CN101479272A

CN101479272A - Diketopyrrolopyrrole polymers as organic semiconductors

Info

Publication number: CN101479272A
Application number: CNA200780024495XA
Authority: CN
Inventors: M·G·R·特比茨; R·A·J·詹森; M·M·韦因克; H·J·柯纳; M·杜格利; B·蒂克; Y·朱
Original assignee: Ciba SC Holding AG
Current assignee: Clap Co Ltd
Priority date: 2006-06-30
Filing date: 2007-06-20
Publication date: 2009-07-08
Anticipated expiration: 2027-06-20
Also published as: CN101479272B

Abstract

The present invention relates to polymers comprising a repeating unit of the formula and their use as organic semiconductor in organic devices, especially a diode, an organic field effect transistor and/or a solar cell, or a device containing a diode and/or an organic field effect transistor, and/or a solar cell. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers according to the invention are used in semiconductor devices or organic photovoltaic (PV) devices (solar cells).

Description

Diketopyrrolopyrrole polymers as organic semiconductors

The invention relates to polymers comprising repeating units of formula (I) and to the use thereof as organic semiconductors in organic devices, in particular in diodes, organic field effect transistors and/or solar cells or devices comprising diodes, organic field effect transistors and/or solar cells. The polymers according to the invention have good solubility in organic solvents and good film-forming properties. Furthermore, when the polymers according to the invention are used in semiconductor devices or organic Photovoltaic (PV) devices (solar cells), efficient energy conversion, good field-effect mobility, good on/off current ratios and/or good stability can be observed.

Smet et al describe in Tetrahedron Lett.42(2001)6527-6530 a process for the preparation of diketopyrrolopyrrole oligomers in rod form using brominated 1, 4-dioxo-3, 6-diphenylpyrrolo [3, 4-c ] pyrrole (DPP) derivatives and 1, 4-dibromo-2, 5-di-n-hexylbenzene as monomers in a Suzuki coupled stepwise sequence.

M Horn et al, Eur. Polymer J.38(2002)2197-2205, describe the synthesis and characterization of thermal meso-polysiloxanes containing 2, 5-dihydropyrrolo [3, 4-c ] pyrrole units in the main chain.

EP-A-787,730 describes polyacrylates and polyurethanes polymerized from DPP of the formulｃA IｃA

Wherein Q₁And Q₄Independently of one another, is a polymerizable reactive group, and Q₂And Q₃Independently of one another are hydrogen, C₁₂～C₂₄Alkyl, C interrupted by 1 or more O or S₆～C₂₄Alkyl or a group of the formula

Wherein Q₅Is C₄～C₁₈Alkyl or C₅～C₁₀A cycloalkyl group. Although it has been mentioned that the compounds Ia can be used for the production of opto-and electrically conductive polymers, no corresponding examples are given. Furthermore, it is not given how to manufacture EL devices comprising DPP-based polymers and how to select suitable DPP-monomer materials for DPP-polymers.

Macromol chem. Phys.200(1999)106-112 describes fluorescent DPP-polymers obtainable by copolymerization of difunctional monomeric DPP-derivatives linked to the N-atom of the DPP-molecule by a functional group with diisocyanates or diols or dicarboxylic acids.

J.am.chem.Soc.117(1995)12426-12435 is involved in the development of a palladium catalyzed Stille coupling reaction for the synthesis of functionalized polymers. In scheme 7, the synthesis of the following polymers is given:

polymer 13: y is 0.05 and x is 0.95

Polymer 14: y is 0 and x is 1

It is not clarified whether the polymer can be used in an EL device.

J.Am.chem.Soc.115(1993)11735-11743 describes DPP-polymers which exhibit photorefractive properties, i.e.optical guiding and secondary nonlinear optical activity. In this device, the photoconductivity was measured by irradiating the device with a laser beam and then measuring the current generated by the irradiation, without measuring the electroluminescence.

Furthermore, it is not elucidated how to select other DPP-polymers.

In Appl. Phys.Lett.64(1994)2489-2491, to investigate photorefractive properties, a further study, i.e.a two-strand coupling experiment, was carried out with the polymer disclosed in J.Am.chem.Soc.115(1993) 11735-11743. The asymmetric energy exchange at zero electric field, i.e., the photorefractive property of the polymer disclosed in J.Am.chem.Soc.115(1993)11735-11743, was verified by two-beam coupling experiments.

U.S. Pat. No. 6, 6451459 (cf. B.Tieke et al, Synth. Met.130(2002) 115-119; Macromol. Rapid Commun.21(4) (2000)182-189) describes diketopyrrolopyrrole-based polymers and copolymers comprising the following units and their use in EL devices.

Wherein x is selected from the range of 0.005-1, preferably 0.01-1; y is 0.995 to 0, preferably 0.99 to 0; and wherein x + y is 1, and

wherein Ar is¹And Ar²Independently of one another, are the following groups:

and m, n are numbers from 1 to 10, and

R¹and R²Independently of one another is H, C₁～C₁₈Alkyl, -C (O) O-C₁～C₁₈Alkyl, perfluoro-C₁～C₁₂Alkyl, unsubstituted or substituted by C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy substituted 1-3 times C₆～C₁₂Aryl, or halo C₆～C₁₂Aryl radical, C₁～C₁₂alkyl-C₆～C₁₂Aryl or C₆～C₁₂aryl-C₁～C₁₂An alkyl group, a carboxyl group,

R³and R⁴Preferably hydrogen, C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, unsubstituted or substituted by C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy substituted 1-3 times C₆～C₁₂Aryl, or halo C₆～C₁₂Aryl, or perfluoro-C₁～C₁₂Alkyl, and

R⁵is preferably C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy, unsubstituted or substituted by C₁～C₁₂Alkyl radical, C₁～C₁₂Alkoxy substituted 1-3 times C₆～C₁₂Aryl, or halo C₆～C₁₂Aryl, or perfluoro-C₁～C₁₂Alkyl groups, and their use in EL devices. The following polymers

Is specifically disclosed in Tieke et al, Synth. Met.130(2002) 115-119. The following polymers

Is specifically disclosed in Macromol. Rapid Commun.21(4) (2000) 182-.

WO05/049695 discloses Diketopyrrolopyrrole (DPP) -based polymers and their use in PLEDs, organic integrated circuits (O-ICs), Organic Field Effect Transistors (OFETs), Organic Thin Film Transistors (OTFTs), organic solar cells (O-SCs) or organic laser diodes, but does not disclose specific DPP-based polymers of formula I. In example 12, the following polymer preparation method is described.

It is an object of the present invention to provide novel polymers which, when used in, for example, semiconductor devices, photodiodes or organic Photovoltaic (PV) devices (solar cells), have excellent properties, such as efficient energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability.

The object is achieved by a polymer comprising repeating units of the formula,

wherein

a. b, c, d, e and f are 0 to 200, in particular 0,1, 2 or 3;

Ar¹and Ar^1’Independently of one another, are a radical of the formula

Or

Ar²、Ar^2’、Ar³、Ar^3’、Ar⁴And Ar^4’Independently of one another, are a radical of the formula

Or

p is 0,1, 2, 3 or 4, if possible,

R¹and R²May be the same or different and is selected from hydrogen; c optionally substituted by E and/or interrupted by D₁～C₂₅Alkyl, alkenyl, alkynyl; can be covered with C₁～C₄Alkyl substituted allyl for 1-3 times; can be covered with C₁～C₈Alkyl radical, C₁～C₈Thioalkoxy or C₁～C₈Cycloalkyl substituted 1 to 3 times by alkoxy, or cycloalkyl which can be fused 1 to 2 times with a phenyl group which can be C-substituted₁～C₄Alkyl, halogen, nitro or cyano for 1-3 times; cycloalkenyl, ketone or aldehyde groups, ester groups, carbamoyl, silyl, siloxane groups, Ar¹⁰or-CR⁵R⁶-(CH₂)_g-Ar¹⁰Wherein

R⁵And R⁶Independently of one another, hydrogen, fluorine, cyano or C which can be substituted by fluorine, chlorine or bromine₁～C₄Alkyl or can be substituted by C₁～C₄A phenyl group substituted with an alkyl group 1 to 3 times,

Ar¹⁰is optionally substituted by G or heteroaryl, in particular by C₁～C₈Alkyl radical, C₁～C₈Thioalkoxy and/or C₁～C₈Phenyl or 1-or 2-naphthyl substituted by alkoxy 1 to 3 times, and g is 0,1, 2, 3 or 4,

R³may be the same or different within a group and is selected from C optionally substituted by E and/or interrupted by D₁～C₂₅Alkyl, C optionally substituted by G₆～C₂₄Aryl, C optionally substituted by G₂～C₂₀Heteroaryl, C optionally substituted by E and/or interrupted by D₁～C₁₈Alkoxy, C in aralkyl, the aryl group of which may optionally be substituted by G₇～C₂₅Aralkyl or-CO-R²⁸Or 2 or more R adjacent to each other³The base forms a ring;

R⁴、R^4’、R⁷and R^7’Independently of one another, hydrogen, C optionally substituted by E and/or interrupted by D₁～C₂₅Alkyl, C optionally substituted by G₆～C₂₄Aryl, C optionally substituted by G₂～C₂₀Heteroaryl, C optionally substituted by E and/or interrupted by D₁～C₁₈Alkoxy, C in aralkyl, aryl being optionally substituted by G₇～C₂₅Aralkyl, or-CO-R²⁸(ii) a Or R⁴And R^4’Forming a ring;

d is-CO-; -COO-; -S-; -SO-; -SO₂-；-O-；-NR²⁵-；-CR²³＝CR²⁴-; or

And

e is-OR²⁹；-SR²⁹；-NR²⁵R²⁶；-COR²⁸；-COOR²⁷；-CONR²⁵R²⁶(ii) a -CN; or halogen;

g is E, C which can be interrupted by D₁～C₁₈Alkyl, or C which is substituted by E and/or interrupted by D₁～C₁₈An alkoxy group,wherein

R²³、R²⁴、R²⁵And R²⁶Independently of one another is H; c₆～C₁₈An aryl group; quilt C₁～C₁₈Alkyl or C₁～C₁₈Alkoxy-substituted C₆～C₁₈An aryl group; c₁～C₁₈An alkyl group; or C interrupted by-O-₁～C₁₈An alkyl group, a carboxyl group,

R²⁷and R²⁸Independently of one another is H; c₆～C₁₈An aryl group; quilt C₁～C₁₈Alkyl or C₁～C₁₈Alkoxy-substituted C₆～C₁₈An aryl group; c₁～C₁₈An alkyl group; or C interrupted by-O-₁～C₁₈An alkyl group, a carboxyl group,

R²⁹is H; c₆～C₁₈An aryl group; quilt C₁～C₁₈Alkyl or C₁～C₁₈Alkoxy-substituted C₆～C₁₈An aryl group; c₁～C₁₈An alkyl group; or C interrupted by-O-₁～C₁₈An alkyl group, a carboxyl group,

R¹⁰⁹and R¹¹⁰Independently of one another is H, C₁～C₁₈Alkyl, C substituted by E and/or interrupted by D₁～C₁₈Alkyl radical, C₆～C₂₄Aryl, C substituted by G₆～C₂₄Aryl radical, C₂～C₂₀Heteroaryl, C substituted by G₂～C₂₀Heteroaryl group, C₂～C₁₈Alkenyl radical, C₂～C₁₈Alkynyl, C₁～C₁₈Alkoxy, C substituted by E and/or interrupted by D₁～C₁₈Alkoxy, or C₇～C₂₅Aralkyl, or

R¹⁰⁹And R¹¹⁰Together form the formula ═ CR¹⁰⁰R¹⁰¹A group of (1), wherein

R¹⁰⁰And R¹⁰¹Independently of one another are H,C₁～C₁₈Alkyl, C substituted by E and/or interrupted by D₁～C₁₈Alkyl radical, C₆～C₂₄Aryl, C substituted by G₆～C₂₄Aryl, or C₂～C₂₀Heteroaryl, or C substituted by G₂～C₂₀Heteroaryl, or

R¹⁰⁹And R¹¹⁰Together form optionally substituted C₁～C₁₈Alkyl-substituted 5-or 6-membered ring, C substituted by E and/or interrupted by D₁～C₁₈Alkyl radical, C₆～C₂₄Aryl, C substituted by G₆～C₂₄Aryl radical, C₂～C₂₀Heteroaryl, C substituted by G₂～C₂₀Heteroaryl group, C₂～C₁₈Alkenyl radical, C₂～C₁₈Alkynyl, C₁～C₁₈Alkoxy, C substituted by E and/or interrupted by D₁～C₁₈Alkoxy radical, C₇～C₂₅Aralkyl, or-C (═ O) -R¹⁸，

R¹¹¹Is H, C in which 1 or more carbon atoms not adjacent to one another in the radical can be replaced by-O-, -S-or-C (═ O) -O-, and/or C in which 1 or more hydrogen atoms can be replaced by F₆～C₂₅Alkyl radical, C₄～C₁₈Cycloalkyl radical, C₁～C₂₅Alkoxy in which 1 or more carbon atoms can be replaced by O, S or N and/or by 1 or more non-aryl radicals R¹¹¹Substituted C₆～C₂₄Aryl or C₆～C₂₄An aryloxy group;

in each case, m may be identical to or different from one another and is 0,1, 2 or 3, in particular 0,1 or 2, more in particular 0 or 1;

X¹is a hydrogen atom or a cyano group,

provided that if Ar is¹And Ar^1’Is formula

A and d are both 1 andAr²and Ar^2’Is different from the following formula

Or

A group of (a);

provided that if Ar is¹And Ar^1’Is formula

A and d are not 0; and with the proviso that no polymer of the formula

Wherein y is 0.05 and x is 0.95.

