U.S. patent application number 11/377567 was filed with the patent office on 2006-07-20 for reactive mesogenic azulenes.
Invention is credited to Louise Diane Farrand, Michael Findlater, Mark Giles, Martin Heeney, Iain McCulloch, Maxim Shkunov, David Sparrowe, Marcus Thompson, Steven Tierney.
Application Number | 20060157693 11/377567 |
Document ID | / |
Family ID | 27771833 |
Filed Date | 2006-07-20 |
United States Patent
Application |
20060157693 |
Kind Code |
A1 |
Farrand; Louise Diane ; et
al. |
July 20, 2006 |
Reactive mesogenic azulenes
Abstract
The invention relates to new reactive mesogenic azulene
derivatives, their use as semiconductors or charge transport
materials, in optical, electro-optical or electronic devices like
for example liquid crystal displays, optical films, organic field
effect transistors (FET or OFET) for thin film transistor liquid
crystal displays and integrated circuit devices such as RFID tags,
electroluminescent devices in flat panel displays, and in
photovoltaic and sensor devices, and to a field effect transistor,
light emitting device or ID tag comprising the reactive mesogenic
azulenes.
Inventors: |
Farrand; Louise Diane;
(Spetisbury, GB) ; Findlater; Michael; (Glasgow,
GB) ; Giles; Mark; (Southampton, GB) ; Heeney;
Martin; (Southampton, GB) ; Tierney; Steven;
(Southampton, GB) ; Thompson; Marcus;
(Fordingbridge, GB) ; Shkunov; Maxim;
(Southampton, GB) ; Sparrowe; David; (Southbourne,
GB) ; McCulloch; Iain; (Kings Somborne, GB) |
Correspondence
Address: |
MILLEN, WHITE, ZELANO & BRANIGAN, P.C.
2200 CLARENDON BLVD.
SUITE 1400
ARLINGTON
VA
22201
US
|
Family ID: |
27771833 |
Appl. No.: |
11/377567 |
Filed: |
March 17, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10314162 |
Dec 9, 2002 |
|
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11377567 |
Mar 17, 2006 |
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Current U.S.
Class: |
257/40 ; 549/510;
549/554; 549/59 |
Current CPC
Class: |
C09K 19/32 20130101 |
Class at
Publication: |
257/040 ;
549/510; 549/554; 549/059 |
International
Class: |
H01L 29/08 20060101
H01L029/08; C07D 409/02 20060101 C07D409/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 10, 2001 |
EP |
01129217.4 |
Claims
1.-24. (canceled)
25. A reactive liquid crystal mixture comprising: one or more
reactive mesogenic azulene compounds of the formula I
P-Sp-T-R.sup.1 I wherein P is CH.sub.2.dbd.CW.sup.1--COO--,
##STR16## CH.sub.2.dbd.CW.sup.2--(O).sub.k1--,
CH.sub.3--CH.dbd.CH--O--, 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--, Phe-CH.dbd.CH--,
HOOC--, OCN-- and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W.sup.2 and W.sup.3
being independently of each other H or alkyl with 1 to 5 C-atoms,
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, Phe being
1,4-phenylene and k.sub.1 and k.sub.2 being independently of each
other 0 or 1, Sp is a single bond or a linear or branched alkylene
group having 1 to 20 C atoms, in which one or more non-adjacent
CH.sub.2 groups are optionally replaced by --O--, --S--, --NH--,
--N(CH.sub.3)--, --CO--, --O--CO--, --S--CO--, --O--COO--,
--CO--S--, --CO--O--, --CH(halogen)-, --C(halogen).sub.2,
--CH(CN)--, --CH.dbd.CH-- or --C.ident.C--, or a siloxane group,
R.sup.1 is H, halogen, CN, NO.sub.2, an aliphatic, alicyclic or
aromatic group with up to 40 C atoms that optionally comprises one
or more hetero atoms and one or more fused rings, or a group P-Sp-,
and T is a mesogenic group of the formula II
-Z.sup.1-(A.sup.1-Z.sup.2).sub.m-(T.sup.1-Z.sup.3).sub.n-(A.sup.2-Z.sup.4-
).sub.0- II wherein A.sup.1 and A.sup.2 are independently of each
other an aromatic or heteroaromatic group with up to 18 C atoms
which is unsubstituted, mono- or polysubstituted with R.sup.1 , and
A.sup.1 may also denote T.sup.1, Z.sup.1 to Z.sup.4 are
independently of each other --O--, --S--, --CO--, --COO--, --OCO--,
--O--COO--, --CO--NR.sup.0--, --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--, --CH.sub.2CH.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, X.sup.1 and X.sup.2 are
independently of each other H, F, Cl or CN, T.sup.1 is a group
consisting of 1, 2, 3, or 4 azulene groups which are optionally
substituted by R.sup.2, R.sup.2 is H, halogen, CN, NO.sub.2,
straight chain, branched or cyclic alkyl with 1 to 20 C-atoms,
which is unsubstituted, mono- or poly-substituted 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--, --OCO--O--, --S--CO--, --CO--S--,
--CH.dbd.CH-- or --C.ident.C-- in such a manner that O and/or S
atoms are not linked directly to one another, or denotes an
aromatic or heteroaromatic group or a group P-Sp, R.sup.0 and
R.sup.00 are independently of each other H or alkyl with 1 to 12
C-atoms, m and o are independently of each other 0, 1, 2 or 3, and
n is 1, 2 or 3; and optionally one or more further reactive
compounds, wherein at least one of said azulene compounds and
optional further reactive compound has mesogenic or liquid
crystalline properties.
26. An anisotropic polymer film with charge transport properties
prepared from a reactive liquid crystal mixture according to claim
25 that is aligned in its liquid crystal phase into macroscopically
uniform orientation and polymerized or crosslinked to fix the
oriented state.
