Abstrict A top-emitting OLED device includes a substrate, a first electrode
disposed over the substrate, and an organic EL media disposed over
the first electrode. The device also includes a transparent or semitransparent
second electrode disposed over the organic EL media, and a light
transmissive desiccating film having a host and molecularly dispersed
desiccant material in such host provided on or over the second electrode.
Claims 1. A top-emitting OLED device comprising: a) a substrate; b) a
first electrode disposed over the substrate; c) an organic EL media
disposed over the first electrode; d) a transparent or semitransparent
second electrode disposed over the organic EL media; and e) a light
transmissive desiccating film having a host and molecularly dispersed
desiccant material in such host provided on or over the second electrode.
2. The top-emitting OLED device of claim 1 including a transparent
inorganic barrier layer disposed between the second electrode and
the light transmissive desiccating film or on the light transmissive
desiccating film.
3. The top-emitting OLED device of claim 1 wherein the molecularly
dispersed desiccant material is selected to be transparent before
and after absorbing water.
4. The top-emitting OLED device of claim 1 further including providing
a cover made of glass over the light transmissive desiccating film.
5. The top-emitting OLED device of claim 1 wherein the desiccant
material includes a Lewis acid organometallic structure having the
formula R.sup.1.sub.n-M-R.sup.2.sub.m (I) wherein: M is a metal;
R.sup.1 is an organic substituent wherein at least one carbon is
directly bonded to the metal; R.sup.2 is a silyl oxide substituent
wherein the oxygen is directly bonded to the metal, or an amide
substituent having a nitrogen directly bonded to the metal; and
n=1 2 3 or 4 and m=0 1 2 or 3 and are selected to fulfill
the coordination requirements of M so that Formula I is neutral
in charge.
6. The top-emitting OLED device of claim 1 wherein the desiccant
material includes a reactive salt of a negatively charged organometallic
complex that, when it reacts with water, forms a carbon-hydrogen
bond but does not form an alcohol having the formula (A.sup.+b).sub.c[M(R.sup.1).sub.n(R.sup.2).sub.m(X).sub.l].sup.-q
wherein: A is a cation having charge b; M is a metal; R.sup.1 is
an organic substituent wherein at least one carbon is directly bonded
to the metal; R.sup.2 is a silyl oxide wherein the oxygen is directly
bonded to the metal, or an amide having a nitrogen directly bonded
to the metal; X is an anionic substituent having a pKa<7; l=1
or 2 n=1 2 3 or 4; m=0 1 2 or 3; q=is the charge of the anionic
organometallic complex and is 1 or 2; and b=q/c.
7. The top-emitting OLED device of claim 1 wherein the desiccant
material has the formula wherein: R.sub.10 is one selected from
the group including an alkyl group, an alkenyl group, an aryl group,
a cycloalkyl group, a heterocyclic group, and an acyl group having
at least one carbon atom; M is a trivalent metal atom; and n is
an integer of two to four.
8. The top-emitting OLED device of claim 1 wherein the desiccant
material has the formula wherein: each of R.sup.11 R.sub.12 R.sub.13
R.sub.14 and R.sub.15 is one selected from the group including an
alkyl group, an alkenyl group, an aryl group, a cycloalkyl group,
a heterocyclic group, and an acyl group having at least one carbon
atom; and M is a trivalent metal atom.
9. The top-emitting OLED device of claim 1 wherein the desiccant
material has the formula wherein: each of R.sub.11 R.sub.12 R.sub.13
R.sub.14 and R.sub.15 is one selected from the group including an
alkyl group, an alkenyl group, an aryl group, a cycloalkyl group,
a heterocyclic group, and an acyl group having at least one carbon
atom; and M is a tetravalent metal atom.
10. The top-emitting OLED device of claim 1 wherein the host includes
a polymer.
11. The top-emitting OLED device of claim 2 wherein the inorganic
barrier layer includes metal oxides or nitrides, or both, and are
deposited by thermal physical vapor deposition, sputtering, chemical
vapor deposition, plasma enhanced chemical vapor deposition, or
atomic layer deposition.
