CN101479272B - Diketopyrrolopyrrole polymers as organic semiconductors - Google Patents

Diketopyrrolopyrrole polymers as organic semiconductors Download PDF

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CN101479272B
CN101479272B CN200780024495.XA CN200780024495A CN101479272B CN 101479272 B CN101479272 B CN 101479272B CN 200780024495 A CN200780024495 A CN 200780024495A CN 101479272 B CN101479272 B CN 101479272B
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alkyl
group
polymkeric substance
independently
formula
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CN101479272A (en
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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
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Clap Co Ltd
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Ciba SC Holding AG
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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

As organic semi-conductor diketopyrrolopyrrolepolymers polymers
The polymkeric substance of the repeating unit that the present invention relates to comprise formula (I) and as organic semiconductor at organic assembly, especially at diode, organic field effect tube and/or solar cell or containing the application in the device of diode, organic field effect tube and/or solar cell.Solvability according to polymkeric substance of the present invention in organic solvent is good and have a good film-forming properties.In addition, when according to polymkeric substance of the present invention during for semiconducter device or organic photovoltaic (PV) device (solar cell), can observe efficient energy transformation, good field-effect mobility, good ON/OFF current ratio and/or good stability.
M.Smet etc. have described by bromination 1 in Tetrahedron Lett.42 (2001) 6527-6530,4-dioxo-3,6-Diphenyl Pyrrole also [3,4-c] pyrroles's (DPP) derivative and 1,4-bis-bromo-2,5-di-n-hexyl benzene, as monomer, with the progressively sequence of Suzuki coupling, is manufactured the method for bar-shaped diketopyrrolopyrrolecocrystals oligomer.
M Horn etc. in J.38 Eur.Polymer has described main chain in (2002) 2197-2205 containing 2,5-pyrrolin also [3,4-c] pyrroles unit hot meso polysiloxane synthetic and characterize.
EP-A-787,730 have described polyacrylic ester and the urethane that the DPP by formula Ia is polymerized
Q wherein 1and Q 4polymerizable reactive group independently of one another, and Q 2and Q 3hydrogen, C independently of one another 12～C 24alkyl, the C being interrupted by one or more O or S 6～C 24the group of alkyl or following formula
Q wherein 5c 4～C 18alkyl or C 5～C 10cycloalkyl.Though mentioned Compound I a in literary composition, can be used for manufacturing light-and conducting polymer, not provide corresponding embodiment.And, do not provide and how to manufacture the El element that comprises DPP-based polyalcohol and the suitable DPP-monomer material of How to choose DPP-polymkeric substance.
Macromol.Chem.Phys.200 (1999) 106-112 describes Liao You functional group and is connected in DPP-molecule two functionality monomer DPP-derivatives on N-atom and vulcabond or dibasic alcohol or dicarboxylic acid copolymerization and obtainable fluorescence DPP-polymkeric substance.
J.Am.Chem.Soc.117 (1995) 12426-12435 is related to the Stille linked reaction of synthetic functionalized polymeric exploitation palladium catalysis.In scheme 7, provided the synthetic of following polymkeric substance:
Polymkeric substance 13:y=0.05, x=0.95
Polymkeric substance 14:y=0, x=1
Whether do not illustrate described polymkeric substance can be used in El element.
J.Am.Chem.Soc.115 (1993) 11735-11743 has described and has presented selling off property of light, presents the optically active DPP-polymkeric substance of photoconductivity and quadratic nonlinearity.In this device, the measuring method of photoconductivity is, uses laser beam irradiation device, then measures the electric current being produced by this irradiation, do not carry out relevant electroluminescent mensuration.
In addition, do not illustrate other DPP-polymkeric substance of How to choose.
In Appl.Phys.Lett.64 (1994) 2489-2491, for selling off property of research light, with disclosed polymkeric substance in J.Am.Chem.Soc.115 (1993) 11735-11743, done further research, i.e. two-beam coupling experiment.Two-beam coupling experimental verification the asymmetric energy exchange under zero electric field, i.e. the selling off property of light of disclosed polymkeric substance in J.Am.Chem.Soc.115 (1993) 11735-11743.
US-B-6451459 is (with reference to B.Tieke etc., Synth.Met.130 (2002) 115-119; Macromol.Rapid Commun.21 (4) (2000) 182-189) described diketopyrrolopyrrolecocrystals based polyalcohol and comprised as the multipolymer of lower unit and their application in El element.
Wherein, x selects in 0.005～1 scope, and preferably 0.01～1; Y is 0.995～0, preferably 0.99～0; And x+y=1 wherein, and
Ar wherein 1and Ar 2following groups independently of one another:
And m, n is 1～10 numeral, and
R 1and R 2h, C independently of one another 1～C 18alkyl ,-C (O) O-C 1～C 18alkyl, perfluor-C 1～C 12-alkyl, do not replace or by C 1～C 12alkyl, C 1～C 12alkoxyl group replaces the C of 1～3 time 6～C 12aryl or halo C 6～C 12aryl, C 1～C 12alkyl-C 6～C 12aryl or C 6～C 12aryl-C 1～C 12alkyl,
R 3and R 4preferably hydrogen, C 1～C 12alkyl, C 1～C 12alkoxyl group, do not replace or by C 1～C 12alkyl, C 1～C 12alkoxyl group replaces the C of 1～3 time 6～C 12aryl, or halo C 6～C 12aryl, or perfluor-C 1～C 12alkyl, and
R 5c preferably 1～C 12alkyl, C 1～C1 2alkoxyl group, do not replace or by C 1～C 12alkyl, C 1～C 12alkoxyl group replaces the C of 1～3 time 6～C 12aryl, or halo C 6～C 12aryl, or perfluor-C 1～C 12alkyl, and their application in El element.Following polymkeric substance
clearly be disclosed in Tieke etc., in Synth.Met.130 (2002) 115-119.Following polymkeric substance
Clearly be disclosed in Macromol.Rapid Commun.21 (4) (2000) 182-189.
WO05/049695 discloses diketopyrrolopyrrolecocrystals (DPP) based polyalcohol and their application in PLED, organic integrated circuits (O-IC), organic field effect tube (OFET), OTFT (OTFT), organic solar batteries (O-SC) or organic laser diode, but the specific DPP based polyalcohol of unexposed formula I.In embodiment 12, the preparation method of following polymkeric substance has been described.
The object of this invention is to provide novel polymeric, they are when as semiconducter device, photorectifier or organic photovoltaic (PV) device (solar cell), there is premium properties, as efficient energy transformation, good field-effect mobility, good ON/OFF current ratio and/or good stability.
Described object has been realized by the polymkeric substance of the repeating unit that comprises following formula,
, wherein a, b, c, d, e and f are 0～200, especially 0,1,2 or 3;
Ar 1and Ar 1 'the group of following formula independently of one another
or
Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'the group of following formula independently of one another
or
P is 0,1,2,3 or 4, as possibility,
R 1and R 2can be identical or different, and be selected from hydrogen; The C that is optionally replaced by E and/or be interrupted by D 1～C 25alkyl, alkenyl, alkynyl; Can be by C 1～C 4alkyl replaces the allyl group of 1～3 time; Can be by C 1～C 8alkyl, C 1～C 8thio alkoxy or C 1～C 8alkoxyl group replaces the cycloalkyl of 1～3 time, or can condense the cycloalkyl of 1～2 time with phenyl, and described phenyl can be by C 1～C 4alkyl, halogen, nitro or cyano group replace 1～3 time; Cycloalkenyl, ketone or aldehyde radical, ester group, formamyl, silyl, siloxanes, Ar 10or-CR 5r 6-(CH 2) g-Ar 10, wherein
R 5and R 6hydrogen, fluorine, cyano group or the C that can be replaced by fluorine, chlorine or bromine independently of one another 1～C 4alkyl, or can be by C 1～C 4alkyl replaces the phenyl of 1～3 time,
Ar 10optionally by G substituting group or heteroaryl, especially can be by C 1～C 8alkyl, C 1～C 8thio alkoxy and/or C 1～C 8alkoxyl group replaces phenyl or 1-or the 2-naphthyl of 1～3 time, and g is 0,1,2,3 or 4,
R 3can be identical or different in a group, and be selected from the C that is optionally replaced by E and/or be interrupted by D 1～C 25alkyl, the C optionally being replaced by G 6～C 24aryl, the C optionally being replaced by G 2～C 20heteroaryl, the C that is optionally replaced by E and/or be interrupted by D 1～C 18aryl in alkoxyl group, aralkyl can optionally be got the C being replaced by G 7～C 25aralkyl or-CO-R 28, or 2 or more R adjacent one another are 3base forms ring;
R 4, R 4 ', R 7and R 7 'the C that is hydrogen independently of one another, is optionally replaced by E and/or be interrupted by D 1～C 25alkyl, the C optionally being replaced by G 6～C 24aryl, the C optionally being replaced by G 2～C 20heteroaryl, the C that is optionally replaced by E and/or be interrupted by D 1～C 18the C that aryl in alkoxyl group, aralkyl is optionally replaced by G 7～C 25aralkyl, or-CO-R 28; Or R 4and R 4 'form ring;
D is-CO-;-COO-;-S-;-SO-;-SO 2-;-O-;-NR 25-;-CR 23=CR 24-; Or ; With
E is-OR 29;-SR 29;-NR 25r 26;-COR 28;-COOR 27;-CONR 25r 26;-CN; Or halogen;
The C that G is E, can be interrupted by D 1～C 18alkyl or the C that can be replaced by E and/or be interrupted by D 1～C 18alkoxyl group, wherein
R 23, R 24, R 25and R 26h independently of one another; C 6～C 18aryl; By C 1～C 18alkyl or C 1～C 18the C that alkoxyl group replaces 6～C 18aryl; C 1～C 18alkyl; Or the C of quilt-O-interruption 1～C 18alkyl,
R 27and R 28h independently of one another; C 6～C 18aryl; By C 1～C 18alkyl or C 1～C 18the C that alkoxyl group replaces 6～C 18aryl; C 1～C 18alkyl; Or the C of quilt-O-interruption 1～C 18alkyl,
R 29h; C 6～C 18aryl; By C 1～C 18alkyl or C 1～C 18the C that alkoxyl group replaces 6～C 18aryl; C 1～C 18alkyl; Or the C of quilt-O-interruption 1～C 18alkyl,
R 109and R 110h, C independently of one another 1～C 18alkyl, the C that is replaced by E and/or be interrupted by D 1～C 18alkyl, C 6～C 24aryl, the C being replaced by G 6～C 24aryl, C 2～C 20heteroaryl, the C being replaced by G 2～C 20heteroaryl, C 2～C 18alkenyl, C 2～C 18alkynyl, C 1～C 18alkoxyl group, the C that is replaced by E and/or be interrupted by D 1～C 18alkoxyl group, or C 7～C 25aralkyl, or
R 109and R 110form together formula=CR 100r 101group, wherein
R 100and R 101h, C independently of one another 1～C 18alkyl, the C that is replaced by E and/or be interrupted by D 1～C 18alkyl, C 6～C 24aryl, the C being replaced by G 6～C 24aryl, or C 2～C 20heteroaryl, or the C being replaced by G 2～C 20heteroaryl, or
R 109and R 110form optionally by C together 1～C 185 yuan of replacing of alkyl or 6 rings, the C that is replaced by E and/or be interrupted by D 1～C 18alkyl, C 6～C 24aryl, the C being replaced by G 6～C 24aryl, C 2～C 20heteroaryl, the C being replaced by G 2～C 20heteroaryl, C 2～C 18alkenyl, C 2～C 18alkynyl, C 1～C 18alkoxyl group, the C that is replaced by E and/or be interrupted by D 1～C 18alkoxyl group, C 7～C 25aralkyl, or-C (=O)-R 18,
R 111be in H, group 1 or a plurality of carbon atoms not adjacent to each other can quilt-O-,-S-or-C (=O)-O-is alternative and/or wherein one or more hydrogen atoms can be replaced by F C 6～C 25alkyl, C 4～C 18cycloalkyl, C 1～C 25alkoxyl group, one or more carbon atoms can by O, S or N substitutes and/or can be by one or more non-aryl R in group 111the C replacing 6～C 24aryl or C 6～C 24aryloxy;
In all cases, m can be same to each other or different to each other, and is 0,1,2 or 3, and especially 0,1 or 2, more specifically 0 or 1;
X 1hydrogen atom or cyano group,
Condition is, if Ar 1and Ar 1 'it is formula group, a and d are 1 and Ar 2and Ar 2 'to be different from following formula or group;
Condition is, if Ar 1and Ar 1 'it is formula group, a and d are not 0; And condition is the polymkeric substance that does not comprise following formula y=0.05 wherein, x=0.95.
