U.S. patent application number 11/846809 was filed with the patent office on 2008-03-06 for electronic device, method, monomer and polymer.
This patent application is currently assigned to KONINKLIJKE PHILIPS ELECTRONICS, N.V.. Invention is credited to Dagobert Michel DE LEEUW, Bart-Hendrik HUISMAN, Johan LUB.
Application Number | 20080058500 11/846809 |
Document ID | / |
Family ID | 27838095 |
Filed Date | 2008-03-06 |
United States Patent
Application |
20080058500 |
Kind Code |
A1 |
HUISMAN; Bart-Hendrik ; et
al. |
March 6, 2008 |
ELECTRONIC DEVICE, METHOD, MONOMER AND POLYMER
Abstract
The electronic device of the invention comprises one or more
active elements, each comprising a first and a second electrode and
an active layer of organic material separating the first and second
electrodes. Examples of active elements are thin-film transistors
and light-emitting diodes. The active layer comprises a polymeric
material having conjugated units A and non-conjugated intermediate
units B, which intermediate units B separate the conjugated units A
from each other, such that no conjugation extends from a first
conjugated unit A.sub.1 to a second conjugated unit A.sub.2. The
polymeric material may be a polymer network, an alternating
copolymer or a polymer in which the conjugated units are present in
side chains. The polymer can be prepared from monomers having a
B.sub.1-A.sub.1-B.sub.2 structure, wherein at least one of B.sub.1
and B.sub.2 comprises a reactive group enabling polymerization.
Inventors: |
HUISMAN; Bart-Hendrik;
(Eindhoven, NL) ; DE LEEUW; Dagobert Michel;
(Eindhoven, NL) ; LUB; Johan; (Eindhoven,
NL) |
Correspondence
Address: |
PHILIPS INTELLECTUAL PROPERTY & STANDARDS
P.O. BOX 3001
BRIARCLIFF MANOR
NY
10510
US
|
Assignee: |
KONINKLIJKE PHILIPS ELECTRONICS,
N.V.
GROENEWOUDSEWEG 1
EINDHOVEN
NL
5621 BA
|
Family ID: |
27838095 |
Appl. No.: |
11/846809 |
Filed: |
August 29, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10507342 |
Sep 10, 2004 |
7279702 |
|
|
11846809 |
Aug 29, 2007 |
|
|
|
Current U.S.
Class: |
528/417 |
Current CPC
Class: |
H01L 51/0003 20130101;
C08G 61/02 20130101; H01L 51/0036 20130101; H01L 51/0545 20130101;
H01L 51/5012 20130101 |
Class at
Publication: |
528/417 |
International
Class: |
C08G 83/00 20060101
C08G083/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 15, 2002 |
EP |
02076053.4 |
Mar 12, 2003 |
IB |
PCT/IB03/01062 |
Claims
1. An electronic device provided with an active element having a
first and a second electrode, which are separated from each other
by an active layer containing a semiconductive or
electroluminescent organic material, characterized in that the
organic material of an active layer is a polymer comprising
conjugated conjugation units which are separated from each other by
non-conjugated intermediate units B in such a manner that the
conjugation of the first and the second conjugation unit A.sub.1,
A.sub.2 is interrupted in an intermediate unit B.sub.1.
2. An electronic device as claimed in claim 1, characterized in
that the polymer is polymer network comprising a first and a second
main chain which are interconnected via side chains, a side chain
containing a B.sub.1-A.sub.1-B.sub.2 structure, with B.sub.1,
B.sub.2 being intermediate units and Al being a conjugation
unit.
3. An electronic device as claimed in claim 1, characterized in
that the polymer is a copolymer comprising a main chain, the
intermediate units B and the conjugation units A being present in
the main chain as alternating units . . .
-A.sub.1-B.sub.1-A.sub.2-B.sub.2- . . . .
4. An electronic device as claimed in claim 1, characterized in
that the polymer comprises a main chain with side chains, a side
chain containing a B.sub.1-A.sub.1-B.sub.2- structure, wherein
B.sub.1, B.sub.2 are intermediate units and Al is a conjugation
unit.