Description FIELD OF THE INVENTION
[0002] The present invention relates to providing a desiccant for
a top-emitting OLED device.
BACKGROUND OF THE INVENTION
[0003] Various microelectronic devices require restrictions on
humidity levels to be in a range of from about 2500 to below 5000
parts per million (ppm) to prevent premature degradation of device
performance within a specified operating and/or storage life of
the device. Control of the environment to this range of humidity
levels within a packaged device is typically achieved by encapsulating
the device or by sealing the device and a desiccant package within
a cover. Desiccant packages include a container for receiving solid
water absorbing particles (a desiccant) or providing such particles
into a binder. Examples of solid water absorbing particles include
molecular sieve materials, silica gel materials, calcium oxide,
and calcium chloride.
[0004] Silica gel and molecular sieves are physical adsorption-type
drying agents. Calcium oxide and calcium chloride are chemisorption-type
drying agents. Since water adsorbed thereby is not driven off at
high temperatures, they are more effective than silica gel and molecular
sieves.
[0005] However, particles of calcium oxide and calcium chloride
desiccants can be slow to absorb water. In addition, the handling
of such particulate materials can be a problem in microelectronic
devices that require clean room conditions. In addition, most desiccants
are white and scatter light, or do so after absorption of water.
Thus, they cannot be used in many applications where they might
cover or obscure a necessary feature.
[0006] Organic light emitting diode (OLED) devices are one class
of moisture sensitive electronic devices that can benefit from desiccants.
However, conventional desiccants have not been used for so-called
top-emitting OLED devices because of the problems noted above. Instead,
the prior art teaches methods to seal hermetically top-emitting
OLEDs using thin film barrier layers to limit the need for desiccants.
Though very useful, it is very difficult to seal OLED devices reliably
with thin film barrier layers. Pin-holes and other defects can still
occur and provide pathways for moisture to enter the device.
SUMMARY OF THE INVENTION
[0007] It is therefore an object of the present invention to provide
moisture protection to a top-emitting OLED device that will not
adversely affect device performance.
[0008] This object is achieved by a top-emitting OLED device comprising:
[0009] a) a substrate;
[0010] b) a first electrode disposed over the substrate;
[0011] c) an organic EL media disposed over the first electrode;
[0012] d) a transparent or semitransparent second electrode disposed
over the organic EL media; and
[0013] e) a light transmissive desiccating film having a host and
molecularly dispersed desiccant material in such host provided on
or over the second electrode.
ADVANTAGES
[0014] The invention provides a top-emitting OLED device that is
protected from moisture thereby achieving longer lifetime and excellent
device performance.
[0015] One advantage of providing the molecularly dispersed desiccant
within a host is that this reduces the formation of aggregates or
particles, especially if the desiccant is a metal complex or organometallic
material. One common byproduct of the reaction of water with such
metal-containing materials is the formation of metal oxides that
are prone to aggregate and form small particles. Such aggregates
and particles can absorb or scatter light.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a cross-sectional view of a prior art OLED device;
[0017] FIG. 2 is a plan view of a prior art OLED substrate with
a first electrode and contact pads;
[0018] FIG. 3 shows the OLED of FIG. 2 after deposition of a patterned
insulator layer;
[0019] FIG. 4A is a plan view of the OLED from FIG. 3 after deposition
of the organic EL media and second electrode;
[0020] FIG. 4B is a cross sectional view of the OLED device of
FIG. 4A taken along lines 4B;
[0021] FIG. 5 is a cross sectional view of a first embodiment of
the present invention;
[0022] FIG. 6 is a cross sectional view of a second embodiment
of the present invention;
[0023] FIG. 7 is a cross sectional view of a third embodiment of
the present invention; and
[0024] FIG. 8 is a cross sectional view of a fourth embodiment
of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention uses a light transmissive desiccating
film having a host and a molecularly dispersed desiccant material
in the host. The light transmissive desiccating film is provided
in a top-emitting OLED device such that light produced in the OLED
passes through the light transmissive desiccating film. The molecularly
dispersed desiccant should be light transmissive both before and
after water absorption.
