U.S. patent application number 11/908150 was filed with the patent office on 2008-12-11 for monomers, oligomers and polymers comprising thiophene and selenophene.
Invention is credited to Warren Duffy, Martin Heeney, Iain McCulloch, Steven Tierney.
Application Number | 20080303000 11/908150 |
Document ID | / |
Family ID | 39307947 |
Filed Date | 2008-12-11 |
United States Patent
Application |
20080303000 |
Kind Code |
A1 |
Heeney; Martin ; et
al. |
December 11, 2008 |
Monomers, Oligomers and Polymers Comprising Thiophene and
Selenophene
Abstract
The invention relates to novel mono-, oligo- and polymeric
compounds comprising thiophene and selenophene, to their use as
semiconductors or charge transport materials, in optical,
electro-optical or electronic devices, and to optical,
electro-optical or electronic devices comprising the novel
compounds.
Inventors: |
Heeney; Martin;
(Southampton, GB) ; Tierney; Steven; (Southampton,
GB) ; Duffy; Warren; (Southampton, GB) ;
McCulloch; Iain; (Southampton, GB) |
Correspondence
Address: |
CONNOLLY BOVE LODGE & HUTZ, LLP
P O BOX 2207
WILMINGTON
DE
19899
US
|
Family ID: |
39307947 |
Appl. No.: |
11/908150 |
Filed: |
February 23, 2006 |
PCT Filed: |
February 23, 2006 |
PCT NO: |
PCT/EP06/01664 |
371 Date: |
July 15, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
60661490 |
Mar 15, 2005 |
|
|
|
Current U.S.
Class: |
252/299.61 ;
528/380; 549/59 |
Current CPC
Class: |
C09K 11/06 20130101;
C09K 2211/1491 20130101; H01L 51/0036 20130101; C09K 2211/1483
20130101; H01B 1/127 20130101; C08G 61/126 20130101; C09K 2323/00
20200801; C09K 19/3804 20130101; Y10T 428/10 20150115; C09K 19/3491
20130101; C09K 19/40 20130101; H05B 33/14 20130101; Y02E 10/549
20130101; C08G 61/123 20130101 |
Class at
Publication: |
252/299.61 ;
528/380; 549/59 |
International
Class: |
C09K 19/40 20060101
C09K019/40; C08G 75/00 20060101 C08G075/00; C07D 421/14 20060101
C07D421/14 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 11, 2005 |
EP |
05005348.7 |
Mar 14, 2005 |
EP |
05005467.5 |
Claims
1-21. (canceled)
22. A monomeric, oligomeric, or polymeric compound comprising one
or more selenophene-2,5-diyl groups and one or more thiophene
2,5-diyl groups, wherein said selenophene-2,5-diyl groups and
thiophene 2,5-diyl groups are optionally substituted in the 3-
and/or 4-position, with the proviso that said compound does not
comprise homopolymers of
2,5-bis(3-octyl-thiophen-2-yl)selenophene.
23. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein said compound comprises units of formula I ##STR00012##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are, independently of each other, and, in case of multiple
occurrence, independently of one another, H; halogen; optionally
substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain,
branched, or cyclic alkyl having up to 20 C atoms, optionally mono-
or polysubstituted by F, Cl, Br, I, or CN; wherein one or more
non-adjacent CH.sub.2 groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--O--CO--O--, --S--CO--, --CO--S--, --CX.sup.1.dbd.CX.sup.2--, or
--C.ident.C--, with the proviso that O and/or S atoms are not
linked directly to one another; R.sup.0 and R.sup.00 are,
independently of each other, H, aryl, or alkyl having up to 12 C
atoms; X.sup.1 and X.sup.2 are, independently of each other, X, F,
Cl, or CN; P is a polymerisable group; P* is a group that can be
converted to or substituted by a polymerisable group P; Sp is a
spacer group or a single bond; a, b, c, and d are, independently of
each other, 0, 1, 2, or 3, wherein the sum of a and c is greater
than 1 and the sum of b and d is greater than 1; n is an integer
greater than or equal to 1; and wherein said recurring units of
formula I are identical or different; with the proviso that said
compound does not comprise recurring units of formula I wherein a,
b, and c are equal to 1; d is equal to 0; R.sup.1 and R.sup.2 are
n-C.sub.8H.sub.17; R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are H;
and n is greater than 1.
24. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein said compound comprises recurring units of formula II
##STR00013## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
and R.sup.6 are, independently of each other, and, in case of
multiple occurrence, independently of one another, H; halogen;
optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-; or
straight chain, branched, or cyclic alkyl having up to 20 C atoms,
optionally mono- or polysubstituted by F, Cl, Br, I, or CN; wherein
one or more non-adjacent CH.sub.2 groups are optionally replaced,
in each case independently from one another, by --O--, --S--,
--NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--,
--OCO--, --O--CO--O--, --S--CO--, --CO--S--,
--CX.sup.1.dbd.CX.sup.2--, or --C.ident.C--, with the proviso that
O and/or S atoms are not linked directly to one another; a, b, c,
and d are, independently of each other, 0, 1, 2, or 3, wherein the
sum of a and c is greater than 1 and the sum of b and d is greater
than 1; n is an integer greater than or equal to 1; R.sup.7 and
R.sup.8 are, independently of each other, and, in case of multiple
occurrence, independently of one another, H; halogen; optionally
substituted aryl or heteroaryl; P-Sp-; P*-Sp-; --Sn(R.sup.0).sub.3;
--B(OR')(OR''); --CH.sub.2C; --CHO; --CH.dbd.CH.sub.2;
--SiR.sup.0R.sup.00R.sup.000; or straight chain, branched, or
cyclic alkyl having up to 20 C atoms, optionally mono- or
polysubstituted by F, Cl, Br, I, or CN; wherein one or more
non-adjacent CH.sub.2 groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--O--CO--O--, --S--CO--, --CO--S--, --CX.sup.1.dbd.CX.sup.2--, or
--C.ident.C--, with the proviso that O and/or S atoms are not
linked directly to one another; R.sup.0, R.sup.00, and R.sup.000
are, independently of each other, H, or aryl or alkyl having up to
12 C atoms; and R' and R'' are, independently of each other, H or
alkyl having up to 12 C atoms, or OR' and OR'' together with the
boron atom optionally define a cyclic group having 2 to 20 C
atoms.
25. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein said compound is selected from formulae I1a, I1b, I1c, I1d,
I1e, or I1f; ##STR00014## wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are, independently
of each other, and, in case of multiple occurrence, independently
of one another, H; halogen; optionally substituted aryl or
heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or cyclic
alkyl having up to 20 C atoms, optionally mono- or polysubstituted
by F, Cl, Br, I, or CN; wherein one or more non-adjacent
C.sub.1H.sub.2 groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--O--CO--O--, --S--CO--, --CO--S--, --CX.sup.1.dbd.CX.sup.2--, or
--C.ident.C--, with the proviso that O and/or S atoms are not
linked directly to one another; a, b, c, and d are, independently
of each other, 0, 1, 2, or 3, wherein the sum of a and c is greater
than 1 and the sum of b and d is greater than 1; and n is an
integer greater than or equal to 1.
26. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are H and R.sup.1
and R.sup.2 are different from H.
27. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein R.sup.1 and R.sup.2 are selected from C.sub.1 to C.sub.20
alkyl, C.sub.1 to C.sub.20 alkoxy, C.sub.1 to C.sub.20 alkenyl,
C.sub.1 to C.sub.20 alkynyl, C.sub.1 to C.sub.20 thioalkyl, C.sub.1
to C.sub.20 silyl, C.sub.1 to C.sub.20 ester, C.sub.1 to C.sub.20
amino, or C.sub.1 to C.sub.20 fluoroalkyl.
28. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein R.sup.1 and R.sup.2 are selected from C.sub.9 to C.sub.20
alkyl, C.sub.9 to C.sub.20 alkoxy, C.sub.6 to C.sub.20 alkenyl,
C.sub.9 to C.sub.20 alkynyl, C.sub.9 to C.sub.20 thioalkyl, C.sub.9
to C.sub.20 silyl, C.sub.9 to C.sub.20 ester, C.sub.9 to C.sub.20
amino, C.sub.9 to C.sub.20 fluoroalkyl, and optionally substituted
aryl or heteroaryl.
29. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein n is an integer from 2 to 5000.
30. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein n is 1 and one or both of R.sup.7 and R.sup.8 are halogen,
--Sn(R.sup.0).sub.3, --B(OR')(OR''), --CH.sub.2Cl, --CHO,
--CH.dbd.CH.sub.2, or --SiR.sup.0R.sup.00R.sup.000.
31. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein n is 1 and one or both of 17 and R.sup.8 are P-Sp- or
P*-Sp-.
32. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein said compound is selected from formulae I1a1, I1a2, I1c1,
or I1c2: ##STR00015## wherein R.sup.7 and R.sup.8 are,
independently of each other, and, in case of multiple occurrence,
independently of one another, H; halogen; optionally substituted
aryl or heteroaryl; P-Sp-; P*-Sp-; or straight chain, branched, or
cyclic alkyl having up to 20 C atoms, optionally mono- or
polysubstituted by F, Cl, Br, I, or CN; wherein one or more
non-adjacent CH.sub.2, groups are optionally replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OCO--,
--O--CO--O--, --S--CO--, --CO--S--, --CX.sup.1.dbd.CX.sup.2--, or
--C.ident.C--, with the proviso that O and/or S atoms are not
linked directly to one another; R is, independently of each other,
and, in case of multiple occurrence, independently of one another,
halogen; optionally substituted aryl or heteroaryl; P-Sp-; P*-Sp-;
or straight chain, branched, or cyclic alkyl having up to 20 C
atoms, optionally mono- or polysubstituted by F, Cl, Br, I, or CN;
wherein one or more non-adjacent CH.sub.2 groups are optionally
replaced, in each case independently from one another, by --O--,
--S--, --NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--,
--COO--, --OCO--, --O--CO--O--, --S--CO--, --CO--S--,
--CX.sup.1.dbd.CX.sup.2--, or --C.dbd.C--, with the proviso that O
and/or S atoms are not linked directly to one another; and n is an
integer greater than or equal to 1.
