U.S. patent application number 14/529078 was filed with the patent office on 2015-02-26 for diketopyrrolopyrrole polymers for use in organic field effect transistors.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to Olivier Frederic Aebischer, Mathias Duggeli, Mahmoud Zaher Eteish, Jean-Charles Flores, Marta Fonrodona Turon, Margherita Fontana, Pascal Hayoz, Marian Lanz, Beat Schmidhalter, Mathieu G.R. Turbiez.
Application Number | 20150056746 14/529078 |
Document ID | / |
Family ID | 41353804 |
Filed Date | 2015-02-26 |
United States Patent
Application |
20150056746 |
Kind Code |
A1 |
Duggeli; Mathias ; et
al. |
February 26, 2015 |
DIKETOPYRROLOPYRROLE POLYMERS FOR USE IN ORGANIC FIELD EFFECT
TRANSISTORS
Abstract
The present invention relates to polymers comprising a repeating
unit of the formula I, or III and their use as organic
semiconductor in organic devices, especially an organic field
effect transistor (OFET), or a device containing a diode and/or an
organic field effect transistor. 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 organic field
effect transistors.
Inventors: |
Duggeli; Mathias; (Thurnen,
CH) ; Eteish; Mahmoud Zaher; (Huningue, FR) ;
Hayoz; Pascal; (Hofstetten, CH) ; Aebischer; Olivier
Frederic; (Dudingen, CH) ; Fonrodona Turon;
Marta; (Blanes, ES) ; Fontana; Margherita;
(Basel, CH) ; Lanz; Marian; (Roschenz, CH)
; Turbiez; Mathieu G.R.; (Rixheim, FR) ;
Schmidhalter; Beat; (Bubendorf, CH) ; Flores;
Jean-Charles; (Mulhouse, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
LUDWIGSHAFEN
DE
|
Family ID: |
41353804 |
Appl. No.: |
14/529078 |
Filed: |
October 30, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13126182 |
Jun 21, 2011 |
8912305 |
|
|
PCT/EP2009/063767 |
Oct 21, 2009 |
|
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14529078 |
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Current U.S.
Class: |
438/99 ;
526/256 |
Current CPC
Class: |
C08G 61/126 20130101;
C08G 2261/3243 20130101; H01L 51/0043 20130101; C08G 2261/3241
20130101; C08G 2261/92 20130101; C08G 2261/3229 20130101; C08G
2261/1412 20130101; H01L 51/0053 20130101; C08G 2261/3223 20130101;
C08G 2261/364 20130101; H01L 51/0036 20130101; H01L 27/283
20130101; C08G 2261/3246 20130101; H01L 51/0007 20130101; C08G
61/12 20130101; C08G 2261/124 20130101; H01L 51/0001 20130101; C08G
2261/228 20130101; C08G 2261/334 20130101; H01L 51/0558 20130101;
C08G 2261/411 20130101; C08G 61/124 20130101; C08G 2261/18
20130101 |
Class at
Publication: |
438/99 ;
526/256 |
International
Class: |
H01L 51/00 20060101
H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 31, 2008 |
EP |
08168010.0 |
Feb 19, 2009 |
EP |
09153172.3 |
May 19, 2009 |
EP |
09160579.0 |
Claims
1.-16. (canceled)
17. A copolymer comprising repeating units of formula (VII)
##STR00122## wherein A is a group of formula ##STR00123## COM.sup.1
is a group of formula ##STR00124## a is an integer of 1 to 5, n is
number which results in a molecular weight of 4,000 to 2,000,000
Daltons, Ar.sup.1 and Ar.sup.1' are a group of formula ##STR00125##
Ar.sup.2 is a group of formula ##STR00126## one of X.sup.1 and
X.sup.2 is N and the other is CH, and R.sup.1 and R.sup.2 are the
same or different and are selected from H or a
C.sub.1-C.sub.100alkyl group.
18. The copolymer according to claim 17, wherein a is an integer of
1 to 3.
19. The copolymer according to claim 17, wherein R.sup.1 and
R.sup.2 are a C.sub.1-C.sub.100alkyl group.
20. The copolymer according to claim 19, wherein R.sup.1 and
R.sup.2 are a C.sub.8-C.sub.36alkyl group.
21. The copolymer according to claim 17, wherein Ar.sup.2 is a
group of formula ##STR00127##
22. A copolymer comprising repeating units of formula (IIa') or
(IIi) ##STR00128## wherein R.sup.1 and R.sup.2 are the same or
different and are selected from a C.sub.8-C.sub.36alkyl group.
23. The copolymer according to claim 17, which has a weight average
molecular weight of 10,000 to 1,000,000 Daltons.
24. The copolymer according to claim 23, which has a weight average
molecular weight of 10,000 to 100,000 Daltons.
25. A semiconductor device comprising the copolymer according to
claim 17.
26. The semiconductor device according to claim 25 is an organic
field effect transistor.
27. A process for preparing an organic semiconductor device, the
process comprising: applying a solution and/or dispersion
comprising the copolymer according to claim 17 in an organic
solvent to a substrate; and removing the solvent.
28. An integrated circuit comprising the organic field effect
transistor according to claim 26.
29. A process for preparing the copolymer of claim 17 comprising:
reacting a dihalogenide X.sup.10-A-X.sup.10 with an equimolar
amount of a diboronic acid or diboronate corresponding to formula
##STR00129## or reacting a dihalogenide of formula ##STR00130##
with an equimolar amount of a diboronic acid or diboronate
corresponding to formula X.sup.11-A-X.sup.11, wherein X.sup.10 is
halogen, and X.sup.11 is independently in each occurrence
--B(OH).sub.2, --B(OY.sup.1).sub.2, ##STR00131## --BF.sub.3Na,
--BF.sub.3N(Y.sup.15).sub.4, or --BF.sub.3K, wherein Y.sup.1 is
independently in each occurrence a C.sub.1-C.sub.10alkyl group and
Y.sup.2 is independently in each occurrence a
C.sub.2-C.sub.10alkylene group, Y.sup.13 and Y.sup.14 are
independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl
group, Y.sup.15 is H, or a C.sub.1-C.sub.25alkyl group, which may
optionally be interrupted by --O--, in a solvent and in the
presence of a catalyst; or reacting a dihalogenide of formula
X.sup.10-A-X.sup.10 with an equimolar amount of an organo tin
compound corresponding to formula or ##STR00132## or reacting a
dihalogenide of formula ##STR00133## with an equimolar amount of an
organo tin compound corresponding to formula X.sup.11'-A-X.sup.11',
wherein X.sup.11' is independently in each occurrence
--SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and
R.sup.209 are identical or different and are H or
C.sub.1-C.sub.6alkyl, or two of the groups R.sup.207R.sup.208 and
R.sup.209 form a ring and these groups are optionally branched.
30. The process according to claim 29, wherein X.sup.10 is Br.
Description
[0001] The present invention relates to polymers comprising a
repeating unit of the formula I, or III and their use as organic
semiconductor in organic devices, especially an organic field
effect transistor (OFET), or a device containing a diode and/or an
organic field effect transistor. 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 organic field
effect transistors.
[0002] U.S. Pat. No. 6,451,459 (cf. B. Tieke et al., Synth. Met.
130 (2002) 115-119; Macromol. Rapid Commun. 21 (4) (2000) 182-189)
describes diketopyrrolopyrrole based polymers and copolymers
comprising the following units
##STR00001##
wherein x is chosen in the range of from 0.005 to 1, preferably
from 0.01 to 1, and y from 0.995 to 0, preferably 0.99 to 0, and
wherein x+y=1, and wherein Ar.sup.1 and Ar.sup.2 independently from
each other stand for
##STR00002##
and m, n being numbers from 1 to 10, and R.sup.1 and R.sup.2
independently from each other stand for H, C.sub.1-C.sub.18alkyl,
--C(O)O--C.sub.1-C.sub.18alkyl, perfluoro-C.sub.1-C.sub.12alkyl,
unsubstituted C.sub.6-C.sub.12aryl or one to three times with
C.sub.1-C.sub.12alkyl, C.sub.12alkoxy, or halogen substituted
C.sub.6-C.sub.12aryl, C.sub.1-C.sub.12alkyl-C.sub.6-C.sub.12aryl,
or C.sub.6-C.sub.12aryl-C.sub.1-C.sub.12alkyl, R.sup.3 and R.sup.4
preferably stand for hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.1-C.sub.12alkoxy, unsubstituted C.sub.6-C.sub.12aryl or one
to three times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy,
or halogen substituted C.sub.6-C.sub.12aryl or
perfluoro-C.sub.1-C.sub.12alkyl, and R.sup.5 preferably stands for
C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, unsubstituted
C.sub.6-C.sub.12aryl or one to three times with
C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, or halogen
substituted C.sub.6-C.sub.12aryl, or
perfluoro-C.sub.1-C.sub.12alkyl, and their use in EL devices. The
following polymer
##STR00003##
is explicitly disclosed in Tieke et al., Synth. Met. 130 (2002)
115-119. The following polymers
##STR00004##
are explicitly disclosed in Macromol. Rapid Commun. 21 (4) (2000)
182-189.
[0003] WO05/049695 discloses diketopyrrolopyrrole (DPP) based
polymers and their use in PLEDs, organic integrated circuits
(O-ICs), organic field effect transistors (OFETs), organic thin
film transistors (OTFTs), organic solar cells (O-SCs), or organic
laser diodes, but fails to disclose the specific DPP based polymers
of formula I.
[0004] A preferred polymer comprises a repeating unit of
formula
##STR00005##
and a repeating unit
##STR00006##
wherein R.sup.1 and R.sup.2 are independently of each other a
C.sub.1-C.sub.25alkyl group, especially a C.sub.4-C.sub.12alkyl
group, which can be interrupted by one or more oxygen atoms, and
Ar.sup.1 and Ar.sup.2 are independently of each other a group of
formula
##STR00007##
wherein --Ar.sup.3-- is a group of formula
##STR00008##
wherein R.sup.6 is hydrogen, C.sub.1-C.sub.18alkyl, or
C.sub.1-C.sub.18alkoxy, and R.sup.32 is methyl, Cl, or OMe, and
R.sup.8 is H, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which
is substituted by E and/or interrupted by D, especially
C.sub.1-C.sub.18alkyl which is interrupted by --O--.
[0005] In Example 12 the preparation of the following polymer is
described:
##STR00009##
WO08/000664 describes polymers comprising (repeating) unit(s) of
the formula
##STR00010##
Ar.sup.1 and Ar.sup.1' are preferably the same and are a group of
formula
##STR00011##
especially
##STR00012##
and Ar.sup.2, Ar.sup.2', Ar.sup.3, Ar.sup.3', Ar.sup.4 and
Ar.sup.4' are independently of each other a group of formula
##STR00013##
wherein p stands for 0, 1, or 2, R.sup.3 may be the same or
different within one group and is selected from
C.sub.1-C.sub.25alkyl, which may optionally be substituted by E
and/or interrupted by D, or C.sub.1-C.sub.18alkoxy, which may
optionally be substituted by E and/or interrupted by D; R.sup.4 is
C.sub.6-C.sub.25alkyl, which may optionally be substituted by E
and/or interrupted by D, C.sub.6-C.sub.12aryl, such as phenyl,
naphthyl, or biphenylyl, which may optionally be substituted by G,
C.sub.1-C.sub.25alkoxy, which may optionally be substituted by E
and/or interrupted by D, or C.sub.7-C.sub.15aralkyl, wherein ar may
optionally be substituted by G, D is --CO--, --COO--, --S--,
--SO--, --SO.sub.2--, --O--, --NR.sup.25--, wherein R.sup.25 is
C.sub.1-C.sub.12alkyl, such as methyl, ethyl, n-propyl, iso-propyl,
n-butyl, isobutyl, or sec-butyl; E is --OR.sup.29; --SR.sup.29;
--NR.sup.25R.sup.25; --COR.sup.28; --COOR.sup.27;
--CONR.sup.25R.sup.25; or --CN; wherein R.sup.25, R.sup.27,
R.sup.28 and R.sup.29 are independently of each other
C.sub.1-C.sub.12alkyl, such as methyl, ethyl, n-propyl, iso-propyl,
n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or
C.sub.6-C.sub.14 aryl, such as phenyl, naphthyl, or biphenylyl, G
has the same preferences as E, or is C.sub.1-C.sub.12alkyl,
especially C.sub.1-C.sub.12alkyl, such as methyl, ethyl, n-propyl,
iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or
2-ethyl-hexyl.