[0026] Preferred desiccants for use in the present invention include
metal complexes and organometallic materials. These desiccant materials
are transparent before and after absorbing water. A "molecularly
dispersed desiccant" is a water reactive molecule or a water
reactive functional group provided within an inert "host"
so that such reactive molecule or group is diluted relative to a
pure film of the desiccant. Molecularly dispersed desiccants are
discussed in more detail below. An advantage of providing the molecularly
dispersed desiccant within a host is that this reduces the formation
of aggregates or particles, especially if the desiccant is a metal
complex or organometallic material. One common byproduct of the
reaction of water with such metal-containing materials is the formation
of metal oxides that are prone to aggregate and form small particles.
Such aggregates and particles can absorb or scatter light. This
is undesirable when light is emitted through the desiccant.
[0027] The term "transparent" means that sufficient light
will pass through to form a light image. More than 75% transparency
is preferred.
[0028] One class of useful desiccant material includes a Lewis
acid organometallic structure that, when it reacts with water, forms
a carbon-hydrogen bond but does not form an alcohol. Alcohols can
adversely affect the performance of an OLED device if they are permitted
to diffuse into the OLED device. This class of material limits this
concern. In one preferred embodiment, the Lewis acid has the structure
shown in Formula (I) R.sup.1.sub.n-M-R.sup.2.sub.m (I) wherein:
[0029] M is a metal;
[0030] R.sup.1 is an organic substituent wherein at least one carbon
is directly bonded to the metal;
[0031] R.sup.2 is a silyl oxide substituent wherein the oxygen
is directly bonded to the metal, or an amide substituent having
a nitrogen directly bonded to the metal; and
[0032] n=1 2 3 or 4 and m=0 1 2 or 3 and are selected to
fulfill the coordination requirements of M so that Formula I is
neutral in charge.
[0033] Metals selected from Group IIB, IIIA, IIIB, or IVB, or first
row transition metals are useful in present invention. Preferably,
they are Al, Zn, Ti, Mg, or B.
[0034] When more than one R.sup.1 substituent is used, the R.sup.1
substituents can be the same or different from each other. Likewise,
when more than one R.sup.2 substituent is used, the R.sup.2 substituents
can be the same or different from each other.
[0035] Some useful examples of organic substituents that can be
used as R.sup.1 include alkyl, alkenyl, aryl, and heteroaryl compounds
where a saturated or unsaturated carbon is bonded to the metal.
These compounds can be further substituted with alkyl, alkenyl,
aryl, heteroaryl, halogen, cyano, ether, ester, or tertiary amine
groups, or combinations thereof. Some non-limiting examples of R.sup.1
methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
i-propyl, t-butyl, cyclohexyl, tetradecyl, octadecyl, benzyl, phenyl,
and pyridyl. In addition, R.sup.1 can be part of an oligomeric or
polymeric system. For example, R.sup.1 can be a part of a polystyrene,
polybutadiene, polymethacrylate, polysiloxane, or polyfluorene structure.
[0036] Silyl oxides with the following Formula II can be selected
as R.sup.2 for the present invention wherein R.sup.3 through R.sup.6
are organic substituents and p is an integer from 0 to 1000. Some
organic substituents useful for R.sup.3 through R.sup.6 include
alkyl, alkenyl, aryl, and heteroaryl compounds, which can be further
substituted with alkyl, alkenyl, aryl, heteroaryl, halogen, cyano,
ether, ester, or tertiary amine groups, or combinations thereof.
Preferably R.sup.3 through R.sup.6 are alkyl or aryl groups.
[0037] Amides with the following Formula III can be selected as
R.sup.2 for the present invention wherein R.sup.8 and R.sup.9 are
organic substituents. Some organic substituents useful for R.sup.8
and R.sup.9 include alkyl, alkenyl, aryl, and heteroaryl compounds,
which can be further substituted with alkyl, alkenyl, aryl, heteroaryl,
halogen, cyano, ether, ester, or tertiary amine groups, or combinations
thereof. R.sup.8 and R.sup.9 can be joined to form a ring system.