33. A polymerisable liquid crystal material comprising one or more
monomeric, oligomeric, or polymeric compounds of claim 22, wherein
said one or more compounds is a thienothiophene compound comprising
at least one polymerisable group, and optionally comprising one or
more further polymerisable compounds, wherein at least one of said
thienothiophene compounds or said one or more further polymerisable
compounds is mesogenic or liquid crystalline.
34. An anisotropic polymer film having charge transport properties
comprising the polymerisable liquid crystal material of claim 33,
wherein said anisotropic polymer film is aligned in its liquid
crystal phase into macroscopically uniform orientation and
polymerised or crosslinked to fix the oriented state.
35. A side chain liquid crystal polymer obtained by polymerisation
of one or more monomeric, oligomeric, or polymeric compounds of
claim 22 or by grafting said compounds to a polymer backbone in a
polymer analogous reaction, optionally with one or more additional
mesogenic or non-mesogenic comonomers.
36. An optical, electrooptical, or electronic component or device;
an organic field effect transistor; an integrated circuit; a thin
film transistor; a flat panel display; a radio frequency
identification tag; an electroluminescent or photoluminescent
device or component; an organic light emitting diode; a display
backlight; a photovoltaic or sensor device; a charge injection
layer; a Schottky diode; a planarising layer; an antistatic film; a
conducting substrate or pattern; a battery electrode material; a
photoconductor; an electrophotographic application; an
electrophotographic recording; an organic memory device; an
alignment layer; a cosmetic or pharmaceutical composition; a
biosensor; or a biochip comprising the monomeric, oligomeric, or
polymeric compound of claim 22.
37. A semiconducting, electroluminescent, or charge transport
material, component or device comprising at least one monomeric,
oligomeric, or polymeric compound of claim 22.
38. A thin film transistor or thin film transistor array for flat
panel displays, a radio frequency identification tag, a field
effect transistor, an electroluminescent display or backlight
comprising the monomeric, oligomeric, or polymeric compound of
claim 22.
39. A security marling or device comprising a field effect
transistor or radio frequency identification tag according to claim
39.
40. The monomeric, oligomeric, or polymeric compound of claim 22,
wherein said compound is oxidatively or reductively doped to form
conducting ionic species.
41. A charge injection layer, a planarising layer, an antistatic
film, or a conducting substrate or pattern for electronic
applications or flat panel displays comprising the monomeric,
oligomeric, or polymeric compound of claim 41.
Description
FIELD OF INVENTION
[0001] The invention relates to novel mono-, oligo- and polymeric
compounds comprising thiophene and selenophene. The invention
further relates to their use as semiconductors or charge transport
materials, in optical, electro-optical or electronic devices. The
invention further relates to optical, electro-optical or electronic
devices comprising the novel compounds.
BACKGROUND AND PRIOR ART
[0002] Organic materials have recently shown promise as the active
layer in organic based thin film transistors and organic field
effect transistors [see H. E. Katz, Z. Bao and S. L. Gilat, Acc.
Chem. Res., 2001, 34, 5, 359]. Such devices have potential
applications in smart cards, security tags and the switching
element in flat panel displays. Organic materials are envisaged to
have substantial cost advantages over their silicon analogues if
they can be deposited from solution, as this enables a fast,
large-area fabrication route.
[0003] The performance of the device is principally based upon the
charge carrier mobility of the semi-conducting material and the
current on/off ratio, so the ideal semiconductor should have a low
conductivity in the off state, combined with a high charge carrier
mobility (>1.times.10.sup.-3 cm.sup.2 V.sup.-1 s.sup.-1). In
addition, it is important that the semi-conducting material is
relatively stable to oxidation i.e. it has a high ionisation
potential, as oxidation leads to reduced device performance.
[0004] Regioregular head-to-tail poly(3-hexylthiophene) has been
reported with charge carrier mobility between 1.times.10.sup.-5 and
4.5.times.10.sup.-2 cm.sup.2V.sup.-1s.sup.-1, but with a rather low
current on/off ratio between 10 and 10.sup.3 [see Z. Bao at al.,
Appl. Pys. Lett., 1996, 69, 4108]. This low on/off current is due
in part to the low ionisation potential of the polymer, which can
lead to oxygen doping of the polymer under ambient conditions, and
a subsequent high off current [see H. Sirringhaus et al., Adv.
Solid State Phys., 1999, 39, 101].
[0005] A high regioregularity leads to improved packing and
optimised microstructure, leading to improved charge carrier
mobility [see H. Sirringhaus et al., Science, 1998, 280, 1741-1744;
H. Sirringhaus et al., Nature, 1999, 401, 685-688; and H.
Sirringhaus, et al., Synthetic Metals, 2000, 111-112, 129-132]. In
general, poly(3-alkylthiophenes) show improved solubility and are
able to be solution processed to fabricate large area films.
However, poly(3-alkylthiophenes) have relatively low ionisation
potentials and are susceptible to doping in air.
[0006] It is an aim of the present invention to provide new
materials for use as semiconductors or charge transport materials,
which are easy to synthesize, have high charge mobility, good
processibility and oxidative stability. Another aim of the
invention is to provide new semiconductor and charge transport
components, and new and improved electrooptical, electronic and
luminescent devices comprising these components. Other aims of the
invention are immediately evident to those skilled in the art from
the following description.
[0007] The inventors have found that these aims can be achieved by
providing mono-, oligo- and polymers of bis(thienyl)selenophene as
claimed in the present invention.
[0008] EP-A-1 439 590 discloses mono-, oligo- and
poly-bis(thienyl)arylenes, but does not disclose compounds of the
present invention. S. Tierney, M. Heeney and 1. McCulloch, Synth
Met., 148(2), 195-198, (2005) discloses
poly-bis(3-octyl-thiophen-2-yl)selenophene, but does not disclose
compounds of the present invention.
SUMMARY OF THE INVENTION
[0009] The invention relates to monomeric, oligomeric or polymeric
compounds comprising one or more selenophene-2,5-diyl groups and
one or more thiophene 2,5-diyl groups, each being optionally
substituted in 3- and/or 4-position, with the proviso that
homopolymers of 2,5-bis(3-octyl-thiophen-2-yl)selenophene are
excluded.
[0010] The invention further relates to a the use of the compounds
of formula I as semiconducting, charge transport or light-emitting
materials.
[0011] The invention further relates to a semiconducting,
electroluminescent or charge transport material, component or
device comprising at least one compound of formula I.
[0012] The invention further relates to the use of compounds of
formula I as charge-transport, semiconducting, electrically
conducting, photoconducting or light-emitting material in optical,
electrooptical or electronic components or devices, organic field
effect transistors (OFET), integrated circuitry (IC), thin film
transistors (TFT), flat panel displays, radio frequency
identification (RFID) tags, electroluminescent or photoluminescent
devices or components, organic light emitting diodes (OLED),
backlights of displays, photovoltaic or sensor devices, charge
injection layers, Schottky diodes, planarising layers, antistatic
films, conducting substrates or patterns, electrode materials in
batteries, photoconductors, electrophotographic applications,
electrophotographic recording, organic memory devices, alignment
layers, cosmetic or pharmaceutical compositions, biosensors,
biochips, or for detecting and discriminating DNA sequences.
[0013] The invention further relates to an optical, electrooptical
or electronic device, FET, integrated circuit (IC), TFT, OLED or
alignment layer comprising a compound, semiconducting or charge
transport material, component or device according to the
invention.
[0014] The invention further relates to a TFT or TFT array for flat
panel displays, radio frequency identification (RFID) tag,
electroluminescent display or backlight comprising a compound,
semiconducting or charge transport material, component or device or
a FET, IC, TFT or OLED according to the invention.
[0015] The invention further relates to a security marking or
device comprising a FET or an RFID tag according to the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows the transfer characteristics of a polymer
according to Example 1 in a transistor device.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The polymers according to the present invention can be
homopolymers, i.e. having identical recurring units, or copolymers
having different recurring units. Particularly preferred are
homopolymers of having identical recurring units.
[0018] The compounds of the present invention are advantageous
because they exhibit higher charge carrier mobilities compared to
the analogous all-thiophene systems. The increased atomic radius of
selenium (103 pm (picometre) over sulfur (88 pm) enhances molecular
overlaps between polymer chains, and facilitates the charge hopping
process. In addition the inclusion of selenophene results in a
red-shift of the maximum absorbance wavelength over the
all-thiophene systems.
[0019] The compounds according to the invention are especially
useful as charge transport or semiconductor materials. Introduction
of alkyl side chains into the thiophene and/or selenophene group
further improves solubility and solution processibility especially
for the polymers.
[0020] The regioregularity in the polymers of the present invention
is preferably at least 90%, in particular 95% or more, very
preferably 98% or more, most preferably from 99 to 100%.
[0021] Regioregular polymers are advantageous as they show strong
interchain pi-pi-stacking interactions and a high degree of
crystallinity, making them effective charge transport materials
with high carrier mobilities.
[0022] Further preferred are mono-, oligo- and polymers that are
mesogenic or liquid crystalline, in particular polymers forming
calamitic phases, and polymerisable monomers comprising one or more
groups P-Sp- and forming calamitic phases.
