U.S. patent application number 15/209441 was filed with the patent office on 2017-01-26 for electroactive materials.
The applicant listed for this patent is E I DU PONT DE NEMOURS AND COMPANY. Invention is credited to Weiying Gao, Norman Herron, Nora Sabina Radu, Ying Wang.
Application Number | 20170025609 15/209441 |
Document ID | / |
Family ID | 57836232 |
Filed Date | 2017-01-26 |
United States Patent
Application |
20170025609 |
Kind Code |
A1 |
Herron; Norman ; et
al. |
January 26, 2017 |
ELECTROACTIVE MATERIALS
Abstract
There is disclosed a compound having Formula I ##STR00001## In
Formula I: Ar.sup.1 is selected from the group consisting of
phenanthrene, triphenylene, triphenylsilyl, triphenylgermyl,
dibenzofuran, dibenzothiophene, polyarylphenyl, substituted
derivatives thereof, or deuterated analogs thereof; Ar.sup.2 and
Ar.sup.3 are the same or different and are hydrocarbon aryl,
heteroaryl, substituted derivatives thereof, or deuterated analogs
thereof, with the proviso that Ar.sup.2 and Ar.sup.3 are not the
same as Ar.sup.1; and a is 0 or 1. In addition, Ar.sup.1, Ar.sup.2,
and Ar.sup.3 have no additional amino substituents.
Inventors: |
Herron; Norman; (Newark,
DE) ; Gao; Weiying; (Landenberg, PA) ; Radu;
Nora Sabina; (Landenberg, PA) ; Wang; Ying;
(Wilmington, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE NEMOURS AND COMPANY |
Wilmington |
DE |
US |
|
|
Family ID: |
57836232 |
Appl. No.: |
15/209441 |
Filed: |
July 13, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62194577 |
Jul 20, 2015 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/0059 20130101;
H01L 51/0094 20130101; C07C 211/61 20130101; H01L 51/5064 20130101;
C07F 7/081 20130101; H01L 51/0054 20130101; H01L 51/0073 20130101;
H01L 51/0052 20130101; H01L 51/006 20130101; C09K 11/025 20130101;
H01L 51/0074 20130101; C07F 7/30 20130101; C07C 211/54
20130101 |
International
Class: |
H01L 51/00 20060101
H01L051/00; C07C 211/61 20060101 C07C211/61; C09K 11/02 20060101
C09K011/02; C07C 211/54 20060101 C07C211/54 |
Claims
1. A compound having Formula I ##STR00028## wherein: Ar.sup.1 is
selected from the group consisting of phenanthrene, triphenylene,
triphenylsilyl, triphenylgermyl, dibenzofuran, dibenzothiophene,
polyarylphenyl, substituted derivatives thereof, and deuterated
analogs thereof; Ar.sup.2 and Ar.sup.3 are the same or different
and are selected from the group consisting of hydrocarbon aryl,
heteroaryl, substituted derivatives thereof, and deuterated analogs
thereof, with the proviso that Ar.sup.2 and Ar.sup.3 are not the
same as Ar.sup.1; and a is 0 or 1; with the proviso that Ar.sup.1,
Ar.sup.2, and Ar.sup.3 have no additional amino substituents.
2. The compound of claim 1 having Formula II ##STR00029## wherein:
Ar.sup.1 is selected from the group consisting of phenanthrene,
triphenylene, triphenylsilyl, triphenylgermyl, dibenzofuran,
dibenzothiophene, polyarylphenyl, substituted derivatives thereof,
and deuterated analogs thereof; Ar.sup.2 and Ar.sup.3 are the same
or different and are selected from the group consisting of
hydrocarbon aryl, heteroaryl, substituted derivatives thereof, and
deuterated analogs thereof, with the proviso that Ar.sup.2 and
Ar.sup.3 are not the same as Ar.sup.1; and with the proviso that
Ar.sup.1, Ar.sup.2, and Ar.sup.3 have no additional amino
substituents.
3. The compound of claim 1, wherein Ar.sup.1 is selected from the
group consisting of triphenylsilyl, triphenylgermyl,
dibenzothiophene, polyarylphenyl, substituted derivatives thereof,
and deuterated analogs thereof.
4. The compound of claim 2, wherein Ar.sup.1 is selected from the
group consisting of triphenylsilyl, triphenylgermyl,
dibenzothiophene, polyarylphenyl, substituted derivatives thereof,
and deuterated analogs thereof.
5. The compound of claim 3, wherein Ar.sup.2 is a hydrocarbon aryl
group or deuterated hydrocarbon aryl group having 6-30 ring carbon
atoms.
6. The compound of claim 5, wherein Ar.sup.2 has one or more
substituents selected from the group consisting of D, F, CN, alkyl,
fluoroalkyl, heteroaryl, silyl, germyl, alkoxy, aryloxy,
fluoroalkoxy, siloxane, siloxy, deuterated alkyl, deuterated
partially-fluorinated alkyl, deuterated heteroaryl, deuterated
silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy,
deuterated fluoroalkoxy, deuterated siloxane, and deuterated
siloxy.
7. The compound of claim 3, wherein Ar.sup.2 has Formula h
##STR00030## where: R.sup.2 is the same or different at each
occurrence and is selected from the group consisting of D, F, CN,
alkyl, fluoroalkyl, hydrocarbon aryl, heteroaryl, silyl, germyl,
alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl,
deuterated partially-fluorinated alkyl, deuterated hydrocarbon
aryl, deuterated heteroaryl, deuterated silyl, deuterated germyl,
deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy,
deuterated siloxane, and deuterated siloxy, where adjacent R.sup.2
groups can be joined together to form an fused aromatic ring or a
deuterated fused aromatic ring; p is the same or different at each
occurrence and is an integer from 0-4; q is an integer from 0-5; r
is an integer from 1 to 5; and * indicates the point of
attachment.
8. The compound of claim 3, wherein Ar.sup.2.noteq. Ar.sup.3.
9. An organic electronic device comprising an anode, a hole
transport layer, a photoactive layer and a cathode, wherein the
hole transport layer comprises a compound according to claim 1.
10. An organic electronic device comprising an anode, a hole
transport layer, a photoactive layer and a cathode, wherein the
photoactive layer comprises a compound according to claim 3.
11. The device of claim 9, wherein the photoactive layer comprises
a compound according to claim 1.
12. The device of claim 11, wherein the hole transport layer is
directly adjacent to and in contact with the photoactive layer.
13. An organic electronic device comprising an anode, a first hole
transport layer, a second hole transport layer, a photoactive
layer, and a cathode, wherein the second hole transport layer
comprises a compound according to claim 1.
14. The device of claim 13, wherein the second hole transport layer
is directly adjacent to and in contact with the photoactive
layer.
15. The device of claim 13, wherein the first hole transport layer
comprises a material selected from the group consisting of a
triarylamine compound, a triarylamine polymer, and deuterated
analogs thereof.
16. The device of claim 13, wherein Ar.sup.1 is selected from the
group consisting of phenanthrene, triphenylene, triphenylsilyl,
triphenylgermyl, polyarylphenyl, substituted derivatives thereof,
and deuterated analogs thereof.
17. A compound selected from the group consisting of ##STR00031##
##STR00032##
Description
CLAIM OF BENEFIT OF PRIOR APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/194,577, filed Jul. 20, 2015, which is
incorporated in its entirety herein by reference.
BACKGROUND INFORMATION
[0002] Field of the Disclosure
[0003] The present disclosure relates to novel electroactive
compounds. The disclosure further relates to electronic devices
having at least one layer comprising such an electroactive
compound.
[0004] Description of the Related Art
[0005] In organic electronic devices, such as organic light
emitting diodes ("OLED"), that make up OLED displays, one or more
organic electroactive layers are sandwiched between two electrical
contact layers. In an OLED at least one organic electroactive layer
emits light through the light-transmitting electrical contact layer
upon application of a voltage across the electrical contact
layers.
[0006] It is well known to use organic electroluminescent compounds
as the light-emitting component in light-emitting diodes. Simple
organic molecules, conjugated polymers, and organometallic
complexes have been used. The light-emitting materials may be used
alone or may be present in an electroactive host material.
[0007] Devices that use electroluminescent materials frequently
include one or more charge transport layers, which are positioned
between a photoactive (e.g., light-emitting) layer and a contact
layer (hole-injecting contact layer). A device can contain two or
more contact layers. A hole transport layer can be positioned
between the photoactive layer and the hole-injecting contact layer.
The hole-injecting contact layer may also be called the anode. An
electron transport layer can be positioned between the photoactive
layer and the electron-injecting contact layer. The
electron-injecting contact layer may also be called the
cathode.
[0008] There is a continuing need for electroactive materials for
use in electronic devices.
SUMMARY
[0009] There is provided a compound having Formula I
##STR00002##
wherein: [0010] Ar.sup.1 is selected from the group consisting of
phenanthrene, triphenylene, triphenylsilyl,triphenylgermyl,
dibenzofuran, dibenzothiophene, polyarylphenyl, substituted
derivatives thereof, and deuterated analogs thereof; [0011]
Ar.sup.2 and Ar.sup.3 are the same or different and are selected
from the group consisting of hydrocarbon aryl, heteroaryl,
substituted derivatives thereof, and deuterated analogs thereof,
with the proviso that Ar.sup.2 and Ar.sup.3 are not the same as
Ar.sup.1; and [0012] a is 0 or 1;
[0013] with the proviso that Ar.sup.1, Ar.sup.2, and Ar.sup.3 have
no additional amino substituents.
[0014] There is also provided an electronic device having at least
one layer comprising a compound having Formula I.
[0015] The foregoing general description and the following detailed
description are exemplary and explanatory only and are not
restrictive of the invention, as defined in the appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Embodiments are illustrated in the accompanying figures to
improve understanding of concepts as presented herein.
[0017] FIG. 1 includes an illustration of one example of an organic
electronic device including a new compound described herein.
[0018] FIG. 2 includes an illustration of another example of an
organic electronic device including a new compound described
herein.
[0019] FIG. 3 includes an illustration of another example of an
organic electronic device including a new compound described
herein.
[0020] FIG. 4 includes an illustration of another example of an
organic electronic device including a new compound described
herein.
[0021] Skilled artisans appreciate that objects in the figures are
illustrated for simplicity and clarity and have not necessarily
been drawn to scale. For example, the dimensions of some of the
objects in the figures may be exaggerated relative to other objects
to help to improve understanding of embodiments.