R.sup.8 or R.sup.9 or both can be part of an oligomeric or polymeric
system. For example, R.sup.8 or R.sup.9 can be a part of a polystyrene,
polybutadiene, polymethacrylate, polysiloxane, or polyfluorene structure.
[0038] Although not shown in Formula I, there can be additional,
non charge-bearing moieties weakly or strongly coordinated to the
metal center. For example, there can be solvent molecules coordinated
to the metal center in addition to R.sup.1.
[0039] Examples of useful desiccant materials for practicing the
present invention include, but are not limited to, Al(C.sub.2H.sub.5).sub.3
Al(C.sub.4H.sub.9).sub.3 B(C.sub.4H.sub.9).sub.3 Zn(C.sub.4H.sub.9).sub.2
Al(t-butyl).sub.3 Ti(t-butyl).sub.4 Mg(t-butyl).sub.2 Al(C.sub.4H.sub.9).sub.2(N(C.sub.6H.sub.5).sub.2),
Al(C.sub.4H.sub.9)(N(C.sub.6H.sub.5).sub.2).sub.2 and the structures
shown below:
[0040] Equations 1-3 show how these moisture-absorbing materials
react with water, using various examples of R.sup.1 and R.sup.2
Formula I wherein M is aluminum. For example: Al(C.sub.4H.sub.9).sub.3+3H.sub.2O.fwdarw.3C.sub.4H.sub.10+Al(OH).sub.3
(1) Al(C.sub.4H.sub.9)((OSi(CH.sub.3).sub.2).sub.50C.sub.2H.sub.5).sub.2+-
3H.sub.2O.fwdarw.C.sub.4H.sub.10+2Si(OH)(CH.sub.3).sub.2).sub.50C.sub.2H.s-
ub.5+Al(OH).sub.3 (2) Al(C.sub.4H.sub.9).sub.2(N(C.sub.6H.sub.5).sub.2)+3H.sub.2O+2C.sub.4H.sub-
.10+2NH(C.sub.6H.sub.5).sub.2+Al(OH).sub.3 (3).
[0041] As can be seen, R.sup.1 of all compounds reacts with water
to form a carbon-hydrogen bond. In the case of R.sup.2 the reaction
with water forms a silyl oxygen-hydrogen bond or a nitrogen-hydrogen
bond. None of these substituents form harmful alcohol species. The
reaction products are also substantially transparent to visible
light. In some instances, it can be advantageous to avoid the build
up gaseous byproducts. When this is desired, R.sup.1 and R.sup.2
should be selected to have 6 or more carbon atoms so that their
reaction products with water have a low vapor pressure at temperatures
less than 50.degree. C.
[0042] Methods for synthesizing the Lewis acid organometallic desiccant
of the present invention can be found in Salt Effects in Organic
and Organometallic Chemistry, VCH Publishers, Inc, New York, 1992.
[0043] Another useful desiccant material for practicing the present
invention includes a reactive salt of a negatively charged organometallic
complex that, when it reacts with water, forms a carbon-hydrogen
bond but does not form an alcohol. In a preferred embodiment, the
reactive salt has the structure shown in Formula (IV) (A.sup.+b).sub.c[M(R.sup.1).sub.n(R.sup.2).sub.m(X).sub.l].sup.-q
(IV) wherein:
[0044] A is a cation having charge b;
[0045] M is a metal;
[0046] R.sup.1 is an organic substituent wherein at least one carbon
is directly bonded to the metal;
[0047] R.sup.2 is a silyl oxide wherein the oxygen is directly
bonded to the metal, or an amide having a nitrogen directly bonded
to the metal;
[0048] X is an anionic substituent having a pKa<7;
[0049] l=1 or 2
[0050] n=1 2 3 or 4;
[0051] m=0 1 2 or 3;
[0052] q=is the charge of the anionic organometallic complex and
is 1 or 2; and
[0053] b=q/c.