[0023] The monomeric, oligomeric and polymeric compounds are
preferably selected of formula I
##STR00001##
wherein [0024] R.sup.1-6 are independently of each other, and in
case of multiple occurrence independently of one another, H,
halogen, optionally substituted aryl or heteroaryl, P-Sp-, P*-Sp-,
or straight chain, branched or cyclic alkyl with 1 to 20 C-atoms,
which is optionally mono- or polysubstituted by F, Cl, Br, I or CN,
and wherein one or more non-adjacent CH.sub.2 groups are optionally
replaced, in each case independently from one another, by --O--,
--S--, --NH--, --NRO--, --SiR.sup.0R.sup.00--, --CO--, --COO--,
--OCO--, --O--CO--O--, --S--CO--, --CO--S--,
--CX.sup.1.dbd.CX.sup.2-- or --C.ident.C-- in such a manner that O
and/or S atoms are not linked directly to one another, [0025]
R.sup.0 and R.sup.00 are independently of each other H, aryl or
alkyl with 1 to 12 C-atoms, [0026] X.sup.1 and X.sup.2 are
independently of each other H, F, Cl or CN, [0027] P is a
polymerisable group, [0028] P* is a group that can be converted to
or substituted by a polymerisable group P, [0029] Sp is a spacer
group or a single bond, [0030] a, b, c and d are independently of
each other 0, 1, 2 or 3, with a+c>1 and b+d>1, [0031] n is an
integer .gtoreq.1, wherein the recurring units are identical or
different, with the proviso that compounds wherein a=b=c=1, d=0,
R.sup.1 and R.sup.2 are n-C.sub.8H.sub.17, R.sup.3, R.sup.4,
R.sup.5 and R.sup.6 are H, and n>1 are excluded.
[0032] Especially preferred are compounds of formula I1
##STR00002##
wherein R.sup.1-6, a, b, c, d and n have the meanings of formula I,
[0033] R.sup.7 and R.sup.8 independently of each other have one of
the meanings of R.sup.1 or denote --Sn(R.sup.0).sub.3,
--B(OR')(OR''), --CH.sub.2Cl, --CHO, --CH.dbd.CH.sub.2 or
--SiR.sup.0R.sup.00R.sup.000, [0034] R.sup.0, R.sup.00, R.sup.000
are independently of each other H, aryl or alkyl with 1 to 12
C-atoms, [0035] R' and R'' are independently of each other H or
alkyl with to 12 C-atoms, or OR' and OR'' together with the boron
atom form a cyclic group having 2 to 20 C atoms.
[0036] Further preferred are compounds of formula I and I1 wherein
[0037] n is an integer from 2 to 5000, preferably from 10 to 5000,
very preferably from 100 to 1000, [0038] the molecular weight (Mw)
is from 5000 to 300,000, in particular from 20,000 to 100,000,
[0039] n is 1, [0040] a and/or c are 1, [0041] b is 1 or 2, [0042]
d is 0, [0043] a=c=1, b=1 or 2, d=0, [0044] a=c=1, b=d=1, [0045]
b=d=1, c=1 or 2, a=0, [0046] a=b=1, c=0, [0047] R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5 and R.sup.8 are independently of each
other halogen, optionally substituted aryl or heteroaryl, P-Sp-,
P*-Sp-, or straight chain, branched or cyclic alkyl with 9 to 20
C-atoms, which is optionally mono- or polysubstituted by F, Cl, Br,
I or CN, and wherein one or more non-adjacent CH.sub.2 groups are
optionally replaced, in each case independently from one another,
by --O--, --S--, --NH--, --NR.sup.0--, --SiR.sup.0R.sup.00--,
--CO--, --COO--, --OCO--, --O--CO--O--, --S--CO--, --CO--S--,
--CX.sup.1.dbd.CX.sup.2-- or --C.ident.C-- in such a manner that O
and/or S atoms are not linked directly to one another [0048]
--R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are H, [0049] R.sup.1 and
R.sup.2 are different from H, [0050] R.sup.1 and R.sup.2 are
identical, [0051] R.sup.1 and R.sup.2 are selected from
C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy,
C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl,
C.sub.1-C.sub.20-thioalkyl, C.sub.1-C.sub.20-silyl,
C.sub.1-C.sub.20-ester, C.sub.1-C.sub.20-amino,
C.sub.1-C.sub.20-fluoroalkyl, and optionally substituted aryl or
heteroaryl, very preferably C.sub.10-C.sub.20-alkyl or
C.sub.10-C.sub.20-fluoroalkyl, [0052] R.sup.1 and R.sup.2 are
selected from C.sub.9-C.sub.20-alkyl, C.sub.9-C.sub.20-alkoxy,
C.sub.9-C.sub.20-alkenyl, C.sub.9-C.sub.20-alkynyl,
C.sub.9-C.sub.20-thioalkyl, C.sub.9-C.sub.20-silyl,
C.sub.9-C.sub.20-ester, C.sub.9-C.sub.20-amino,
C.sub.9-C.sub.20-fluoroalkyl, and optionally substituted aryl or
heteroaryl, very preferably C0-CO.sub.2-alkyl or
C.sub.9-C.sub.20-fluoroalkyl, most preferably
C.sub.10-C.sub.20-alkyl or C.sub.10-C.sub.20-fluoroalkyl, R.sup.1,
R.sup.2, R.sup.5 and R.sup.6 are H, [0053] R.sup.3 and R.sup.4 are
different from H, [0054] R.sup.3 and R.sup.4 are identical, [0055]
R.sup.3 and R.sup.4 are selected from C.sub.1-C.sub.20-alkyl,
C.sub.1-C.sub.20-alkoxy, C.sub.2-C.sub.20-alkenyl,
C.sub.2-C.sub.20-alkynyl, C.sub.1-C.sub.20-thioalkyl,
C.sub.1-C.sub.20-silyl, C.sub.1-C.sub.20-ester,
C.sub.1-C.sub.20-amino, C.sub.1-C.sub.20-fluoroalkyl, and
optionally substituted aryl or heteroaryl, very preferably
C.sub.1-C.sub.20-alkyl or C.sub.1-C.sub.20-fluoroalkyl, [0056]
R.sup.3 and R.sup.4 are selected from C.sub.9-C.sub.20-alkyl
C.sub.9-C.sub.20-alkoxy, C.sub.9-C.sub.20-alkenyl,
C.sub.9-C.sub.20-alkynyl, C.sub.9-C.sub.20-thioalkyl,
C.sub.9-C.sub.20-silyl, C.sub.9-C.sub.20-ester,
C.sub.9-C.sub.20-amino, CO.sub.9CO.sub.20-fluoroalkyl, and
optionally substituted aryl or heteroaryl, very preferably
C.sub.9-C.sub.20-alkyl or C.sub.9-C.sub.20-fluoroalkyl, most
preferably C.sub.10-C.sub.20-alkyl or
C.sub.10-C.sub.20-fluoroalkyl, [0057] R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are H, [0058] R.sup.5 and R.sup.6 are different from H,
[0059] R.sup.5 and R.sup.6 are identical, [0060] R.sup.5 is H and
R.sup.6 is different from H, [0061] R.sup.6 is H and R.sup.5 is
different from H, [0062] R.sup.5 and/or R.sup.6 are selected from
C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy,
C.sub.2-C.sub.20-alkenyl, C.sub.2-C.sub.20-alkynyl,
C.sub.1-C.sub.20-thioalkyl, C.sub.1-C.sub.20-silyl,
C.sub.1-C.sub.20-ester, C.sub.1-C.sub.20-amino,
C.sub.1-C.sub.20-fluoroalkyl, and optionally substituted aryl or
heteroaryl, very preferably C.sub.1-C.sub.20-alkyl or
C.sub.1-C.sub.20-fluoroalkyl, [0063] R.sup.5 and/or R.sup.6 are
selected from C.sub.9-C.sub.20-alkyl, C.sub.9-C.sub.20-alkoxy,
C.sub.9-C.sub.20-alkenyl, C.sub.9-C.sub.20-alkynyl,
C.sub.9-C.sub.20-thioalkyl, C.sub.9-C.sub.20-silyl,
C.sub.9-C.sub.20-ester, C.sub.9-C.sub.20-amino,
C.sub.9-C.sub.20-fluoroalkyl, and optionally substituted aryl or
heteroaryl, very preferably C.sub.9-C.sub.20-alkyl or
C.sub.9-C.sub.20-fluoroalkyl, most preferably
C.sub.10-C.sub.20-alkyl or C.sub.10-C.sub.20-fluoroalkyl, [0064] P*
is --OH or --O--S.sup.1--R.sup.0R.sup.00R.sup.000, preferably
wherein R.sup.0, R.sup.00 and R.sup.000 are identical or different
groups selected from aryl or C.sub.1-12-alkyl, preferably
C.sub.1-C.sub.6-alkyl, like methyl, ethyl, isopropyl, tert-butyl or
phenyl, [0065] R.sup.7 and R.sup.8 are selected from H, halogen,
Sn(R.sup.0).sub.3, B(OR')(OR''), CH.sub.2Cl, CHO, CH.dbd.CH.sub.2,
SiR.sup.0R.sup.00R.sup.000 and optionally substituted aryl or
heteroaryl, [0066] n is 1 and one or both of R.sup.7 and R.sup.8
are halogen which is preferably Br, Cl or I, Sn(R.sup.0).sub.3,
B(OR')(OR''), CH.sub.2Cl, CHO, CH.dbd.CH.sub.2 or
SiR.sup.0R.sup.00R.sup.000, [0067] at least one of R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is P-Sp-, [0068] n
is 1 and one or both of R.sup.7 and R.sup.8 are P-Sp- or
P*-Sp-.
[0069] Especially preferred are compounds of the following
formulae
##STR00003##
wherein R.sup.1-8 and n have the meanings of formula 11.
[0070] Especially preferred are the following compounds
##STR00004##
wherein n has the meaning of formula I and R has one of the
meanings of R.sup.1 in formula I different from H.
[0071] If one of R.sup.1-8 is aryl or heteroaryl, it is preferably
a mono-, bi- or tricyclic aromatic or heteroaromaic group with up
to 25 C atoms, wherein the rings can be fused. Heteroaromatic
groups contain at least one hetero ring atom preferably selected
from N, O and S. The aromatic or heteroaromatic groups are
optionally substituted with one or more groups L.