DETAILED DESCRIPTION
[0022] There is provided a compound having Formula I, as described
in detail below.
[0023] There is further provided an electronic device having at
least one layer comprising a compound or copolymer having any of
the above formulae.
[0024] Many aspects and embodiments have been described above and
are merely exemplary and not limiting. After reading this
specification, skilled artisans appreciate that other aspects and
embodiments are possible without departing from the scope of the
invention.
[0025] Other features and benefits of any one or more of the
embodiments will be apparent from the following detailed
description, and from the claims. The detailed description first
addresses Definitions and Clarification of Terms followed by the
Compound having Formula I, the Electronic Device, and finally
Examples.
1. Definitions and Clarification of Terms
[0026] Before addressing details of embodiments described below,
some terms are defined or clarified.
[0027] As used herein, the term "alkyl" includes branched and
straight-chain saturated aliphatic hydrocarbon groups. Unless
otherwise indicated, the term is also intended to include cyclic
groups. Examples of alkyl groups include methyl, ethyl, propyl,
isopropyl, isobutyl, secbutyl, tertbutyl, pentyl, isopentyl,
neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl and the like.
The term "alkyl" further includes both substituted and
unsubstituted hydrocarbon groups. In some embodiments, the alkyl
group may be mono-, di- and tri-substituted. One example of a
substituted alkyl group is trifluoromethyl. Other substituted alkyl
groups are formed from one or more of the substituents described
herein. In certain embodiments alkyl groups have 1 to 20 carbon
atoms. In other embodiments, the group has 1 to 6 carbon atoms. The
term is intended to include heteroalkyl groups. Heteroalkyl groups
may have from 1-20 carbon atoms.
[0028] The term "aromatic compound" is intended to mean an organic
compound comprising at least one unsaturated cyclic group having
4n+2 delocalized pi electrons. The term is intended to encompass
both aromatic compounds having only carbon and hydrogen atoms, and
heteroaromatic compounds wherein one or more of the carbon atoms
within the cyclic group has been replaced by another atom, such as
nitrogen, oxygen, sulfur, or the like.
[0029] The term "aryl" or "aryl group" means a moiety derived from
an aromatic compound. The aryl group may be a single ring
(monocyclic) or multiple rings (bicyclic, or more) fused together
or linked covalently. Examples of aryl moieties include, but are
not limited to, phenyl, 1-napthyl, 2-naphthyl, dihydronaphthyl,
tetrahydronaphthyl, biphenyl. anthryl, phenanthryl, fluorenyl,
indanyl, biphenylenyl, acenaphthenyl, acenaphthylenyl, and the
like. In some embodiments, aryl groups have 6 to 60 ring carbon
atoms; in some embodiments, 6 to 30 ring carbon atoms. The term is
intended to include heteroaryl groups having at least one ring
heteroatom. Heteroaryl groups may have from 4-50 ring carbon atoms;
in some embodiments, 4-30 ring carbon atoms.
[0030] The term "alkoxy" is intended to mean the group --OR, where
R is alkyl.
[0031] The term "aryloxy" is intended to mean the group --OR, where
R is aryl.
[0032] Unless otherwise indicated, all groups can be substituted or
unsubstituted. An optionally substituted group, such as, but not
limited to, alkyl or aryl, may be substituted with one or more
substituents which may be the same or different. Suitable
substituents include D, alkyl, aryl, nitro, cyano, --N(R')(R''),
halo, hydroxy, carboxy, alkenyl, alknyl, cycloalkyl, heteroaryl,
alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, perfluoroalkyl,
perfluoroalkoxy, arylalkyl, silyl, siloxy, siloxane, thioalkoxy,
--S(O).sub.2--, --C(.dbd.O)--N(R')(R''), (R')(R'')N-alkyl,
(R')(R'')N-alkoxyalkyl, (R')(R'')N-alkylaryloxyalkyl,
--S(O).sub.s-aryl (where s=0-2) or --S(O).sub.s-heteroaryl (where
s=0-2). Each R'and R'' is independently an optionally substituted
alkyl, cycloalkyl, or aryl group. R'and R'', together with the
nitrogen atom to which they are bound, can form a ring system in
certain embodiments. Substituents may also be crosslinking groups.
Any of the preceding groups with available hydrogens, may also be
deuterated.
[0033] The term "charge transport," when referring to a layer,
material, member, or structure is intended to mean such layer,
material, member, or structure facilitates migration of such charge
through the thickness of such layer, material, member, or structure
with relative efficiency and small loss of charge. Hole transport
materials facilitate positive charge; electron transport materials
facilitate negative charge. Although light-emitting materials may
also have some charge transport properties, the term "charge
transport layer, material, member, or structure" is not intended to
include a layer, material, member, or structure whose primary
function is light emission.
[0034] The term "compound" is intended to mean an electrically
uncharged substance made up of molecules that further include
atoms, wherein the atoms cannot be separated from their
corresponding molecules by physical means without breaking chemical
bonds. The term is intended to include oligomers and polymers.
[0035] The term "crosslinkable group" or "crosslinking group" is
intended to mean a group on a compound or polymer chain that can
link to another compound or polymer chain via thermal treatment,
use of an initiator, or exposure to radiation, where the link is a
covalent bond. In some embodiments, the radiation is UV or visible.
Examples of crosslinkable groups include, but are not limited to
vinyl, acrylate, perfluorovinylether, 1-benzo-3,4-cyclobutane,
o-quinodimethane groups, siloxane, cyanate groups, cyclic ethers
(epoxides), cycloalkenes, and acetylenic groups.
[0036] The term "deuterated" is intended to mean that at least one
hydrogen ("H") has been replaced by deuterium ("D"). The term
"deuterated analog" refers to a structural analog of a compound or
group in which one or more available hydrogens have been replaced
with deuterium. In a deuterated compound or deuterated analog, the
deuterium is present in at least 100 times the natural abundance
level.
[0037] The term "electroactive" as it refers to a layer or a
material, is intended to indicate a layer or material which
electronically facilitates the operation of the device. Examples of
electroactive materials include, but are not limited to, materials
which conduct, inject, transport, or block a charge, where the
charge can be either an electron or a hole, or materials which emit
radiation or exhibit a change in concentration of electron-hole
pairs when receiving radiation. Examples of inactive materials
include, but are not limited to, planarization materials,
insulating materials, and environmental barrier materials.
[0038] The prefix "fluoro" is intended to indicate that one or more
hydrogens in a group has been replaced with fluorine.
[0039] The term "germyl" refers to the group R.sub.3Ge--, where R
is the same or different at each occurrence and is H, D, C1-20
alkyl, deuterated alkyl, fluoroalkyl, aryl, or deuterated aryl. In
some embodiments, one or more carbons in an R alkyl group are
replaced with Ge.
[0040] The prefix "hetero" indicates that one or more carbon atoms
has been replaced with a different atom. In some embodiments, the
heteroatom is O, N, S, or combinations thereof.
[0041] The term "liquid composition" is intended to mean a liquid
medium in which a material is dissolved to form a solution, a
liquid medium in which a material is dispersed to form a
dispersion, or a liquid medium in which a material is suspended to
form a suspension or an emulsion.
[0042] The term "photoactive" refers to a material or layer that
emits light when activated by an applied voltage (such as in a
light emitting diode or chemical cell), that emits light after the
absorption of photons (such as in down-converting phosphor
devices), or that responds to radiant energy and generates a signal
with or without an applied bias voltage (such as in a photodetector
or a photovoltaic cell).
[0043] The term "siloxane" refers to the group
R.sub.3SiOR.sub.2Si--, where R is the same or different at each
occurrence and is H, D, C1-20 alkyl, deuterated alkyl, fluoroalkyl,
aryl, or deuterated aryl. In some embodiments, one or more carbons
in an R alkyl group are replaced with Si.
[0044] The term "siloxy" refers to the group R.sub.3SiO--, where R
is the same or different at each occurrence and is H, D, C1-20
alkyl, deuterated alkyl, fluoroalkyl, aryl, or deuterated aryl.
[0045] The term "silyl" refers to the group R.sub.3Si--, where R is
the same or different at each occurrence and is H, D, C1-20 alkyl,
deuterated alkyl, fluoroalkyl, aryl, or deuterated aryl. In some
embodiments, one or more carbons in an R alkyl group are replaced
with Si.
[0046] In a structure where a substituent bond passes through one
or more rings as shown below,
##STR00003##
it is meant that the substituent R may be bonded at any available
position on the one or more rings.
[0047] The phrase "adjacent to," when used to refer to layers in a
device, does not necessarily mean that one layer is immediately
next to another layer. On the other hand, the phrase "adjacent R
groups," is used to refer to R groups that are next to each other
in a chemical formula (i.e., R groups that are on atoms joined by a
bond). Exemplary adjacent R groups are shown below:
##STR00004##
[0048] In this specification, unless explicitly stated otherwise or
indicated to the contrary by the context of usage, where an
embodiment of the subject matter hereof is stated or described as
comprising, including, containing, having, being composed of or
being constituted by or of certain features or elements, one or
more features or elements in addition to those explicitly stated or
described may be present in the embodiment. An alternative
embodiment of the disclosed subject matter hereof, is described as
consisting essentially of certain features or elements, in which
embodiment features or elements that would materially alter the
principle of operation or the distinguishing characteristics of the
embodiment are not present therein. A further alternative
embodiment of the described subject matter hereof is described as
consisting of certain features or elements, in which embodiment, or
in insubstantial variations thereof, only the features or elements
specifically stated or described are present.
[0049] Further, unless expressly stated to the contrary, "or"
refers to an inclusive or and not to an exclusive or. For example,
a condition A or B is satisfied by any one of the following: A is
true (or present) and B is false (or not present), A is false (or
not present) and B is true (or present), and both A and B are true
(or present).
[0050] Also, use of "a" or "an" are employed to describe elements
and components described herein. This is done merely for
convenience and to give a general sense of the scope of the
invention. This description should be read to include one or at
least one and the singular also includes the plural unless it is
obvious that it is meant otherwise.
[0051] Group numbers corresponding to columns within the Periodic
Table of the elements use the "New Notation" convention as seen in
the CRC Handbook of Chemistry and Physics, 81.sup.st Edition
(2000-2001).