[0054] Metals selected from Group IIB, IIIA, IIIB, or IVB, or first
row transition metals are useful in present invention. Preferably,
they are Al, Zn, Ti, Mg, or B.
[0055] When more than one R.sup.1 substituent is used, the R.sup.1
substituents can be the same or different from each other. Likewise,
when more than one R.sup.2 or X substituent is used, the R.sup.2
or X substituents can be the same or different from each other.
[0056] Some useful examples of R.sup.1 and R.sup.2 are those previously
described in relation to Formula I.
[0057] The substituent X can be an inorganic anionic material such
as fluoride, chloride, bromide, iodide, nitrate, sulfate, tetrafluoroborate,
hexafluorophosphate, or perchlorate. Alternatively, X can be an
organic anionic material including a carboxylate, a sulfonate, or
a phosphonate. When X is organic, it can be part of an oligomeric
or polymeric system. Some examples of organic materials suitable
for X include acetate, formate, succinate, toluenesulfonate, and
polystyrenesulfonate.
[0058] The cation A can be a positively charged metal ion such
as an alkali, alkaline, or alkaline earth metal. Cation A can be
a positively charged metal complex, for example, a complex of an
alkali, alkaline, or alkaline earth metal with a crown ether, an
alkylpolyamine, or the like. Alternatively, cation A can be a positively
charged organic compound. Preferred positively charged organic compounds
include those that contain nitrogen or phosphorous. Some examples
of positively charged organic compounds suitable as cation A include
tetraalkylammonium, alkylpyridinium, and tetraalkylphosphonium compounds.
When cation A is a positively charged metal complex or organic compound,
it can be part of an oligomeric or polymeric system such as a polyvinylpyridinium
system.
[0059] Although not shown in Formula IV, there can be additional,
non charge-bearing moieties weakly or strongly coordinated to the
metal center. For example, there can be solvent molecules coordinated
to the metal center in addition to R.sup.1 and X.
[0060] A few non-limiting examples of useful desiccant materials
for practicing the present invention include K[Al(C.sub.2H.sub.5).sub.3F],
[N(CH.sub.3).sub.4][Al(C.sub.4H.sub.9).sub.3Cl], [N(C.sub.4H.sub.9).sub.4][B(C.sub.5H.sub.5).sub.3F],
[N-t-butylpyridinium][B(C.sub.5H.sub.5).sub.3(OC(.dbd.O)--C.sub.5H.sub.5)-
], Li.sub.2[Zn(C.sub.4H.sub.9).sub.2Cl], and K[(i-Bu).sub.3Al--F--Al(i-Bu).sub.3].
[0061] Equation 4 shows one example of how these moisture-absorbing
materials react with water K[Al(C.sub.2H.sub.5).sub.3F]+3H.sub.2O.fwdarw.3C.sub.2H.sub.5+Al(OH).sub.-
3+KF (4).
[0062] As can be seen, R.sup.1 reacts with water to form a carbon-hydrogen
bond. In the case of R.sup.2 (not shown) the reaction with water
forms a silyl oxygen-hydrogen bond or a nitrogen-hydrogen bond.
None of these substituents form harmful alcohol species. The reaction
products are also substantially transparent to visible light. In
some instances, it can be advantageous to avoid the build up gaseous
byproducts. When this is desired, R.sup.1 and R.sup.2 should be
selected to have 6 or more carbon atoms so that their reaction products
with water have a low vapor pressure at temperatures less than 50.degree.
C.
[0063] The reactive salt can be synthesized by reacting the corresponding
Lewis acid organometallic complex [M(R.sup.1).sub.n(R.sup.2).sub.m].sup.0
with the a salt of X, e.g., (A.sup.+b).sub.cX. Methods for synthesizing
the Lewis acid organometallic desiccant of the present invention
can be found in Salt Effects in Organic and Organometallic Chemistry,
VCH Publishers, Inc, New York, 1992.