27. A side chain liquid crystal polymer obtained by polymerizing
one or more azulene compounds according to the following formula I
or by grafting one or more azulene compounds according to the
following formula I to a polymer backbone in a polymer analoguous
reaction, optionally with one or more additional mesogenic or
non-mesogenic comonomers: P-Sp-T-R.sup.1 I wherein P is
CH.sub.2.dbd.CW.sup.1--COO--, ##STR17##
CH.sub.2.dbd.CW.sup.2--(O).sub.k1--, CH.sub.3--CH.dbd.CH--O--,
HO--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-, Phe-CH.dbd.CH--,
HOOC--, OCN-- and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W.sup.2 and W.sup.3
being independently of each other H or alkyl with 1 to 5 C-atoms,
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, Phe being
1,4-phenylene and k.sub.1 and k.sub.2 being independently of each
other 0 or 1, Sp is a single bond or a linear or branched alkylene
group having 1 to 20 C atoms, in which one or more non-adjacent
CH.sub.2 groups are optionally replaced by --O--, --S--, --NH--,
--N(CH.sub.3)--, --CO--, --O--CO--, --S--CO--, --O--COO--,
--CO--S--, --CO--O--, --CH(halogen)-, --C(halogen).sub.2,
--CH(CN)--, --CH.dbd.CH-- or --C.ident.C--, or a siloxane group,
R.sup.1 is H, halogen, CN, NO.sub.2, an aliphatic, alicyclic or
aromatic group with up to 40 C atoms that optionally comprises one
or more hetero atoms and one or more fused rings, or a group P-Sp-,
and T is a mesogenic group of the formula II
-Z.sup.1-(A.sup.1-Z.sup.2).sub.m-(T.sup.1-Z.sup.3).sub.n-(A.sup.2-Z.sup.4-
).sub.0- II wherein A.sup.1 and A.sup.2 are independently of each
other an aromatic or heteroaromatic group with up to 18 C atoms
which is unsubstituted, mono- or polysubstituted with R.sup.1, and
A.sup.1 may also denote T.sup.1, Z.sup.1 to Z.sup.4 are
independently of each other --O--, --S--, --CO--, --COO--, --OCO--,
--O--COO--, --CO--NR.sup.0--, --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--, --CH.sub.2CH.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, X.sup.1 and X.sup.2 are
independently of each other H, F, Cl or CN, T.sup.1 is a group
consisting of 1, 2, 3, or 4 azulene groups which are optionally
substituted by R.sup.2, R.sup.2 is H, halogen, CN, NO.sub.2,
straight chain, branched or cyclic alkyl with 1 to 20 C-atoms,
which is unsubstituted, mono- or poly-substituted 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--, --SiR.sup.0R.sup.0--, --CO--,
--COO--, --OCO--, --OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH--
or --C.ident.C-- in such a manner that O and/or S atoms are not
linked directly to one another, or denotes an aromatic or
heteroaromatic group or a group P-Sp, R.sup.0 and R.sup.00 are
independently of each other H or alkyl with 1 to 12 C-atoms, m and
o are independently of each other 0, 1, 2 or 3, and n is 1, 2 or
3.
28. A semiconductor or charge transport material, comprising a
polymer of claim 27.
29. A field effect transistor, comprising one or more polymers
according to claim 27.
30. A security marking or device comprising one or more or polymers
according to claim 27.
31. A field effect transistor, comprising one or more polymer films
according to claim 26.
32. A security marking or device comprising one or more or polymer
films according to claim 26.
33. A polymer film according to claim 26, which is oxidatively or
reductively doped to form conducting ionic species.
34. A charge injection layer, planarizing layer, antistatic film or
conducting substrate or pattern for electronic applications or flat
panel displays, comprising one or more polymer films according to
claim 33.
35. A component for integrated circuitry, a thin film transistor, a
radio frequency identification tag, an organic light emitting
diode, a backlight or light-modulating component for a liquid
crystal display, an optical film, an electrode material, a
photoconductor or an electrophotographic photovoltaic or sensor
device, comprising one or more anisotropic polymer films according
to claim 26.
36. A component for integrated circuitry, a radio frequency
identification tag, an organic light emitting diode, a backlight or
light-modulating component for a liquid crystal display, an optical
film, an electrode material, a photoconductor or an
electrophotographic photovoltaic or sensor device, comprising one
or more polymers according to claim 27.
37. A security marking or device, a radio frequency identification
tag, a flat panel display or an integrated circuit comprising a
field effect transistor according to claim 29.
38. A security marking or device, a radio frequency identification
tag, a flat panel display or an integrated circuit comprising a
field effect transistor according to claim 31.
39. The reactive liquid crystal mixture of claim 25, wherein the
reactive mesogenic azulene compound is of one of the following
formulae: ##STR18## wherein P is CH.sub.2.dbd.CW.sup.1--COO--,
##STR19## CH.sub.2.dbd.CW.sup.2--(O).sub.k1--,
CH.sub.3--CH.dbd.CH--O--, 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--, Phe-CH.dbd.CH--,
HOOC--, OCN-- and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W.sup.2 and W.sup.3
being independently of each other H or alkyl with 1 to 5 C-atoms,
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, Phe being
1,4-phenylene and k.sub.1 and k.sub.2 being independently of each
other 0 or 1, Sp is a linear or branched alkylene group having 1 to
20 C atoms, in which one or more non-adjacent CH.sub.2 groups are
optionally replaced by --O--, --S--, --NH--, --N(CH.sub.3)--,
--CO--, --O--CO--, --S--CO--, --O--COO--, --CO--S--, --CO--O--,
--CH(halogen)-, --C(halogen).sub.2, --CH(CN)--, --CH.dbd.CH-- or
--C.ident.C--, or a siloxane group, provided that the first group
adjacent to the azulene ring is --O--, and z are independently of
each other --O--, --S--, --CO--, --COO--, --OCO--, --O--COO--,
--CO--NR.sup.0--, --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--, --CH.sub.2CH.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--, or
--OCO--CH.dbd.CH--.
40. The polymer film of claim 26, wherein the reactive mesogenic
azulene compound is of one of the following formulae: ##STR20##
where P is CH.sub.2.dbd.CW.sup.1--COO--, ##STR21##
CH.sub.2.dbd.CW.sup.2--(O).sub.k1--, CH.sub.3--CH.dbd.CH--O--,
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--, Phe-CH.dbd.CH--,
HOOC--, OCN-- and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W.sup.2 and W.sup.3
being independently of each other H or alkyl with 1 to 5 C-atoms,
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, Phe being
1,4-phenylene and k.sub.1 and k.sub.2 being independently of each
other 0 or 1, Sp is a linear or branched alkylene group having 1 to
20 C atoms, in which one or more non-adjacent CH.sub.2 groups are
optionally replaced by --O--, --S--, --NH--, --N(CH.sub.3)--,
--CO--, --O--CO--, --S--CO--, --O--COO--, --CO--S--, --CO--O--,
--CH(halogen)-, --C(halogen).sub.2, --CH(CN)--, --CH.dbd.CH-- or
--C.ident.C--, or a siloxane group, provided that the first group
adjacent to the azulene ring is --O--, and z are independently of
each other --O--, --S--, --CO--, --COO--, --OCO--, --O--COO--,
--CO--NR.sup.0--, --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--, --CH.sub.2CH.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--, or
--OCO--CH.dbd.CH--.