R in molecule 1and/or R 2that the polymkeric substance of hydrogen can obtain with the blocking group that can remove after polymerization that (see, for example, EP-A-0 648 770; EP-A-0 648 817; EP-A-0 742 255, and EP-A-0 761 772, WO98/32802; WO98/45757; WO98/58027, WO99/01511, WO00/17275; WO00/39221, WO00/63297 and EP-A-1086984).Pigment precursors uses fragmentation method under known conditions to the conversion of its pigment form, as heat, is optionally having extra catalyst, and the catalyzer as described in WO00/36210 carries out under existing.
The example of this blocking group is formula group, wherein L is any expectation group that is applicable to giving solubleness.L is following formula preferably or , group, wherein,
Y 1, Y 2and Y 3c independently of one another 1～C 6alkyl,
Y 4and Y 8c independently of one another 1～C 6alkyl, by oxygen, sulphur or N (Y 12) 2the C being interrupted 1～C 6alkyl, or do not replace or C 1～C 6alkyl-, C 1～C 6alkoxyl group-, halogen-, cyano group-or nitro phenyl or xenyl of replacing,
Y 5, Y 6and Y 7hydrogen or C independently of one another 1～C 6alkyl,
Y 9hydrogen, C 1～C 6alkyl or following formula or group,
Y 10and Y 11hydrogen, C independently of one another 1～C 6alkyl, C 1～C 6alkoxyl group, halogen, cyano group, nitro, N (Y 12) 2, or do not replace or halogen-, cyano group-, nitro-, C 1～C 6alkyl-or C 1～C 6the phenyl of alkoxyl group-replacement,
Y 12and Y 13c 1～C 6alkyl, Y 14hydrogen or C 1～C 6alkyl, and Y 15hydrogen, C 1～C 6alkyl, or do not replace or C 1～C 6the phenyl that alkyl replaces,
Q does not replace or by C 1～C 6alkoxyl group, C 1～C 6alkylthio or C 2～C 12the p of dialkyl amido list-or many-replace, q-C 2～C 6alkylidene group, wherein p and q are different positional numbers,
X is selected from the heteroatoms of following a group: nitrogen, oxygen and sulphur,
M value: when X is oxygen, m=0, when X is nitrogen, m=1,
L 1and L 2do not replace or single-or many-C independently of one another 1～C 12alkoxyl group-,-C 1～C 12alkylthio-,-C 2～C 24dialkyl amido-,-C 6～C 12aryloxy-,-C 6～C 12arylthio-,-C 7～C 24alkyl aryl amino-or-C 12～C 24the C of ammonia diaryl base-replacement 1～C 6alkyl or [(p ', q '-C 2～C 6alkylidene group)-Z-] n,-C 1～C 6alkyl, n ' is 1～1000 numeral, and p ' and q ' they are different positional numbers, and it is heteroatoms oxygen, sulphur or C that each Z is independent of any other ground 1～C 12the nitrogen that alkyl replaces, and, repeating unit [C 2～C 6alkylidene group)-Z-] in-C 2～C 6alkylidene group can be identical or different, and
L 1and L 2can be saturated or unsaturated 1～10 time, can be not interrupted or at an arbitrary position by 1～10 be selected from-(C=O)-and-C 6h 4-group be interrupted, and can be not with other substituting group or to be selected from other of halogen, cyano group and nitro with 1～10 substituent.
Most preferred L is formula group.
Polymkeric substance of the present invention can be used as charge transport, partly leads, e1 leads, electrode materials, oriented layer in photoconduction, light-emitting material, surface modifying material, battery, or causes-or backlight, the photovoltaic of photo luminescent devices, indicating meter or senser element, electric charge injection layer, Schottky diode, memory device (as FeFET), complanation layer, antistatic, conduction base or figure, optical conductor or electrofax application (record) for OFET, IC, TFT, indicating meter, RFITD sign, electricity.
Polymkeric substance of the present invention can comprise the repeating unit of one or more (different) formula I, suc as formula the repeating unit of Ia and Ib.
The repeating unit of formula I can have unsymmetrical structure, but preferred symmetrical structure: a=d; B=e; C=f; Ar 1=Ar 1 '; Ar 2=Ar 2 '; Ar 3=Ar 3 '; Ar 4=Ar 4 '.
R 1and R 2the C of can be identical or different and being preferably selected from hydrogen, being optionally interrupted by one or more Sauerstoffatoms 1～C 25alkyl, C 1～C 25perfluoroalkyl, optionally by C 1～C 4alkyl replaces the allyl group of 1～3 time; Can be by C 1～C 8alkyl, C 1～C 8thio alkoxy or C 1～C 8alkoxyl group replaces the cycloalkyl of 1～3 time, maybe can by phenyl, condense the cycloalkyl of 1 time or 2 times, and described phenyl is optionally by C 1～C 4alkyl, halogen, nitro or cyano group replace 1～3 time, alkenyl, cycloalkenyl, alkynyl, haloalkyl, halogenated alkenyl, halo alkynyl, ketone group or aldehyde radical, ester group, formamyl, ketone group, silyl, siloxanes, Ar 10or-CR 5r 6-(CH 2) g-Ar 10, wherein
R 5and R 6hydrogen, fluorine, cyano group or the C that optionally replaced by fluorine, chlorine, bromine independently of one another 1～C 4alkyl, or can be by C 1～C 4alkyl replaces the phenyl of 1～3 time.
R 1and R 2more preferably be selected from the C being optionally interrupted by one or more Sauerstoffatoms 1～C 25alkyl, can be by C 1～C 8alkyl and/or C 1～C 8the C that alkoxyl group replaces 5～C 12cycloalkyl, especially cyclohexyl, maybe can condense by phenyl the C of 1～2 time 5～C 12cycloalkyl, cyclohexyl especially, described phenyl is optionally by C 1～C 4alkyl, halogen, nitro or cyano group replace 1～3 time, or can be by C 1～C 8alkyl and/or C 1～C 8alkoxyl group replaces phenyl or 1-or the 2-naphthyl of 1～3 time, or-CR 5r 6-(CH 2) g-Ar 10, R wherein 3and R 4for hydrogen, Ar 10can be by C 1～C 8alkyl and/or C 1～C 8alkoxyl group replaces phenyl or 1-or the 2-naphthyl of 1～3 time, and g is 0 or 1.Quilt-O-is interrupted 1 time or alkyl repeatedly should be understood to be to be interrupted 1 time by-O-or repeatedly, for example, is interrupted straight chain or the branching C of 1 time, 2 times or 3 times 2～C 25alkyl diradical, produces following structural unit :-(CH 2) 2oCH 3,-(CH 2cH 2o) 2cH 2cH 3,-CH 2-O-CH 3,-CH 2cH 2-O-CH 2cH 3,-CH 2cH 2cH 2-O-CH (CH 3) 2,-[CH 2cH 2o]Y 1-CH 3, Y1=1-10 wherein ,-CH 2-CH (CH 3)-O-CH 2-CH 2cH 3with-CH 2-CH (CH 3)-O-CH 2-CH 3.
Most preferred R 1and R 2c 1～C 25alkyl, especially C 4～C 25alkyl, as normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2,2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-hexyl decyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl, wherein preferred group can be used formula representative, wherein m1=n1+4, and m1+n1≤22.
Chiral side chain, as R 1and R 2, can be homochiral or racemic, they can affect the form of polymkeric substance.
The present invention does not comprise the polymkeric substance of the formula I that meets following condition:
R 1and R 2the C that can be interrupted by one or more Sauerstoffatoms independently of one another 1～C 25alkyl, especially C 4～C 12alkyl,
Ar 1and Ar 1 'it is the group of following formula
or
R wherein 6hydrogen, C 1～C 18alkyl or C 1～C 18alkoxyl group, and R 32methyl, Cl or OMe, a=b=c=f=0; D=e=1;
Ar 2 'be selected from or wherein
R 6hydrogen, C 1～C 18alkyl or C 1～C 18alkoxyl group, and
Ar 3 'be selected from , or , wherein
X 1hydrogen atom or cyano group.
Ar 1and Ar 1 'can be different, but preferably identical and be following formula , especially or group, and
Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'following formula independently of one another , or group, wherein
P represents 0,1 or 2, R 3can be identical or different in a group, and be selected from the C that is optionally replaced by E and/or be interrupted by D 1～C 25alkyl, or the C that is optionally replaced by E and/or be interrupted by D 1～C 18alkoxyl group; R 4the C that is optionally replaced by E and/or be interrupted by D 6～C 25alkyl, the C optionally being replaced by G 6～C 14aryl, as phenyl, naphthyl or xenyl, the C that is optionally replaced by E and/or be interrupted by D 1～C 25alkoxyl group, or the C that optionally replaced by G of the aryl in group 7～C 15aralkyl,
D is-CO-,-COO-,-S-,-SO-,-SO 2-,-O-,-NR 25-, R wherein 25c 1～C 12alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or sec-butyl;
E is-OR 29;-SR 29;-NR 25r 25;-COR 28;-COOR 27;-CONR 25r 25; Or-CN; R wherein 25, R 27, R 28and R 29c independently of one another 1～C 12alkyl, as methyl, ethyl, n-propyl,
Sec.-propyl, normal-butyl, isobutyl-, sec-butyl, hexyl, octyl group or 2-ethylhexyl, or C 6～C 14aryl, as phenyl, naphthyl or xenyl,
G is preferably identical with E's, or C 1～C 18alkyl, especially C 1～C 12alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, hexyl, octyl group or 2-ethylhexyl.
Unit with can be different, but preferably identical and be formula or group, wherein
representative is connected to the key on diketopyrrolopyrrolecocrystals skeleton, R 4as defined above, and R 4 'with R 4same meaning.
In another embodiment of the invention, unit with can be different, but preferably identical and be formula group, wherein
R 4the C being optionally interrupted by one or more Sauerstoffatoms 6～C 25alkyl.
In another embodiment of the invention, the repeating unit that polymkeric substance comprises following formula
Wherein,
A, b, c, d, e, f, R 1, R 2, Ar 1, Ar 1 ', Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'all as defined above,
H is 1, and
Ar 5it is formula or group, R wherein 7and R 7 'as above definition; Or
This polymkeric substance has following formula structure
*-[the first repeating unit] q-[branching unit] t- *(III), wherein
" the first repeating unit " is the repeating unit of formula I,
" branching unit " is the unit that contains 2 above keyed jointing points, and
Q and t are integers, and wherein q/t is the repeating unit of formula I and the ratio of " branching unit ".
The repeating unit of formula II preferably has symmetrical structure: a=d; B=e; C=f; Ar 1=Ar 1'; Ar 2=Ar 2 '; Ar 3=Ar 3 '; Ar 4=Ar 4 '.
" branching unit " is the unit that has 2 above keyed jointing points.The example of branching unit is described in, for example, D.A.Tomalia, J.M.J.Frechet chief editor's Dendrimers and OtherDendritic Polymers (branch aggressiveness and other tree-shaped polymkeric substance), John Wiley & Sons, Ltd.2002; M.K.Mishra and S.Kobayashi chief editor's Star and HyperbranchedPolymers (star and hyperbranched polymer), in Marcel Dekker 2000.