[0064] Another useful set of desiccant materials includes those
defined by Formula V
[0065] In Formula V, R.sub.10 is one selected from the group including
an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group,
a heterocyclic group, and an acyl group having at least one carbon
atom, M is a trivalent metal atom, and n is an integer of two to
four.
[0066] Another useful set of desiccant materials includes those
defined by Formula VI
[0067] In Formula VI, each of R.sub.11 R.sub.12 R.sub.13 R.sub.14
and R.sub.15 is one selected from the group including an alkyl group,
an alkenyl group, an aryl group, a cycloalkyl group, a heterocyclic
group, and an acyl group having at least one carbon atom, and M
is a trivalent metal atom.
[0068] Another useful set of desiccant materials includes those
defined by Formula VII
[0069] In Formula VII, each of R.sub.11 R.sub.12 R.sub.13 R.sub.14
and R.sub.15 is one selected from the group including an alkyl group,
an alkenyl group, an aryl group, a cycloalkyl group, a heterocyclic
group, and an acyl group having at least one carbon atom, and M
is a tetravalent metal atom.
[0070] Although the materials defined in Formulas V-VII form alcohols
when they react with water, they can be useful in the present invention
if proper precautions are taken. For example, a barrier layer between
the desiccant and the OLED can be useful to stop diffusion of the
alcohol. The R groups can be selected so that they are large enough
to prevent any significant diffusion. Also, they can be part of
a polymeric backbone that cannot diffuse.
[0071] The desiccating film host can be any number of inert materials
that serves to dilute the desiccant material in order to reduce
aggregation and particle formation that would normally occur for
the pure desiccant material. The host can be organic or inorganic,
but preferably organic.
[0072] The desiccating film host and the molecularly dispersed
desiccant can be incorporated into an OLED device in numerous ways.
These materials can be codeposited by thermal vapor deposition to
form a film of the desiccant. The film thickness is not limited,
but it is believed that a thickness range of from 0.05 microns to
500 microns is suitable, depending on the application and the required
of water absorption capacity.
[0073] The desiccating film host and the molecularly dispersed
desiccant can be dissolved in an organic solvent such as acetates,
ketones, and cyclohexanes, and provided over the OLED device, for
example by spin coating, dip coating, curtain coating, ink jet deposition,
and the like. More preferably, the desiccating film host can comprise
inert polymeric matrix, for example poly(butyl methacrylate), which
can be cast from an organic solvent such acetates, ketones, or cyclohexanes,
or mixtures thereof. A typical loading of molecularly dispersed
desiccant relative to the polymer host is 0.05 to 50% by weight.
Other polymers that can be used as a desiccating film host include,
but are not limited to, polymethacrylates, polysiloxanes, polyvinylacetate,
polystyrenes, polyacrylates, polybutadiene, or cycoloefine polymers.
When the desiccating film host is a polymer or oligomer, the desiccant
material can be covalently or ionicly bound to the host so long
as the desiccant moieties are molecularly dispersed relative to
each other. The desiccant can be part of a pendant group or incorporated
into the backbone of the host polymer.
[0074] The desiccant can also be molecularly dispersed into a polymer
host without the presence of solvent by heating the polymer to reduce
its viscosity, and mixing in the desiccant.
General OLED Device Architecture
[0075] The present invention can be employed in most OLED device
configurations where light is transmitted through a desiccant. These
include very simple structures comprising a single anode and cathode
to more complex devices, such as passive matrix displays comprised
of orthogonal arrays of anodes and cathodes to form pixels, and
active-matrix displays where each pixel is controlled independently,
for example, with thin film transistors (TFTs).
[0076] There are numerous configurations of the organic layers
wherein the present invention can be successfully practiced. A schematic
of a pixel area of the device, not to scale, is shown in FIG. 1.
It includes a substrate 101 an anode 103 a hole-injecting layer
105 a hole-transporting layer 107 a light-emitting layer 109
an electron-transporting layer 111 and a cathode 113. These layers
are described in more detail below. Note that the substrate can
alternatively be located adjacent to the cathode, or the substrate
can actually constitute the anode or cathode. The organic layers
between the anode and cathode are conveniently referred to as the
organic EL element or organic EL media. The total combined thickness
of the organic layers is preferably less than 500 nm.
