U.S. patent application number 16/850250 was filed with the patent office on 2020-08-13 for treatment liquid containing ionic compound, organic electronic element, and method for producing organic electronic element.
This patent application is currently assigned to HITACHI CHEMICAL COMPANY, LTD.. The applicant listed for this patent is HITACHI CHEMICAL COMPANY, LTD.. Invention is credited to Naoki ASANO, Shigeaki FUNYUU, Kenichi ISHITSUKA.
Application Number | 20200259085 16/850250 |
Document ID | 20200259085 / US20200259085 |
Family ID | 1000004794604 |
Filed Date | 2020-08-13 |
Patent Application | download [pdf] |
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United States Patent
Application |
20200259085 |
Kind Code |
A1 |
FUNYUU; Shigeaki ; et
al. |
August 13, 2020 |
TREATMENT LIQUID CONTAINING IONIC COMPOUND, ORGANIC ELECTRONIC
ELEMENT, AND METHOD FOR PRODUCING ORGANIC ELECTRONIC ELEMENT
Abstract
An embodiment of the present invention relates to a treatment
liquid which contains an ionic compound and a solvent, and is used
for adhering the ionic compound to at least one surface selected
from the group consisting of a surface on which a layer having hole
transport properties is to be formed, and a surface of a layer
having hole transport properties.
Inventors: |
FUNYUU; Shigeaki;
(Tsuchiura-shi, JP) ; ASANO; Naoki; (Tsukuba-shi,
JP) ; ISHITSUKA; Kenichi; (Tsukuba-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HITACHI CHEMICAL COMPANY, LTD. |
Tokyo |
|
JP |
|
|
Assignee: |
HITACHI CHEMICAL COMPANY,
LTD.
|
Family ID: |
1000004794604 |
Appl. No.: |
16/850250 |
Filed: |
April 16, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
14773490 |
Sep 8, 2015 |
10665786 |
|
|
PCT/JP2014/055838 |
Mar 6, 2014 |
|
|
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16850250 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 2261/3142 20130101;
C08G 2261/794 20130101; C08G 2261/312 20130101; H01L 51/0043
20130101; C08G 2261/3162 20130101; C08G 2261/3223 20130101; C08G
2261/3246 20130101; C08G 2261/76 20130101; C08G 2261/512 20130101;
C08G 65/22 20130101; H01L 51/5056 20130101; C08G 2261/135 20130101;
H01L 51/42 20130101; H01L 51/5088 20130101; C08G 2261/95 20130101;
C08G 61/12 20130101; H01L 51/0065 20130101; H01L 51/0003 20130101;
C08G 65/18 20130101; H01L 51/005 20130101; C08G 2261/3241 20130101;
C08G 2261/5222 20130101; C08G 2261/411 20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C08G 61/12 20060101 C08G061/12; C08G 65/22 20060101
C08G065/22; C08G 65/18 20060101 C08G065/18 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 8, 2013 |
JP |
2013-046723 |
Claims
1-17. (canceled)
18. A method for producing an organic electronic element,
comprising a step of applying a treatment liquid to a surface of an
anode, wherein the treatment liquid contains a compound having a
polymerizable substituent.
19. The method for producing an organic electronic element
according to claim 18, further comprising: a step of forming a
layer (A) having hole transport properties on a surface of the
anode to which the treatment liquid has been applied, and a step of
forming a cathode.
20. The method for producing an organic electronic element
according to claim 18, further comprising a step of forming a
light-emitting layer.
21. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent has at least one group selected from the group
consisting of an oxetanyl group, epoxy group, vinyl group, vinyl
ether group, acrylate group and methacrylate group.
22. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent has at least one group selected from the group
consisting of an oxetanyl group, epoxy group and vinyl ether
group.
23. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent has at least one group selected from the group
consisting of an oxetanyl group and an epoxy group.
24. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent has two or more of same or different polymerizable
substituents.
25. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent has two same polymerizable substituents.
26. The method for producing an organic electronic element
according to claim 1, wherein the compound having a polymerizable
substituent has two different polymerizable substituents.
27. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent includes a structure containing a conjugated system in
addition to the structure of the polymerizable substituent.
28. The method for producing an organic electronic element
according to claim 18, wherein the compound having a polymerizable
substituent does not have a structure containing a conjugated
system in addition to the structure included in the polymerizable
substituent.
29. The method for producing an organic electronic element
according to claim 18, wherein the treatment liquid further
contains an ionic compound.
30. The method for producing an organic electronic element
according to claim 29, wherein the ionic compound has at least one
anion selected from the group consisting of anions represented by
any one of formula (1A) to formula (5A) shown below: ##STR00049##
wherein E.sup.1 represents an oxygen atom, E.sup.2 represents a
nitrogen atom, E.sup.3 represents a carbon atom, E.sup.4 represents
a boron atom or a gallium atom, and E.sup.5 represents a phosphorus
atom or an antimony atom, each of Y.sup.1 to Y.sup.6 independently
represents a single bond or a divalent linking group, and each of
R.sup.1 to R.sup.16 independently represents an
electron-withdrawing monovalent group (wherein R.sup.2 and R.sup.3,
at least two groups selected from among R.sup.4 to R.sup.6, at
least two groups selected from among R.sup.7 to R.sup.10, and at
least two groups selected from among R.sup.11 to R.sup.16 may be
bonded together).
31. The method for producing an organic electronic element
according to claim 29, wherein the ionic compound has at least one
cation selected from the group consisting of cations of elements
belonging to group 1 or group 2 of the IUPAC Periodic Table of
Elements, and cations represented by any one of formula (1B) to
formula (3B) shown below: ##STR00050## wherein A.sup.1 represents
an element belonging to group 17 or group 14 of the IUPAC Periodic
Table of Elements, A.sup.2 represents an element belonging to group
16 or group 14 of the IUPAC Periodic Table of Elements, A.sup.3
represents an element belonging to group 15 of the IUPAC Periodic
Table of Elements, and each of R.sup.1 to R.sup.9 independently
represents a hydrogen atom or an organic group (wherein R.sup.1 and
R.sup.2, at least two groups selected from among R.sup.3 to
R.sup.5, and at least two groups selected from among R.sup.6 to
R.sup.9 may be bonded together).
32. The method for producing an organic electronic element
according to claim 29 wherein a mass ratio between the ionic
compound and the compound having a polymerizable substituent is
within a range from 1:1,000 to 1,000:1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of U.S.
application Ser. No. 14/773,490, filed Sep. 8, 2015, which is a 371
of International Application No. PCT/JP2014/055838, filed Mar. 6,
2014, which claims priority to JP 2013-046723, filed Mar. 8, 2013,
the contents of each of which are incorporated herein by
reference.
TECHNICAL FIELD
[0002] Embodiments of the present invention relate to a treatment
liquid containing an ionic compound, an organic electronic element,
and a method for producing an organic electronic element. Further,
other embodiments of the present invention relate to an organic
electroluminescent element, a display element, an illumination
device, a display device, and an organic photoelectric conversion
element.
Background Art
[0003] Organic electronic elements are elements that use organic
substances to perform electrical operations. Organic electronic
elements are expected to yield significant advantages, including
energy conservation, low price and superior flexibility, and are
therefore attracting considerable attention as potential
replacements for conventional inorganic semiconductors based mainly
on silicon.
[0004] Examples of organic electronic elements include organic
electroluminescent elements (hereafter also referred to as "organic
EL elements"), organic photoelectric conversion elements and
organic transistors.
[0005] Among organic electronic elements, organic EL elements are
attracting attention as potential large-surface area solid state
light sources for use instead of incandescent lamps or gas-filled
lamps or the like. Further, organic EL elements are also attracting
much attention as the leading candidate for light-emitting displays
that can replace liquid crystal displays (LCD) used in the field of
flat panel displays (FPD), and actual production of such
light-emitting displays is now proceeding.
[0006] In organic EL elements, research is currently being
conducted into the use of a layer having charge transport
properties, such as a charge injection layer or charge transport
layer, between the light-emitting layer and the anode, for the
purpose of improving the properties of the element such as the
light emission efficiency or the lifespan of the element.
[0007] Further, the production processes for organic EL elements
can be broadly classified into dry processes that use vacuum
deposition or the like, and wet processes that use printing with
inkjet technology or the like. Wet processes enable the size of the
organic EL element to be increased more easily, and are also
thought to provide higher productivity.
[0008] Examples of known organic EL elements include those
mentioned below.
[0009] Patent Document 1 discloses an organic EL element which
includes, between the light-emitting layer and the anode, an anode
protective layer formed from a polyethylene dioxythiophene (PEDT)
and a polystyrene sulfonate (PSS).
[0010] Patent Document 2 discloses an organic EL element which
includes, between the light-emitting layer and the anode, a hole
injection layer and/or a hole transport layer formed using a charge
transport film composition containing a charge transport compound
and an ionic compound.
CITATION LIST
Patent Literature
[0011] PLT1: JP 3724589 B1
[0012] PLT2: JP 2006-233162 A
SUMMARY OF INVENTION
Technical Problem
[0013] An object of one embodiment of the present invention is to
provide a treatment liquid that is capable of improving the
properties of a layer having hole transport properties. Further, an
object of another embodiment of the present invention is to provide
an organic electronic element having excellent properties and a
method for producing the element. Moreover, objects of other
embodiments of the present invention are to provide an organic
electroluminescent element, a display element, an illumination
device, a display device and an organic photoelectric conversion
element having excellent properties.
Solution to Problem
[0014] As a result of intensive research, the inventors of the
present invention discovered that by performing a simple treatment,
either before or after the formation of a layer having hole
transport properties, the properties of an organic electronic
element could be improved, and they were thus able to complete the
present invention, including a variety of embodiments.
[0015] One embodiment of the present invention relates to a
treatment liquid which contains an ionic compound and a solvent,
and is used for adhering the ionic compound to at least one surface
selected from the group consisting of a surface on which a layer
having hole transport properties is to be formed, and a surface of
a layer having hole transport properties.
[0016] Further, another embodiment of the present invention relates
to an organic electronic element having an anode, a surface to
which an ionic compound is adhered, a layer (A) having hole
transport properties, and a cathode, in that order.
[0017] Yet another embodiment of the present invention relates to a
method for producing an organic electronic element having a step of
forming an anode, a step of forming a layer (A) having hole
transport properties, and a step of forming a cathode, the method
also having at least one step selected from the group consisting of
a step of adhering an ionic compound to the surface on which the
layer (A) having hole transport properties is to be formed, and a
step of adhering an ionic compound to the surface of the layer (A)
having hole transport properties. Further, another embodiment of
the present invention relates to an organic electronic element
produced using the above method.
[0018] Other embodiments of the present invention relate to an
organic electroluminescent element that uses the above organic
electronic element, a display element that includes the organic
electroluminescent element, an illumination device that includes
the organic electroluminescent element, a display device that
includes the above illumination device and a liquid crystal element
as a display unit, and an organic photoelectric conversion element
that uses the above organic electronic element.
[0019] Examples of the above embodiments are presented below.
[0020] Examples of the treatment liquid described above include a
treatment liquid which contains the ionic compound and the solvent,
and is to be applied to the surface on which a layer having hole
transport properties is to be formed; a treatment liquid which also
contains a compound having a polymerizable substituent; a treatment
liquid in which the ionic compound has at least one anion selected
from the group consisting of anions represented by any one of
formula (1A) to formula (5A) shown below; a treatment liquid in
which the ionic compound has at least one cation selected from the
group consisting of cations of elements belonging to group 1 or
group 2 of the IUPAC Periodic Table of the Elements, and cations
represented by any one of formula (1B) to formula (3B) shown below;
and a treatment liquid in which the compound having a polymerizable
substituent has at least one group selected from the group
consisting of an oxetanyl group, epoxy group, vinyl group, vinyl
ether group, acrylate group and methacrylate group.
[0021] Further, examples of the organic electronic element
described above include an organic electronic element in which the
surface to which an ionic compound is adhered is a surface to which
a treatment liquid containing the ionic compound and a solvent has
been applied; an organic electronic element in which the treatment
liquid also contains a compound having a polymerizable substituent;
an organic electronic element in which the surface to which an
ionic compound is adhered is the surface of the anode; an organic
electronic element which also includes a layer (B) having hole
transport properties between the anode and the layer (A) having
hole transport properties, and in which the surface to which an
ionic compound is adhered is the surface of the layer (B) having
hole transport properties; and an organic electronic element which
also includes a light-emitting layer between the layer (A) having
hole transport properties and the cathode.
[0022] Moreover, examples of the aforementioned method for
producing an organic electronic element include a method for
producing an organic electronic element in which the step of
adhering an ionic compound is a step of applying a treatment liquid
containing the ionic compound and a solvent; a method for producing
an organic electronic element in which the treatment liquid also
contains a compound having a polymerizable substituent; a method
for producing an organic electronic element which includes a step
of forming an anode, a step of applying a treatment liquid
containing an ionic compound and a solvent to the surface of the
anode, a step of forming a layer (A) having hole transport
properties on the surface of the anode to which the treatment
liquid has been applied, and a step of forming a cathode, in that
order; a method for producing an organic electronic element which
includes a step of forming an anode, a step of forming a layer (B)
having hole transport properties, a step of applying a treatment
liquid containing an ionic compound and a solvent to the surface of
the layer (B) having hole transport properties, a step of forming a
layer (A) having hole transport properties on the surface of the
layer (B) having hole transport properties to which the treatment
liquid has been applied, and a step of forming a cathode, in that
order; and a method for producing an organic electronic element
which also includes a step of forming a light-emitting layer.
[0023] This Application is related to the subject matter disclosed
in prior Japanese Application 2013-046723 filed on Mar. 8, 2013,
the entire contents of which are incorporated by reference
herein.
Advantageous Effects of Invention
[0024] One embodiment of the present invention is able to provide a
treatment liquid that is capable of improving the properties of a
layer having hole transport properties. Further, another embodiment
of the present invention is able to provide an organic electronic
element having excellent properties and a method for producing the
element. Moreover, other embodiments of the present invention are
able to provide an organic electroluminescent element, a display
element, an illumination device, a display device and an organic
photoelectric conversion element having excellent properties.
BRIEF DESCRIPTION OF DRAWINGS
[0025] FIG. 1A to FIG. 1D are schematic plan views illustrating: in
FIG. 1A an example of an anode, in FIG. 1B an example of a
continuous coating film, and in FIGS. 1C and 1D examples of coating
films having non-continuous portions.