41. The polymer of claim 27, wherein the reactive mesogenic azulene
compound is of one of the following formulae: ##STR22## wherein P
is CH.sub.2.dbd.CW.sup.1--COO--, ##STR23##
CH.sub.2.dbd.CW.sup.2--(O).sub.k1--, CH.sub.3--CH.dbd.CH--O--,
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--, Phe-CH.dbd.CH--,
HOOC--, OCN-- and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, phenyl or alkyl with 1 to 5 C-atoms, W.sup.2 and W.sup.3
being independently of each other H or alkyl with 1 to 5 C-atoms,
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, Phe being
1,4-phenylene and k.sub.1 and k.sub.2 being independently of each
other 0 or 1, Sp is a linear or branched alkylene group having 1 to
20 C atoms, in which one or more non-adjacent CH.sub.2 groups are
optionally replaced by --O--, --S--, --NH--, --N(CH.sub.3)--,
--CO--, --O--CO--, --S--CO--, --O--COO--, --CO--S--, --CO--O--,
--CH(halogen)-, --C(halogen).sub.2, --CH(CN)--, --CH.dbd.CH-- or
--C.ident.C--, or a siloxane group, provided that the first group
adjacent to the azulene ring is --O--, and z are independently of
each other --O--, --S--, --CO--, --COO--, --OCO--, --O--COO--,
--CO--NR.sup.0--, --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--, --CH.sub.2CH.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--, or
--OCO--CH.dbd.CH--.
42. A reactive liquid crystal mixture of claim 25, wherein, for the
reactive mesogenic azulene compound of formula I: T.sup.1 is of one
of the following subformulae: ##STR24## wherein R.sup.3 to R.sup.8
have independently of each other one of the meanings of R.sup.2 in
formula II; A.sup.1 and A.sup.2 are selected from the group
consisting of 1,4-phenylene, 1,4-cyclohexa-1,3-diene,
1,4-cyclohexenylene in which one or more CH groups are optionally
replaced by N and one or two non-adjacent CH.sub.2 groups are
optionally replaced by O and/or S; thiophene-2,5-diyl,
thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl,
1,4-bicyclo-(2,2,2)-octylene, naphthalene-2,6-diyl, furan-2,5-diyl,
and indane-2,5-diyl; wherein all of the above are unsubstituted,
mono- or polysubstituted by L, with L being halogen, CN, SCN,
NO.sub.2, SF.sub.5 or an alkyl, alkoxy, alkylcarbonyl or
alkoxycarbonyl group with 1 to 4 C atoms, wherein one or more H
atoms are optionally substituted with F or Cl; and R.sup.1 is H, F,
Cl or straight chain, branched or cyclic alkyl with 1 to 20
C-atoms, which is unsubstituted, mono- or poly-substituted 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--, --OCO--O--,
--S--CO--, --CO--S--, --CH.dbd.CH--or --C.ident.C-- in such a
manner that O and/or S atoms are not linked directly to one
another, or an aromatic or heteroaromatic group.
43. A polymer film of claim 26, wherein, for the reactive mesogenic
azulene compound of formula I: T.sup.1 is of one of the following
subformulae: ##STR25## wherein R.sup.3 to R.sup.8 have
independently of each other one of the meanings of R2 in formula
II; A.sup.1 and A.sup.2 are selected from the group consisting of
1,4-phenylene, 1,4-cyclohexa-1,3-diene, 1,4-cyclohexenylene in
which one or more CH groups are optionally replaced by N and one or
two non-adjacent CH.sub.2 groups are optionally replaced by O
and/or S; thiophene-2,5-diyl, thienothiophene-2,5-diyl,
dithienothiophene-2,6-diyl, 1,4-bicyclo-(2,2,2)-octylene,
naphthalene-2,6-diyl, furan-2,5-diyl, and indane-2,5-diyl; wherein
all of the above are unsubstituted, mono- or polysubstituted by L,
with L being halogen, CN, SCN, NO.sub.2, SF.sub.5 or an alkyl,
alkoxy, alkylcarbonyl or alkoxycarbonyl group with 1 to 4 C atoms,
wherein one or more H atoms are optionally substituted with F or
Cl; and R.sup.1 is H, F, Cl or straight chain, branched or cyclic
alkyl with 1 to 20 C-atoms, which is unsubstituted, mono- or
poly-substituted 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--,
--OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in
such a manner that O and/or S atoms are not linked directly to one
another, or an aromatic or heteroaromatic group.
44. A polymer of claim 27, wherein, for the reactive mesogenic
azulene compound of formula I: T.sup.1 is of one of the following
subformulae: ##STR26## wherein R.sup.3 to R.sup.8 have
independently of each other one of the meanings of R.sup.2 in
formula II; A.sup.1 and A.sup.2 are selected from the group
consisting of 1,4-phenylene, 1,4-cyclohexa-1,3-diene,
1,4-cyclohexenylene in which one or more CH groups are optionally
replaced by N and one or two non-adjacent CH.sub.2 groups are
optionally replaced by O and/or S; thiophene-2,5-diyl,
thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl,
1,4-bicyclo-(2,2,2)-octylene, naphthalene-2,6-diyl, furan-2,5-diyl,
and indane-2,5-diyl; wherein all of the above are unsubstituted,
mono- or polysubstituted by L, with L being halogen, CN, SCN,
NO.sub.2, SF.sub.5 or an alkyl, alkoxy, alkylcarbonyl or
alkoxycarbonyl group with 1 to 4 C atoms, wherein one or more H
atoms are optionally substituted with F or Cl; and R.sup.1 is H, F,
Cl or straight chain, branched or cyclic alkyl with 1 to 20
C-atoms, which is unsubstituted, mono- or poly-substituted 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--, --OCO--O--,
--S--CO--, --CO--S--, --CH.dbd.CH-- or --C.ident.C-- in such a
manner that O and/or S atoms are not linked directly to one
another, or an aromatic or heteroaromatic group.