[0077] The anode and cathode of the OLED are connected to a voltage/current
source 150 through electrical conductors 160. The OLED is operated
by applying a potential between the anode and cathode such that
the anode is at a more positive potential than the cathode. Holes
are injected into the organic EL element from the anode and electrons
are injected into the organic EL element at the anode. Enhanced
device stability can sometimes be achieved when the OLED is operated
in an alternating current (AC) mode where, for some time period
in the cycle, the potential bias is reversed and no current flows.
An example of an AC driven OLED is described in U.S. Pat. No. 5552678.
Substrate
[0078] The OLED device of the present invention is typically provided
over a supporting substrate where either the cathode or anode can
be in contact with the substrate. The substrate can have a simple
or a complex structure with numerous layers, for example, a glass
support with electronic elements such as TFT elements, planarizing
layers, and wiring layers. The electrode in contact with the substrate
is conveniently referred to as the bottom electrode. Conventionally,
the bottom electrode is the anode, but the present invention is
not limited to that configuration. The substrate can either be light
transmissive or opaque. For applications where the EL emission is
viewed through the top electrode, the transmissive characteristic
of the bottom support is immaterial, and therefore can be light
transmissive, light absorbing, or light reflective. Substrates for
use in this case include, but are not limited to, glass, plastic,
semiconductor materials, silicon, ceramics, metal foil, and circuit
board materials. Of course it is necessary to provide in these device
configurations a light-transparent top electrode. When EL emission
is viewed through both the top and bottom electrodes, then it is
necessary to provide a substrate that is light-transparent, such
as glass or plastic.
Anode
[0079] When EL emission is viewed through anode 103 the anode
should be transparent or substantially transparent to the emission
of interest. Common transparent anode materials used in the present
invention are indium-tin oxide (ITO), indium-zinc oxide (IZO) and
tin oxide, but other metal oxides can work including, but not limited
to, aluminum- or indium-doped zinc oxide, magnesium-indium oxide,
and nickel-tungsten oxide. In addition to these oxides, metal nitrides,
such as gallium nitride, and metal selenides, such as zinc selenide,
and metal sulfides, such as zinc sulfide, can be used as the anode.
For applications where EL emission is viewed only through the cathode
electrode, the transmissive characteristics of anode are immaterial
and any conductive material can be used, transparent, opaque or
reflective. Example conductors for this application include, but
are not limited to, gold, iridium, molybdenum, palladium, and platinum.
Typical anode materials, transmissive or otherwise, have a work
function of 4.1 eV or greater. Desired anode materials are commonly
deposited by any suitable way such as evaporation, sputtering, chemical
vapor deposition, or electrochemical means. Anodes can be patterned
using well known photolithographic processes. Optionally, anodes
can be polished prior to application of other layers to reduce surface
roughness so as to reduce shorts or enhance reflectivity.
Hole-Injecting Layer (HIL)
[0080] While not always necessary, it is often useful to provide
a hole-injecting layer 105 between anode 103 and hole-transporting
layer 107. The hole-injecting material can serve to improve the
film formation property of subsequent organic layers and to facilitate
injection of holes into the hole-transporting layer. Suitable materials
for use in the hole-injecting layer include, but are not limited
to, porphyrinic compounds as described in U.S. Pat. No. 4720432
plasma-deposited fluorocarbon polymers as described in U.S. Pat.
Nos. 6127004 6208075 and 6208077 some aromatic amines,
for example, m-MTDATA (44',4''-tris[(3-methylphenyl)phenylamino]triphenylamine),
and inorganic oxides including vanadium oxide (VOx), molybdenum
oxide (MoOx), and nickel oxide (NiOx). Alternative hole-injecting
materials reportedly useful in organic EL devices are described
in EP 0 891 121 A1 and EP 1 029 909 A1.