[0026] FIG. 2A to FIG. 2D are schematic cross-sectional views
illustrating: in FIG. 2A an example of an anode, in FIG. 2B an
example of a continuous coating film, and in FIGS. 2C and 2D
examples of coating films having non-continuous portions.
[0027] FIG. 3 is a schematic cross-sectional view illustrating one
example of an embodiment of an organic EL element.
[0028] FIG. 4 is a schematic cross-sectional view illustrating one
example of an embodiment of an organic EL element.
[0029] FIG. 5 is a graph illustrating the evaluation results for
charge transport evaluation elements prepared in the examples.
[0030] FIG. 6 is a schematic cross-sectional view illustrating one
example of a conventional organic EL element.
DESCRIPTION OF EMBODIMENTS
[0031] Embodiments of the present invention are described
below.
[Treatment Liquid]
[0032] The treatment liquid contains an ionic compound and a
solvent. The treatment liquid may also contain a compound having a
polymerizable substituent.
[0033] The treatment liquid is used for adhering the ionic compound
to a surface on which a layer having hole transport properties is
to be formed, a surface of a layer having hole transport
properties, or both these types of surfaces. The treatment liquid
is, for example, to be applied to a surface on which a layer having
hole transport properties is to be formed. Examples of the layer
having hole transport properties include a hole injection layer or
a hole transport layer in an organic EL element, and a buffer layer
in an organic photoelectric conversion element. Examples of the
surface on which a layer having hole transport properties is to be
formed include the surface of an anode and the surface of another
layer having hole transport properties. Details relating to the
layer having hole transport properties and the anode are described
below.
[Ionic Compound]
[0034] The ionic compound is a compound having at least one anion
and at least one cation. The ionic compound typically includes the
anion(s) and the cation(s) in a state where the charges of the
anion(s) and the cation(s) are balanced. The treatment liquid may
contain only a single ionic compound, or may contain two or more
ionic compounds. The anion and cation are described below in
further detail, but the anion and the cation are not limited to the
examples presented below.
[Anion]
[0035] The ionic compound preferably has an anion with an
electron-withdrawing substituent, and more preferably has at least
one anion selected from the group consisting of anions represented
by any one of formula (1A) to formula (5A) shown below.
##STR00001##
[0036] In the formulas, E.sup.1 represents an oxygen atom, E.sup.2
represents a nitrogen atom, E.sup.3 represents a carbon atom,
E.sup.4 represents a boron atom or a gallium atom, and E.sup.5
represents a phosphorus atom or an antimony atom, each of Y.sup.1
to Y.sup.6 independently represents a single bond or a divalent
linking group, and each of R.sup.1 to R.sup.16 independently
represents an electron-withdrawing monovalent group (wherein
R.sup.2 and R.sup.3, at least two groups selected from among
R.sup.4 to R.sup.6, at least two groups selected from among R.sup.7
to R.sup.10, and at least two groups selected from among R.sup.11
to R.sup.16 may be bonded together).
[0037] In formula (1A) to formula (5A), each of R.sup.1 to R.sup.16
independently represents an electron-withdrawing monovalent group.
The electron-withdrawing monovalent group is a substituent which,
compared with a hydrogen atom, withdraws electrons more readily
from atoms bonded to the substituent. R.sup.1 to R.sup.16 are
preferably organic groups. An organic group is an atom grouping
containing one or more carbon atoms. This definition of an organic
group also applies below. R.sup.2 and R.sup.3, at least two groups
selected from among R.sup.4 to R.sup.6, at least two groups
selected from among R.sup.7 to .sup.10, and at least two groups
selected from among R.sup.11 to R.sup.16 may be bonded together.
The bonded groups may form a ring.
[0038] Specific examples of the electron-withdrawing monovalent
group include halogen atoms such as a fluorine atom, chlorine atom
and bromine atom; a cyano group; a thiocyano group; a nitro group;
alkylsulfonyl groups (typically having a carbon number of 1 to 12,
and preferably a carbon number of 1 to 6) such as a mesyl group;
arylsulfonyl groups (typically having a carbon number of 6 to 18,
and preferably a carbon number of 6 to 12) such as a tosyl group;
alkyloxysulfonyl groups (typically having a carbon number of 1 to
12, and preferably a carbon number of 1 to 6) such as a
methoxysulfonyl group; aryloxysulfonyl groups (typically having a
carbon number of 6 to 18, and preferably a carbon number of 6 to
12) such as a phenoxysulfonyl group; acyl groups (typically having
a carbon number of 1 to 12, and preferably a carbon number of 1 to
6) such as a formyl group, acetyl group and benzoyl group; acyloxy
groups (typically having a carbon number of 1 to 20, and preferably
a carbon number of 1 to 6) such as a formyloxy group and an acetoxy
group; alkoxycarbonyl groups (typically having a carbon number of 2
to 10, and preferably a carbon number of 2 to 7) such as a
methoxycarbonyl group and an ethoxycarbonyl group; aryloxycarbonyl
groups or heteroaryloxycarbonyl groups (typically having a carbon
number of 4 to 25, and preferably a carbon number of 5 to 15) such
as a phenoxycarbonyl group and a pyridyloxycarbonyl group;
haloalkyl groups, haloalkenyl groups and haloalkynyl groups
(typically having a carbon number of 1 to 10, and preferably a
carbon number of 1 to 6) in which a linear, branched or cyclic
alkyl group, alkenyl group or alkynyl group has been substituted
with one or more halogen atoms, such as a trifluoromethyl group and
a pentafluoroethyl group; haloaryl groups (typically having a
carbon number of 6 to 20, and preferably a carbon number of 6 to
12) in which an aryl group has been substituted with one or more
halogen atoms, such as a pentafluorophenyl group; and haloarylalkyl
groups (typically having a carbon number of 7 to 19, and preferably
a carbon number of 7 to 13) in which an arylalkyl group has been
substituted with one or more halogen atoms, such as a
pentafluorophenylmethyl group.
[0039] An aryl group is an atom grouping in which one hydrogen atom
has been removed from an aromatic hydrocarbon. The term aromatic
hydrocarbon includes compounds having condensed rings. Further, the
term aromatic hydrocarbon also includes compounds in which two or
more independent single rings or condensed rings are bonded
together directly (via a single bond) or via a group such as a
vinylene group. A heteroaryl group is an atom grouping in which one
hydrogen atom has been removed from an aromatic compound having a
hereto atom. The term aromatic compound includes compounds having
condensed rings. Further, the term aromatic compound also includes
compounds in which two or more independent single rings or
condensed rings are bonded together directly or via a group such as
a vinylene group. These definitions of an aryl group and a
heteroaryl group also apply below.
[0040] Moreover, from the viewpoint of enabling efficient
delocalization of the negative charge, examples of preferred
electron-withdrawing monovalent groups include groups in which some
or all of the hydrogen atoms of an "organic group having hydrogen
atoms" selected from among the examples of electron-withdrawing
monovalent groups mentioned above have each been substituted with a
halogen atom. Specific examples of such groups include
perfluoroalkylsulfonyl groups, perfluoroarylsulfonyl groups,
perfluoroalkyloxysulfonyl groups, perfluoroaryloxysulfonyl groups,
perfluoroacyl groups, perfluoroacyloxy groups,
perfluoroalkoxycarbonyl groups, perfluoroaryloxycarbonyl groups,
perfluoroalkyl groups, perfluoroalkenyl groups, perfluoroalkynyl
groups, perfluoroaryl groups, and perfluoroarylalkyl groups.
[0041] Particularly preferred electron-withdrawing monovalent
groups include linear or branched perfluoroalkyl groups having a
carbon number of 1 to 8, cyclic perfluoroalkyl groups having a
carbon number of 3 to 6, and perfluoroaryl groups having a carbon
number of 6 to 18.
[0042] The electron-withdrawing monovalent group is not limited to
the groups described above. The examples of the
electron-withdrawing monovalent group mentioned above may further
include a substituent or a hetero atom.
[0043] Specific examples of the electron-withdrawing monovalent
group include the groups of a substituent group (1) shown below.
<Substituent Group (1)>
##STR00002## ##STR00003##
[0044] In formulas (1A) to (5A), each of Y.sup.1 to Y.sup.6
independently represents a single bond or a divalent linking group.
The cases where Y.sup.1 to Y.sup.6 represent single bonds describe
those cases where E and R are bonded together directly. Examples of
the divalent linking group include groups represented by any one of
formulas (1c) to (11c) shown below.
##STR00004##
[0045] In the above formulas, each R independently represents a
hydrogen atom or a monovalent group.
[0046] R is preferably an organic group. From the viewpoints of
enhancing the electron-accepting properties and improving the
solubility in the solvent and the like, each R preferably
independently represents an alkyl group, alkenyl group, alkynyl
group, aryl group or heteroaryl group. These groups may have a
substituent, and may include a hetero atom. Further, R is
preferably an electron-withdrawing monovalent group, and examples
of the electron-withdrawing monovalent group include the examples
of electron-withdrawing monovalent groups mentioned above, and the
groups shown in the above substituent group (1).
[0047] The anion is preferably an anion in which the negative
charge resides mainly on an oxygen atom, nitrogen atom, carbon
atom, boron atom or gallium atom, and is more preferably an anion
in which the negative charge resides mainly on an oxygen atom,
nitrogen atom, carbon atom or boron atom. Specific examples include
anions represented by formulas (6A) to (9A) shown below.
##STR00005##
[0048] In the above formulas, each of R.sup.1 to R.sup.10
independently represents an electron-withdrawing monovalent group
(wherein R.sup.2 and R.sup.3, at least two groups selected from
among R.sup.4 to R.sup.6, and at least two groups selected from
among R.sup.7 to R.sup.10, may be bonded together).
[0049] R.sup.1 to R.sup.10 are preferably organic groups. Examples
of the electron-withdrawing monovalent group include the examples
of electron-withdrawing monovalent groups mentioned above, and the
groups shown in the above substituent group (1). A group from the
above substituent group (1) is preferred.
[Cation]
[0050] The ionic compound preferably has at least one cation
selected from the group consisting of cations of elements belonging
to group 1 or group 2 of the IUPAC Periodic Table of the Elements
(version date: 1 Jun. 2012, this also applies below), and cations
represented by any one of formula (1B) to formula (3B) shown below.
It is more preferable that the ionic compound has a cation
represented by one of formula (1B) to formula (3B).
##STR00006##
[0051] In the above formulas, A.sup.1 represents an element
belonging to group 17 or group 14 of the IUPAC Periodic Table of
the Elements, A.sup.2 represents an element belonging to group 16
or group 14 of the IUPAC Periodic Table of the Elements, A.sup.3
represents an element belonging to group 15 of the IUPAC Periodic
Table of the Elements, and each of R.sup.1 to R.sup.9 independently
represents a hydrogen atom or an organic group (wherein R.sup.1 and
R.sup.2, at least two groups selected from among R.sup.3 to
R.sup.5, and at least two groups selected from among R.sup.6 to
R.sup.9 may be bonded together).
[0052] Each of R.sup.1 to R.sup.9 independently represents a
hydrogen atom or an organic group. From the viewpoint of factors
such as the stability of the ionic compound and the solubility in
the solvent, each of R.sup.1 to R.sup.9 preferably independently
represents a hydrogen atom, or an alkyl group, alkenyl group,
alkynyl group, arylalkyl group, aryl group or heteroaryl group.
These groups may also have a substituent. R.sup.1 and R.sup.2, at
least two groups selected from among R.sup.3 to R.sup.5, and at
least two groups selected from among R.sup.6 to R.sup.9 may be
bonded together to form a ring. At least one group selected from
among R.sup.1 and R.sup.2, at least one group selected from among
R.sup.3 to R.sup.5, and at least one group selected from among
R.sup.6 to R.sup.9 are preferably organic groups.
[0053] From the viewpoints of the stability and the ease of
synthesis and purification of the ionic compound, A.sup.1 in
formula (1B) is preferably a bromine atom, iodine atom or carbon
atom, A.sup.2 in formula (2B) is preferably an oxygen atom, carbon
atom, sulfur atom or selenium atom, and A.sup.3 in formula (3B) is
preferably a nitrogen atom, phosphorus atom, arsenic atom, antimony
atom or bismuth atom.
[0054] Additional specific examples of the cation include cations
represented by formula (4B) shown below.
##STR00007##
[0055] In the formula, Ar represents an aryl group or a heteroaryl
group, each of R.sup.1 and R.sup.2 independently represents a
hydrogen atom or an alkyl group, benzyl group, aryl group or
heteroaryl group, and at least two groups selected from among Ar,
R.sup.1 and R.sup.2 may be bonded together to form a ring. However,
at least one of R.sup.1 and R.sup.2 is a hydrogen atom, an alkyl
group or a benzyl group.
[0056] When solubility of the ionic compound in the solvent is
considered, at least one of R.sup.1 and R.sup.2 is preferably an
alkyl group or a benzyl group, and compounds in which each of
R.sup.1 and R.sup.2 is either an alkyl group or a benzyl group are
particularly preferable. In formula (4B), R.sup.1 and R.sup.2
cannot both be aryl groups or heteroaryl groups.
[0057] Specific examples of R.sup.1 and R.sup.9 in formulas (1B) to
(3B), and R.sup.1 and R.sup.2 in formula (4B) are described below.
However, examples of R.sup.1 to R.sup.9, R.sup.1 and R.sup.2, and
examples of substituents within these groups are not limited to the
examples presented below.
[0058] The aforementioned alkyl group may be linear, branched or
cyclic, may have a substituent, and has a carbon number that is
preferably from 1 to 24, and more preferably from 2 to 18. Specific
examples include a methyl group, ethyl group, propyl group,
i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl
group, hexyl group, cyclohexyl group, heptyl group, octyl group,
2-ethylhexyl group, nonyl group, decyl group, dodecyl group,
tetradecyl group, octadecyl group, 3,7-dimethyloctyl group, lauryl
group, trifluoromethyl group, pentafluoroethyl group,
perfluorobutyl group, perfluorohexyl group and perfluorooctyl
group.
[0059] The aforementioned alkenyl group may be linear, branched or
cyclic, may have a substituent, and has a carbon number that is
preferably from 2 to 12, and more preferably from 2 to 6. Specific
examples include a vinyl group, 1-propenyl group, 2-propenyl group,
isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl
group, 1-octenyl group, 1-decenyl group and 1-octadecenyl
group.
[0060] The aforementioned alkynyl group may be linear, branched or
cyclic, may have a substituent, and has a carbon number that is
preferably from 2 to 12, and more preferably from 2 to 6. Specific
examples include an ethynyl group, 1-propynyl group, 2-propynyl
group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl
group, 1-decynyl group and 1-octadecynyl group.