[0006] The following polymers were disclosed in the Examples:
##STR00014##
(Example 1, Homopolymer; Adv. Mat. 2008, 20, 13, 2556-2560);
##STR00015##
(Example 2, Homopolymer; Adv. Mat. 2008, 20, 11, 2217-2224);
##STR00016##
(Example 3, Homopolymer);
##STR00017##
[0007] (Example 4, Homopolymer);
##STR00018##
[0008] (Example 5, Co-polymer);
##STR00019##
[0009] (Example 6, Co-polymer).
[0010] EP2034537A2, which enjoys an earlier priority date (6, Sep.
2007) than the present invention (31, Oct. 2008), but has been
published (11, Mar. 2009) after the priority date of the present
invention, is directed to a thin film transistor device comprising
a semiconductor layer, the semiconductor layer comprising a
compound comprising a chemical structure represented by:
##STR00020##
wherein each X is independently selected from S, Se, O, and NR'',
each R'' is independently selected from hydrogen, an optionally
substituted hydrocarbon, and a hetero-containing group, each Z is
independently one of an optionally substituted hydrocarbon, a
hetero-containing group, and a halogen, d is a number which is at
least 1, e is a number from zero to 2; a represents a number that
is at least 1; b represents a number from 0 to 20; and n represents
a number that is at least 1.
[0011] The following polymers are explicitly disclosed:
##STR00021##
wherein n is the number of repeat units and can be from about 2 to
about 5000, R''' and R'''' can be the same or different
substituent, and wherein the substituent is independently selected
from the group consisting of an optionally substituted hydrocarbon
group and a heteroatom-containing group.
[0012] It is the object of the present invention to provide
polymers, which show high efficiency of energy conversion,
excellent field-effect mobility, good on/off current ratios and/or
excellent stability, when used in organic field effect
transistors.
[0013] Said object has been solved by polymers comprising one or
more (repeating) unit(s) of the formula
##STR00022##
wherein a is an integer of 1 to 5, b is an integer of 1 to 3, c is
an integer of 1 to 3, d is an integer 1, 2, or 3, e is an integer
1, 2, or 3, the sum of a, b and c is equal, or smaller than 7,
Ar.sup.1, Ar.sup.1', Ar.sup.3 and Ar.sup.3' are independently of
each other a group of formula
##STR00023##
or a group --Ar.sup.4--Ar.sup.5--[Ar.sup.6].sub.f--, Ar.sup.4 is a
group of formula
##STR00024##
Ar.sup.5 and Ar.sup.6 have independently of each other the meaning
of Ar.sup.1, f is 0, or an integer 1, Ar.sup.2 is a group of
formula
##STR00025##
one of and X.sup.1 is X.sup.2 and the other is CH, and R.sup.1,
R.sup.2, R.sup.1' and R.sup.2' may be the same or different and are
selected from hydrogen, a C.sub.1-C.sub.100alkyl group, especially
a C.sub.3-C.sub.36alkyl group, a C.sub.6-C.sub.24aryl, in
particular phenyl or 1- or 2-naphthyl which can be substituted one
to three times with C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8thioalkoxy, and/or C.sub.1-C.sub.8alkoxy, or
pentafluorophenyl; with the proviso that polymers of formula
##STR00026##
having a molecular weight below 10000 are excluded, and with the
further proviso that polymers of formula
##STR00027##
having a molecular weight below 10000 are excluded.
[0014] In a preferred embodiment of the present invention e is 2,
or 3. d is preferably equal to e.
[0015] Polymers comprising repeating units of the formula I are
preferred against polymers comprising repeating units of the
formula III.
[0016] In a preferred embodiment the present invention is directed
to a polymer comprising one or more (repeating) unit(s) of the
formula
##STR00028##
wherein a is an integer of 1 to 5, Ar.sup.1 and Ar.sup.1' are
independently of each other a group of formula
##STR00029##
Ar.sup.2 is a group of formula
##STR00030##
and R.sup.1 and R.sup.2 may be the same or different and are
selected from hydrogen, a C.sub.1-C.sub.100alkyl group, especially
a C.sub.8-C.sub.36alkyl group, a C.sub.6-C.sub.24aryl, in
particular phenyl or 1- or 2-naphthyl which can be substituted one
to three times with C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8thioalkoxy, and/or C.sub.8alkoxy, or
pentafluorophenyl.
[0017] Advantageously, the polymer of the present invention, or an
organic semiconductor material, layer or component, comprising the
polymer of the present invention can be used in OFETs. Ar.sup.1,
Ar.sup.1', Ar.sup.3 and Ar.sup.3' can be the same and can be
different, but are preferably the same. Ar.sup.1, Ar.sup.1',
Ar.sup.3 and Ar.sup.3' can be a group of formula
##STR00031##
wherein a group of formula
##STR00032##
is preferred. Ar.sup.2 can be a group of formula
##STR00033##
wherein groups of formula
##STR00034##
are preferred and a group of formula
##STR00035##
is even more preferred. If a is equal to, or greater than 2,
Ar.sup.2 can be composed of groups of formula
##STR00036##
i.e. can, for example, be a group of formula
##STR00037##
[0018] As indicated by the formula
##STR00038##
the group
##STR00039##
can be attached to the DPP basic unit, or arranged in the polymer
chain in two ways
##STR00040##
The notation
##STR00041##
should comprise both possibilities. a is preferably an integer of 1
to 5, especially an integer of 1 to 3. b is an integer of 1 to 3. c
is an integer of 1 to 3. The sum of a, b and c is equal, or smaller
than 7. R.sup.1, R.sup.2, R.sup.1' and R.sup.2' can be different,
but are preferably the same. R.sup.1, R.sup.2, R.sup.1' and
R.sup.2' can be linear, but are preferably branched. R.sup.1,
R.sup.2, R.sup.1' and R.sup.2' are preferably a
C.sub.8-C.sub.36alkyl group, especially a C.sub.12-C.sub.24alkyl
group, such as n-dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, 2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl,
2-hexyldecyl, 2-decyl-tetradecyl, heptadecyl, octadecyl, eicosyl,
heneicosyl, docosyl, or tetracosyl. The C.sub.8-C.sub.36alkyl and
C.sub.12-C.sub.24alkyl group can be linear, or branched, but are
preferably branched. In a particularly preferred embodiment of the
present invention R.sup.1, R.sup.2, R.sup.1' and R.sup.2' are a
2-hexyldecyl or 2-decyl-tetradecyl group.
[0019] Advantageously, the groups R.sup.1, R.sup.2, R.sup.1' and
R.sup.2' can be represented by formula
##STR00042##
wherein m1=n1+4 and m1+n1.ltoreq.22.
[0020] Chiral side chains, such as R.sup.1, R.sup.2, R.sup.1' and
R.sup.2', can either be homochiral, or racemic, which can influence
the morphology of the polymers.
[0021] In a preferred embodiment the present invention is directed
to co-polymers of the formula
##STR00043##
wherein R.sup.1 and R.sup.2 are a branched C.sub.8-C.sub.36alkyl
group, especially a branched C.sub.12-C.sub.24alkyl group, such as,
for example, a 2-hexyldecyl or 2-decyl-tetradecyl group. Said
polymers have a weight average molecular weight of preferably
10,000 to 100,000 Daltons and most preferably 20,000 to 60,000
Daltons. Said polymers preferably have a polydispersibility of 1.1
to 3.0, most preferred 1.5 to 2.5.
[0022] In a preferred embodiment the present invention is directed
to homopolymers of the formula
##STR00044##
wherein R.sup.1' and R.sup.2' are a branched C.sub.8-C.sub.36alkyl
group, especially a branched C.sub.12-C.sub.24alkyl group, such as,
for example, a 2-hexyldecyl or 2-decyl-tetradecyl group. Said
polymers have a weight average molecular weight of preferably
10,000 to 100,000 Daltons and most preferably 20,000 to 60,000
Daltons. Said polymers preferably have a polydispersibility of 1.1
to 3.0, most preferred 1.5 to 2.5. Said polymers can show
ambipolarity.
[0023] In a preferred embodiment the present invention is directed
to polymers, comprising one or more (repeating) unit(s) of the
formula
##STR00045## ##STR00046## ##STR00047##
wherein a is an integer of 1 to 5, especially 1 to 3, b is an
integer of 2, or 3, b' is an integer of 2, b'' is an integer of 3,
one of X.sup.1 and X.sup.2 is N and the other is CH, and R.sup.1
and R.sup.2 may be the same or different and are selected from
hydrogen, or a C.sub.8-C.sub.36alkyl group.
[0024] Even more preferred are polymers, comprising one or more
(repeating) unit(s) of the formula
##STR00048##
wherein R.sup.1 and R.sup.2 may be the same or different and are
selected from a C.sub.8-C.sub.36alkyl group.
[0025] In a preferred embodiment of the present invention the
polymer comprises two, or more different repeating units of formula
I. Advantageously, the repeating units are selected from repeating
units of formula IIa, IIb, IIc, IId, IIe, IIf, IIg and IIh. A
polymer comprising repeating units of formula IIa' and IIa'' shows,
for example, excellent field effect mobility and on/off current
ratio.
[0026] According to the present invention a homopolymer is a
polymer derived from one species of (real, implicit, or
hypothetical) monomer. Many polymers are made by the mutual
reaction of complementary monomers. These monomers can readily be
visualized as reacting to give an "implicit monomer", the
homopolymerisation of which would give the actual product, which
can be regarded as a homopolymer. Some polymers are obtained by
chemical modification of other polymers, such that the structure of
the macromolecules that constitute the resulting polymer can be
thought of having been formed by the homopolymerisation of a
hypothetical monomer.
[0027] Accordingly a copolymer is a polymer derived from more than
one species of monomer, e.g. bipolymer, terpolymer, quaterpolymer,
etc.
[0028] The term polymer comprises oligomers as well as polymers.
The oligomers of this invention have a weight average molecular
weight of <4,000 Daltons. The polymers of this invention
preferably have a weight average molecular weight of 4,000 Daltons
or greater, especially 4,000 to 2,000,000 Daltons, very especially
10,000 to 1,000,000 Daltons, more preferably 10,000 to 100,000
Daltons and most preferred 20,000 to 60,000 Daltons. Molecular
weights are determined according to high-temperature gel permeation
chromatography (HT-GPC) using polystyrene standards. The polymers
of this invention preferably have a polydispersibility of 1.01 to
10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5.
[0029] In a preferred embodiment of the present invention the
polymer is a copolymer, comprising repeating units of formula
##STR00049##
especially, wherein A is a group of formula
##STR00050##
COM.sup.1 is a group of formula
##STR00051##
and R.sup.1, R.sup.2, Ar.sup.1, Ar.sup.1' Ar.sup.2 and a are as
defined above.
[0030] Copolymers of formula VII can be obtained, for example, by
the Suzuki reaction. The condensation reaction of an aromatic
boronate and a halogenide, especially a bromide, commonly referred
to as the "Suzuki reaction", is tolerant of the presence of a
variety of organic functional groups as reported by N. Miyaura and
A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995).
Preferred catalysts are
2-dicyclohexylphosphino-2',6'-di-alkoxybiphenyl/palladium(11)acetates,
tri-alkyl-phosphonium salts/palladium (0) derivatives and
tri-alkylphosphine/palladium (0) derivatives. Especially preferred
catalysts are 2-dicyclohexylphosphino-2',6'-di-methoxybiphenyl
(sPhos)/palladium(II)acetate and, tri-tert-butylphosphonium
tetrafluoroborate
((t-Bu).sub.3P*HBF.sub.4)/tris(dibenzylideneacetone)dipalladium (0)
(Pd.sub.2(dba).sub.3) and tri-tert-butylphosphine
(t-Bu).sub.3P/tris(dibenzylideneacetone)dipalladium (0)
(Pd.sub.2(dba).sub.3). Preferred solvents are tetrahydrofuran
(THF), or mixtures of THF and toluene. Preferred bases are aq.
K.sub.2CO.sub.3 or aq. Na.sub.2CO.sub.3. This reaction can be
applied to preparing high molecular weight polymers and
copolymers.