Description
FIELD OF INVENTION
[0001] The invention relates to new reactive mesogenic azulene
derivatives. The invention further relates to their use as
semiconductors or charge transport materials, for example, in
optical, electro-optical or electronic devices like for example
liquid crystal displays, optical films, organic field effect
transistors (FET or OFET) for thin film transistor liquid crystal
displays and integrated circuit devices such as RFID tags,
electroluminescent devices in flat panel displays, and in
photovoltaic and sensor devices. The invention further relates to a
field effect transistor, light emitting device or ID tag comprising
the reactive mesogenic azulenes.
BACKGROUND OF THE INVENTION
[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.2V.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 ionization
potential, as oxidation leads to reduced device performance.
[0004] A known compound which has been shown to be an effective
p-type semiconductor for OFETs is pentacene [see S. F. Nelson, Y.
Y. Lin, D. J. Gundlach and T. N. Jackson, Appl. Phys. Lett., 1998,
72, 1854]. When deposited as a thin film by vacuum deposition, it
was shown to have carrier mobilities in excess of 1 cm.sup.2
V.sup.-1 s.sup.-1 with very high current on/off ratios greater than
10.sup.6. However, vacuum deposition is an expensive processing
technique that is unsuitable for the fabrication of large-area
films.
[0005] Regular 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.2 V.sup.-1 s.sup.-1, but with a rather low current on/off
ratio between 10 and 10.sup.3 [see Z. Bao et al., Appl. Phys. Lett.
1997, 78, 2184]. 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 [see H.
Sirringhaus et al., Adv. Solid State Phys. 1999, 39, 101].
SUMMARY OF THE INVENTION
[0006] It was an aim of the present invention to provide new
organic materials for use as semiconductors or charge transport
materials, which are easy to synthesize, have high charge mobility
and good processability. The materials should be easily processable
to form thin and large-area films for use in semiconductor devices.
Other aims of the invention are immediately evident to those
skilled in the art from the following description.
[0007] It was found that the above aims can be achieved by
providing reactive mesogenic azulene compounds, also referred to as
reactive azulene mesogens, according to the present invention as
described below. They consist of a central mesogenic core
comprising one or more azulene groups, and optionally comprising
further unsaturated organic groups that form a conjugated system
together with the azulene groups, said mesogenic core being linked,
optionally via a spacer group, to one or more polymerizable groups.
The reactive mesogenic azulenes can induce or enhance liquid
crystal phases or are liquid crystalline themselves. They can be
oriented in their mesophase and the polymerizable group can be
polymerized or crosslinked in situ to form polymer films with a
high degree of order, thus yielding improved semiconductor
materials with high stability and high charge carrier mobility.
[0008] Grell et al., J. Korean Phys. Soc. 2000, 36(6), 331 suggest
a reactive mesogen comprising a conjugated distyrylbenzene core
with two reactive acrylate end groups as a model compound for
molecular electronics. However, there is no disclosure of reactive
mesogens of azulene.
[0009] Non-reactive, low molar mass azulene derivatives for use as
components of liquid crystal compositions are shown for example in
JP-A-02-069437, JP-A-02-069441 and JP-A-03-122189. The synthesis
and polymerization of an acrylate with an azulene group is
described in Wada et al., J. Polym. Sci., Polym. Chem. Ed. 1978,
16(8), 2085. The azulenes and polymers produced by Wada are
excluded from this invention.
[0010] A further aspect of the invention relates to liquid crystal
polymers, in particular liquid crystal side chain polymers obtained
from the azulene reactive mesogens according to the present
invention, which are then further processed e.g. from solution as
thin layers for use in semiconductor devices.
Definition of Terms
[0011] The terms `liquid crystalline or mesogenic material` or
`liquid crystalline or mesogenic compound` mean materials or
compounds comprising one or more rod-shaped, lath-shaped or
disk-shaped mesogenic groups, i.e. groups with the ability to
induce liquid crystal phase behavior. The compounds or materials
comprising mesogenic groups do not necessarily have to exhibit a
liquid crystal phase themselves. It is also possible that they show
liquid crystal phase behavior only in mixtures with other
compounds, or when the mesogenic compounds or materials, or the
mixtures thereof, are polymerized.
[0012] The term `reactive group` or `reactive compound` includes
compounds or groups that are capable of participating in a
polymerization reaction, like radicalic or ionic chain
polymerization, polyaddition or polycondensation, as well as
compounds or groups that are capable of being grafted for example
by condensation or addition to a polymer backbone in a
polymeranaloguous reaction.
[0013] The term `film` includes self-supporting, i.e.
free-standing, films that show more or less pronounced mechanical
stability and flexibility, as well as coatings or layers on a
supporting substrate or between two substrates.
DETAILED DESCRIPTION OF THE INVENTION
[0014] One object of the invention is reactive mesogenic azulenes,
consisting of a central mesogenic core comprising one or more
azulene groups, and optionally comprising further unsaturated
organic groups that form a conjugated system together with the
azulene groups, said mesogenic core being linked, optionally via
spacer groups, to one or more reactive groups.
[0015] Another object of the invention is the use of reactive
mesogenic azulenes as semiconductors or charge transport materials,
in particular in optical, electro-optical or electronic devices,
like for example in field effect transistors as components of
integrated circuitry, as thin film transistors in flat panel
display applications or RFID tags, or in semi-conducting components
for organic light emitting diode (OLED) applications such as
electroluminescent displays or backlights of flat panel displays,
for photovoltaic or sensor devices, or as light-modulating
components for liquid crystal displays, optical films or other
optical or electrooptical devices.
[0016] Another object of the invention is a field effect
transistor, for example as a component of integrated circuitry, as
a thin film transistor in flat panel display applications, or in an
RFID tag, comprising one or more reactive or polymerized mesogenic
azulenes according to the present invention.
[0017] Another object of the invention is a semi-conducting
component, for example in OLED applications like electroluminescent
displays or backlights of flat panel displays, in photovoltaic or
sensor devices, comprising one or more reactive or polymerized
mesogenic azulenes according to the present invention.