5. An electronic device as claimed in claim 1, characterized in
that the intermediate unit B.sub.1 comprises a mesogenic group.
6. An electronic device as claimed in any one of the preceding
claims, characterized in that the conjugation unit is a unit of
formula Y.sub.n, wherein 2.ltoreq.n.ltoreq.8 and Y is selected from
the group composed of ##STR4## wherein Ar is an aromatic ring
system with 4 to 6 carbon atoms that may be substituted with a
substituent selected from the group composed of an unbranched
C.sub.1-C.sub.20-alkyl-, C.sub.3-C.sub.20-alkoxy-,
C.sub.1-C.sub.20-alkylsulphate-, a branched
C.sub.3-C.sub.20-alkyl-, phenyl or benzyl group, and that may
comprise up to 4 heteroatoms selected from the group composed of
oxygen, sulfur and nitrogen in the aromatic ring system, and
R.sub.2 and R''.sub.2 are selected from the group composed of a
hydrogen atom and a C.sub.1-C.sub.20alkyl- and a
C.sub.4-C.sub.20-aryl group, which groups may comprise
substituents.
7. An electronic device as claimed in claim 1, characterized in
that a second active element is present, which contains a first and
a second electrode which are mutually separated by the active
layer, and in that the active layer has a relief structure, so that
the active layer between the first and the second active element is
removed.
8. An electronic device as claimed in claim 1 or 7, characterized
in that the active element is a transistor wherein a third
electrode is present which is separated from the active layer by a
dielectric, and wherein the active layer comprises an intrinsic,
undoped semiconductive material.
9. A method of preparing a polymer comprising conjugated
conjugation units A and non-conjugated intermediate units B, an
intermediate unit B.sub.1 mutually separating a first and a second
conjugation unit A.sub.1, A.sub.2 in such a manner that the
conjugation of the first and the second conjugation unit A.sub.1,
A.sub.2 is interrupted in the intermediate unit B.sub.1,
characterized in that the polymer is prepared from a monomer having
a B.sub.1-A.sub.1-B.sub.2 structure, wherein at least one of the
groups B.sub.1, B.sub.2 comprises a reactive end group.
10. A monomer having a B.sub.1-A.sub.1-B.sub.2 structure, wherein
A.sub.1 is a conjugated unit of formula Y.sub.n, wherein
2.ltoreq.n.ltoreq.8 and Y is selected from the group composed of
##STR5## wherein Ar is an aromatic ring system with 4 to 6 carbon
atoms that may be substituted with a substituent selected from the
group composed of an unbranched C.sub.1-C.sub.20-alkyl-,
C.sub.3-C.sub.20-alkoxy-, C.sub.1-C.sub.20-alkyl sulphate-, a
branched C.sub.3-C.sub.20-alkyl-, phenyl- or benzyl group, and that
may contain up to 4 heteroatoms selected from the group composed of
oxygen, sulfur and nitrogen in the aromatic ring system, and
R.sub.2 and R''.sub.2 are selected from the group composed of a
hydrogen atom and a C.sub.1-C.sub.20-alkyl- and a
C.sub.4-C.sub.20-aryl group, which groups may comprise
substituents, and wherein B.sub.1, B.sub.2 are non-conjugated
groups.
11. A method as claimed in claim 9, characterized in that the
monomer used is the monomer as claimed in claim 10.
12. A polymer that can be obtained by means of the method as
claimed in claim 9.
Description
[0001] The invention relates to an electronic device provided with
an active element having a first and a second electrode, which are
separated from each other by an active layer containing a
semiconductive or electroluminescent organic material.
[0002] The invention also relates to a method of preparing a
polymer comprising conjugated conjugation units A and
non-conjugated intermediate units B, an intermediate unit B.sub.1
mutually separating a first and a second conjugation unit A.sub.1,
A.sub.2 in such a manner that the conjugation of the first and the
second conjugation unit A.sub.1, A.sub.2 is interrupted in the
intermediate unit B.sub.1.