[0031] To prepare polymers corresponding to formula
##STR00052##
wherein A is a group of formula
##STR00053##
COM.sup.1 is a group of formula
##STR00054##
a is an integer of 1 to 5, n is number which results in a molecular
weight of 4,000 to 2,000,000 Daltons, and R.sup.1, R.sup.2,
Ar.sup.1, Ar.sup.1', Ar.sup.1 and a are as defined above, a
dihalogenide, X.sup.10-A-X.sup.10, such as a dibromide or
dichloride, or diiodide, especially a dibromide corresponding to
formula Br-A-Br is reacted with an equimolar amount of a diboronic
acid or diboronate corresponding to formula
##STR00055##
or a dihalogenide of formula
##STR00056##
is reacted with an equimolar amount of a diboronic acid or
diboronate corresponding to formula X.sup.11-A-X.sup.11, wherein
X.sup.10 is halogen, especially Br, and X.sup.11 is independently
in each occurrence --B(OH).sub.2, --B(OY.sup.1).sub.2,
##STR00057##
--BF.sub.3Na, --BF.sub.3N(Y.sup.15).sub.4, or --BF.sub.3K, wherein
Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl
group and Y.sup.2 is independently in each occurrence a
C.sub.2-C.sub.10alkylene group, such as
--CY.sup.3Y.sup.4--CY.sup.5Y.sup.6--, or
--CY.sup.7Y.sup.8--CY.sup.9Y.sup.10--CY.sup.11Y.sup.12--, wherein
Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7Y.sup.9, Y.sup.10,
Y.sup.11 and Y.sup.12 are independently of each other hydrogen, or
a C.sub.1-C.sub.10alkyl group, especially
--C(CH.sub.3).sub.2C(CH.sub.3).sub.2--, or
--C(CH.sub.3).sub.2CH.sub.2C(CH.sub.3).sub.2--,
--CH.sub.2C(CH.sub.3).sub.2CH.sub.2--, and Y.sup.13 and Y.sup.14
are independently of each other hydrogen, or a
C.sub.1-C.sub.10alkyl group, Y.sup.15 is H, or a
C.sub.1-C.sub.25alkyl group, which may optionally be interrupted by
--O--, in a solvent and in the presence of a catalyst; such as, for
example, under the catalytic action of Pd and
triphenylphosphine.
[0032] The reaction is typically conducted at about 0.degree. C. to
180.degree. C. in an aromatic hydrocarbon solvent such as toluene,
xylene, anisole, chlorobenzene, fluorobenzene. Other solvents such
as dimethylformamide, dioxane, dimethoxyethan,
2-methyltetrahydrofuran, cyclopentylmethylether and tetrahydrofuran
can also be used alone, or in mixtures with an aromatic
hydrocarbon. Most preferred are THF or THF/toluene. An aqueous base
(such as, for example, for example, alkali and alkaline earth metal
hydroxides, carboxylates, carbonates, fluorides and phosphates such
as sodium and potassium hydroxide, acetate, carbonate, fluoride and
phosphate or also metal alcoholates), preferably sodium carbonate
or bicarbonate, potassium phosphate, potassium carbonate or
bicarbonate is used as the HBr scavenger. A polymerization reaction
may take 0.2 to 100 hours. Organic bases, such as, for example,
tetraalkylammonium hydroxide, and phase transfer catalysts, such
as, for example TBAB, can promote the activity of the boron (see,
for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42
(2003) 1407 and references cited therein). Other variations of
reaction conditions are given by T. I. Wallow and B. M. Novak in J.
Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G.
Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Controll of
molecular weight is possible by using either an excess of
dibromide, diboronic acid, or diboronate, or a chain
terminator.
[0033] The palladium catalyst is present in the reaction mixture in
catalytic amounts. The term "catalytic amount" as used herein
refers to an amount that is clearly below one equivalent of
dihalogenide and diboronic acid or diboronate used, preferably 0.01
to 5 mol. %, most preferably 0.01 to 1 mol. %, based on the
equivalents of dihalogenide and diboronic acid or diboronate
used.
[0034] The amount of phosphines or phosphonium salts in the
reaction mixture is preferably from 0.02 to 10 mol. %, most
preferably 0.02 to 2 mol. %, based on the equivalents of
dihalogenide and diboronic acid or diboronate used. The preferred
ratio of Pd:phosphine is 1:2. It is preferable that at least 1.5
equivalents of said base per functional boron group is present in
the reaction mixture.
[0035] For polymerisations that are performed in a single solvent
or a solvent mixture, it is possible to add a secondary or tertiary
co-solvent once the polymerisation has initiated and after a given
period of time. The purpose of this co-solvent addition is to keep
the growing polymer chains in solution during the polymerisation
process. This also assist the recovery of the polymer from the
reaction mixture at the end of the reaction and therefore improve
the isolated yield of the polymer.
[0036] If desired, a monofunctional aryl halide or aryl boronate
may be used as a chain-terminator in such reactions, which will
result in the formation of a terminal aryl group.
##STR00058## ##STR00059##
[0037] It is possible to control the sequencing of the monomeric
units in the resulting copolymer by controlling the order and
composition of monomer feeds in the Suzuki reaction.
[0038] After polymerisation the polymer is preferably recovered
from the reaction mixture, for example by conventional work-up, and
purified. This can be achieved according to standard methods known
to the expert and described in the literature.
[0039] The polymers of the present invention can also be
synthesized by the Stille coupling (see, for example, Babudri et
al, J. Mater. Chem., 2004, 14, 11-34; J. K. Stille, Angew. Chemie
Int. Ed. Engl. 1986, 25, 508). To prepare polymers corresponding to
formula VII a dihalogenide, such as a dibromide or dichloride,
especially a dibromide corresponding to formula Br-A-Br is reacted
with a compound of formula
##STR00060##
wherein X.sup.21 is a group --SnR.sup.207R.sup.208R.sup.209, in an
inert solvent at a temperature in range from 0.degree. C. to
200.degree. C. in the presence of a palladium-containing catalyst,
wherein R.sup.207, R.sup.208 and R.sup.209 are identical or
different and are H, or C.sub.1-C.sub.6alkyl, wherein two radicals
optionally form a common ring and these radicals are optionally
branched or unbranched. It must be ensured here that the totality
of all monomers used has a highly balanced ratio of organotin
functions to halogen functions. In addition, it may prove
advantageous to remove any excess reactive groups at the end of the
reaction by end-capping with monofunctional reagents. In order to
carry out the process, the tin compounds and the halogen compounds
are preferably introduced into one or more inert organic solvents
and stirred at a temperature of from 0 to 200.degree. C.,
preferably from 30 to 170.degree. C. for a period of from 1 hour to
200 hours, preferably from 5 hours to 150 hours. The crude product
can be purified by methods known to the person skilled in the art
and appropriate for the respective polymer, for example repeated
re-precipitation or even by dialysis.
[0040] Suitable organic solvents for the process described are, for
example, ethers, for example diethyl ether, dimethoxyethane,
diethylene glycol dimethyl ether, tetrahydrofuran, dioxane,
dioxolane, diisopropyl ether and tert-butyl methyl ether,
hydrocarbons, for example hexane, isohexane, heptane, cyclohexane,
benzene, toluene and xylene, alcohols, for example methanol,
ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol,
2-butanol and tert-butanol, ketones, for example acetone, ethyl
methyl ketone and isobutyl methyl ketone, amides, for example
dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,
nitriles, for example acetonitrile, propionitrile and
butyronitrile, and mixtures thereof.
[0041] The palladium and phosphine components should be selected
analogously to the description for the Suzuki variant.
[0042] Alternatively, the polymers of the present invention can
also be synthesized by the Negishi reaction using zinc reagents
(A-(ZnX.sup.22).sub.2, wherein X.sup.22 is halogen) and halides or
triflates (COM.sup.1-(X.sup.23).sub.2, wherein X.sup.23 is halogen
or triflate). Reference is, for example, made to E. Negishi et al.,
Heterocycles 18 (1982) 117-22.
[0043] The polymers, wherein R.sup.1 and/or R.sup.2 are hydrogen
can be obtained by using a protecting group which can be removed
after polymerization (see, for example, EP-A-0648770, EP-A-0648817,
EP-A-0742255, EP-A-0761772, WO98/32802, WO98/45757, WO98/58027,
WO99/01511, WO00/17275, WO00/39221, WO00/63297 and EP-A-1086984).
Conversion of the pigment precursor into its pigmentary form is
carried out by means of fragmentation under known conditions, for
example thermally, optionally in the presence of an additional
catalyst, for example the catalysts described in WO00/36210.
[0044] An example of such a protecting group is group of
formula
##STR00061##
wherein L is any desired group suitable for imparting
solubility.
[0045] L is preferably a group of formula
##STR00062##
wherein Z.sup.1, Z.sup.2 and Z.sup.3 are independently of each
other C.sub.1-C.sub.6alkyl, Z.sup.4 and Z.sup.8 are independently
of each other C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkyl
interrupted by oxygen, sulfur or N(Z.sup.12).sub.2, or
unsubstituted or C.sub.1-C.sub.6alkyl-, C.sub.1-C.sub.6alkoxy-,
halo-, cyano- or nitro-substituted phenyl or biphenyl, Z.sup.5,
Z.sup.6 and Z.sup.7 are independently of each other hydrogen or
C.sub.1-C.sub.6alkyl, Z.sup.9 is hydrogen, C.sub.1-C.sub.6alkyl or
a group of formula
##STR00063##
Z.sup.10 and Z.sup.11 are each independently of the other hydrogen,
C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxy, halogen, cyano, nitro,
N(Z.sup.12).sub.2, or unsubstituted or halo-, cyano-, nitro-,
C.sub.1-C.sub.6alkyl- or C.sub.1-C.sub.6alkoxy-substituted phenyl,
Z.sup.12 and Z.sup.13 are C.sub.1-C.sub.6alkyl, Z.sup.14 is
hydrogen or C.sub.1-C.sub.6alkyl, and Z.sup.15 is hydrogen,
C.sub.1-C.sub.6alkyl, or unsubstituted or
C.sub.1-C.sub.6alkyl-substituted phenyl, Q is
p,q-C.sub.2-C.sub.6alkylene unsubstituted or mono- or
poly-substituted by C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkylthio
or C.sub.2-C.sub.12dialkylamino, wherein p and q are different
position numbers, X is a hetero atom selected from the group
consisting of nitrogen, oxygen and sulfur, m' being the number 0
when X is oxygen or sulfur and m being the number 1 when X is
nitrogen, and L.sup.1 and L.sup.2 are independently of each other
unsubstituted or mono- or poly-C.sub.1-C.sub.12alkoxy-,
--C.sub.1-C.sub.12alkylthio-, --C.sub.2-C.sub.24dialkylamino-,
--C.sub.6-C.sub.12aryloxy-, C.sub.6-C.sub.12arylthio-,
--C.sub.7-C.sub.24alkylarylamino- or
--C.sub.12-C.sub.24diarylamino-substituted C.sub.1-C.sub.6alkyl or
[-(p',q'-C.sub.2-C.sub.6alkylene)-Z--].sub.n'--C.sub.1-C.sub.6alkyl,
n' being a number from 1 to 1000, p' and q' being different
position numbers, each Z independently of any others being a hetero
atom oxygen, sulfur or C.sub.1-C.sub.12alkyl-substituted nitrogen,
and it being possible for C.sub.2-C.sub.6alkylene in the repeating
[--C.sub.2-C.sub.6alkylene-Z--] units to be the same or different,
and L.sub.1 and L.sub.2 may be saturated or unsaturated from one to
ten times, may be uninterrupted or interrupted at any location by
from 1 to 10 groups selected from the group consisting of
--(C.dbd.O)-- and --C.sub.6H.sub.4--, and may carry no further
substituents or from 1 to 10 further substituents selected from the
group consisting of halogen, cyano and nitro. Most preferred L is a
group of formula
##STR00064##
[0046] The synthesis of the compounds of formula Br-A-Br is
described in WO05/049695, WO08/000664, and WO09/047104, or can be
done in analogy to the methods described therein. The synthesis of
N-aryl substituted compounds of formula Br-A-Br can be done in
analogy to the methods described in U.S. Pat. No. 5,354,869 and
WO03/022848.
[0047] In another embodiment the present invention is directed to
polymers of formula III.
[0048] In said embodiment polymers are preferred, comprising one or
more (repeating) unit(s) of the formula
##STR00065##
wherein R.sup.1' and R.sup.2' may be the same or different and are
selected from a C.sub.8-C.sub.36alkyl group.
[0049] In another preferred embodiment the present invention is
directed to homopolymers of the formula
##STR00066##
or copolymers of formula
##STR00067##
wherein R.sup.1, R.sup.2, R.sup.1' and R.sup.2' are a branched
C.sub.8-C.sub.36alkyl group, especially a branched
C.sub.12-C.sub.24alkyl group, or a copolymer of formula
##STR00068##
having a Mw of 51'500 and a Polydispersity of 2.0 (measured by
HT-GPC).