Intramolecular R¹And/or R²Polymers which are hydrogen can be obtained using protecting groups which can be removed after polymerization (see, for example, EP-A-0648770, EP-A-0648817, EP-A-0742255, EP-A-0761772, WO98/32802, WO98/45757, WO98/58027, WO99/01511, WO00/17275, WO00/39221, WO00/63297 and EP-A-1086984). The conversion of the pigment precursor into its pigmentary form is carried out by fragmentation under known conditions, such as heat, optionally in the presence of an added catalyst, such as that described in WO 00/36210.

Examples of such protecting groups are of the formula

Wherein L is any desired group suitable to impart solubility. L is preferably of the formula

Or

The group of (a), wherein,

Y¹、Y²and Y³Independently of one another is C₁～C₆An alkyl group, a carboxyl group,

Y⁴and Y⁸Independently of one another is C₁～C₆Alkyl by oxygen, sulfur or N (Y)¹²)₂Interrupted C₁～C₆Alkyl, or unsubstituted or C₁～C₆Alkyl-, C₁～C₆Alkoxy-, halogen-, cyano-or nitro-substituted phenyl or biphenyl radicals,

Y⁵、Y⁶and Y⁷Independently of one another, hydrogen or C₁～C₆An alkyl group, a carboxyl group,

Y⁹is hydrogen, C₁～C₆Alkyl or of the formula

Or

The group of (a) or (b),

Y¹⁰and Y¹¹Independently of one another are hydrogen, C₁～C₆Alkyl radical, C₁～C₆Alkoxy, halogen, cyano, nitro, N (Y)¹²)₂Or unsubstituted or halogen-, cyano-, nitro-, C₁～C₆Alkyl-or C₁～C₆An alkoxy-substituted phenyl group, wherein the phenyl group is substituted with an alkoxy group,

Y¹²and Y¹³Is C₁～C₆Alkyl radical, Y¹⁴Is hydrogen or C₁～C₆Alkyl, and Y¹⁵Is hydrogen, C₁～C₆Alkyl, or unsubstituted or C₁～C₆A phenyl group substituted with an alkyl group,

q is unsubstituted or substituted by C₁～C₆Alkoxy radical, C₁～C₆Alkylthio or C₂～C₁₂Dialkylamino mono-or poly-substituted p, q-C₂～C₆Alkylene, where p and q are different numbers of positions,

x is a heteroatom selected from the group consisting of: nitrogen, oxygen and sulfur, and a combination of nitrogen, oxygen and sulfur,

the value of m is as follows: when X is oxygen, m is 0, when X is nitrogen, m is 1,

L¹and L²Independently of one another, unsubstituted or mono-or poly-C₁～C₁₂Alkoxy-, -C₁～C₁₂Alkylthio-, -C₂～C₂₄Dialkylamino-, -C₆～C₁₂Aryloxy-, -C₆～C₁₂Arylthio-, -C₇～C₂₄alkylarylamino-or-C₁₂～C₂₄Diarylamino-substituted C₁～C₆Alkyl or [ - (p ', q' -C)₂～C₆Alkylene) -Z-]_n’-C₁～C₆Alkyl, n ' is a number from 1 to 1000, p ' and q ' are different numbers of positions, each Z is independently of any other heteroatom oxygen, sulfur or C₁～C₁₂Nitrogen substituted by alkyl, and, repeating unit [ -C [ - ]₂～C₆Alkylene) -Z-]Of (1) C₂～C₆The alkylene groups may be the same or different, and

L¹and L²May be saturated or unsaturated 1 to 10 times, may be uninterrupted or may be interrupted in any position by 1 to 10 substituents selected from- (C ═ O) -and-C₆H₄The radical (a) is interrupted and may have no further substituents or 1 to 10 further substituents selected from halogen, cyano and nitro. Most preferably L is of formula

A group of (1).

The polymers of the invention can be used as charge transport, semiconducting, e1 conducting, photoconducting, light emitting materials, surface modifying materials, electrode materials in batteries, orientation layers, or in OFETs, ICs, TFTs, displays, RFITD tags, electro-or photoluminescent devices, backlights of displays, photovoltaic or sensor devices, charge injection layers, Schottky diodes, memory devices (e.g. fefets), planarising layers, antistatics, conductive substrates or patterns, photoconductors or electrophotographic applications (recording).

The polymer of the invention can comprise one or more (different) repeating units of formula I, such as repeating units of formulae Ia and Ib.

The repeating unit of formula I may have an asymmetric structure, but a symmetric structure is preferred: a ═ d; b ═ e; c ═ f; ar (Ar)¹＝Ar^1’；Ar²＝Ar^2’；Ar³＝Ar^3’；Ar⁴＝Ar^4’。

R¹And R²C, which may be identical or different and is preferably chosen from hydrogen, C optionally interrupted by 1 or more oxygen atoms₁～C₂₅Alkyl radical, C₁～C₂₅Perfluoroalkyl, optionally substituted with C₁～C₄Alkyl substituted allyl for 1-3 times; can be covered with C₁～C₈Alkyl radical, C₁～C₈Thioalkoxy or C₁～C₈Cycloalkyl substituted 1 to 3 times by alkoxy, or cycloalkyl which may be fused 1 or 2 times by phenyl, which may optionally be C substituted₁～C₄Alkyl, halogen, nitro or cyano substituted 1 to 3 times, alkenyl, cycloalkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, keto or aldehyde group, ester group, carbamoyl group, keto group, silyl group, siloxane group, Ar¹⁰or-CR⁵R⁶-(CH₂)_g-Ar¹⁰Wherein

R⁵And R⁶Independently of one another, hydrogen, fluorine, cyano or C which is optionally substituted by fluorine, chlorine, bromine₁～C₄Alkyl radicals, or may be substituted by C₁～C₄Phenyl substituted 1-3 times by alkyl.

R¹And R²More preferably C, optionally interrupted by 1 or more oxygen atoms₁～C₂₅Alkyl, may be substituted by C₁～C₈Alkyl and/or C₁～C₈Alkoxy-substituted C₅～C₁₂Cycloalkyl, especially cyclohexyl, or C which may be condensed 1-2 times by phenyl₅～C₁₂Cycloalkyl, especially cyclohexyl, said phenyl optionally being substituted by C₁～C₄Alkyl, halogen, nitro or cyano substituted 1 to 3 times, or can be C₁～C₈Alkyl and/or C₁～C₈Phenyl or 1-or 2-naphthyl substituted by alkoxy 1-to 3-times, or-CR⁵R⁶-(CH₂)_g-Ar¹⁰Wherein R is³And R⁴Is hydrogen, Ar¹⁰Can be replaced by C₁～C₈Alkyl and/or C₁～C₈Phenyl or 1-or 2-naphthyl substituted by alkoxy 1-to 3-times, and g is 0 or 1. Alkyl interrupted 1 or more times by-O-is understood to mean a straight-chain or branched C which may be interrupted 1 or more times by-O-, for example 1, 2 or 3 times₂～C₂₅Alkyl radicals, which give rise to the following structural units: - (CH)₂)₂OCH₃，-(CH₂CH₂O)₂CH₂CH₃，-CH₂-O-CH₃，-CH₂CH₂-O-CH₂CH₃，-CH₂CH₂CH₂-O-CH(CH₃)₂，-[CH₂CH₂O]Y₁-CH₃Wherein Y1 is 1-10, -CH₂-CH(CH₃)-O-CH₂-CH₂CH₃and-CH₂-CH(CH₃)-O-CH₂-CH₃。

Most preferred R¹And R²Is C₁～C₂₅Alkyl, especially C₄～C₂₅Alkyl radicals, such as the n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1, 3, 3-tetramethylbutyl and 2-ethylhexyl radicals, n-nonyl, n-decyl, n-undecyl, n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-hexyldecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl radicals, where preferred radicals can be used in the formula

Where m1 is n1+4 and m1+ n1 is 22.

Chiral side chains, e.g. R¹And R²Either homochiral or racemic, which affect the morphology of the polymer.

The invention does not comprise polymers of formula I which satisfy the following conditions:

R¹and R²Independently of one another, C which can be interrupted by 1 or more oxygen atoms₁～C₂₅Alkyl, especially C₄～C₁₂An alkyl group, a carboxyl group,

Ar¹and Ar^1’Is a radical of the formula

Or

Wherein R is⁶Is hydrogen, C₁～C₁₈Alkyl or C₁～C₁₈Alkoxy, and R³²Is methyl, Cl or OMe, a ═ b ═ c ═ f ═ 0; d ═ e ═ 1;

Ar^2’is selected from

Or

Wherein

R⁶Is hydrogen, C₁～C₁₈Alkyl or C₁～C₁₈Alkoxy radical, and

Ar^3’is selected from

OrWherein

X¹Is a hydrogen atom or a cyano group.

Ar¹And Ar^1’May be different but are preferably the same and are of the formula

Especially

Or

A group of (A), and

Ar²、Ar^2’、Ar³、Ar^3’、Ar⁴and Ar^4’Independently of one another of the formulaOr

A group of (1), wherein

p represents 0,1 or 2, R³May be the same or different within a group and is selected from C optionally substituted by E and/or interrupted by D₁～C₂₅Alkyl, or C optionally substituted by E and/or interrupted by D₁～C₁₈An alkoxy group; r⁴Is C optionally substituted by E and/or interrupted by D₆～C₂₅Alkyl, C optionally substituted by G₆～C₁₄Aryl, such as phenyl, naphthyl or biphenyl, C optionally substituted by E and/or interrupted by D₁～C₂₅Alkoxy, or C in the radical of which aryl is optionally substituted by G₇～C₁₅An aralkyl group,

d is-CO-, -COO-, -S-, -SO₂-、-O-、-NR²⁵-, wherein R²⁵Is C₁～C₁₂Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or sec-butyl;

e is-OR²⁹；-SR²⁹；-NR²⁵R²⁵；-COR²⁸；-COOR²⁷；-CONR²⁵R²⁵(ii) a or-CN; wherein R is²⁵、R²⁷、R²⁸And R²⁹Independently of one another is C₁～C₁₂Alkyl radicals, such as the methyl, ethyl, n-propyl radical,

Isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl or 2-ethylhexyl, or C₆～C₁₄Aryl radicals, such as the phenyl, naphthyl or biphenyl radical,

g and E are preferably the same, or C₁～C₁₈Alkyl, especially C₁～C₁₂Alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl or 2-ethylhexyl radical.

Unit cell

And

may be different but are preferably the same and are of formula

Or

A group of (1), wherein

Represents a bond to the diketopyrrolopyrrole skeleton, R⁴As defined above, and R^4’And R⁴The meaning is the same.

In another embodiment of the invention, the unitAndmay be different but are preferably the same and are of formula

A group of (1), wherein

R⁴Is C which is optionally interrupted by 1 or more oxygen atoms₆～C₂₅An alkyl group.

In another embodiment of the present invention, the polymer comprises a repeat unit of the formula

Wherein,

a、b、c、d、e、f、R¹、R²、Ar¹、Ar^1’、Ar²、Ar^2’、Ar³、Ar³’、Ar⁴and Ar^4’Are all as defined above in the above-mentioned specification,

h is 1, and

Ar⁵is formulaOr

Wherein R is⁷And R^7’As defined above; or

The polymer has the following structure

^*- [ first repeating Unit]_q- [ branching Unit]_t-^*(III) in which

The "first repeat unit" is a repeat unit of formula I,

a "branching unit" is a unit containing more than 2 bonding points, and

q and t are integers, where q/t is the ratio of repeat units to "branching units" of formula I.

