrene sulfonic acid (PEDOT:PSS), molybdenum oxide, or poly- aniline:dodecylbenzenesulfonic acid (PANI:DBS) and fluorine tin oxide (FTO), indium tin oxide (ITO), conductive polymer layers or graphene or single-walled carbon nanotubes (SWCNT) or grids or meshes of metals such as gold or silver.
  • the cathode is any material able to conduct electrons and collect them from organic layers.
  • the cathode may comprise of layers such as lithium fluoride, calcium, barium, 2,9-dimethyl- 4,7-diphenyl-1 , 10-phenanthroline (BCP), or aluminium oxide and metals such as aluminium, gold, silver, indium, ytterbium, a calcium:silver alloy, an aluminum:lithium alloy, or a magnesium:silver alloy or graphene or single-walled carbon nanotubes (SWCNT).
  • layers such as lithium fluoride, calcium, barium, 2,9-dimethyl- 4,7-diphenyl-1 , 10-phenanthroline (BCP), or aluminium oxide and metals such as aluminium, gold, silver, indium, ytterbium, a calcium:silver alloy, an aluminum:lithium alloy, or a magnesium:silver alloy or graphene or single-walled carbon nanotubes (SWCNT).
  • BCP 10-phenanthroline
  • aluminium oxide and metals such as aluminium, gold, silver, indium
  • the solvent is selected to solubilise an appropriate amount of a compound of Formula 1 for solution based processing of thin film components.
  • the solvent is preferably selected form a volatile solvent.
  • the solvent may be an organic solvent. Any suitable solvent can be used to dissolve, and/or disperse a compound of the Formula 1 , provided it is inert and can be removed partly, or completely from the substrate by conventional drying means (e.g. application of heat, reduced pressure, airflow etc.).
  • Suitable organic solvents for processing the semiconductors include, but are not limited to, aromatic or aliphatic hydrocarbons, halogenated such as chlorinated or fluorinated hydrocarbons, esters, ethers and amides, and mixtures thereof. Examples of such solvents are chloroform,
  • tetrachloroethane tetrahydrofuran, toluene, tetrahydronaphthalene, anisole, xylene, mesitylene, ethyl acetate, methyl ethyl ketone, dimethyl formamide, chlorobenzene, dichlorobenzene, trichlorobenzene and propylene glycol monomethyl ether acetate (PGMEA).
  • PMEA propylene glycol monomethyl ether acetate
  • the solution, and/or dispersion is then applied by a method, such as, spin- coating, dip-coating, screen printing, microcontact printing, doctor blading or other solution application techniques known in the art on the substrate to obtain thin films of the semiconducting material.
  • a transistor device includes a gate electrode, a gate insulating layer, source/drain electrodes, and a channel-forming region that are disposed on a base, the channel-forming region may be composed of a semiconductor. Furthermore, such a transistor device can also be configured as any of the bottom gate/bottom contact type field-effect transistor (FET), the bottom gate/top contact type FET, the top gate/bottom contact type FET, and the top gate/top contact type FET which will be described below.
  • FET bottom gate/bottom contact type field-effect transistor
  • the bottom gate/bottom contact type FET includes (1) a gate electrode disposed on a base, (2) a gate insulating layer disposed on the gate electrode, (3) source/drain electrodes disposed on the gate insulating layer, and (4) a channel-forming region disposed between the source/drain electrodes and on the gate insulating layer.
  • a surface treatment (5) may optionally be applied to the gate insulating layer.
  • the bottom gate/top contact type FET includes (1) a gate electrode disposed on a base, (2) a gate insulating layer disposed on the gate electrode, (3) a channel-forming region and a channel-forming region extension disposed on the gate insulating layer, and (4) source/drain electrodes disposed on the channel-forming region extension ( Figure 6).
  • a surface treatment (5) may optionally be applied to the gate insulating layer.
  • the top gate/bottom contact type FET includes (1) source/drain electrodes disposed on a base, (2) a channel-forming region disposed between the source/drain electrodes and on the base, (3) a gate insulating layer disposed on the channel-forming region, and (4) a gate electrode disposed on the gate insulating layer.
  • the top gate/top contact type FET includes (1) a channel- forming region and a channel-forming region extension disposed on a base, (2) source/drain electrodes disposed on the channel-forming region extension, (3) a gate insulating layer disposed on the source/drain electrodes and the channel-forming region, and (4) a gate electrode disposed on the gate insulating layer.