[0003] The invention also relates to a monomer and to a
polymer.
[0004] Such a device is known from, inter alia, WO-A 01/92369. This
device comprises an active layer of polyphenylene-vinylene--PPV-,
polythienylene-vinylene--PTV- or a similar material. PPV is a
material having electroluminescent properties that is employed in
display screens with light-emitting diodes as the active elements.
PTV is a material having semiconductive properties that is used in
transponders and liquid crystalline display screens with
transistors as the active elements.
[0005] A drawback of the known device resides in that the active
layer is very sensitive to oxygen and moisture. This adversely
affects the service life of the device unless the device is very
well encapsulated. Such an encapsulation is expensive however and
adversely affects the flexibility. Devices comprising active layers
of an oligomer material that is less sensitive to the influence of
air and moisture, such as pentacene, are known from, for example,
Brown et al., Synt. Met. 88 (1997), 37-55. However such a material
is poorly processable from solution, as is also indicated by Brown
et al.
[0006] Therefore a first object of the invention is to provide an
electronic device of the type mentioned in the opening paragraph,
the active layer of which has an improved stability with respect to
air, light and moisture and is also readily processable from
solution.
[0007] This first object is achieved in that the organic material
of an active layer is a polymer comprising conjugated conjugation
units which are separated from each other by non-conjugated
intermediate units B in such a manner that the conjugation of the
first and the second conjugation unit A.sub.1, A.sub.2 is
interrupted in an intermediate unit B.sub.1.
[0008] The device comprises an active layer wherein in fact
oligomers are incorporated in a polymer matrix. The conjugation of
the conjugation units is interrupted by the intermediate units. By
conjugation of the conjugated units is meant that delocalized 7
orbitals are present which spread over various atoms. This forms
the basis of the electroluminescent and semiconductive behavior,
which is not observed in polymers without conjugation. The
localization enables the electrons in the delocalized orbitals to
move, which occurs when there is a voltage difference between the
first and the second electrode. The mobility is comparatively low
because "hopping" between the polymer chains should take place.
This explanation is confirmed by the fact that higher mobilities
were found for crystalline oligomers. The active layer of the
invention shows the electroluminescent and semiconductive behavior
as well, even though iys conjugation is interrupted.
[0009] It has been found that the active layer in the device in
accordance with the invention is not, or hardly, sensitive to the
influence of light, air and moisture, and that in addition said
layer can be readily processed from solution. Besides, by using
this active layer an active element is obtained which is sensitive
to the voltages applied. In particular, a transistor is obtained
which can be turned on and off.
[0010] Polymers comprising conjugated conjugation units A and
non-conjugated intermediate units B, with an intermediate unit
B.sub.1 mutually separating a first and a second conjugation unit
A.sub.1, A.sub.2 in such a manner that the conjugation of the first
and the second conjugation unit A.sub.1, A.sub.2 is interrupted in
the intermediate unit B.sub.1 are known per se, for example, from
Polymer 41 (2000), 5681-5687 and from Synt. Met. 81 (1996),
157-162. Said known polymers are only known, however, for their
electrochromic properties. Besides, all of the known polymers are
doped. In the device in accordance with the invention, however, the
organic material is not doped, because doping of the organic
semiconducive material is undesirable. This can be elucidated by
means of an example of a transistor: at a voltage difference
between the first and the second electrode--the source and the
drain electrode--a current will flow through the active layer in
this element. However, this current can be suppressed by applying a
voltage to a third electrode, i.e. the gate electrode. The active
layer will then go into a state of depletion, causing the
resistance of the active layer to increase substantially. Owing to
the presence of charge carriers due to the doping, it is no longer
possible, however, to suppress current in the active layer by means
of said gate electrode.