[0050] The polymers comprising repeating units of formula III are
preferably homopolymers, which can be prepared by dehalogenative
polycondensation (reductive coupling) of the corresponding
dihaloaromatic compounds such as Br-A-Br with 0-valent Ni complexes
(Yamamoto coupling reaction). As Nickel source
bis(cyclooctadiene)nickel can be used in combination with
bipyridine, triarylphosphine or trialyklphosphine. Reference is,
for example, made to T. Yamamoto, et al., Synthetic Metals (1993),
55(2-3), 1214-20.
[0051] Alternatively, such polymers can be prepared by reacting a
dihalogenide X.sup.10-A-X.sup.10 with an equimolar amount of a
diboronic acid or diboronate corresponding to formula
X.sup.11-A-X.sup.11.
[0052] A further embodiment of the present invention is directed to
compounds of formula
##STR00069##
wherein d is an integer 1, 2, or 3, e is an integer 1, 2, or 3,
Ar.sup.3 and Ar.sup.3' are independently of each other a group of
formula
##STR00070##
or a group --Ar.sup.4--Ar.sup.5--[Ar.sup.6].sub.f--, Ar.sup.4 is a
group of formula
##STR00071##
Ar.sup.5 and Ar.sup.6 have independently of each other the meaning
of Ar.sup.3, f is 0, or an integer 1, R1' and R2' are as defined in
claim 1,
X.sup.12 is --B(OH).sub.2, --B(OY.sup.1).sub.2,
##STR00072##
[0053] --BF.sub.3Na, --BF.sub.3N(Y.sup.15).sub.4, or --BF.sub.3K,
wherein Y.sup.1 is independently in each occurrence a
C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each
occurrence a C.sub.2-C.sub.10alkylene group, such as
--CY.sup.3Y.sup.4--CY.sup.5Y.sup.6--, or
--CY.sup.7Y.sup.8--CY.sup.9Y.sup.10--CY.sup.11Y.sup.12--, wherein
Y.sup.3, Y.sup.4, Y.sup.5, Y.sup.6, Y.sup.7, Y.sup.8, Y.sup.9,
Y.sup.10, Y.sup.11 and Y.sup.12 are independently of each other
hydrogen, or a C.sub.1-C.sub.10alkyl group, especially
--C(CH.sub.3).sub.2C(CH.sub.3).sub.2--, or
--C(CH.sub.3).sub.2CH.sub.2C(CH.sub.3).sub.2-- and Y.sup.15 is H,
or a C.sub.1-C.sub.25alkyl group, which may optionally be
interrupted by O.
[0054] The compounds of formula X represent intermediates for the
synthesis of the polymers of the present invention. Specific
examples of such compounds are shown below:
##STR00073##
[0055] The polymers of the invention can be used as the
semiconductor layer in semiconductor devices. Accordingly, the
present invention also relates to semiconductor devices, comprising
a polymer of the present invention, or an organic semiconductor
material, layer or component. The semiconductor device is
especially an organic field effect transistor (OFET).
[0056] There are numerous types of semiconductor devices. Common to
all is the presence of one or more semiconductor materials.
Semiconductor devices have been described, for example, by S. M.
Sze in Physics of Semiconductor Devices, 2.sup.nd edition, John
Wiley and Sons, New York (1981). Such devices include rectifiers,
transistors (of which there are many types, including p-n-p, n-p-n,
and thin-film transistors), light emitting semiconductor devices
(for example, organic light emitting diodes in display applications
or backlight in e.g. liquid crystal displays), photoconductors,
current limiters, solar cells, thermistors, p-n junctions,
field-effect diodes, Schottky diodes, and so forth. In each
semiconductor device, the semiconductor material is combined with
one or more metals, metal oxides, such as, for example, indium tin
oxide (ITO), and/or insulators to form the device. Semiconductor
devices can be prepared or manufactured by known methods such as,
for example, those described by Peter Van Zant in Microchip
Fabrication, Fourth Edition, McGraw-Hill, New York (2000). In
particular, organic electronic components can be manufactured as
described by D. R. Gamota et al. in Printed Organic and Molecular
Electronics, Kluver Academic Publ., Boston, 2004.
[0057] A particularly useful type of transistor device, the
thin-film transistor (TFT), generally includes a gate electrode, a
gate dielectric on the gate electrode, a source electrode and a
drain electrode adjacent to the gate dielectric, and a
semiconductor layer adjacent to the gate dielectric and adjacent to
the source and drain electrodes (see, for example, S. M. Sze,
Physics of Semiconductor Devices, 2.sup.nd edition, John Wiley and
Sons, page 492, New York (1981)). These components can be assembled
in a variety of configurations. More specifically, an OFET has an
organic semiconductor layer.
[0058] Typically, a substrate supports the OFET during
manufacturing, testing, and/or use. Optionally, the substrate can
provide an electrical function for the OFET. Useful substrate
materials include organic and inorganic materials. For example, the
substrate can comprise silicon materials inclusive of various
appropriate forms of silicon, inorganic glasses, ceramic foils,
polymeric materials (for example, acrylics, polyester, epoxies,
polyamides, polycarbonates, polyimides, polyketones,
poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene)
(sometimes referred to as poly(ether ether ketone) or PEEK),
polynorbornenes, polyphenyleneoxides, poly(ethylene
naphthalenedicarboxylate) (PEN), poly(ethylene terephthalate)
(PET), poly(phenylene sulfide) (PPS)), filled polymeric materials
(for example, fiber-reinforced plastics (FRP)), and coated metallic
foils.
[0059] The gate electrode can be any useful conductive material.
For example, the gate electrode can comprise doped silicon, or a
metal, such as aluminum, chromium, gold, silver, nickel, palladium,
platinum, tantalum, and titanium. Conductive oxides, such as indium
tin oxide, or conducting inks/pastes comprised of carbon
black/graphite or colloidal silver dispersions, optionally
containing polymer binders can also be used. Conductive polymers
also can be used, for example polyaniline or
poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate)
(PEDOT:PSS). In addition, alloys, combinations, and multilayers of
these materials can be useful. In some OFETs, the same material can
provide the gate electrode function and also provide the support
function of the substrate. For example, doped silicon can function
as the gate electrode and support the OFET.
[0060] The gate dielectric is generally provided on the gate
electrode. This gate dielectric electrically insulates the gate
electrode from the balance of the OFET device. Useful materials for
the gate dielectric can comprise, for example, an inorganic
electrically insulating material.
[0061] The gate dielectric (insulator) can be a material, such as,
an oxide, nitride, or it can be a material selected from the family
of ferroelectric insulators (e.g. organic materials such as
poly(vinylidene fluoride/trifluoroethylene or poly(m-xylylene
adipamide)), or it can be an organic polymeric insulator (e.g.
poly(methacrylate)s, poly(acrylate)s, polyimides, benzocyclobutenes
(BCBs), parylenes, polyvinylalcohol, polyvinylphenol (PVP),
polystyrenes, polyester, polycarbonates) as for example described
in J. Veres et al. Chem. Mat. 2004, 16, 4543 or A. Facchetti et al.
Adv. Mat. 2005, 17, 1705. Specific examples of materials useful for
the gate dielectric include strontiates, tantalates, titanates,
zirconates, aluminum oxides, silicon oxides, tantalum oxides,
titanium oxides, silicon nitrides, barium titanate, barium
strontium titanate, barium zirconate titanate, zinc selenide, and
zinc sulphide, including but not limited to
PbZr.sub.xTi.sub.1-xO.sub.3 (PZT), Bi.sub.4Ti.sub.3O.sub.12,
BaMgF.sub.4, Ba(Zr.sub.1-xTi.sub.x)O.sub.3 (BZT). In addition,
alloys, hybride materials (e.g. polysiloxanes or
nanoparticle-filled polymers) combinations, and multilayers of
these materials can be used for the gate dielectric. The thickness
of the dielectric layer is, for example, from about 10 to 1000 nm,
with a more specific thickness being about 100 to 500 nm, providing
a capacitance in the range of 0.1-100 nanofarads (nF).
[0062] The source electrode and drain electrode are separated from
the gate electrode by the gate dielectric, while the organic
semiconductor layer can be over or under the source electrode and
drain electrode. The source and drain electrodes can be any useful
conductive material favourably providing a low resistance ohmic
contact to the semiconductor layer. Useful materials include most
of those materials described above for the gate electrode, for
example, aluminum, barium, calcium, chromium, gold, silver, nickel,
palladium, platinum, titanium, polyaniline, PEDOT:PSS, other
conducting polymers, alloys thereof, combinations thereof, and
multilayers thereof. Some of these materials are appropriate for
use with n-type semiconductor materials and others are appropriate
for use with p-type semiconductor materials, as is known in the
art.
[0063] The thin film electrodes (that is, the gate electrode, the
source electrode, and the drain electrode) can be provided by any
useful means such as physical vapor deposition (for example,
thermal evaporation or sputtering) or (ink jet) printing methods.
The patterning of these electrodes can be accomplished by known
methods such as shadow masking, additive photolithography,
subtractive photolithography, printing, microcontact printing, and
pattern coating.
[0064] The present invention further provides an organic field
effect transistor device comprising a plurality of electrically
conducting gate electrodes disposed on a substrate; a gate
insulator layer disposed on said electrically conducting gate
electrodes; a plurality of sets of electrically conductive source
and drain electrodes disposed on said insulator layer such that
each of said sets is in alignment with each of said gate
electrodes; an organic semiconductor layer disposed in the channel
between source and drain electrodes on said insulator layer
substantially overlapping said gate electrodes; wherein said
organic semiconductor layer comprises a polymer of the present
invention, or a mixture containing a polymer of the present
invention.
[0065] The present invention further provides a process for
preparing a thin film transistor device comprising the steps of:
[0066] depositing a plurality of electrically conducting gate
electrodes on a substrate; [0067] depositing a gate insulator layer
on said electrically conducting gate electrodes; [0068] depositing
a plurality of sets of electrically conductive source and drain
electrodes on said layer such that each of said sets is in
alignment with each of said gate electrodes; [0069] depositing a
layer of a polymer of the present invention on said insulator layer
such that said layer of the compound of the present invention, or a
mixture containing a polymer of the present invention,
substantially overlaps said gate electrodes; thereby producing the
thin film transistor device.
[0070] A mixture containing a polymer of the present invention
results in a semi-conducting layer comprising a polymer of the
present invention (typically 5% to 99.9999% by weight, especially
20 to 85% by weight) and at least another material. The other
material can be, but is not restricted to a fraction of the same
polymer of the present invention with different molecular weight,
another polymer of the present invention, a semi-conducting
polymer, organic small molecules, carbon nanotubes, a fullerene
derivative, inorganic particles (quantum dots, quantum rods,
quantum tripods, TiO.sub.2, ZnO etc.), conductive particles (Au, Ag
etc.), insulator materials like the ones described for the gate
dielectric (PET, PS etc.).
[0071] Accordingly, the present invention also relates to an
organic semiconductor material, layer or component, comprising a
polymer according to the present invention.
[0072] The polymers of the present invention can be blended with
small molecules described, for example, in European patent
application no. 09155919.5, WO09/047104, U.S. Pat. No. 6,690,029,
WO2007082584, and WO2008107089.
WO2007082584:
##STR00074## ##STR00075## ##STR00076##
[0073] WO2008107089:
##STR00077##
[0074] wherein one of Y.sub.1 and Y.sub.2 denotes --CH.dbd. or
.dbd.CH-- and the other denotes --X--, one of Y.sub.3 and Y.sub.4
denotes --CH.dbd. or .dbd.CH-- and the other denotes --X--,
X is --O--, --S--, --Se-- or
[0075] R.sub.3 is cyclic, straight-chain or branched alkyl or
alkoxy having 1 to 20 C-atoms, or aryl having 2-30 C-atoms, all of
which are optionally fluorinated or perfluorinated, R' is H, F, Cl,
Br, I, CN, straight-chain or branched alkyl or alkoxy having 1 to
20 C-atoms and optionally being fluorinated or perfluorinated,
optionally fluorinated or perfluorinated aryl having 6 to 30
C-atoms, or CO.sub.2R'', with R'' being H, optionally fluorinated
alkyl having 1 to 20 C-atoms, or optionally fluorinated aryl having
2 to 30 C-atoms, R''' is H or cyclic, straight-chain or branched
alkyl with 1 to 10 C-atoms, y is 0, or 1, x is 0, or 1.
##STR00078## ##STR00079##
[0076] The polymer can contain a small molecule, or a mixture of
two, or more small molecule compounds.
[0077] Alternatively, an OFET is fabricated by, for example, by
solution deposition of a polymer on a highly doped silicon
substrate covered with a thermally grown oxide layer followed by
vacuum deposition and patterning of source and drain
electrodes.