  • the base can be composed of a silicon oxide-based material or spin-on glass (SOG); silicon nitride; aluminum oxide; or a metal oxide high dielectric constant insulating film.
  • the base may be formed on (or above) a support composed of any of the materials described below. That is, examples of the material for the support and/or a base other than the base described above include organic polymers, such as polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinyl phenol (PVP), polyethersulfone (PES), polyimide, polycarbonate, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN); and mica.
  • PMMA polymethyl methacrylate
  • PVA polyvinyl alcohol
  • PVP polyvinyl phenol
  • PES polyethersulfone
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the polymeric materials are formed into plastic films, plastic sheets, and plastic substrates having flexibility.
  • a base composed of any of such flexible polymeric materials, for example, the resulting field- effect transistor can be built in or integrated into a display device or electronic apparatus having curved surfaces.
  • the base include various glass substrates, various glass substrates provided with insulating films on the surfaces thereof, quartz substrates, quartz substrates provided with insulating films on the surfaces thereof, silicon substrates provided with insulating films on the surfaces thereof, and metal substrates composed of various alloys or various metals, such as stainless steel.
  • a support having electrical insulating properties an appropriate material may be selected from the materials described above.
  • the support include conductive substrates, such as a substrate composed of a metal (e.g., gold), a substrate composed of highly oriented graphite, and a stainless steel substrate.
  • conductive substrates such as a substrate composed of a metal (e.g., gold), a substrate composed of highly oriented graphite, and a stainless steel substrate.
  • the semiconductor device may be provided on a support.
  • a support can be composed of any of the materials described above.
  • Examples of the material constituting the gate electrode, source/drain electrodes, and interconnect lines include metals, such as platinum, gold, palladium, chromium, molybdenum, nickel, aluminum, silver, tantalum, tungsten, copper, titanium, indium, and tin, alloys containing these metal elements, conductive particles composed of these metals, conductive particles composed of alloys containing these metals, and conductive materials, such as impurity-containing polysilicon. A stacked structure including layers containing these elements may be employed.
  • an organic material such as poly(3,4- ethylenedioxythiophene)/polystyrene sulfonic acid [PEDOT/PSS]
  • PEDOT/PSS polystyrene sulfonic acid
  • interconnect lines may be the same or different.
  • Examples of the method for forming the gate electrode, source/drain electrodes, and interconnect lines include, although depending on the materials constituting them, physical vapor deposition (PVD) methods; various chemical vapor deposition (CVD) methods, such as MOCVD; spin coating methods; various printing methods, such as screen printing, ink-jet printing, offset printing, reverse offset printing, gravure printing, and microcontact printing; various coating methods, such as air- doctor coating, blade coating, rod coating, knife coating, squeeze coating, reverse roll coating, transfer roll coating, gravure coating, kiss coating, cast coating, spray coating, slit orifice coating, calender coating, and dipping; stamping methods; lift-off methods; shadow-mask methods; plating methods, such as electrolytic plating, electroless plating, or a combination of both; and spraying methods.
  • PVD methods include (a) various vacuum deposition methods, such as electron beam heating, resistance heating, flash vapor deposition, and crucible heating; (b) plasma deposition methods; (c) various sputtering methods, such as diode sputtering, DC sputtering, DC magnetron sputtering, RF sputtering, magnetron sputtering, ion beam sputtering, and bias sputtering; and (d) various ion plating methods, such as a direct current (DC) method, an RF method, a multi-cathode method, an activation reaction method, an electric field deposition method, an RF ion plating method, and a reactive ion plating method.
  • DC direct current
  • Examples of the material constituting the gate insulating layer include inorganic insulating materials, such as silicon oxide-based materials, silicon nitride, and metal oxide high-dielectric-constant insulating films; and organic insulating materials, such as polymethyl methacrylate (PMMA), polyvinyl phenol (PVP), and polyvinyl alcohol (PVA). These materials may be used in combination.
  • inorganic insulating materials such as silicon oxide-based materials, silicon nitride, and metal oxide high-dielectric-constant insulating films
  • organic insulating materials such as polymethyl methacrylate (PMMA), polyvinyl phenol (PVP), and polyvinyl alcohol (PVA). These materials may be used in combination.