The repeating unit of formula II preferably has a symmetrical structure: a ═ d; b ═ e; c ═ f; ar (Ar)¹＝Ar^1’；Ar²＝Ar^2’；Ar³＝Ar^3’；Ar⁴＝Ar^4’。

A "branching unit" is a unit having more than 2 bonding points. Examples of branching units are described, for example, in dendromers and other Dendrimers, John Wiley & Sons, ltd.2002; star and superbranched polymers (Star and hyperbranched polymers) as master eds of M.K.Mishra and S.Kobayashi, Marcel Dekker 2000.

Examples of particularly suitable "branching units" are shown below:

wherein B and C are, independently of one another, an optionally fused aromatic or heteroaromatic ring, e.g.

Or

Is a bond to the DPP skeleton, especially

Wherein R is²⁰⁰、R²⁰¹And R²⁰²Independently of one another, H or C₁～C₂₅Alkyl, aryl, heteroaryl, and heteroaryl,

s is 1 or 2, and s is,

such as

Such as

Or

Or

Such as

Or

Using polyfunctional units ("branching units")

Producing a branched polymeric material as shown below for 2 multifunctional units:

(A is a repeating unit of the formula I, o, q, r and t are 0 to 500), or

Formula (II)

The "branching units" of (a) and polymers derived therefrom are novel and constitute other inventive aspects of the present invention.

In another preferred embodiment of the invention, the polymer comprises repeating units of the formula:

Especially

Especially

or

Wherein

R¹And R²Independently of one another is C₁～C₂₅Alkyl, and

R³and R^3’Independently of one another, C which is optionally interrupted by 1 or more oxygen atoms₆～C₂₅An alkyl group, a carboxyl group,

R⁴and R^4’Independently of one another, C which is optionally interrupted by 1 or more oxygen atoms₆～C₂₅Alkyl, and

R⁷and R^7’Independently of one another, C which is optionally interrupted by 1 or more oxygen atoms₆～C₂₅An alkyl group.

In another embodiment of the invention, the polymer is a polymer of the formula

Wherein

R¹And R²Independently of one another, hydrogen or C₁～C₂₅Alkyl, and

In one embodiment, the polymer according to the invention consists solely of one or more recurring units of the formula I. In a preferred embodiment, the polymer according to the invention consists precisely of one repeat unit of the formula I (homopolymer).

According to the present invention, the term "polymer" encompasses both polymers, in which the polymer is a molecule of high relative molecular mass whose structure comprises predominantly repeats of units derived, actually or conceptually, from low relative molecular mass, and oligomers, in which the structure comprises predominantly minority units derived, actually or conceptually, from lower relative molecular mass. A molecule is considered to have a high relative molecular mass if its properties do not change significantly with the removal of one or several units. A molecule is considered to have a medium molecular mass if its properties do change significantly with the removal of one or several units.

According to the invention, a homopolymer is derived from a (actual, implicit or hypothetical) monomer. Many polymers are formed by the reaction of complementary monomers with each other. It is easy to imagine that these units react to form "latent monomers" and their homopolymerization will give the actual product which can be regarded as a homopolymer. Some polymers are obtained by chemical modification of other polymers, so that the structure of the macromolecules that make up the resulting polymer can be considered to have been homopolymerized from a hypothetical monomer.

Thus, a copolymer is a polymer derived from more than one monomer, e.g., a copolymer, terpolymer, tetrapolymer, or the like.

The weight average molecular weight of the oligomer is less than 2000 Da. The weight average molecular weight of the polymer of the present invention is preferably 2000Da or more, particularly 2,000 to 2,000,000Da, more preferably 10,000 to 1,000,000Da, most preferably 10,000 to 750,000 Da. Molecular weight was determined by gel permeation chromatography using polystyrene standards.

In a preferred embodiment, the polymer of the invention is a homopolymer comprising repeat units of formula I, and can be represented by the formula

Wherein A is a repeat unit of formula I. In the said invention, the polymer preferably comprises recurring units of one of the formulae Ia to Ii, with recurring units of the formulae Ie, Id, Ih and Ii being particularly preferred.

Copolymer of formula VII comprising repeating units of formula I and COM¹Or COM²(v-0.995-0.005, w-0.005-0.995), and can also be obtained by a coupling reaction, such as a nickel coupling reaction:

or

Wherein A is as previously defined, -COM¹-a repeating unit selected from the following formulae:

or

And

wherein R is⁷And R^7’As defined above, the above-mentioned,

R⁴⁴and R⁴¹Is hydrogen, C₁～C₁₈Alkyl or C₁～C₁₈Alkoxy, and

R⁴⁵is H, C₁～C₁₈Alkyl or C1-C substituted by E and/or interrupted by D₁₈Alkyl, especially C interrupted by-O-)₁～C₁₈Alkyl, wherein D and E are as previously defined,

and-COM²Is of the formula

Or

A group of (1), wherein

R¹¹⁶And R¹¹⁷Independently of one another, H, C optionally interrupted by O₁～C₁₈Alkyl, or C optionally interrupted by O₁～C₁₈An alkoxy group,

R¹¹⁹and R¹²⁰Independently of one another, H, C optionally interrupted by O₁～C₁₈Alkyl, or

R¹¹⁹And R¹²⁰Together form the formula ═ CR¹⁰⁰R¹⁰¹A group of (1), wherein

R¹⁰⁰And R¹⁰¹Independently of one another is H, C₁～C₁₈Alkyl, or

R¹¹⁹And R¹²⁰Together form optionally substituted C₁～C₁₈Alkyl-substituted five-or six-membered rings.

In such embodiments, the polymer is a polymer of the formula

Wherein

A、COM¹And COM²As defined above, the above-mentioned,

the value of o is 1, and the value of O is,

q is 0.005 to 1,

r is a number of 0 or 1,

s is 0 or 1, wherein if d is 0, then e is not 1,

t is 0.995-0, wherein the sum of c and f is 1.

Homopolymers of the formula VII are obtained, for example, by nickel coupling reactions, in particular the Yamamoto reaction:

wherein A is a repeat unit of formula I.

Polymerization processes involving only dihalo-functional reactants can be carried out with nickel coupling reactions. One such coupling reaction has been described by Colon et al in J.pol.Sci., part A, Polymer chemistry Edition 28(1990)367 and by Colon et al in J.org.chem.51(1986) 2627. The reaction is generally carried out in a polar aprotic solvent (e.g., dimethylacetamide) containing a catalytic amount of a nickel salt, a sufficient amount of triphenylphosphine, and a large excess of zinc dust. A modification of this process has been described by loyda et al in Bull. chem. Soc. Jpn, 63(1990)80, in which an organic soluble iodide is used as an accelerator.

Another nickel-coupling reaction has been disclosed by Yamamoto in Procgress in Polymer science 17(1992)1153, in which a mixture of dihaloaromatic compounds is treated with an excess of a nickel (1, 5-cyclooctadiene) complex in an inert solvent. All nickel-coupling reactions, when applied to reaction mixtures of 2 or more aromatic dihalides, yield predominantly random copolymers. Such polymerization reactions can be terminated by adding a small amount of water to the polymerization mixture, which will replace the terminal halogen with a hydrogen group. Alternatively, monofunctional aryl halides can be used as chain terminators in such reactions, which will result in the formation of terminal aryl groups.

Nickel-coupled polymerization yields predominantly homopolymers or random copolymers comprising units incorporating DPP groups and units derived from other comonomers.

Homopolymers of formula VIId or VIIe may be obtained, for example, from the Suzuki reaction:

or

Wherein, A, COM¹And COM²As previously defined. Examples of preferred homopolymers of formula VIId or VIIe are shown below:

and

another example of a homopolymer of formula VIId is a polymer of the formula:

wherein

R¹And R²Independently of one another, H or C₁～C₂₅Alkyl, and

The condensation reaction of aromatic borates and halides, especially bromides, commonly referred to as the "Suzuki reaction", can have many organic functional groups, as reported by n.miyaura and a.suzuki in chemical reviews, vol.95, pp.457-2483 (1995). A preferred catalyst is 2-dicyclohexylphosphino-2 ', 6' -di-alkoxybiphenyl/palladium (II) acetate. A particularly preferred catalyst is 2-dicyclohexylphosphino-2 ', 6' -di-methoxybiphenyl (sPhos)/palladium (II) acetate. This reaction can be used to make high molecular weight polymers and copolymers.

To prepare the polymers corresponding to the formula VIId or VIIe, dihalides, such as dibromides or dichlorides, especially dibromides corresponding to the formula Br-A-Br, are reacted with equimolar amounts

OrWith diboronic acid or diboronate, in the presence of Pd and triphenylphosphine, wherein X¹¹In each case independently of the other, -B (OH)₂，-B(OY¹)₂OrWherein Y is¹In any case independently C₁～C₁₀Alkyl radical, Y²In any case independently C₂～C₁₀Alkylene radicals, e.g. -CY³Y⁴-CY⁵Y⁶-, or-CY⁷Y⁸-CY⁹Y¹⁰-CY¹¹Y¹²-, in which Y³、Y⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰、Y¹¹And Y¹²Are each independently of the other hydrogen or C₁～C₁₀Alkyl, especially-C (CH)₃)₂C(CH₃)₂-or-C (CH)₃)₂CH₂C(CH₃)₂-,. The reaction is generally carried out in an aromatic hydrocarbon solvent such as toluene at a temperature of from about 70 ℃ to 180 ℃. Other solvents, such as dimethylformamide and tetrahydrofuran, can also be used alone or in a mixture with aromatic hydrocarbons. An aqueous base, preferably sodium carbonate or bicarbonate, is used as the HBr scavenger. Depending on the reactivity of the reactants, the polymerization reaction can be carried out for 2 to 100 hours. Organic bases, such as tetraalkylammonium hydroxides, and phase change catalysts, such as TBAB, can increase boron activity (see, e.g., Leadbed @)&Marco; angew. chem. int. ed. eng.42(2003)1407 and references cited therein). Other variations of reaction conditions have been given by T.I.Wallow and B.MNovak in J.org chem.59(1994) 5034-.

If desired, monofunctional aryl halides or borate aryl salts can be used as chain terminators in such reactions, which will result in the formation of terminal aryl groups.

It is possible to control the sequence of monomer units in the resulting copolymer by controlling the order and composition of the monomer feeds in the Suzuki reaction.

The polymers of the present invention can also be synthesized using Stille coupling methods (see, e.g., Babudri et al, J.Mater.Chem., 2004, 14, 11-34; J.K.Stille, Angew.Chemie int.Ed.Engl.1986, 25, 508). To prepare the polymers corresponding to formula VIId or VIIe, a dihalide, such as a dibromide or dichloride, in particular a dibromide corresponding to the formula Br-A-Br, is reacted with a compound of formulaOr

A compound of (1), wherein X¹¹is-SnR²⁰⁷R²⁰⁸R²⁰⁹The reaction is carried out in an inert solvent at 0-200 ℃ in the presence of a palladium-containing catalyst. In this case, it is necessary to ensure that the totality of all monomers used isThe organotin functionality is well balanced with the halogen functionality. Furthermore, it can be shown that capping with a monofunctional agent at the end of the reaction facilitates the removal of the excess reactive groups. To carry out the process, the tin compound and the halogen compound are preferably introduced into 1 or more inert organic solvents and stirred at a temperature of from 0 ℃ to 200 ℃, preferably from 30 ℃ to 170 ℃, for from 1h to 200h, preferably from 5h to 150 h. The crude product can be purified by methods known to the person skilled in the art and suitable for the respective polymer, for example repeated reprecipitation or even dialysis.

Organic solvents suitable for the process are, for example, ethers such as diethyl ether, dimethoxyethane, diglyme, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether; hydrocarbons such as hexane, isohexane, heptane, cyclohexane, benzene, toluene, and xylene; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tert-butanol; ketones such as acetone, methyl ethyl ketone and isobutyl methyl ketone; amides such as Dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile, propionitrile, and butyronitrile, and mixtures thereof.

The palladium and phosphine components should be selected analogously to the description of the Suzuki variant.

Alternatively, the polymers of the invention may be treated with a zinc reagent (A- (ZnX)¹²)₂Wherein X is¹²Is halogen) and halide or triflate (COM)¹-(X¹¹)₂Wherein X is¹¹Is halogen or triflate) by Negishi reaction. Reference is made, for example, to E.Negishi et al, Heterocycles18(1982) 117-22.