[0061] The aforementioned aryl group may have a substituent. The
carbon number of the monovalent aryl group in an unsubstituted
state is preferably from 6 to 60, and more preferably from 6 to 18.
Specific examples include a phenyl group, C1 to C12 alkoxyphenyl
groups (here C1 to C12 means that the carbon number of the
substituent is from 1 to 12, this numbering system also applies
below), C1 to C12 alkylphenyl groups, and a 1-naphthyl group,
2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group,
9-anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl
group and pentafluorophenyl group, and of these, a C1 to C12
alkoxyphenyl group or a C1 to C12 alkylphenyl group is
preferred.
[0062] Specific examples of the C1 to C12 alkoxy substituent
include methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy,
t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy,
2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy and
lauryloxy substituents.
[0063] Specific examples of the C1 to C12 alkyl substituent include
methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl,
hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl,
3,7-dimethyloctyl and lauryl substituents.
[0064] The aforementioned heteroaryl group may have a substituent.
The carbon number of the monovalent heteroaryl group in an
unsubstituted state is preferably from 4 to 60, and more preferably
from 4 to 20. Specific examples include a thienyl group, C1 to C12
alkylthienyl groups, pyrrolyl group, furyl group, pyridyl group and
C1 to C12 alkylpyridyl groups, and of these, a thienyl group, C1 to
C12 alkylthienyl group, pyridyl group or C1 to C12 alkylpyridyl
group is preferred. Examples of the C1 to C12 alkyl substituent are
as mentioned above.
[0065] The aforementioned arylalkyl group is a group in which at
least one hydrogen atom of an alkyl group has been substituted with
an aryl group. The arylalkyl group may have a substituent. The
carbon number of the monovalent arylalkyl group in an unsubstituted
state is preferably from 7 to 19, and more preferably from 7 to 13.
Examples of the alkyl group include the alkyl groups mentioned
above, and examples of the aryl group include the aryl groups
mentioned above. Specific examples of the arylalkyl group include a
benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl
group and diphenylmethyl group.
[0066] Further, the cation of the ionic compound is preferably an
iodonium, sulfonium, phosphonium, carbenium (trityl), bismuthonium,
ammonium, selenium, oxonium or tropylium ion.
[0067] Examples of the iodonium ion include diphenyliodonium,
di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium,
bis(4-methoxyphenypiodonium, (4-octyloxyohenyl)phenyliodonium,
bis(4-decyloxyphenyl)iodonium,
4-(2-hydroxytetradecyloxy)phenylphenyliodonium,
4-isopropylphenyl(p-tolyl)iodonium and
isobutylphenyl(p-tolyl)iodonium ions. These types of ions are
disclosed in Macromolecules, 10, 1307 (1977), JP 6-184170 A, U.S.
Pat. Nos. 4,256,828, 4,351,708, JP 56-135519 A, JP 58-38350 A, JP
10-195117 A, JP 2001-139539 A, JP 2000-510516 A, and JP 2000-119306
A and the like.
[0068] Examples of the sulfonium ion include triarylsulfonium ions
such as triphenylsulfonium, tri-p-tolylsulfonium,
tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium,
1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium,
tris(4-fluorophenyl)sulfonium, tri-l-naphthylsulfonium,
tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium,
4-(phenylthio)phenyldiphenylsulfonium,
4-(p-tolylthio)phenyldi-p-tolylsulfonium,
4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium,
4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium,
4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium,
4-(phenylthio)phenyldi-p-tolylsulfonium,
bis[4-(diphenylsulfonio)phenyl]sulfide,
bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide,
bis{4-[bis (4-fluorophenyl)sulfonio]phenyl}sulfide,
bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide,
bis{4-[bis(4-methoxyphenypsulfonio]phenyl}ulfide,
4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium,
4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium,
4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium,
4-(4-benzoylphenylthio)phenyldiphenylsulfonium,
7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium,
7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium,
2-[(di-p-tolypsulfonio]thioxanthone,
2-[(diphenyl)sulfonio]thioxanthone,
4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium,
4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium,
4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium,
4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium,
5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium,
5-tolylthianthrenium, 5-(4-ethoxyphenyl)thianthrenium and
5-(2,4,6-trimethylphenyl)thianthrenium ions; diarylsulfonium ions
such as diphenylphenacylsulfonium,
diphenyl-4-nitrophenacylsulfonium, diphenylbenzylsulfonium and
diphenylmethylsulfonium ions; monoarylsulfonium ions such as
phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium,
4-methoxyphenylmethylbenzylsulfonium,
4-acetocarbonyloxyphenylmethylbenzylsulfonium,
2-naphthylmethylbenzylsulfonium,
2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium,
phenylmethylphenacylsulfonium,
4-hydroxyphenylmethylphenacylsulfonium,
4-methoxyphenylmethylphenacylsulfonium,
4-acetocarbonyloxyphenylmethylphenacylsulfonium,
2-naphthylmethylphenacylsulfonium,
2-naphthyloctadecylphenacylsulfonium and
9-anthracenylmethylphenacylsulfonium ions; and trialkylsulfonium
ions such as dimethylphenacylsulfonium,
phenacyltetrahydrothiophenium, dimethylbenzylsulfonium,
benzyltetrahydrothiophenium and octadecylmethylphenacylsulfonium
ions. These types of ions are disclosed in the following
documents.
[0069] Documents related to the triarylsulfonium ions include U.S.
Pat. Nos. 4,231,951, 4,256,828, JP 7-61964 A, JP 8-165290 A, JP
7-10914 A, JP 7-25922 A, JP 8-27208 A, JP 8-27209 A, JP 8-165290 A,
JP 8-301991 A, JP 9-143212 A, JP 9-278813 A, JP 10-7680 A, JP
10-287643 A, JP 10-245378 A, JP 8-157510 A, JP 10-204083 A, JP
8-245566 A, JP 8-157451 A, JP 7-324069 A, JP 9-268205 A, JP
9-278935 A, JP 2001-288205 A, JP 11-80118 A, JP 10-182825 A, JP
10-330353 A, JP 10-152495 A, JP 5-239213 A, JP 7-333834 A, JP
9-12537 A, JP 8-325259 A, JP 8-160606 A and JP 2000-186071 A (U.S.
Pat. No. 6,368,769); documents related to the diarylsulfonium ions
include JP 7-300504 A, JP 64-45357 A and JP 64-29419 A; documents
related to the monoarylsulfonium ions include JP 6-345726 A, JP
8-325225 A, JP 9-118663 A (U.S. Pat. No. 6,093,753), JP 2-196812 A,
JP 2-1470 A, JP 2-196812 A, JP 3-237107 A, JP 3-17101 A, JP
6-228086 A, JP 10-152469 A, JP 7-300505 A, JP 2003-277353 A and JP
2003-277352 A; and documents related to the trialkylsulfonium ions
include JP 4-308563 A, JP 5-140210 A, JP 5-140209 A, JP 5-230189 A,
JP 6-271532 A, JP 58-37003 A, JP 2-178303 A, JP 10-338688 A, JP
9-328506 A, JP 11-228534 A, JP 8-27102 A, JP 7-333834 A, JP
5-222167 A, JP 11-21307 A, JP 11-35613 A and U.S. Pat. No.
6,031,014.
[0070] Examples of the phosphonium ion include tetraarylphosphonium
ions such as tetraphenylphosphonium, tetra-p-tolylphosphonium,
tetrakis(2-methoxyphenyl)phosphonium,
tetrakis(3-methoxyphenyl)phosphonium and
tetrakis(4-methoxyphenyl)phosphonium ions; triarylphosphonium ions
such as triphenylbenzylphosphonium, triphenylphenacylphosphonium,
triphenylmethylphosphonium and triphenylbutylphosphonium ions; and
tetraalkylphosphonium ions such as triethylbenzylphosphonium,
tributylbenzylphosphonium, tetraethylphosphonium,
tetrabutylphosphonium, tetrahexylphosphonium,
triethylphenacylphosphonium and tributylphenacylphosphonium ions.
These types of ions are disclosed in JP 6-157624 A, JP 5-105692 A,
JP 7-82283 A, and JP 9-202873 A and the like.
[0071] Examples of the carbenium ion include trialkylcarbenium ions
such as trimethylcarbenium and triethylcarbeium ions, and
triarylcarbenium ions such as triphenylcarbenium and
tri-p-tolylcarbenium ions.
[0072] Bismuthonium ions are disclosed, for example, in JP
2008-214330 A.
[0073] Examples of the ammonium ion include tetraalkylammonium ions
such as tetramethylammonium, ethyltrimethylammonium,
diethyldimethylammonium, triethylmethylammonium,
tetraethylammonium, trimethyl-n-propylammonium,
trimethylisopropylammonium, trimethyl-n-butylammonium,
trimethylisobutylammonium, trimethyl-t-butylammonium,
trimethyl-n-hexylammonium, dimethyldi-n-propylammonium,
dimethyldiisopropylammonium, dimethyl-n-propylisopropylammonium,
methyltri-n-propylammonium and methyltriisopropylammonium ions;
pyrrolidinium ions such as N,N-dimethylpyrrolidinium,
N-ethyl-N-methylpyrrolidinium and N,N-diethylpyrrolidinium ions;
imidazolinium ions such as N,N'-dimethylimidazolinium,
N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium,
1,2,3-trimethylimidazolinium, 1,3,4-trimethylimidazolinium,
1,3-diethyl-2-methylimidazolinium,
1,3-diethyl-4-methylimidazolinium and
1,2,3,4-tetramethylimidazolinium ions; tetrahydropyrimidinium ions
such as N,N'-dimethyltetrahydropyrimidinium,
N,N'-diethyltetrahydropyrimidinium,
N-ethyl-N'-methyltetrahydropyrimidinium and
1,2,3-trimethyltetrahydropyrimidinium ions; morpholinium ions such
as N,N-dimethylmorpholinium, N-ethyl-N-methyhmorpholinium and
N,N-diethylmorpholinium ions; piperidinium ions such as
N,N-dimethylpiperidinium, N-ethyl-N-methylpiperidinium and
N,N-diethylpiperidinium ions; pyridinium ions such as
N-methylpyridinium, N-ethylpyridinium, N-n-propylpyridinium,
N-isopropylpyridinium, N-n-butylpyridinium, N-benzylpyridinium and
N-phenacylpyridinium ions; imidazolium ions such as
N,N'-dimethylimidazolium, N-ethyl-N'-methylimidazolium,
N,N'-diethylimidazolium, 1,2-diethyl-3-methylimidazolium,
1,3-diethyl-2-methylimidazolium and
1-methyl-3-n-proypl-2,4-dimethylimidazolium ions; quinolinium ions
such as N-methylquinolinium, N-ethylquinolinium,
N-n-propylquinolinium, N-isopropylquinolinium,
N-n-butylquinolinium, N-benzylquinolinium and N-phenacylquinolinium
ions; isoquinolinium ions such as N-methylisoquinolinium,
N-ethylisoquinolinium, N-n-propylisoquinolinium,
N-isopropylisoquinolinium, N-n-butylisoquinolinium,
N-benzylisoquinolinium and N-phenacylisoquinolinium ions;
thiazonium ions such as benzylbenzothiazonium and
phenacylbenzothiazonium ions; and acridinium ions such as
benzylacridinium and phenacylacridinium ions. Further, examples of
the ammonium ion include anilinium ions, aminium ions, and imonium
ions.
[0074] These types of ions are disclosed in U.S. Pat. No.
4,069,055, JP 2519480 Bl, JP 5-222112 A, JP 5-222111 A, JP 5-262813
A, JP 5-255256 A, JP 7-109303 A, JP 10-101718 A, JP 2-268173 A, JP
9-328507 A, JP 5-132461 A, JP 9-221652 A, JP 7-43854 A, JP 7-43901
A, JP 5-262813 A, JP 4-327574 A, JP 2-43202 A, JP 60-203628 A, JP
57-209931 A, and JP 9-221652 A and the like.
[0075] Examples of the selenium ion include triarylselenium ions
such as triphenylselenium, tri-p-tolylselenium,
tri-o-tolylselenium, tris(4-methoxyphenyl)selenium,
1-naphthyldiphenylselenium, tris(4-fluorophenyl)selenium,
tri-l-naphthylselenium, tri-2-naphthylselenium,
tris(4-hydroxyphenyl)selenium, 4-(phenylthio)phenyldiphenylselenium
and 4-(p-tolylthio)phenyldi-p-tolylselenium ions; diarylselenium
ions such as diphenylphenacylselenium, diphenylbenzylselenium and
diphenylmethylselenium ions; monoarylselenium ions such as
phenylmethylbenzylselenium, 4-hydroxyphenylmethylbenzylselenium,
phenylmethylphenacylselenium, 4-hydroxyphenylmethylphenacylselenium
and 4-methoxyphenylmethylphenacylselenium ions; and
trialkylselenium ions such as dimethylphenacylselenium,
phenacyltetrahydroselenophenium, dimethylbenzylselenium,
benzyltetrahydroselenophenium and octadecylmethylphenacylselenium
ions. These types of ions are disclosed in JP 50-151997 A, JP
50-151976 A, and JP 53-22597 A and the like.
[0076] Examples of the oxonium ion include trimethyloxonium,
triethyloxonium, tripropyloxonium, tributyloxonium,
trihexyloxonium, triphenyloxonium, pyrylium, chromenilium and
xanthylium ions.
[0077] Tropylium ions are disclosed, for example, in J. Polym. Sci.
Part A; Polym. Chem., 42, 2166 (2004).
[0078] From the viewpoint of enhancing the hole transport
properties, the anion (3A), (4A) or (5A) is preferable, and the
anion (3A) or (4A) is more preferable. Similarly, from the
viewpoint of enhancing the hole transport properties, the cation
(1B) or (3B) is preferable. The ionic compound is preferably a
compound having at least one anion selected from among these
anions, and at least one cation selected from among these
cations.
[0079] More specifically, compounds containing at least one anion
selected from among fluoroalkane sulfonyl methide ions (for
example, (3A)) and borate ions (for example, (4A)), and at least
one cation selected from among ammonium ions and iodonium ions are
preferred.