[0072] L is F, Cl, Br, I, CN or straight chain, branched or cyclic
alkyl having 1 to 20 C atoms, which is unsubstituted, mono- or
poly-substituted by F, Cl, Br, I, --CN or --OH, and in which one or
more non-adjacent CH.sub.2 groups are optionally replaced, in each
case independently from one another, by --O--, --S--, --NH--,
--NRO--, --SiR.sup.0R.sup.00--, --CO--, --COO--, OCO--, --OCO--O,
--S--CO--, --CO--S--, --CH--CH-- or --C.ident.C-- in such a manner
that O and/or S atoms are not linked directly to one another.
[0073] Especially preferred aryl and heteroaryl groups are phenyl,
fluorinated phenyl, pyridine, pyrimidine, biphenyl, naphthalene,
optionally fluorinated or alkylated or fluoroalkylated
benzo[1,2-b:4,5-b']dithiophene, optionally fluorinated or alkylated
or fluoroalkylated thieno[3,2-b]thiophene, optionally fluorinated
or alkylated or fluoroalkylated 2,2-dithiophene, thiazole and
oxazole, all of which are unsubstituted, mono- or polysubstituted
with L as defined above.
[0074] If one of R.sup.1-8 is an alkyl or alkoxy radical, i.e.
where the terminal CH.sub.2 group is replaced by --O--, this may be
straight-chain or branched. It is preferably straight-chain, has 2
to 8 carbon atoms and accordingly is preferably ethyl, propyl,
butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy,
pentoxy, hexyloxy, heptoxy, or octoxy, furthermore methyl, nonyl,
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy,
decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for
example.
[0075] Fluoroalkyl or fluorinated alkyl or alkoxy is preferably
straight chain (O)C.sub.iF.sub.2i+1, wherein i is an integer from 1
to 20, in particular from 1 to 15, very preferably (O)CF.sub.3,
(O)C.sub.2F.sub.5, (O)C.sub.3F.sub.7, (O)C.sub.4F.sub.9,
(O)C.sub.5F.sub.11, (O)C.sub.6F.sub.13, (O)C.sub.7F.sub.15 or
(O)C.sub.8F.sub.17, most preferably (O)C.sub.6F.sub.13.
[0076] CX.sup.1.dbd.CX.sup.2 is preferably --CH.dbd.CH--,
--CH.dbd.CF--, --CF.dbd.CH--, --CF.dbd.CF--, --CH--C(CN)-- or
--C(CN).dbd.CH--.
[0077] Halogen is preferably F, Br or Cl.
[0078] Hetero atoms are preferably selected from N, O and S.
[0079] The polymerisable group P is a group that is capable of
participating in a polymerisation reaction, like radicalic or ionic
chain polymerisation, polyaddition or polycondensation, or capable
of being grafted, for example by condensation or addition, to a
polymer backbone in a polymeranaloguous reaction. Especially
preferred are polymerisable groups for chain polymerisation
reactions, like radicalic, cationic or anionic polymerisation. Very
preferred are polymerisable groups comprising a C--C double or
triple bond, and polymerisable groups capable of polymerisation by
a ring-opening reaction, like oxetanes or epoxides.
[0080] Very preferably the polymerisable group P is selected from
CH.sub.2.dbd.CW.sup.1--COO--,
##STR00005##
CH.sub.2.dbd.CW.sup.2--(O).sub.k1--, CH.sub.3--CH.dbd.CH--O--,
(CH.sub.2.dbd.CH).sub.2CH--OCO--,
(CH.sub.2.dbd.CH--CH.sub.2).sub.2CH--OCO--,
(CH.sub.2.dbd.CH).sub.2CH--O--,
(CH.sub.2.dbd.CH--CH.sub.2).sub.2N--,
(CH.sub.2.dbd.CH--CH.sub.2).sub.2N--CO--, HO--CW.sup.2W.sup.3--,
HS--CW.sup.2W.sup.3--, HW.sup.2N--, HO--CW.sup.2W.sup.3--NH--,
CH.sub.2.dbd.CW.sup.1--CO--NH--,
CH.sub.2.dbd.CH--(COO).sub.k1-Phe-(O).sub.k2--,
CH.sub.2.dbd.CH--(CO).sub.k1-Phe-(O).sub.k2--, Phe-CH.dbd.CH--,
HOOC--, OCN--, and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, CF.sub.3, phenyl or alkyl with 1 to 5 C-atoms, in
particular H, Cl or CH.sub.3, W.sup.2 and W.sup.3 being
independently of each other H or alkyl with 1 to 5 C-atoms, in
particular H, methyl, ethyl or n-propyl, W.sup.4, W.sup.5 and
W.sup.6 being independently of each other Cl, oxaalkyl or
oxacarbonylalkyl with 1 to 5 C-atoms, W.sup.7 and W.sup.8 being
independently of each other H, Cl or alkyl with 1 to 5 C-atoms, Phe
being 1,4-phenylene that is optionally substituted by one or more
groups L as defined above, and k.sub.1 and k.sub.2 being
independently of each other 0 or 1.
[0081] Especially preferred groups P are CH.sub.2.dbd.CH--COO--,
CH.sub.2.dbd.C(CH.sub.8)--COO--, CH.sub.2.dbd.CH--,
CH.sub.2.dbd.CH--O--, (CH.sub.2.dbd.CH).sub.2CH--OCO--,
(CH.sub.2.dbd.CH).sub.2CH--O--,
##STR00006##
[0082] Very preferred are acrylate and oxetane groups. Oxetanes
produce less shrinkage upon polymerisation (cross-linking), which
results in less stress development within films, leading to higher
retention of ordering and fewer defects. Oxetane cross-linking also
requires cationic initiator, which unlike free radical initiator is
inert to oxygen.
[0083] As spacer group Sp all groups can be used that are known for
this purpose to the skilled in the art. The spacer group Sp is
preferably of formula Sp'-X, such that P-Sp- is P-Sp'-X-- and
P*-Sp- is P*-Sp'-X--, wherein [0084] Sp' is alkylene with up to 20
C atoms which may be unsubstituted, mono- or poly-substituted by F,
Cl, Br, I or CN, it being also possible for one or more
non-adjacent CH.sub.2 groups to be replaced, in each case
independently from one another, by --O--, --S--, --NH--,
--NR.sup.0--, --SiR.sup.0R.sup.00--, --CO--, --COO--, --OC--,
--OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in
such a manner that Q and/or S atoms are not linked directly to one
another, [0085] X is --O--, --S--, --CO--, --COO--, --OCO--,
--O--COO--, --CO--NR.sup.0--, --NR.sup.0--CO--,
--CO--NR.sup.0--CO--, --OCH.sub.2--, --CH.sub.2O--, --SCH.sub.2--,
--CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--, --CF.sub.2S--,
--SCF.sub.2--, --CF.sub.2CH.sub.2--, --CH.sub.2CF.sub.2--,
--CF.sub.2CF.sub.2--, --CH.dbd.N--, --N.dbd.CH--, --N.dbd.N--,
--CH.dbd.CR.sup.0--, --CX.sup.1.dbd.CX.sup.2--, --C.ident.C--,
--CH.dbd.CH--COO--, --OCO--CH.dbd.CH-- or a single bond, and [0086]
R.sup.0, R.sup.00, X.sup.1 and X.sup.2 have one of the meanings
given above.
[0087] X is preferably --O--, --S--, --OCH.sub.2--, --CH.sub.2O--,
--SCH.sub.2--, --CH.sub.2S--, --CF.sub.2O--, --OCF--,
--CF.sub.2S--, --SCF.sub.2--, --CH.sub.2CH.sub.2--,
--CF.sub.2CH.sub.2--, --CH.sub.2CF.sub.2--, --CF.sub.2CF.sub.2--,
--CH.dbd.N--, --N--COH--, --N.dbd.N--, --CH.dbd.CR.sup.0--,
--CX.sup.1.dbd.CX.sup.2--, --C.ident.C-- or a single bond, in
particular --O--, --S--, --C.ident.C--, --CX.sup.1.dbd.CX.sup.2--
or a single bond, very preferably a group that is able to from a
conjugated system, such as --C.ident.C-- or
--CX.sup.1.dbd.CX.sup.2--, or a single bond.
[0088] Typical groups Sp' are, for example, --(CH.sub.2).sub.p--,
--(CH.sub.2CH.sub.2O).sub.q--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--S--CH.sub.2CH.sub.2-- or
--CH.sub.2CH.sub.2--NH--CH.sub.2CH.sub.2-- or
--(SiR.sup.0R.sup.00--O).sub.p--, with p being an integer from 2 to
12, q being an integer from 1 to 3 and R.sup.0 and R.sup.00 having
the meanings given above.
[0089] Preferred groups Sp' are ethylene, propylene, butylene,
pentylene, hexylene, heptylene, octylene, nonylene, decylene,
undecylene, dodecylene, octadecylene, ethyleneoxyethylene,
methyleneoxybutylene, ethylene-thioethylene,
ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene,
propenylene and butenylene for example.
[0090] Further preferred are compounds with one or two groups P-Sp-
or P*-Sp- wherein Sp is a single bond.
[0091] In case of compounds with two groups P-Sp or P*-Sp-,
respectively, each of the groups P or P* and the spacer groups Sp
can be identical or different.
[0092] Another preferred embodiment relates to compounds comprising
one or more groups P*-Sp-, wherein P* is a group that can be
converted to or substituted by a polymerisable group P as defined
above. Preferably P* is a group that is less reactive than P, for
example towards spontaneous polymerisation. These compounds can be
used for example as intermediates in the synthesis of polymerisable
compounds of formula I having one or more groups P, or as a
precursor material for polymerisable compounds which are too
reactive to be stored or transported for longer periods of time.
The group P* is preferably chosen such that it can easily be
transformed into or substituted by a group P by known methods. For
example, it can be a protected form of group P. Further preferred
groups P* are for example --OH or silyl groups like
--O--Si--R.sup.0R.sup.00R.sup.000, for example
--O--Si(CH.sub.3).sub.3, --O--Si-(isopropyl).sub.3,
--O--Si-(phenyl).sub.3, --O--Si--(CH.sub.3).sub.2(phenyl),
--O--Si(CH.sub.3).sub.2(tert-butyl) or the like, which can be
reacted e.g. into polymerisable (meth)acrylate end groups.