  • silicon oxide-based materials examples include silicon oxide, silicon oxynitride (SiON), spin-on glass (SOG), and low- dielectric-constant materials (e.g., polyaryl ethers, cycloperfluoro carbon polymers, benzocyclobutene, cyclic fluorocarbon resins, polytetrafluoroethylene, fluoroaryl ethers, polyfluoroimide, amorphous carbon, and organic SOG).
  • silicon oxide silicon oxide
  • SiON silicon oxynitride
  • SOG spin-on glass
  • low- dielectric-constant materials e.g., polyaryl ethers, cycloperfluoro carbon polymers, benzocyclobutene, cyclic fluorocarbon resins, polytetrafluoroethylene, fluoroaryl ethers, polyfluoroimide, amorphous carbon, and organic SOG.
  • the gate insulating layer may be formed by oxidizing or nitriding the surface of the gate electrode or by depositing an oxide film or a nitride film on the surface of the gate electrode.
  • an oxidation method using oxygen plasma or an anodic oxidation method may be mentioned.
  • a nitriding method using nitrogen plasma may be mentioned.
  • a gate insulating layer may be formed in a self-assembling manner on the surface of the gate electrode by coating the surface of the gate electrode with insulating molecules having functional groups capable of forming chemical bonds with the gate electrode, such as linear hydrocarbon molecules with one end being modified with a mercapto group, using a dipping method or the like.
  • a supplementary insulating layer may be formed in a self-assembling manner on the surface of the gate insulating layer by coating the surface of the gate electrode with insulating molecules having functional groups capable of forming chemical bonds with the gate electrode, such as linear hydrocarbon molecules with one end being modified with a silane group, using a dipping method or the like.
  • Examples of the method for forming the channel-forming region, or the channel- forming region and the channel-forming region extension include the various PVD methods described above; spin coating methods; various printing methods described above; various coating methods described above; dipping methods; casting methods; and spraying methods. As necessary, additives may be added.
  • monolithic integrated circuits in which many semiconductor devices are integrated on supports may be fabricated, or the individual semiconductor devices may be separated by cutting to produce discrete components. Furthermore, the semiconductor devices may be sealed with resins.
  • 2,7-Dibromofluorene (2.25 g, 6.94 mmol) was dissolved into THF (50 ml_) and chilled to 0°C.
  • Sodium tert-butoxide (1.70 g, 17.7 mmol) was added at 0°C under N 2 and the reaction stirred at 0°C for 15 mins.
  • 1-Bromo-2-ethylhexane (5.00 ml_, 28.1 mmol) was added dropwise at 0°C, the reaction was allowed to warm to room temperature and was stirred for 3 hrs.
  • Saturated NH 4 CI solution (50 ml_) was added and the product extracted into DCM (2 x 25 ml_).
  • This aldehyde was synthesised in a similar manner to 5,5'-(9,9-dioctyl-9/-/- fluorene-2,7-diyl)bis(thiophene-2-carbaldehyde).
  • a bilayer organic solar cell (1) according to one embodiment of the invention is illustrated in Figure 1.
  • the bilayer organic solar cell comprises a transparent layer of indium tin oxide as the anode (2) supported on a transparent thin film support (3), and a cathode (4) in the form of a metal cathode, opposite. Between the anode and cathode are layers of an electron donor material (or p-conductor) (5), for example
  • the device may contain multiple layers, and the term "bilayer" should be interpreted as encompassing 2 or more layered devices.
  • the device may be in the form of a single cell, or multiple cells connected in parallel and/or series.
  • the device typically further comprises positive and negative terminals (not illustrated) for connection to an energy storage device or other electrical component(s) or circuit(s).
  • a bulk heterojunction organic solar cell (7) according to one embodiment of the invention is illustrated in Figure 2.
  • the bulk heterojunction organic solar cell (7) comprises a transparent layer of indium tin oxide as the anode (2) supported on a transparent thin film support (3), and a cathode (4) in the form of a metal cathode, opposite.
  • an active material comprising a blend of electron acceptor material (6) (or n-conductor), for example a compound of Formula 1 , and an electron donor (or p-conductor) material (5), for example P3HT.
  • the concentration of each component (5) and (6) gradually increases when approaching to the corresponding electrode.
  • the device may be in the form of a single cell, or multiple cells connected in parallel and/or series.
  • the device typically further comprises positive and negative terminals (not illustrated) for connection to an energy storage device or other electrical component(s) or circuit(s).