[0080] From the viewpoint of enabling the treatment liquid to be
used with various coating processes, the amount of the ionic
compound, relative to the total mass of the treatment liquid, is
preferably at least 0.01% by mass, more preferably at least 0.1% by
mass, and still more preferably 0.3% by mass or greater. The above
range is also preferred in terms of enabling the hole transport
properties to be enhanced with a single treatment. Further, in
order to enable the treatment liquid to be used with various
coating processes, the amount of the ionic compound, relative to
the total mass of the treatment liquid, is preferably not more than
50% by mass, more preferably 20% by mass or less, and still more
preferably 10% by mass or less. This range is also preferred in
terms of preventing short-circuits within the various layers due to
precipitation of crystals of the ionic compound. Specifically, the
amount of the ionic compound, relative to the total mass of the
treatment liquid, is preferably from 0.01 to 50% by mass, more
preferably from 0.1 to 20% by mass, and still more preferably from
0.3 to 10% by mass.
[Solvent]
[0081] The solvent is preferably a solvent capable of dissolving or
dispersing the ionic compound, and is more preferably a solvent
capable of dissolving the ionic compound. The treatment liquid may
contain only a single solvent, or may contain two or more
solvents.
[0082] Water and organic solvents and the like can be used as the
solvent. Examples of the organic solvents include alcohols such as
methanol, ethanol and isopropyl alcohol; alkanes such as pentane,
hexane and octane; cyclic alkanes such as cyclohexane; aromatic
hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin
and diphenylmethane; aliphatic ethers such as ethylene glycol
dimethyl ether, ethylene glycol diethyl ether and propylene
glycol-l-monomethyl ether acetate; aromatic ethers such as
1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole,
2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene,
2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic esters such
as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl
lactate; aromatic esters such as phenyl acetate, phenyl propionate,
methyl benzoate, ethyl benzoate, propyl benzoate and n-butyl
benzoate; amides such as N,N-dimethylformamide and
N,N-dimethylacetamide; as well as dimethyl sulfoxide,
tetrahydrofuran, acetone, chloroform and methylene chloride. From
the viewpoint of the solubility of the ionic compound, the use of
an aromatic hydrocarbon, aliphatic ester, aromatic ester, aliphatic
ether or aromatic ether is preferable. If productivity is also
taken into consideration, then the use of a solvent having a
boiling point at one atmosphere of 50 to 300.degree. C. is
preferred.
[Compound having Polymerizable Substituent]
[0083] The treatment liquid may also include a compound having a
polymerizable substituent. Use of a compound having a polymerizable
substituent is desirable from the viewpoint of improving the
lifespan properties of the organic electronic element. The
treatment liquid may contain only a single compound having a
polymerizable substituent, or may contain two or more such
compounds.
[0084] The polymerizable substituent is a group that can form bonds
through application of heat and/or light. The compound having a
polymerizable substituent is preferably a compound having at least
one group selected from the group consisting of an oxetanyl group
(oxetane group), epoxy group (oxiranyl group), vinyl group, vinyl
ether group (vinyloxy group), acrylate group (acryloyloxy group)
and methacrylate group (methacryloyloxy group). The polymerizable
substituent is preferably an oxetanyl group, epoxy group or vinyl
ether group, and is more preferably an oxetanyl group or an epoxy
group. From the viewpoint of improving the lifespan properties of
the organic electronic element, these compounds having a
polymerizable substituent may also include an oxygen atom derived
from an ether linkage or a hydroxyl group or the like, in a portion
of the molecule outside the aforementioned polymerizable
substituent.
[0085] The compound having a polymerizable substituent has at least
one polymerizable substituent per molecule. The compound may have
two or more of the same or different polymerizable substituents
within each molecule. Further, from the viewpoint of the stability
of the treatment liquid, the total number of polymerizable
substituents is preferably not more than 100 per molecule.
[0086] The compound having a polymerizable substituent may be a
low-molecular weight compound, or a polymer or oligomer of a
monomer.
[0087] In one embodiment, the compound having a polymerizable
substituent may include a structure containing a conjugated system
in addition to the structure of the polymerizable substituent.
Further, in another embodiment, the compound having a polymerizable
substituent may not have a structure containing a conjugated system
in addition to the structure included in the polymerizable
substituent. Examples of the conjugated system include conjugated
structures that can be included within a layer having hole
transport properties, and conjugated structures which exhibit hole
transport properties, and specific examples include structures
described below as units having hole transport properties, aromatic
hydrocarbon structures, and aromatic compound structures having a
hetero atom. From the viewpoint of enabling enhancement of the
properties of the organic electronic element using a treatment
liquid that can be prepared simply and cheaply, and from the
viewpoint of reducing the absorption of light emitted from the
light-emitting layer toward the anode side, thereby improving the
light emission efficiency of the organic EL element, the compound
having a polymerizable substituent preferably does not have a
structure containing a conjugated system except for conjugated
systems included in the polymerizable substituent.
[0088] Examples of the compound having a polymerizable substituent
are listed below.
[0089] A "compound having an oxetanyl group" refers to an oxetane
compound having at least one oxetanyl group within the molecule.
Conventional compounds having an oxetanyl group can be used without
any particular restrictions.
[0090] Specific examples of the compound having an oxetanyl group
include 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,
3-ethyl-3-(dodecyloxymethyl)oxetane,
3-ethyl-3-(octadecyloxymethyl)oxetane,
3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane,
1,4-bis{[3-ethyl-3-oxetanyl)methoxy]methyl}benzene,
bis[(3-ethyl-3-oxetanyl)methyl] ether, bis[2-(3-oxetanyl)butyl]
ether, 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene,
1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene,
1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene,
4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl,
2,2'-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl,
3,3',5,5'-tetramethyl[4,4'-bis(3-ethyloxetan-3-yl)methoxy]biphenyl,
2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene,
1,6-bis[(3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane,
3(4),8(9)-bis[(1-ethyl-3-oxetanyl)methoxymethyl]-tricyclo[5.2.1.0.sup.2.6-
]decane, 1,2-bis[2-{(1-ethyl-3-oxetanyl)methoxy}ethylthio]ethane,
4,4'-bis[(1-ethyl-3-oxetanyl)methyl]thiodibenzene thioether,
2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane,
2-ethyl-2-[(3-ethyloxetan-3-yl)methoxymethyl]-1,3-O-bis[(1-ethyl-3-oxetan-
yl)methyl]-propane-1,3-diol,
2,2-dimethyl-1,3-O-bis[(3-ethyloxetan-3-yl)methyl]-propane-1,3-diol,
2-butyl-2-ethyl-1,3-O-bis[(3-ethyloxetan-3-yl)methyl]-propane-1,3-diol,
1,4-O-bis[(3-ethyloxetan-3-yl)methyl]-butane-1,4-diol,
2,4,6-O-tris[(3-ethyloxetan-3-yl)methyl]cyanuric acid, and ether
compounds obtained by reacting bisphenol A and
3-ethyl-3-chloromethyloxetane (hereafter abbreviated as OXC), ether
compounds obtained by reacting bisphenol F and OXC, ether compounds
obtained by reacting phenol novolac and OXC, ether compounds
obtained by reacting cresol novolac and OXC, and oxetanyl
silsesquioxanes. These compounds can be obtained, for example, from
Toagosei Co., Ltd. and Ube Industries, Ltd. and the like.
[0091] A "compound having an epoxy group" refers to an epoxy
compound having at least one epoxy group within the molecule.
Conventional compounds having an epoxy group can be used as the
epoxy compound without any particular restrictions.
[0092] Examples of the compound having an epoxy group include
bisphenol-type epoxy compounds derived from epichlorohydrin and
bisphenol A or bisphenol F or the like; novolac-type epoxy
compounds such as cresol novolac epoxy compounds and phenol novolac
epoxy compounds; glycidyl ether-type epoxy compounds such as
monoglycidyl ethers, diglycidyl ethers and trifunctional or higher
polyglycidyl ethers; glycidyl ester-type epoxy compounds such as
monoglycidyl esters, diglycidyl esters and trifunctional or higher
polyglycidyl esters; glycidyl amine-type epoxy compounds such as
monoglycidyl amines, diglycidyl amines and trifunctional or higher
polyglycidyl amines; copolymers of glycidyl (meth)acrylates and
copolymerizable vinyl monomers; alicyclic epoxy compounds; aromatic
epoxy compounds; and triglycidyl isocyanurate. These compounds can
be obtained, for example, from Nagase ChemteX Corporation,
Mitsubishi Chemical Corporation, Nippon Steel & Sumikin
Chemical Co., Ltd., DIC Corporation, New Japan Chemical Co., Ltd.,
and Daicel Corporation and the like.
[0093] Examples of the bisphenol-type epoxy compounds include
bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S
epoxy resins and bisphenol AD epoxy resins.
[0094] Examples of the novolac-type epoxy compounds include cresol
novolac epoxy resins, phenol novolac epoxy resins, naphthol novolac
epoxy resins and bisphenol A novolac epoxy resins.
[0095] The glycidyl ether-type epoxy compounds are compounds having
a glycidyl ether group within the molecule. Specific examples of
the glycidyl ether-type epoxy compounds include methyl glycidyl
ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl
ether, pentyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl
glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl
ether, cyclohexane glycidyl ether, p-t-butylphenyl glycidyl ether,
o-cresyl glycidyl ether, biphenyl glycidyl ether, pentaerythritol
polyglycidyl ether, diglycerol polyglycidyl ether, glycerol
polyglycidyl ether, trimethylolpropane polyglycidyl ether,
neopentyl glycol diglycidyl ether, 1,6-hexanediol polyglycidyl
ether, polyethylene glycol diglycidyl ether, polypropylene glycol
diglycidyl ether, 1,4-bis(glycidyloxymethyl)benzene and
1,4-bis(glycidyloxymethyl)cyclohexane.
[0096] The glycidyl amine-type epoxy compounds are compounds having
a glycidylamino group within the molecule. Specific examples of the
glycidyl amine-type epoxy compounds include
N-(oxiranylmethyl)-N,N-dimethylamine,
N-(oxiranylmethyl)-N,N-diethylamine,
N-ethyl-N-(oxiranylmethyl)aniline,
N-methyl-N-(oxiranylmethyl)aniline, N,N-bis(oxiranylmethyl)aniline,
1,3-bis(diglycidylaminomethyl)cyclohexane, and
tetraglycidyldiaminodiphenylmethane.
[0097] The glycidyl ester-type epoxy compounds are compounds having
a glycidyl ester group within the molecule. Specific examples of
the glycidyl ether-type epoxy compounds include glycidyl acetate,
glycidyl propionate, glycidyl butyrate, glycidyl valerate, glycidyl
benzoate, diglycidyl phthalate, diglycidyl hexahydrophthalate and
diglycidyl tetrahydrophthalate.
[0098] The alicyclic epoxy compounds are compounds having an epoxy
group formed from one oxygen atom and two of the carbon atoms that
constitute a cyclic hydrocarbon structure within the molecule.
Examples of the alicyclic epoxy compounds include cyclohexene
oxide-containing compounds and cyclopentene oxide-containing
compounds obtained by oxidizing cyclohexene or cyclopentene
ring-containing compounds. More specific examples include
2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexane)-meta-dioxane,
3,4-epoxy-l-methylcyclohexyl-3,4-epoxy-1-methylhexane carboxylate,
3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane
carboxylate,
3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane
carboxylate, 3,4-epoxy-6-methylcyclohexyl carboxylate,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane
carboxylate, ethylenebis(3,4-epoxycyclohexane carboxylate),
dicyclopentadiene diepoxide, bis(3,4-epoxycyclohexylmethyl) adipate
and methylenebis(3,4-epoxycyclohexane).
[0099] A "compound having a vinyl group" is a compound having at
least one vinyl group in the molecule. However, this definition
excludes "compounds having a vinyl ether group", "compounds having
an acrylate group" and "compounds having a methacrylate group".
Examples of the compound having a vinyl group include butadiene,
1,3-pentadiene, 1-buten-3-ol, 1-penten-3-ol, 1-hexen-3-ol,
1-vinylcyclohexane, styrene and divinylbenzene.
[0100] A "compound having a vinyl ether group" is a compound having
at least one vinyl ether group in the molecule. Examples of the
compound having a vinyl ether group include divinyl ether, methyl
vinyl ether, ethyl vinyl ether, 1,4-butanediol divinyl ether,
cyclohexanedimethanol divinyl ether,diethylene glycol divinyl
ether, triethylene glycol divinyl ether and
1,4-bis(vinyloxymethyl)cyclohexane.
[0101] A "compound having an acrylate group" is a compound having
at least one acrylate group in the molecule, and a "compound having
a methacrylate group" is a compound having at least one
methacrylate group in the molecule. Examples of compounds having a
(meth)acrylate group (wherein the expression "compounds having a
(meth)acrylate group" includes both compounds having an acrylate
group and compounds having a methacrylate group) include methyl
(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl
(meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate,
carbitol (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl
(meth)acrylate, butoxyethyl (meth)acrylate, hydroxyethyl
(meth)acrylate, hydroxypropyl (meth)acrylate, butylene glycol
(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate,
N,N-diethylaminoethyl (meth)acrylate, tetrahydrofurfuryl
(meth)acrylate, pentaerythritol mono(meth)acrylate,
trimethylolpropane mono(meth)acrylate, 1,3-propylene glycol
di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, 1,6-hexane
glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
dipropylene glycol di(meth)acrylate,
2,2-bis-(4-(meth)acryloxydiethoxyphenyl)propane,
2,2-bis-(4-(meth)acryloxypropoxyphenyl)propane, trimethylolpropane
di(meth)acrylate, pentaerythritol di(meth)acrylate,
trimethylolpropane tri(meth)acrylate, pentaerythritol
tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate.
[0102] The compound having a polymerizable substituent may have one
or more of each of two or more different types of polymerizable
substituent within the same molecule. Examples of compounds having
two or more types of polymerizable substituents include
3-(vinyloxymethyl)oxetane, 3-oxetanyl (meth)acrylate,
(3-methyl-3-oxetanyl)methyl (meth)acrylate,
(3-ethyl-3-oxetanyl)methyl (meth)acrylate,
2-(vinyloxymethyl)oxirane, 2-oxiranylmethyl (meth)acrylate,
(2-methyl-2-oxiranyl)methyl (meth)acrylate and 2-(ethenyloxy)ethyl
(meth)acrylate. These compounds can be obtained, for example, from
Osaka Organic Chemical Industry Ltd.