[0052] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
methods and materials similar or equivalent to those described
herein can be used in the practice or testing of embodiments of the
present invention, suitable methods and materials are described
below. All publications, patent applications, patents, and other
references mentioned herein are incorporated by reference in their
entirety, unless a particular passage is cited. In case of
conflict, the present specification, including definitions, will
control. In addition, the materials, methods, and examples are
illustrative only and not intended to be limiting.
[0053] To the extent not described herein, many details regarding
specific materials, processing acts, and circuits are conventional
and may be found in textbooks and other sources within the organic
light-emitting diode display, photodetector, photovoltaic, and
semiconductive member arts.
[0054] 2. Compound having Formula I
[0055] In some embodiments, the electroactive compound has Formula
I
##STR00005##
wherein: [0056] Ar.sup.1 is selected from the group consisting of
phenanthrene, triphenylene, triphenylsilyl, triphenylgermyl,
dibenzofuran, dibenzothiophene, polyarylphenyl, substituted
derivatives thereof, and deuterated analogs thereof; [0057]
Ar.sup.2 and Ar.sup.3 are the same or different and are selected
from the group consisting of hydrocarbon aryl, heteroaryl,
substituted derivatives thereof, and deuterated analogs thereof,
with the proviso that Ar.sup.2 and Ar.sup.3 are not the same as
Ar.sup.1; and [0058] a is 0 or 1;
[0059] with the proviso that Ar.sup.1, Ar.sup.2, and Ar.sup.3 have
no additional amino substituents.
[0060] In some embodiments of Formula I, Ar.sup.1, Ar.sup.2, and
Ar.sup.3 have no carbazole or substituted carbazole
substituents.
[0061] In some embodiments, the compound having Formula I is
deuterated. In some embodiments, the compound is at least 10%
deuterated. By "% deuterated" or "% deuteration" is meant the ratio
of deuterons to the sum of protons plus deuterons, expressed as a
percentage. In some embodiments, the compound is at least 10%
deuterated; in some embodiments, at least 20% deuterated; in some
embodiments, at least 30% deuterated; in some embodiments, at least
40% deuterated; in some embodiments, at least 50% deuterated; in
some embodiments, at least 60% deuterated; in some embodiments, at
least 70% deuterated; in some embodiments, at least 80% deuterated;
in some embodiments, at least 90% deuterated; in some embodiments,
100% deuterated.
[0062] In some embodiments of Formula I, a=0.
[0063] In some embodiments of Formula I, a=1.
[0064] Ar.sup.1, Ar.sup.2, and Ar.sup.3 have no additional amino
substituents. There is a single amino group in the compound having
Formula I, as shown.
[0065] In some embodiments of Formula I, Ar.sup.1 is selected from
the group consisting of phenanthrene, triphenylene, triphenylsilyl,
triphenylgermyl, polyarylphenyl, substituted derivatives thereof,
and deuterated analogs thereof.
[0066] In some embodiments of Formula I, Ar.sup.1 is selected from
the group consisting of triphenylsilyl, triphenylgermyl,
dibenzothiophene, polyarylphenyl, substituted derivatives thereof,
and deuterated analogs thereof.
[0067] In some embodiments of Formula I, Ar.sup.1 is selected from
the group consisting of triphenylsilyl, polyarylphenyl, substituted
derivatives thereof, and deuterated analogs thereof.
[0068] In some embodiments of Formula I, Ar.sup.1 is
phenanthrene.
[0069] In some embodiments, the phenanthrene has Formula a
##STR00006##
where: [0070] R.sup.1 is the same or different at each occurrence
and is selected from the group consisting of D, alkyl, silyl,
germyl, hydrocarbon aryl, heteroaryl, deuterated alkyl, deuterated
silyl, deuterated germyl, deuterated hydrocarbon aryl, and
deuterated heteroaryl; [0071] b1 and b2 are the same or different
and are an integer from 0-4; and [0072] the dashed line represents
a possible point of attachment.
[0073] In some embodiments of Formula a, b1=0.
[0074] In some embodiments of Formula a, b1=1.
[0075] In some embodiments of Formula a, b1=2.
[0076] In some embodiments of Formula a, b1=3.
[0077] In some embodiments of Formula a, b1=4.
[0078] In some embodiments of Formula a, b1>0 and at least one
R.sup.1 is D.
[0079] In some embodiments of Formula a, b1>0 and at least one
R.sup.1 is an alkyl or deuterated alkyl having 1-12 carbons.
[0080] In some embodiments of Formula a, b1>0 and at least one
R.sup.1 is an aryl or deuterated aryl having 6-18 ring carbons.
[0081] In some embodiments of Formula a, b2=0.
[0082] In some embodiments of Formula a, b2=1.
[0083] In some embodiments of Formula a, b2=2.
[0084] In some embodiments of Formula a, b2=3.
[0085] In some embodiments of Formula a, b2=4.
[0086] In some embodiments of Formula a, b2>0 and at least one
R.sup.1 is D.
[0087] In some embodiments of Formula a, b2>0 and at least one
R.sup.1 is an alkyl or deuterated alkyl having 1-12 carbons.
[0088] In some embodiments of Formula a, b2>0 and at least one
R.sup.1 is an aryl or deuterated aryl having 6-18 ring carbons.
[0089] In some embodiments of Formula I, Ar.sup.1 is a
triphenylene.
[0090] In some embodiments, the triphenylene has Formula b
##STR00007##
where c1 is an integer from 0-8; and R.sup.1 and the dashed lines
are as defined above for Formula a.
[0091] In some embodiments of Formula b, c1=0.
[0092] In some embodiments of Formula b, c1=1.
[0093] In some embodiments of Formula b, c1=2.
[0094] In some embodiments of Formula b, c1=3.
[0095] In some embodiments of Formula b, c1=4.
[0096] In some embodiments of Formula b, c1=5.
[0097] In some embodiments of Formula b, c1=6.
[0098] In some embodiments of Formula b, c1=7.
[0099] In some embodiments of Formula b, c1=8.
[0100] In some embodiments of Formula b, c1>0 and at least one
R.sup.1 is as described above for Formula a.
[0101] In some embodiments of Formula I, Ar.sup.1 is
triphenylsilyl.
[0102] In some embodiments, the triphenylsilyl has Formula c
##STR00008##
where d1, d2, and d3 are the same or different and are an integer
from 0-5; and R.sup.1 and the dashed line are as defined above for
Formula a.
[0103] In some embodiments of Formula c, d1=0.
[0104] In some embodiments of Formula c, d1=1.
[0105] In some embodiments of Formula c, d1=2.
[0106] In some embodiments of Formula c, d1=3.
[0107] In some embodiments of Formula c, d1=4.
[0108] In some embodiments of Formula c, d1=5.
[0109] In some embodiments of Formula c, d1>0 and at least one
R.sup.1 is as described above for Formula a.
[0110] In some embodiments of Formula c, d2=0.
[0111] In some embodiments of Formula c, d2=1.
[0112] In some embodiments of Formula c, d2=2.
[0113] In some embodiments of Formula c, d2=3.
[0114] In some embodiments of Formula c, d2=4.
[0115] In some embodiments of Formula c, d2=5.
[0116] In some embodiments of Formula c, d2=6.
[0117] In some embodiments of Formula c, d2=7.
[0118] In some embodiments of Formula c, d2=8.
[0119] In some embodiments of Formula c, d2>0 and at least one
R.sup.1 is as described above for Formula a.
[0120] In some embodiments of Formula c, d3=0.
[0121] In some embodiments of Formula c, d3=1.
[0122] In some embodiments of Formula c, d3=2.
[0123] In some embodiments of Formula c, d3=3.
[0124] In some embodiments of Formula c, d3=4.
[0125] In some embodiments of Formula c, d3=5.
[0126] In some embodiments of Formula c, d3=6.
[0127] In some embodiments of Formula c, d3=7.
[0128] In some embodiments of Formula c, d3=8.
[0129] In some embodiments of Formula c, d3>0 and at least one
R.sup.1 is as described above for Formula a.
[0130] In some embodiments of Formula I, Ar.sup.1 is
triphenylgermyl.
[0131] In some embodiments, the triphenylgermyl has Formula d
##STR00009##
where d4, d5, and d6 are the same or different and are an integer
from 0-5; and R.sup.1 and the dashed line are as defined above for
Formula a.
[0132] In some embodiments of Formula d, d4=0.
[0133] In some embodiments of Formula d, d4=1.
[0134] In some embodiments of Formula d, d4=2.
[0135] In some embodiments of Formula d, d4=3.
[0136] In some embodiments of Formula d, d4=4.
[0137] In some embodiments of Formula d, d4=5.
[0138] In some embodiments of Formula d, d4>0 and at least one
R.sup.1 is as described above for Formula a.
[0139] In some embodiments of Formula d, d5=0.
[0140] In some embodiments of Formula d, d5=1.
[0141] In some embodiments of Formula d, d5=2.
[0142] In some embodiments of Formula d, d5=3.
[0143] In some embodiments of Formula d, d5=4.
[0144] In some embodiments of Formula d, d5=5.
[0145] In some embodiments of Formula d, d5>0 and at least one
R.sup.1 is as described above for Formula a.
[0146] In some embodiments of Formula d, d6=0.
[0147] In some embodiments of Formula d, d6=1.
[0148] In some embodiments of Formula d, d6=2.
[0149] In some embodiments of Formula d, d6=3.
[0150] In some embodiments of Formula d, d6=4.
[0151] In some embodiments of Formula d, d6=5.
[0152] In some embodiments of Formula d, d6>0 and at least one
R.sup.1 is as described above for Formula a.
[0153] In some embodiments of Formula I, Ar.sup.1 is a
dibenzofuran.
[0154] In some embodiments, the dibenzofuran has Formula e
##STR00010##
where b3 is an integer from 0-4, e1 is an integer from 0-3, and
R.sup.1 and the dashed line are as defined above for Formula a.
[0155] In some embodiments of Formula e, b3=0.
[0156] In some embodiments of Formula e, b3=1.
[0157] In some embodiments of Formula e, b3=2.
[0158] In some embodiments of Formula e, b3=3.
[0159] In some embodiments of Formula e, b3=4.
[0160] In some embodiments of Formula e, b3>0 and at least one
R.sup.1 is as described above for Formula a.
[0161] In some embodiments of Formula e, e1=0.