[0018] The reactive azulenes according to the present invention
provide several advantages over prior art materials [0019] by
adding substituent chains and other groups to the azulene core they
can be made more soluble, thus being suitable for spin coating or
solution coating techniques, rather than vacuum deposition, to
prepare thin films for use, e.g., in electronic devices such as
transistors, [0020] they can be made mesogenic or liquid
crystalline, thus exhibiting a higher degree of order that leads to
particularly high charge carrier mobility, in particular when being
aligned in their mesophase into macroscopically ordered orientation
[0021] their macroscopic mesophase properties can be frozen in by
in situ polymerization, [0022] they combine the properties of a
semi-conducting material with those of a mesogenic material to give
novel materials with a rigid, planar conjugated core and a flexible
chain to increase solubility and to decrease the melting point,
which show high charge carrier mobility when being aligned in their
mesophase.
[0023] The inventive reactive mesogenic azulenes are useful as
charge transport semiconductors, in that they have high carrier
mobilities. In particular, the introduction of side groups to the
conjugated rings bonded to the azulene core improves their
solubility and therefore their solution processability. In the
compounds according to the present invention, the azulene group is
a mesogenic group or part of a mesogenic group. These compounds are
therefore particularly useful as semiconductors or charge transport
materials, as they can be processed while in the highly ordered
mesophase morphology, and readily aligned by conventional
techniques in a preferred direction. Both smectic and nematic
mesophase ordering allows close packing of molecular pi-electron
systems, which maximizes intermolecular charge transfer which
occurs through a hopping mechanism between adjacent molecules. This
ordered, and oriented microstructure can be permanently "frozen-in"
by polymerizing the mesogens, which can also create a structure
with long range order, or "monodomain." Formation of a monodomain
also maximizes charge transfer by eliminating charge trap sites at
grain boundaries, while the polymerization also improves the
mechanical properties of the film. Further, by cross-linking the
mesogens, a highly stable structure results, which has an
additional advantage of being impervious to subsequent processing
solvents during device fabrication, thus allowing a wider range of
solvents to be used in deposition of the next layer of the device
by solution techniques. In addition, it is often observed that this
cross-linking further densifies the film, leading to smaller
intermolecular distances and improved charge transport.
[0024] It is also possible to co-polymerize azulenes of the present
invention with other mesogenic or liquid crystal monomers that are
known from prior art, or with other reactive azulenes of the
present invention, in order to induce or enhance liquid crystal
phase behavior.
[0025] Thus, another object of the invention is a polymerizable
liquid crystal mixture comprising one or more reactive azulenes of
the present invention, and optionally comprising one or more
further reactive compounds, wherein at least one of the reactive
azulenes and the further reactive compounds is mesogenic or liquid
crystalline.
[0026] Particularly preferred are reactive liquid crystal azulenes
of the present invention, or liquid crystal mixtures comprising one
or more reactive azulenes of the present invention, that exhibit a
nematic and/or smectic liquid crystal phase.
[0027] Another object of the present invention is an anisotropic
polymer film with charge transport properties obtainable from a
polymerizable liquid crystal mixture as defined above that is
aligned in its liquid crystal phase into macroscopically ordered
orientation and polymerized or cross-linked to fix the oriented
state.
[0028] Another object of the invention is a liquid crystal side
chain polymer (SCLCP) obtained from a polymerizable liquid crystal
material as defined above by polymerization or polymeranaloguous
reaction. Particularly preferred are SCLCPs obtained from one or
more reactive azulenes or from a polymerizable mixture comprising
one or more azulenes as described above.
[0029] Another object of the invention is an SCLCP obtained from
one or more reactive azulenes or from a polymerizable liquid
crystal mixture as defined above, by copolymerization or
polymeranaloguous reaction together with one or more additional
mesogenic or non-mesogenic comonomers.
[0030] 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.
[0031] Another object of the invention is the use of reactive
mesogenic azulenes of the present invention, or liquid crystal
mixtures or polymer films obtained thereof, as light-modulating
component in liquid crystal displays, which may for example be
switchable between two different states by an electric field, for
components of liquid crystal displays, in particular optical
retardation or compensation films, alignment layers or polarizers,
or in other optical or electrooptical devices.
[0032] Another object of the invention is a liquid crystal display,
component of a liquid crystal display, in particular an optical
retardation or compensation films, alignment layer or polarizer, or
an other optical or electrooptical device comprising reactive
azulenes according to the present invention, or liquid crystal
mixtures or polymer films obtained thereof.
[0033] The azulene groups in the inventive compounds are preferably
linked to their neighbouring groups at the 2- and 6-position.
[0034] Especially preferred are compounds selected of formula I
P-Sp-T-R.sup.1 I wherein [0035] P is a polymerizable or reactive
group, [0036] Sp is a spacer group or a single bond, [0037] R.sup.1
is H, halogen, CN, NO.sub.2, an aliphatic, alicyclic or aromatic
group with up to 40 C atoms that optionally comprise one or more
hetero atoms and one or more fused rings, or P-Sp-, and [0038] T is
a mesogenic group comprising one or more azulene groups that are
optionally substituted and optionally comprise fused azulene
groups, with the proviso that azulene groups linked to their
neighboured groups at the 1- and 3-position are excluded.
[0039] R.sup.1 in formula I is preferably H, F, Cl or straight
chain, branched or cyclic alkyl with 1 to 20 C-atoms, which is
unsubstituted, mono- or poly-substituted 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--, --OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH--
or --C.ident.C-- in such a manner that O and/or S atoms are not
linked directly to one another, or an aromatic or heteroaromatic
group.
[0040] Particularly preferably R.sup.1 is optionally fluorinated
alkyl or alkoxy with 1 to 15 C atoms.
[0041] Further preferred are compounds of formula I wherein R.sup.1
is P-Sp.
[0042] T in formula I preferably comprises 1 or 2 azulene
groups.