[0093] SCLCPs obtained from the inventive compounds or mixtures by
polymerisation or copolymerisation have a backbone that is formed
by the polymerisable group P.
[0094] The mono-, oligo- and polymers of the present invention can
be synthesized according to or in analogy to methods that are known
or described in the examples
[0095] A further aspect of the invention relates to both the
oxidised and reduced form of the compounds and materials according
to this invention. Either loss or gain of electrons results in
formation of a highly delocalised ionic form, which is of high
conductivity. This can occur on exposure to common dopants.
Suitable dopants and methods of doping are known to those skilled
in the art, e.g. from EP 0 528 662, U.S. Pat. No. 5,198,153 or WO
96/21659.
[0096] The doping process typically implies treatment of the
semiconductor material with an oxidating or reducing agent in a
redox reaction to form delocalised ionic centres in the material,
with the corresponding counterions derived from the applied
dopants. Suitable doping methods comprise for example exposure to a
doping vapor in the atmospheric pressure or at a reduced pressure,
electrochemical doping in a solution containing a dopant, bringing
a dopant into contact with the semiconductor material to be
thermally diffused, and ion-implantation of the dopant into the
semiconductor material.
[0097] When electrons are used as carriers, suitable dopants are
for example halogens (e.g., I.sub.2, Cl.sub.2, Br.sub.2, ICl,
ICl.sub.3, IBr and IF), Lewis acids (e.g., PF.sub.5, AsF.sub.5,
SbF.sub.5, BF.sub.3, BCl.sub.3, SbCl.sub.5, BBr.sub.3 and
SO.sub.3), protonic acids, organic acids, or amino acids (e.g., HF,
HCl, HNO.sub.3, H.sub.2SO.sub.4, HClO.sub.4, FSO.sub.3H and
ClSO.sub.3H), transition metal compounds (e.g., FeCl.sub.3, FeOCl,
Fe(ClO.sub.4).sub.3, Fe(4-OH.sub.3C.sub.6H.sub.4SO.sub.3).sub.3,
TiCl.sub.4, ZrCl.sub.4, HfCl.sub.4, NbF.sub.5, NbCl.sub.5,
TaCl.sub.5, MoF.sub.5, MoCl.sub.5, WF.sub.5, WCl.sub.6, UF.sub.6
and LnCl.sub.3 (wherein Ln is a lanthanoid), anions (e.g.,
Cl.sup.-, Br.sup.-, I.sup.-, I.sub.3.sup.-, HSO.sub.4.sup.-,
SO.sub.4.sup.2-, NO.sub.3.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, AsF.sub.6.sup.-, SbF.sub.6.sup.-, FeCl.sub.4.sup.-,
Fe(CN).sub.6.sup.3-, and anions of various sulfonic acids, such as
aryl-SO.sub.3.sup.-). When holes are used as carriers, examples of
dopants are cations (e.g., H.sup.+, Li.sup.+, Na.sup.+, K.sup.+,
Rb.sup.+ and Cs.sup.+), alkali metals (e.g., Li, Na, K, Rb, and
Cs), alkaline-earth metals (e.g., Ca, Sr, and Ba), O.sub.2,
XeOF.sub.4, (NO.sub.2.sup.+)(SbF.sub.6.sup.-), (NO.sub.2.sup.+)
(SbCl.sub.6.sup.-), (NO.sub.2.sup.+)(BF.sub.4--), AgClO.sub.4,
H.sub.2IrCl.sub.6, La(NO.sub.3).sub.3.6H.sub.2O,
FSO.sub.2OOSO.sub.2F, Eu, acetylcholine, R.sub.4N.sup.+, (R is an
alkyl group), R.sub.4P.sup.+ (R is an alkyl group), R.sub.6As.sup.+
(R is an alkyl group), and R.sub.3S.sup.+ (R is an alkyl
group).
[0098] The conducting form of the compounds and materials of the
present invention can be used as an organic "metal" in
applications, for example, but not limited to, charge injection
layers and ITO planarising layers in organic light emitting diode
applications, films for flat panel displays and touch screens,
antistatic films, printed conductive substrates, patterns or tracts
in electronic applications such as printed circuit boards and
condensers.
[0099] A preferred embodiment of the present invention relates to
mono-, oligo- and polymers of formula I and I1 and their preferred
subformulae that are mesogenic or liquid crystalline, and very
preferably comprise one or more polymerisable groups. Very
preferred materials of this type are monomers and oligomers of
formula I or I1 and their preferred subformulae wherein n is an
integer from 1 to 15 and R.sup.7 and/or R.sup.8 denote P-Sp-.
[0100] These materials are particularly useful as semiconductors or
charge transport materials, as they can be aligned into uniform
highly ordered orientation in their liquid crystal phase by known
techniques, thus exhibiting a higher degree of order that leads to
particularly high charge carrier mobility. The highly ordered
liquid crystal state can be fixed by in situ polymerisation or
crosslinking via the groups P to yield polymer films with high
charge carrier mobility and high thermal, mechanical and chemical
stability.
[0101] For example, if a device is made from a polymerisable liquid
crystal material by polymerisation in situ, the liquid crystal
material preferably comprises one or more mono- or oligomers of
formula I1 and its preferred subformulae wherein one or both of
R.sup.7 and R.sup.8 denote P-Sp-. If a liquid crystal polymer is
prepared first, for example by polymerisation in solution, and the
isolated polymer is used to make the device, the polymer is
preferably made from a liquid crystal material comprising one or
more mono- or oligomers of formula II and its preferred subformulae
wherein one of R.sup.7 and R.sup.8 denotes P-Sp-.
[0102] It is also possible to copolymerise the polymerisable mono-,
oligo- and polymers according to the present invention with other
polymerisable mesogenic or liquid crystal monomers that are known
from prior art, in order to induce or enhance liquid crystal phase
behaviour.
[0103] Thus, another aspect of the invention relates to a
polymerisable liquid crystal material comprising one or more mono-,
oligo- or polymers of the present invention as described above and
below comprising at least one polymerisable group, and optionally
comprising one or more further polymerisable compounds, wherein at
least one of the polymerisable mono-, oligo- and polymers of the
present invention and/or the further polymerisable compounds is
mesogenic or liquid crystalline.
[0104] Particularly preferred are liquid crystal materials having a
nematic and/or smectic phase. For FET applications smectic
materials are especially preferred. For OLED applications nematic
or smectic materials are especially preferred. Especially preferred
are smectic A (S.sub.A) phases, furthermore highly ordered smectic
phases like the S.sub.B, S.sub.E, S.sub.G and S.sub.F phase.
[0105] Another aspect of the present invention relates to an
anisotropic polymer film with charge transport properties
obtainable from a polymerisable liquid crystal material as defined
above that is aligned in its liquid crystal phase into
macroscopically uniform orientation and polymerised or crosslinked
to fix the oriented state.
[0106] Preferably polymerisation is carried out as in-situ
polymerisation of a coated layer of the material, preferably during
fabrication of the electronic or optical device comprising the
inventive semiconductor material. In case of liquid crystal
materials, these are preferably aligned in their liquid crystal
state into homeotropic orientation prior to polymerisation, where
the conjugated pi-electron systems are orthogonal to the direction
of charge transport. This ensures that the intermolecular distances
are minimised and hence then energy required to transport charge
between molecules is minimised. The molecules are then polymerised
or crosslinked to fix the uniform orientation of the liquid crystal
state. Alignment and curing are carried out in the liquid crystal
phase or mesophase of the material. This technique is known in the
art and is generally described for example in D. J. Broer, et al.,
Angew. Makromol. Chem. 183, (1990), 45-66
[0107] Alignment of the liquid crystal material can be achieved for
example by treatment of the substrate onto which the material is
coated, by shearing the material during or after coating, by
application of a magnetic or electric field to the coated material,
or by the addition of surface-active compounds to the liquid
crystal material. Reviews of alignment techniques are given for
example by 1. Sage in "Thermotropic Liquid Crystals", edited by G.
W. Gray, John Wiley & Sons, 1987, pages 75-77, and by T. Uchida
and H. Seki in "Liquid Crystals--Applications and Uses Vol. 3",
edited by B. Bahadur, World Scientific Publishing, Singapore 1992,
pages 1-63. A review of alignment materials and techniques is given
by J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1 (1981),
pages 1-77.
[0108] Polymerisation takes place by exposure to heat or actinic
radiation. Actinic radiation means irradiation with light, like UV
light, IR light or visible light, irradiation with X-rays or gamma
rays or irradiation with high energy particles, such as ions or
electrons. Preferably polymerisation is carried out by UV
irradiation at a non-absorbing wavelength. As a source for actinic
radiation for example a single UV lamp or a set of UV lamps can be
used. When using a high lamp power the curing time can be reduced.
Another possible source for actinic radiation is a laser, like e.g.
a UV laser, an IR laser or a visible laser.
[0109] Polymerisation is preferably carried out in the presence of
an initiator absorbing at the wavelength of the actinic radiation.
For example, when polymerising by means of UV light, a
photoinitiator can be used that decomposes under UV irradiation to
produce free radicals or ions that start the polymerisation
reaction. When curing polymerisable materials with acrylate or
methacrylate groups, preferably a radical photoinitiator is used,
when curing polymerisable materials with vinyl, epoxide and oxetane
groups, preferably a cationic photoinitiator is used. It is also
possible to use a polymerisation initiator that decomposes when
heated to produce free radicals or ions that start the
polymerisation. As a photoinitiator for radical polymerisation for
example the commercially available Irgacure 651, Irgacure 184,
Darocure 1173 or Darocure 4205 (all from Ciba Geigy AG) can be
used, whereas in case of cationic photopolymerisation the
commercially available UVI 6974 (Union Carbide) can be used.
[0110] The polymerisable material can additionally comprise one or
more other suitable components such as, for example, catalysts,
sensitizers, stabilizers, inhibitors, chain-transfer agents,
co-reacting monomers, surface-active compounds, lubricating agents,
wetting agents, dispersing agents, hydrophobing agents, adhesive
agents, flow improvers, defoaming agents, deaerators, diluents,
reactive diluents, auxiliaries, colourants, dyes or pigments.