  • ITO Indium tin oxide coated glass with a sheet resistance of 15 ⁇ /square was purchased from Kintek. Polyethylenedioxythiophene/polystyrenesulfonate
  • PEDOT/PSS Battery Diffraction S
  • PCBM and C60 were purchased from Nano-C.
  • Calcium pellets and 2,9-dimethyl-4,7-diphenyl-1 , 10- phenanthroline (BCP) were purchased from Aldrich. Aluminium pellets (99.999%) were purchased from KJ Lesker.
  • UV-ozone cleaning of ITO substrates was performed using a Novascan PDS- UVT, UV/ozone cleaner with the platform set to maximum height, the intensity of the lamp is greater than 36 mW/cm 2 at a distance of 100 cm. At ambient conditions the ozone output of the UV cleaner is greater than 50 ppm.
  • C60 was evaporated from a boron nitride crucible positioned inside a Radak furnace.
  • BCP was also evaporated from a boron nitride crucible positioned inside a Radak furnace.
  • Ca was evaporated from separate open tungsten boat supplied by RD Mathis. Al (4 pellets) was evapoated from alumina coated graphite boat which was supplied by Momentive Performance Materials. Al and Ca were supplied by K. J. Lesker.
  • ITO coated glass was cleaned by standing in a stirred solution of 5% (v/v) Deconex 12PA detergent at 90 °C for 20 mins. The ITO was successively sonicated for 10 minutes each in distilled water, acetone and / ' so-propanol. The substrates were then exposed to a UV-ozone clean (at room temperature) for 10 minutes. The PEDOT/PSS solution was filtered (0.2 ⁇ RC filter) and deposited by spin coating at 5000 rpm for 20 sec to give a 38 nm layer. The PEDOT/PSS layer was then annealed on a hotplate in the glovebox at 140 °C for 10 minutes.
  • 5% (v/v) Deconex 12PA detergent at 90 °C for 20 mins.
  • the ITO was successively sonicated for 10 minutes each in distilled water, acetone and / ' so-propanol.
  • the substrates were then exposed to a UV-ozone clean (at room temperature) for 10 minutes
  • solutions of the organic blends were deposited onto the PEDOT/PSS layer by spin coating inside a glovebox (H 2 0 and 0 2 levels both ⁇ 1 ppm).
  • a Laurell WS-650SZ6-NPP Lite spin coater was used.
  • Spinning conditions and film thicknesses were optimised for each blend.
  • the devices were transferred (without exposure to air) to a vacuum evaporator in an adjacent glovebox.
  • single layers of the organic materials were deposited sequentially by thermal evaporation at pressures below 2* 10 "6 mbar.
  • organic layers were dissolved in a semitransparent glass vial inside the glove box with appropriate weight/volume in a solvent such as chlorobenezene and 1 ,2- dichlorobenezene.
  • Well dissolved solutions were readily spin coated using a Laurell WS-650SZ-23NPP Lite single wafer spin processor. The spin parameters ranges from 2000-3000 RPM with an acceleration of 6000 RPM.
  • the thin films were further thermally annealed at 120°C for 10 minutes.
  • a layer of Ca was deposited by thermal evaporation at pressures below 2* 10 ⁇ 7 mbar.
  • a layer of Al was deposited by Angstrom Engineering evaporator at pressures below 2* 10 ⁇ 7 mbar. Where noted, the devices were then annealed on a hotplate in the glovebox.
  • a small amount of silver paint (Silver Print II, GC electronics, Part no.: 22-023) was deposited onto the connection points of the electrodes.
  • Completed devices were encapsulated with glass and a UV-cured epoxy (Lens Bond type J-91) by exposing to 254nm UV-light inside a glovebox (H 2 0 and 0 2 levels both ⁇ 1 ppm) for 10 minutes. Electrical connections were made using alligator clips.
  • the cells were tested with an Oriel solar simulator fitted with a 1000W Xe lamp filtered to give an output of 100mW/cm 2 at AM 1.5.
  • the lamp was calibrated using a standard, filtered Si cell from Peccell limited (The output of the lamp was adjusted to give a JSC of 0.605 mA).
  • the estimated mismatch factor of the lamp is 0.95. Values were not corrected for this mismatch.
  • Compound 1 was used in a blend device as an electron acceptor material with P3HT as the electron donor material.
  • Device structure ITO / PEDOT:PSS (38 nm) / Compound 1 : P3HT (1 : 1.2) (1 10 nm) / Ca ( 20 nm) / AI (100nm).