[0011] The intermediate units and the conjugation units in the
polymeric material of the active layer can be distributed in
various ways. The polymer may be a polymer network comprising a
first and a second main chain which are interconnected via side
chains, a side chain containing a B.sub.1-A.sub.1-B.sub.2
structure, with B.sub.1, B.sub.2 being intermediate units and
A.sub.1 being a conjugation unit. Such a polymer network can be
prepared from monomers with a B.sub.1-A.sub.1-B.sub.2 structure,
wherein both intermediate units B.sub.1, B.sub.2 contain a reactive
group. The reactive group, such as an acrylate or an epoxide, can
react with a reactive group in the polymer that is used for the
main chain. Alternatively, the polymerization in the main chain may
take place during or after the formation of the side chains. A
polymer network has the advantage that it can be excellently
structured.
[0012] Alternatively, the polymer may be a copolymer comprising a
main chain, the intermediate units B and the conjugation units A
being present in the main chain as alternating units . . .
-A.sub.1-B.sub.1-A.sub.2-B.sub.2 . . . . This copolymer has the
advantage, inter alia, that it can be readily processed and that it
enables p-type and n-type-conjugated units to be combined.
[0013] It is additionally possible for the polymer to comprise a
main chain with side chains, a side chain containing a
B.sub.1-A.sub.1-B.sub.2- structure, wherein B.sub.1, B.sub.2 are
intermediate units and A.sub.1 is a conjugation unit. This type of
polymer has the advantage that it permits a high mobility. If there
is sufficient flexibility in the intermediate units B.sub.1,
B.sub.2 and steric hindrance between the different conjugation
units A.sub.1 is substantially or completely precluded, the chains
may become ordered relative to each other. As a result of said
increased degree of order, the distance between neighboring polymer
chains is reduced and hence there is a lower energy barrier for
"hopping" of electrons from a first to a second chain, with the
accompanying increase in mobility.
[0014] Advantageously, the intermediate unit B.sub.1 comprises a
mesogenic group. Mesogenic groups are known per se and comprise,
for example, cyano or alkoxy biphenyl groups which are coupled by
an ether or an ester group to an atom. The advantage of such
mesogenic groups is that they exhibit liquid crystalline behavior.
This enables the conjugation units to be aligned. By means of a
subsequent cross-linking operation, the mesogenic groups are fixed
in the desired position with the desired order of the aligned
conjugation units. However, it has surprisingly been found that the
bisacrylates themselves show liquid crystalline behavior already,
even without the presence of additional mesogenic groups, if the
alkyl chain in the `intermediate unit` B.sub.1,B.sub.2 has a chain
length of 6 or more, i.e. the alkyl chain is hexyl, heptyl, octyl,
or longer. The liquid crystalline properties indicate that
higher-order phases can be obtained for these compounds and hence a
higher mobility can be achieved.
[0015] In principle, each oligomeric unit can suitably be used as a
conjugation unit. Examples thereof are given in Katz et al., Acc.
Chem. Res. 34 (2001), 359-369. The conjugation units may be n-type
conductive or p-type conductive. Suitable conjugation units are,
inter alia, units of formula Y.sub.n, wherein 2.ltoreq.n.ltoreq.8
and Y is selected from the group ##STR1## wherein [0016] Ar is an
aromatic ring system with 4 to 6 carbon atoms that may be
substituted with a substituent selected from the group composed of
an unbranched C.sub.1-C.sub.20-alkyl-, C.sub.3-C.sub.20-alkoxy-,
C.sub.1-C.sub.20-alkyl sulfate-, a branched
C.sub.3-C.sub.20-alkyl-, phenyl or benzyl or alkaryl or aralkyl
group, and that may comprise up to 4 heteroatoms selected from the
group composed of oxygen, sulfur and nitrogen in the aromatic ring
system, and
[0017] R.sub.2 and R''.sub.2 are selected from the group composed
of a hydrogen atom and a C.sub.1-C.sub.20alkyl- and a
C.sub.4-C.sub.20-aryl group, and alkaryl and arakylgroups which
groups may contain substituents.
[0018] Particularly suitable examples of said conjugation units are
units on the basis of thienyl and phenyl groups comprising 3-6
groups per unit. Such units correspond to oligomers such as
sexithiophene and pentacene. Any further side chains may be chosen
and used to improve the solubility and further properties, as is
known the skilled person. Such sidechains might further be
functionalized.