[0103] If the treatment liquid contains an ionic compound, a
compound having a polymerizable substituent and a solvent, then
from the viewpoint of enabling the treatment liquid to be used with
various coating processes, the combined amount of the ionic
compound and the compound having a polymerizable substituent,
relative to the total mass of the treatment liquid, is preferably
at least 0.2% by mass, more preferably at least 0.3% by mass, and
still more preferably 0.5% by mass or greater. Further, in order to
enable the treatment liquid to be used with various coating
processes, the combined amount of the ionic compound and the
compound having a polymerizable substituent, relative to the total
mass of the treatment liquid, is preferably not more than 50% by
mass, more preferably 30% by mass or less, and still more
preferably 20% by mass or less. Specifically, the combined amount
of the ionic compound and the compound having a polymerizable
substituent, relative to the total mass of the treatment liquid, is
preferably from 0.2 to 50% by mass, more preferably from 0.3 to 30%
by mass, and still more preferably from 0.5 to 20% by mass. The
solvent is preferably a solvent, selected from among the solvents
mentioned above, that is capable of dissolving the ionic compound
and the compound having a polymerizable substituent.
[0104] From the viewpoint of better enhancing the hole transport
properties, the mass ratio between the ionic compound and the
compound having a polymerizable substituent is set so that,
relative to 1 part by mass of the ionic compound, the mass of the
compound having a polymerizable substituent is preferably not more
than 1,000 parts, more preferably not more than 100 parts, and
still more preferably 10 parts or less. Similarly, from the
viewpoint of better enhancing the hole transport properties, the
mass of the ionic compound relative to 1 part by mass of the
compound having a polymerizable substituent is preferably not more
than 1,000 parts, more preferably not more than 100 parts, and
still more preferably 10 parts or less. More specifically, the mass
ratio between the ionic compound and the compound having a
polymerizable substituent is preferably within a range from 1:1,000
to 1,000:1, more preferably from 1:100 to 100:1, and still more
preferably from 1:10 to 10:1.
[Other Optional Components]
[0105] The treatment liquid contains at least the ionic compound
and the solvent, and in some cases also contains the compound
having a polymerizable substituent. In one embodiment, the
treatment liquid may contain a compound having hole transport
properties. In another embodiment, the treatment liquid may not
contain a compound having hole transport properties. In those cases
when the treatment liquid contains a compound having hole transport
properties, from the viewpoint of enhancing the properties of the
organic electronic element, the mass ratio between the ionic
compound and the compound having hole transport properties is set
so that, relative to 1 part by mass of the ionic compound, the mass
of the compound having hole transport properties is preferably not
more than 10 parts, more preferably not more than 1 part, still
more preferably not more than 0.1 parts, and particularly
preferably 0.01 parts or less. From the viewpoint of enabling
enhancement of the properties of the organic electronic element
using a treatment liquid that can be prepared simply and cheaply,
and from the viewpoint of reducing the absorption of light emitted
from the light-emitting layer, thereby improving the light emission
efficiency of the organic EL element, the treatment liquid
preferably does not contain a compound having hole transport
properties. Examples of the compound having hole transport
properties include the types of hole-transporting compounds that
can be used in the layer having hole transport properties described
below.
[0106] In one embodiment, the treatment liquid may also contain one
or more optional components such as dispersants, surfactants or
oxidizing agents. However, in another embodiment, the treatment
liquid may not contain optional components such as dispersants,
surfactants or oxidizing agents. When the treatment liquid contains
these types of optional components, from the viewpoint of achieving
a combination of good dispersion stability and superior hole
transport properties, the mass ratio between the ionic compound and
the optional components is set so that, relative to 1 part by mass
of the ionic compound, the mass of the optional components is
preferably not more than 100 parts, more preferably not more than
10 parts, and still more preferably 1 part or less. From the
viewpoint of enhancing the properties of the organic electronic
element using a treatment liquid that can be prepared simply and
cheaply, and from the viewpoint of maximizing the hole transport
properties, the treatment liquid preferably may not contain any
optional components.
[Usage Methods]
[0107] The treatment liquid is used for adhering the ionic compound
to a surface on which a layer having hole transport properties is
to be formed, a surface of a layer having hole transport
properties, or both these types of surfaces. The treatment liquid
is, for example, to be applied to a surface on which a layer having
hole transport properties is to be formed. Conventional methods can
be employed as the application method, and examples include spin
coating methods, casting methods, dipping methods, and printing
methods such as relief printing, intaglio printing, offset
printing, lithographic printing, relief reversal offset printing,
screen printing, gravure printing and inkjet printing. The
application process is typically conducted in a temperature range
from -20 to +300.degree. C., preferably from 10 to 100.degree. C.,
and particularly preferably from 15 to 50.degree. C. Following
application, the obtained coating film may be dried using a
hotplate or an oven to remove the solvent. The drying temperature
is typically from +30 to +300.degree. C., preferably from 60 to
250.degree. C., and particularly preferably from 80 to 220.degree.
C. The drying time is typically from 10 seconds to 2 hours,
preferably from 1 minute to 1 hour, and particularly preferably
from 1 to 10 minutes.
[0108] In those cases when the treatment liquid contains a compound
having a polymerizable substituent, it is preferable that following
application of the treatment liquid, the applied coating film is
subjected to irradiation with light and/or a heat treatment or the
like to cause the polymerizable substituent to react. For the light
irradiation, a low-pressure mercury lamp, medium-pressure mercury
lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp,
metal halide lamp, xenon lamp, fluorescent lamp, light-emitting
diode, or sunlight or the like may be used as the light source,
whereas the heating may be performed on a hotplate or in an oven.
The heating temperature is typically from +60 to +300.degree. C.,
preferably from 80 to 250.degree. C., and particularly preferably
from 100 to 220.degree. C. The heating time is typically from 10
seconds to 2 hours, preferably from 1 minute to 1 hour, and
particularly preferably from 1 to 10 minutes.
[0109] Following the drying, light irradiation or heat treatment,
the coating film may be washed to remove any unneeded components.
The washing must be performed such that the effect of enhancing the
hole transport properties is retained. The washing treatment may be
performed by methods such as rinsing the surface to which the
treatment liquid has been applied with water or an organic solvent,
or dipping the surface in water or an organic solvent.
[0110] The coating film obtained by applying the treatment liquid
may be a continuous film or a non-continuous film. Further, the
thickness of the film may be uniform or non-uniform. FIGS. 1A-1D
and 2A-2D illustrate examples of coating films. In FIGS. 1A-1D and
2A-2D, the surface of an anode is the surface on which the layer
having hole transport properties is to be formed, and the treatment
liquid is applied to the surface of the anode. FIGS. 1A-1D are
schematic plan views illustrating: in FIG. 1A the anode, in FIG. 1B
a continuous coating film, and in FIG. 1C and FIG. 1D coating films
having non-continuous portions. FIGS. 2A-2D are schematic
cross-sectional views illustrating: in FIG. 2A the anode, in FIG.
2B a continuous coating film, and in FIG. 2C and FIG. 2D coating
films having non-continuous portions. The coating film illustrated
in FIG. 1D and FIG. 2D is an island-type coating film.
[0111] From the viewpoint of enhancing the hole transport
properties, the thickness of the coating film following the drying,
light irradiation, heating and/or washing treatment is preferably
not more than 100 nm, more preferably not more than 30 nm, and
still more preferably 10 nm or less.
[0112] Regardless of whether the coating film is a continuous
coating film or a coating film having non-continuous portions, the
thickness of the coating film refers to the average value of the
thickness at 10 random points selected from portions where the
treatment liquid has been applied. The thickness of the coating
film can be measured, for example, by ellipsometry or using a
stylus-type thickness meter. The use of a stylus-type thickness
meter is preferable.
[Layer having Hole Transport Properties]
[0113] Next is a description of the layer having hole transport
properties. The expression "having hole transport properties" means
"having the capability of transporting holes". The layer having
hole transport properties can be formed using, for example, a
polymer or oligomer (namely, a macromolecular compound that is a
polymeric form of a monomer) having a unit with hole transport
properties, or a low-molecular weight compound having a structure
with hole transport properties (in the following description, a
polymer or oligomer having a unit with hole transport properties is
also referred to as a "polymer or oligomer having hole transport
properties", a low-molecular weight compound having hole transport
properties is also referred to as a "hole-transporting
low-molecular weight compound", and a hole-transporting polymer or
oligomer and a hole-transporting low-molecular weight compound may
be referred to jointly as a "hole-transporting compound"). From the
viewpoint of ensuring suitability with wet processes, a
hole-transporting polymer or oligomer can be used particularly
favorably. Further, from the viewpoint of enabling high-purity
compounds to be obtained with relative ease using a purification
technique such as sublimation purification, a hole-transporting
low-molecular weight compound can be used particularly
favorably.
[Hole-Transporting Polymer or Oligomer]
[0114] The unit having hole transport properties may be any unit
with the capability of transporting holes, and examples include
units containing an aromatic amine structure, units containing a
carbazole structure, and units containing a thiophene structure.
Units containing an aromatic amine structure and/or units
containing a carbazole structure are preferable. The
hole-transporting polymer or oligomer may contain two or more types
of these units. Further, the hole-transporting polymer or oligomer
may have a branched structure within the molecule, and may have
three or more terminals. A branched structure describes a structure
in which the hole-transporting polymer or oligomer has a branched
portion, with the units that constitute the chain of the polymer or
oligomer extending in three or more directions from the branched
portion. The hole-transporting polymer or oligomer may have a unit
that becomes the branch origin as the branch portion. A
hole-transporting polymer or oligomer having a branched structure
and having three or more terminals is composed of a main chain and
one or more side chains.
[0115] Examples of units having hole transport properties are shown
below in formulas (1a) to (93a). The units represented by formulas
(85a) to (93a) are units that can become a branch origin.
<Formulas (1a) to (84a)>
##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##
##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##
##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##
##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027##
##STR00028## ##STR00029## ##STR00030##
[0116] In formulas (1a) to (84a), each E independently represents
--R.sup.1, --OR.sup.2, --SR.sup.3, --OCOR.sup.4, --COOR.sup.5,
--SiR.sup.6R.sup.7R.sup.8, any of formulas (1) to (3) shown below,
or a group having a polymerizable substituent.
##STR00031##
[0117] Each of R.sup.1 to R.sup.11 represents a hydrogen atom, a
linear, cyclic or branched alkyl group having a carbon number of 1
to 22, or an aryl group or heteroaryl group having a carbon number
of 2 to 30, and each of a, b and c represents an integer of 1 or
greater. Here, an aryl group is an atom grouping in which one
hydrogen atom has been removed from an aromatic hydrocarbon, and
may have a substituent, whereas a heteroaryl group is an atom
grouping in which one hydrogen atom has been removed from an
aromatic compound having a hetero atom, and may have a
substituent.
[0118] Examples of the substituent include an alkyl group, alkoxy
group, alkylthio group, aryl group, aryloxy group, arylthio group,
arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl
group, arylalkynyl group, hydroxyl group, hydroxyalkyl group, amino
group, substituted amino group, silyl group, substituted silyl
group, silyloxy group, substituted silyloxy group, halogen atom,
acyl group, acyloxy group, imino group, amide group (--(NH)--COR),
imide group (--N(COR).sub.2), carboxyl group, substituted carboxyl
group, cyano group and monovalent heterocyclic group. Further, each
of a, b and c is preferably an integer of 1 to 4.
[0119] Examples of the polymerizable substituent include an
oxetanyl group (oxetane group), epoxy group (oxiranyl group), vinyl
ether group (vinyloxy group), acrylate group (acryloyloxy group)
and methacrylate group (methacryloyloxy group). Examples of the
group having a polymerizable substituent include an alkyl group or
alkylene oxide group or the like in which at least one hydrogen
atom has been substituted with one of the above polymerizable
substituents.
[0120] In the above description, examples of the alkyl group
include a methyl group, ethyl group, n-propyl group, n-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group,
n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group,
isopropyl group, isobutyl group, sec-butyl group, tert-butyl group,
2-ethylhexyl group, 3,7-dimethyloctyl group, cyclohexyl group,
cycloheptyl group and cyclooctyl group. Examples of the aryl group
include phenyl, biphenylyl, terphenylyl, naphthalenyl anthracenyl,
tetracenyl, fluorenyl and phenanthrenyl groups. Examples of the
heteroaryl group include pyridinyl, pyrazinyl, quinolinyl,
isoquinolinyl, acridinyl, phenanthrolinyl, furanyl, pyrrolyl,
thiophenyl, carbazolyl, oxazolyl, oxadiazolyl, thiadiazolyl,
triazolyl, benzoxazolyl, benzoxadiazolyl, benzothiadiazolyl,
benzotriazolyl and benzothiophenyl groups. These examples can also
be used for subsequent mentions of alkyl groups, aryl groups and
heteroaryl groups in the following description.
[0121] Each Ar independently represents an arylene group or
heteroarylene group having a carbon number of 2 to 30, or an aryl
group or heteroaryl group having a carbon number of 2 to 30. An
arylene group is an atom grouping in which two hydrogen atoms have
been removed from an aromatic hydrocarbon, and may have a
substituent, whereas a heteroarylene group is an atom grouping in
which two hydrogen atoms have been removed from an aromatic
compound having a hetero atom, and may have a substituent. Further,
an aryl group is an atom grouping in which one hydrogen atom has
been removed from an aromatic hydrocarbon, and may have a
substituent, whereas a heteroaryl group is an atom grouping in
which one hydrogen atom has been removed from an aromatic compound
having a hetero atom, and may have a substituent. Examples of the
substituent include the same groups as those mentioned above for E.
In a similar manner to that described above for the terms aryl
group and heteroaryl group, the terms arylene group and
heteroarylene group include condensed ring groups and groups in
which two or more rings are bonded together.
[0122] Examples of the arylene group include phenylene,
biphenyl-diyl, terpheyl-diyl, naphthalene-diyl, anthracene-diyl,
tetracene-diyl, fluorene-diyl and phenanthrene-diyl groups.
Examples of the heteroarylene groups include pyridine-diyl,
pyrazine-diyl, quinoline-diyl, isoquinoline-diyl, acridine-diyl,
phenanthroline-diyl, furan-diyl, pyrrole-diyl, thiophene-diyl,
carbazole-diyl, oxazole-diyl, oxadiazole-diyl, thiadiazole-diyl,
triazole-diyl, benzoxazole-diyl, benzoxadiazole-diyl,
benzothiadiazole-diyl, benzotriazole-diyl and benzothiophene-diyl
groups. These examples can also be used for subsequent mentions of
arylene groups and heteroarylene groups in the following
description.
[0123] Each of X and Z independently represents a divalent linking
group, and although there are no particular limitations, a group in
which one additional hydrogen atom has been removed from one of the
aforementioned E groups having one or more hydrogen atoms, or a
group of the linking group set (A) described below is preferred.