In addition, halogen derivatives of DPP may be oxidatively polymerized (e.g., with FeCl)₃See, inter alia, P.Kovacic et al, chem.Ber.87(1987) 357-379; M.Wenda et al, Macromolecules25(1992)5125) or electrochemical polymerization (see, inter alia, N.Saito et al, Polymer.Bull.30 (1993) 285).

A monomer of the formula

And

are novel monomers and form a further aspect of the invention, wherein B and C are, independently of one another, an optionally fused aromatic or heteroaromatic ring,

a、b、c、d、e、f、Ar¹、Ar^1’、Ar²、Ar^2’、Ar³、Ar^3’、Ar⁴and Ar^4’As defined in claim 1 and X is ZnX¹²、-SnR²⁰⁷R²⁰⁸R²⁰⁹Wherein R is²⁰⁷、R²⁰⁸And R²⁰⁹Are identical or different and are H or C₁～C₆Alkyl, wherein 2 groups optionally form a common ring and these groups are optionally branched or unbranched, and X¹²Is a halogen atom, more particularly I or Br; or-OS (O)₂CF₃、-OS(O)₂Aryl radicals, in particular

-OS(O)₂CH₃，-B(OH)₂，-B(OY¹)₂，

-BF₄Na or-BF₄K, wherein Y¹In any case independently C₁～C₁₀Alkyl and Y²In any case independently C₂～C₁₀Alkylene radicals, e.g. -CY³Y⁴-CY⁵Y⁶-, or-CY⁷Y⁸-CY⁹Y¹⁰-CY¹¹Y¹²-, in which Y³、Y⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰、Y¹¹And Y¹²Are each independently of the other hydrogen or C₁～C₁₀Alkyl radicals, especiallyIt is-C (CH)₃)₂C(CH₃)₂-or-C (CH)₃)₂CH₂C(CH₃)₂With the proviso that if Ar is¹And Ar^1’Is formulaA and d are not 0 and Ar²And Ar^2’Is a group other than

Or

With the proviso that if Ar¹And Ar^1’Is formula

A and d are not 0.

Yet another aspect of the invention relates to the oxidized and reduced forms of the polymers and materials according to the invention. Whether electrons are lost or gained, results in the formation of highly delocalized ionic species with high conductivity. This can occur upon exposure to common dopants. Suitable dopants and doping methods are known to the person skilled in the art, see, for example, EP0528662, US 5,198,153 or WO 96/21659.

The doping process generally refers to treating a semiconductor material with an oxidizing or reducing agent to form delocalized ionic centers and corresponding counterions derived from the dopant used within the material in a redox reaction. Suitable doping methods include, for example, exposure to doping vapor at atmospheric pressure or reduced pressure, electrochemical doping in a dopant-containing solution, contacting the dopant with the semiconductor material to be thermally diffused, and ion implantation of the dopant into the semiconductor material.

When electrons are used as carriers, suitable dopants are, for example, halogens (e.g.I)₂、Cl₂、Br₂、ICl、ICl₃IBr and IF), Lewis acids (e.g. PF₅、AsF₅、SbF₅、BF₃、BCl₃、SbCl₅、BBr₃And SO₃) Protic acids, organic acids or amino acids (e.g. HF, HCl, HNO)₃、H₂SO₄、HClO₄、FSO₃H and ClSO₃H) Transition metal compound (e.g., FeCl)₃，FeOCl，Fe(ClO₄)₃，Fe(4-CH₃C₆H₄SO₃)₃，TiCl₄，ZrCl₄，HfCl₄，NbF₅，NbCl₅，TaCl₅，MoF₅，MoCl₅，WF₅，WCl₆，UF₆And LnCl₃(wherein Ln is a lanthanide), an anion (e.g., Cl)^-，Br^-，l^-，l^3-，HSO₄ ^-，SO^2-，NO^3-，ClO^4-，BF^4-，PF^6-，AsF^6-，SbF^6-，FeCl^4-，Fe(CN)₆ ^3-Anions of various sulfonic acids, e.g. aryl-SO₃ ^-)。

Examples of dopants are cations (e.g. H) when holes are used as carriers⁺、Li⁺、Na⁺、K⁺、Rb⁺And Cs⁺) Alkali metals (e.g., Li, Na, K, Rb and Cs), alkaline earth metals (e.g., Ca, Sr and Ba) O₂，XeOF₄，(NO₂ ⁺)(SbF₆ ^-)，(NO₂ ⁺)(SbCl₆ ^-)，(NO₂ ⁺)(BF₄ ^-)，AgClO₄，H₂lrCl₆，La(NO₃)₃·6H₂O，FSO₂OOSO₂F, Eu, acetylcholine, R₄N⁺(R is an alkyl group), R₄P⁺(R is an alkyl group), R₆As⁺(R is alkyl) and R₃S⁺(R is an alkyl group).

The conductive forms of the compounds and materials of the present invention can be used as organic "metals" in applications such as, but not limited to, charge injection layers and ITO planarising layers in organic light emitting diode applications, thin films for flat panel displays and touch screens, antistatic films, printed conductive substrates, patterns or traces in electronic applications, such as printed circuit boards and capacitors.

Halogen is fluorine, chlorine, bromine and iodine.

If possible, C₁～C₂₅The alkyl groups are generally linear or branched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethylpropyl, 1, 3, 3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1, 3, 3, 5, 5-hexamethylhexyl, n-heptyl, isoheptyl, 1, 3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1, 3, 3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl. C₁～C₈Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1, 3, 3-tetramethylbutyl and 2-ethylhexyl. C₁～C₄Alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl.

C₁～C₂₅Alkoxy is straight-chain or branched alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy or tert-pentoxy, heptoxy, octoxy, isooctoxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. C₁～C₈Examples of alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1, 3, 3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁～C₄Alkoxy, typically, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy. The term "alkylthio" refers to the same group as an alkoxy group except that the oxygen atom of the ether linkage is replaced with a sulfur atom.

C₂～C₂₅Alkenyl is straight-chain or branched alkenyl, such as vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2, 4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C_2-24Alkynyl is straight-chain or branched, and preferably C_2-8Alkynyl, which may be unsubstituted or substituted, is, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1, 4-pentadiyn-3-yl, 1, 3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-pent-4-yn-1-yl, trans-3-methyl-2-pent-4-yn-1-yl, 1, 3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-tetracosyn-24-yl.

The term "haloalkyl, haloalkenyl and haloalkynyl" means groups obtained by partially or wholly substituting the above-mentioned alkyl, alkenyl and alkynyl groups with halogen, such as trifluoromethyl and the like. The "aldehyde group, ketone group, ester group, carbamoyl group and amino group" includes those substituted with an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted. The term "silyl" refers to the formula-SiR⁶²R⁶³R⁶⁴Wherein R is⁶²、R⁶³And R⁶⁴Independently of one another is C₁～C₈Alkyl, especially C₁～C₄Alkyl radical, C₆～C₂₄Aryl or C₇～C₁₂Aralkyl groups, such as trimethylsilyl.

The term "cycloalkyl" is typically C₅～C₁₂Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, which may be unsubstituted or substituted. The term "cycloalkenyl" refers to an unsaturated alicyclic hydrocarbon group containing 1 or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted. Cycloalkyl, especially cyclohexyl, can be fused 1 or 2 times by phenyl, which can be C₁～C₄Alkyl, halogen and cyano are substituted 1 to 3 times. Such fused cyclohexyl radicals are

OrEspecially

Or

Wherein R is⁵¹、R⁵²、R⁵³、R⁵⁴、R⁵⁵And R⁵⁶Independently of one another is C₁～C₈Alkyl radical, C₁～C₈Alkoxy, halogen and cyano, especially hydrogen.

The term "aryl" is typically C₆～C₂₄Aryl radicals, e.g. phenyl, indenyl, azulenyl, naphthyl, biphenyl, as-indacenyl, s-indacenyl, acenaphthenyl, fluorenyl, phenanthryl, fluoranthenyl, terphenyl,

Radical, tetracene radical, picene radical, perylene radical, pentacene radical and hexacene radicalPyrenyl or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2-or 9-fluorenyl, 3-or 4-biphenyl, which may be unsubstituted or substituted. C₆～C₁₂Examples of aryl are phenyl, 1-naphthyl, 2-naphthyl, 3-or 4-biphenyl, 2-or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted.

The term "aralkyl" is generally C₇～C₂₄Aralkyl radicals, such as benzyl, 2-benzyl-2-propyl, beta-phenyl-ethyl, alpha-dimethylbenzyl, omega-phenyl-butyl, omega-dimethyl-omega-phenyl-butyl, omega-phenyl-dodecyl, omega-phenyl-octadecyl, omega-phenyl-eicosyl or omega-phenyl-docosyl, preferably C₇～C₁₈Aralkyl radicals, such as benzyl, 2-benzyl-2-propyl, beta-phenyl-ethyl, alpha-dimethylbenzyl, omega-phenyl-butyl, omega-dimethyl-omega-phenyl-butyl, omega-phenyl-dodecyl or omega-phenyl-octadecyl, and C is particularly preferred₇～C₁₂Aralkyl radicals, such as benzyl, 2-benzyl-2-propyl, β -phenyl-ethyl, α -dimethylbenzyl, ω -phenyl-butyl or ω, ω -dimethyl- ω -phenyl-butyl, in which the aliphatic and aromatic hydrocarbon radicals may be unsubstituted or substituted.

The term "aryl ether group" is generally C₆～C₂₄Aryloxy, that is to say, O-C₆～₂₄Aryl radicals, such as phenoxy or 4-methoxyphenyl. The term "arylthioether radical" is generally C_6-24Arylthio radicals, i.e. S-C_6～24Aryl, such as phenylthio or 4-methoxyphenylthio. The term "carbamoyl" is typically C_1～18Carbamoyl, preferably C_1～8Carbamoyl, which may be unsubstituted or substituted, such as carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

In alkylamino, dialkylamino, alkylarylamino, arylamino and diaryl, the term "aryl" is used "And "alkyl" is typically C respectively₁～C₂₅Alkyl and C₆～C₂₄And (4) an aryl group.

Alkylaryl means an alkyl-substituted aryl radical, especially C₇～C₁₂An alkylaryl group. Examples are tolyl, such as 3-methyl-or 4-methylphenyl, or xylyl, such as 3, 4-dimethylphenyl, or 3, 5-dimethylphenyl.

Heteroaryl is typically C₂～C₂₆Heteroaryl, i.e. a ring or fused ring system containing 5 to 7 ring atoms, in which nitrogen, oxygen or sulfur are possible heteroatoms, and is generally an unsaturated heterocyclic radical containing 5 to 30 atoms and having at least 6 conjugated pi-electrons, e.g. thienyl, benzo [ b ]]Thienyl, dibenzo [ b, d]Thienyl, thianthryl, furyl, furfuryl, 2H-pyranyl, benzofuryl, isobenzofuryl, dibenzofuryl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, quinolonol, isoquinonyl, 2, 3-diazananyl, 1, 5-diazananyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which may be unsubstituted or substituted.

Possible substituents of the above-mentioned groups are C₁～C₈Alkyl, hydroxy, mercapto, C₁～C₈Alkoxy radical, C₁～C₈Alkylthio, halogen, halogeno C₁～C₈Alkyl, cyano, aldehyde, ketone, carboxyl, ester, carbamoyl, amino, nitro or silyl.

As mentioned above, the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course only possible in the case of groups having at least 2 carbon atoms which are bonded by single bonds;C₆～C₈the aryl group is uninterrupted; interrupted aralkyl or alkaryl contains the unit D in the alkyl moiety. C substituted by 1 or more E and/or interrupted by 1 or more units D₁～C₁₈Alkyl is, for example, (CH)₂CH₂O)_1-9-R^xWherein R is^xIs H or C₁～C₁₀Alkyl or C₂～C₁₀Alkanoyl (e.g. CO-CH (C)₂H₅)C₄H₉)、CH₂-CH(OR^y’)-CH₂-O-R^yWherein R is^yIs C₁～C₁₈Alkyl radical, C₅～C₁₂Cycloalkyl, phenyl, C₇～C₁₅Phenylalkyl, and R^y’Comprising an image R^yThe same definition or is H; c₁～C₈alkylene-COO-R^zE.g. CH₂COOR^z、CH(CH₃)COOR^z、C(CH₃)₂COOR^zWherein R is^zIs H, C₁～C₁₈Alkyl group, (CH)₂CH₂O)_1-9R^xAnd R^xIncluding the definitions set forth above; CH (CH)₂CH₂-O-CO-CH＝CH₂；CH₂CH(OH)CH₂-O-CO-C(CH₃)＝CH₂。

The polymer of the present invention can be used as a semiconductor layer for a semiconductor device. The invention therefore also relates to a semiconductor device comprising a polymer of formula I. The semiconductor component is in particular a diode, an organic field effect transistor and/or a solar cell, or a component comprising a diode and/or an organic field effect transistor and/or a solar cell. There are many types of semiconductor devices. Commonality is the presence of one or more semiconductor materials. Semiconductor Devices have been described by, for example, s.m. sze in Physics of semiconductor Devices, 2 nd edition, John Wiley and sons, New York (1981). Such devices include rectifiers, transistors (of many types including p-n-p, n-p-n, and thin film transistors), light emitting semiconductor devices (such as organic light emitting diodes in display applications or backlights in liquid crystal displays), photoconductors, current limiters, solar cells, thermistors, p-n junctions, field effect diodes, Schottky diodes, and the like. In each semiconductor device, a semiconductor material is combined with one or more metals and/or insulators into a device. Semiconductor devices can be fabricated by known methods such as those described by Peter Van Zant in Microchip Fabrication, 4 th edition, McGraw-Hill, New York (2000). In particular, Organic electronic components can be manufactured as described in d.r. gamota et al Printed Organic and molecular electronics, Kluver Academic pub., Boston, 2004.