  • a 1 cm 3 solution of Compound 1 (15 mg) in 0.5 ml of ortho-dichlorobenzene and P3HT (18 mg) in 0.5 ml of ortho-dichlorobenzene were separately prepared by stirring for 30 mins.
  • the solutions were mixed, filtered (0.2 ⁇ RC filter) and spin coated at 3000 rpm for 60 second with an acceleration of 6000 rpm.
  • the thin films Prior to the vacuum deposition of electrodes, the thin films were annealed at 120°C for 10 minutes. Vacuum deposition of the Ca (20 nm) and Al (100 nm) layers were done using an Agstrom evaporator in the glove box.
  • Voc 830 mV
  • Isc 4.8 mA/cm 2
  • FF 52.53 %
  • PCE 2.04%.
  • Compound 7 was used in a blend device as an electron acceptor material with P3HT as the electron donor material.
  • a 1 cm 3 solution of Compound 7 (15 mg) in 0.5 ml of ortho- dichlorobenzene and P3HT (12 mg) in 0.5 ml of ortho-dichlorobenzene were separately prepared by stirring for 30 mins. The solutions were mixed, filtered (0.2 ⁇ RC filter) and spin coated at 3000 rpm for 60 second with an acceleration of 6000 rpm. Prior to the vacuum deposition of electrodes, the thin films were annealed at 120°C for 10 minutes.
  • Compound 46 was used in a blend device as an electron acceptor material with P3HT as the electron donor material.
  • a 1 cm 3 solution of Compound 46 (15 mg) in 0.5 ml of ortho-dichlorobenzene and P3HT (12 mg) in 0.5 ml of ortho-dichlorobenzene were separately prepared by stirring for 30 mins.
  • the solutions were mixed, filtered (0.2 ⁇ RC filter) and spin coated at 3000 rpm for 60 second with an acceleration of 6000 rpm.
  • the thin films Prior to the vacuum deposition of electrodes, the thin films were annealed at 120°C for 10 minutes. Vacuum deposition of the Ca (20 nm) and Al (100 nm) layers were done using an Agstrom evaporator in the glove box.
  • the l-V curve for the device is shown in Figure 5.
  • Figure 6 shows bottom gate/top contact transistor architecture with a surface treatment applied to the dielectric layer.
  • Transistor substrates (“substrates") of thermally grown silicon dioxide (“Si02”, “dielectric”, “dielectric layer”) of thickness 230nm on an n-doped (N ⁇ 3 ⁇ 10 17 cm “3 ) silicon (“n-Si”) wafer ("Gate", "Gate electrode”) were obtained from the Fraunhofer Institute. Solvents used for cleaning, acetone and / ' so-propanol, were of the Empure grade and were used as purchased from Merck KGaA.
  • HMDS Hexamethyldisilazane
  • OTS octadecyltrichlorosilane
  • Anhydrous cyclohexane was purchased from Sigma-Aldrich. Gold pieces (99.9999%) were purchased from Saffo. The organic materials were prepared as described.
  • a Binder vacuum oven connected to an Edwards RV3 vacuum pump was used to store substrates at elevated temperatures under vacuum following solvent cleaning.
  • UV-ozone cleaning of transistor substrates was performed using a Novascan PDS- UVT, UV/ozone cleaner with the platform set to maximum height, the intensity of the lamp is greater than 36 mW/cm 2 at a distance of 10 cm.
  • the ozone output of the UV cleaner is greater than 50 ppm.
  • a Laurell WS- 650SZ6-NPP Lite spin coater was used for spincoating, which was carried out in air
  • Vacuum depositions were carried out using an Angstrom Engineering evaporator opening into an M Braun glovebox, thermal evaporations being carried out at pressures below CCC with source to substrate distances of approximately 0.5m.
  • Deposition rates and film thicknesses were measured and controlled by Sigma-SQS- 242 software using a calibrated quartz thickness monitor inside the vacuum chamber and confirmed by subsequent measurement using a Dektak 6M Profilometer and by atomic force microscopy on blank samples and on completed devices after electrical measurements had been taken.
  • Organic compounds were evaporated from an
  • a contact pad to facilitate the making of the electrical connection from the Analyser to the Gate electrode of the device was made by drilling through the gate dielectric layer and into the Gate electrode using a Dremel drill and applying High Purity Silver Paint purchased from SPI-Paint to form the contact pad.