[0019] Intermediate units are preferably alkyl groups with a chain
length of the order of 4-20 units. Alternatively phenyl groups,
toluyl-, benzyl- and other alkaryl and aralkyl groups can be
applied. It is favorable for the chain length of the intermediate
units to fairly correspond to the chain length of an adjoining
conjugation unit. The chain length is an optimum between the
processability and stability requirements. It is not necessary for
all intermediate units to have the same chain length; on the
contrary, in the case of a polymer in which the conjugation units
are mainly present in side chains, it is advantageous if there is
some spread in the chain length of the intermediate units. This
spread precludes steric hindrance. The intermediate units may
comprise customary side chains to influence solubility and
reactivity. Measurements of characteristics of transistors
comprising the monomer units as semiconductor material show that
the length of the alkyl spacer group has a minor effect on the
transistor characteristics. The characteristics improve slightly
with increasing spacer length. However, from a theoretical point of
view, this appears to be bound to a maximum; the conjugated
oligomer parts A.sub.1 of the molecules should be in contact with
other oligomer groups A.sub.1, A.sub.x, particularly in other
molecules, to allow movement of charge carriers through the
material.
[0020] Reactive end groups at the intermediate units may lead to
polymerization. Dependent upon the type of end group, radical
polymerization, anionic or cationic polymerization or condensation
polymerization may take place. In the case of condensation
polymerization, for example, a mixture of bisalcohols and
bisacrylic acids is polymerized. An example of a suitable end group
is R--O--C(O)--CH.sub.2.dbd.CH.sub.2, wherein R indicates the alkyl
residue of the intermediate unit. The attachment of an acrylate
group apparently does not dramatically affect the semiconductor
properties of the monomer units, even though oxygen atoms, which
are rich in electrons, are introduced into the molecule. In
comparison with bisalcohols, the use of bisacrylates leads to a
slight decrease in mobility but a substantial increase in
modulation.
[0021] In a further embodiment of the device in accordance with the
invention, a second active element is present, which contains a
first and a second electrode which are mutually separated by the
active layer. In said second active element, the active layer has a
relief structure, so that the active layer between the first and
the second active element is removed. Such a relief structure can
favorably be used to preclude leakage currents through the active
layer between neighboring transistors. The application of such a
relief structure is highly preferred in the case of a liquid
crystalline display screen with transistors as active elements.
Structuring may take place in a customary manner by applying a
resist layer, providing this resist layer with a desired pattern by
means of photolithography and etching the active layer. Such a
method may however put the properties of the active layer at risk.
Therefore, it is more favorable to provide the active layer by
means of a printing technique. Alternatively, the polymer can be
obtained by photopolymerization of the organic material. In a
suitable embodiment, a photoinitiator is added to the solution of
the monomer that has been derived from the semiconducting monomer.
Polymerization was initiated photochemically by exposing the
monomer layer to patterned radiation through a mask. Subsequent
development of the layer resulted in a structured layer. For the
development use is preferably made of the solvent of the monomer.
The resolution of the patterns is of the order of micrometers.
[0022] A method of the type mentioned in the opening paragraph is
disclosed, inter alia, in Ohsedo et al., Synt. Met. 81 (1996),
157-162. In the known method, a polymer is formed in which the
conjugation units--terthiophene--are present in the side
chains.
[0023] A drawback of said method resides in that it is sensitive to
the coupling of two conjugation units.
[0024] Therefore, a second object of the invention is to provide a
different method of the type mentioned in the opening
paragraph.
[0025] This object is achieved in that the polymer is prepared from
a monomer having a B.sub.1-A.sub.1-B.sub.2 structure, wherein at
least one of the groups B.sub.1, B.sub.2 comprises a reactive end
group. In the method in accordance with the invention, a monomer is
applied wherein the conjugation unit is present in a center part.
As a result, the reactivity of the monomer is largely determined by
the intermediate units B.sub.1 and B.sub.2.