Further, x represents an integer of 0 to 2. Y represents a
trivalent linking group, and although there are no particular
limitations, a group in which two additional hydrogen atoms have
been removed from one of the aforementioned E groups having two or
more hydrogen atoms is preferred.
<Linking Group Set (A)>
##STR00032##
[0125] In the above formulas, each R independently represents a
hydrogen atom, a linear, cyclic or branched alkyl group having a
carbon number of 1 to 22 which may have a substituent, or an aryl
group or heteroaryl group having a carbon number of 2 to 30 which
may have a substituent. Ar represents a trivalent or tetravalent
linking group, and is preferably an atom grouping in which an
additional one or two hydrogen atoms have been removed from an
arylene group or heteroarylene group having a carbon number of 2 to
30.
<Formulas (85a) to (93a)>
##STR00033## ##STR00034##
[0126] In formulas (85a) to (93a), each Ar independently represents
an arylene group or heteroarylene group having a carbon number of 2
to 30, or an aryl group or heteroaryl group having a carbon number
of 2 to 30, and Y represents a divalent linking group. The units
represented by formulas (85a) to (93a) may have a substituent, and
examples of the substituent include the same groups as those
mentioned above for E in formulas (1a) to (84a).
[0127] Y in formulas (89a) and (93a) is preferably a divalent
linking group represented by one of the following formulas.
##STR00035##
[0128] In the above formulas, each R independently represents a
hydrogen atom, a linear, cyclic or branched alkyl group having a
carbon number of 1 to 22 which may have a substituent, or an aryl
group or heteroaryl group having a carbon number of 2 to 30 which
may have a substituent.
[0129] The hole-transporting polymer or oligomer may be a copolymer
having two or more units constituting the polymer or oligomer chain
The copolymer may be an alternating, random, block or graft
copolymer, or a copolymer having an intermediate type structure,
such as a random copolymer having block-like properties.
[0130] In order to adjust the solubility, the heat resistance or
the electrical properties, the hole-transporting polymer or
oligomer may be a copolymer which, in addition to the units
described above, includes an aforementioned arylene group or
heteroarylene group, or a structure represented by one of formulas
(1) to (31) shown below, as a copolymer unit. The units represented
by formulas (29) to (31) are units that can become a branch
origin.
<Formulas (1) to (28)>
##STR00036## ##STR00037## ##STR00038## ##STR00039##
##STR00040##
[0132] In formulas (1) to (28), examples of R include the same
groups as those mentioned above for E in formulas (1a) to
(84a).
<Formulas (29) to (31)>
##STR00041##
[0134] In formulas (29) to (31), W represents a trivalent linking
group, and is preferably an atom grouping in which an additional
one hydrogen atom has been removed from an arylene group or
heteroarylene group having a carbon number of 2 to 30. Each Ar
independently represents an arylene group or heteroarylene group
having a carbon number of 2 to 30, and Z represents a carbon atom,
silicon atom or phosphorus atom. Each of the units represented by
formulas (29) to (31) may have a substituent, and examples of the
substituent include the same groups as those mentioned above for E
in formulas (1a) to (84a).
[0135] The hole-transporting polymer or oligomer may have a
polymerizable substituent at a terminal of the molecular chain In
such a case, a monomer having an oxetanyl group, epoxy group
(oxiranyl group), vinyl ether group (vinyloxy group), acrylate
group (acryloyloxy group), or methacrylate group (methacryloyloxy
group) or the like can be used as the monomer for introducing the
polymerizable substituent. Specific examples of the monomer include
monomers having a polymerizable substituent, and also having an
aromatic hydrocarbon structure or an aromatic compound structure
containing a hetero atom.
[0136] From the viewpoint of enabling another layer to be easily
laminated onto the layer having hole transport properties by a
coating method, the hole-transporting polymer or oligomer
preferably has a polymerizable substituent at the molecular chain
terminals or on a side chain
[0137] From the viewpoints of suppressing crystallization and
obtaining favorable film-forming properties, the weight-average
molecular weight of the hole-transporting polymer or oligomer is
preferably at least 1,000, more preferably at least 2,000, and
still more preferably 3,000 or greater. Further, from the viewpoint
of improving the solubility in the solvent, the weight-average
molecular weight of the hole-transporting polymer or oligomer is
preferably not more than 1,000,000, more preferably not more than
900,000, and still more preferably 800,000 or less. The
weight-average molecular weight refers to the
polystyrene-equivalent weight-average molecular weight determined
by gel permeation chromatography (GPC).
[0138] More specifically, the weight-average molecular weight of
the hole-transporting polymer or oligomer is preferably from 1,000
to 1,000,000, more preferably from 2,000 to 900,000, and still more
preferably from 3,000 to 800,000.
[0139] From the viewpoint of ensuring favorable film formation
stability, the average value for the number of units within the
hole-transporting polymer or oligomer is preferably at least 2,
more preferably at least 5, and still more preferably 10 or
greater. Further, from the viewpoint of improving the solubility in
the solvent, and from the viewpoint of ensuring a satisfactory
change in solubility, thus enabling easy lamination of an organic
layer, in those cases where the polymer or oligomer has a
polymerizable substituent, the average value for the number of
units is preferably not more than 1,000, more preferably not more
than 500, and still more preferably 200 or less. The "average value
for the number of units" can be determined from the weight-average
molecular weight of the hole-transporting polymer or oligomer, the
molecular weight of each of the units, and the proportion of each
unit within the hole-transporting polymer or oligomer. The
"proportion of each unit" can be determined from the ratio (molar
ratio) between the monomers corresponding with the various
repeating units used in synthesizing the polymer or oligomer.
[0140] More specifically, the average value for the number of units
within the hole-transporting polymer or oligomer is preferably from
2 to 1,000, more preferably from 5 to 500, and still more
preferably from 10 to 200.
[0141] Further, from the viewpoint of obtaining superior hole
transport properties, the proportion of units represented by any of
formulas (1a) to (93a) relative to the total number of units within
the hole-transporting polymer or oligomer is preferably at least
10%, more preferably at least 25%, and still more preferably 50% or
greater. Further, the proportion of units represented by any of
formulas (1a) to (93a) may be 100%, but if consideration is given
to factors such as the introduction of polymerizable substituents
at the terminals, then the proportion is preferably not more than
95%, more preferably not more than 90%, and still more preferably
80% or less.
[0142] More specifically, the proportion of units represented by
any of formulas (1a) to (93a) relative to the total number of units
within the hole-transporting polymer or oligomer is preferably from
10 to 95%, more preferably from 25 to 90%, and still more
preferably from 50 to 80%.
[0143] If the hole-transporting polymer or oligomer has a branched
structure, then from the viewpoint of obtaining a satisfactory
weight-average molecular weight, and from the viewpoint of
increasing the number of terminals with an introduced polymerizable
substituent, thereby increasing the change in solubility, the
proportion of units represented by any of formulas (85a) to (93a)
and formulas (29) to (31) relative to the total number of units
within the hole-transporting polymer or oligomer is preferably at
least 1%, more preferably at least 3%, and still more preferably
10% or greater. Further, from the viewpoint of preventing synthesis
failure due to gelling during synthesis of the hole-transporting
polymer or oligomer, the proportion of units represented by any of
formulas (85a) to (93a) and formulas (29) to (31) is preferably not
more than 50%, more preferably not more than 30%, and still more
preferably 25% or less.
[0144] More specifically, the proportion of units represented by
any of formulas (85a) to (93a) and formulas (29) to (31) relative
to the total number of units within the hole-transporting polymer
or oligomer is preferably from 1 to 50%, more preferably from 3 to
30%, and still more preferably from 10 to 25%.
[0145] The hole-transporting polymer or oligomer can be produced
using various synthesis methods well known to those in the art. For
example, in those cases where each of the monomer units used in the
synthesis of the hole-transporting polymer or oligomer has an
aromatic ring, and the polymer or oligomer is produced by bonding
aromatic rings together, methods that can be used include those
disclosed by T. Yamamoto et al., Bull. Chem. Soc. Jpn., vol. 51,
No. 7, page 2091 (1978), M. Zembayashi et al., Tet. Lett., vol. 47,
page 4089 (1977), and A. Suzuki, Synthetic Communications, vol. 11,
No. 7, page 513 (1981). In particular, the method described by A.
Suzuki is typical for the production of a hole-transporting polymer
or oligomer. Monomer units corresponding with the units described
above can be used as the various monomer units.
[0146] The method disclosed by A. Suzuki is a method of causing a
cross-coupling reaction (commonly called the "Suzuki reaction")
between an aromatic boronic acid derivative and an aromatic halide
using a Pd catalyst. By bonding together the desired aromatic
rings, a hole-transporting polymer or oligomer can be produced.
[0147] Further, in the Suzuki reaction, a soluble Pd compound such
as a Pd(II) salt or a Pd(0) complex is typically used as the Pd
catalyst. Examples of preferred Pd sources include
Pd(Ph.sub.3P).sub.4, and a Pd(OAc).sub.2 complex, a
Pd.sub.2(dba).sub.3 complex and a PdCl.sub.2(dppf) complex with a
tertiary phosphine ligand, which can be used in an amount of 0.01
to 5 mol % relative to the amount of aromatic reactants.
[0148] In this reaction, a base is typically also used, and the
base is preferably an aqueous alkali carbonate or bicarbonate, or a
tetraalkylammonium hydroxide. Further, a phase transfer catalyst
may be used to promote the reaction in non-polar solvents. Examples
of solvents that can be used include N,N-dimethylformamide,
toluene, anisole, dimethoxyethane and tetrahydrofuran.
[Hole-Transporting Low-Molecular Weight Compound]
[0149] The hole-transporting low-molecular weight compound may be
any compound with the capability of transporting holes, and
examples include triazole derivatives, oxadiazole derivatives,
imidazole derivatives, pyrazoline derivatives, pyrazolone
derivatives, phenylenediamine derivatives, arylamine derivatives,
carbazole derivatives, styrylanthracene derivatives, fluorenone
derivatives, hydrazone derivatives and stilbene derivatives.
Further examples include low-molecular weight compounds having one
of the units represented by any of the aforementioned formulas (1a)
to (93a) within the molecule.
[0150] Commercially available conventional compounds may be used as
the hole-transporting polymer or oligomer, or the hole-transporting
low-molecular weight compound.
[0151] The layer having hole transport properties may be formed by
a dry process such as vacuum deposition or sputtering, or formed
via a wet process such as inkjet printing. The coating method used
in the wet process may employ the same methods as the coating
methods used for applying the treatment liquid.
[0152] A composition containing the hole-transporting compound and
a solvent is typically used for the coating process. The amount of
the solvent in such a composition may be determined with due
consideration of the applicability of the composition to various
coating methods. For example, the amount of solvent may be set so
that the proportion of the hole-transporting compound relative to
the solvent is preferably at least 0.1% by mass, more preferably at
least 0.2% by mass, and still more preferably 0.5% by mass or
greater. Further, the amount of solvent is set so that the
proportion of the hole-transporting compound relative to the
solvent is preferably not more than 10% by mass, more preferably
not more than 5% by mass, and still more preferably 3% by mass or
less. More specifically, the amount of the solvent in the
composition is set so that the proportion of the hole-transporting
compound relative to the solvent is preferably from 0.1 to 10% by
mass, more preferably from 0.2 to 5% by mass, and still more
preferably from 0.5 to 3% by mass.
[0153] The composition may also contain other additives such as
polymerization inhibitors, stabilizers, thickeners, gelling agents,
flame retardants, antioxidants, reduction inhibitors, oxidizing
agents, reducing agents, surface modifiers, emulsifiers,
antifoaming agents, dispersants and surfactants.
[0154] The thickness of the layer having hole transport properties
may be set as appropriate depending on the application. For
example, the thickness may be set within a range from 5 nm to 10
p.m. Particularly in those cases where the layer having hole
transport properties is used as a hole injection layer and/or a
hole transport layer of an organic EL element, from the viewpoint
of moderating the surface roughness of the anode and reducing the
possibility of short-circuits, the thickness of the layer having
hole transport properties is preferably at least 5 nm, more
preferably at least 10 nm, and still more preferably 20 nm or
greater. Further, from the viewpoint of reducing the drive voltage
of the organic EL element, the thickness of the layer having hole
transport properties is preferably not more than 500 nm, more
preferably not more than 200 nm, and still more preferably 100 nm
or less. Specifically, the thickness is preferably from 5 to 500
nm, more preferably from 10 to 200 nm, and still more preferably
from 20 to 100 nm.
[Organic Electronic Element and Production Method Therefor]
[0155] The organic electronic element that represents one
embodiment of the present invention has an anode, a surface to
which the ionic compound has been adhered, a layer (A) having hole
transport properties, and a cathode, in that order. The organic
electronic element may also contain one or more optional layers
positioned between the above layers, and may have a substrate.
Further, the method for producing an organic electronic element
that represents another embodiment of the present invention has a
step of forming an anode, a step of forming a layer (A) having hole
transport properties, and a step of forming a cathode, the method
also having at least one step selected from among a step of
adhering an ionic compound to the surface on which the layer (A)
having hole transport properties is to be formed, and a step of
adhering an ionic compound to the surface of the layer (A) having
hole transport properties. The method for producing an organic
electronic element may also include one or more other optional
steps in addition to the above steps. Examples of the organic
electronic element include an organic EL element and an organic
photoelectric conversion element.
[Organic EL Element]
[0156] A conventional organic EL element includes an anode, a
light-emitting layer and a cathode, in that order, and may also
include other layers such as a hole injection layer, electron
injection layer, hole transport layer or electron transport layer.
The organic EL element may also have a substrate. FIG. 6
illustrates one example of a conventional organic EL element. On
the other hand, the organic EL element that represents one
embodiment of the present invention includes at least an anode, a
surface to which the ionic compound has been adhered, a layer (A)
having hole transport properties, and a cathode, in that order. The
layer (A) having hole transport properties can function as a
light-emitting layer and as another layer, and preferably functions
as a hole injection layer and/or a hole transport layer.
Accordingly, one example of the organic EL element of the present
embodiment includes, an anode, a surface to which the ionic
compound has been adhered, a layer (A) having hole transport
properties that functions as a hole injection layer and/or hole
transport layer, and a cathode, in that order. Specific examples of
the ionic compound are as described above.
[0157] The ionic compound can be adhered by a wet process such as a
coating method or a dry process such as a vapor deposition method.
The adhesion of the ionic compound is preferably performed by
applying the treatment liquid described above.