[0162] In some embodiments of Formula e, e1=1.
[0163] In some embodiments of Formula e, e1=2.
[0164] In some embodiments of Formula e, e1=3.
[0165] In some embodiments of Formula e, e1>0 and at least one
R.sup.1 is as described above for Formula a.
[0166] In some embodiments of Formula I, Ar.sup.1 is a
dibenzothiophene.
[0167] In some embodiments, the dibenzothiophene has Formula f
##STR00011##
where b4 is an integer from 0-4, e2 is an integer from 0-3, and
R.sup.1 and the dashed line are as defined above for Formula a.
[0168] In some embodiments of Formula f, b4=0.
[0169] In some embodiments of Formula f, b4=1.
[0170] In some embodiments of Formula f, b4=2.
[0171] In some embodiments of Formula f, b4=3.
[0172] In some embodiments of Formula f, b4=4.
[0173] In some embodiments of Formula f, b4>0 and at least one
R.sup.1 is as described above for Formula a.
[0174] In some embodiments of Formula f, e2=0.
[0175] In some embodiments of Formula f, e2=1.
[0176] In some embodiments of Formula f, e2=2.
[0177] In some embodiments of Formula f, e2=3.
[0178] In some embodiments of Formula f, e2>0 and at least one
R.sup.1 is as described above for Formula a.
[0179] In some embodiments of Formula I, Ar.sup.1 is a
polyarylphenyl.
[0180] In some embodiments, the polyarylphenyl has Formula g
##STR00012##
where d7 is an integer from 0-5, f is an integer of 2-4; and
R.sup.1 and the dashed line are as defined above for Formula a.
[0181] In some embodiments of Formula g, d7=0.
[0182] In some embodiments of Formula g, d7=1.
[0183] In some embodiments of Formula g, d7=2.
[0184] In some embodiments of Formula g, d7=3.
[0185] In some embodiments of Formula g, d7=4.
[0186] In some embodiments of Formula g, d7=5.
[0187] In some embodiments of Formula g, d7>0 and at least one
R.sup.1 is as described above for Formula a.
[0188] In some embodiments of Formula g, f=2.
[0189] In some embodiments of Formula g, f=3.
[0190] In some embodiments of Formula g, f=4.
[0191] In some embodiments of Formula I, Ar.sup.2 and Ar.sup.3 are
hydrocarbon aryl groups having no fused rings, substituted
derivatives thereof, or deuterated analogs thereof.
[0192] In some embodiments of Formula I, Ar.sup.2 is a hydrocarbon
aryl group or deuterated hydrocarbon aryl group having 6-30 ring
carbon atoms; in some embodiments, 6-18 ring carbon atoms.
[0193] In some embodiments of Formula I, Ar.sup.2 is a hydrocarbon
aryl group having no fused rings.
[0194] In some embodiments of Formula I, Ar.sup.2 is a hydrocarbon
aryl group having no substituents.
[0195] In some embodiments of Formula I, Ar.sup.2 is a deuterated
hydrocarbon aryl group having no additional substituents. In some
embodiments of Formula I, Ar.sup.2 is a hydrocarbon aryl group
having one or more substituents selected from the group consisting
of D, F, CN, alkyl, fluoroalkyl, heteroaryl, silyl, germyl, alkoxy,
aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl,
deuterated partially-fluorinated alkyl, deuterated heteroaryl,
deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated
aryloxy, deuterated fluoroalkoxy, deuterated siloxane, and
deuterated siloxy.
[0196] In some embodiments of Formula I, Ar.sup.2 is a hydrocarbon
aryl group having one or more substituents selected from the group
consisting of D, F, CN, alkyl, fluoroalkyl, silyl, germyl,
deuterated alkyl, deuterated partially-fluorinated alkyl,
deuterated silyl, and deuterated germyl.
[0197] In some embodiments of Formula I, Ar.sup.2 has Formula h
##STR00013##
where: [0198] R.sup.2 is the same or different at each occurrence
and is selected from the group consisting of D, F, CN, alkyl,
fluoroalkyl, hydrocarbon aryl, heteroaryl, silyl, germyl, alkoxy,
aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl,
deuterated partially-fluorinated alkyl, deuterated hydrocarbon
aryl, deuterated heteroaryl, deuterated silyl, deuterated germyl,
deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy,
deuterated siloxane, and deuterated siloxy, where adjacent R.sup.2
groups can be joined together to form an fused aromatic ring or a
deuterated fused aromatic ring; [0199] p is the same or different
at each occurrence and is an integer from 0-4; [0200] q is an
integer from 0-5; [0201] r is an integer from 1 to 5; and [0202] *
indicates the point of attachment.
[0203] In some embodiments of Formula h, R.sup.2 is the same or
different at each occurrence and is selected from the group
consisting of D, F, CN, alkyl, fluoroalkylsilyl, germyl, deuterated
alkyl, deuterated partially-fluorinated alkyl, deuterated silyl,
and deuterated germyl, where adjacent R.sup.2 groups can be joined
together to form an fused aromatic ring or a deuterated fused
aromatic ring
[0204] In some embodiments of Formula h, p=0.
[0205] In some embodiments of Formula h, p=1.
[0206] In some embodiments of Formula h, p=2.
[0207] In some embodiments of Formula h, p=3.
[0208] In some embodiments of Formula h, p=4.
[0209] In some embodiments of Formula h, p>0 and at least one
R.sup.2 is D.
[0210] In some embodiments of Formula h, p>0 and at least one
R.sup.2 is an alkyl or deuterated alkyl having 1-12 carbon
atoms.
[0211] In some embodiments of Formula h, p>0 and at least one
R.sup.2 is silyl or deuterated silyl.
[0212] In some embodiments of Formula h, p>0 and at least one
R.sup.2 is germyl or deuterated germyl.
[0213] In some embodiments of Formula h, p>0 and at least one
R.sup.2 is heteroaryl. In some embodiments the heteroaryl is
derived from a compound selected from the group consisting
carbazole, substituted derivatives thereof, and deuterated analogs
thereof.
[0214] In some embodiments of Formula h, r=0.
[0215] In some embodiments of Formula h, r=1.
[0216] In some embodiments of Formula h, r=2.
[0217] In some embodiments of Formula h, r=3.
[0218] In some embodiments of Formula h, r=4.
[0219] In some embodiments of Formula h, r>0 and at least one
R.sup.2 is D.
[0220] In some embodiments of Formula h, .sup.r>0 and at least
one R.sup.2 is an alkyl or deuterated alkyl having 1-12 carbon
atoms.
[0221] In some embodiments of Formula h, r>0 and at least one
R.sup.2 is silyl or deuterated silyl.
[0222] In some embodiments of Formula h, r>0 and at least one
R.sup.2 is germyl or deuterated germyl.
[0223] In some embodiments of Formula h, r>0 and at least one
R.sup.2 is heteroaryl. In some embodiments the heteroaryl is
derived from a compound selected from the group consisting
carbazole, substituted derivatives thereof, and deuterated analogs
thereof.
[0224] In some embodiments of Formula I, Ar.sup.2 has Formula i
##STR00014##
where R.sup.2, p, q, r and *are as in Formula h.
[0225] The embodiments of R.sup.2, p, q, and r described above for
Formula h apply equally to Formula i.
[0226] The embodiments of Ar.sup.2 described above apply equally to
Ar.sup.3.
[0227] In some embodiments of Formula I, Ar.sup.2=Ar.sup.3.
[0228] In some embodiments of Formula I, Ar.sup.2 .noteq.
Ar.sup.3.
[0229] In some embodiments, the electroactive compound has Formula
II
##STR00015##
wherein: [0230] Ar.sup.1 is selected from the group consisting of
phenanthrene, triphenylene, triphenylsilyl, triphenylgermyl,
dibenzofuran, dibenzothiophene, polyarylphenyl, substituted
derivatives thereof, and deuterated analogs thereof; [0231]
Ar.sup.2 and Ar.sup.3 are the same or different and are selected
from the group consisting of hydrocarbon aryl, heteroaryl,
substituted derivatives thereof, and deuterated analogs thereof,
with the proviso that Ar.sup.2 and Ar.sup.3 are not the same as
Ar.sup.1; and
[0232] with the proviso that Ar.sup.1, Ar.sup.2, and Ar.sup.3 have
no additional amino substituents.
[0233] The embodiments of Ar.sup.1, Ar.sup.2, and Ar.sup.3
described above for Formula I apply equally to Formula II.
[0234] Any of the above embodiments for Formula I or Formula II can
be combined with one or more of the other embodiments, so long as
they are not mutually exclusive. For example, the embodiment in
Ar.sup.1 is phenanthrene having Formula a can be combined with the
embodiment in which b1>0 and at least one R.sup.1 is an alkyl or
deuterated alkyl having 1-12 carbons and the embodiment in which
b2=0. The same is true for the other non-mutually-exclusive
embodiments discussed above. The skilled person would understand
which embodiments were mutually exclusive and would thus readily be
able to determine the combinations of embodiments that are
contemplated by the present application.
[0235] The compounds of Formula I or Formula II can be made using
any technique that will yield a C--C or C--N bond. A variety of
such techniques are known, such as Suzuki, Yamamoto, Stille, and
metal-catalyzed C--N couplings as well as metal catalyzed and
oxidative direct arylation.
[0236] Deuterated compounds can be prepared in a similar manner
using deuterated precursor materials or, more generally, by
treating the non-deuterated compound with deuterated solvent, such
as benzene-d6, in the presence of a Lewis acid H/D exchange
catalyst, such as trifluoromethanesulfonic acid, aluminum
trichloride or ethyl aluminum dichloride.
[0237] Exemplary preparations are given in the Examples.
[0238] Some non-limiting examples of compounds having Formula I are
shown below.
##STR00016## ##STR00017##
[0239] The compounds can be formed into layers for electronic
devices. The term "layer" is used interchangeably with the term
"film" and refers to a coating covering a desired area. The term is
not limited by size. The area can be as large as an entire device
or as small as a specific functional area such as the actual visual
display, or as small as a single sub-pixel. Layers and films can be
formed by any conventional deposition technique, including vapor
deposition, liquid deposition (continuous and discontinuous
techniques), and thermal transfer. Continuous liquid deposition
techniques, include but are not limited to, spin coating, gravure
coating, curtain coating, dip coating, slot-die coating, spray
coating, and continuous nozzle coating. Discontinuous liquid
deposition techniques include, but are not limited to, ink jet
printing, gravure printing, and screen printing.