[0026] In principle, each oligomeric unit can suitably be used as a
conjugation unit. Examples thereof are given in Katz et al., Acc.
Chem. Res. 34 (2001), 359-369. The conjugation units may be n-type
conductive or p-type conductive. In a favorable embodiment use is
made of a monomer having a B.sub.1-A.sub.1-B.sub.2 structure,
wherein A.sub.1 is a conjugated unit having the formula Y.sub.n,
wherein 2.ltoreq.n.ltoreq.8 and Y is selected from the group formed
by ##STR2## wherein [0027] Ar is an aromatic ring system with 4 to
6 carbon atoms that may be substituted with a substituent selected
from the group composed of an unbranched C.sub.1-C.sub.20-alkyl-,
C.sub.3-C.sub.20-alkoxy-, C.sub.1-C.sub.20-alkyl sulphate-, a
branched C.sub.3-C.sub.20-alkyl-, phenyl- or benzyl group, and that
may contain up to 4 heteroatoms selected from the group composed of
oxygen, sulfur and nitrogen in the aromatic ring system, and [0028]
R.sub.2 and R''.sub.2 are selected from the group composed of a
hydrogen atom and a C.sub.1-C.sub.20-alkyl- and a
C.sub.4-C.sub.20-aryl group, which groups may comprise
substituents, [0029] and wherein B.sub.1, B.sub.2 are
non-conjugated groups.
[0030] These and other aspects of the invention will be explained
in greater detail with reference to an embodiment and a drawing,
wherein:
[0031] FIG. 1 is a diagrammatic sectional view of a first
embodiment of the device; and
[0032] FIG. 2 shows the characteristic of a transistor as shown in
FIG. 1.
EMBODIMENT 1
Synthesis of 2,2'''-bis(6-acryloyloxyhexyl)quaterthiophene
[0033] ##STR3##
[0034] A quantity of 0.38 g (4.2 mmol) acryloic acid was added to a
mixture of 1.0 g (1.9 mmol) of bisalcohol
2,2'''-bis(6-hydroxyhexyl)quaterthiophene and 0.5 g (4.2 mmol)
dimethylaniline in 27 ml of dichloromethane at 0.degree. C. in an
inert atmosphere. The mixture was allowed to heat up to room
temperature and stirred overnight. The resulting solution was
filtered and washed with dichloromethane. The remaining
dimethylaniline was extracted with hydrochloric acid, and the
organic phase was washed with a saturated solution of sodium
chrlodide. It was dried over magnesium sulphate and filtered
through a layer of silica gel after which the solvent was
evaporated. The orange product was washed with ethanol and dried
overnight in a desiccator. It was identified as
2,2'''-bis(6-acryloyloxyhexyl)quaterthiophene. The yield was 0.35 g
(35%).
EMBODIMENT 2
[0035] The bisacrylate derivative as prepared in embodiment 1 was
spin-coated onto a test substrate wherein electrodes were already
provided. An initiator (Irgacure) was added as the additive. A good
film was obtained which was subsequently polymerized in situ by
means of photopolymerization. It was found that the transistor was
stable in air and light. Transistor characteristics are shown in
FIG. 2 wherein the current between source and drain electrode
I.sub.SD and the mobility are plotted against the voltage on the
gate electrode V.sub.g. The specific mobility of this material is
10.sup.-5 cm.sup.2 Vs.
EMBODIMENT 3
[0036] The thin-film transistor 10 shown in FIG. 1 comprises an
electrically insulating substrate 1 on which a first electrode
layer 2 is provided. In this layer 2, a source electrode 21 and a
drain electrode 22 are defined, which electrodes 21, 22 are
mutually separated by a channel 23. A second electrode layer 3
wherein a gate electrode 24 is defined is also present on the
substrate 1. If the gate electrode 24 is perpendicularly projected
onto the first electrode layer 2 then the gate electrode 24 and the
channel 23 demonstrate a substantial overlap. In addition, an
intermediate layer 4 and an active layer 5 are present.