A particularly useful class of transistor Devices, Thin Film Transistors (TFTs), generally includes a gate electrode, a gate dielectric over the gate electrode, a source electrode and a drain electrode adjacent the gate dielectric, and a Semiconductor layer adjacent the gate dielectric and adjacent the source electrode and the drain electrode (see, e.g., s.m. sze, Physics of Semiconductor Devices, 2 nd edition, John Wiley and Sons, p. 492, New York (1981)). These components can be assembled in a variety of configurations. More specifically, an Organic Thin Film Transistor (OTFT) has an organic semiconductor layer.

The OTFT is supported on a substrate during manufacture, testing and/or use. Optionally, the base can also provide electrical functionality to the OTFT. Suitable substrate materials include organic and inorganic materials. For example, the substrate may comprise a silicon material including any of a variety of suitable silicon forms, inorganic glasses, ceramic foils, polymeric materials (e.g., acrylics, polyesters, epoxies, polyamides, polycarbonates, polyimides, polyketones, poly (oxy-1, 4-phenyleneoxy-1, 4-phenylenecarbonyl-1, 4-phenylenes) (sometimes referred to as polyetheretherketones or PEEK), polynorbornenes, polyphenylene ethers, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyphenylene sulfide (PPS)), filled polymeric materials (e.g., Fiber Reinforced Plastics (FRP)), and coated metal foils.

The gate electrode can be any suitable conductive material. For example, the gate electrode may comprise doped silicon or a metal such as aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, and titanium. Conductive inks/pastes consisting of carbon black/graphite or colloidal silver dispersions, optionally with a polymeric binder, may also be used. Conducting polymers such as polyaniline or poly (3, 4-ethylenedioxythiophene)/poly (phenylsulfonate) (PEDOT: PSS) may also be used. In addition, alloys, combinations, and multilayers of these materials are also suitable. In some OTFTs, the same material provides both the gate electrode function and the support function for the underlying substrate. For example, doped silicon can function as a gate electrode and support an OTFT.

A gate dielectric is typically provided over the gate electrode. The gate dielectric insulates the gate electrode from the rest of the OTFT device. Suitable materials for use as the gate dielectric may include, for example, inorganic electrically insulating materials.

The gate dielectric (insulator) may be a material such as an oxide, nitride, or a material selected from ferroelectric insulators (e.g., organic materials such as polyvinylidene fluoride/trifluoroethylene or poly-m-xylylene adipamide), or organic polymer insulators (e.g., polymethacrylates), polyacrylates, polyimides, benzocyclobutene (BCB), parylene, polyvinyl alcohol, polyvinylphenol (PVP), polystyrene, polyesters, polycarbonates) as described in j.veres et al, chem.mat.2004, 16, 4543, or in a.facchetti et al, adv.mat.2005, 17, 1705. Specific examples of materials suitable for the gate dielectric include strontiates, tantalates, titanates, zirconates, aluminum oxide, silicon oxide, tantalum oxide, titanium oxide, silicon nitride, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, and zinc sulfide, including but not limited to PbZr_xTi_1-xO₃(PZT)、Bi₄Ti₃O₁₂、BaMgF₄、Ba(Zr_1-xTi_x)O₃(BZT). In addition, alloys, hybrid material (e.g., polysiloxane or nanoparticle filled polymer) combinations and multilayers of these materials can also be used as gate dielectrics. The thickness of the dielectric layer is, for example, about 10 to 1000nm, and more specifically about 100 to 500nm, providing a capacitance of 0.1 to 100 nF.

The source and drain electrodes are separated from the gate electrode by a gate dielectric, and the organic semiconductor layer can be above or below the source and drain electrodes. The source and drain electrodes may be any suitable conductive material that facilitates providing a low resistance ohmic contact with the semiconductor layer. Suitable materials include most of the materials described above for the gate electrode, for example, aluminum, barium, calcium, chromium, gold, silver, nickel, palladium, platinum, titanium, polyaniline, PEDOT: PSS, other conductive polymers, alloys thereof, combinations thereof and multilayers thereof. Some of these materials are suitable for n-type semiconductor materials, while others are suitable for p-type semiconductor materials, as is well known in the art.

The thin film electrodes (i.e., gate, source and drain electrodes) can be formed by any suitable method, such as physical vapor deposition (e.g., thermal evaporation or sputtering) or ink jet printing. Patterning of these electrodes can be achieved by known methods such as shadow masking, additive lithography, subtractive lithography, printing, microcontact printing and pattern coating.

The present invention also provides a thin film transistor device comprising:

a plurality of conductive gate electrodes deposited on the base;

a gate insulating layer deposited on the conductive gate electrode;

a plurality of sets of conductive source and drain electrodes deposited on the insulating layer, each of the sets being aligned with a respective one of the gate electrodes;

an organic semiconductor layer deposited on said insulating layer substantially covering said gate electrode in the channel between the source and drain electrodes; wherein the organic semiconductor layer comprises a polymer of formula I or a mixture comprising polymers of formula I.

The present invention also provides a method of fabricating a thin film transistor device, comprising the steps of:

depositing a plurality of conductive gate electrodes on the base;

depositing a gate insulating layer on the conductive gate electrode;

depositing sets of conductive source and drain electrodes on the layer, each set aligned with a respective gate electrode;

depositing a layer I polymer on the insulating layer such that the layer of the compound of formula I or the mixture comprising the polymer of formula I substantially covers the gate electrode; thereby forming a thin film transistor device.

The mixture comprising the polymer of formula I produces a semiconductive layer comprising the polymer of formula I (typically 5 wt% to 99.9999 wt%, especially 20 to 85 wt%) and at least one further material. The other material may be, but is not limited to, a portion of a polymer of the same formula I but different in molecular weight, another polymer of formula I, a semiconducting polymer, a small organic molecule, a carbon nanotube, a fullerene derivative, an inorganic particle (quantum dot, quantum rod, quantum tripod, TiO)₂ZnO, etc.), conductive particles (Au, Ag, etc.), insulating materials such as those described for the gate dielectric (PET, PS, etc.).

For a heterojunction solar cell, the active layer preferably comprises a mixture of a polymer of formula I and a fullerene in a weight ratio of 1:1 to 1:3, such as [60] PCBM (═ 6, 6-phenyl-C61-methyl butyrate) or [70] PCBM.

Any suitable substrate can be used to make the polymer film of the present invention. The substrate used to make the above-described films is preferably metal, silicon, plastic, paper, coated paper, fabric, glass or coated glass.

Alternatively, the TFT can also be fabricated as follows: a polymer is solution deposited on the highly doped silicon substrate that has been covered with a thermally grown oxide layer, followed by vacuum deposition and patterning of the source and drain electrodes.

In another approach, the TFT is fabricated as follows: the source and drain electrodes are deposited on a highly doped silicon substrate that has been covered with a thermally grown oxide, and then a polymer is solution deposited to form a thin film.

The gate electrode may also be a patterned metal gate electrode on a substrate or conductive material such as a conductive polymer, and then an insulator is coated on the patterned gate electrode by a solution coating method or a vacuum deposition method.

Any suitable solvent can be used to dissolve and/or disperse the polymer herein, so long as it is inert and can be partially or completely removed from the substrate by conventional drying methods (e.g., heating, reduced pressure, air flow, etc.). Organic solvents suitable for processing the semiconductors of the present invention include, but are not limited to, aromatic or aliphatic hydrocarbons, halogenated hydrocarbons such as chlorinated or fluorinated, esters, ethers, amides such as chloroform, tetrachloroethane, tetrahydrofuran, toluene, 1, 2, 3, 4-tetrahydronaphthalene, anisole, xylene, ethyl acetate, methyl ethyl ketone, dimethylformamide, dichlorobenzene, trichlorobenzene, Propylene Glycol Monomethyl Ether Acetate (PGMEA) and mixtures thereof. The solution and/or dispersion is then coated on the substrate by a method such as spin coating, dip coating, screen printing, microcontact printing, blade coating, or other solution coating methods known in the art to obtain a thin film of the semiconductor material.

The term "dispersion" encompasses any composition comprising the semiconducting material of the present invention that is not completely soluble in a solvent. The dispersion was prepared as follows:

-selecting a composition comprising at least a polymer of formula I or a mixture comprising a polymer of formula I and a solvent, wherein the polymer has a lower solubility in said solvent at room temperature and a higher solubility in a high temperature solvent, wherein the composition gels when the temperature is reduced from the high temperature to the first lower temperature without stirring;

-dissolving at least part of the polymer in a solvent at elevated temperature;

-reducing the temperature of the composition from the elevated temperature to a first lower temperature; agitating the composition to break any gels, wherein agitation is initiated at any time before, simultaneously with, or after the composition is reduced from the elevated temperature to the first lower temperature; depositing a layer of the composition, wherein the composition is at a second, lower temperature than the elevated temperature; the layer is then at least partially dried.

The dispersion may also consist of the following components: (a) a continuous phase comprising a solvent, a binder resin and, optionally, a dispersant, and (b) a dispersed phase comprising a polymer of formula I or a mixture comprising a polymer of formula I of the present invention. The solubility of the polymer of formula I in the solvent may vary, for example, from 0% to about 20%, especially from 0% to 5%.

Preferably, the organic semiconductor layer has a thickness of about 5 to about 1000nm, especially about 10 to about 100 nm.

The polymers of the present invention may be used alone or in combination as organic semiconductor layers in semiconductor devices. The layer may be provided by any suitable method, such as vapour deposition (for lower molecular weight materials) and printing techniques. The compounds of the invention may be sufficiently soluble in organic solvents and capable of solution deposition and patterning (e.g., by spin coating, dip coating, ink jet printing, gravure printing, flexographic printing, offset printing, screen printing, microcontact (wave) printing, drop or area casting, or other known methods).

The polymers of the present invention can be used in integrated circuits and a wide variety of electronic articles comprising a plurality of OTFTs. Such articles include, for example, Radio Frequency (RFID) tags, backplanes for flexible displays (e.g., for personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g., optical-, image-, biological-, chemical-, mechanical-, or temperature sensors), particularly photodiodes, or security devices, and the like. Due to its ambipolarity, this material can also be used in Organic Light Emitting Transistors (OLETs).

The present invention provides organic Photovoltaic (PV) devices (solar cells) comprising the polymers according to the invention.

The PV device comprises in the following order:

(a) cathode (electrode)

(b) An optional transition layer, such as a basic halide, especially lithium fluoride,

(c) a light-active layer, a light-emitting layer,

(d) optionally a smoothing layer, which is applied to the substrate,

(e) anode (electrode)

(f) A base.

The photoactive layer comprises a polymer of the present invention. The photoactive layer is preferably made of the conjugated polymer of the invention as an electron donor and a fullerene, especially functionalized fullerene PCBM, as an electron acceptor.

The size (number of carbon atoms per molecule) ranges of fullerenes suitable for use in the present invention can vary widely. The term fullerene, as used herein, includes a variety of pure carbon cage-like molecules, including Buckminster fullerenes (C)₆₀) And related "spherical" fullerenes as well as carbon nanotubes. The fullerene may be selected from those known in the art, such as C₂₀～C₁₀₀₀. Preferably the fullerene is selected from C₆₀～C₉₆. Most preferably the fullerene is C₆₀Or C₇₀E.g. [60]]PCBM or [70]]PCBM. Chemically modified fullerenes may also be used, as long as the modified fullerenes retain the acceptor type and electron mobility characteristics. The receptor material may also be a material selected from the group consisting of: another polymer of formula I or any semiconducting polymer, as long as the polymer retains the acceptor type and electron mobility characteristics; organic small molecule, carbon nanotube, inorganic particle (quantum dot, quantum rod, quantum tripod, TiO)₂ZnO, etc.).