[0240] In some embodiments, the new compounds having Formula I have
high triplet energy levels. In some embodiments, the first triplet
energy level is at least 2.4 eV.
[0241] In some embodiments, the new compound having Formula I have
sufficient solubility in common organic solvents to allow for
solution processing. In some embodiments, the solubility in toluene
is at least 20 mg/ml.
[0242] In some embodiments, the new compounds having Formula I have
a Tg sufficient to allow for heated drying of subsequent layers in
devices. In some embodiments, the Tg is at least 90.degree. C.
[0243] In some embodiments, the new compounds having Formula I can
be used as hole transport materials in devices.
[0244] In some embodiments, the new compounds having Formula I are
electroluminescent and can be used as emissive materials in
devices.
[0245] In some embodiments, the new compounds having Formula I can
be used as hosts for electroluminescent materials.
[0246] In some embodiments, the new compounds having Formula I can
be used as electron transport materials in devices.
3. Electronic Devices
[0247] Organic electronic devices that may benefit from having one
or more layers including at least one compound as described herein
include, but are not limited to, (1) devices that convert
electrical energy into radiation (e.g., a light-emitting diode,
light emitting diode display, lighting device, luminaire, or diode
laser), (2) devices that detect signals through electronics
processes (e.g., photodetectors, photoconductive cells,
photoresistors, photoswitches, phototransistors, phototubes, IR
detectors, biosensors), (3) devices that convert radiation into
electrical energy, (e.g., a photovoltaic device or solar cell), (4)
devices that convert light of one wavelength to light of a longer
wavelength, (e.g., a down-converting phosphor device); and (5)
devices that include one or more electronic components that include
one or more organic semi-conductor layers (e.g., a transistor or
diode); or any combination of devices in items (1) through (5).
Other uses for the compositions according to the present invention
include coating materials for memory storage devices, antistatic
films, biosensors, electrochromic devices, solid electrolyte
capacitors, energy storage devices such as a rechargeable battery,
and electromagnetic shielding applications.
[0248] One illustration of an organic electronic device structure
including at least one compound as described herein, is shown in
FIG. 1. The device 100 has a first electrical contact layer, an
anode layer 110 and a second electrical contact layer, a cathode
layer 160, and a photoactive layer 140 between them. Additional
layers may optionally be present. Adjacent to the anode may be a
hole injection layer 120, sometimes referred to as a buffer layer.
Adjacent to the hole injection layer may be a hole transport layer
130, including hole transport material. Adjacent to the cathode may
be an electron transport layer 150, including an electron transport
material. As an option, devices may use one or more additional hole
injection or hole transport layers (not shown) next to the anode
110 and/or one or more additional electron injection or electron
transport layers (not shown) next to the cathode 160. Layers 120
through 150 are individually and collectively referred to as the
organic active layers.
[0249] In some embodiments, in order to achieve full color, the
light-emitting layers is pixellated, with subpixel units for each
of the different colors. An illustration of a pixellated device is
shown in FIG. 2. The device 200 has anode 110, hole injection layer
120, hole transport layer 130, photoactive layer 140, electron
transport layer 150, and cathode 160. The photoactive layer is
divided into subpixels 141, 142, 143, which are repeated across the
layer. In some embodiments, the subpixels represent red, blue and
green color emission. Although three different subpixel units are
depicted in FIG. 2, two or more than three subpixel units may be
used.
[0250] In some embodiments, the device has the structure shown in
FIG. 3. Between hole injection layer 120 and photoactive layer 140
in device 300, there is a first hole transport layer 131 and a
second hole transport layer 132. Layers 110, 120, 140, 150, and 160
are as defined in FIG. 1.
[0251] In some embodiments, the device has the structure shown in
FIG. 4. Between hole injection layer 120 and photoactive layer 140
in device 400, there is a first hole transport layer 131 and a
second hole transport layer 132. Layers 110, 120, 141, 142, 143,
150, and 160 are as defined in FIG. 2.
[0252] The different layers will be discussed further herein with
reference to FIG. 1 and FIG. 3. However, the discussion applies to
FIG. 2, FIG. 4, and other configurations as well.
[0253] In some embodiments, the different layers have the following
range of thicknesses: anode 110, 100-5000 .ANG., in some
embodiments, 200-750 .ANG.; hole injection layer 120, 50-2000
.ANG., in some embodiments, 200-1500 .ANG.; total of hole transport
layers 130 or 131+132, 50-3000 .ANG., in some embodiments, 200-2000
.ANG.; photoactive layer 140, 10-2000 .ANG., in some embodiments,
100-1000 .ANG.; electron transport layer 150, 50-2000 .ANG., in
some embodiments, 100-1000 .ANG.; cathode 160, 200-10000 .ANG., in
some embodiments, 300-5000 .ANG.. The desired ratio of layer
thicknesses will depend on the exact nature of the materials
used.
[0254] One or more of the new compounds having Formula I described
herein may be present in one or more of the electroactive layers of
a device.
[0255] In some embodiments, devices including the new compounds
having Formula I have greater efficiency.
[0256] In some embodiments, devices including the new compounds
having Formula I have longer lifetime.
[0257] In some embodiments, the new compounds having Formula I are
useful as hole transport materials in layer 130.
[0258] In some embodiments, because the new compounds having
Formula I have high triplet energy levels, they are useful as hole
transport materials for devices having blue photoactive materials
in layer 140.
[0259] In some embodiments, the new compounds having Formula I are
useful in a second hole transport layer 132 between hole transport
layer 131 and photoactive layer 140. The new compounds are
particularly useful in a second hole transport layer when the
photoactive layer has blue photoactive materials.
[0260] In some embodiments, an organic electronic device includes,
in order, an anode, a hole transport layer, a photoactive layer,
and a cathode, where the hole transport layer includes a compound
having Formula I. Additional layers may be present in the
device.
[0261] In some embodiments, the new compounds having Formula I are
useful as host materials for photoactive dopant materials in
photoactive layer 140. The term "dopant" is intended to mean a
material, within a layer including a host material, that changes
the electronic characteristic(s) or the targeted wavelength(s) of
radiation emission, reception, or filtering of the layer compared
to the electronic characteristic(s) or the wavelength(s) of
radiation emission, reception, or filtering of the layer in the
absence of such material. The term "host material" is intended to
mean a material to which a dopant is added. The host material may
or may not have electronic characteristic(s) or the ability to
emit, receive, or filter radiation. In some embodiments, the host
material is present in higher concentration.
[0262] In some embodiments, the new compounds having Formula I are
useful as hosts for phosphorescent materials having red, yellow, or
green emission color.
[0263] In some embodiments, the new compounds having Formula I are
useful as a first host material in combination with a second host
material. In some embodiments, the second host material is an
electron transporting host.
[0264] In some embodiments, an organic electronic device includes
an anode, a cathode, and at least one organic active layer
therebetween, where the organic active layer includes a compound
having Formula I.
[0265] In some embodiments, an organic electronic device includes
an anode, a cathode, and a photoactive layer therebetween, where
the photoactive layer includes a compound having Formula I.
[0266] In some embodiments, an organic electronic device includes
an anode, a cathode, and a photoactive layer therebetween, and
further includes an additional organic active layer including a
compound having Formula I. In some embodiments, the additional
organic active layer is a hole transport layer.
[0267] In some embodiments, an organic electronic device includes,
in order, an anode, a hole transport layer, a photoactive layer,
and a cathode, where the hole transport layer includes a compound
having Formula I.
[0268] In some embodiments, an organic electronic device includes,
in order, an anode, a first hole transport layer, a second hole
transport layer, a photoactive layer, and a cathode, where the
second hole transport layer includes a compound having Formula I.
In some embodiments, the second hole transport layer is directly
adjacent to and in contact with the photoactive layer.
[0269] In some embodiments, an organic electronic device includes
an anode, a hole transport layer, a photoactive layer, and a
cathode, where both the hole transport layer and the photoactive
layer include a compound having Formula I. In some embodiments, the
hole transport layer is directly adjacent to and in contact with
the photoactive layer.
[0270] In all of the above-described devices, additional layers may
be present.
[0271] The anode 110 is an electrode that is particularly efficient
for injecting positive charge carriers. It can be made of, for
example materials containing a metal, mixed metal, alloy, metal
oxide or mixed-metal oxide, or it can be a conducting polymer, and
mixtures thereof. Suitable metals include the Group 11 metals, the
metals in Groups 4, 5, and 6, and the Group 8-10 transition metals.
If the anode is to be light-transmitting, mixed-metal oxides of
Groups 12, 13 and 14 metals, such as indium-tin-oxide, are
generally used. The anode may also include an organic material such
as polyaniline as described in "Flexible light-emitting diodes made
from soluble conducting polymer," Nature vol. 357, pp 477 479 (11
Jun. 1992). At least one of the anode and cathode should be at
least partially transparent to allow the generated light to be
observed.
[0272] Optional hole injection layer 120 includes hole injection
materials. The term "hole injection layer" or "hole injection
material" is intended to mean electrically conductive or
semiconductive materials and may have one or more functions in an
organic electronic device, including but not limited to,
planarization of the underlying layer, charge transport and/or
charge injection properties, scavenging of impurities such as
oxygen or metal ions, and other aspects to facilitate or to improve
the performance of the organic electronic device. Hole injection
materials may be polymers, oligomers, or small molecules, and may
be in the form of solutions, dispersions, suspensions, emulsions,
colloidal mixtures, or other compositions.
[0273] The hole injection layer can be formed with polymeric
materials, such as polyaniline (PANI) or polyethylenedioxythiophene
(PEDOT), which are often doped with protonic acids. The protonic
acids can be, for example, poly(styrenesulfonic acid),
poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and the like.
The hole injection layer 120 can include charge transfer compounds,
and the like, such as copper phthalocyanine and the
tetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In
some embodiments, the hole injection layer 120 is made from a
dispersion of a conducting polymer and a colloid-forming polymeric
acid. Such materials have been described in, for example, published
U.S. patent applications 2004-0102577, 2004-0127637, and
2005-0205860.
[0274] In some embodiments, the hole injection layer is a small
molecule. In some embodiments, the hole injection layer is selected
from the group consisting of
1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile,
tetracyanoquinodimethane, and
tetracyano-2,3,5,6-tetrafluoroquinodimethane.