[0043] Particularly preferably T is selected of formula II
-Z.sup.1-(A.sup.1-Z.sup.2).sub.m--(T.sup.1-Z.sup.3).sub.n-(A.sup.2-Z.sup.-
4).sub.0- II wherein [0044] A.sup.1 and A.sup.2 are independently
of each other an aromatic, heteroaromatic, group with up to 18 C
atoms which is unsubstituted, mono- or polysubstituted with
R.sup.1, and A.sup.1 may also denote T.sup.1, [0045] Z.sup.1 to
Z.sup.4 are independently of each other --O--, --S--, --CO--,
--COO--, --OCO--, --O--COO--, --CO--NR.sup.0--, --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--,
--CH.sub.2CH.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=CX.sup.2--, --C.ident.C--,
--CH.dbd.CH-- COO--, --OCO--CH.dbd.CH-- or a single bond, [0046]
X.sup.1 and x.sup.2 are independently of each other H, F, Cl or CN,
[0047] T.sup.1 is a group consisting of 1, 2, 3, or 4 azulene units
which are optionally substituted by R.sup.2, [0048] R.sup.2 is H,
halogen, CN, NO.sub.2, straight chain, branched or cyclic alkyl
with 1 to 20 C-atoms, which is unsubstituted, mono- or
poly-substituted 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--,
--OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH--or --C.ident.C-- in
such a manner that O and/or S atoms are not linked directly to one
another, or denotes an aromatic or heteroaromatic group or P-Sp,
[0049] R.sup.0 and R.sup.00 are independently of each other H or
alkyl with 1 to 12 C-atoms, [0050] m and o are independently of
each other 0, 1, 2 or 3, and [0051] n is 1, 2 or 3
[0052] Particularly preferred groups T are those wherein Z.sup.1,
A.sup.1, Z.sup.2, T.sup.1, Z.sup.3, A.sup.2 and Z.sup.4 form a
conjugated system. Therein A.sup.1 and A.sup.2 are preferably
arylene or heteroarylene and Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4
are preferably a single bond or a conjugated link such as
--CX.sup.1.dbd.CX.sup.2-- or --C.ident.C--.
[0053] Further preferred groups T are those wherein m and o are 0,
further those wherein m and o are 1 or 2.
[0054] Further preferred groups T are those wherein T.sup.1 is
azulene that is optionally substituted with R.sup.2 as defined in
formula II, furthermore those wherein n is 1 or 2 and Z.sup.2 is a
single bond or a conjugated link such as --CX.sup.1.dbd.CX.sup.2--
or --C.ident.C--.
[0055] Particularly preferred groups T are those of the following
formulae -Z.sup.1-T.sup.1-Z.sup.3- II1
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3- II2
-Z.sup.1-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3- II3
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-A.sup.2-Z.sup.4- II4
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3- II5
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.3-T.sup.1-Z.sup.3- II6
-Z.sup.1-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3- II7
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-A.sup.2-Z.sup.4-
II8
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.2-Z-
.sup.3- II9
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.2-Z.sup.3-
II10
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.2--
Z.sup.3- II11
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3-A.sup.2-Z.sup.4-
II12
-Z.sup.1-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.2--
Z.sup.3- II13
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3-
II14
-Z.sup.1-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.1--
Z.sup.3- II15
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II16
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3--
A.sup.1-Z.sup.4- II17
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-A.sup.2-Z.sup.4--
A.sup.2-Z.sup.4- II18
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II19
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II20
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II21
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3--
A.sup.2-Z.sup.4- II22
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3--
A.sup.2-Z.sup.4- II23
-Z.sup.1-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II24
-Z.sup.1-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3--
T.sup.1-Z.sup.3- II25
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3--
T.sup.1-Z.sup.3- II26
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II27
-Z.sup.1-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3-T.sup.1-Z.sup.3--
A.sup.2-Z.sup.4- II28
-Z.sup.1-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2--
T.sup.1-Z.sup.3- II29
-Z.sup.1-T.sup.1-Z.sup.2-A.sup.1-Z.sup.2-A.sup.1-Z.sup.2-T.sup.1-Z.sup.3--
T.sup.1-Z.sup.3- II30
[0056] wherein Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, A.sup.1, A.sup.2
and T.sup.1 have in each case independently one of the meanings of
formula II.
[0057] T.sup.1 is preferably 2,6-azulene, furthermore
[2,6']-bisazulene-6,2'-diyl, [2,2']-bisazulene-6,6'-diyl or
[6,6']-bisazulene-2,2'-diyl, all of which are optionally mono-:or
polysubstituted by R.sup.2 as defined in formula II.
[0058] T.sup.1 is preferably selected from the following
subformulae ##STR1##
[0059] wherein R.sup.3 to R.sup.8 have independently of each other
one of the meanings of R.sup.1 in formula II, and are preferably
halogen, methyl, ethyl, propyl, CO.sub.2Me, CO.sub.2Et, CN,
COCH.sub.3 or CHO.
[0060] A.sup.1 and A.sup.2 are preferably selected from
1,4-phenylene, 1,4-cyclohexa-1,3-diene, 1,4-cyclohexenylene in
which, in addition, one or more CH groups are optionally replaced
by N and one or two non-adjacent CH.sub.2 groups are optionally
replaced by O and/or S, thiophene-2,5-diyl,
thienothiophene-2,5-diyl, dithienothiophene-2,6-diyl,
1,4-bicyclo-(2,2,2)-octylene, naphthalene-2,6-diyl, furan-2,5-diyl,
and indane-2,5-diyl, wherein these groups are unsubstituted, mono-
or polysubstituted by L, with L being halogen, CN, SCN, NO.sub.2,
SF.sub.5 or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group
with 1 to 4 C atoms, wherein one or more H atoms are optionally
substituted with F or Cl.
[0061] A.sup.1 and A.sup.2 are particularly preferably
1,4-phenylene that is substituted with 1, 2 or 3 groups L as
defined above, or thiophene-2,5-diyl, all of which are optionally
substituted with one or more groups L as defined above.
[0062] Z.sup.1-4 are preferably selected from --O--, --S--,
--OCH.sub.2--, --CH.sub.2O--, --SCH.sub.2--, --CH.sub.2S--,
--CF.sub.2O--, --OCF.sub.2--, --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.dbd.CH--, --N.dbd.N--,
--CH.dbd.CR.sup.0--, --CX.sup.1.dbd.CX.sup.2--, --C.ident.C-- and a
single bond, in particular from --CH.dbd.N--, --N.dbd.CH--,
--N.dbd.N--, --CH.dbd.CR.sup.0--, --CX.sup.1.dbd.CX.sup.2--,
--C.ident.C-- and a single bond.