[0158] For example, in the case where the organic EL element
includes, in order, a substrate, an anode, a surface to which the
ionic compound has been adhered, a layer (A) having hole transport
properties that functions as a hole injection layer, a
light-emitting layer and a cathode, examples of the method for
producing the organic EL element include the methods described
below.
[0159] A production method including, in order, (1) a step of
forming the anode on the substrate, (2) a step of applying the
treatment liquid to a surface of the anode (namely, the surface on
which the layer (A) having hole transport properties is to be
formed), (3) a step of forming the layer (A) having hole transport
properties on the surface of the anode to which the treatment
liquid has been applied, (4) a step of forming the light-emitting
layer, and (5) a step of forming the cathode. In this method, the
surface of the anode is the surface to which the ionic compound has
been adhered.
[0160] An alternative method includes, in order, (1) a step of
forming the cathode on the substrate, (2) a step of forming the
light-emitting layer, (3) a step of forming the layer (A) having
hole transport properties, (4) a step of applying the treatment
liquid to the surface of the layer (A) having hole transport
properties, and (5) a step of forming the anode. In this method,
the surface of the layer (A) having hole transport properties is
the surface to which the ionic compound has been adhered.
[0161] Either method may also include, either between, before or
after the various steps, additional optional steps such as a step
of forming an electron injection layer, a step of forming an
electron transport layer, a washing step, and an encapsulation
step.
[0162] FIG. 3 illustrates a schematic cross-sectional view of one
example of an organic EL element having a substrate 6, an anode 1,
a surface 1a to which an ionic compound is adhered, a layer (A) 3
having hole transport properties that functions as a hole injection
layer, a light-emitting layer 4 and a cathode 5. In FIG. 3, the
surface la to which the ionic compound is adhered and the layer (A)
3 having hole transport properties make contact via a coating film
2. However, in cases such as when the coating film 2 includes
non-continuous portions, the surface la to which the ionic compound
is adhered and the layer (A) 3 having hole transport properties may
also make direct contact.
[0163] Further, the organic EL element may also have a layer (B)
having hole transport properties between the anode and the layer
(A) having hole transport properties. For example, in the case
where the organic EL element includes, in order, a substrate, an
anode, a layer (B) having hole transport properties that functions
as a hole injection layer, a surface to which an ionic compound is
adhered, a layer (A) having hole transport properties that
functions as a hole transport layer, a light-emitting layer and a
cathode, examples of the method for producing the organic EL
element include the methods described below.
[0164] A production method including, in order, (1) a step of
forming the anode on the substrate, (2) a step of forming the layer
(B) having hole transport properties, (3) a step of applying the
treatment liquid to the surface of the layer (B) having hole
transport properties (namely, the surface on which the layer (A)
having hole transport properties is to be formed), (4) a step of
forming the layer (A) having hole transport properties on the
surface of the layer (B) having hole transport properties to which
the treatment liquid has been applied, (5) a step of forming the
light-emitting layer, and (6) a step of forming the cathode. In
this method, the surface of the layer (B) having hole transport
properties is the surface to which the ionic compound has been
adhered.
[0165] An alternative method includes, in order, (1) a step of
forming the cathode on the substrate, (2) a step of forming the
light-emitting layer, (3) a step of forming the layer (A) having
hole transport properties, (4) a step of applying the treatment
liquid to the surface of the layer (A) having hole transport
properties, (5) a step of forming the layer (B) having hole
transport properties, and (6) a step of forming the anode. In this
method, the surface of the layer (A) having hole transport
properties is the surface to which the ionic compound has been
adhered.
[0166] Either method may also include, either between, before or
after the various steps, additional optional steps such as a step
of forming an electron injection layer, a step of forming an
electron transport layer, a washing step, and an encapsulation
step. Further, the former production method may have "a step of
applying the treatment liquid to the surface of the anode (namely,
the surface on which the layer (B) having hole transport properties
is to be formed)" between step (1) and step (2), whereas the latter
production method may have "a step of applying the treatment liquid
to the surface of the layer (B) having hole transport properties"
between step (5) and step (6).
[0167] FIG. 4 illustrates a schematic cross-sectional view of one
example of an organic EL element having a substrate 6, an anode 1,
a layer (B) 7 having hole transport properties that functions as a
hole injection layer, a surface 7a to which an ionic compound is
adhered, a layer (A) 3 having hole transport properties that
functions as a hole transport layer, a light-emitting layer 4 and a
cathode 5. In FIG. 4, the surface 7a to which the ionic compound is
adhered and the layer (A) 3 having hole transport properties make
contact via a coating film 2. However, the surface 7a to which the
ionic compound is adhered and the layer (A) 3 having hole transport
properties may also make direct contact in some cases. In the
organic EL element illustrated in FIG. 4, the surface of the anode
1 may also be a surface to which an ionic compound is adhered.
[0168] In the organic EL element, depending on factors such as the
amount of the ionic compound adhered, the method used for adhering
the ionic compound, the state following adhesion, and the effects
of the layers laminated on the surface to which the ionic compound
has been adhered, the existence of the ionic compound on the
surface to which the ionic compound has been adhered can sometimes
not be confirmed. For example, in the case where a treatment liquid
has been applied, it is sometimes impossible to confirm following
application whether a "continuous coating film" or a "coating film
having non-continuous portions" has been formed. However, by
including a surface to which an ionic compound has been adhered,
and preferably a surface to which the aforementioned treatment
liquid has been applied, effects including improvements in
properties such as the current efficiency and the lifespan can be
obtained for the organic EL element.
[0169] Descriptions of each of the layers of the organic EL element
are presented below.
[Light-Emitting Layer]
[0170] The material used for the light-emitting layer may be a
low-molecular weight compound, a polymer or oligomer, or a
dendrimer or the like. Examples of low-molecular weight compounds
that use fluorescence emission include perylene, coumarin, rubrene,
quinacridone, color laser dyes (such as rhodamine and DCM1),
aluminum complexes (such as tris(8-hydroxyquinolinato)aluminum(III)
(Alq.sub.3)), stilbene, and derivatives of these compounds.
Examples of polymers or oligomers using fluorescence emission that
can be used favorably include polyfluorene, polyphenylene,
polyphenylenevinylene (PPV), polyvinylcarbazole (PVK),
fluorene-benzothiadiazole copolymers, fluorene-triphenylamine
copolymers, and derivatives and mixtures of these compounds.
[0171] On the other hand, in recent years, in order to further
improve the efficiency of organic EL elements, phosphorescent
organic EL elements are also being actively developed. In a
phosphorescent organic EL element, not only singlet state energy,
but also triplet state energy can be used, and therefore the
internal quantum yield can, in principle, be increased to 100%. In
a phosphorescent organic EL element, a metal complex-based
phosphorescent material containing a heavy metal such as platinum
or iridium is used as a phosphorescence-emitting dopant for doping
a host material, thus enabling the extraction of a phosphorescence
emission (see M. A. Baldo et al., Nature, vol. 395, p. 151 (1998),
M. A. Baldo et al., Applied Physics Letters, vol. 75, p. 4 (1999),
M. A. Baldo et al., Nature, vol. 403, p. 750 (2000)).
[0172] In the organic EL element that represents an embodiment of
the present invention, a phosphorescent material can be used for
the light-emitting layer in order to increase the element
efficiency. Examples of materials that can be used favorably as the
phosphorescent material include metal complexes and the like
containing Ir or Pt or the like as a central metal. Specific
examples of Ir complexes include Flr(pic) (iridium(III)
bis[(4,6-difluorophenyl)-pyridinato-N,C.sup.2]picolinate) which
emits blue light, Ir(ppy).sub.3 (fac-tris(2-phenylpyridine)iridium)
which emits green light (see M. A. Baldo et al., Nature, vol. 403,
p. 750 (2000)), and (btp).sub.2Ir(acac)
{bis[2-(2'-benzo[4,5-.alpha.]thienyl)pyridinato-N,C.sup.3]iridium(acetyl--
acetonate)} (see Adachi et al., Appl. Phys. Lett., 78 No. 11, 2001,
1622) and Ir(piq).sub.3 (tris(1-phenylisoquinoline)iridium) which
emit red light. Specific examples of Pt complexes include platinum
2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin (PtOEP) which emits
red light. The phosphorescent material can use a low-molecular
weight compound or a dendrite such as an iridium core dendrimer.
Derivatives of these compounds can also be used favorably.
[0173] Further, when a phosphorescent material is incorporated in
the light-emitting layer, a host material is preferably included in
addition to the phosphorescent material. The host material may be a
low-molecular weight compound, a polymer or oligomer, or a
dendrimer or the like.
[0174] Examples of low-molecular weight compounds that can be used
include CBP (4,4'-bis(carbazol-9-yl)-biphenyl), mCP
(1,3-bis(9-carbazolyl)benzene), CDBP
(4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl) and a-NPD
(4,4'-bis[(1-naphthyl)phenylamino]-1,1'-biphenyl. Examples of
polymers or oligomers that can be used include polyvinylcarbazole,
polyphenylene and polyfluorene. Further, derivatives of these
compounds can also be used.
[0175] The light-emitting layer may be formed by a vapor deposition
method or a coating method. Forming the light-emitting layer by a
coating method enables the organic EL element to be formed more
cheaply, and is consequently preferred. Formation of the
light-emitting layer by a coating method can be achieved by using a
conventional coating method to apply a solution containing the
phosphorescent material, and if necessary a host material, to a
desired substrate. Examples of the coating method include spin
coating methods, casting methods, dipping methods, and printing
methods such as relief printing, intaglio printing, offset
printing, lithographic printing, relief reversal offset printing,
screen printing, gravure printing and inkjet printing.
[Cathode]
[0176] The cathode material is preferably a metal or a metal alloy,
such as Li, Ca, Mg, Al, In, Cs, Ba, Mg/Ag, LiF or CsF.
[Anode]
[0177] A metal (for example, Au) or another material having
metal-like conductivity can be used as the anode. Examples of the
other materials include oxides (for example, ITO: indium oxide/tin
oxide) and conductive polymers (for example,
polythiophene-polystyrene sulfonate mixtures (PEDOT:PSS)).
[Electron Transport Layer, Electron Injection Layer]
[0178] Examples of materials for the electron transport layer and
the electron injection layer include phenanthroline derivatives
(such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)),
bipyridine derivatives, nitro-substituted fluorene derivatives,
diphenylquinone derivatives, thiopyran dioxide derivatives,
condensed-ring tetracarboxylic acid anhydrides of naphthalene and
perylene and the like, carbodiimides, fluorenylidenemethane
derivatives, anthraquinodimethane and anthrone derivatives,
oxadiazole derivatives (such as
2-(4-biphenylyl)-5-(4-tert-butylphenyl-1,3,4-oxadiazole (PBD)), and
aluminum complexes (such as tris(8-hydroxyquinolinato)aluminum(III)
(Alq.sub.3) and bis(2-methyl-8-quinolinolato)-4-phenylphenolate
aluminum (III) (Balq)). Moreover, thiadiazole derivatives in which
the oxygen atom in the oxadiazole ring of the oxadiazole
derivatives mentioned above has been substituted with a sulfur
atom, and quinoxaline derivatives having a quinoxaline ring that is
well known as an electron-withdrawing group can also be used.
[Substrate]
[0179] In terms of substrates that can be used in the organic EL
element, various types of glass and plastic can be used without any
particular restrictions. Further, a transparent substrate is
preferable, and glass, quartz and light-transmitting resin films
and the like can be used favorably. If a resin film is used, then
the organic EL element can also be imparted with flexibility
(namely, a flexible substrate), which is particularly
desirable.
[0180] Examples of the resin film include polyethylene
terephthalate (PET), polyethylene naphthalate (PEN),
polyethersulfone (PES), polyetherimide, polyetheretherketone,
polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC),
cellulose triacetate (TAC) and cellulose acetate propionate
(CAP).
[0181] Furthermore, in those cases when a resin film is used, an
inorganic substance such as silicon oxide or silicon nitride may be
coated onto the resin film to inhibit the transmission of water
vapor and oxygen and the like.
[Encapsulation]
[0182] The organic EL element that represents an embodiment of the
present invention may be encapsulated to reduce the effect of the
outside atmosphere and extend the life of the element. Materials
that can be used for the encapsulation include glass, plastic films
such as epoxy resins, acrylic resins, PET and PEN, and inorganic
substances such as silicon oxide and silicon nitride. There are no
particular limitations on the encapsulation method. Examples of
methods that can be used include methods in which the encapsulation
material is formed directly on the organic EL element by vacuum
deposition, sputtering, or a coating method or the like, and
methods in which an encapsulation material such as glass or a
plastic film is bonded to the organic EL element with an
adhesive.
[Emission Color]
[0183] Although there are no particular limitations on the color of
the light emission from the organic EL element, white
light-emitting elements can be used for various lighting fixtures,
including domestic lighting, in-vehicle lighting, watches and
liquid crystal backlights, and are consequently preferred.
[0184] Because generating white light emission from a single
material is currently impossible, the method used for forming a
white light-emitting element involves using a plurality of
light-emitting materials to emit a plurality of colors
simultaneously, and then mixing the emitted colors to obtain a
white light emission. There are no particular limitations on the
combination of the plurality of emission colors, and examples
include combinations that include three maximum emission
wavelengths for blue, green and red, and combinations that include
two maximum emission wavelengths and utilize the complementary
color relationship between blue and yellow, or yellowish green and
orange. Further, control of the emission color can also be achieved
by appropriate adjustment of the type and amount of the
phosphorescent material.
[Display Element, Illumination Device, Display Device]
[0185] The display element includes the organic EL element
described above. For example, by using the organic EL element
described above as the element corresponding with each color pixel,
such as red, green and blue (RGB), a color display element can be
obtained.
[0186] Image formation may employ a simple matrix in which organic
EL elements arrayed in a panel are driven directly by an electrode
arranged in a matrix, or an active matrix in which a thin-film
transistor is positioned on, and drives, each element. The former
has a simpler structure, but there is a limit to the number of
vertical pixels, and therefore these types of displays are
typically used for displaying text or the like. The latter has a
lower drive voltage, requires less current and yields a bright
high-quality image, and is therefore typically used for
high-quality displays.
[0187] Further, the illumination device includes the organic EL
element described above. Moreover, the display device includes the
illumination device and a liquid crystal element as a display unit.
A display device that uses the illumination device as a backlight
(white light emitting source) and uses a liquid crystal element as
the display unit, namely a liquid crystal display device, is also
possible. This configuration is merely a conventional liquid
crystal display device in which only the backlight has been
replaced with the aforementioned illumination device, with the
liquid crystal element portion employing conventional
technology.