[0275] In some embodiments, an optional short reduction layer (not
shown) is present between the anode and the hole injection layer.
The short reduction layer includes hole injection material. In some
embodiments, the hole injection layer comprises an electrically
conductive polymer and a polymeric acid. In some embodiments, the
polymeric acid is fluorinated; in some embodiments, at least 90%
fluorinated. In some embodiments, the short reduction layer has a
greater thickness than the hole injection layer.
[0276] Layer 130 includes hole transport material.
[0277] In some embodiments, layer 130 includes a compound having
Formula I, where additional materials that would materially alter
the principle of operation or the distinguishing characteristics of
the layer are not present.
[0278] In some embodiments, a second hole transport layer 132 is
present between hole transport layer 131 and photoactive layer 140,
and the second hole transport layer includes a compound having
Formula I. In some embodiments, the second hole transport layer 132
includes only a compound having Formula I, where additional
materials that would materially alter the principal of operation or
the distinguishing characteristics of the layer are not
present.
[0279] In some embodiments, layer 130 includes other hole transport
materials. Examples of hole transport materials for the hole
transport layer have ben summarized for example, in Kirk-Othmer
Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p.
837-860 1996, by Y. Wang. Both hole transporting small molecules
and polymers can be used. Commonly used hole transporting molecules
include, but are not limited to:
4,4',4''-tris(N,N-diphenyl-amino)-triphenylamine (TDATA);
4,4',4''-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine
(MTDATA);
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine
(TPD); 4,4'-bis(carbazol-9-yl)biphenyl (CBP);
1,3-bis(carbazol-9-yl)benzene (mCP); 1,1-bis[(di-4-tolylamino)
phenyl]cyclohexane (TAPC);
N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)bip-
henyl]-4,4'-diamine (ETPD);
tetrakis-(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA);
.alpha.-phenyl-4-N,N-diphenylaminostyrene (TPS);
p-(diethylamino)benzaldehyde diphenylhydrazone (DEH);
triphenylamine (TPA);
bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane
(MPMP);
1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]
pyrazoline (PPR or DEASP);
1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB);
N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
(TTB); N,N'-bis(naphthalen-1-yl)-N,N'-bis-(phenyl)benzidine
(.alpha.-NPB); and porphyrinic compounds, such as copper
phthalocyanine. Commonly used hole transporting polymers include,
but are not limited to, polyvinylcarbazole,
(phenylmethyl)polysilane, poly(dioxythiophenes), polyanilines, and
polypyrroles. It is also possible to obtain hole transporting
polymers by doping hole transporting molecules such as those
mentioned above into polymers such as polystyrene and
polycarbonate. In some cases, triarylamine polymers are used,
especially triarylamine-fluorene copolymers. In some cases, the
polymers and copolymers are crosslinkable. Examples of
crosslinkable hole transport polymers can be found in, for example,
published US patent application 2005-0184287 and published PCT
application WO 2005/052027. In some embodiments, the hole transport
layer is doped with a p-dopant, such as
tetrafluorotetracyanoquinodimethane and
perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride.
[0280] Layer 131 can include any of the hole transport materials
described above for layer 130.
[0281] In some embodiments, layer 131 includes a triarylamine
compound, a triarylamine polymer, or deuterated analog thereof.
[0282] Depending upon the application of the device, the
photoactive layer 140 can be a light-emitting layer that is
activated by an applied voltage (such as in a light-emitting diode
or light-emitting electrochemical cell), a layer of material that
absorbs light and emits light having a longer wavelength (such as
in a down-converting phosphor device), or a layer of material that
responds to radiant energy and generates a signal with or without
an applied bias voltage (such as in a photodetector or photovoltaic
device).
[0283] In some embodiments, the photoactive layer includes a
compound having Formula I as host material and additionally
includes a photoactive dopant. The photoactive dopant can be an
organic electroluminescent ("EL") material. Any EL material can be
used in t he devices, including, but not limited to, small molecule
organic fluorescent compounds, fluorescent and phosphorescent metal
complexes, conjugated polymers, and mixtures thereof. Examples of
fluorescent compounds include, but are not limited to, chrysenes,
pyrenes, perylenes, rubrenes, coumarins, anthracenes, thiadiazoles,
benzofluorenes, stilbenes, derivatives thereof, and mixtures
thereof. Examples of metal complexes include, but are not limited
to, metal chelated oxinoid compounds, such as tris
(8-hydroxyquinolato)aluminum (AlQ3); cyclometalated iridium and
platinum electroluminescent compounds, such as complexes of iridium
with phenylpyridine, phenylquinoline, or phenylpyrimidine ligands
are disclosed in Petrov et al., U.S. Pat. No. 6,670,645 and
Published PCT Applications WO 03/063555 and WO 2004/016710, and
organometallic complexes described in, for example, Published PCT
Applications WO 03/008424, WO 03/091688, and WO 03/040257, and
mixtures thereof. In some cases the small molecule fluorescent or
organometallic materials are deposited as a dopant with a host
material to improve processing and/or electronic properties.
Examples of conjugated polymers include, but are not limited to
poly (phenylenevinylenes), polyfluorenes, poly(spirobifluorenes),
polythiophenes, poly(p-phenylenes), copolymers thereof, and
mixtures thereof.
[0284] In some embodiments, photoactive layer 140 includes a
photoactive dopant and a host material having Formula I. In some
embodiments, photoactive layer 140 includes only a photoactive
dopant and a host material having Formula I, where additional
materials that would materially alter the principle of operation or
the distinguishing characteristics of the layer are not
present.
[0285] In some embodiments, photoactive layer 140 includes a
photoactive dopant, a host material having Formula I, and a second
host material. Examples of second host materials include, but are
not limited to, quinoxalines, phenylpyridines, indolocarbazoles,
indoloindoles, and metal quinolinate complexes, substituted
derivatives thereof, and deuterated analogs thereof.
[0286] In some embodiments, the second host is selected from the
group consisting of chrysenes, phenanthrenes, triphenylenes,
phenanthrolines, triazines, naphthalenes, anthracenes, quinolines,
isoquinolines, quinoxalines, phenylpyridines, carbazoles,
indolocarbazoles, indoloindoles, furans, benzofurans,
dibenzofurans, benzodifurans, metal quinolinate complexes,
substituted derivatives thereof, and deuterated analogs
thereof.
[0287] In some embodiments, the second host is selected from the
group consisting of triphenylenes, carbazoles, indolocarbazoles,
indoloindoles, furans, benzofurans, dibenzofurans, substituted
derivatives thereof, and deuterated analogs thereof.
[0288] In some embodiments, photoactive layer 140 includes only a
photoactive dopant, a first host material having Formula I, and a
second host material, where additional materials that would
materially alter the principle of operation or the distinguishing
characteristics of the layer are not present.
[0289] Optional layer 150 can function both to facilitate electron
transport, and also serve as a confinement layer to prevent
quenching of the exciton at layer interfaces. Preferably, this
layer promotes electron mobility and reduces exciton quenching.
[0290] In some embodiments, layer 150 includes other electron
transport materials. Examples of electron transport materials which
can be used in the optional electron transport layer 150, include
metal chelated oxinoid compounds, including metal quinolate
derivatives such as tris (8-hydroxyquinolato)aluminum (AlQ),
bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAlq),
tetrakis-(8-hydroxyquinolato)hafnium (HfQ) and
tetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds
such as 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxydiazole
(PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole
(TAZ), and 1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI);
quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline;
phenanthrolines such as 4,7-diphenyl-1,10-phenanthroline (DPA) and
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); triazines;
fullerenes; and mixtures thereof. In some embodiments, the electron
transport material is selected from the group consisting of metal
quinolates and phenanthroline derivatives. In some embodiments, the
electron transport layer further includes an n-dopant. N-dopant
materials are well known. The n-dopants include, but are not
limited to, Group 1 and 2 metals; Group 1 and 2 metal salts, such
as LiF, CsF, and Cs.sub.2CO.sub.3; Group 1 and 2 metal organic
compounds, such as Li quinolate; and molecular n-dopants, such as
leuco dyes, metal complexes, such as W.sub.2(hpp).sub.4 where
hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]-pyrimidine and
cobaltocene, tetrathianaphthacene, bis
(ethylenedithio)tetrathiafulvalene, heterocyclic radicals or
diradicals, and t he dimers, oligomers, polymers, dispiro compounds
and polycycles of heterocyclic radical or diradicals.
[0291] An optional electron injection layer may be deposited over
the electron transport layer. Examples of electron injection
materials include, but are not limited to, Li-containing
organometallic compounds, LiF, Li.sub.2O, Li quinolate,
Cs-containing organometallic compounds, CsF, Cs.sub.2O, and
Cs.sub.2CO.sub.3. This layer may react with the underlying electron
transport layer, the overlying cathode, or both. When an electron
injection layer is present, the amount of material deposited is
generally in the range of 1-100 .ANG., In some embodiments 1-10
.ANG..
[0292] The cathode 160, is an electrode that is particularly
efficient for injecting electrons or negative charge carriers. The
cathode can be any metal or nonmetal having a lower work function
than the anode. Materials for the cathode can be selected from
alkali metals of Group 1 (e.g., Li, Cs), the group 2 (alkaline
earth) metals, the Group 12 metals, including the rare earth
elements and lanthanides, and the actinides. Materials such as
aluminum, indium, calcium, barium, samarium and magnesium, as well
as combinations, can be used.
[0293] It is known to have other layers in organic electronic
devices. For example, there can be a layer (not shown) between the
anode 110 and hole injection layer 120 to control the amount of
positive charge injected and/or to provide band-gap matching of the
layers, or to function as a protective layer. Layers that are known
in the art can be used, such as copper phthalocyanine, silicon
oxy-nitride, fluorocarbons, silanes, or an ultra-thin layer of a
metal, such as Pt. Alternatively, some or all of anode layer 110,
active layers 120, 130, 140, and 150, or cathode layer 160, can be
surface-treated to increase charge carrier transport efficiency.
The choice of materials for each of the component layers is
preferably determined by balancing the positive and negative
charges in the emitter layer to provide a device with high
electroluminescence efficiency.
[0294] It is understood that each functional layer can be made up
of more than one layer.