[0078] In yet another approach, an OFET is fabricated by deposition
of source and drain electrodes on a highly doped silicon substrate
covered with a thermally grown oxide and then solution deposition
of the polymer to form a thin film.
[0079] The gate electrode could also be a patterned metal gate
electrode on a substrate or a conducting material such as, a
conducting polymer, which is then coated with an insulator applied
either by solution coating or by vacuum deposition on the patterned
gate electrodes.
[0080] Any suitable solvent can be used to dissolve, and/or
disperse the polymers of the present application, provided it is
inert and can be removed partly, or completely from the substrate
by conventional drying means (e.g. application of heat, reduced
pressure, airflow etc.). Suitable organic solvents for processing
the semiconductors of the invention include, but are not limited
to, aromatic or aliphatic hydrocarbons, halogenated such as
chlorinated or fluorinated hydrocarbons, esters, ethers amides,
such as chloroform, tetrachloroethane, tetrahydrofuran, toluene,
tetraline, decaline, anisole, xylene, ethyl acetate, methyl ethyl
ketone, dimethyl formamide, chloroform, chlorobenzene,
dichlorobenzene, trichlorobenzene, propylene glycol monomethyl
ether acetate (PGMEA) and mixtures thereof. Preferred solvents are
xylene, toluene, tetraline, decaline, chlorinated ones such as
chloroform, chlorobenzene, ortho-dichlorobenzene, trichlorobenzene
and mixtures thereof. The solution, and/or dispersion is then
applied by a method, such as, spin-coating, dip-coating, screen
printing, microcontact printing, doctor blading or other solution
application techniques known in the art on the substrate to obtain
thin films of the semiconducting material.
[0081] The term "dispersion" covers any composition comprising the
semiconductor material of the present invention, which is not fully
dissolved in a solvent. The dispersion can be done selecting a
composition including at least a polymer of the present invention,
or a mixture containing a polymer of the present invention, and a
solvent, wherein the polymer exhibits lower solubility in the
solvent at room temperature but exhibits greater solubility in the
solvent at an elevated temperature, wherein the composition gels
when the elevated temperature is lowered to a first lower
temperature without agitation; [0082] dissolving at the elevated
temperature at least a portion of the polymer in the solvent;
lowering the temperature of the composition from the elevated
temperature to the first lower temperature; agitating the
composition to disrupt any gelling, wherein the agitating commences
at any time prior to, simultaneous with, or subsequent to the
lowering the elevated temperature of the composition to the first
lower temperature; depositing a layer of the composition wherein
the composition is at a second lower temperature lower than the
elevated temperature; and drying at least partially the layer.
[0083] The dispersion can also be constituted of (a) a continuous
phase comprising a solvent, a binder resin, and optionally a
dispersing agent, and (b) a disperse phase comprising a polymer of
the present invention, or a mixture containing a polymer of the
present invention. The degree of solubility of the polymer of the
present invention in the solvent may vary for example from 0% to
about 20% solubility, particularly from 0% to about 5%
solubility.
[0084] Preferably, the thickness of the organic semiconductor layer
is in the range of from about 5 to about 1000 nm, especially the
thickness is in the range of from about 10 to about 100 nm.
[0085] The polymers of the invention can be used alone or in
combination as the organic semiconductor layer of the semiconductor
device. The layer can be provided by any useful means, such as, for
example, vapor deposition (for materials with relatively low
molecular weight) and printing techniques. The compounds of the
invention may be sufficiently soluble in organic solvents and can
be solution deposited and patterned (for example, by spin coating,
dip coating, ink jet printing, gravure printing, flexo printing,
offset printing, screen printing, microcontact (wave)-printing,
drop or zone casting, or other known techniques).
[0086] The polymers of the invention can be used in integrated
circuits comprising a plurality of OTFTs, as well as in various
electronic articles. Such articles include, for example,
radio-frequency identification (RFID) tags, backplanes for flexible
displays (for use in, for example, personal computers, cell phones,
or handheld devices), smart cards, memory devices, sensors (e.g.
light-, image-, bio-, chemo-, mechanical- or temperature sensors),
especially photodiodes, or security devices and the like. Due to
its solid state fluorescence the material can also be used in
Organic Light Emitting Transistors (OLET).
[0087] A further aspect of the present invention is an organic
semiconductor material, layer or component comprising one or more
polymers of the present invention. A further aspect is the use of
the polymers or materials of the present invention in an organic
field effect transistor (OFET). A further aspect is an OFET
comprising a polymer or material of the present invention.
[0088] The polymers of the present invention are typically used as
organic semiconductors in form of thin organic layers or films,
preferably less than 30 microns thick. Typically the semiconducting
layer of the present invention is at most 1 micron (=1 .mu.m)
thick, although it may be thicker if required. For various
electronic device applications, the thickness may also be less than
about 1 micron thick. For example, for use in an OFET the layer
thickness may typically be 100 nm or less. The exact thickness of
the layer will depend, for example, upon the requirements of the
electronic device in which the layer is used.
[0089] For example, the active semiconductor channel between the
drain and source in an OFET may comprise a layer of the present
invention.
[0090] An OFET device according to the present invention preferably
comprises: [0091] a source electrode, [0092] a drain electrode,
[0093] a gate electrode, [0094] a semiconducting layer, [0095] one
or more gate insulator layers, and [0096] optionally a substrate,
wherein the semiconductor layer comprises one or more polymers of
the present invention.
[0097] The gate, source and drain electrodes and the insulating and
semiconducting layer in the OFET device may be arranged in any
sequence, provided that the source and drain electrode are
separated from the gate electrode by the insulating layer, the gate
electrode and the semiconductor layer both contact the insulating
layer, and the source electrode and the drain electrode both
contact the semiconducting layer.
[0098] Preferably the OFET comprises an insulator having a first
side and a second side, a gate electrode located on the first side
of the insulator, a layer comprising a polymer of the present
invention located on the second side of the insulator, and a drain
electrode and a source electrode located on the polymer layer.
[0099] The OFET device can be a top gate device or a bottom gate
device.
[0100] Suitable structures and manufacturing methods of an OFET
device are known to the skilled in the art and are described in the
literature, for example in WO03/052841.
[0101] The gate insulator layer may comprise for example a
fluoropolymer, like e.g. the commercially available Cytop
809M.RTM., or Cytop 107M.RTM. (from Asahi Glass). Preferably the
gate insulator layer is deposited, e.g. by spin-coating, doctor
blading, wire bar coating, spray or dip coating or other known
methods, from a formulation comprising an insulator material and
one or more solvents with one or more fluoro atoms
(fluorosolvents), preferably a perfluorosolvent. A suitable
perfluorosolvent is e.g. FC75.RTM. (available from Acros, catalogue
number 12380). Other suitable fluoropolymers and fluorosolvents are
known in prior art, like for example the perfluoropolymers Teflon
AFC) 1600 or 2400 (from DuPont), or Fluoropel.RTM. (from Cytonix)
or the perfluorosolvent FC 43.RTM. (Acros, No. 12377).
[0102] The semiconducting layer comprising a polymer of the present
invention may additionally comprise at least another material. The
other material can be, but is not restricted to another polymer of
the present invention, a semi-conducting polymer, a polymeric
binder, organic small molecules different from a polymer of the
present invention, carbon nanotubes, a fullerene derivative,
inorganic particles (quantum dots, quantum rods, quantum tripods,
TiO.sub.2, ZnO etc.), conductive particles (Au, Ag etc.), and
insulator materials like the ones described for the gate dielectric
(PET, PS etc.). As stated above, the semiconductive layer can also
be composed of a mixture of one or more polymers of the present
invention and a polymeric binder. The ratio of the polymers of the
present invention to the polymeric binder can vary from 5 to 95
percent. Preferably, the polymeric binder is a semicristalline
polymer such as polystyrene (PS), high-density polyethylene (HDPE),
polypropylene (PP) and polymethylmethacrylate (PMMA). With this
technique, a degradation of the electrical performance can be
avoided (cf. WO2008/001123A1).
[0103] Digital circuits are largely based on complimentary metal
oxide (CMOS) structures that use both p-type and n-type unipolar
transistors. The advantages of CMOS circuits are lower power
dissipation, greater speed, and greater tolerance of variability
and shifts in transistor operating characteristics. These CMOS
circuits may be constructed using unipolar transistors with either
p-type or n-type semiconductors.
[0104] For example
poly[2-methoxyx-5-(3',7'-dimethyloctyloxy)]-p-phenylene vinylene
(OC.sub.1C.sub.10--PPV) p-type semiconductor and [6,6]-phenyl
C.sub.61-butyric acid methyl ester (PCBM) n-type semiconductor each
show mobilities of about 10.sup.-2 cm.sup.2/Vs when each is used as
an unipolar transistor. However the mobility of these
semiconductors decreases to 10.sup.-04 cm2/Vs and 10.sup.-05
cm2/Vs, respectively, in ambipolar transistors with a mixture of
OC.sub.1C.sub.10--PPV and PCBM [E. J. Meijer, et al Nature
Materials, 2003, Vol. 2 page 678). WO2008/122778 discloses an
improved blend composition to achieve a balanced mobility but still
the mobility is low. At these levels, the mobility is too low to
have practical use for electronic devices such as radio frequency
identification tags.
[0105] Fabrication of discrete organic n- and p-channel transistors
with lateral dimensions of a few micrometers, typically required
for large scale integration, is still very challenging.
[0106] In order to design more efficient circuits based on solution
processable transistors, there is an urgent need for complementary
technology, where both p-type and n-type operation are realized as
single component transistor. Ideally, the transistor should exhibit
high mobility, balanced on current and/or balanced mobility.
[0107] US20080099758 and WO20080246095 disclose single component
ambipolar polymers and monomers which show hole and electron
mobilities in the order of 2.times.10.sup.-4 cm.sup.2/Vs, Adv.
Material. 2008, 20, 2217-2224 discloses as example a homopolymer
according formula
##STR00080##
measured in different device configurations that reach maximum
values of hole mobility of 0.05 cm.sup.2/Vs the electron mobility
was not determined using bottom contact gold electrodes. Using top
contact gold electrodes 0.11 cm.sup.2/Vs for hole mobility and
electron mobilities in the range of 0.04-0.09 cm.sup.2/Vs are
determined. The polymers of the present invention can show up a
factor 5 to 10 better hole and electron mobility in a bottom gate
bottom contact device structure. Due to low contact resistance of
this type of polymers the ambipolarity can be induced by a single
contact material like gold for both type of carriers, no longer
relying on reactive low work function metals such as Ca, Mg for
injecting electrons. Injection is even achieved with Ag and Cu or
alloys thereof as source and drain electrodes.
[0108] For example, using top contact gold electrodes 0.43
cm.sup.2/Vs for hole mobility and electron mobilities in the range
of 0.35 cm.sup.2/Vs are determined for the polymer of example
1:
##STR00081##
[0109] Accordingly, the present invention also provides an
ambipolar organic field effect transistor (OFET), comprising a
p-type and n-type behaviour, especially an organic thin film
transistor (OTFT), comprising a gate electrode, a gate insulating
layer, an organic active layer, and source/drain electrodes on a
substrate, wherein the organic active layer includes a polymer of
the present invention. Preferably, the active layer is composed of
a polymer of the present invention. The composition of the active
(semiconductor) layer is such as to transport both electrons and
holes, with the mobility of the holes being substantially equal to
the mobility of the electrons, such that the transistor
substantially exhibits ambipolarity in its transfer
characteristics.
[0110] The ambipolar OTFT may include a substrate, a gate
electrode, a gate insulating layer, source/drain electrodes, and an
active layer, or alternatively may include a substrate, a gate
electrode, a gate insulating layer, an active layer, and
source/drain electrodes, but example embodiments may not be limited
thereto.
[0111] In order to form the organic active layer using the polymer
of the present invention, a composition for the organic active
layer including chloroform or chlorobenzene may be used. Examples
of the solvent used in the composition for the organic active layer
may include chloroform, chlorobenzene, dichlorobenzene,
trichlorobenzene, and toluene.