[0037] Said layers 2, 3, 4, 5 are present on the substrate 1 in the
following sequence: second electrode layer 3, intermediate layer 4,
first electrode layer 2 and active layer 5. To planarize the
substrate, an insulating planarization layer of polyvinyl alcohol
(not shown) is present. The second electrode layer 3 contains Au
and is provided in accordance with a desired pattern in known
manner by means of an exposed and developed photosensitive resist.
Between the second electrode layer 3 and the intermediate layer 4,
there is provided a monolayer (not shown) of
CH.sub.3--(CH.sub.2).sub.15--SH to preclude pinholes in the
intermediate layer 4. The intermediate layer 4 comprises a
photostructurable organic dielectric, such as benzocyclobutene,
polyimide, polyvinyl phenol or a photoresist, in this case the
photoresist HPR504. The first electrode layer 2 comprises, in this
case, poly(3,4-ethylene dioxythiophene) and a polystyrene sulfhonic
acid. The first electrode layer 2 is provided by means of
spin-coating and structured by exposure to light.
[0038] The active layer 5 is spin-coated in a thickness of 50 nm
onto the first electrode layer 2. The active layer 5 comprises a
polymer network having quaterthiophene as the conjugation unit, and
is prepared as indicated in example 1. The weight ratio between the
carrier material and the semiconductor is 1. At least a part of the
semiconductor layer 5 is present in the channel 23.
[0039] The invention described herein may be applied in different
variants and yields a device comprising an active layer which is
not, or hardly, sensitive to the influence of light and air. Active
layers can be prepared in accordance with the invention. It is
additionally possible for the active layer to be mixed with a
carrier polymer, as described in the non-prepublished application
EP01203720.6 (NL010691).
EMBODIMENT 4
[0040] A quantity of 0.84 g (9.3 mmol) acryloic acid was added to a
mixture of 2.0 g (4.2 mmol) of the bisalcohol
2,2'''-bis(6-hydroxybutyl)quaterthiophene and 1.1 g (9.3 mmol)
dimethylaniline in 50 ml of dichloromethane at 0.degree. C. in an
inert atmosphere. The mixture was allowed to heat up to room
temperature and was stirred overnight. The resulting solution was
filtered, washed with, in succession, hydrochloric acid and brine,
dried over magnesium sulphate and filtered through a layer of
silica gel after which the solvent was evaporated. The orange
product was washed with ethanol and dried overnight in a
desiccator. It was identified as
2,2'''-bis(6-acryloyloxybutyl)quaterthiophene. The yield was 2.019
g (82.4%).
[0041] Films were prepared by spin-coating a 0.5 weight % solution
of oligothiophene in chloroform at a rate of 500 rpm for 30
seconds. The photoinitiator Irgacure was added to the solution for
photopolymerization experiments in a quantity of 5% of the
oligothiophene. Transistor measurements were performed immediately
after the preparation, using a HP 4564B semiconductor analyzer in
air and light.
EMBODIMENT 5
[0042] In order to measure the effect of the acrylate groups and
the polymerization, transistor characteristics, particularly the
mobility (in cm.sup.2/Vs) and the modulation were measured. The
results obtained are shown in Table 1. The decrease in modulation
in the monoacrylate polymer appears to be due to initiator residues
from thermal initiation, or to non-optimized heating.
TABLE-US-00001 TABLE I modulation and mobility as a function of
monomer and polymer structure. monomer or alkyl group mobility
modulation polymer or spacer end group (cm.sup.2/Vs) (I.sub.vd,
on/I.sub.vd, off) monomer butyl bisalcohol 5.10.sup.-3 600 .sup.
monomer hexyl bisalcohol 2.10.sup.-2 1000 .sup. monomer butyl
bisacrylate 3.10.sup.-4 10.sup.5 monomer hexyl bisacrylate
4.10.sup.-3 10.sup.5 polymer hexyl acrylate 5.10.sup.-4 10.sup.5
(network) monomer hexyl monoacrylate 5.10.sup.-4 10.sup.5 polymer
hexyl acrylate 4.10.sup.-5 10.sup.4 (oligomer in side chain)
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