[0295] The device layers can be formed by any deposition technique,
or combinations of techniques, including vapor deposition, liquid
deposition, and thermal transfer. Substrates such as glass,
plastics, and metals can be used. Conventional vapor deposition
techniques can be used, such as thermal evaporation, chemical vapor
deposition, and the like. The organic layers can be applied from
solutions or dispersions in suitable solvents, using conventional
coating or printing techniques, including but not limited to
spin-coating, dip-coating, roll-to-roll techniques, ink-jet
printing, continuous nozzle printing, screen-printing, gravure
printing and the like.
[0296] For liquid deposition methods, a suitable solvent for a
particular compound or related class of compounds can be readily
determined by one skilled in the art. For some applications, it is
desirable that the compounds be dissolved in non-aqueous solvents.
Such non-aqueous solvents can be relatively polar, such as C.sub.1
to C.sub.20 alcohols, ethers, and acid esters, or can be relatively
non-polar such as C.sub.1 to C.sub.12 alkanes or aromatics such as
toluene, xylenes, trifluorotoluene and the like. Other suitable
liquids for use in making the liquid composition, either as a
solution or dispersion as described herein, including the new
compounds, includes, but not limited to, chlorinated hydrocarbons
(such as methylene chloride, chloroform, chlorobenzene), aromatic
hydrocarbons (such as substituted and non-substituted toluenes and
xylenes), including trifluorotoluene), polar solvents (such as
tetrahydrofuran (THP), N-methyl pyrrolidone) esters (such as
ethylacetate) alcohols (isopropanol), ketones (cyclopentatone) and
mixtures thereof. Suitable solvents for electroluminescent
materials have been described in, for example, published PCT
application WO 2007/145979.
[0297] In some embodiments, the device is fabricated by liquid
deposition of the hole injection layer, the hole transport layer,
and the photoactive layer, and by vapor deposition of the anode,
the electron transport layer, an electron injection layer and the
cathode.
[0298] It is understood that the efficiency of devices made with
the new compositions described herein, can be further improved by
optimizing the other layers in the device. For example, more
efficient cathodes such as Ca, Ba or LiF can be used. Shaped
substrates and novel hole transport materials that result in a
reduction in operating voltage or increase quantum efficiency are
also applicable. Additional layers can also be added to tailor the
energy levels of the various layers and facilitate
electroluminescence.
[0299] In some embodiments, the device has the following structure,
in order: anode, hole injection layer, hole transport layer,
photoactive layer, electron transport layer, electron injection
layer, cathode.
[0300] In some embodiments, the device has the following structure,
in order: anode, short reduction layer, hole injection layer, hole
transport layer, photoactive layer, electron transport layer,
electron injection layer, cathode.
[0301] In some embodiments, the device has the following structure,
in order: anode, hole injection layer, first hole transport layer,
second hole transport layer, photoactive layer, electron transport
layer, electron injection layer, cathode.
[0302] Although methods and materials similar or equivalent to
those described herein can be used in the practice or testing of
the present invention, suitable methods and materials are described
below. In addition, the materials, methods, and examples are
illustrative only and not intended to be limiting. All
publications, patent applications, patents, and other references
mentioned herein are incorporated by reference in their
entirety.
EXAMPLES
[0303] The concepts described herein will be further described in
the following examples, which do not limit the scope of the
invention described in the claims.
Synthesis Example 1
[0304] This example illustrates the preparation of compounds having
Formula I, where a=0.
[0305] The compounds can generally be prepared according to
[0306] Scheme 1 or Scheme 2 shown below.
##STR00018##
##STR00019##
In the above schemes: Ar.sup.1, Ar.sup.2, and Ar.sup.3 are as
defined in Formula I; Pd/P represents a palladium catalyst in
combination with a phosphine compound; X=halide; r.t. represents
room temperature; and .DELTA. represents heating. In some
embodiments, the heating temperature is 50-100.degree. C.; in some
embodiments, 70-90.degree. C.
Synthesis Example 2
[0307] This example illustrates the preparation of compounds having
Formula I, where a=1.
[0308] The compounds can generally be prepared according to Scheme
3 shown below.
##STR00020##
In the above scheme: Ar.sup.1, Ar.sup.2, and Ar.sup.3 are as
defined in Formula I; Pd/P represents a palladium catalyst in
combination with a phosphine compound; X=halide; r.t. represents
room temperature; and .DELTA. represents heating. In some
embodiments, the heating temperature is 50-100.degree. C.; in some
embodiments, 70-90.degree. C.
Synthesis Example 3
[0309] This example illustrates the preparation of a compound
having Formula I, Compound 2.
Step 1
##STR00021##
[0311] Equimolar amounts of materials 1 and 2 were dissolved in
toluene and stirred until the solution was clear. To this was added
4 mol equivalents of 2M Na.sub.2CO.sub.3 solution and the solution
was sparged with argon for 30 min. To this was added 0.05 mol
equivalents of Pd(PPh.sub.3).sub.4 and the mixture stirred for 6 h
at 90.degree. C.
[0312] After cooling to room temperature, the reaction mixture was
filtered through celite/florisil/silica pad and washed with ethyl
acetate. The filtrate was washed with water and brine solution. The
organic layer was dried with anhydrous Na.sub.2SO.sub.4 and
concentrated under reduced pressure to obtain the crude material 3.
The crude material was purified by one time column chromatography
using 230-400 silica gel and the column was eluted with pet ether
to get the pure compound.
Step 2
##STR00022##
[0314] Equimolar amounts of materials 4 and 6 were dissolved in
toluene and stirred until the solution was clear. To this was added
1.5 mol equivalents of 2M Na.sub.2CO.sub.3 solution, the reaction
mixture was sparged with argon gas for 30 min, and 0.0005 mol
equivalents of (AMPHOS).sub.2PdCl.sub.2 was added. The reaction
mixture was heated to 90.degree. C. and stirred for 1.5 h.
[0315] After cooling to room temperature, the reaction mixture was
filtered through celite/florisil/silica pad and washed with ethyl
acetate. The organic layer was dried with anhydrous
Na.sub.2SO.sub.4 and concentrated under reduced pressure to obtain
the crude material 7. The crude material was purified by washing
with n-pentane and dried under vacuum.
Step 3.
##STR00023##
[0317] Equimolar amounts of materials 7 and 8 were dissolved in
anhydrous toluene under nitrogen and stirred until the solution was
clear. To this was added 1.5 mol equivalents of NaO.sup.tBu, 0.05
mol equivalents of Pd.sub.2(dba).sub.3 and 0.1 mol equivalents of
.sup.tBu.sub.3P (50% w/w in toluene), and the resulting reaction
mixture was stirred for 16 h at rt.
[0318] The reaction mixture was diluted with ethyl acetate, brine
solution and filtered through celite/florisil/silica pad and washed
with ethyl acetate. The organic layer was separated, dried over
anhydrous Na.sub.2SO.sub.4 and concentrated under reduced pressure
to get the crude material 10. The crude material was purified by
washings with acetonitrile, dried, and again washed with toluene to
get pure material.
Step 4.
##STR00024##
[0320] 1 mol equivalent of material 10 and 1.2 mol equivalents of
material 3 were dissolved in anhydrouse o-xylene under nitrogen and
stirred until the solution was clear. To this was added 2 mol
equivalents of NaO.sup.tBu, 0.05 mol equivalents of
Pd.sub.2(dba).sub.3 and 0.1 mol equivalents of
1,1-bis(diphenylphosphino)ferrocene, and the resulting reaction
mixture was stirred for 16 h at 150.degree. C.
[0321] The reaction mixture was allowed to cool to room
temperature, diluted with ethyl acetate and diluted with brine
solution (degassed with argon). The reaction mixture was then
filtered through celite/florisil/silica pad and washed with ethyl
acetate. The organic layer was separated, dried over anhydrous
Na.sub.2SO.sub.4 and concentrated under reduced pressure to
minimize the o-xylene volume.
[0322] The reaction mixture in o-xylene was poured in to pet ether
and stirred for 1 h. The resulting solid was filtered, washed with
acetonitrile and dried. The compound was then purified by column
chromatography (silica 230-400 mesh) and the column was gradually
eluted with 30% CH.sub.2Cl.sub.2 in pet ether. The column fractions
were evaporated under reduced pressure. The resulting solid was
washed with n-pentane and dried to get >99% purity by UPLC.
[0323] Compound 2 was further purified by adding ethanol (30
volumes) and heating to reflux for 20 minutes. At the same
temperature toluene (18 volumes) was slowly added, and then again
the temperature was brought to 120.degree. C. (internal
temperature) for 15 min. After that, the reaction mixture was
brought to 35.degree. C. and kept at that temperature for 3 h. The
mixture was filtered to collect the solid. The solid was again
washed with ethanol (4 vol) to get the pure Compound 2. The pure
compound was dried under vacuum (0.05 mm of Hg) for 4 h.
Synthesis Example 4
[0324] This example illustrates the preparation of a compound
having Formula I, Compound 1.
Step 1.
[0325] The secondary amine, material 10, was made as in Synthesis
Example 3.
Step 2.
##STR00025##
[0327] Equimolar amounts of secondary amine 10 and
9-bromophenanthrene were dissolved in anhydrous toluene under
nitrogen and stirred until the solution was clear. To this was
added 1.2 mol equivalents of NaO.sup.-tBu, 0.05 mol equivalents of
Pd.sub.2(dba).sub.3 and 0.1 mol equivalents of P(t-Bu).sub.3. The
resulting reaction mixture was stirred overnight at 90.degree.
C.
[0328] The resulting mixture was allowed to cool to room
temperature, filtered through celite/florisil/silica pad, washed
and concentrated. The product was purified by column
chromatography.
Synthesis Example 5
[0329] This example illustrates the preparation of a compound
having Formula I, Compound 4.
[0330] The compound can be prepared according to the following
scheme.
##STR00026## ##STR00027##
DEVICE EXAMPLES
(1) Materials
[0331] Dopant D1 is a bis(diarylamino)benzofluorene. Such materials
have been described in, for example, US Pat. No. 8,465,848. [0332]
Dopant D2 is a cyclometallated iridium complex having yellow
emission. [0333] ET-1 is an azine-substituted fluoranthene [0334]
ET-2 is lithium quinolate. [0335] ET-3 is an aryl phosphine oxide.