The electrodes are preferably composed of metal or "metal substitutes". Here, the term "metal" is used to include two types of materials: elemental pure metals, e.g., Mg, and metal alloys consisting of 2 or more elemental pure metals, e.g., Mg and Ag together, labeled Mg: Ag. The term "metal substitute" as used herein refers to a material that is not a metal in its ordinary sense, but which has desirable metal-like properties in some suitable applications. Common metal substitutes for electrodes and charge transport layers include doped wide-bandgap semiconductors, e.g., transparent conducting oxides such as Indium Tin Oxide (ITO), Gallium Indium Tin Oxide (GITO), and Zinc Indium Tin Oxide (ZITO). Another suitable class of metal substitutes is the transparent conducting polymer Polyaniline (PANI) and its chemical congener or PEDOT: PSS. The metal substitute may also be selected from a wide variety of non-metallic materials, where the term "non-metallic material" broadly refers to a broad class of materials, so long as no chemically bound form of metal is present in the material. High transparent non-metallic low resistance cathodes or high efficiency low resistance metallic/non-metallic composite cathodes are disclosed in, for example, US-B-6,420,031 and US-B-5,703,436.

The substrate may be, for example, a plastic (flexible substrate) or a glass substrate.

In another preferred embodiment of the invention, a smoothing layer is located between the anode and the photoactive layer. Preferred materials for the smoothing layer comprise 3, 4-polyethylene dioxythiophene (PEDOT) or 3, 4-polyethylene dioxythiophene: films of polyphenylsulfonate (PEDOT: PSS).

In a preferred embodiment of the invention, the photovoltaic cell comprises, as described in US-B-6,933,436, a transparent glass support on which an electrode layer made of indium/tin oxide (ITO) has been coated. The electrode layer typically has a relatively rough surface structure and is therefore covered with a smooth layer made of polymer, typically PEDOT, which is made conductive by doping. The photovoltaic layer is made of 2 components, with a layer thickness of, for example, 100nm to several μm, depending on the coating method, and is applied to the smooth layer. The photovoltaic layer is made of the conjugated polymer of the invention as an electron donor and fullerenes, especially functionalized fullerenes PCBM as an electron acceptor. These 2 components are mixed with a solvent and applied as a solution to the smooth layer by, for example, spin coating, casting, Langmuir-Blodgett ("LB"), ink jet printing, and sagging. Such photovoltaic layers can also be applied over a larger surface by a squeegee or printing process. It is preferred to use a dispersant, such as chlorobenzene, as the solvent instead of the typical toluene. Among the above methods, the vacuum deposition method, the spin coating method, the ink-jet printing method, and the casting method are particularly preferable from the viewpoints of ease of handling and cost.

In the case of forming a layer by spin coating, casting, and inkjet printing, the coating may be performed using a solution and/or dispersion prepared by dissolving or dispersing the composition in a suitable organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1, 2-dichlorobenzene, and a mixture thereof, at a concentration of 0.01 to 90 wt%.

Before the counter electrode is applied, a thin transition layer of a thickness of, for example, 0.6nm, which must be electrically insulating, is applied on the photovoltaic layer 4. In the exemplary embodiment, the transition layer is comprised of a material having a composition in the range of 2.10^-6A basic halide, i.e., lithium fluoride, that is vapor deposited at a rate of 0.2nm/min in a vacuum of torr.

If ITO is used as the hole-collecting electrode, aluminum vapor-deposited on the electrically insulating transition layer is used as the electron-collecting electrode. The electrical insulation of the transition layer obviously defeats the function of blocking the carrier crossing, especially in the transition region from the photovoltaic layer to the transition layer.

In yet another embodiment of the invention, one or more layers may be treated with a plasma prior to deposition of the next layer. For PEDOT: PSS layer, a mild plasma treatment before deposition of the next layer is particularly advantageous.

Photovoltaic (PV) devices may also consist of multijunction solar cells processed on top of each other to absorb more of the solar spectrum. Such structures are described, for example, in app. phys. let.90, 143512(2007), adv. funct. mater.16, 1897-1903(2006) and WO 2004/112161.

The so-called "tandem solar cell" comprises in the following order:

(a) a cathode (electrode) which is a cathode,

(c) a light-active layer, a light-emitting layer,

(d) optionally a smoothing layer, which is applied to the substrate,

(e) intermediate electrodes (e.g., Au, Al, ZnO),TiO₂Etc.)

(f) Optionally, additional electrodes, to match the energy level,

(g) an optional transition layer, such as a basic halide, especially lithium fluoride,

(h) a light-active layer, a light-emitting layer,

(i) optionally a smoothing layer, which is applied to the substrate,

(j) anode (electrode)

(k) A base.

PV devices can also be processed on fibers as described in US 20070079867 and US 20060013549.

Due to the excellent self-assembly properties of the composites of the present invention, the materials or films can also be used alone or together with other materials in or as orientation layers in LCD or OLED devices, as described in US 2003/0021913.

The following examples are included for illustration only and do not limit the scope of the claims. All parts or percentages are by weight unless otherwise indicated. Weight average molecular weight (M)_w) And polydispersity (M)_w/M_n(PD) by Gel Permeation Chromatography (GPC), [ 2 ]Instrument for measuring the position of a moving object: GPC from Viscotek (Houston, TX, USA)max+ TDA302, the response forms produced are Refractive Index (RI), Low Angle Light Scattering (LALS), Right Angle Light Scattering (RALS), and differential viscosity (DP) measurements.Chromatographic analysis conditions: column: PL from Polymer Laboratories (Church Stretton, UK)_gelMixing C (300X 7.5mm, 5 μm particles) to cover a molecular weight range of about 1X 10³About 2.5X 10⁶Da; mobile phase: tetrahydrofuran, containing 5g/l sodium trifluoroacetate; mobile phase flow rate: 0.5 or 0.7 ml/min; the solute concentration: about 1-2 mg/ml; injection volume: 100 mul; and (3) detection: RI, LALS, RALS, DP.Molecular weight calibration method: relative calibration was performed using a set of 10 polystyrene standards obtained from Polymer Laboratories (Church Stretto, UK) with molecular weights ranging from 1,930,000Da to 5,050Da, i.e., PS1,930,000PS1,460,000, PS1,075,000, PS 560,000, PS 330,000, PS 96,000, PS 52,000, PS 30,300, PS 10,100, PS 5,050 Da. Absolute calibration is based on LALS, RALS and DP responses. Based on experience from a number of studies, the above combinations provide the best calculation of molecular weight data. PS 96,000 is usually used as molecular weight standard, but each other PS standard within the molecular weight range to be determined can generally be selected for this purpose]。

All polymer structures given in the examples below are idealized representations of the polymer product obtained by the polymerization process. If more than 2 components are copolymerized with one another, the sequence in the polymer may be of alternating or random type, depending on the polymerization conditions.

Examples

Example 1

a) 4.5g of DPP1, 6.23g K₂CO₃And a solution of 8.68g of 1-bromo-2-ethyl-hexyl in 60ml of N-methylpyrrolidone (NMP) were heated to 140 ℃ and thermostatted for 6 h. The mixture was washed with water and extracted with dichloromethane. The organic phase is then dried and dried on a double layer of silica gel and

(CAS 91053-39-3; Fluka 56678) and concentrated. The residue was dissolved in 100ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide were added portionwise over 1 h. After the reaction was complete, the mixture was washed with water. The organic phase is extracted, dried and concentrated. The compound was then purified on a silica gel column to give 1.90g of DPP 2 as a violet powder.

C₁₂H₂₅Is n-dodecyl

b) 500mg of DPP 2 dibromide, 990mg of tin derivative and 85mg of Pd (PPh) under inert conditions₃)₄The solution in 30ml of dry toluene was refluxed overnight. After cooling, it is on a double-layer silica gel-

The mixture was filtered, concentrated with methanol and precipitated. The precipitate was filtered off and rinsed with methanol to yield 530mg of blue solid DPP 3.

c) A solution of 2.55g of the corresponding monomer 3 in chlorobenzene was degassed with argon at 50 ℃ for 15 min. Then 1.6g FeCl was added to the nitromethane₃And the mixture was stirred while degassing at 50 ℃ for 4 h. The solution was then poured into methanol and the blue precipitate was filtered off and washed with methanol. The solid was then purified by Soxhlet extraction, purified with methanol and hexane, and 2g of the polymer fraction (4) was extracted with chloroform.

M_w＝13301

Fe content 75ppm

The photophysical properties are as follows:

the UV spectra of spin-coated films on glass substrates were measured from hot chlorobenzene solutions and annealed at different temperatures:

annealing conditions	Ultraviolet-visible absorption
annealing conditions	Ultraviolet-visible absorption	At room temperature	680nm
100℃，20min	720nm，800nm	At room temperature	680nm
100℃，20min	720nm，800nm	150℃，20min	720nm，800nm

The growth of the band at 800nm indicates that strong aggregation behavior occurs upon annealing.

Application example 1a DPP-Polymer based field Effect transistor

a) Experiment:

bottom gate Thin Film Transistors (TFTs) with p-Si gates were used in all experiments. High quality thermal SiO₂Capacitor C per unit area_i＝32.6nF/cm²The gate insulator. The source and drain electrodes were patterned directly on the gate-oxide using photolithography (bottom contact configuration). There were 16 transistors on each base, with Au source/drain electrodes defining channels of different lengths. Derivatization of SiO with Hexamethyldisilazane (HMDS) or Octadecyltrichlorosilane (OTS) prior to deposition of the organic semiconductor₂A surface. Films were made by spin casting or drop casting solutions of the polymer obtained in example 1 in different solvents. Transistor behavior was measured on an automated tester, transistor probe TP-10, refined with CSEM.

b) Transistor performance:

thin film transistors exhibit clear p-type transistor behavior. From a linear fit to the root mean square of the saturation transfer characteristic, a field effect mobility of 0.15cm can be measured²Vs. The threshold voltage of the transistor is about 0V to 5V. The transistor has a gate electrode 10⁴～10⁷Good on/off current ratio.

Annealing of the sample resulted in a dramatic increase in properties (especially mobility), which can be correlated with better aggregation of the solid polymer. Tests on a group of OFETs exposed to air for 2 months showed very good stability, since the mobility hardly changed. The on/off current ratio, which is usually the most problematic, is reduced by only a factor of 10.

Application example 1b

DPP-polymer-based high-capacity heterojunction solar cell

a) Experiment:

the solar cell has the following structure: al electrode/LiF layer/organic layer comprising the polymer/[ poly 3, 4-ethylenedioxythiophene (PEDOT)/polyphenylsulfonic acid (PSS) of the invention]ITO electrode/glass substrate. The manufacturing method of the solar cell is to spin a layer of PEDOT-PSS on pre-patterned ITO on a glass substrate. The polymer of example 1 (0.5 wt%) was then spin coated: [60]PCBM (substituted C60 fullerene:) A 1:4 mixture (organic layer). LiF and Al were sublimated through a shadow mask under high vacuum.

b) Performance of solar cell:

the solar cell was measured under a solar simulator. The current under AM1.5 conditions was then estimated using an External Quantum Efficiency (EQE) plot.

It follows that the overall efficiency is estimated for 1.62% measured before annealing, with J_sc＝4.1mA/cm²FF is 0.539 and V_oc0.733V. After 10min at 100 ℃, the efficiency was estimated to increase to 2%. By changing the deposition solvent, polymer/[ 60]]The PCBM ratio optimizes the form of the active layer, and the performance of the device can be improved to 3.06% (J)_sc＝9.5mA/cm²FF is 0.46 and V_oc＝0.7V)。

Example 2

a) 25g of DPP1, 46.07g K₂CO₃And a solution of 75g of 1-bromo-2-hexyl-decyl in 300ml of N-methylpyrrolidone (NMP) are heated to 140 ℃ and thermostated for 6 h. The mixture was washed with water and extracted with dichloromethane. The organic phase is then dried and dried on a double layer of silica gel and

filtering and concentrating. The residue was dissolved in 100ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide were added portionwise over 1 h. After the reaction was complete, the mixture was washed with water. The organic phase is extracted, dried and concentrated. The compound was then purified on a silica gel column to give 19g of DPP5 as a purple powder.

b) Under inert conditions, 18.5g of DPP dibromide 5, 27.47g of tin derivative and 2.36g of Pd (PPh)₃)₄The solution in 250ml of dry toluene was refluxed overnight. After cooling, on a silica gel column (CHCl)₃Hexane 3/7) to yield 20.2g of blue solid DPP 6.

c) 10g of DPP derivative 6 are dissolved in 300ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide are added in portions over 1 h. After the reaction was complete, the mixture was washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate was filtered off and rinsed with methanol to give 10g of blue solid DPP 7.