[0063] Particularly preferred are the following compounds ##STR2##
##STR3## wherein P, Sp and n have the meanings of formula I, [0064]
Sp.sup.1 and Sp.sup.2 are different groups Sp as defined in formula
I, that is they are both selected from the groups Sp but Sp.sup.1
and Sp.sup.2 are not simultaneously the same, [0065] Z and Z' have
independently of each other one of the meanings of Z.sup.1 in
formula II, and are preferably --CH.dbd.CH--, --CH.dbd.CF--,
--CF.dbd.CH--, CH.dbd.CCl--, --CCl.dbd.CH--, --CF.dbd.CF--,
--CCl.dbd.CCl--, --C.ident.C-- or a single bond, [0066] Z'' has one
of the meanings of Z.sup.1 in formula II, and is preferably
--CH.dbd.CH--, --CH.dbd.CF--, --CF.dbd.CH--, CH.dbd.CCl--,
--CCl.dbd.CH--, --CF.dbd.CF--, --CCl.dbd.CCl--or --C.ident.C--,
[0067] R has in each case independently one of the meanings of
R.sup.1 of formula I, and is preferably halogen, an optionally
fluorinated alkyl groups with 1 to 15 C atoms or P-Sp-, [0068] R'
has in each case independently one of the meanings of R.sup.2 in
formula II, and is preferably halogen, an optionally fluorinated
alkyl group with 1 to 15 C atoms or P-Sp-,
[0069] and wherein the azulene group is optionally mono-or
polysubstituted by R.sup.2 as defined in formula II.
[0070] Further preferred are compounds of the preferred formulae I6
to I29, wherein the azulene-2,6-diyl groups are replaced by
[2,6']-bisazulene-6,2'-diyl, [2,2']-bisazulene-6,6'-diyl or
[6,6']-bisazulene-2,2'-diyl, all of which are optionally mono- or
polysubstituted by R.sup.2 as defined in formula II.
[0071] In the foregoing and the following, arylene and
heteroarylene preferably denote a bivalent mono- bi- or tricyclic
aromatic or heteroaromatic group with up to 15 C atoms that may
also comprise fused rings and is optionally substituted with one or
more groups selected from H, halogen, CN, NO.sub.2, straight chain,
branched or cyclic alkyl with 1 to 20 C-atoms, which is
unsubstituted, mono- or poly-substituted 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--, --OCO--O--, --S--CO--, --CO--S--, --CH.dbd.CH--
or --C.ident.C-- in such a manner that O and/or S atoms are not
linked directly to one another, and P-Sp as defined in formula I.
Very preferred arylene and heteroarylene groups are those having
one of the preferred meanings of A.sup.1 as given above and
below.
[0072] Aryl and heteroaryl preferably denote a mono-, bi- or
tricyclic aromatic or heteroaromatic group with up to 25 C atoms
that may also comprise fused rings and is optionally substituted
with one or more groups selected from H, halogen, CN, NO.sub.2,
straight chain, branched or cyclic alkyl with 1 to 20 C-atoms,
which is unsubstituted, mono- or poly-substituted 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--, --OCO--O--, --S--CO--, --CO--S--,
--CH.dbd.CH-- or --C.ident.C-- in such a manner that O and/or S
atoms are not linked directly to one another, and P-Sp as defined
in formula I.
[0073] Especially preferred aryl and heteroaryl groups are phenyl
in which, in addition, one or more CH groups are optionally
replaced by N, naphthalene, thiophene, thienothiophene,
dithienothiophene, alkyl fluorene and oxazole, all of which can be
unsubstituted, mono- or polysubstituted with L, wherein L is
halogen or an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group
with 1 to 12 C atoms, wherein one or more H atoms are optionally
replaced by F or Cl.
[0074] Further preferred aryl and heteroaryl groups include
five-membered heterocyclics like oxazole or isoxazole,
N-substituted imidazole or pyrazole, thiazole or isothiazole,
oxadiazole, N-substituted triazole, six-membered heterocyclics like
pyridine, pyridazine, pyrimidine, pyrazine, triazine and tetrazine,
heterocyclics with fused rings like benzoxazole, benzothiazole,
benzimidazole, quinoline, isoquinoline, cinnoline, quinazoline,
quinoxaline, phthalazine, benzothiadiazole, benzotriazole,
benzotriazine, phenazine, phenanthridine, acridine, or condensed
polycyclics like acenaphthene, phenanthrene, anthracene,
fluoranthene, pyrene, perylene, rubrene, chrysene, naphthacene,
coronene or triphenylene, all of which can be unsubstituted, mono-
or polysubstituted with L as defined above.
[0075] --CX.sup.1=CX.sup.2-- is preferably --CH.dbd.CH--,
--CH.dbd.CF--, --CF.dbd.CH--, --CF.dbd.CF--, --CH.dbd.C(CN)-- or
--C(CN).dbd.CH--.
[0076] If one of R.sup.1 to R.sup.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, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is
preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,
ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy,
furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy,
tridecoxy or tetradecoxy, for example.
[0077] Oxaalkyl, i.e. where one CH.sub.2 group is replaced by
--O--, is preferably straight-chain 2-oxapropyl(=methoxymethyl),
2-(=ethoxymethyl) or 3-oxabutyl(=2-methoxyethyl), 2-, 3-, or
4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or
6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, -2-, 3-, 4-, 5-, 6-,
7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for
example.
[0078] Halogen is preferably F or Cl.
[0079] The polymerizable or reactive group P is preferably selected
from CH.sub.2.dbd.CW.sup.1--COO--, ##STR4##
CH.sub.2.dbd.CW.sup.2--(O).sub.k1--, CH.sub.3--CH.dbd.CH--O--,
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--, Phe-CH.dbd.CH--,
HOOC--, OCN-- and W.sup.4W.sup.5W.sup.6Si--, with W.sup.1 being H,
Cl, CN, 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 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, Phe
being 1,4-phenylene and k, and k.sub.2 being independently of each
other 0 or 1.
[0080] Especially preferred groups P are CH.sub.2.dbd.CH--COO--,
CH.sub.2.dbd.C(CH.sub.3)--COO--, CH.sub.2.dbd.CH--,
CH.sub.2.dbd.CH--O-- and ##STR5##
[0081] Very preferred are acrylate and oxetane groups. Oxetanes
produce less shrinkage upon polymerization (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.