[0112] Examples of the process of forming the organic active layer
may include, but may not be limited to, screen printing, printing,
spin coating, dipping or ink jetting. As such, in the gate
insulating layer included in the ambipolar OTFT any insulator
having a high dielectric constant may be used as long as it is
typically known in the art. Specific examples thereof may include,
but may not be limited to, a ferroelectric insulator, including
Ba.sub.0.33Sr.sub.0.66TiO.sub.3 (BST: Barium Strontium Titanate),
Al.sub.2O.sub.3, Ta.sub.2O.sub.5, La.sub.2O.sub.5, Y.sub.2O.sub.5,
or TiO.sub.2, an inorganic insulator, including
PbZr.sub.0.33Ti.sub.0.66O.sub.3 (PZT), Bi.sub.4Ti.sub.3O.sub.12,
BaMgF.sub.4, SrBi.sub.2(TaNb).sub.2O.sub.9, Ba(ZrTi)O.sub.3(BZT),
BaTiO.sub.3, SrTiO.sub.3, Bi.sub.4Ti.sub.3O.sub.12, SiO.sub.2,
SiN.sub.x, or AlON, or an organic insulator, including polyimide,
benzocyclobutane (BCB), parylene, polyvinylalcohol, or
polyvinylphenol. In the gate electrode and the source/drain
electrodes included in the ambipolar OTFT of the present invention,
a typical metal may be used, specific examples thereof include, but
are not limited to, gold (Au), silver (Ag), copper (Cu), aluminum
(Al), nickel (Ni), and indium tin oxide (ITO). Preferably, the
material of at least one of the gate, source and drain electrodes
is selected from the group Cu, Ag, Au or alloys thereof. Examples
of material for the substrate in the ambipolar OTFT of the present
invention may include, but may not be limited to, glass,
polyethylenenaphthalate (PEN), polyethyleneterephthalate (PET),
polycarbonate, polyvinylalcohol, polyacrylate, polyimide,
polynorbornene, or polyethersulfone (PES).
[0113] The present invention also provides an electronic device
comprising the ambipolar organic field effect transistor (OFET),
especially the organic thin film transistor (OTFT) of the present
invention. Because the polymer of the present invention serves to
improve the device characteristics of an ambipolar organic thin
film transistor, the polymer may be effectively used to fabricate a
variety of electronic devices, including liquid crystal display
(LCD) devices, photovoltaic devices, organic light-emitting devices
(OLEDs), sensors, memory devices and/or integrated circuits.
[0114] The method of fabricating an ambipolar organic thin film
transistor may include forming a gate electrode, a gate insulating
layer, an organic active layer, and source/drain electrodes on a
substrate, wherein the organic active layer includes the polymer of
the present invention. The organic active layer may be formed into
a thin film through screen printing, printing, spin coating,
dipping or ink jetting. The insulating layer may be formed using
material selected from the group consisting of a ferroelectric
insulator, including Ba.sub.0.33Sr.sub.0.66TiO.sub.3 (BST: Barium
Strontium Titanate), Al.sub.2O.sub.3, Ta.sub.2O.sub.5,
La.sub.2O.sub.5, Y.sub.2O.sub.5, or TiO.sub.2, an inorganic
insulator, including PbZr.sub.0.33Ti.sub.0.66O.sub.3 (PZT),
Bi.sub.4Ti.sub.3O.sub.12, BaMgF.sub.4,
SrBi.sub.2(TaNb).sub.2O.sub.9, Ba(ZrTi)O.sub.3(BZT), BaTiO.sub.3,
SrTiO.sub.3, Bi.sub.4Ti.sub.3O.sub.12, SiO.sub.2, SiN.sub.x, or
AlON, or an organic insulator, including polyimide,
benzocyclobutane (BCB), parylene, polyvinylalcohol, or
polyvinylphenol
[0115] The substrate may be formed using material selected from the
group consisting of glass, polyethylenenaphthalate (PEN),
polyethyleneterephthalate (PET), polycarbonate, polyvinylalcohol,
polyacrylate, polyimide, polynorbornene, and polyethersulfone
(PES). The gate electrode and the source/drain electrodes may be
formed using material selected from the group consisting of gold
(Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), and
indium tin oxide (ITO).
[0116] The polymers of the present invention may also be used in
organic photovoltaic (PV) devices (solar cells). Accordingly, the
invention provides PV devices comprising a polymer according to the
present invention.
[0117] The PV device comprise in this order: [0118] (a) a cathode
(electrode), [0119] (b) optionally a transition layer, such as an
alkali halogenide, especially lithium fluoride, [0120] (c) a
photoactive layer, [0121] (d) optionally a smoothing layer, [0122]
(e) an anode (electrode), [0123] (f) a substrate.
[0124] The photoactive layer comprises the polymers of the present
invention. Preferably, the photoactive layer is made of a
conjugated polymer of the present invention, as an electron donor
and an acceptor material, like a fullerene, particularly a
functionalized fullerene PCBM, as an electron acceptor.
[0125] For heterojunction solar cells the active layer comprises
preferably a mixture of a polymer of the present invention and a
fullerene, such as [60]PCBM (=6,6-phenyl-C.sub.61-butyric acid
methyl ester), or [70]PCBM, in a weight ratio of 1:1 to 1:3.
[0126] Further preferred is an integrated circuit comprising a
field effect transistor according to the present invention.
[0127] The following examples are included for illustrative
purposes only and do not limit the scope of the claims. Unless
otherwise stated, all parts and percentages are by weight.
Weight-average molecular weight (Mw) and polydispersity (Mw/Mn=PD)
are determined by Heat Temperature Gel Permeation Chromatography
(HT-GPC) [Apparatus: GPC PL 220 from Polymer laboratories (Church
Stretton, UK; now Varian) yielding the responses from refractive
index (RI), Chromatographic conditions: Column: 3 "PLgel Olexis"
column from Polymer Laboratories (Church Stretton, UK); with an
average particle size of 13 .mu.m (dimensions 300.times.8 mm I.D.)
Mobile phase: 1,2,4-trichlorobenzene purified by vacuum
distillation and stabilised by butylhydroxytoluene (BHT, 200 mg/l),
Chromatographic temperature: 150.degree. C.; Mobile phase flow: 1
ml/min; Solute concentration: about 1 mg/ml; Injection volume: 200
.mu.l; Detection: RI, Procedure of molecular weight calibration:
Relative calibration is done by use of a set of 10 polystyrene
calibration standards obtained from Polymer Laboratories (Church
Stretton, UK) spanning the molecular weight range from 1'930'000
Da-5'050 Da, i.e., PS 1'930'000, PS 1'460'000, 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. A polynomic calibration is used to calculate the
molecular weight.
[0128] All polymer structures given in the examples below are
idealized representations of the polymer products obtained via the
polymerization procedures described. If more than two components
are copolymerized with each other sequences in the polymers can be
either alternating or random depending on the polymerisation
conditions.
EXAMPLES
Example 1
##STR00082##
[0130] Starting material 1 for polymer 3 is prepared according to
Example 2a of WO2008000664. In a three neck-flask, 1.45 g of
potassium phosphate (K.sub.3PO.sub.4) dissolved in 5 ml of water
(previously degassed) is added to a degassed solution of 2.07 g of
1, 0.74 g of 2,5-thiopheneboronic acid bis(pinacol) ester, 32.1 mg
of tri-tert-butylphosphonium tetrafluoroborate
((t-Bu).sub.3P*HBF.sub.4) and 52.2 mg of
tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3) in
20 ml of tetrahydrofuran. The reaction mixture is heated at reflux
temperature for two hours. Subsequently, 18 mg bromo-thiophene and
20 minutes later 24 mg thiophene-boronic acid pinacol ester are
added to stop the polymerisation reaction. The reaction mixture is
cooled to room temperature and precipitated in methanol. The
residue is purified by soxhlet extraction using pentane and heptane
and the polymer is then extracted with cyclohexane to give 1.45 g
of a dark powder. Mw=39'500, Polydispersity=2.2 (measured by
HT-GPC).
Application Example 1a
[0131] Bottom-gate thin film transistor (TFT) structures with p-Si
gate (10 cm) are used for all experiments. A high-quality thermal
SiO.sub.2 layer of 300 nm thickness served as gate-insulator of
C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and
drain electrodes are patterned by photolithography directly on the
gate-oxide. Gold source drain electrodes defining channels of width
W=10 mm and varying lengths L=4, 8, 15, 30 .mu.m are used. Prior to
deposition of the organic semiconductor the SiO.sub.2 surface is
derivatized either with hexadimethylsilazane (HMDS) by exposing to
a saturated silane vapour at 160.degree. C. for 2 hours, or
treating the substrate at 60.degree. C. with a 0.1 m solution of
octadecyltrichlorosilane (OTS) in toluene for 20 minutes. After
rinsing with iso-propanol the substrates are dried.
Transistor Performance in Xylene
[0132] The semiconductor thin film is prepared either by
spin-coating, or drop casting the DPP derivative of the formula 3
obtained in example 1 in a 1% (w/w) solution in xylene. Before use
the solution is filtered through a 0.2 m filter. The spin coating
is accomplished at a spinning speed of 800 rpm (rounds per minute)
for about 20 seconds in ambient conditions. The devices are dried
at 80.degree. C. for 1 hour before evaluation.
[0133] The transistor behaviour is measured on an automated
transistor prober (TP-10). From a linear fit to the square root of
the saturated transfer characteristics a field effect mobility of
2.4.times.10.sup.-1 cm.sup.2/Vs with an on/off current ratio of
8.5.times.10.sup.5 can be determined. The threshold voltage is at
-2.7 V.
Transistor Performance in Chloroform
[0134] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 3
obtained in example 1 in a 0.5% (w/w) solution in chloroform. The
spin coating is accomplished at a spinning speed of 3000 rpm
(rounds per minute) for about 20 seconds in ambient conditions. The
devices are dried at 120.degree. C. for 15 minutes before
evaluation.
[0135] The transistor behaviour is measured on an automated
transistor prober (TP-10).
[0136] From a linear fit to the square root of the saturated
transfer characteristics a field effect mobility of
2.1.times.10.sup.-1 cm.sup.2/Vs with an on/off current ratio of
5.7.times.10.sup.6 can be determined. The threshold voltage is at
2.0 V.
Measurement of the Ambipolarity
Application Example 1b
[0137] The ambipolar transistor just described in application
example 1 using o-xylene as solvent is measured at a drain bias of
(+-30 V) by sweeping the gate from -60 V to 60 V and back. FIG. 1
shows the transfer curve, which shows a very balanced ratio between
the p-type and the n-type region. The p-type mobility is 0.43
cm.sup.2/Vs whereas the n-type mobility is 0.35 cm.sup.2/Vs. In
comparison to the measurement disclosed in Adv. Mat. 2008, 2011,
2217-2224 the p-type mobility is improved by a factor of 10 and for
the same source-drain electrodes (Au) an almost equal performance
of the n-type behavior can be demonstrated.
Application Example 1c
[0138] Application example 1a is repeated, except that instead of
the gold source and drain electrodes silver contact electrodes are
used (1c). The results are shown in the table below:
TABLE-US-00001 Bottom Bottom Example Gate Insulator Contacts
.mu..sub.h [cm.sup.2/Vs] .mu..sub.e[cm.sup.2/Vs Reference.sup.1) Si
SiO.sub.2/OTS Au 0.05 ND 1b Si SiO.sub.2/OTS Au 0.43 0.35 1c Si
SiO.sub.2/OTS Ag 0.026 0.022 .sup.1)Adv. Mater. 2008, 20, 2217-2224
(table 1, type A)
Example 2
##STR00083##
[0140] The starting material 4 is prepared according to example 2a
of WO2008000664 using decyl-tetradecyl-iodide. 2.0 g of 4, 0.59 g
of 2,5-thiopheneboronic acid bis(pinacol) ester, 24.4 mg of
tri-tert-butylphosphonium tetrafluoroborate
((t-Bu).sub.3P*HBF.sub.4), 48.6 mg of
tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3) in
50 ml of tetrahydrofuran and 1.13 g of potassium phosphate
(K.sub.3PO.sub.4) dissolved in 10 ml of water (previously degassed)
is used. After 2 hours of reflux 24 mg bromo-thiophene and 20
minutes later 31 mg thiophene-boronic acid pinacol ester is added
to stop the polymerisation reaction. The reaction mixture is cooled
to room temperature and precipitated in methanol. The residue is
purified by soxhlet extraction using pentane and the polymer is
then extracted with cyclohexane to give 1.67 g of a dark powder.
Mw=43'300, Polydispersity=1.9 (measured by HT-GPC).
Application Example 2
DPP-Polymer 5 Based Organic Field Effect Transistors
[0141] Bottom-gate thin film transistor (TFT) structures with p-Si
gate (10 cm) are used for all experiments. A high-quality thermal
SiO.sub.2 layer of 300 nm thickness served as gate-insulator of
C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and
drain electrodes are patterned by photolithography directly on the
gate-oxide. Gold source drain electrodes defining channels of width
W=10 mm and varying lengths L=4, 8, 15, 30 .mu.m are used. Prior to
deposition of the organic semiconductor the SiO.sub.2 surface is
derivatized either with hexadimethylsilazane (HMDS) by exposing to
a saturated silane vapour at 160.degree. C. for 2 hours or treating
the substrate at 60.degree. C. with a 0.1 m solution of
octadecyltrichlorosilane (OTS) in toluene for 20 minutes. After
rinsing with iso-propanol the substrates are dried.