In a Schlenk tube, 240mg of Ni (COD)₂And a solution of 140mg of bipyridine in 10ml of toluene was degassed for 15 min. To this solution was added 1g of the corresponding dibrominated monomer 7, and the mixture was then heated to 80 ℃ and stirred vigorously overnight. The solution was poured onto 100ml 1/1/1 of a methanol/HCl/acetone mixture and stirred for 1 h. The precipitate was then filtered off and dissolved in CHCl₃Neutralized and reacted with Ethylene Diamine Tetraacetic Acid (EDTA) at 60 deg.C) The aqueous tetrasodium salt solution was stirred vigorously for an additional 1 h. The organic phase is washed with water, concentrated and precipitated in methanol. The residue was purified by Soxhelt extraction with methanol and hexane, then with CHCl₃The polymer was extracted to yield 250mg of violet fiber.

M_w＝77465

Ni content 65ppm

Solubility in toluene >10 wt%

The photophysical properties are as follows:

annealing conditions	Ultraviolet-visible absorption
annealing conditions	Ultraviolet-visible absorption	At room temperature	680nm
100℃，20min	720nm，800nm	At room temperature	680nm

Application example 2 DPP-Polymer based field Effect transistor

a) Experiment:

application example 1a was repeated, but the polymer obtained in example 1 was replaced by the polymer obtained in example 2.

b) Transistor performance:

thin film transistors exhibit clear p-type transistor behavior. From a linear fit to the root mean square of the saturation transfer characteristic, a field effect mobility of 0.013cm was determined²Vs. The threshold voltage of the transistor is about 0V to 4V. The transistor has a gate electrode 10⁵～10⁷Is goodOn/off current ratio. Tests on a group of OFETs exposed to air for 7 days showed that the stability was very good, since the mobility was almost unchanged or even better, usually the on/off current ratio, which is most prone to problems, was reduced by only a factor of 5. The composites have up to 10 in conventional equipment^-3cm²Electron mobility of/Vs. After optimizing the device with an upper contact transistor, the bipolar of the polymer is even more pronounced, with holes and electrons having up to 0.1cm²Similar mobility of/Vs.

Example 3

a) 25g of DPP1, 46.07g K₂CO₃And a solution of 55g of 1-bromo-2-butyl-hexyl in 300ml of N-methylpyrrolidone (NMP) were heated to 140 ℃ and the temperature was kept constant for 6 h. The mixture was washed with water and extracted with dichloromethane. The organic phase is then dried and dried on a double layer of silica gel and

filtering and concentrating. The residue was dissolved in 100ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide were added portionwise over 1 h. After the reaction was completed, the mixture was washed with water. The organic phase is extracted, dried and concentrated. The complex is then purified on a silica gel column to give 9.5g of DPP 8 as a violet powder.

b) Under inert conditions, 2.24g of DPP dibromide 8, 4.11g of tin derivative and 351mg of Pd (PPh)₃)₄The solution in 50ml of dry toluene was refluxed overnight. After cooling, on a silica gel column (CHCl)₃Hexane 3/7) to yield 2.37g of blue solid DPP 9.

c) 1.27g of DPP derivative 9 are dissolved in 60ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide are added portionwise over 1 h. After the reaction was completed, the mixture was washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate was filtered off and rinsed with methanol to give 1.32g of blue solid DPP 10.

d) In a Schlenk tube, 244mg of Ni (COD)₂And a solution of 142mg of bipyridine in 10ml of toluene was degassed for 15 min. To this solution was added 1g of the corresponding dibrominated monomer 10, and the mixture was then heated to 80 ℃ and stirred vigorously overnight. The solution was poured onto 100ml 1/1/1 of a methanol/HCl/acetone mixture and stirred for 1 h. The precipitate was then filtered off and dissolved in CHCl₃Neutralized and vigorously stirred at 60 ℃ with an aqueous solution of tetrasodium salt of ethylenediaminetetraacetic acid (EDTA) for an additional 1 h. The organic phase was washed with water, concentrated and precipitated in methanol. The residue was purified by Soxhelt extraction with methanol and hexane, then with CHCl₃The polymer was extracted to give 650mg of violet fibres.

M_w＝30000

Ni content 52ppm

In CHCl₃The solubility of the component (C) is 0.5 wt%

The photophysical properties are as follows:

annealing conditions	Ultraviolet-visible absorption
annealing conditions	Ultraviolet-visible absorption	At room temperature	720nm，810nm

The band at 810nm is due to the aggregation behavior.

Application example 3 DPP-Polymer based field Effect transistor

a) Experiment:

application example 1a was repeated, but the polymer obtained in example 1 was replaced by the polymer obtained in example 3.

b) Transistor performance:

thin film transistors exhibit clear p-type transistor behavior. From a linear fit to the root mean square of the saturation transfer characteristic, a field effect mobility up to 0.1cm at maximum can be measured²Vs. The threshold voltage of the transistor is about 6V. The transistor has a gate electrode 10⁴～10⁵Good on/off current ratio.

Example 4

a) 3.5g of DPP 11, 3.04g K₂CO₃And a solution of 4.13g of 1-bromo-2-hexyl-decyl in 60ml of N-methylpyrrolidone (NMP) is heated to 140 ℃ and thermostated for 6 h. The mixture was washed with water and extracted with dichloromethane. The organic phase is then dried and dried on a double layer of silica gel and

filtering and concentrating. The residue was dissolved in 100ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide were added portionwise over 1 h. After the reaction was completed, the mixture was washed with water. The organic phase is extracted, dried and concentrated. The compound was then purified on a silica gel column to give 17g of DPP 12 as violet powder.

b) Under inert conditions, 1.6g of DPP dibromide 12, 0.65g of tin derivative and 150mg Pd (PPh)₃)₄The solution in 60ml of dry toluene was refluxed overnight. After cooling, on a silica gel column (CHCl)₃Hexane 3/7) to yield 1.27g of blue solid DPP 13.

c) 1.27g of DPP derivative 13 is dissolved in 50ml of chloroform, cooled to 0 ℃ and then 2 equivalents of N-bromosuccinimide are added in portions over 1 h. After the reaction was complete, the mixture was washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate was filtered and rinsed with methanol to give 1.22g of blue solid DPP 14.

d) In a Schlenk tube, 292mg of Ni (COD)₂And a solution of 170mg bipyridine in 10ml toluene was degassed for 15 min. To this solution was added 1.2g of the corresponding dibrominated monomer 14, and the mixture was heated to 65 ℃ and stirred vigorously for 41 h. The solution was poured onto 100ml 1/1/1 of a methanol/HCl/acetone mixture and stirred for 1 h. The precipitate was then filtered off and dissolved in CHCl₃And vigorously stirred with an aqueous solution of tetrasodium salt of Ethylene Diamine Tetraacetic Acid (EDTA) at 60 ℃ for another 1 h. The organic phase was washed with water, concentrated and precipitated in methanol. The residue was purified by Soxhelt extraction with methanol and hexane, then with CHCl₃The polymer was extracted to give 730mg of violet fiber.

M_w＝30000

Ni content 14ppm

In CHCl₃The solubility of the component (C) is 0.5 wt%

The photophysical properties are as follows:

annealing conditions	Ultraviolet-visible absorption
annealing conditions	Ultraviolet-visible absorption	At room temperature	720nm，800nm

The band at 800nm is due to the aggregation behavior.

Application example 4 DPP-Polymer based field Effect transistor

a) Experiment:

application example 1a was repeated, but the polymer obtained in example 1 was replaced by the polymer obtained in example 4.

b) Transistor performance:

thin film transistors exhibit clear p-type transistor behavior. From the linear fit to the root mean square of the saturation transfer characteristic, the field effect mobility can be measured up to 0.013cm²Vs. The threshold voltage of the transistor is about 4V to 8V. The transistor has a gate electrode 10⁴～10⁵Good on/off current ratio. Tests on a group of OFETs exposed to air for 2 months showed very good stability, since the mobility was even better (up to 0.028 cm)²Vs), the on/off current ratio, which is usually the most problematic, is also increased by a factor of 5 to 10 and the threshold voltage is 0V to 4V.

Example 5

In a three-necked flask, 5g of 7, 1.185g of 1, 4-benzenediboronic acid dippinacol ester, 3.773g of K₃PO₄A degassed solution of 88.5mg of sPhos (2-dicyclohexylphosphino-2 ', 6' -dimethoxybiphenyl) and 80.6mg of palladium acetate in 60ml of toluene, 20ml of dioxane and 10ml of water was heated to 90 ℃ and stirred vigorously overnight. Then excess bromobenzene was added to cap the polymer after 2h at the same temperature with excess pinacol ester of phenylboronic acid. After capping was completed for 2h, 100mL of NaCN (1 wt%) in water was added, and the mixture was stirred at 90 ℃ for 3 h. The organic phase was extracted and precipitated in methanol. The residue was redissolved in toluene and treated with NaCN and the organic phase was precipitated in methanol. By Soxhlet extraction with acetone and Et₂The residue was purified O and then CHCl₃The polymer was extracted to give 2.5g of violet fibers.

M_w＝27000

Pb content of 30ppm

In CHCl₃The solubility of the component (C) is 1 wt%

The photophysical properties are as follows:

annealing conditions	Ultraviolet-visible absorption
annealing conditions	Ultraviolet-visible absorption	At room temperature	630nm，680nm

The band at 680nm is due to the aggregation behavior.

Example 6

In a dry flask purged with nitrogen, 1g7, 82mg Pd (PPh)₃)₄(10 mol%) and 13.5mg of copper iodide (10 mol%) were dissolved in diethylamine (0.85ml) and THF (2 ml). The flask was then placed under vacuum, purged with nitrogen, and this was repeated 3 times. 328mg of the diyne derivative were then added, the flask sealed under nitrogen, heated to 85 ℃ and stirred overnight. The reaction mixture was dissolved in 50ml of CHCl₃Triturate in 500ml MeOH, then filter. This operation was repeated 1 time. The solid was then purified by Soxhlet extraction with MeOH, acetone, and heptane, followed by CHCl₃The polymer was extracted to obtain 0.5g of violet fibers (M)_w38000; in CHCl₃Solubility of (1) ═ 0.5 wt%).

The photophysical properties are as follows:

annealing conditions	Ultraviolet-visible absorption
annealing conditions	Ultraviolet-visible absorption	At room temperature	650nm，700nm

The band at 700nm is due to the aggregation behavior.