[0082] As for the spacer group Sp, all groups can be used that are
known for this purpose to those skilled in the art. The spacer
group Sp is preferably a linear or branched alkylene group having 1
to 20 C atoms, in particular 1 to 12 C atoms, in which, in
addition, one or more non-adjacent CH.sub.2 groups are optionally
replaced by --O--, --S--, --NH--, --N(CH.sub.3)--, --CO--,
--O--CO--, --S--CO--, --O--COO--, --CO--S--, --CO--O--,
--CH(halogen)-, --C(halogen).sub.2, --CH(CN)--, --CH.dbd.CH-- or
--C.ident.C--, or a siloxane group.
[0083] Typical spacer groups are for example --(CH.sub.2).sub.p--,
--(CH.sub.2CH.sub.2O).sub.r--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, r being an integer from 1 to 3 and R.sup.0 and R.sup.00 having
the meanings given in formula I.
[0084] Preferred spacer groups 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.
[0085] Further preferred are compounds with one or two groups
P-Sp-X wherein Sp and/or X is a single bond.
[0086] In case of compounds with two groups P-Sp-X, each of the two
polymerizable groups P, the two spacer groups Sp, and the two
linkage groups X can be identical or different.
[0087] SCLCPs obtained from the inventive compounds or mixtures by
polymerization or copolymerization have a backbone that is formed
by the polymerizable group P in formula I.
[0088] The compounds of formula I can be synthesized according to
or in analogy to methods that are known to the skilled in the art
and are described for example in T. Nozoe, T. Asao and M. Oda,
Bull. Chem. Soc. Jpn. 1974, 47, 681; D. Balschukat and E. V.
Dehmlow, Chem. Ber., 1986, 119, 2272-2288 and T. Morita and K.
Takase, Bull. Chem. Soc. Jpn., 1982, 55, 1144-1152 and T. Nozoe, S.
Seto and S. Matsumura, Bull. Chem. Soc. Jpn., 1962, 35, 1990.
Furthermore, they can be prepared according to or in analogy to the
following reaction schemes. ##STR6## ##STR7## ##STR8## ##STR9##
##STR10## ##STR11## ##STR12## ##STR13## ##STR14## ##STR15##
[0089] A preferred embodiment of the present invention relates to
reactive azulenes, in particular those of formula I, that are
mesogenic or liquid crystalline. 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
polymerization or crosslinking via the groups P to yield polymer
films with high charge carrier mobility and high thermal,
mechanical and chemical stability.
[0090] It is also possible to copolymerize the azulenes according
to the present invention with other polymerizable mesogenic or
liquid crystal monomers that are known from prior art, in order to
induce or enhance liquid crystal phase behavior.
[0091] Thus, another object of the invention is a polymerizable
liquid crystal material comprising one or more reactive azulenes of
the present invention as described above and below comprising at
least one reactive group, and optionally comprising one or more
further reactive compounds, wherein at least one of the reactive
azulenes of the present invention and/or the further reactive
compounds is mesogenic or liquid crystalline.
[0092] 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.
[0093] Another object of the present invention is an anisotropic
polymer film with charge transport properties obtainable from a
polymerizable liquid crystal material as defined above that is
aligned in its liquid crystal phase into macroscopically uniform
orientation and polymerized or crosslinked to fix the oriented
state.
[0094] Polymerization is preferably carried out by in-situ
polymerization 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 polymerization, where
the conjugated pi-electron systems are orthogonal to the direction
of charge transport. This ensures that the intermolecular distances
are minimized and hence then energy required to transport charge
between molecules is minimized. The molecules are then polymerized
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
[0095] 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 I. 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.
[0096] Polymerization 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 polymerization 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.
[0097] Polymerization is preferably carried out in the presence of
an initiator absorbing at the wavelength of the actinic radiation.
For example, when polymerizing by means of UV light, a
photoinitiator can be used that decomposes under UV irradiation to
produce free radicals or ions that start the polymerization
reaction. When curing polymerizable materials with acrylate or
methacrylate groups, preferably a radical photoinitiator is used,
when curing polymerizable materials with vinyl, epoxide and oxetane
groups, preferably a cationic photoinitiator is used. It is also
possible to use a polymerization initiator that decomposes when
heated to produce free radicals or ions that start the
polymerization. As a photoinitiator for radical polymerization 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 photopolymerization the
commercially available UVI 6974 (Union Carbide) can be used.
[0098] The polymerizable 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, colorants, dyes or pigments.
[0099] Reactive azulenes comprising one or more groups P-SP-X can
also be copolymerized with polymerizable mesogenic compounds to
induce, or, in case of mesogenic materials of formula I, enhance
liquid crystal phase behavior. Polymerizable 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.
[0100] SCLCPs can be prepared from the polymerizable compounds or
mixtures according to the invention by the methods described above,
or by conventional polymerization techniques which are known to
those skilled in the art, including for example radicalic, anionic
or cationic chain polymerization, polyaddition or polycondensation.
Polymerization can be carried out for example as polymerization in
solution, without the need of coating and prior alignment, or
polymerization 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 copolymerization 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 polymerizable group capable of undergoing
the desired polymer-forming reaction, like for example a
polymerizable 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 and WO 97/00600.
Typical non mesogenic comonomers are for example alkyl mono- or
diacrylates or alkyl mono- or dimethacrylates with alkyl groups of
1 to 20 C atoms, like methyl acrylate or methyl methacrylate,
trimethylpropane trimethacrylate or pentaerythritol
tetraacrylate.
[0101] 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) 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.
[0102] 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.
[0103] 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.
[0104] 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 money value, like stamps, tickets, shares, cheques etc.
[0105] Alternatively, the materials 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.
[0106] 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.
[0107] A further aspect of the invention relates to both the
oxidized and reduced form of the compounds and materials according
to this invention. Either loss or gain of electrons results in
formation of a highly delocalized 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.
[0108] The doping process typically implies treatment of the
semiconductor material with an oxidating or reducing agent in a
redox reaction to form delocalized ionic centers 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-implantantion of the dopant into the
semiconductor material.
[0109] 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-CH.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.3.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.sup.-), 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).
[0110] 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.
[0111] The entire disclosure of all applications, patents and
publications, cited herein and of corresponding European Patent
application No. 01129217.4, filed Dec. 10, 2001, are incorporated
by reference herein.
[0112] The preceding examples can be repeated with similar success
by substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in the
preceding examples.
[0113] From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this invention
and, without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
* * * * *