Transistor Performance in Toluene
[0142] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 5
obtained in example 2 in a 0.5% (w/w) solution in toluene. The spin
coating is accomplished at a spinning speed of 6000 rpm (rounds per
minute) for about 10 seconds in ambient conditions. The devices are
dried at 100.degree. C. for 15 minutes before evaluation.
[0143] The transistor behaviour is measured on an automated
transistor prober (TP-10).
[0144] From a linear fit to the square root of the saturated
transfer characteristics a field effect mobility of
2.8.times.10.sup.-2 cm.sup.2/Vs with an on/off current ratio of
4.7.times.10.sup.5 can be determined. The threshold voltage is at
5.6 V.
Transistor Performance in Chloroform
[0145] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 5
obtained in example 2 in a 0.5% (w/w) solution in chloroform. The
spin coating is accomplished at a spinning speed of 3000 rpm
(rounds per minute) for about 20 seconds in ambient conditions. The
devices are evaluated after deposition.
[0146] The transistor behaviour is measured on an automated
transistor prober (TP-10).
[0147] From a linear fit to the square root of the saturated
transfer characteristics a field effect mobility of
1.0.times.10.sup.-2 cm.sup.2/Vs with an on/off current ratio of
3.3.times.10.sup.4 can be determined. The threshold voltage is at
5.4 V.
Example 3
##STR00084##
[0149] 7.1 g of 4, 2.62 g of 2,2'-bithiophene-5,5'-diboronic acid
bis(pinacol) ester, 86.2 mg of tri-tert-butylphosphonium
tetrafluoroborate ((t-Bu).sub.3P*HBF.sub.4), 172.3 mg of
tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3),
140 ml of tetrahydrofuran and 3.99 g of potassium phosphate
(K.sub.3PO.sub.4) dissolved in 28 ml of water (previously degassed)
is used. After 2 hours of reflux 94 mg bromo-thiophene and 20
minutes later 110 mg thiophene-boronic acid pinacol ester are added
to stop the polymerisation reaction. The reaction mixture is cooled
to room temperature and precipitated in methanol. The residue is
purified by soxhlet extraction using THF and the polymer is then
extracted with chloroform to give 5.34 g of a dark powder.
Mw=54'500, Polydispersity=1.7 (measured by HT-GPC).
Application Example 3
[0150] Bottom-gate thin film transistor (TFT) structures with p-Si
gate (10 cm) are used for all experiments. A high-quality thermal
SiO.sub.2 layer of 300 nm thickness served as gate-insulator of
C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and
drain electrodes are patterned by photolithography directly on the
gate-oxide. Gold source drain electrodes defining channels of width
W=10 mm and varying lengths L=4, 8, 15, 30 .mu.m are used. Prior to
deposition of the organic semiconductor the SiO.sub.2 surface is
derivatized either with hexadimethylsilazane (HMDS) by exposing to
a saturated silane vapour at 160.degree. C. for 2 hours or treating
the substrate at 60.degree. C. with a 0.1 m solution of
octadecyltrichlorosilane (OTS) in toluene for 20 minutes. After
rinsing with iso-propanol the substrates are dried.
Transistor Performance in Xylene
[0151] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 7
obtained in example 3 in a 1% (w/w) solution in xylene. Before use
the solution is filtered through 0.2 m filter. The spin coating is
accomplished at a spinning speed of 800 rpm (rounds per minute) for
about 20 seconds in ambient conditions. The devices are dried at
80.degree. C. for 1 hour before evaluation.
[0152] The transistor behaviour is measured on an automated
transistor prober (TP-10).
[0153] From a linear fit to the square root of the saturated
transfer characteristics a field effect mobility of
2.5.times.10.sup.-1 cm.sup.2/Vs with an on/off current ratio of
8.9.times.10.sup.8 can be determined. The threshold voltage is at
0.5 V.
Transistor Performance in Chloroform
[0154] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 7
obtained in example 1 in a 0.5% (w/w) solution in chloroform. The
spin coating is accomplished at a spinning speed of 3000 rpm
(rounds per minute) for about 20 seconds in ambient conditions. The
devices are dried at 100.degree. C. for 15 minutes before
evaluation.
[0155] The transistor behaviour is measured on an automated
transistor prober (TP-10).
[0156] From a linear fit to the square root of the saturated
transfer characteristics a field effect mobility of
3.0.times.10.sup.-1 cm.sup.2/Vs with an on/off current ratio of
9.3.times.10.sup.6 can be determined. The threshold voltage is at
0.8 V.
Example 4
##STR00085##
[0158] 1.0 g of 4, 148 mg of 2,5-thiopheneboronic acid bis(pinacol)
ester, 185 mg 2,2'-bithiophene-5,5'-diboronic acid bis(pinacol)
ester, 12.2 mg of tri-tert-butylphosphonium tetrafluoroborate
((t-Bu).sub.3P*HBF.sub.4), 24.3 mg of
tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3), 25
ml of tetrahydrofuran and 0.56 g of potassium phosphate
(K.sub.3PO.sub.4) dissolved in 5 ml of water (previously degassed)
is used. After 2 hours of reflux 12 mg bromo-thiophene and 20
minutes later 16 mg thiophene-boronic acid pinacol ester is added
to stop the polymerisation reaction. The reaction mixture is cooled
to room temperature and precipitated in methanol. The residue is
purified by soxhlet extraction using pentane and the polymer is
then extracted with cyclohexane to give 0.83 g of a dark powder.
Mw=51'500, Polydispersity=2.0 (measured by HT-GPC).
Application Example 4
DPP-Polymer 8 Based Organic Field Effect Transistors
[0159] Bottom-gate thin film transistor (TFT) structures with p-Si
gate (10 cm) are used for all experiments. A high-quality thermal
SiO.sub.2 layer of 300 nm thickness served as gate-insulator of
C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and
drain electrodes are patterned by photolithography directly on the
gate-oxide. Gold source drain electrodes defining channels of width
W=10 mm and varying lengths L=4, 8, 15, 30 m are used. Prior to
deposition of the organic semiconductor the SiO.sub.2 surface is
derivatized either with hexadimethylsilazane (HMDS) by exposing to
a saturated silane vapour at 160.degree. C. for 2 hours or treating
the substrate at 60.degree. C. with a 0.1 m solution of
octadecyltrichlorosilane (OTS) in toluene for 20 minutes. After
rinsing with iso-propanol the substrates are dried.
Transistor Performance in Toluene
[0160] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 8
obtained in example 4 in a 0.5% (w/w) solution in toluene. The spin
coating is accomplished at a spinning speed of 6000 rpm (rounds per
minute) for about 10 seconds in ambient conditions. The devices are
dried at 130.degree. C. for 15 minutes before evaluation.
[0161] The transistor behaviour is measured on an automated
transistor prober (TP-10).
[0162] From a linear fit to the square root of the saturated
transfer characteristics a field effect mobility of
2.1.times.10.sup.-1 cm.sup.2/Vs with an on/off current ratio of
1.9.times.10.sup.7 can be determined. The threshold voltage is at
0.4 V.
Example 5
##STR00086##
[0164] a) 228.06 g of 2-decyl-1-tetradecanol are mixed with 484.51
g 47% hydroiodic acid and the mixture is refluxed overnight. The
product is extracted with t-butyl-methylether. Then the organic
phase is dried and concentrated. The product is purified over a
silica gel column to give 211.54 g of the desired compound 9 (73%).
.sup.1H-NMR data (ppm, CDCl.sub.3): 3.26 2H d, 1.26-1.12 41H m,
0.88 6H t;
##STR00087##
[0165] b) A mixture of 30 mg FeCl.sub.3, 10.27 g sodium and 600 mL
t-amylalcohol is heated to 110.degree. C. for 30 minutes before a
mixture of 30.52 g of the nitrile and 24.83 g di-tert-amylsuccinate
is added dropwise. The reaction mixture is stirred at 110.degree.
C. over night before it is poured onto water--methanol mixture.
Buchner filtration and exhaustive washing with methanol affords
33.60 g of the desired compound 10 as dark blue powder with 90%
yield. MS m/z: 464;
##STR00088##
[0166] c) 33.55 g of the compound 10 are reacted with 12.22 g
K.sub.2CO.sub.3 and 74.4 g 2-decyl-1-tetradecyl iodide 9 in 1300 ml
DMF at 110.degree. C. overnight. The reaction mixture is poured on
ice and extracted with methylene chloride. Purification is achieved
by column chromatography over silica gel and affords 35.1 g of the
desired compound 11 (42.7%). .sup.1H-NMR data (ppm, CDCl.sub.3):
8.91 2H d, 7.35-7.32 6H m, 7.09 2H d.times.d, 4.05 4H d, 1.98 2H m,
1.35-1.20 80H m, 0.89 6H t, 0.87 6H t;
##STR00089##
[0167] d) 10.00 g of 11 and one drop of perchloric acid are
dissolved in 200 ml of chloroform, cooled down to 0.degree. C. and
2 equivalents of N-bromosuccinimide are then added portion wise
over a period of 1 h. After the reaction is completed, the mixture
is washed with water. The organic phase is extracted, dried and
concentrated. The compound is then purified over a silica gel
column to give 5.31 g of a dark violet powder of the formula 12
(47%). .sup.1H-NMR data (ppm, CDCl.sub.3): 8.85 2H d, 7.22 2H d,
7.03 4H d.times.d, 4.00 4H d, 1.93 2H m, 1.29-1.21 80H m, 0.87 6H
t, 0.85 6H t.
##STR00090##
[0168] e) 300 mg of compound 12, 78 mg thiophene-di-boronic acid
pinacol ester, 5 mg Pd.sub.2(dba).sub.3
(tris(dibenzylideneacetone)-di-palladium) and 3 mg
tri-tert-butyl-phosphonium-tetrafluoroborate are dissolved in 3 ml
of tetrahydrofurane. This solution is degassed with 3 cycles of
freeze/pump/thaw (Ar). The reaction mixture is then heated to
reflux temperature. Then 149 mg of K.sub.3PO.sub.4 are dissolved in
0.7 ml of water and degassed under argon. The water solution is
added to the THF solution and the reaction mixture is refluxed over
night. Then 5 mg of 2-thiophene-mono-boronic-acid-pinacol-ester are
added, and the mixture is refluxed for another 30 minutes. Then 4
mg of 2-bromo-thiophene are added, and the mixture is refluxed for
another 30 minutes. The reaction mixture is cooled to room
temperature and diluted with water and then extracted with
chloroform. The chloroform solution is then refluxed with a
solution of NaCN in water for 1 hour. The water is separated and
the chloroform solution dried. The residue is then Soxhlet
extracted with tetrahydrofuran. The organic phase is evaporated to
give 224 mg of the desired polymer 13.
Example 6
##STR00091##
[0170] To a mixture of 1.006 g of 4, 0.349 g of
2,5-thieno[3,2-b]thiophenediboronic acid bis(pinacol) ester (e.g.
made by esterification of the corresponding diboronic acid (J. Org.
Chem., 1978, 43(11), p 2199) with pinacol in refluxing toluene), 13
mg of tri-tert-butylphosphonium tetrafluoroborate
((t-Bu).sub.3P*HBF.sub.4), 21 mg of
tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3) in
20 ml of tetrahydrofuran (degassed under Ar), a solution of 0.572 g
of potassium phosphate (K.sub.3PO.sub.4) dissolved in 1.7 ml of
water (previously degassed) is added. After 2 hours of reflux 4 mg
bromo-thiophene and 20 minutes later 5 mg thiophene-boronic acid
pinacol ester is added to stop the polymerization reaction. The
reaction mixture is cooled down and diluted with chloroform. Then
water is added. The layers are separated and the organic layer is
washed once more with water. The organic layer is then concentrated
under reduced pressure. The chloroform solution is then refluxed
over night together with a 1% NaCN solution in water. The layers
are separated, the organic layer is then washed once more with
water and concentrated under reduced pressure. The crude product is
precipitated by the addition of methanol and filtered. The product
is then isolated by soxhlet extraction. A first fraction extracted
with tetrahydrofurane is discarded, and the second fraction
extracted with chloroform is precipitated by the addition of
methanol to give 76 mg of the desired polymer of formula A as dark
powder, Mw=25'800, polydispersity=2.0 (measured by HT-GPC).