Example 7

a) A solution of 17.3g DPP 15, 8.18g KOH (dissolved in 5ml water) and 52g 1-iodo-2-hexyl-decyl in 200ml N-methylpyrrolidone (NMP) was heated to 140 ℃ and thermostated for 6 h. The mixture was cooled to room temperature and filtered. The filter cake was washed with methanol, then dissolved in dichloromethane and precipitated in DMSO. The precipitate is filtered off and dried. 9.5g of the precipitate were dissolved in 160ml of hexane, and then 2 equivalents of N-bromosuccinimide were added in portions. To the reaction mixture was added 0.75ml of perchloric acid (70% aqueous solution). After the reaction was complete, the mixture was washed with water. The organic phase is extracted, dried and concentrated. The compound was then purified as follows: it is dissolved in methylene chloride and precipitated in methanol to give 9.4g of DPP16 as a violet powder.

b) In a three-necked flask, 5g of 16, 2.46g of 4-hexylthiophene-2-boronic acid diprenyl ester, and 5.64g K₃PO₄*H₂A degassed solution of O, 114g of sPhos (2-dicyclohexylphosphino-2 ', 6' -dimethoxybiphenyl) and 52.2mg of palladium acetate in 30ml of toluene, 30ml of dioxane and 18ml of water was heated to 90 ℃ and stirred vigorously overnight. The reaction mixture was then washed with water, dried and concentrated. The residue was dissolved in dichloromethane and precipitated in methanol to give 5.67g of blue solid DPP 17.

c) 4g of DPP derivative 17 are dissolved in 100ml of hexane, and then 0.5ml of perchloric acid (70% in water) and 2 equivalents of N-bromosuccinimide are added in portions. After the reaction was completed, the mixture was washed with water. The organic phase is extracted, dried, concentrated and precipitated with methanol. The precipitate was filtered off and rinsed with methanol to give 3.9g of blue solid DPP 18.

d) In a Schlenk tube, 600mg of Ni (COD)₂And a solution of 420mg of bipyridine in 30ml of toluene was degassed for 15 min. To this solution was added 2g of the corresponding dibrominated monomer 18, and the mixture was heated to 80 ℃ and stirred vigorously overnight. The solution was poured onto 100ml 1/1/1 of a methanol/HCl/acetone mixture and stirred for 1 h. The precipitate was then filtered off and dissolved in CHCl₃And vigorously stirred with an aqueous solution of tetrasodium salt of Ethylene Diamine Tetraacetic Acid (EDTA) at 60 ℃ for another 1 h. The organic phase was washed with water, concentrated and precipitated in methanol. The residue was purified by Soxhelt extraction with pentane and the polymer was then extracted with cyclohexane to give 500mg of violet fibres (M)_w＝83,000)。

Example 8

In a three-necked flask, 2g of 7, 0.477g of bis-pinacol 2, 5-thiophenylboronate, 1.74g K₃PO₄A degassed solution of 35mg of sPhos (2-dicyclohexylphosphino-2 ', 6' -dimethoxybiphenyl) and 16mg of palladium acetate in 10ml of toluene, 10ml of dioxane and 6ml of water was heated to 90 ℃ and stirred vigorously overnight. The organic phase was then extracted and precipitated in methanol. The residue was purified by Soxhlet extraction with acetone and pentane, followed by extraction of the polymer with cyclohexane to give 0.3g of violet fibres (M)_w＝16000)。

Application example 8 DPP-Polymer based field Effect transistor

a) Experiment:

application example 1a was repeated, but the polymer obtained in example 1 was replaced by the polymer obtained in example 8.

b) Transistor performance:

p-type transistor with clear thin film transistorAnd (6) behaviors. From a linear fit to the root mean square of the saturation transfer characteristic, a field effect mobility up to 0.029cm can be measured²Vs. The threshold voltage of the transistor is 0V to-3V. The transistor has a width of about 10⁴Without a wrong on/off current ratio.

Comparative example 1 DPP-Polymer based field Effect transistor

a) Experiment:

application example 1a was repeated, but the polymer obtained in example 12 of WO2005049695 was used instead of the polymer obtained in example 1.

b) Transistor performance:

thin film transistors exhibit very poor transistor performance (almost immeasurable). From a linear fit to the root mean square of the saturation transfer characteristic, a field effect mobility of up to 1.110 can be measured^-8cm²Vs. The threshold voltage of the transistor is about 3.5V. The transistor has a maximum of 10³Very poor on/off current ratio (average of 55).

Claims

1. A polymer comprising (repeating) units of the formula

Wherein

a. b, c, d, e and f are 0 to 200, in particular 0,1, 2 or 3;

Ar¹and Ar^1’Independently of one another, are a radical of the formula

Or

Or

p represents 0,1, 2, 3 or 4, if possible,

Ar¹⁰is aryl or heteroaryl optionally substituted by G, in particular by C₁～C₈Alkyl radical, C₁～C₈Thioalkoxy and/or C₁～C₈Phenyl or 1-or 2-naphthyl substituted by alkoxy 1 to 3 times, and g is 0,1, 2, 3 or 4,

R³may be the same or different within a group and is selected from C optionally substituted by E and/or interrupted by D₁～C₂₅Alkyl, C optionally substituted by G₆～C₂₄Aryl, C optionally substituted by G₂～C₂₀Heteroaryl, C optionally substituted by E and/or interrupted by D₁～C₁₈Alkoxy, C in aralkyl, the aryl group of which may optionally be substituted by G₇～C₂₅Aralkyl, or-CO-R²⁸Or 2 or more R adjacent to each other³Forming a ring;

d is-CO-; -COO-; -S-; -SO-; -SO₂-；-O-；-NR²⁵-；-CR²³＝CR²⁴-; or-C ≡ C; and

g is E, C which can be interrupted by D₁～C₁₈Alkyl, or C substituted by E and/or interrupted by D₁～C₁₈Alkoxy radical, wherein

R¹⁰⁰And R¹⁰¹Independently of one another is H, C₁～C₁₈Alkyl, C substituted by E and/or interrupted by D₁～C₁₈Alkyl radical, C₆～C₂₄Aryl, C substituted by G₆～C₂₄Aryl, or C₂～C₂₀Heteroaryl, or C substituted by G₂～C₂₀Heteroaryl, or

R¹⁰⁹And R¹¹⁰Together form optionally substituted C₁～C₁₈Alkyl-substituted 5-or 6-membered ring, C substituted by E and/or interrupted by D₁～C₁₈Alkyl radical, C₆～C₂₄Aryl, C substituted by G₆～C₂₄Aryl radical, C₂～C₂₀Heteroaryl, C substituted by G₂～C₂₀Heteroaryl group, C₂～C₁₈Alkenyl radical, C₂～C₁₈Alkynyl, C₁～C₁₈Alkoxy, C substituted by E or interrupted by D₁～C₁₈Alkoxy radical, C₇～C₂₅Aralkyl or-C (═ O) -R¹⁸，

R¹¹¹Is H, C₁～C₂₅Alkyl radical, C₄～C₁₈Cycloalkyl, C in which 1 or more carbon atoms which are not adjacent to one another can be replaced by-O-, -S-or-C (═ O) -O-, and/or in which one or more hydrogen atoms can be replaced by F₁～C₂₅Alkoxy radical, C₆～C₂₄Aryl, or in which one or more carbon atoms can be replaced by O, S or N and/or by 1 or more non-aryl radicals R¹¹¹Substituted C₆～C₂₄An aryloxy group;

in each case, m may be the same or different and is 0,1, 2 or 3, especially 0,1 or 2, more especially 0 or 1;

X¹is a hydrogen atom or a cyano group,

provided that if Ar is¹And Ar^1’Is formula

A and d are both 1 and Ar²And Ar^2’Is different from the following formula

Or

The group of (a) or (b),

provided that if Ar is¹And Ar^1’Is formulaAnd a and d are not 0; and with the proviso that no polymer of the formula

Wherein y is 0.05 and x is 0.95.

2. A polymer according to claim 1, wherein R is¹And R²Independently of one another, hydrogen, C optionally interrupted by 1 or more oxygen atoms₁～C₂₅Alkyl, can be substituted by C₁～C₈Alkyl and/or C₁～C₈Alkoxy substituted 1-3 times C₅～C₁₂Cycloalkyl, especially cyclohexyl, or C which can be condensed 1-2 times with phenyl₅～C₁₂Cycloalkyl, especially cyclohexyl, the phenyl radical being able to be substituted by C₁～C₄Alkyl, halogen, nitro or cyano substituted 1 to 3 times, able to be substituted by C₁～C₈Alkyl and/or C₁～C₈Phenyl or 1-or 2-naphthyl substituted by alkoxy 1-to 3-times, or-CR⁵R⁶-(CH₂)_g-Ar¹⁰Wherein R is⁵And R⁶Is hydrogen, Ar¹⁰Is can be covered with C₁～C₈Alkyl and/or C₁～C₈Phenyl or 1-or 2-naphthyl substituted 1-to 3 times by alkoxy, and g is 0 or 1.

3. A polymer according to claim 1 or 2, wherein Ar¹And Ar^1’Identical and is a group of formula:

Especiallyor

And

Ar²、Ar^2’、Ar³、Ar^3’、Ar⁴and Ar^4’Independently of one another are a group of the formula:

or

Wherein

p is 0,1 or 2, R³May be the same or different within a group and is selected from C optionally substituted by E and/or interrupted by D₁～C₂₅Alkyl, or C optionally substituted by E and/or interrupted by D₁～C₁₈An alkoxy group;

R⁴is C optionally substituted by E and/or interrupted by D₆～C₂₅Alkyl, C optionally substituted by G₆～C₁₄Aryl, such as phenyl, naphthyl or biphenyl, optionally substituted by G, C optionally substituted by E and/or interrupted by D₁～C₂₅Alkoxy, or C wherein the aryl group of the aralkyl group may be optionally substituted by G₇～C₁₅An aralkyl group,

d is-CO-, -COO-, -S-, -SO₂-、-O-、-NR²⁵-, wherein R²⁵Is C₁～C₁₂Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl;

e is-OR²⁹；-SR²⁹；-NR²⁵R²⁵；-COR²⁸；-COOR²⁷；-CONR²⁵R²⁵(ii) a or-CN; wherein R is²⁵、R²⁷、R²⁸And R²⁹Independently of one another is C₁～C₁₂Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl or 2-ethylhexyl, or C₆～C₁₄Aryl radicals, such as the phenyl, naphthyl or biphenyl radical,

4. According to the rightThe polymer of claim 3, wherein

And

may be different, but preferably are the same and are a group of the formula

Or

Wherein,

represents a bond to the diketopyrrolopyrrole skeleton, R⁴As defined in claim 3 and R^4’And R⁴The meaning is the same.

5. A polymer according to any one of claims 1 to 4, wherein the polymer comprises repeating units of the formula

Wherein

a、b、c、d、e、f、R¹、R²、Ar¹、Ar^1’、Ar²、Ar^2’、Ar³、Ar^3’、Ar⁴And Ar^4’As defined in claim 1, wherein the first and second groups are,

h is 1, and

Ar⁵is of the formulaOr

The group of (a) or (b),

wherein R is⁷And R^7’As claimed inSolving for the definition in 1; or

The polymer has the structure of

^*- [ first repeating Unit]_q- [ branching Unit]_t-^*(III)，

Wherein the first repeating unit is a repeating unit of formula I according to claim 1, the branching unit is a unit having more than 2 bonding points, and q and t are integers.

6. A polymer according to any one of claims 1 to 5, comprising repeating units of the formula

Especially

Especially

Or

Wherein,

R¹and R²Independently of one another is C₁～C₂₅Alkyl, and

R⁴and R^4’Independently of one another, C which is optionally interrupted by 1 or more oxygen atoms₆～C₂₅An alkyl group, a carboxyl group,

7. Semiconductor device, in particular a diode, a photodiode, an organic field-effect transistor and/or a solar cell, or a device comprising a diode and/or a photodiode and/or an organic field-effect transistor and/or a solar cell, comprising a polymer of formula I according to claim 1.

8. A process for the manufacture of organic semiconductor devices, which comprises coating a solution and/or dispersion of a polymer of the formula I according to claim 1 in an organic solvent on a suitable substrate and then removing the solvent.

9. A monomer of the formula:

or

Wherein

B and C are each independently of the other an optionally fused aromatic or heteroaromatic ring,

a、b、c、d、e、f、R¹、R²、Ar1、Ar^1’、Ar²、Ar^2’、Ar³、Ar^3’、Ar⁴and Ar^4’As defined in claim 1 and X is ZnX¹²，-SnR²⁰⁷R²⁰⁸R²⁰⁹Wherein R is²⁰⁷、R²⁰⁸And R²⁰⁹Are identical or different and are H or C₁～C₆Alkyl, wherein 2 groups optionally form a common ring and the groups are optionally branched or unbranched, and X¹²Is a halogen atom, more particularly I or Br; or-OS (O)₂CF₃、-OS(O)₂Aryl radicals, in particular

OS(O)₂CH₃，-B(OH)_2，-B(OY¹)₂

-BF₄Na, or-BF₄K, wherein Y¹In each case independently C₁～C₁₀Alkyl and Y²In each case independently C₂～C₁₀Alkylene radicals, e.g. -CY³Y⁴-CY⁵Y⁶-or-CY⁷Y⁸-CY⁹Y¹⁰-CY¹¹Y¹²-, in which Y³、Y⁴、Y⁵、Y⁶、Y⁷、Y⁸、Y⁹、Y¹⁰、Y¹¹And Y¹²Are each independently of the other hydrogen or C₁～C₁₀Alkyl, especially- (CH)₃)₂C(CH₃)₂-or-C (CH)₃)₂CH₂C(CH₃)₂With the proviso that if Ar is¹And Ar^1’Is formula

A and d are not 0 and Ar²And Ar^2’Is a group other than

Or

With the proviso that if Ar¹And Ar^1’Is formula

A and d are not 0.

10. Use of a polymer of the formula I according to any of claims 1 to 7 as charge transport, semiconducting, e1 conducting, photoconducting, light emitting material, surface modifying material, electrode material in batteries, orientation layers or in the field of OFETs, ICs, TFTs, displays, RFITD tags, electro-or photoluminescent devices, backlights of displays, photovoltaic or sensor devices, charge injection layers, Schottky diodes, memory devices (such as fefets), planarising layers, antistatic agents, conductive substrates or patterns, photoconductors or electrophotography (recording).