[0111] Mono-, oligo- and polymers comprising one or more groups
P-Sp- can also be copolymerised with polymerisable mesogenic
compounds to induce or enhance liquid crystal phase behaviour.
Polymerisable mesogenic compounds that are suitable as comonomers
are known in prior art and disclosed for example in WO 93/22397; EP
0,261,712; DE 195,04,224; WO 95/22586 and WO 97/00600.
[0112] Another aspect of the invention relates to a liquid crystal
side chain polymer (SCLCP) obtained from a polymerisable liquid
crystal material as defined above by polymerisation or
polymeranaloguous reaction. Particularly preferred are SCLCPs
obtained from one or more monomers of formula I1 and its preferred
subformulae wherein one or both, preferably one, of R.sup.7 and
R.sup.8 are a polymerisable or reactive group, or from a
polymerisable mixture comprising one or more of said monomers.
[0113] Another aspect of the invention relates to an SCLCP obtained
from one or more monomers of formula I1 and its preferred
subformulae wherein one or both of R.sup.7 and R.sup.8 are a
polymerisable group, or from a polymerisable liquid crystal mixture
as defined above, by copolymerisation or polymeranaloguous reaction
together with one or more additional mesogenic or non-mesogenic
comonomers.
[0114] Side chain liquid crystal polymers or copolymers (SCLCPs),
in which the semiconducting component is located as a pendant
group, separated from a flexible backbone by an aliphatic spacer
group, offer the possibility to obtain a highly ordered lamellar
like morphology. This structure consists of closely packed
conjugated aromatic mesogens, in which very close (typically <4
.ANG.) pi-pi stacking can occur. This stacking allows
intermolecular charge transport to occur more easily, leading to
high charge carrier mobilities. SCLCPs are advantageous for
specific applications as they can be readily synthesized before
processing and then e.g. be processed from solution in an organic
solvent. If SCLCPs are used in solutions, they can orient
spontaneously when coated onto an appropriate surface and when at
their mesophase temperature, which can result in large area, highly
ordered domains.
[0115] SCLCPs can be prepared from the polymerisable compounds or
mixtures according to the invention by the methods described above,
or by conventional polymerisation techniques which are known to
those skilled in the art, including for example radicalic, anionic
or cationic chain polymerisation, polyaddition or polycondensation.
Polymerisation can be carried out for example as polymerisation in
solution, without the need of coating and prior alignment, or
polymerisation in situ. It is also possible to form SCLCPs by
grafting compounds according to the invention with a suitable
reactive group, or mixtures thereof, to presynthesized isotropic or
anisotropic polymer backbones in a polymeranaloguous reaction. For
example, compounds with a terminal hydroxy group can be attached to
polymer backbones with lateral carboxylic acid or ester groups,
compounds with terminal isocyanate groups can be added to backbones
with free hydroxy groups, compounds with terminal vinyl or vinyloxy
groups can be added, e.g., to polysiloxane backbones with Si--H
groups. It is also possible to form SCLCPs by copolymerisation or
polymeranaloguous reaction from the inventive compounds together
with conventional mesogenic or non mesogenic comonomers. Suitable
comonomers are known to those skilled in the art. In principle it
is possible to use all conventional comonomers known in the art
that carry a reactive or polymerisable group capable of undergoing
the desired polymer-forming reaction, like for example a
polymerisable or reactive group P as defined above. Typical
mesogenic comonomers are for example those mentioned in WO
93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586, WO 97/00600 and
GB 2 351 734. Typical non mesogenic comonomers are for example
alkyl acrylates or alkyl methacrylates with alkyl groups of 1 to 20
C atoms, like methyl acrylate or methyl methacrylate.
[0116] The mono-, oligo- and polymers of the present invention are
useful as optical, electronic and semiconductor materials, in
particular as charge transport materials in field effect
transistors (FETs), e.g., as components of integrated circuitry, ID
tags or TFT applications. Alternatively, they may be used in
organic light emitting diodes (OLEDs) in electroluminescent display
applications or as backlight of, e.g., liquid crystal displays, as
photovoltaics or sensor materials, for electrophotographic
recording, and for other semiconductor applications.
[0117] Especially the oligomers and polymers according to the
invention show advantageous solubility properties which allow
production processes using solutions of these compounds. Thus
films, including layers and coatings, may be generated by low cost
production techniques, e.g., spin coating. Suitable solvents or
solvent mixtures comprise alkanes and/or aromatics, especially
their fluorinated derivatives.
[0118] The materials of the present invention are useful as
optical, electronic and semiconductor materials, in particular as
charge transport materials in field effect transistors (FETs), as
photovoltaics or sensor materials, for electrophotographic
recording, and for other semiconductor applications. Such FETs,
where an organic semiconductive material is arranged as a film
between a gate-dielectric and a drain and a source electrode, are
generally known, e.g., from U.S. Pat. No. 5,892,244, WO 00/79617,
U.S. Pat. No. 5,998,804, and from the references cited in the
background and prior art chapter and listed below. Due to the
advantages, like low cost production using the solubility
properties of the compounds according to the invention and thus the
processibility of large surfaces, preferred applications of these
FETs are such as integrated circuitry, TFT-displays and security
applications.
[0119] In security applications, field effect transistors and other
devices with semiconductive materials, like transistors or diodes,
may be used for ID tags or security markings to authenticate and
prevent counterfeiting of documents of value like banknotes, credit
cards or ID cards, national ID documents, licenses or any product
with monetary value, like stamps, tickets, shares, cheques etc.
[0120] Alternatively, the mono-, oligo- and polymers according to
the invention may be used in organic light emitting devices or
diodes (OLEDs), e.g., in display applications or as backlight of
e.g. liquid crystal displays. Common OLEDs are realized using
multilayer structures. An emission layer is generally sandwiched
between one or more electron-transport and/or hole-transport
layers. By applying an electric voltage electrons and holes as
charge carriers move towards the emission layer where their
recombination leads to the excitation and hence luminescence of the
lumophor units contained in the emission layer. The inventive
compounds, materials and films may be employed in one or more of
the charge transport layers and/or in the emission layer,
corresponding to their electrical and/or optical properties.
Furthermore their use within the emission layer is especially
advantageous, if the compounds, materials and films according to
the invention show electroluminescent properties themselves or
comprise electroluminescent groups or compounds. The selection,
characterization as well as the processing of suitable monomeric,
oligomeric and polymeric compounds or materials for the use in
OLEDs is generally known by a person skilled in the art, see, e.g.,
Meerholz, Synthetic Materials, 111-112, 2000, 31-34, Alcala, J.
Appl. Phys., 88, 2000, 7124-7128 and the literature cited
therein.
[0121] According to another use, the inventive compounds, materials
or films, especially those which show photoluminescent properties,
may be employed as materials of light sources, e.g., of display
devices such as described in EP 0 889 350 A1 or by C. Weder et al.,
Science, 279, 1998, 835-837.
[0122] According to another use, the inventive compounds, materials
or films can be used alone or together with other materials in or
as alignment layers in LCD or OLED devices, as described for
example in US 2003/0021913. The use of charge transport compounds
according to the present invention can increase the electrical
conductivity of the alignment layer. When used in an LCD, this
increased electrical conductivity can reduce adverse residual dc
effects in the switchable LCD cell and suppress image sticking or,
for example in ferroelectric LCDs, reduce the residual charge
produced by the switching of the spontaneous polarisation charge of
the ferroelectric LCs. When used in an OLED device comprising a
light emitting material provided onto the alignment layer, this
increased electrical conductivity can enhance the
electroluminescence of the light emitting material. The compounds
or materials according to the present invention having mesogenic or
liquid crystalline properties can form oriented anisotropic films
as described above, which are especially useful as alignment layers
to induce or enhance alignment in a liquid crystal medium provided
onto said anisotropic film. The materials according to the present
invention may also be combined with photoisomerisable compounds
and/or chromophores for use in or as photoalignment layers, as
described in US 2003/0021913.
[0123] According to another use the materials and polymers
according to the present invention, especially their water-soluble
derivatives (for example with polar or ionic side groups) or
ionically doped forms, can be employed as chemical sensors or
materials for detecting and discriminating DNA sequences. Such uses
are described for example in L. Chen, D. W. McBranch, H. Wang, R.
Helgeson, F. Wudi and D. G. Whitten, Proc. Natl. Acad. Sci. U.S.A.
1999, 96, 12287; D. Wang, X. Gong, P. S. Heeger, F. Rininsland, G.
C. Bazan and A. J. Heeger, Proc. Natl. Acad. Sci. U.S.A. 2002, 99,
49; N. DiCesare, M. R. Pinot, K. S. Schanze and J. R. Lakowicz,
Langmuir 2002, 18, 7785; D. T. McQuade, A. E. Pullen, T. M. Swager,
Chem. Rev. 2000, 100, 2537.
[0124] The compounds and materials according to the present
invention can also be used in cosmetic or pharmaceutical
compositions, for example in cosmetic compositions for hair
treatment as disclosed in EP 1 498 112 A2.
[0125] The examples below serve to illustrate the invention without
limiting it. In the foregoing and the following, all temperatures
are given in degrees Celsius, and all percentages are by weight,
unless stated otherwise.
EXAMPLE 1
[0126] Polymer 1 is prepared as described below:
##STR00007##
2,5-Bis(trimethylstannyl)selenophene
[0127] To a solution of selenophene (7.4 g, 56.5 mmol) in a
solution of anhydrous hexane (90 ml) and TMEDA (17.4 g, 150 mmol)
at 0.degree. C. under nitrogen is added a solution of n-BuLi (56 ml
of a 2.5M solution in hexanes, 137.5 mmol) dropwise over 5 min. The
resulting solution is refluxed for 30 min and then cooled to
0.degree. C. and trimethyltin chloride (25.6 g, 129 mmol) is added
at once as a solid. The resulting solution is allowed to warm to
room temperature and stirred at that temperature for 20 h. The
solution is quenched with water (100 ml), and ethyl acetate (100
ml) is added. The layers is separated and the organic layer is
washed with further water (4.times.100 ml), brine (100 ml), dried
(Na.sub.2SO.sub.4), filtered and concentrated under reduced
pressure. The resulting solid is recrystallized form acetonitrile
four times to afford the product as white needles (25.8 g, 83%).