[Organic Photoelectric Conversion Element]
[0188] Organic photoelectric conversion elements include organic
solar cells and organic photosensors. A conventional organic
photoelectric conversion element includes an anode, a photoelectric
conversion layer and a cathode, in that order, and may also have
other layers such as a buffer layer or an electron transport layer.
The organic photoelectric conversion element may also have a
substrate. On the other hand, the organic photoelectric conversion
element that represents an embodiment of the present invention has
a layer (A) having hole transport properties. This layer (A) having
hole transport properties may, for example, function as the
photoelectric conversion layer or as another layer, and is
preferably used as a buffer layer. Accordingly, one example of the
organic photoelectric conversion element includes, in order, an
anode, the layer (A) having hole transport properties as a buffer
layer, a photoelectric conversion layer and a cathode, and may also
include other optional layers between the above layers. For
example, the organic photoelectric conversion element has a surface
to which an ionic compound has been adhered between the anode and
the layer (A) having hole transport properties. The ionic compound
may be adhered to the surface of the anode or the surface of the
buffer layer. The anode, the buffer layer, the photoelectric
conversion layer, the cathode and the substrate may use
conventional materials, and can be provided using conventional
methods.
[0189] The element structure and production method have been
described above using the examples of an organic EL element and an
organic photoelectric conversion element. However, in other organic
electronic elements, a surface to which an ionic compound has been
adhered may be provided between the anode and a layer having hole
transport properties in a similar manner to that described above,
and the thus obtained organic electronic element will exhibit
excellent properties. The surface to which the ionic compound has
been adhered enhances the properties of the layer having hole
transport properties. Although the action of the ionic compound is
not entirely clear, possibilities that have been considered include
the ionic compound changing the energy level of the anode, thereby
improving the injection of holes into the layer having hole
transport properties, the ionic compound functioning as a charge
transport path, thereby enhancing the hole injection properties
and/or hole transport properties, and the ionic compound doping the
surface of the layer having hole transport properties, thereby
enhancing the hole injection properties and/or hole transport
properties.
EXAMPLES
[0190] The embodiments of the present invention are described below
in further detail using a series of examples, but the present
invention is in no way limited by the following examples.
<Preparation and Evaluation of Organic EL Elements>
Example 1
[0191] An ionic compound 1 (10 mg) and toluene (1,000 .mu.L) were
mixed to obtain a composition (treatment liquid). The thus obtained
composition was applied by spin coating at a revolution rate of
3,000 min.sup.-1 to a glass substrate on which ITO had been
patterned with a width of 1.6 mm. Subsequently, the glass substrate
was heated on a hotplate at 180.degree. C. for 10 minutes.
##STR00042##
[0192] Next, the obtained glass substrate was transferred into a
vacuum deposition apparatus, and .alpha.-NPD (film thickness: 50
nm), CBP+Ir(ppy).sub.3 (CBP:Ir(ppy).sub.3=100:6, film thickness: 30
nm), BAlq (film thickness: 10 nm), Alq.sub.3 (film thickness: 30
nm), LiF (film thickness: 0.8 nm) and Al (film thickness: 150 nm)
were deposited in that order.
[0193] Following deposition, the glass substrate was transferred
under a dry nitrogen atmosphere without exposure to the external
atmosphere. Subsequently, an encapsulating glass having a
countersink (namely, a concave portion) with a depth of 0.4 mm
formed in an alkali-free glass with a thickness of 0.7 mm and the
glass substrate were bonded together using a photocurable epoxy
resin, thereby encapsulating and completing preparation of an
organic EL element having a multilayer structure. Subsequent
operations were performed in an open atmosphere at room temperature
(25.degree. C.).
[0194] When a voltage was applied to the organic EL element using
the ITO as the anode and the Al as the cathode, a green light
emission was observed at a voltage of 4 V. The current efficiency
at a luminance of 1,000 cd/m.sup.2 was 20 cd/A. The current-voltage
characteristics were measured using a microammeter 4140B
manufactured by Hewlett-Packard Company, and the emission luminance
was measured using a luminance meter Pritchard 1980B manufactured
by Photo Research, Inc.
[0195] Further, evaluation of the lifespan properties by measuring
the time (lifespan) for the luminance to decrease to 70% of the
initial luminance (3,000 cd/m.sup.2) when a constant current was
applied yielded a time of 24 hours. The emission luminance was
measured using a luminance meter BM-7 manufactured by Topcon
Technohouse Corporation.
Example 2
[0196] With the exception of replacing the ionic compound 1 with an
ionic compound 2, an organic EL element was prepared using the same
method as Example 1. The current efficiency for this organic EL
element at a luminance of 1,000 cd/m.sup.2 was 22 cd/A, and the
lifespan was 32 hours.
##STR00043##
Example 3
[0197] The ionic compound 1 (10 mg), a compound 1 having a
polymerizable substituent (10 mg, manufactured by Toagosei Co.,
Ltd.) and toluene (1,000 .mu.L) were mixed to obtain a composition.
The thus obtained composition was used to prepare an organic EL
element using the same method as Example 1. The current efficiency
for the obtained organic EL element at a luminance of 1,000
cd/m.sup.2 was 22 cd/A, and the lifespan was 85 hours.
##STR00044##
Example 4
[0198] With the exception of replacing the compound 1 having a
polymerizable substituent with a compound 2 having a polymerizable
substituent (manufactured by Toagosei Co., Ltd.), an organic EL
element was prepared using the same method as Example 3. The
current efficiency for this organic EL element at a luminance of
1,000 cd/m.sup.2 was 21 cd/A, and the lifespan was 64 hours.
##STR00045##
Example 5
[0199] With the exception of replacing the compound 1 having a
polymerizable substituent with a compound 3 having a polymerizable
substituent (manufactured by Osaka Organic Chemical Industry Ltd.),
an organic EL element was prepared using the same method as Example
3. The current efficiency for this organic EL element at a
luminance of 1,000 cd/m.sup.2 was 22 cd/A, and the lifespan was 80
hours.
##STR00046##
Example 6
[0200] With the exception of replacing the compound 1 having a
polymerizable substituent with a compound 4 having a polymerizable
substituent (manufactured by New Japan Chemical Co., Ltd.), an
organic EL element was prepared using the same method as Example 3.
The current efficiency for this organic EL element at a luminance
of 1,000 cd/m.sup.2 was 22 cd/A, and the lifespan was 40 hours.
##STR00047##
Comparative Example 1
[0201] A glass substrate on which ITO had been patterned with a
width of 1.6 mm was transferred into a vacuum deposition apparatus,
and a-NPD (film thickness: 50 nm), CBP +Ir(ppy).sub.3
(CBP:Ir(ppy).sub.3 =100:6, film thickness: 30 nm), BAlq (film
thickness: 10 nm), Alq.sub.3 (film thickness: 30 nm), LiF (film
thickness: 0.8 nm) and Al (film thickness: 150 nm) were deposited
in that order on the substrate. Subsequent steps were performed in
the same manner as Example 1 to complete preparation of an organic
EL element. When a voltage was applied to the organic EL element, a
green light emission was observed at 4 V. The current efficiency at
a luminance of 1,000 cd/m.sup.2 was 20 cd/A. Further, the lifespan
was 2 hours.
[0202] The results are illustrated in Table 1. As illustrated in
Table 1, the organic EL elements of Examples 1 to 6 each exhibited
enhanced current efficiency and lifespan compared with the organic
EL element of Comparative Example 1. By using the treatment liquid
according to an embodiment of the present invention, an organic
electronic element having excellent properties can be prepared.
TABLE-US-00001 TABLE 1 Compound having Current Ionic polymerizable
efficiency Lifespan compound substituent (cd/A) (hr) Example 1 1 --
20 24 Example 2 2 -- 22 32 Example 3 1 1 22 85 Example 4 1 2 21 64
Example 5 1 3 22 80 Example 6 1 4 22 40 Comparative -- -- 20 2
Example 1
<Preparation and Evaluation of Elements for Evaluating Charge
Transport Properties>
(Preparation of Pd Catalyst)
[0203] In a glove box under a nitrogen atmosphere and at room
temperature, tris(dibenzylideneacetone)dipalladium (73.2 mg, 80
.sub.itmol) was weighed into a sample tube, anisole (15 mL) was
added, and the resulting mixture was agitated for 30 minutes. In a
similar manner, tri-tert-butylphosphine (129.6 mg, 640 .mu.mol) was
weighed into a sample tube, anisole (5 mL) was added, and the
resulting mixture was agitated for 5 minutes. The two solutions
were then mixed together and stirred for 30 minutes at room
temperature to prepare a catalyst. All the solvents were deaerated
by nitrogen bubbling for at least 30 minutes prior to use.
(Synthesis of Polymer A)
[0204] A three-neck round-bottom flask was charged with a monomer 1
shown below (2.0 mmol), a monomer 2 shown below (5.0 mmol), a
monomer 3 shown below (4.0 mmol) and anisole (20 mL), and the
prepared Pd catalyst solution (7.5 mL) was then added. After
stirring for 30 minutes, a 10% aqueous solution of
tetraethylammonium hydroxide (20 mL) was added. All the solvents
were deaerated by nitrogen bubbling for at least 30 minutes prior
to use. The resulting mixture was refluxed under heat for 2 hours.
All the operations up to this point were conducted under a stream
of nitrogen.
[0205] After completion of the reaction, the organic layer was
washed with water, and the organic layer was then poured into
methanol-water (9:1). The resulting precipitate was collected by
suction filtration, and washed with methanol-water (9:1). The thus
obtained precipitate was dissolved in toluene, and re-precipitated
from methanol. The resulting precipitate was collected by suction
filtration and dissolved in toluene, a metal absorbent
(triphenylphosphine, polymer-bound on styrene-divinylbenzene
copolymer, manufactured by Strem Chemicals Inc., 200 mg per 100 mg
of precipitate) was added, and the resulting mixture was stirred
overnight. Following completion of the overnight stirring, the
metal absorbent and any insoluble matter were removed by
filtration, and the filtrate was concentrated using a rotary
evaporator. The concentrate was dissolved in toluene, and then
re-precipitated from methanol-acetone (8:3). The generated
precipitate was collected by suction filtration and washed with
methanol-acetone (8:3). The resulting precipitate was then dried
under vacuum to obtain a polymer A. The weight-average molecular
weight was measured by GPC (relative to polystyrene standards)
using THF as the eluent. The measurement conditions are described
below. The thus obtained weight-average molecular weight for the
polymer A was 31,000.
##STR00048##
[0206] The measurement conditions for measuring the weight-average
molecular weight were as follows. [0207] Liquid delivery pump:
L-6050, manufactured by Hitachi High-Technologies Corporation
UV-Vis detector: L-3000, manufactured by Hitachi High-Technologies
Corporation Columns: Gelpack .sup.(R) GL-A160S/GL-A150S,
manufactured by Hitachi Chemical Co., Ltd. Eluent: THF
(manufactured by Wako Pure Chemical Industries, Ltd., HPLC grade,
containing no stabilizers) [0208] Flow rate: 1 mL/min [0209] Column
temperature: room temperature [0210] Molecular weight standards:
standard polystyrenes
Example 7
[0211] The ionic compound 2 (5 mg) and toluene (1.1 mL) were mixed
to obtain a composition. The thus obtained composition was applied
by spin coating at a revolution rate of 3,000 min.sup.-1 to a glass
substrate on which ITO had been patterned with a width of 1.6 mm,
and the glass substrate was then heated on a hotplate at
180.degree. C. for 10 minutes. Meanwhile, the polymer A (50 mg) and
toluene (1.1 mL) were mixed to obtain a composition. The thus
obtained composition was applied by spin coating at a revolution
rate of 3,000 min' to the glass substrate. The substrate was then
heated on a hotplate at 180.degree. C. for 10 minutes to complete
preparation of a charge transport film (150 nm). Next, the thus
obtained glass substrate was transferred to a vacuum deposition
apparatus, and a film of aluminum (film thickness: 100 nm) was
deposited. Following the aluminum deposition, the glass substrate
was transferred under a dry nitrogen atmosphere without exposure to
the external atmosphere. Subsequently, an encapsulating glass
having a countersink (namely, a concave portion) with a depth of
0.4 mm formed in an alkali-free glass with a thickness of 0 7 mm
and the glass substrate were bonded together using a photocurable
epoxy resin, thereby encapsulating and completing preparation of an
element for evaluating the charge transport properties.
Example 8
[0212] The ionic compound 2 (5 mg), the compound 1 having a
polymerizable substituent (5 mg) and toluene (1.1 mL) were mixed to
obtain a composition. With the exception of using this composition
instead of the composition obtained from the ionic compound 2 and
toluene, an element for evaluating the charge transport properties
was obtained in the same manner as Example 7.
Comparative Example 2
[0213] The polymer A (50 mg) and toluene (1.1 mL) were mixed to
prepare a composition. With the exception of applying this
composition directly to a glass substrate on which ITO had been
patterned with a width of 1.6 mm, without first applying the
composition obtained from the ionic compound 2 and toluene, an
element for evaluating the charge transport properties was obtained
in the same manner as Example 7.
[0214] For each of the elements for evaluating charge transport
properties obtained in Examples 7 and 8 and Comparative Example 2,
a voltage was applied using the ITO as the anode and the aluminum
as the cathode, and the current-voltage characteristics were
evaluated. The evaluation results are shown in FIG. 5. As
illustrated in FIG. 5, the elements for evaluating charge transport
properties obtained in Examples 7 and 8 exhibited enhanced charge
transport properties compared with the element for evaluating
charge transport properties obtained in Comparative Example 2. By
using the treatment liquid according to an embodiment of the
present invention, an organic electronic element that can be driven
at a lower voltage can be prepared.
[0215] The effects of the embodiments of the present invention have
been illustrated above using a series of examples. Even for
elements other than those described in the examples, by using the
ionic compound, similar superior effects can be obtained. In other
words, according to the various embodiments of the present
invention, the properties of organic electronic elements can be
easily improved.
REFERENCE SIGNS LIST
[0216] 1: Anode [0217] 2: Coating film [0218] 3: Layer (A) having
hole transport properties [0219] 4: Light-emitting layer [0220] 5:
Cathode [0221] 6: Substrate [0222] 7: Layer (B) having hole
transport properties [0223] 1a: Surface to which ionic compound is
adhered (surface of anode) [0224] 7a : Surface to which ionic
compound is adhered (surface of layer (B) having hole transport
properties)
* * * * *