The example of " branching unit " of particularly suitable is as follows:
wherein, B and C are aromatic ring or the hetero-aromatic ring optionally condensing independently of one another, as or the key being connected on DPP skeleton, especially r wherein 200, R 201and R 202h or C independently of one another 1～C 25alkyl, s=1 or 2, as as or or as or use polyfunctionality unit (" branching unit ") to produce branched polymer material, as below to as shown in 2 polyfunctionality unit:
(A is the repeating unit of formula I, and o, q, r and t are 0～500), or
Formula " branching unit " and derived from its polymkeric substance, be new and form other inventive point of the present invention.
In another preferred embodiment of the present invention, the repeating unit that polymkeric substance comprises following formula:
especially
especially
or
wherein
R 1and R 2c independently of one another 1～C 25alkyl, and
R 3and R 3 'the C being optionally interrupted by one or more Sauerstoffatoms independently of one another 6～C 25alkyl,
R 4and R 4 'the C being optionally interrupted by one or more Sauerstoffatoms independently of one another 6～C 25alkyl, and
R 7and R 7 'the C being optionally interrupted by one or more Sauerstoffatoms independently of one another 6～C 25alkyl.
In another embodiment of the invention, polymkeric substance is the polymkeric substance of following formula
wherein
R 1and R 2hydrogen or C independently of one another 1～C 25alkyl, and
R 4the C being optionally interrupted by one or more Sauerstoffatoms 6～C 25alkyl.
In one embodiment, according to polymkeric substance of the present invention, only by the repeating unit of one or more formulas I, formed.In preferred embodiments, according to polymkeric substance of the present invention, accurately by the repeating unit of a kind of formula I, form (homopolymer).
According to the present invention, term " polymer " " comprise polymkeric substance and oligomer; and therein; polymkeric substance is the molecule of high molecular weight; its structure mainly comprises the repetition of actual or the conceptive unit derived from low relative molecular mass; and oligomer is the molecule of medium molecule quality, its structure mainly comprises actual or conceptive derived from compared with the fewer cells of low relative molecular mass.If the performance of molecule not with one or several unit remove and considerable change thinks that this molecule has high molecular weight.If the performance of molecule truly has considerable change with one or removing of several unit, think that this molecule has medium molecule quality.
According to the present invention, homopolymer is derived from a kind of (reality, implicit expression or hypothesis) monomer.A lot of polymkeric substance are reacted to each other and are formed by complementary monomer.Very easily imagine that these unit generate " implicit expression monomer " with reaction, their equal polymerization will provide the actual product that can be counted as homopolymer.Some polymkeric substance obtains by the chemical modification of other polymkeric substance, thereby the macromolecular structure that forms resulting polymers can be regarded as and formed by the homopolymerization of hypothesis monomer.
Therefore, multipolymer is the polymkeric substance derived from more than one monomers, for example, and copolymer, terpolymer, tetrapolymer etc.
The weight-average molecular weight of oligomer of the present invention is less than 2000Da.The weight-average molecular weight of polymkeric substance of the present invention is preferably 2000Da or higher, and especially 2,000～2,000,000Da, more preferably 10,000～1,000,000Da, most preferably 10,000～750,000Da.Molecular weight is measured by polystyrene standards by gel permeation chromatography.
In preferred embodiments, polymkeric substance of the present invention is the homopolymer of the repeating unit that comprises formula I, can represent with following formula
(VII), wherein A is the repeating unit of formula I.In described inventive point, polymkeric substance preferably comprises the repeating unit of one of formula Ia～Ii, wherein the repeating unit of preferred formula Ie, Id, Ih and Ii especially.
The multipolymer of formula VII, the repeating unit that comprises formula I and COM 1or COM 2(v=0.995～0.005, w=0.005～0.995), also can be obtained by linked reaction, as nickel linked reaction:
or wherein A as previously defined ,-COM 1-be selected from the repeating unit of following formula:
or with r wherein 7and R 7 'as previously defined,
R 44and R 41hydrogen, C 1～C 18alkyl or C 1～C 18alkoxyl group, and
R 45h, C 1～C 18alkyl or the C that is replaced by E and/or be interrupted by D 1～C 18alkyl, the C being especially interrupted by-O- 1～C 18alkyl, wherein D and E as previously defined,
And-COM 2-be formula or group, wherein
R 116and R 117the C that is H independently of one another, is optionally interrupted by O 1～C 18alkyl or the C being optionally interrupted by O 1～C 18alkoxyl group,
R 119and R 120h independently of one another, the C being optionally interrupted by O 1～C 18alkyl, or
R 119and R 120form together formula=CR 100r 101group, wherein
R 100and R 101h, C independently of one another 1～C 18alkyl, or
R 119and R 120form optionally by C together 1～C 18five yuan or six-ring that alkyl replaces.
In described embodiment, polymkeric substance is the polymkeric substance of following formula
wherein
A, COM 1and COM 2as previously defined,
O is 1,
Q is 0.005～1,
R is 0 or 1,
S is 0 or 1, and wherein, if d is 0, e is not 1,
T is 0.995～0, and wherein c and f sum are 1.
The homopolymer of formula VII is for example by nickel linked reaction, and especially Yamamoto reacts and obtains:
wherein A is the repeating unit of formula I.
The polymerization process that only relates to dihalo-functionality reactant can be undertaken by nickel linked reaction.Such linked reaction is described in a J.Pol.Sci. by Colon etc., part A, and PolymerChemistry Edition 28 (1990) 367 neutralizations are described in J.Org.Chem.51 (1986) 2627 by Colon etc.This reaction generally the polarity containing catalytic amount nickel salt, q.s triphenyl phosphine and large excessive zinc fume to sprotic solvent (as N,N-DIMETHYLACETAMIDE) in carry out.The remodeling of the method is described in Bull.Chem.Soc.Jpn by loyda etc., in 63 (1990) 80, uses therein organic soluble iodide as promotor.
Another kind of nickel-linked reaction is disclosed in Procgress in PolymerScience 17 (1992) 1153 by Yamamoto, therein, be used in the mixture of excessive nickel (1,5-cyclooctadiene) the title complex processing dihalogenated aromatic compounds in inert solvent.All nickel-linked reactions, when being applied to the reaction mixture of 2 kinds or multiple aromatics dihalide, mainly produce random copolymers.This type of polymerization can stop by add a small amount of water in polymerization reaction mixture, and this will replace end halogen with hydrogen base.Or also can be with single functionality aryl halide as chain terminator in this class reaction, this will cause forming end aryl.
Nickel-coupling polymerization mainly produce homopolymer or comprise in have DPP base unit and derived from the random copolymers of the unit of other comonomer.
The homopolymer of formula VIId or VIIe can be by, for example, and Suzuki reaction and obtaining:
or , wherein, A, COM 1and COM 2as previously defined.The example of the preferred homopolymer of formula VIId or VIIe is as follows:
with
Another example of the homopolymer of formula VIId is the polymkeric substance of following formula:
Wherein
R 1and R 2h or C independently of one another 1～C 25alkyl, and
R 4the C being optionally interrupted by one or more Sauerstoffatoms 6～C 25alkyl.
Aromatics borate and halogenide, especially bromide condense reaction, be generally called " Suzuki reaction ", can there are a lot of organo-functional groups, if N.Miyaura and A.Suzuki are at ChemicalReviews, Vol.95, report in pp.457-2483 (1995).Preferred catalyzer is 2-dicyclohexyl phosphino--2 ', 6 '-bis--alkoxyl group xenyl/acid chloride (II).Particularly preferred catalyzer is 2-dicyclohexyl phosphino--2 ', 6 '-bis--methoxyl biphenyl base (sPhos)/acid chloride (II).This reaction can be used for manufacturing high-molecular weight polymer and multipolymer.
For preparation is corresponding to the polymkeric substance of formula VIId or VIIe, make dihalide, as dibromide or dichloride, especially corresponding to the dibromide of formula Br-A-Br, with equimolar amount corresponding to formula or hypoboric acid or biborate, under the katalysis of Pd and triphenyl phosphine, react, wherein X 11all under any circumstance-B (OH) independently 2,-B (OY 1) 2or y wherein 1all under any circumstance C independently 1～C 10alkyl, Y 2all under any circumstance C independently 2～C 10alkylidene group, as-CY 3y 4-CY 5y 6-, or-CY 7y 8-CY 9y 10-CY 11y 12-, Y wherein 3, Y 4, Y 5, Y 6, Y 7, Y 8, Y 9, Y 10, Y 11and Y 12all hydrogen or C independently of one another 1～C 10alkyl, especially-C (CH 3) 2c (CH 3) 2-or-C (CH 3) 2cH 2c (CH 3) 2-.This reaction is generally carried out in as toluene at aromatic solvent at approximately 70 ℃～180 ℃.Other solvent, as dimethyl formamide and tetrahydrofuran (THF), also can be used separately or use with the mixture with aromatic hydrocarbons.By aqueous bases, preferably sodium carbonate or sodium bicarbonate are as HBr scavenging agent.The reactivity that depends on reactant, polyreaction can be carried out 2～100h.Organic bases, as tetraalkylammonium hydroxide, with phase-change catalyst, as TBAB, can improve boron activity (see, for example, Leadbeater & Marco; Angew.Chem.Int.Ed.Eng.42 (2003) 1407 and the reference of wherein quoting).Other of reaction conditions changes by T.I.Wallow and B.MNovak in J.Org Chem.59 (1994) 5034-5037 and M.Remmers, and M.Schulze and G.Wegner provide in Macromol.Rapid Commun.17 (1996) 239-252.
If needed, in this class reaction, can use single functionality aryl halide or boric acid aryl salt as chain terminator, this will cause forming end aryl.
Likely the order by controlling monomer feeding in Suzuki reaction with form the sequence of controlling monomeric unit in gained multipolymer.
Polymkeric substance of the present invention also can synthesize with Stille coupling method (see, for example, Babudri et al, J.Mater.Chem., 2004,14,11-34; J.K.Stille, Angew.Chemie Int.Ed.Engl.1986,25,508).For making the polymkeric substance corresponding to formula VIId or VIIe, make dihalide, as dibromide or dichloride, especially corresponding to dibromide and the formula of formula Br-A-Br or compound, X wherein 11be-SnR 207r 208r 209, in the inert solvent of 0 ℃～200 ℃, having palladium-containing catalyst to react under existing.Now must guarantee that in all monomers used overall, organotin functionality and halogen functionality have good equilibrium ratio.In addition, can prove, when reaction finishes, with simple function group reagent end-blocking, be conducive to remove excessive reactive group.For implementing this technique, preferably tin compound and halogen compound are introduced in one or more inert organic solvents and at 0 ℃～200 ℃, at the temperature of preferably 30 ℃～170 ℃, stir 1h～200h, preferably 5h～150h.Crude product can be purified by method well known by persons skilled in the art and that be suitable for each polymkeric substance, for example, and redeposition or even use dialysis repeatedly.
The organic solvent that is applicable to described method is that for example, ether, as diethyl ether, glycol dimethyl ether, diglyme, tetrahydrofuran (THF), diox, dioxolane, diisopropyl ether and t-butyl methyl ether; Hydrocarbon, as hexane, isohexane, heptane, hexanaphthene, benzene, toluene and dimethylbenzene; Alcohol, as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, ethylene glycol, n-butyl alcohol, 2-butanols and the trimethyl carbinol; Ketone, as acetone, methylethylketone and isobutyl methyl ketone; Acid amides, as dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone; Nitrile, as acetonitrile, propionitrile and butyronitrile, and their mixture.
Palladium and phosphine component should be similar to be selected the explanation of Suzuki modification.
Or polymkeric substance of the present invention also can be used zincon (A-(ZnX 12) 2, X wherein 12halogen) and halogenide or fluoroform sulphonate (COM 1-(X 11) 2, X wherein 11halogen or trifluoromethanesulfonic acid root), synthetic with Negishi reaction.Reference, for example, E.Negishi etc., Heterocycles18 (1982) 117-22.
In addition, the halogen derivative of DPP can oxypolymerization (for example, be used FeCl 3, especially see P.Kovacic etc., Chem.Ber.87 (1987) 357-379; M.Wenda etc., Macromolecules25 (1992) 5125) or electrochemical polymerization (especially see N.Saito etc., Polym.Bull.30 (1993) 285) form.