[0336] HIJ-1 is a hole injection material which is made from an
aqueous dispersion of an electrically conductive polymer and a
polymeric fluorinated sulfonic acid. [0337] HIJ-2 is
1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile. [0338] Host H1 is
a deuterated diaryl anthracene. The compound can be made using
known C--C coupling techniques. [0339] Host H2 is a deuterated
indolocarbazole having an N-heteroaryl substituent. The host can be
made using known C--C and C--N coupling techniques. [0340] HTM-1 is
a triarylamine polymer. The polymer can be made using known C--C
and C--N coupling techniques.
(2) Device Fabrication
[0341] OLED devices were fabricated by a combination of solution
processing and thermal evaporation techniques. Patterned indium tin
oxide (ITO) coated glass substrates from Thin Film Devices, Inc
were used. These ITO substrates are based on Corning 1737 glass
coated with ITO having a sheet resistance of 30 ohms/square and 80%
light transmission. The patterned ITO substrates were cleaned
ultrasonically in aqueous detergent solution and rinsed with
distilled water. The patterned ITO was subsequently cleaned
ultrasonically in acetone, rinsed with isopropanol, and dried in a
stream of nitrogen.
[0342] Device type 1: Immediately before device fabrication the
cleaned, patterned ITO substrates were treated with UV ozone for 10
minutes. Immediately after cooling, an aqueous dispersion of HIJ-1
was spin-coated over the ITO surface and heated to remove solvent,
to form a hole injection layer ("HIL"). After cooling, the
workpieces were then spin-coated with a solution of first hole
transport material in anisole:toluene (9:1 v/v) and then heated to
remove solvent, to form a first hole transport layer ("HTL1"). In
the examples of the invention, the cooled workpieces were then
spin-coated with a solution of second hole transport material in
[solvent?] and heated to remove solvent, to form a second hole
transport layer ("HTL2"). In the comparative examples, HTL1 was the
only hole transport layer. After cooling, the workpieces were then
spin-coated with a solution of the photoactive and host materials
in methylbenzoate, to form the photoactive layer or emissive layer
("EML"). The workpieces were then placed in a vacuum chamber and
the electron transport materials, electron injection materials, and
the Al cathode were then deposited sequentially by thermal
evaporation using the appropriate masks, to form the electron
transport layer ("ETL"), and the electron injection layer ("EIL"),
followed by the cathode. The chamber was vented, and the devices
were encapsulated using a glass lid, desiccant, and UV curable
epoxy.
[0343] Device Type 2: Immediately before device fabrication the
cleaned, patterned ITO substrates were treated with UV ozone for 10
minutes. Immediately after cooling, an aqueous dispersion of HIJ-1
was spin-coated over the ITO surface and heated to remove solvent,
to form a short reduction layer ("SRL"). The workpieces were then
placed in a vacuum chamber. The hole injection material, one or
more hole transport materials, the photoactive and host materials,
electron transport materials, electron injection material, and the
Al cathode were then deposited sequentially by thermal evaporation
using the appropriate masks, to form the hole injection layer
("HIL"), one or more hole transport layers ("HTL"), the photoactive
layer or emissive layer ("EML"), the electron transport layer
("ETL"), and the electron injection layer ("EIL"), followed by the
cathode. The chamber was vented, and the devices were encapsulated
using a glass lid, desiccant, and UV curable epoxy.
(3) Device Characterization
[0344] The OLED devices were characterized by measuring their (1)
current-voltage (I-V) curves, (2) electroluminescence radiance
versus voltage, and (3) electroluminescence spectra versus voltage.
All three measurements were performed at the same time and
controlled by a computer. The current efficiency of the device at a
certain voltage is determined by dividing the electroluminescence
radiance of the LED by the current density needed to run the
device. The unit is a cd/A. The power efficiency is the current
efficiency divided by the operating voltage. The unit is lm/W. The
color coordinates were determined using either a Minolta CS-100
meter or a photoresearch PR-705 meter.
Device Example 1 and Comparative Example A
[0345] This example illustrates the performance of a device having
a second hole transport layer including the new compound having
Formula I.
[0346] The device was made as described in Device Type 1, with the
device structure, in order (all percentages are by weight, based on
the total weight of the layer):
Glass substrate [0347] Anode: ITO (50 nm) [0348] HIL: HIJ-1 (100
nm)
HTL1
[0349] Example 1: HTM-1 (85 nm)
[0350] Comparative A: HTM-1 (105 nm
HTL2
[0351] Example 1: Compound 2 (20 nm)
[0352] Comparative A: none [0353] EML: H1:D1 in 13:1 weight ratio
(33 nm) [0354] ETL: ET-1 (20 nm) [0355] EIL: ET-2 (3.8 nm) [0356]
Cathode: Al (100 nm)
[0357] The results are given in Table 1.
TABLE-US-00001 TABLE 1 Device results CE EQE Ex. cd/A (%) CIEx CIEy
V Lum. T 80 A 8.3 9.2 0.140 0.101 4.3 1369 740 1 9.9 11.8 0.142
0.092 4.4 1634 1500
All data at 1000 nits, unless otherwise specified. CE is the
current efficiency; EQE=external quantum efficiency; CIEx and CIEy
refer to the x and y color coordinates according to the C.I.E.
chromaticity scale (Commission Internationale de L'Eclairage,
1931); V is the voltage @ 15 mA/cm.sup.2; Lum. is the lifetest
luminance in nits; T80 is the time in hours for a device to reach
80% of the initial luminance at a current density of 16.5
mA/cm.sup.2 and 50.degree. C.
Device Example 2 and Comparative Example B
[0358] This example illustrates the performance of a device having
a second hole transport layer including the new compound having
Formula I.
[0359] The device was made as described in Device Type 1, with the
device structure, in order (all percentages are by weight, based on
the total weight of the layer):
Glass substrate [0360] Anode: ITO (50 nm) [0361] HIL: HIJ-1 (100
nm
HTL1
[0362] Example 1: HTM-1 (85 nm)
[0363] Comparative B: HTM-1 (105 nm)
HTL2
[0364] Example 1: Compound 1 (20 nm)
[0365] Comparative B: none [0366] EML: H1:D1 in 13:1 weight ratio
(33 nm) [0367] ETL: ET-1 (20 nm) [0368] EIL: ET-2 (3.8 nm) [0369]
Cathode: Al (100 nm)
[0370] The results are given in Table 2.
TABLE-US-00002 TABLE 2 Device results EQE Ex. C.E. (%) CIEx CIEy V
Lum. T 80 B 8.0 8.9 0.139 0.101 4.5 1316 860 2 9.4 10.7 0.139 0.100
4.6 1565 1360
All data at 1000 nits, unless otherwise specified. CE is the
current efficiency; EQE=external quantum efficiency; CIEx and CIEy
refer to the x and y color coordinates according to the C.I.E.
chromaticity scale (Commission Internationale de L'Eclairage,
1931); V is the voltage @ 15 mA/cm.sup.2; Lum. is the lifetest
luminance in nits; T80 is the time in hours for a device to reach
80% of the initial luminance at a current density of 16.5
mA/cm.sup.2 and 50.degree. C.
[0371] It can be seen from the results in Tables 1 and 2, that
device efficiency and lifetime are increased when the device has a
second hole transport layer including a compound having Formula
I.
Device Examples 3 and 4 and Comparative Example C
[0372] This example illustrates the performance of a device
including the new compound having Formula I in the hole transport
layer and as a cohost in the photoactive layer.
[0373] The device was made as described in Device Type 2, with the
device structure, in order (all percentages are by weight, based on
the total weight of the layer):
Glass substrate [0374] Anode: ITO (50 nm) [0375] SRL: HIJ-1 (60 nm)
[0376] HIL: HIJ-2 (5 nm) [0377] HTL: Compound 2 (30 nm) [0378] EML:
16% D2 in the host shown in Table 3 below (30 nm) [0379] ETL:
ET-3:ET-2 in 3:2 weight ratio [0380] EIL: ET-2 (ETL+EIL=40 nm)
[0381] Cathode: Al (100 nm)
[0382] The results are shown in Table 3.
TABLE-US-00003 TABLE 3 Device results EQE Ex. Host C.E. (%) V T95 C
84% H2 93.5 27.8 4.35 870 3 10% Compound 2 94 27.5 3.9 1780 74% H2
4 30% Compound 2 83 24.5 4.1 2150 54% H2
All data at 3000 nits, unless otherwise specified. CE is the
current efficiency; EQE=external quantum efficiency; V is the; T95
is the time in hours for a device to reach 95% of the initial
luminance at a current density of 10 mA/cm.sup.2.
[0383] It can be seen from the results in Table 3, that device
lifetime is increased when the device has a host material having
Formula I, where the hole transport layer also includes a compound
having Formula I.
[0384] Note that not all of the activities described above in the
general description or the examples are required, that a portion of
a specific activity may not be required, and that one or more
further activities may be performed in addition to those described.
Still further, the order in which activities are listed are not
necessarily the order in which they are performed.
[0385] In the foregoing specification, the concepts have been
described with reference to specific embodiments. However, one of
ordinary skill in the art appreciates that various modifications
and changes can be made without departing from the scope of the
invention as set forth in the claims below. Accordingly, the
specification and figures are to be regarded in an illustrative
rather than a restrictive sense, and all such modifications are
intended to be included within the scope of invention.
[0386] Benefits, other advantages, and solutions to problems have
been described above with regard to specific embodiments. However,
the benefits, advantages, solutions to problems, and any feature(s)
that may cause any benefit, advantage, or solution to occur or
become more pronounced are not to be construed as a critical,
required, or essential feature of any or all the claims.
[0387] It is to be appreciated that certain features are, for
clarity, described herein in the context of separate embodiments,
may also be provided in combination in a single embodiment.
Conversely, various features that are, for brevity, described in
the context of a single embodiment, may also be provided separately
or in any subcombination. The use of numerical values in the
various ranges specified herein is stated as approximations as
though the minimum and maximum values within the stated ranges were
both being preceded by the word "about." In this manner, slight
variations above and below the stated ranges can be used to achieve
substantially the same results as values within the ranges. Also,
the disclosure of these ranges is intended as a continuous range
including every value between the minimum and maximum average
values including fractional values that can result when some of
components of one value are mixed with those of different value.
Moreover, when broader and narrower ranges are disclosed, it is
within the contemplation of this invention to match a minimum value
from one range with a maximum value from another range and vice
versa.
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