M/Z cluster centred at 456 (M.sup.+). Found C, 26.3; H, 4.6. Calc.
for C.sub.10H.sub.20SeSn.sub.2 C, 26.3; H, 4.2. .sup.1H NMR (300
MHz, CDCl.sub.3) .delta. 7.68 (s, 2H), 0.37 (s, 18H). .sup.13C NMR
(75 MHz, CDCl.sub.3) .delta. 150.2, 138.7, -7.7.
5,5'-Dibromo-4,4'-bis(decyl)-2,2'-bithiophene
[0128] 4,4'-Bis(decyl)-2,2'-bithiophene is prepared in analogy to
the published procedure (see M. Zagorska and B. Krische Polymer,
1990, 31, p 1379).
[0129] To a solution of 4,4'-bis(decyl)-2,2'-bithiophene (6.60 g,
14.8 mmol) in chloroform (100 ml) and glacial acetic acid (100 ml)
at 5.degree. C. in the dark is added N-bromosuccinimide (5.40 g, 30
mmol) portionwise over 1 h. The resulting solution is warmed to
20.degree. C. and stirred for a further 16 h. The solvent is
removed under reduced pressure and the residue suspended in MTBE
(200 ml). Filtration of the solution removed succinimide byproduct.
The filtrate is washed with 5% sodium carbonate (100 ml), water
(100 ml) and brine (100 ml), dried (sodium sulfate), filtered and
concentrated under reduced pressure. The resulting crude product is
further purified by reverse phase column chromatography over RP18
silica (23 g) eluting with acetonitrile/THF 2:1. A final
recrystallisation from ethyl acetate affords the product (2.94 g).
HRMS 602.1248 (calc. for C.sub.28H.sub.44S.sub.2Br.sup.79.sub.2
602.1251). .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 6.77 (s, 2H),
2.70 (t, 4H), 1.57 (quint, 4H), 1.28 (m, 28H), 0.88 (t, 6H).
.sup.13C NMR (75 MHz, CDCl.sub.3) .delta. 143.0, 136.1, 124.5,
107.9, 31.9, 29.62, 29.57, 29.40, 29.35, 29.2, 22.7, 14.2.
Poly(2,5-bis(3-decylthiophen-2-yl)selenophene) [1]
[0130] A 20 ml glass vial is charged with a stirrer bar,
5,5'-dibromo-4,4'-bis(decyl)-2,2'-bithiophene (604.6 mg, 1 mmol),
2,5-bis-trimethylstannylselenophene (456.6 mg, 1 mmol),
tris(dibenzylideneacetone)dipalladium (0) (18.3 mg, 0.02 mmol, 4
mol % Pd), tri(o-tolyl)phosphine (24.4 mg, 0.08 mmol, 8 mol %) and
chlorobenzene (15 ml). The glass vial is purged with nitrogen and
securely sealed. The glass vial is placed into a microwave reactor
(Emrys Creator, Personal Chemistry Ltd) and heated sequentially to
140.degree. C. for 1 min, then 160.degree. C. for 1 min and finally
to 185.degree. C. for 20 min. After cooling to RT, the reaction
mixture is precipitated into a mixture of methanol (150 mL) and 37%
hydrochloric acid (15 mL), and stirred for 14 h. The polymer is
filtered, washed with methanol, and dried under vacuum. The polymer
is washed (via Soxhlet extraction) with methanol ((6 h), acetone
(24 h) and hexane (24 h). The resulting polymer is dissolved in hot
chloroform (50 ml), filtered and precipitated into methanol, to
afford the product (540 mg). GPC (Chlorobenzene, 60.degree. C.) Mn
(127,100 g/mol), Mw (58,700 g/mol). .lamda..sub.max 570 nm (solid
film). .sup.1H NMR (300 MHz, 50.degree. C., CDCl.sub.3) .delta.
7.25 (s, 2H, obscured by CHCl.sub.3 peak) 7.01 (s, 2H), 2.76 (t,
4H), 1.70 (m, 4H), 1.45-1.20 (m, 28H), 0.88 (t, 6H).
EXAMPLE 2
[0131] Polymer 2 is prepared as described below:
##STR00008##
5,5'-Dibromo-4,4'-bis(dodecyl)-2,2'-bithiophene
[0132] 4,4'-Bis(dodecyl)-2,2'-bithiophene is prepared in analogy to
the published procedure (see M. Zagorska and B. Krische Polymer,
1990, 31, p 1379).
[0133] To a solution of 4,4'-bis(dodecyl)-2,2'-bithiophene (28.8 g,
57.3 mmol) in chloroform (200 ml) and glacial acetic acid (200 ml)
at 25.degree. C. in the dark is added N-bromosuccinimide (19.88 g,
111.7 mmol) portionwise over 1 h. The resulting solution is stirred
for 6 h. The solvent is removed under reduced pressure and the
residue dissolved in a mixture of dichloromethane (1000 ml) and
water (500 ml). The organic layer is separated and the aqueous
layer extracted with dichloromethane (500 ml). The combined
organics were washed with 5% sodium carbonate (500 ml), water (500
ml) and brine (500 ml), dried (sodium sulfate), filtered and
concentrated under reduced pressure. The resulting crude product is
filtered through a plug of silica (eluent: petrol 40-60.degree. C.)
and concentrated under reduced pressure. Recrystallisation from
butanone afforded the product (43.1 g, 73%) as pale yellow
crystals. M/Z 660 (M+). Found C, 58.1; H, 7.9; S, 9.2. Calc. for
C.sub.32H.sub.52S.sub.2Br.sub.2 C, 58.2; H, 7.9; S, 9.7. .sup.1H
NMR (300 MHz, CDCl.sub.3) .delta. 6.77 (s, 2H), 2.51 (t, 4H), 1.57
(quint, 4H), 1.28 (m, 36H), 0.88 (t, 6H). .sup.13C NMR (75 MHz,
CDCl.sub.3) .delta. 142.8, 136.0, 124.3, 107.7, 31.8, 29.6 (2C),
29.5 (4C), 29.2 (2C), 29.0, 22.6, 14.0.
Poly(2,5-bis(3-dodecylthiophen-2-yl)selenophene) [2]
[0134] A 20 ml glass vial is charged with a stirrer bar,
5,5'-dibromo-4,4'-bis(dodecyl)-2,2'-bithiophene (660.7 mg, 1 mmol),
2,5-bis-trimethylstannylselenophene (466.6 mg, 1 mmol),
tris(dibenzylideneacetone)dipalladium (0) (18.3 mg, 0.02 mmol, 4
mol % Pd), tri(o-tolyl)phosphine (24.4 mg, 0.08 mmol, 8 mol %) and
chlorobenzene (15 ml). The glass vial is purged with nitrogen and
securely sealed. The glass vial is placed into a microwave reactor
(Emrys Creator, Personal Chemistry Ltd) and heated sequentially to
140.degree. C. for 1 min, then 160.degree. C. for 1 min and finally
to 180.degree. C. for 15 min. After cooling to RT, the reaction
mixture is precipitated into a mixture of methanol (150 mL) and 37%
hydrochloric acid (15 mL), and stirred for 14 h. The polymer is
filtered, washed with methanol, and dried under vacuum. The polymer
is washed (via Soxhlet extraction) with methanol (6 h), acetone (24
h) and hexane (24 h). The resulting polymer is dissolved in hot
chlorobenzene (50 ml), filtered through a plug of silica (2 g) and
precipitated into methanol at 60.degree. C., to afford the product
(466 mg). GPC (Chlorobenzene, 60.degree. C.) Mn (23,800 g/mol), Mw
(46,400 g/mol). .lamda..sub.max (solid film) 572, 620 (sh) nm.
.lamda..sub.max (CHCl.sub.3) 486 nm. .sup.1H NMR (300 MHz,
50.degree. C., CDCl.sub.3) .delta. 7.25 (s, 2H, obscured by
CHCl.sub.3 peak) 7.01 (s, 2H), 2.75 (t, 4H), 1.70 (m, 4H),
1.45-1.20 (m, 36H), 0.87 (t, 6H).
EXAMPLE 3
[0135] Polymer 3 is prepared as described below:
##STR00009##
4,4'-Bis(hexyl)-2,2'-biselenophene
[0136] 3-Hexylselenophene is prepared according to the published
procedure (C. Mahatsekake et al, Phosphorus, Sulfur and Silicon,
1990, 47, 35-41; 1.0 g, 4.64 mmol)
[0137] To a solution of 3-hexylselenophene (4.30 g, 20 mmol) and
N,N,N',N'-tetramethylethylenediamine (2.44 g, 21 mmol) in anhydrous
THF (25 ml) at -40.degree. C. is added n-BuLi (8.5 ml of a 2.5M
solution in hexanes, 21.3 mmol). The solution is allowed to warm to
25.degree. C. over 30 min, and stirred at 25.degree. C. for 45 min.
The resulting solution is cooled to -20.degree. C. and copper(II)
chloride (2.96 g, 22 mmol) is added at once as a solid. The
reaction is stirred at 25.degree. C. for a further 16 h, and
quenched by the addition of 5% HCl (50 ml). The organics were
extracted with ethyl acetate (3.times.50 ml). The combined organics
were washed with 5% HCl (2.times.50 ml), water (50 ml) and
saturated sodium chloride (50 ml), dried (Na.sub.2SO.sub.4),
filtered and concentrated under reduced pressure. The resulting oil
is further purified by column chromatography over silica (eluant:
petrol 40-60.degree. C.). The first fraction contained
3-hexylselenophene and the second fraction contained the product.