The monomer of following formula
with
be new monomer and form another inventive point of the present invention, wherein B and C are aromatic ring or the hetero-aromatic ring optionally condensing independently of one another,
A, b, c, d, e, f, Ar 1, Ar 1 ', Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'znX with X as defined in claim 1 12,-SnR 207r 208r 209, R wherein 207, R 208and R 209identical or different, and be H or C 1～C 6alkyl, wherein optionally to form common ring and these groups be branching or nonbranched optionally for 2 groups, and X 12halogen atom, more specifically I or Br; Or-OS (O) 2cF 3,-OS (O) 2-aryl, especially -OS (O) 2cH 3,-B (OH) 2,-B (OY 1) 2, -BF 4na or-BF 4k, wherein Y 1all under any circumstance C independently 1～C 10alkyl and Y 2all under any circumstance C independently 2～C 10alkylidene group, as-CY 3y 4-CY 5y 6-, or-CY 7y 8-CY 9y 10-CY 11y 12-, Y wherein 3, Y 4, Y 5, Y 6, Y 7, Y 8, Y 9, Y 10, Y 11and Y 12all hydrogen or C independently of one another 1～C 10alkyl, especially-C (CH 3) 2c (CH 3) 2-or-C (CH 3) 2cH 2c (CH 3) 2-,
Condition is, if Ar 1and Ar 1 'it is formula group, a and d are not 0 and Ar 2and Ar 2 'it is the group that is different from following formula or
Another condition is, if Ar 1and Ar 1 'it is formula group, a and d are not 0.
Another inventive point of the present invention relates to according to the oxidation of polymkeric substance of the present invention and material and reduction form.No matter lose or obtain the ionic species that electronics all causes forming the height delocalization with high conductivity.When this can be in being exposed to common dopants, occur.Applicable doping agent and adulterating method are well known by persons skilled in the art, for example, see EP0528662, US5,198,153 or WO 96/21659.
Doping process generally refers to oxidation or reductive agent processes semiconductor material, forms the ion center of delocalization and derived from the corresponding gegenion of doping agent used with redox reaction in material.Applicable adulterating method comprises, and for example, is exposed in the doping steam under normal atmosphere or decompression, carrying out electrochemical doping containing in the solution of doping agent, makes doping agent and will be contacted by the semiconductor material of thermodiffusion, and make dopant ion inject semiconductor material.
When using electronics as current carrier, applicable doping agent is that for example, halogen is (as I 2, Cl 2, Br 2, ICl, ICl 3, IBr and IF), Lewis acid is (as PF 5, AsF 5, SbF 5, BF 3, BCl 3, SbCl 5, BBr 3and SO 3), protonic acid, organic acid or amino acid is (as HF, HCl, HNO 3, H 2sO 4, HClO 4, FSO 3h and ClSO 3h), transistion metal compound is (as FeCl 3, FeOCl, Fe (ClO 4) 3, Fe (4-CH 3c 6h 4sO 3) 3, TiCl 4, ZrCl 4, HfCl 4, NbF 5, NbCl 5, TaCl 5, MoF 5, MoCl 5, WF 5, WCl 6, UF 6and LnCl 3(wherein Ln is lanthanon), negatively charged ion are (as Cl -, Br -, I -, I 3-, HSO 4 -, SO 2-, NO 3-, ClO 4-, BF 4-, PF 6-, AsF 6-, SbF 6-, FeCl 4-, Fe (CN) 6 3-, the negatively charged ion of various sulfonic acid, as aryl-SO 3 -).
When using hole as current carrier, the example of doping agent is that positively charged ion is (as H +, Li +, Na +, K +, Rb +and Cs +), basic metal (as Li, Na, K, Rb and Cs), alkaline-earth metal (as Ca, Sr and Ba) O 2, XeOF 4, (NO 2 +) (SbF 6 -), (NO 2 +) (SbCl 6 -), (NO 2 +) (BF 4 -), AgClO 4, H 2irCl 6, La (NO 3) 36 H 2o, FSO 2oOSO 2f, Eu,, vagusstoff, R 4n +(R is alkyl), R 4p +(R is alkyl), R 6as +(R is alkyl) and R 3s +(R is alkyl).
The conduction form of compound of the present invention and material can be as organic " metal " for application, for example, but be not limited to, electric charge injection layer and ITO complanation layer in Organic Light Emitting Diode application, printing conductive base, figure or track in the film of flat-panel monitor and touch-screen, antistatic film, electronic application, as printed circuit board (PCB) and electrical condenser.
Halogen is fluorine, chlorine, bromine and iodine.
As possibility, C 1～C 25alkyl is generally linear or branching.Example is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2, 2-dimethyl propyl, 1, 1, 3, 3-tetramethyl-amyl group, n-hexyl, 1-methyl hexyl, 1, 1, 3, 3, 5, 5-hexamethyl hexyl, n-heptyl, different heptyl, 1, 1, 3, 3-tetramethyl butyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1, 1, 3, 3-tetramethyl butyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl.C 1～C 8alkyl is generally methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2,2-dimethyl-propyl group, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethyl butyl and 2-ethylhexyl.C 1～C 4alkyl is generally methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl.
C 1～C 25alkoxyl group is straight chain or branched alkoxy, as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy or tertiary pentyloxy, heptan oxygen base, octyloxy, different octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, heptadecane oxygen base and octadecane oxygen base.C 1～C 8the example of alkoxyl group is methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethyl propoxy-, positive hexyloxy, positive heptan oxygen base, n-octyloxy, 1,1,3,3-tetramethyl-butoxy and 2-ethyl hexyl oxy, preferably C 1～C 4alkoxyl group, typically, as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy.The Sauerstoffatom that term " alkylthio " refers to but ehter bond identical with alkoxyl group is by group that sulphur atom replaced.
C 2～C 25alkenyl is straight chain or branched chain thiazolinyl, as vinyl, allyl group, methylallyl, pseudoallyl, crotyl, 3-butenyl, isobutenyl, positive penta-2,4-dialkylene, 3-methyl-but-2-ene base, positive oct-2-ene base, positive 12 carbon-2-thiazolinyl, different dodecenyl succinic, positive 12 carbon-2-thiazolinyl or positive moroctic acid-thiazolinyl.
C 2-24alkynyl is straight chain or branching, and preferred C 2-8alkynyl, they can be not replace or replace, as ethynyl, 1-propine-3-base, ethyl acetylene-4-base, 1-pentyne-5-base, 2-methyl-3-crotonylene-Ji, 1,4-pentadiine-3-base, 1,3-pentadiine-5-base, 1-hexin-6-base, cis-3-methyl-2-penta-4-alkynes-1-base, trans-3-methyl-2-penta-4-alkynes-1-base, 1,3-hexadiyne-5-base, 1-octyne-8-base, 1-n-heptylacetylene-9-base, 1-decine-10-base or 1-24 alkynes-24-base.
Term " haloalkyl, halogenated alkenyl and halo alkynyl " refers to halogen and partly or entirely replaces the resulting group of abovementioned alkyl, alkenyl and alkynyl, as trifluoromethyl etc." aldehyde radical, ketone group, ester group, formamyl and amino " comprises those that are replaced by alkyl, cycloalkyl, aryl, aralkyl or heterocyclic radical, and wherein alkyl, cycloalkyl, aryl, aralkyl and heterocyclic radical can be not replace or replace.Term " silyl " refers to formula-SiR 62r 63r 64group, R wherein 62, R 63and R 64c independently of one another 1～C 8alkyl, especially C 1～C 4alkyl, C 6～C 24aryl or C 7～C 12aralkyl, as trimethyl silyl.
Term " cycloalkyl " is generally C 5～C 12cycloalkyl, as cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, ring undecyl, cyclo-dodecyl, preferred cyclopentyl, cyclohexyl, suberyl or ring octyl group, they can be not replace or replace.Term " cycloalkenyl " refers to the unsaturated lipid cyclic hydrocarbon radical containing one or more pair of key, and as cyclopentenyl, cyclopentadienyl, cyclohexenyl etc., they can be not replace and replace.Cycloalkyl, especially cyclohexyl, can be condensed 1 or 2 time by phenyl, and described phenyl can be by C 1～C 4alkyl, halogen and cyano group replace 1～3 time.This class fused rings hexyl is or especially or r wherein 51, R 52, R 53, R 54, R 55and R 56c independently of one another 1～C 8alkyl, C 1～C 8alkoxyl group, halogen and cyano group, especially hydrogen.
Term " aryl " is generally C 6～C 24aryl, as phenyl, indenyl, camomile cyclic group, naphthyl, xenyl, as-indacenyl, s-indacenyl, acenaphthenyl, fluorenyl, phenanthryl, fluoranthene base, terphenyl, base, naphthacenyl, Pi Ji, perylene base, pentacenyl, hexacenyl, pyrenyl or anthryl, preferred phenyl, 1-naphthyl, 2-naphthyl, 4-xenyl, 9-phenanthryl, 2-or 9-fluorenyl, 3-or 4-xenyl, they can be not replace or replace.C 6～C 12the example of aryl is phenyl, 1-naphthyl, 2-naphthyl, 3-or 4-xenyl, 2-or 9-fluorenyl or 9-phenanthryl, and they can be not replace or replace.
Term " aralkyl " is generally C 7～C 24aralkyl, as benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C 7～C 18aralkyl, as benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, alpha, alpha-dimethylbenzyl, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and especially preferred C 7～C 12aralkyl, as benzyl, 2-benzyl-2-propyl group, beta-phenyl-ethyl, alpha, alpha-dimethylbenzyl, ω-phenyl-butyl or ω, ω-dimethyl-ω-phenyl-butyl, aliphatic radical and aryl can be not replace or replace therein.
Term " aryl ether group " is generally C 6～C 24aryloxy, that is to say, O-C 6~ 24aryl, as phenoxy group or 4-p-methoxy-phenyl.Term " fragrant thioether group " is generally C 6- 24arylthio, that is to say, S-C 6～24aryl, as thiophenyl or 4-anisole sulfenyl.Term " formamyl " is generally C 1～18formamyl, preferably C 1～8formamyl; they can be not replace or replace, as formamyl, methylamino formyl radical, ethylamino formyl radical, normal-butyl formamyl, tertiary butyl formamyl, dimethylamino methanoyl, morpholine formamyl or tetramethyleneimine formamyl.
In alkylamino, dialkyl amido, alkyl aryl amino, arylamino and diaryl, term " aryl " and " alkyl " are respectively generally C 1～C 25alkyl and C 6～C 24aryl.
Alkaryl refers to the aryl that alkyl replaces, especially C 7～C 12alkylaryl.Example is tolyl, as 3-methyl-or 4-aminomethyl phenyl, or xylyl, as 3,4-3,5-dimethylphenyl, or 3,5-3,5-dimethylphenyl.
Heteroaryl is generally C 2～C 26heteroaryl, containing ring or fused rings system, the wherein nitrogen of 5～7 annular atomses, oxygen or sulphur are possible heteroatomss, and are generally the unsaturated heterocycle bases that has at least 6 conjugated pi-electronics containing 5～30 atoms, as thienyl, benzo [b] thienyl, dibenzo [b, d] thienyl, thianthrenyl, furyl, furfuryl group, 2H-pyranyl, benzofuryl, isobenzofuran-base, dibenzofuran group, phenoxy group thienyl, pyrryl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidyl, pyrazinyl, pyridazinyl, indolizine base, isoindolyl, indyl, indazolyl, purine radicals, quinolizinyl, chinol base, different chinol base, 2，3-benzodiazine base, naphthyridine base, quinoxalinyl (Chinoxalinyl), quinazolyl, cinnolines base, pteridyl, carbazyl, carbolinyl, benzotriazole base, benzoxazolyl, phenanthridinyl, acridyl, pyrimidyl, phenanthroline base, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazan base Huo phenoxazinyl, they can be not replace or replace.
The possible substituting group of above-mentioned group is C 1～C 8alkyl, hydroxyl, sulfydryl, C 1～C 8alkoxyl group, C 1～C 8alkylthio, halogen, halo C 1～C 8alkyl, cyano group, aldehyde radical, ketone group, carboxyl, ester group, formamyl, amino, nitro or silyl.