Example 7
##STR00092##
[0172] In a schlenk tube, a solution of 1.13 g of Ni(COD).sub.2 and
0.65 g bipyridine in 90 ml of toluene is degassed for 15 min. 3 g
of the corresponding dibrominated monomer 1 is added to this
solution and then the mixture is heated to 80.degree. C. and
stirred vigorously overnight. The solution is poured on 500 ml of a
3/1/1 methanol/HCl (4N)/acetone mixture and stirred for 1 h. The
precipitate is then filtrated, dissolved in CHCl.sub.3 and stirred
vigorously at 60.degree. C. with an aqueous solution of
ethylenediaminetetraacetic acid (EDTA) tetrasodium salt for one
additional hour. The organic phase is washed with water,
concentrated and precipitated in methanol. The residue is purified
by soxhlet extraction using methanol, diethylether, cyclohexane and
the polymer is then extracted with CHCl.sub.3 to give 1.7 g of a
dark powder. Mw=37'000, Polydispersity=2.3 (measured by
HT-GPC).
Application Example 5
[0173] Bottom-gate thin film transistor (TFT) structures with p-Si
gate (10 cm) are used for all experiments. A high-quality thermal
SiO.sub.2 layer of 300 nm thickness served as gate-insulator of
C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and
drain electrodes are patterned by photolithography directly on the
gate-oxide. Gold source drain electrodes defining channels of width
W=10 mm and varying lengths L=4, 8, 15, 30 .mu.m are used. Prior to
deposition of the organic semiconductor the SiO.sub.2 surface is
derivatized either with hexadimethylsilazane (HMDS) by exposing to
a saturated silane vapour at 160.degree. C. for 2 hours, by spin
coating the HMDS at a spinning speed of 800 rpm (rounds per minute)
for about a minute or by treating the substrate at 60.degree. C.
with a 0.1 M solution of octadecyltrichlorosilane (OTS) in toluene
for 20 minutes. After rinsing with iso-propanol the substrates are
dried.
Transistor Performance in Chloroform
[0174] The semiconductor thin film is prepared either by
spin-coating or drop casting the DPP derivative of the formula 15
obtained in example 7 in a 0.5% (w/w) solution in chloroform.
[0175] The spin coating is accomplished at a spinning speed of 3000
rpm (rounds per minute) for about 20 seconds in ambient conditions.
The devices are evaluated as deposited as well as after drying at
120.degree. C. for 15 minutes.
[0176] The transistor behaviour is measured on an automated
transistor prober (TP-10). The DPP derivative of the formula 15
shows good ambipolar behaviour in the standard device
configuration.
Example 8
##STR00093##
[0178] a) To a solution of 5.0 g Dithienyl-DPP (16) and 3.73 g
2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxoborolane in 30 ml THF
under nitrogen at -25.degree. C. is added drop-wise a freshly
prepared LDA solution (from 5.4 ml butyllithium 2.7 M and 2.2 ml
diisopropylamin in 20 ml THF,) over 15 minutes. The resulting
reaction mixture is stirred for 1 hour at 0.degree. C. and then
quenched with 100 ml 1 M HCl. The product is extracted with
2.times.50 ml TBME and the combined organic layers are washed twice
with brine and dried with sodium sulfate. After evaporation of the
solvent the residue is dissolved in 20 ml methylenchloride and then
slowly added to 200 ml of heavily stirred acetone. The precipitate
is collected by filtration, washed several times with acetone and
dried at 40.degree. C. in a vacuum-oven, affording 6.3 g of
pinkish-violet powder. .sup.1H-NMR (ppm, CDCl.sub.3): 8.90 2H, d,
.sup.3J=3.9 Hz; 7.71 2H, d, .sup.3J=3.9 Hz; 4.05 4H d, .sup.3J=7.7
Hz; 1.84 2H m; 1.37 24H m; 1.35-1.2 48, m; 0.9-0.8 12H m.
##STR00094## ##STR00095##
[0179] b) According to the procedure for the synthesis of polymer 3
described in example 1, 0.91 g of 1 and 1.004 g of 17 are reacted
to give polymer 15. After the reaction, the mixture is poured into
methanol and washed with acetone, yielding in 1.2 g of polymer
15.
Example 9
##STR00096##
[0181] According to the procedure for the synthesis of polymer 3
described in example 1, 0.5 g of 17 and 0.12 g of dibromothiophene
are reacted to give polymer 3. After the reaction, the mixture is
poured into methanol and washed with acetone, yielding in 0.380 g
of polymer 3. Mw=20'000, Polydispersity=2.3 (measured by
HT-GPC).
Example 10
##STR00097##
[0183] According to the procedure for the synthesis of polymer 3
described in example 1, 0.5 g of 17 and 0.12 g of
2,5-dibromothiazole are reacted to give polymer 18. The residue is
purified by soxhlet extraction using pentane and the polymer is
then extracted with cyclohexane to give 0.26 g of a dark powder.
Mw=17'700, Polydispersity=2.0 (measured by HT-GPC).
Example 11
##STR00098##
[0185] According to the procedure for the synthesis of polymer 3
described in example 1, 0.15 g of 17 and 0.05 g of
2,2'-Dibromo-[5,5']bithiazolylare reacted to give polymer 19. After
the reaction, the mixture is poured into methanol and washed with
acetone, yielding in 0.13 g of polymer 19.
Example 12
##STR00099##
[0187] According to the procedure for the synthesis of polymer 3
described in example 1, 2.3 g of 1 and 1 g
2,5-thieno[3,2-b]thiophenediboronic acid bis(pinacol) ester (e.g.
made by esterification of the corresponding diboronic acid (J. Org.
Chem., 1978, 43(11), p 2199) with pinacol in refluxing toluene)
have been reacted to give polymer 20. After the reaction, the
mixture was poured into methanol and washed with acetone, yielding
in 2.0 g of polymer 20.
##STR00100##
Example 13
[0188] a) A mixture of 5 mg iron trichloride (FeCl.sub.3), 2.6 g of
sodium and 100 ml of t-amylalcohol is heated to 110.degree. C. for
20 minutes before a mixture of 5.0 g of the thiazole-2-nitrile of
the formula 21 and 8.25 g of di-tert-amyl succinate of the formula
22 is added dropwise. The reaction mixture is stirred at
110.degree. C. for 3 hours before it is poured onto 8.15 g acetic
acid in a water-methanol mixture (200 ml/100 ml). Buchner
filtration and exhaustive washing with methanol affords 5.2 g of
the desired 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) derivative of the
formula 23 as dark blue powder: ESI-MS m/z (% int.): 303.13
([M+H]+, 100%).
##STR00101##
[0189] b) A solution of 4 g of the 1,4-diketopyrrolo[3,4-c]pyrrole
(DPP) derivative of the formula 3, 2.9 g of KOH in 3 ml of water
and 18.5 g of 1-bromo-2-hexyl-decyl in 50 ml of
N-methyl-pyrrolidone (NMP) is heated to 140.degree. C. for 6 h. The
mixture is washed with water and extracted with dichloromethane.
Purification is achieved by column chromatography over silica gel
and precipitation out of chloroform/methanol which affords 0.4 g of
the desired DPP 24 as blue solid. ESI-MS m/z (% int.): 751.93
([M+H]+, 100%). .sup.1H-NMR (ppm, CDCl.sub.3): 8.05 2H, d,
.sup.3J=3.1 Hz; 7.70 2H, d, .sup.3J=3.1 Hz; 4.34 4H d, .sup.3J=7.4
Hz; 1.86 2H m; 1.3-1.2 48, m; 0.9-0.8 12H t.
##STR00102##
[0190] c) Compound 25 is obtained in analogy to example 5d.
##STR00103##
[0191] d) Polymer 26 is obtained in analogy to example 5e.
##STR00104##
[0192] e) Polymer 27 is obtained in analogy to example 7.
Example 14
##STR00105##
[0194] a) 554.6 g of potassium tert-butoxide, 424.2 g g of dimethyl
carbonate and 3 L of anhydrous toluene are heated to 100.degree. C.
with stirring. 300 g of 1-acetyl thiophene is added drop by drop
during three hours and stirred at 100.degree. C. for 15 hours. The
reaction mixture is allowed to cool to room temperature and poured
onto 4 L of ice. The water layer is separated and two times
extracted with 200 ml of ethyl acetate. The organic layers are
combined and dried over sodium sulfate, filtered, evaporated and
dried, giving 363.7 g of 28. The crude product is used for the next
reaction step without further purification.
##STR00106##
[0195] b) 363.7 g of 28, 322.7 g of methyl bromooacetate, 288.7 g
potassium carbonate, 1100 ml of acetone and 750 ml of
1,2-dimethoxyethane are placed in a vessel. The mixture is stirred
at 80.degree. C. for 20 hours. After the mixture has cooled down to
room temperature, it is filtered and dried. 460 g of 29 are
obtained. The crude product is used for the next reaction step
without further purification.
##STR00107##
[0196] c) 218 g of 29, 643 g of ammonium acetate and 680 ml of
acetic acid are stirred at 115.degree. C. for 3 hours. After the
reaction mixture has cooled down to room temperature, it is poured
into 3 L of acetone. The produced solid is separated and washed
with methanol and dried. 99.6 g of 30 are obtained.
##STR00108##
[0197] d) A mixture of 5 mg iron trichloride (FeCl.sub.3), 2 g of
sodium and 40 ml of t-amylalcohol is heated to 110.degree. C. for
20 minutes before a mixture of 3.9 g of the thiazole-2-nitrile of
the formula 21 and 7.82 g of 30 is added portionwise. The reaction
mixture is stirred at 110.degree. C. for 3 hours before it is
poured onto 6.3 g acetic acid in a water-methanol mixture (100
ml/100 ml). Buchner filtration and exhaustive washing with methanol
affords 4.5 g of the desired 1,4-diketopyrrolo[3,4-c]pyrrole (DPP)
derivative of the formula 31 as dark blue powder; ESI-MS m/z (%
int.): 302.15 ([M+H]+, 100%).
##STR00109##
[0198] e) Compound 32 is obtained in analogy to example 5c.
##STR00110##
[0199] f) Compound 33 is obtained in analogy to example 5d.
##STR00111##
[0200] g) Polymer 34 is obtained in analogy to example 5e.
##STR00112##
[0201] h) Polymer 35 is obtained in analogy to example 7.
Example 15
[0202] Polymer 36 is obtained from compound 12 in analogy to
example 7.
##STR00113##
Example 16
##STR00114##
[0204] a) In a three neck-flask, 83.6 g of potassium phosphate
(K.sub.3PO.sub.4) dissolved in 110 ml of water (previously
degassed) is added to a degassed solution of 20 g of thienylboronic
acid, 22.0 g of 2-bromothiazole, 2.3 g of tri-tert-butylphosphonium
tetrafluoroborate ((t-Bu).sub.3P*HBF.sub.4) and 3.6 g of
tris(dibenzylideneacetone)dipalladium (0) (Pd.sub.2(dba).sub.3) in
350 ml of tetrahydrofuran. The reaction mixture is heated at reflux
temperature overnight. The reaction mixture is cooled to room
temperature and 100 ml water was added. The reaction mixture was
extracted with ethylacetate and the organic layer was dried and
evaporated under reduced pressure. It was further purified with
column chromatography using a gradient of hexane/ehtylacetate on
silicagel. 8.0 g of 2-thiophen-2-yl-thiazole 37 was obtained,
spectral data correspond to the ones described in literature using
Negishi-cross coupling reaction. (J. Jensen et al., Synthesis,
2001, 1, 128).
##STR00115##
[0205] b) Compound 38 is obtained using the procedure known in
literature (P. Chauvin et al., Bull. Soc. Chim. Fr. 1974, 9-10,
2099).
##STR00116##
[0206] c) Compound 39 is obtained in analogy to the procedure known
in literature (A. D. Borthwick et al.; J. Chem. Soc., Perkin Trans
1, 1973; 2769).
##STR00117##
[0207] d) Compound 40 is obtained in analogy to example 5b.
##STR00118##
[0208] e) Compound 41 is obtained in analogy to example 5c.
##STR00119##
[0209] f) Compound 42 is obtained in analogy to example 5d.
##STR00120##
[0210] g) Polymer 43 is obtained in analogy to example 5e.
##STR00121##
[0211] h) Polymer 44 is obtained in analogy to example 7.
[0212] The polymers of the present invention can show higher
field-effect mobility as the polymers disclosed in WO08/000664.
* * * * *