  • Transistor substrates were cleaned by rinsing briefly in acetone and then successively sonicating for 5 minutes each in acetone and then in / ' so-propanol.
  • Substrates were then dried in a stream of Nitrogen gas before being placed under vacuum in a vacuum oven at 100°C overnight. Substrates were then removed from the vacuum oven, placed on the platform of the UV-ozone cleaner for two minutes and then given a UV-ozone treatment for 10 minutes with the platform set to maximum height, the intensity of the lamp is greater than 36 mW/cm 2 at a distance of 10 cm. At ambient conditions the ozone output of the UV cleaner is greater than 50 ppm.
  • HMDS hexamethyldisilazane
  • octadecyltrichlorosilane (OTS) treatment of the freshly cleaned dielectric layer was applied by soaking freshly cleaned substrates in a 2mM solution of OTS in anhydrous cyclohexane for 16 hours in a dessicator under anhydrous conditions. Substrates were then rinsed briefly in neat anhydrous cyclohexane and then dried in a stream of nitrogen gas. Substrates were then transferred to a glovebox (H 2 0 and 0 2 levels both ⁇ 1 ppm) and maintained under an inert atmosphere throughout the rest of the fabrication process and until after electrical testing of the completed devices.
  • OTS octadecyltrichlorosilane
  • the evaporator was vented and the completed devices were transferred, without exposure to air, to an electrical testing station in an adjacent glovebox.
  • a Dremel drill was used to drill through the dielectric layer and into the underlying Gate electrode of the device. Silver paint was applied to this region so as to make an electrically conductive pathway between the Gate electrode and the contact pad formed by the Silver paint on top of the device. The device was then readied for measurement by making Gate, Source and Drain electrode connections to the Analyser by the use of Suss Microtech probes.
  • An Output' curve (I D-VD curve) was first measured by sweeping the drain voltage ( V D ) between 0V and +80V at 1 .0V intervals for gate voltages ( V G ) varied between and 0 and +80V at 10V intervals.
  • a 'transfer' curve (I D-VG curve) was then measured in the forward and reverse directions by sweeping the gate voltage (V G ) between -20 and +80V at 0.5V intervals (forward sweep) and then from +80V to -20V at intervals of -0.5V (reverse sweep) for drain voltages ( V D ) of +40V to +80V at 10V intervals.
  • the field effect electron mobility in the saturation regime e sa f is calculated from the forward sweep of the transfer curve for a drain voltage of +80V by obtaining t of V/ D against V G and using the standard transistor equation:
  • Compound 48 was used in a transistor as the electron transporting material on an OTS-treated Si02 surface. Film thicknesses of evaporated layers are shown in brackets.
  • Id-Vd and Id-Vg curves for one of the two devices on the substrate are shown in Figure 7 and 8 and are representative of both devices on the substrate.
  • a value of 0.083 cm 2 /Vs was calculated for the field effect electron mobility in the saturation regime for this device.
  • Compound 48 was used in a transistor as the electron transporting material on an HMDS-treated Si02 surface.
  • a value of 0.0026 cm 2 /Vs was calculated for the field effect electron mobility in the saturation regime for this device.
  • Compound 47 was used in a transistor as the electron transporting material on an OTS-treated Si02 surface.
  • a value of 0.01 1 cm 2 /Vs was calculated for the field effect electron mobility in the saturation regime for this device.

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Abstract

La présente invention concerne des dispositifs optoélectroniques photoactifs, par exemple des dispositifs photovoltaïques organiques, et des dispositifs à transistors, et des composés organiques utilisables dans les dispositifs optoélectroniques et à transistors. La présente invention concerne aussi des procédés de préparation de dispositifs optoélectroniques photoactifs et à transistors. Les dispositifs optoélectroniques photoactifs comprennent une première et une seconde électrode, et au moins une couche électroactive absorbant la lumière organique en connexion électrique avec les première et seconde électrodes qui génère un courant électrique en réponse à un rayonnement électromagnétique. La couche électroactive absorbant la lumière comprend un matériau donneur d'électrons et un matériau accepteur d'électrons, le matériau accepteur d'électrons comprenant un composé tel que décrit ici :
PCT/AU2013/000914 2012-08-17 2013-08-16 Dispositifs optoélectroniques photoactifs et à transistors WO2014026244A1 (fr)

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