As mentioned above, aforementioned group can be replaced by E and/or, if needed, by D, be interrupted.Be interrupted certainly only in the situation that just may containing at least 2 groups by singly linked carbon atom; C 6～C 8aryl is not interrupted; The aralkyl being interrupted or alkaryl contain cells D at moieties.The C that is replaced and/or be interrupted by one or more cells D by one or more E 1～C 18alkyl is, for example, and (CH 2cH 2o) 1-9-R x, R wherein xh or C 1～C 10alkyl or C 2～C 10alkyloyl is (as CO-CH (C 2h 5) C 4h 9), CH 2-CH (OR y ')-CH 2-O-Ry, wherein R yc 1～C 18alkyl, C 5～C 12cycloalkyl, phenyl, C 7～C 15phenylalkyl, and R y 'comprise and resemble R ythe same definition or H; C 1～C 8alkylidene group-COO-R z, for example, CH 2cOOR z, CH (CH 3) COOR z, C (CH 3) 2cOOR z, R wherein zh, C 1～C 18alkyl, (CH 2cH 2o) 1-9r x, and R xcomprise the definition shown in above; CH 2cH 2-O-CO-CH=CH 2; CH 2cH (OH) CH 2-O-CO-C (CH 3)=CH 2.
Polymkeric substance of the present invention can be as semiconductor layer for semiconducter device.Therefore, the invention still further relates to the semiconducter device of the polymkeric substance that comprises formula I.Semiconducter device is diode, organic field effect tube and/or solar cell especially, or contains the device of diode and/or organic field effect tube and/or solar cell.The type of semiconducter device is a lot.General character is to have one or more semiconductor materials.Semiconducter device by, for example, S.M.Sze is described in Physics ofSemiconductor Devices (physics of semiconductor device), the 2nd edition, John Wiley andSons, in New York (1981).This class device comprises rectifier, transistor (have a lot of classes, comprise p-n-p, n-p-n and thin film transistor), luminous semiconductor device (as in the Organic Light Emitting Diode in display application or liquid-crystal display backlight), optical conductor, restrictor, solar cell, thermistor, p-n junction, field-effect diode, Schottky diode etc.In each semiconducter device, semiconductor material and one or more metals and/or isolator are combined into device.Semiconducter device can be used currently known methods, if Peter Van Zant is at Microchip Fabrication, and the 4th edition, McGraw-Hill, those methods described in New York (2000) are manufactured.Especially, organic electronic parts can be if D.R.Gamota etc. be at Printed Organic and MolecularElectronics (the organic and molecular electronic device of printing), Kluver Academic Publ., and Boston, manufactures described in 2004 like that.
A useful especially transistorlike device, be thin film transistor (TFT), generally comprising gate medium on gate electrode, gate electrode, the source electrode adjacent with gate medium and drain electrode and adjacent with gate medium and adjacent with drain electrode with source electrode semiconductor layer (sees, for example, S.M.Sze, Physics of Semiconductor Devices, the 2nd increases version, John Wiley and Sons, 492 pages, New York (1981)).These parts can be with multiple configuration assembling.More specifically, OTFT (OTFT) has one deck organic semiconductor layer.
In manufacture, test and/or between the usage period, OTFT is supported on base.Optionally, base can also provide Electricity Functional to OTFT.Applicable base material comprises organic and inorganic materials.For example, base can comprise silicon materials, unorganic glass, the ceramic foil that comprises multiple suitable silicon form, polymer materials (for example, acrylic acid or the like, polyester, epoxide, polymeric amide, polycarbonate, polyimide, polyketone, poly-(oxygen-1,4-penylene oxygen-1,4-penylene carbonyl-Isosorbide-5-Nitrae-penylene) (be sometimes referred to as polyether-ether-ketone or PEEK), polynorbornene, polyphenylene oxide, poly-naphthalene dicarboxylic acids second diester (PEN), polyethylene terephthalate (PET), polyphenylene sulfide (PPS)), filled polymer material (as fibre reinforced plastics (FRP)) and band coating tinsel.
Gate electrode can be any applicable electro-conductive material.For example, gate electrode can comprise silicon or the metal having adulterated, as aluminium, chromium, gold and silver, nickel, palladium, platinum, tantalum and titanium.Also can use conductive oxide, as indium tin oxide, or be formed by carbon black/graphite or colloidal silver dispersion, optionally contain the electrically conductive ink/thickener of polymer binder.Also can use conductive polymers, as polyaniline or poly-(3,4-ethylidene dioxy thiophene)/polyphenyl sulphonate (PEDOT:PSS).In addition, the alloy of these materials, combination and multilayer are also applicable.In some OTFT, same material can provide gate electrode function that the support function to base is provided again.For example, doped silicon can play gate electrode and support OTFT.
Gate medium is generally provided on gate electrode.Gate medium makes the other parts insulation of gate electrode and OTFT device.The material that is applicable to do gate medium can comprise, for example, and inorganic electrically insulating material.
Gate medium (isolator) can be oxide compound, the material of nitride and so on, also can be selected from ferroelectric family isolator material (for example, organic materials, as polyvinylidene difluoride (PVDF)/trifluoro-ethylene or poly-m-dimethylbenzene adipamide), also can be organic polymer isolator (as polymethacrylate), polyacrylic ester, polyimide, benzocyclobutene (BCB), poly-para xylylene, polyvinyl alcohol, polyvinylphenol (PVP), polystyrene, polyester, polycarbonate), as at J.Veres etc., Chem.Mat.2004, 16, in 4543 or at A.Facchetti etc., Adv.Mat.2005, 17, described in 1705.The specific examples that is applicable to the material of gate medium comprises strontium hydrochlorate, tantalate, titanate, zirconate, aluminum oxide, silicon oxide, tantalum oxide, titanium oxide, silicon nitride, barium titanate, barium strontium, zirconic acid barium titanate, zinc selenide and zinc sulphide, includes but not limited to PbZr xti 1-xo 3(PZT), Bi 4ti 3o 12, BaMgF 4, Ba (Zr 1-xti x) O 3(BZT).In addition, can also be for example, by alloy, hybrid materials (, polysiloxane or nano particle filled polymer) combination and the multilayer of these materials as gate medium.The thickness of dielectric layer is, for example, about 10～1000nm, thickness is about 100～500nm more specifically, and the electric capacity of 0.1～100nF is provided.
Source electrode and drain electrode separate with gate electrode by gate medium, and organic semiconductor layer can source electrode and above drain electrode or below.Source electrode and drain electrode can be any applicable electro-conductive materials that is conducive to provide with semiconductor layer low-resistance Ohm contact.Suitable material comprises that great majority are above to the material described in gate electrode, for example, and aluminium, barium, calcium, chromium, gold and silver, nickel, palladium, platinum, titanium, polyaniline, PEDOT:PSS, other conductive polymers, their alloy, their combination and their multilayer.In these materials, some is applicable to n-N-type semiconductorN material, and other are applicable to p-N-type semiconductorN material, as known in this area.
Membrane electrode (being gate electrode, source electrode and drain electrode) can be used any usability methods, as physical vapor deposition (as thermal evaporation or sputter) or ink jet printing method form.These electrodes graphically can use currently known methods, as shadow mask method, additivity photolithography, subtractive photolithography, print process, micro-contact-printing and figure coating method are realized.
The present invention also provides the film transistor device that comprises following parts:
Be deposited on a plurality of conductive gate electrode on base;
Be deposited on the gate insulation layer in described conductive gate electrode;
Lead power electrode and drain electrode for many groups that are deposited on described insulation layer, make to organize and aim at gate electrode described in each described in each;
Be deposited on the described insulation layer of the described gate electrode of basic covering the organic semiconductor layer in passage between source electrode and drain electrode; The polymkeric substance that described organic semiconductor layer comprises formula I therein or containing the mixture of the polymkeric substance of formula I.
The present invention also provides the method for manufacturing film transistor device, comprises the following step:
On base, deposit a plurality of conductive gate electrode;
In described conductive gate electrode, deposit gate insulation layer;
On described layer, deposit many groups and lead power electrode and drain electrode, make to organize and aim at gate electrode described in each described in each;
On described insulation layer, deposit the polymkeric substance of a laminar I, make the compound of described formula I or cover described gate electrode containing the layer of the mixture of formula I polymkeric substance is basic; Thereby formation film transistor device.
Containing the mixture of the polymkeric substance of formula I, produce the polymkeric substance (being generally 5wt%～99.9999wt%, especially 20～85wt%) that comprises formula I and the semiconductor layer of at least another kind of material.Described another kind of material can be, but be not limited to, but the different polymkeric substance of formula I of the same race of a part of molecular weight are, the polymkeric substance of another kind of formula I, semi-conducting polymer, organic molecule, carbon nanotube, fullerene derivate, inorganic particle (quantum dot, quantum rod, quantum trivet, TiO 2, ZnO etc.), conductive particle (Au, Ag etc.), insulating material, as those (PET, the PS etc.) as described in to gate medium.
For heterojunction solar battery, active coating preferably comprises the polymkeric substance of formula I and soccerballene and take the mixture that weight ratio is 1:1～1:3, as [60] PCBM (=6,6-phenyl-C61-butyric acid methyl ester) or [70] PCBM.
Any applicable base can be used for manufacturing the film of polymkeric substance of the present invention.The base that is used for manufacturing above-mentioned film is metal, silicon, plastics, paper, band coating paper, fabric, glass or band coating glass preferably.
Or TFT also can manufacture as follows: be coated with solution deposition polymkeric substance on the highly doped silicon base of thermal growth oxide layer, then vacuum moulding machine graphical source electrode and drain electrode.
In another method, it is as follows that TFT manufactures: be coated with deposition source electrode and drain electrode on the highly doped silicon base of thermal growth oxide, solution deposition polymkeric substance then, to form film.
Gate electrode can be also at base or electro-conductive material as the graphical metal gate electrode on conductive polymers, then with solution coat method or vacuum deposition method, on graphical gate electrode, be coated with isolator.
Any suitable solvent can be used for dissolving and/or disperseing the application's polymkeric substance, as long as it is inertia and can partially or completely removes from base with traditional drying method (as heating, decompression, airflow etc.).Being suitable for processing semi-conductive organic solvent of the present invention comprises, but be not limited to, aromatic hydrocarbons or aliphatic hydrocarbon, chlorination or halon, ester, ether, the acid amides fluoridized and so on, as chloroform, tetrachloroethane, tetrahydrofuran (THF), toluene, 1,2,3,4-tetraline, phenylmethylether, dimethylbenzene, ethyl acetate, methylethylketone, dimethyl formamide, dichlorobenzene, trichlorobenzene, propylene glycol monomethyl ether (PGMEA) and their mixture.Then use a kind of method, as spin coating, dip-coating, silk screen printing, micro-contact printing, blade coating or other solution coat method known in the art, coating solution and/or dispersion on base, to obtain the film of semiconductor material.
Term " dispersion " is included and is comprised any composition that can not be dissolved in the semiconductor material of solvent completely of the present invention.Dispersion method for making is as follows:
-select to comprise the polymkeric substance of formula I at least or containing the mixture of polymkeric substance and the composition of solvent of formula I, wherein polymkeric substance has lower solubleness in solvent described in room temperature, and in high-temperature solvent, there is higher solubleness, therein, when temperature is down to the first lesser temps from high temperature under without stirring, composition gels;
-at high temperature make at least part of polymer dissolution in solvent;
-make the temperature of composition be down to the first lesser temps from high temperature; Stir composition to destroy all gels, therein, be stirred in composition from any moment before high temperature drops to the first lesser temps, simultaneously or afterwards; Deposit a layer composition, wherein composition is under second lesser temps lower than high temperature; Then be dried at least partly this layer.
Dispersion also can consist of following component: (a) comprise solvent, adhesive resin and, optionally, the external phase of dispersion agent, and the polymkeric substance that (b) comprises formula I of the present invention or containing the disperse phase of the mixture of the polymkeric substance of formula I.The solubleness of the polymkeric substance of formula I in solvent can be, for example, 0%～approximately 20% is not etc., and especially 0%～5% is not etc.