Rexstallisation from THF/acetonitrile at -70.degree. C. afforded
the product as a white solid, M/Z 430 (M+). 114 NMR (300 MHz,
CDCl.sub.3) .delta. 7.36 (s, 2H), 7.11 (s, 2H), 2.52 (t, 4H), 1.60
(quint, 4H), 1.30 (m, 12), 0.89 (t, 6H). .sup.13C NMR (75 MHz,
CDCl.sub.3) .delta. 145.9, 144.0, 128.3, 122.9, 32.3, 31.7, 30.2,
29.0, 22.7, 14.2.
5,5'-Dibromo-4,4'-bis(hexyl)-2,2'-biselenophene
[0138] To a solution of 4,4'-bis(hexyl)-2,2'-biselenophene (1.0 g,
2.33 mmol) in tetrahydrofuran (25 ml) at 25.degree. C. in the dark
is added N-bromosuccinimide (0.84 g, 4.72 mmol) in two portions
over 30 min. The resulting solution is stirred for 6 h. The solvent
is removed under reduced pressure and the residue dissolved in
ethyl acetate (50 ml) washed with water (2.times.30 ml) and
saturated sodium chloride (30 ml), filtered and concentrated under
reduced pressure. The resulting crude product is filtered through a
plug of silica (eluent: petrol 40-60.degree. C.) and concentrated
under reduced pressure. Recrystallisation from ethanol afforded the
product (0.75 g, 55%) as white crystals. M/Z triplet centred at 456
(M.sup.+). .sup.1H NMR (300 MHz, CDCl3) .delta. 6.84 (s, 2H), 2.48
(t, 4H), 1.55 (quint, 4H), 1.3 (m, 12H), 0.89 (t, 6H). .sup.13C NMR
(75 MHz, CDCl.sub.3) .delta. 145.3, 142.9, 127.7, 110.3, 31.6,
30.9, 39.6, 29.6, 22.6, 14.2.
Poly(2,5-bis(3-hexylselophen-2-yl)thiophene) [3]
[0139] A 10 ml glass vial is charged with a stirrer bar,
5,5'-dibromo-4,4'-bis(hexyl)-2,2'-biselenophene (300 mg, 0.512
mmol), 2,5-bis-trimethylstannylthiophene (209.7 mg, 0.512 mmol),
tris(dibenzylideneacetone)dipalladium (0) (9.37 mg, 0.01 mmol, 4
mol % Pd), tri(o-tolyl)phosphine (12.46 mg, 0.04 mmol, 8 mol %) and
chlorobenzene (5 ml). The glass vial is purged with nitrogen and
securely sealed. The glass vial is placed into a microwave reactor
(Emrys Creator, Personal Chemistry Ltd) and heated sequentially to
140.degree. C. for 1 min, then 160.degree. C. for 1 min and finally
to 180.degree. C. for 15 min. After cooling to RT, the reaction
mixture is precipitated into a mixture of methanol (50 mL) and 37%
hydrochloric acid (5 mL), and stirred for 14 h. The polymer is
filtered, washed (via Soxhlet extraction) with methanol (6 h),
acetone (24 h) and isohexane (24 h). The resulting polymer is
dissolved in hot chloroform and precipitated into methanol to
afford the product (210 mg). GPC (Chlorobenzene, 60.degree. C.) Mn
(12,700 g/mol), Mw (26,000 g/mol). .lamda..sub.max (solid film)
550, 578 (sh), 628 (sh) nm. .lamda..sub.max (CHCl.sub.3) 483 nm.
.sup.1H NMR (300 MHz, 50.degree. C., CDCl.sub.3) .delta. 7.11 (s,
2H), 7.01 (s, 2H), 2.73 (t, 4H), 1.68 (m, 4H), 1.45-1.20 (m, 12H),
0.90 (t, 6H).
EXAMPLE 4
[0140] Polymer 4 is prepared as described below:
##STR00010##
Poly(2,5-bis(3-hexylselophen-2-yl)thiophene) [1]
[0141] A 10 ml glass vial is charged with a stirrer bar,
5,5'-dibromo-4,4'-bis(hexyl)-2,2'-biselenophene (300 mg, 0.512
mmol), 5,5'-bis-trimethylstannyl-[2,2']bithiophenyl (251.7 mg,
0.512 mmol), tris(dibenzylideneacetone)dipalladium (0) (9.37 my,
0.01 mmol, 4 mol % Pd), tri(o-olyl)phosphine (12.46 mg, 0.04 mmol,
8 mol %) and chlorobenzene (6 ml). The glass vial is purged with
nitrogen and securely sealed. The glass vial is placed into a
microwave reactor (Emrys Creator, Personal Chemistry Ltd) and
heated sequentially to 140.degree. C. for 1 min, then 160.degree.
C. for 1 min and finally to 190.degree. C. for 15 min. After
cooling to RT, the reaction mixture is precipitated into a mixture
of methanol (50 mL) and 37% hydrochloric acid (5 mL), and stirred
for 14 h. The polymer is filtered, washed (via Soxhlet extraction)
with methanol (6 h), acetone (16 h) and isohexane (16 h). The
resulting polymer is dissolved in hot chloroform and precipitated
into methanol to afford the product (230 mg). GPC (Chlorobenzene,
60.degree. C.) Mn (18,500 g/mol), Mw (40,700 g/mol).
.lamda..sub.max 544 nm (solid film). .lamda..sub.max 482 nm
(CHCl.sub.3) .sup.1H NMR (300 MHz, F 50.degree. C., CDCl.sub.3)
.delta. 7.11 (br s, 4H), 6.98 (d, 2H), 2.73 (t, 4H), 1.68 (m, 4H),
1.45-1.20 (m, 12H), 0.90 (t, 6H).
EXAMPLE 5
[0142] Polymer 5 is prepared as described below:
##STR00011##
Poly(2,5-bis(3,4-didecylthiophen-2-yl)selenophene) [5]
[0143] A 10 ml glass vial is charged with a stirrer bar,
2,5-dibromo-3,4,-didecylthiophene (100 mg, 0.19 mmol),
2,5-bis-trimethylstannylselenophene (87.2 mg, 0.191 mmol),
tris(dibenzylideneacetone)dipalladium (0) (3.5 mg, 0.004 mmol, 4
mol % Pd), tri(o-tolyl)phosphine (4.65 mg, 0.016 mmol, 8 mol %) and
chlorobenzene (3 ml). The glass vial is purged with nitrogen and
securely sealed. The glass vial is placed into a microwave reactor
(Emrys Creator, Personal Chemistry Ltd) and heated sequentially to
140.degree. C. for 2 min, then 160.degree. C. for 2 min and finally
to 180.degree. C. for 15 min. After cooling to RT, the reaction
mixture is precipitated into a mixture of methanol (75 mL) and 37%
hydrochloric acid (25 mL), and stirred for 1.5 h. The polymer is
filtered, washed (via Soxhlet extraction) with acetone (4 h). The
resulting polymer is extracted with chloroform and concentrated
under reduced pressure to afford the product (60 mg), GPC
(Chlorobenzene, 60.degree. C.) Mn (4,700 g/mol), Mw (7,000 g/mol).
.lamda..sub.max 514 nm (solid film), .lamda..sub.max (CHCl.sub.3)
454 nm .sup.1H NMR (300 MHz, THF-d.sub.8) .delta. 7.33 (br S, 2H),
2.77 (br t, 4H), 1.63 (m, 4H), 1.4-1.2 (m, 28H), 0.9 (br t,
6H).
Transistor Fabrication and Measurement:
[0144] Thin-film organic field-effect transistors (OFETs) are
fabricated on highly doped silicon substrates with thermally grown
silicon oxide (SiO.sub.2) insulating layer, where the substrate
served as a common gate electrode. Transistor source-drain gold
electrodes are photolithographically defined on the SiO.sub.2
layer. Prior to organic semiconductor deposition, FET substrates
are treated with a silylating agent hexamethyldisilazane (HMDS) or
octyltrichlorosilane (OTS). Thin semiconductor films are then
deposited by spin-coating polymer solutions in chloroform, xylene,
chlorobenzene or dichlorobenzene (0.4-1.0 wt %) on FET substrates.
The electrical characterization of the transistor devices, is
carried out under ambient atmosphere using computer controlled
Agilent 4155C Semiconductor Parameter Analyser.
[0145] Transistor characteristics are measured on films prepared by
spin coating. The films are heated to 100.degree. C. for 10 min
under nitrogen to remove residual solvent, and then cooled to room
temperature to measure the transistor characteristics.
[0146] FIG. 1 shows the current (I)-voltage (V) transfer
characteristics of example 1 in a transistor device with 10 micron
channel length and 20,000 micron channel width. The transistor gate
voltage (V.sub.g) is varied between 40 and -60 volts for two
different setting of Source--Drain voltage (V.sub.sd). The I.sub.sd
is plotted versus V.sub.g for V.sub.sd=-5V (line a) and -60 V (line
b), respectively.
[0147] The devices show typical p-type behaviour with good current
modulation, and well-defined linear and saturation regimes. Field
effect mobility is calculated in the saturation regime
(V.sub.d>(V.sub.d-V.sub.0)) using equation (1):
( I d sat V g ) V d = WC i L .mu. sat ( V g - V 0 ) ( 1 )
##EQU00001##
where W is the channel width, L the channel length, C.sub.j the
capacitance of insulating layer, V.sub.g the gate voltage, V.sub.d
the drain voltage, I.sub.d is the drain current, V.sub.0 the
turn-on voltage and .mu..sup.sat is the saturated charge carrier
mobility. The turn-on voltage (V.sub.0) is determined as the onset
of source-drain current (FIG. 1). The mobility values for compounds
I-3 are summarised in table 1.
TABLE-US-00001 TABLE 1 Summary of the electrical data for polymers
1-3. Compound .mu..sup.sat (cm.sup.2/Vs) .mu..sup.lin (cm.sup.2/Vs)
On/off 1 0.1 0.04 10.sup.6 2 0.18 0.07 10.sup.6 3 0.01 0.004
10.sup.6
* * * * *