Preferably the thickness of organic semiconductor layer is approximately 5～about 1000nm, and thickness is especially approximately 10～about 100nm.
Polymkeric substance of the present invention can be alone or in combination as the organic semiconductor layer in semiconducter device.This layer can be used any usability methods, as steam deposition (for the lower material of molecular weight) and printing technology provide.Compound of the present invention can be enough to be dissolved in organic solvent and can carry out solution deposition and graphical (for example,, with spin coating, dip-coating, ink jet printing, intaglio printing, flexographic printing, offset printing, silk screen printing, micro-contact (ripple) printing, drop or region cast or other currently known methods).
Polymkeric substance of the present invention can be for unicircuit and the various electronic products that comprises a plurality of OTFT.This based article comprises, for example, the backboard of radio frequency (RFID) sign, flexible display (for example, for Personal Computer, mobile phone or handheld device), smart card, memory device, sensor (for example, light-, image-, biological-, chemistry-, machinery-or temperature sensor), especially photorectifier, or safety equipment etc.Due to its bipolarity, this material also can be for organic light-emitting transistor (OLET).
The invention provides organic photovoltaic (PV) device (solar cell) comprising according to polymkeric substance of the present invention.
PV device comprises by following order:
(a) negative electrode (electrode)
(b) optional transition layer, as alkaline halide, lithium fluoride especially,
(c) photoactive layer,
(d) optional smooth layer,
(e) anode (electrode)
(f) base.
Photoactive layer comprises polymkeric substance of the present invention.Photoactive layer preferably by conjugated polymers of the present invention as electron donor(ED) and soccerballene, especially functionalized soccerballene PCBM, makes as electron acceptor(EA).
Size (carbonatoms in each molecule) variable rangeization that is applicable to soccerballene of the present invention is very large.Term soccerballene, as used herein, comprise and the cage shape molecule of multiple pure carbon comprise Buckminster soccerballene (C 60) and relevant " spherical " soccerballene and carbon nanotube.Soccerballene can be selected from known in the art those, as C 20～C 1000.Preferably soccerballene is selected from C 60～C 96.Most preferably soccerballene is C 60or C 70, as [60] PCBM or [70] PCBM.Also can be with the soccerballene of chemical modification, as long as modification soccerballene keeps receptor type and electronic mobility characteristic.Acceptor material can be to be also selected from the material of following a group: the polymkeric substance of another kind of formula I or any semi-conducting polymer, as long as polymkeric substance keeps receptor type and electronic mobility characteristic; Organic molecule, carbon nanotube, inorganic particle (quantum dot, quantum rod, quantum trivet, TiO 2, ZnO etc.).
Electrode is preferably comprised of metal or " metal surrogate ".Here, term " metal " is used for comprising two class materials: element pure metal, for example, and Mg, and the metal alloy being formed by 2 kinds or multiple element pure metal, for example, Mg, together with Ag, is designated as Mg:Ag.Here, term " metal surrogate " refers on common meaning and is nonmetal but in some suitable applications, have the material of expectation metal shape performance.The common metal surrogate of electrode and charge transport layer comprises adulterated wide-gap semiconductor, and for example, transparent conductive oxide, as indium tin oxide (ITO), gallium indium tin oxide compound (GITO) and zinc indium tin oxide (ZITO).Another kind of applicable metal surrogate is transparent conductive polymer polyaniline (PANI) and the similar or PEDOT:PSS of chemistry thereof.Metal surrogate also can be selected from a lot of non-metallic material, and wherein term " non-metallic material " general reference one large class material, needs only in material and do not have the not metal of chemically bound form.High transparent nonmetal low-resistance negative electrode or efficient low-resistance metal/non-metal composite cathode are disclosed in, and for example, US-B-6, in 420,031 and US-B-5,703,436.
Base can be, for example, and plastics (flexible base) or glass base.
In another preferred embodiment of the present invention, smooth layer is between anode and photoactive layer.The preferred material of smooth layer comprises the poly-ethylidene dioxy thiophene (PEDOT) of 3,4-or the poly-ethylidene dioxy thiophene of 3,4-: the film of polyphenyl sulfonate (PEDOT:PSS).
In a preferred embodiment of the invention, photovoltaic cell comprises, and as US-B-6, described in 933,436, transparent glass carrier, has scribbled the electrode layer of being made by indium/tin-oxide (ITO) on it.This electrode layer generally has more coarse surface tissue, so will cover by polymkeric substance, is generally by doping, to be made into the made smooth layer of PEDOT of conduction.Photovoltaic layer is made by 2 components, and bed thickness is that for example, 100nm～number μ m, depends on coating process, and be applied on this smooth layer.Photovoltaic layer is by conjugated polymers of the present invention as electron donor(ED) and soccerballene, and especially Functional Fullerene PCBM makes as electron acceptor(EA).Using these 2 components and solvent and as solution use, for example, spin-coating method, casting, Langmuir-Blodgett (" LB ") method, ink jet printing method and sagging method, be applied on smooth layer.Also can scrape or print process is coated with this class photovoltaic layer on larger surface with glue.Preferably use dispersion agent, as chlorobenzene, replace typical toluene as solvent.From easy to operate and viewpoint cost, particularly preferably vacuum deposition method, spin-coating method, ink jet printing method and casting in aforesaid method.
Using in spin-coating method, casting and the cambial situation of ink jet printing method, coating can be undertaken by solution and/or dispersion, the preparation method of solution and/or dispersion is, composition is dissolved or is dispersed in suitable organic solvent as benzene,toluene,xylene, tetrahydrofuran (THF), methyltetrahydrofuran, N with the concentration of 0.01～90wt%, dinethylformamide, acetone, acetonitrile, phenylmethylether, methylene dichloride, methyl-sulphoxide, chlorobenzene, 1, in 2-dichlorobenzene and their mixture.
Before coating counter electrode, on photovoltaic layer 4, be coated with must be that the thickness of electrical isolation is, for example, and the thin transition layer of 0.6nm.In this typical embodiments, transition layer is by 210 -6in the vacuum of torr, with the alkaline halide of the speed steam deposition of 0.2nm/min, lithium fluoride is made.
If as hole collector electrode, be deposited on aluminium on electrical isolation transition layer as electronic collection electrode with steam with ITO.The electrical insulating property of transition layer obviously makes to hinder the effect that current carrier passes through and lost efficacy, especially in zone of transition from photovoltaic layer to transition layer.
In yet another embodiment of the present invention, one or more layers can first process with plasma body before one deck under deposition.To PEDOT:PSS layer, under deposition, carry out gentle Cement Composite Treated by Plasma before one deck especially favourable.
Photovoltaic (PV) device also can be comprised of in the multijunction solar cell of upper surface each other processing, to absorb more solar spectrum.This class formation is described in, for example, App.Phys.Let.90,143512 (2007), Adv.Funct.Mater.16, in 1897-1903 (2006) and WO2004/112161.
So-called " tandem solar cell " comprises by following order:
(a) negative electrode (electrode),
(b) optional transition layer, as alkaline halide, lithium fluoride especially,
(c) photoactive layer,
(d) optional smooth layer,
(e) target is (as Au, Al, ZnO, TiO 2deng)
(f) optional additional pole, to mate energy level,
(g) optional transition layer, as alkaline halide, lithium fluoride especially,
(h) photoactive layer,
(i) optional smooth layer,
(j) anode (electrode)
(k) base.
Also can on fiber, process PV device, described in US20070079867 and US20060013549.
Due to the good self-assembly of mixture of the present invention, material or film also can separately or be used from other material one or be used as the oriented layer in LCD or OLED device, described in US2003/0021913.
The following example is only for explanation is included and do not limit the scope of claim.Except as otherwise noted, all umbers or percentage ratio all refer to weight.Weight-average molecular weight (M w) and polymolecularity (M w/ M n=PD) with gel permeation chromatography (GPC) measure [ instrument: from the GPC of Viscotek (Houston, TX, USA) max+ TDA302, the response forms of generation has specific refractory power (RI), low angle scattering of light (LALS), right angle scattering of light (RALS) and differential viscosity (DP) to measure. chromatographiccondition: pillar: from the PL of Polymer Laboratories (Church Stretton, UK) gelmixed C (300 * 7.5mm, 5 μ m particles), the molecular weight ranges of covering is approximately 1 * 10 3～approximately 2.5 * 10 6da; Mobile phase: tetrahydrofuran (THF), containing 5g/l sodium trifluoroacetate; Mobile phase flow rate: 0.5 or 0.7ml/min; Solute concentration: about 1～2mg/ml; Inject volume: 100 μ l; Detect: RI, LALS, RALS, DP. molecular weight standardization: relative Calibration is used available from one group of 10 polystyrene standards of Polymer Laboratories (Church Stretton, UK) and is carried out, and molecular weight ranges is 1,930,000 Da～5,050 Da, PS 1,930,000, PS1,460,000, PS 1,075,000, PS 560,000, PS 330,000, PS 96,000, PS 52,000, PS 30,300, PS 10,100, PS 5,050 Da.Absolute calibration carries out based on LALS, RALS and DP response.According to the experience of large quantity research, aforesaid combination provides the optimal computed of molecular weight data.Conventionally use PS 96,000 as molecular weight standard specimen, but generally can select to be positioned at each other PS standard specimen of intending determining molecular weight scope for this reason].
The all polymer architectures that provide in following examples are all the idealized representatives of the polymer product that obtains by described polymerization.If make component of more than two kinds copolymerization each other, the sequence in polymkeric substance can be alternate type or random, depends on polymerizing condition.
Embodiment
Embodiment 1
A) 4.5g DPP 1,6.23g K 2cO 3be heated to 140 ℃, constant temperature 6h with the solution of the bromo-2-ethyl-hexyl of 8.68g 1-in 60mlN-methyl-2-pyrrolidone (NMP).Water clean this mixture and with dichloromethane extraction it.Then dry organic phase and at double-deck silica dioxide gel and (CAS 91053-39-3; Fluka56678) after upper filtration, concentrate it.Residue is dissolved in 100ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water washed mixture.Extraction, dry and concentrated organic phase.Then this compound of purifying on silica dioxide gel post, obtains 1.90g purple powder DPP2.
C 12h 25it is dodecyl
B), under inert conditions, make 500mg dibrominated DPP 2,990mg tin derivative and 85mg Pd (PPh 3) 4solution in 30ml dry toluene refluxes and spends the night.After cooling, double-deck silica dioxide gel/ this mixture of upper filtration, concentrates and precipitates it with methyl alcohol.Leach throw out and with methanol rinse it, obtain 530mg blue solid DPP 3.
C) with argon gas, at 50 ℃, make the solution degassed 15min of the corresponding monomer 3 of 2.55g in chlorobenzene.Then in Nitromethane 99Min., add 1.6g FeCl 3and stir this mixture, simultaneously at 50 ℃ of degassed 4h.Then this solution poured into methanol, then leach blue throw out and with washed with methanol it.Then with Soxhlet extraction process purifying solid, with methyl alcohol and hexane, purify, and by chloroform extraction 2g polymer fractions (4).
M w＝13301
Fe content=75ppm
Photophysics:
On glass base, the UV spectrum of spin-coated thin film is measured after annealing from hot chlorobenzene solution and under differing temps:
Annealing conditions Ultraviolet-ray visible absorbing
Room temperature 680nm
100℃，20min 720nm，800nm
150℃，20min 720nm，800nm
The growth of 800nm place band shows to have occurred strong gathering behavior when annealing.
Application Example 1a-DPP-polymer-based carbon field-effect transistor
A) experiment:
In all experiments, all use the bottom gate thin film transistor (TFT) with p-Si grid.The hot SiO of high-quality 2layer plays the capacitor C of unit surface i=32.6nF/cm 2the effect of gate insulator.With photolithography directly graphical source electrode and drain electrode (end, contacts configuration) on grid-oxide compound.On each base, there are 16 transistors, with Au source/drain electrode, define the passage of different lengths.Before deposition organic semiconductor, with hexamethyldisilazane (HMDS) or octadecyl trichlorosilane alkane (OTS) derivatize SiO 2surface.Film with the polymkeric substance of gained in rotary casting or drop cast embodiment 1 solution in different solvents make.Transistor behavior, with the refining automatization trier of CSEM, is measured on trnasistor detector TP-10.
B) transistor performance:
Thin film transistor presents p-transistor npn npn behavior clearly.From to the root mean square linear fit of saturated transport property, can record field-effect mobility is 0.15cm 2/ Vs.Transistorized threshold voltage is about 0V～5V.Transistor has 10 4～10 7good ON/OFF current ratio.
The annealing of sample is increased sharply performance (especially mobility), and this can better assemble and be associated with solid polymer.One group of test that is exposed to the OFET of air conditions after lower 2 months is shown to stability is very good, because mobility is almost constant.Conventionally the ON/OFF current ratio that is prone to most problem only reduces a factor 10.
Application Example 1b
The large capacity heterojunction solar battery of DPP-polymer-based carbon
A) experiment:
This solar cell has following structure: Al electrode/LiF layer/organic layer, comprises polymkeric substance of the present invention/[poly-3,4-ethylidene dioxy thiophene (PEDOT)/polyphenyl sulfonic acid (PSS)]/ITO electrode/glass base.The manufacture method of solar cell is spin coating one deck PEDOT-PSS on pre-patterned ITO on glass base.Then the polymkeric substance of spin coating embodiment 1 (0.5wt%): [60] PCBM (replace C60 soccerballene: ) be the mixture (organic layer) of 1:4.Under high vacuum, make LiF and Al distillation pass through shadow mask.
B) performance of solar cell:
Under sunlight simulator, measure solar cell.Then use external quantum efficiency (EQE) figure to estimate the electric current under AM1.5 condition.
Obtain thus, the 1.62% estimation total efficiency for recording before annealing, has J sc=4.1mA/cm 2, FF=0.539 and V oc=0.733V.At 100 ℃, after 10min, estimated efficiency rises to 2%.By changing the ratio etc. of deposition solvent, polymkeric substance/[60] PCBM, optimizing after the form of active coating, the performance of device can be brought up to 3.06% (J sc=9.5mA/cm 2, FF=0.46 and V oc=0.7V).
Embodiment 2
A) 25g DPP 1,46.07g K 2cO 3be heated to 140 ℃, constant temperature 6h with the solution of the bromo-2-hexyl-decyl of 75g 1-in 300mlN-methyl-2-pyrrolidone (NMP).Water clean this mixture and with dichloromethane extraction it.Then dry organic phase and at double-deck silica dioxide gel and upper filtration concentrates it afterwards.Residue is dissolved in 100ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water washed mixture.Extraction, dry and concentrated organic phase.Then this compound of purifying on silica dioxide gel post, obtains 19g purple powder DPP5.
B), under inert conditions, make 18.5g dibrominated DPP5,27.47g tin derivative and 2.36g Pd (PPh 3) 4solution in 250ml dry toluene refluxes and spends the night.After cooling, at silica dioxide gel post (CHCl 3/ hexane 3/7) upper this mixture of purifying, obtains 20.2g blue solid DPP6.
C) 10g DPP derivative 6 is dissolved in 300ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water washed mixture.Extraction, dry, concentrated and organic phase and with methanol extraction it.Leach throw out and with methanol rinse it, obtain 10g blue solid DPP 7.
In Schlenk pipe, make 240mg Ni (COD) 2with the degassed 15min of the solution of 140mg dipyridyl in 10ml toluene.In this solution, add the corresponding dibrominated monomer 7 of 1g, then mixture is heated to 80 ℃ and vigorous stirring and spends the night.Solution be poured in methyl alcohol/HCl/ acetone mixture of 100ml 1/1/1 and stir 1h.Then leach throw out, it is dissolved in to CHCl 3in and at 60 ℃ with ethylene diaminetetraacetic acid (EDTA) tetra-na salt aqueous solution vigorous stirring 1h again.Water cleans organic phase, concentrates and precipitates in methyl alcohol.With Soxhelt extraction process, with methyl alcohol and hexane, purify resistates, then use CHCl 3extraction polymkeric substance, obtains 250mg purple fiber.
M w＝77465
Ni content=65ppm
Solubleness >10wt% in toluene
Photophysics:
On glass base, the UV spectrum of spin-coated thin film is measured in annealing from hot chlorobenzene solution and under differing temps:
Annealing conditions Ultraviolet-ray visible absorbing
Room temperature 680nm
100℃，20min 720nm，800nm
The growth of 800nm place band shows to have occurred strong gathering behavior when annealing.
Application Example 2-DPP-polymer-based carbon field-effect transistor
A) experiment:
Repeated application embodiment 1a, but with the polymkeric substance that obtains in embodiment 2, replace the polymkeric substance that obtains in embodiment 1.
B) transistor performance:
Thin film transistor presents p-transistor npn npn behavior clearly.From to the root mean square linear fit of saturated transport property, can record field-effect mobility is 0.013cm 2/ Vs.Transistorized threshold voltage is about 0V～4V.Transistor has 10 5～10 7good ON/OFF current ratio.One group of test that is exposed to the OFET of air conditions after lower 7 days is shown to stability is very good, because mobility is almost constant even better, be conventionally prone to most the ON/OFF current ratio of problem, only reduce a factor 5.This mixture has up to 10 in conventional equipment -3cm 2the electronic mobility of/Vs.Optimize after this equipment using contact transistor, the bipolarity of this polymkeric substance is even more remarkable, and hole and electronics all have up to 0.1cm 2the similar mobility of/Vs.
Embodiment 3
A) 25g DPP 1,46.07g K 2cO 3be heated to 140 ℃, constant temperature 6h with the solution of the bromo-2-butyl-hexyl of 55g 1-in 300mlN-methyl-2-pyrrolidone (NMP).Water clean this mixture and with dichloromethane extraction it.Then dry organic phase and at double-deck silica dioxide gel and upper filtration concentrates it afterwards.Residue is dissolved in 100ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water cleans this mixture.Extraction, dry and concentrated organic phase.Then this mixture of purifying on silica dioxide gel post, obtains 9.5g purple powder DPP8.
B), under inert conditions, make 2.24g dibrominated DPP 8,4.11g tin derivative and 351mg Pd (PPh 3) 4solution in 50ml dry toluene refluxes and spends the night.After cooling, at silica dioxide gel post (CHCl 3/ hexane 3/7) upper this mixture of purifying, obtains 2.37g blue solid DPP9.
C) 1.27g DPP derivative 9 is dissolved in 60ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water cleans this mixture.Extraction, dry, concentrated organic phase and with methanol extraction it.Leach throw out and with methanol rinse it, obtain 1.32g blue solid DPP10.
D), in Schlenk pipe, make 244mg Ni (COD) 2with the degassed 15min of the solution of 142mg dipyridyl in 10ml toluene.In this solution, add the corresponding dibrominated monomer 10 of 1g, then this mixture is heated to 80 ℃ and vigorous stirring and spends the night.Solution be poured in methyl alcohol/HCl/ acetone mixture of 100ml 1/1/1 and stir 1h.Then leach throw out, it is dissolved in to CHCl 3in and at 60 ℃ with ethylene diaminetetraacetic acid (EDTA) tetra-na salt aqueous solution vigorous stirring 1h again.Water cleans organic phase, concentrates and precipitate it in methyl alcohol.With Soxhelt extraction process, with methyl alcohol and hexane, purify resistates, then use CHCl 3extraction polymkeric substance, obtains 650mg purple fiber.
M w＝30000
Ni content=52ppm
At CHCl 3in solubleness=0.5wt%
Photophysics:
On glass base, the UV spectrum of spin-coated thin film is measured after annealing from hot chlorobenzene solution and under differing temps:
Annealing conditions Ultraviolet-ray visible absorbing
Room temperature 720nm，810nm
The band at 810nm place is owing to gathering behavior.
Application Example 3-DPP-polymer-based carbon field-effect transistor
A) experiment:
Repeated application embodiment 1a, but with the polymkeric substance that obtains in embodiment 3, replace the polymkeric substance that obtains in embodiment 1.
B) transistor performance:
Thin film transistor presents p-transistor npn npn behavior clearly.From to the root mean square linear fit of saturated transport property, can record field-effect mobility maximum and reach 0.1cm 2/ Vs.Transistorized threshold voltage is about 6V.Transistor has 10 4～10 5good ON/OFF current ratio.
Embodiment 4
A) 3.5g DPP 11,3.04g K 2cO 3be heated to 140 ℃, constant temperature 6h with the solution of the bromo-2-hexyl-decyl of 4.13g 1-in 60mlN-methyl-2-pyrrolidone (NMP).Water clean this mixture and with dichloromethane extraction it.Then dry organic phase and at double-deck silica dioxide gel and upper filtration concentrates it afterwards.Residue is dissolved in 100ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water cleans this mixture.Extraction, dry and concentrated organic phase.Then this compound of purifying on silica dioxide gel post, obtains 1.7g purple powder DPP12.
B), under inert conditions, make 1.6g dibrominated DPP 12,0.65g tin derivative and 150mgPd (PPh 3) 4solution in 60ml dry toluene refluxes and spends the night.After cooling, at silica dioxide gel post (CHCl 3/ hexane 3/7) upper this mixture of purifying, obtains 1.27g blue solid DPP 13.
C) 1.27g DPP derivative 13 is dissolved in 50ml chloroform, is cooled to 0 ℃, then in 1h, add 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water washed mixture.Extraction, dry, concentrated organic phase and with methanol extraction it.Filtering precipitate and with methanol rinse it, obtain 1.22g blue solid DPP 14.
D), in Schlenk pipe, make 292mg Ni (COD) 2with the degassed 15min of the solution of 170mg dipyridyl in 10ml toluene.In this solution, add the corresponding dibrominated monomer 14 of 1.2g, then mixture is heated to 65 ℃ and vigorous stirring 41h.Solution be poured in methyl alcohol/HCl/ acetone mixture of 100ml 1/1/1 and stir 1h.Then leach throw out, it is dissolved in to CHCl 3in and at 60 ℃ with ethylene diaminetetraacetic acid (EDTA) tetra-na salt aqueous solution vigorous stirring 1h again.Water cleans organic phase, concentrates and precipitate it in methyl alcohol.With Soxhelt extraction process, with methyl alcohol and hexane, purify resistates, then use CHCl 3extraction polymkeric substance, obtains 730mg purple fiber.
M w＝30000
Ni content=14ppm
At CHCl 3in solubleness=0.5wt%
Photophysics:
On glass base, the UV spectrum of spin-coated thin film is measured after annealing from hot chlorobenzene solution and under differing temps:
Annealing conditions Ultraviolet-ray visible absorbing
Room temperature 720nm，800nm
The band at 800nm place is owing to gathering behavior.
Application Example 4-DPP-polymer-based carbon field-effect transistor
A) experiment:
Repeated application embodiment 1a, but with the polymkeric substance that obtains in embodiment 4, replace the polymkeric substance that obtains in embodiment 1.
B) transistor performance:
Thin film transistor presents p-transistor npn npn behavior clearly.From to the root mean square linear fit of saturated transport property, can record field-effect mobility maximum and reach 0.013cm 2/ Vs.Transistorized threshold voltage is about 4V～8V.Transistor has 10 4～10 5good ON/OFF current ratio.One group of test that is exposed to the OFET of air conditions after lower 2 months is shown to stability is very good, because mobility even better (is up to 0.028cm 2/ Vs), the ON/OFF current ratio that is conventionally prone to most problem has also improved a factor 5～10 and threshold voltage is 0V～4V.
Embodiment 5
In three-necked flask, the two pinacol esters of 5g 7,1.185g Isosorbide-5-Nitrae-benzene hypoboric acid, 3.773gK 3pO 4, 88.5mg sPhos (2-dicyclohexyl phosphino--2 ', 6 '-dimethoxy-biphenyl base) and the de-gassed solution of 80.6mg acid chloride in 60ml toluene, 20ml diox and 10ml water be heated to 90 ℃ and vigorous stirring and spend the night.Then add excessive bromo benzo after 2h, to add excessive benzene ylboronic acid pinacol ester at the same temperature, so that blocked with polymer.After end-blocking completes 2h, add 100mL NaCN (1wt%) aqueous solution, then at 90 ℃, stir this mixture 3h.Extracted organic phase also precipitates it in methyl alcohol.Residue is dissolved in toluene again and carries out NaCN processing again, and in methyl alcohol, precipitate organic phase.With acetone and Et for Soxhlet extraction process 2o purifying resistates, then uses CHCl 3extraction polymkeric substance, obtains 2.5g purple fiber.
M w＝27000
Pb content=30ppm
At CHCl 3in solubleness=1wt%
Photophysics:
On glass base, the UV spectrum of spin-coated thin film is measured after annealing from hot chlorobenzene solution and under differing temps:
Annealing conditions Ultraviolet-ray visible absorbing
Room temperature 630nm，680nm
The band at 680nm place is owing to gathering behavior.
Embodiment 6
In the dry flask cleaning at nitrogen, 1g 7,82mg Pd (PPh 3) 4(10mol%) be dissolved in diethylamine (0.85ml) and THF (2ml) with 13.5mg cupric iodide (10mol%).Then flask is placed under vacuum, with nitrogen cleaning, so repeats 3 times.Then add 328mg dialkynes derivative, at this flask of nitrogen atmosphere lower seal, be heated to 85 ℃ and also stir and spend the night.Reaction mixture is dissolved in to 50ml CHCl 3in, in 500ml MeOH, develop, then filter.Repeat this operation 1 time.Then with Soxhlet for extraction process MeOH, acetone and heptane purify solid, then use CHCl 3extraction polymkeric substance, obtains 0.5g purple fiber (M w=38000; At CHCl 3in solubleness=0.5wt%).
Photophysics:
On glass base, the UV spectrum of spin-coated thin film is measured after annealing from hot chlorobenzene solution and under differing temps:
Annealing conditions Ultraviolet-ray visible absorbing
Room temperature 650nm，700nm
The band at 700nm place is owing to gathering behavior.
Embodiment 7
A) 17.3g DPP 15,8.18g KOH (being dissolved in 5ml water) and the solution of the iodo-2-hexyl-decyl of 52g 1-in 200ml N-Methyl pyrrolidone (NMP) are heated to 140 ℃, constant temperature 6h.Cooling this mixture is to room temperature and filter it.Use washed with methanol filter cake, then make it to be dissolved in methylene dichloride and precipitate in DMSO.Leach throw out and be dried it.9.5g throw out is dissolved in 160ml hexane, then adds 2 equivalent N-bromosuccinimides in batches.In this reaction mixture, add 0.75ml to cross chloric acid (70% aqueous solution).After reaction finishes, water washed mixture.Extraction, dry and concentrated organic phase.Then this compound of purifying is as follows: it is dissolved in methylene dichloride and in methyl alcohol and precipitates it, obtain 9.4g purple powder DPP16.
B) in three-necked flask, 5g 16, the two pinacol esters of 2.46g 4-hexyl thiophene-2-boric acid, 5.64g K 3pO 4* H 2o, 114g sPhos (2-dicyclohexyl phosphino--2 ', 6 '-dimethoxy-biphenyl base) and the de-gassed solution of 52.2mg acid chloride in 30ml toluene, 30ml diox and 18ml water are heated to 90 ℃ and vigorous stirring and spend the night.Then water cleans this reaction mixture, is dried and concentrates it.Residue is dissolved in methylene dichloride and in methyl alcohol and precipitates it, obtain 5.67g blue solid DPP 17.
C) 4g DPP derivative 17 is dissolved in 100ml hexane, then adds 0.5ml to cross chloric acid (70% aqueous solution) and 2 equivalent N-bromosuccinimides in batches.After reaction finishes, water cleans this mixture.Extraction, dry, concentrated organic phase and with methanol extraction it.Leach throw out and with methanol rinse it, obtain 3.9g blue solid DPP 18.
D), in Schlenk pipe, make 600mg Ni (COD) 2with the degassed 15min of the solution of 420mg dipyridyl in 30ml toluene.In this solution, add the corresponding dibrominated monomer 18 of 2g, then mixture is heated to 80 ℃ and vigorous stirring and spends the night.Solution be poured in methyl alcohol/HCl/ acetone mixture of 100ml 1/1/1 and stir 1h.Then leach throw out, it is dissolved in to CHCl 3in and at 60 ℃ with ethylene diaminetetraacetic acid (EDTA) tetra-na salt aqueous solution vigorous stirring 1h again.Water cleans organic phase, concentrates and precipitate it in methyl alcohol.With Soxhelt extraction process, with pentane, purify resistates, then with hexanaphthene, extract polymkeric substance, obtain 500mg purple fiber (M w=83,000).
Embodiment 8
In three-necked flask, 2g 7,0.477g 2, the two pinacol esters of 5-thio phenyl boric acid, 1.74g K 3pO 4, 35mg sPhos (2-dicyclohexyl phosphino--2 ', 6 '-dimethoxy-biphenyl base) and the de-gassed solution of 16mg acid chloride in 10ml toluene, 10ml diox and 6ml water be heated to 90 ℃ and vigorous stirring and spend the night.Then extracted organic phase precipitate it in methyl alcohol.With Soxhlet extraction process, with acetone and pentane, purify resistates, then with hexanaphthene, extract polymkeric substance, obtain 0.3g purple fiber (M w=16000).
Application Example 8-DPP-polymer-based carbon field-effect transistor
A) experiment:
Repeated application embodiment 1a, but with the polymkeric substance that obtains in embodiment 8, replace the polymkeric substance that obtains in embodiment 1.
B) transistor performance:
Thin film transistor presents p-transistor npn npn behavior clearly.From to the root mean square linear fit of saturated transport property, can record field-effect mobility maximum and reach 0.029cm 2/ Vs.Transistorized threshold voltage is 0V～-3V.Transistor has approximately 10 4good ON/OFF current ratio.
Comparative example 1-DPP-polymer-based carbon field-effect transistor
A) experiment:
Repeated application embodiment 1a, but with the polymkeric substance that obtains in WO2005049695 embodiment 12, replace the polymkeric substance that obtains in embodiment 1.
B) transistor performance:
Thin film transistor presents the transistor performance (can survey hardly) of extreme difference.From to the root mean square linear fit of saturated transport property, can record field-effect mobility maximum and reach 1.110 -8cm 2/ Vs.Transistorized threshold voltage is about 3.5V.Transistor has and is 10 to the maximum 3extreme difference ON/OFF current ratio (mean value is 55).

Claims (10)

1. the polymkeric substance that comprises the repeating unit of following formula
, wherein
A, b, c, d, e and f are 0,1,2 or 3;
Ar 1and Ar 1 'the group of following formula independently of one another
ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'the group of following formula independently of one another
or
P represents 0,1,2,3 or 4,
R 1and R 2can be identical or different, and be selected from hydrogen; C 1～C 25alkyl,
R 3can be identical or different in a group, and be selected from the C that is optionally replaced by E and/or be interrupted by D 1～C 25alkyl;
R 4, R 4 ', R 7and R 7 'the C that is hydrogen independently of one another, is optionally replaced by E and/or be interrupted by D 1～C 25alkyl;
D is-CO-;-COO-;-S-;-SO-;-SO 2-;-O-;-NR 25-;-CR 23=CR 24-; Or-C c; With
E is-OR 29;-SR 29;-NR 25r 26;-COR 28;-COOR 27;-CONR 25r 26;-CN; Or halogen;
Wherein
R 23, R 24, R 25and R 26h independently of one another; C 6～C 18aryl; By C 1～C 18alkyl or C 1～C 18the C that alkoxyl group replaces 6～C 18aryl; C 1～C 18alkyl; Or the C of quilt-O-interruption 1～C 18alkyl,
R 27and R 28h independently of one another; C 6～C 18aryl; By C 1～C 18alkyl or C 1～C 18the C that alkoxyl group replaces 6～C 18aryl; C 1～C 18alkyl; Or the C of quilt-O-interruption 1～C 18alkyl,
R 29h; C 6～C 18aryl; By C 1～C 18alkyl or C 1～C 18the C that alkoxyl group replaces 6～C 18aryl; C 1～C 18alkyl; Or the C of quilt-O-interruption 1～C 18alkyl,
Condition is, if Ar 1and Ar 1 'it is formula group and a and d be not 0.
2. according to the polymkeric substance of claim 1, wherein Ar 1and Ar 1 'identical and be the group of following formula:
, , and
Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'the group of following formula independently of one another:
, wherein
R 4the C that is optionally replaced by E and/or be interrupted by D 6～C 25alkyl,
D is-CO-,-COO-,-S-,-SO-,-SO 2-,-O-,-NR 25-, R wherein 25c 1～C 12alkyl;
E is-OR 29;-SR 29;-NR 25r 25;-COR 28;-COOR 27;-CONR 25r 25; Or-CN; R wherein 25, R 27, R 28and R 29c independently of one another 1～C 12alkyl.
3. according to the polymkeric substance of claim 1, wherein with can be similar and different, and be the group of following formula , , or , wherein,
representative connects the key of diketopyrrolopyrrolecocrystals skeleton, R 4as the definition in claim 2 and R 4 'with R 4same meaning.
4. according to the polymkeric substance of claim 1, the repeating unit that wherein this polymkeric substance comprises following formula
Wherein
A, b, c, d, e, f, R 1, R 2, Ar 1, Ar 1 ', Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'as defined in claim 1,
H is 1, and
Ar 5it is following formula , or group,
R wherein 7and R 7 'as defined in claim 1.
5. according to the polymkeric substance of claim 1, the repeating unit that comprises following formula
, wherein,
R 1and R 2c independently of one another 1～C 25alkyl, and
R 3and R 3 'the C being optionally interrupted by one or more Sauerstoffatoms independently of one another 6～C 25alkyl,
R 4and R 4 'the C being optionally interrupted by one or more Sauerstoffatoms independently of one another 6～C 25alkyl,
R 7and R 7 'the C being optionally interrupted by one or more Sauerstoffatoms independently of one another 6～C 25alkyl.
6. comprise according to the semiconducter device of the polymkeric substance of the formula I of claim 1.
7. an organic photovoltaic devices, following order comprises:
(a) negative electrode
(b) optional transition layer,
(c) photoactive layer,
(d) optional smooth layer,
(e) anode
(f) base,
Wherein photoactive layer comprises according to formula claimed in claim 1 (I) polymkeric substance.
8. manufacture the method for organic semiconductor device, the method is included on suitable base and is coated with according to the polymkeric substance of the formula I of claim 1 solution in organic solvent and/or dispersion, then except desolventizing.
9. the monomer of following formula:
，
Wherein
A, b, c, d, e, f, R 1, R 2, Ar 1, Ar 1 ', Ar 2, Ar 2 ', Ar 3, Ar 3 ', Ar 4and Ar 4 'znX with X as defined in claim 1 12,-SnR 207r 208r 209, R wherein 207, R 208and R 209identical or different and be H or C 1～C 6alkyl, wherein 2 groups optionally form public ring, and these groups are branching or nonbranched optionally, and X 12that halogen is former
Son; Or-OS (O) 2cF 3,-OS (O) 2-aryl ,- , or , Y wherein 1at all situations
Under be all C independently 1～C 10alkyl and Y 2all C in all cases independently 2～C 10alkylidene group,
Condition is, if Ar 1and Ar 1 'it is formula group, a and d are not 0.
According to the polymkeric substance of the formula I of any one in claim 1～5 as electric charge transmit, partly lead, electricity is led, photoconduction, light-emitting material, surface modifying material, electrode materials in battery, the purposes of oriented layer or cause at organic field effect tube, unicircuit, thin film transistor, indicating meter, RFITD sign, electricity-or backlight, the photovoltaic of photo luminescent devices, indicating meter or the application in senser element, electric charge injection layer, Schottky diode, memory device, complanation layer, static inhibitor, conduction base or figure, optical conductor or electrofax field.
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