Hole-Transporting Layer (HTL)
[0081] The hole-transporting layer 107 contains at least one hole-transporting
compound such as an aromatic tertiary amine, where the latter is
understood to be a compound containing at least one trivalent nitrogen
atom that is bonded only to carbon atoms, at least one of which
is a member of an aromatic ring. In one form the aromatic tertiary
amine can be an arylamine, such as a monoarylamine, diarylamine,
triarylamine, or a polymeric arylamine. Exemplary monomeric triarylamines
are illustrated by Klupfel et al. U.S. Pat. No. 3180730. Other
suitable triarylamines substituted with one or more vinyl radicals
and/or comprising at least one active hydrogen containing group
are disclosed by Brantley et al. U.S. Pat. Nos. 3567450 and 3658520.
[0082] A more preferred class of aromatic tertiary amines are those
which include at least two aromatic tertiary amine moieties as described
in U.S. Pat. Nos. 4720432 and 5061569. The hole-transporting
layer can be formed of a single or a mixture of aromatic tertiary
amine compounds. Illustrative of useful aromatic tertiary amines
are the following:
[0083] 11-Bis(4-di-p-tolylaminophenyl)cyclohexane;
[0084] 11-Bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane;
[0085] N,N,N',N'-tetraphenyl-44'''-diamino-11':4',1'':4'',1'''-quaterphe-
nyl;
[0086] Bis(4-dimethylamino-2-methylphenyl)phenylmethane;
[0087] 14-bis[2-[4-[N,N-di(p-toly)amino]phenyl]vinyl]benzene (BDTAPVB);
[0088] N,N,N',N'-Tetra-p-tolyl-44'-diaminobiphenyl;
[0089] N,N,N',N'-Tetraphenyl-44'-diaminobiphenyl;
[0090] N,N,N',N'-tetra-1-naphthyl-44'-diaminobiphenyl;
[0091] N,N,N',N'-tetra-2-naphthyl-44'-diaminobiphenyl;
[0092] N-Phenylcarbazole;
[0093] 44'-Bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB);
[0094] 44'-Bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl (TNB);
[0095] 44'-Bis[N-(1-naphthyl)-N-phenylamino]p-terphenyl;
[0096] 44'-Bis[N-(2-naphthyl)-N-phenylanino]biphenyl;
[0097] 44'-Bis[N-(3-acenaphthenyl)-N-phenylamino]biphenyl;
[0098] 15-Bis[N-(1-naphthyl)-N-phenylamino]naphthalene;
[0099] 44'-Bis[N-(9-anthryl)-N-phenylamino]biphenyl;
[0100] 44'-Bis[N-(1-anthryl)-N-phenylamino]-p-terphenyl;
[0101] 44'-Bis[N-(2-phenanthryl)-N-phenylamino]biphenyl;
[0102] 44'-Bis[N-(8-fluoranthenyl)-N-phenylaminolbiphenyl;
[0103] 44'-Bis[N-(2-pyrenyl)-N-phenylamino]biphenyl;
[0104] 44'-Bis[N-(2-naphthacenyl)-N-phenylamino]biphenyl;
[0105] 44'-Bis[N-(2-perylenyl)-N-phenylamino]biphenyl;
[0106] 44'-Bis[N-(1-coronenyl)-N-phenylamino]biphenyl;
[0107] 26-Bis(di-p-tolylamino)naphthalene;
[0108] 26-Bis[di-(1-naphthyl)amino]naphthalene;
[0109] 26-Bis[N-(1-naphthyl)-N-(2-naphthyl)amino]naphthalene;
[0110] N,N,N',N'-Tetra(2-naphthyl)-44''-diamino-p-terphenyl;
[0111] 44'-Bis {N-phenyl-N-[4-(1-naphthyl)-phenyl]amino}biphenyl;
[0112] 26-Bis[N,N-di(2-naphthyl)amino]fluorene;
[0113] 44',4''-tris[(3-methylphenyl)phenylamino]triphenylamine
(MTDATA); and
[0114] 44'-Bis[N-(3-methylphenyl)-N-phenylamino]biphenyl (TPD).
[0115] Another class of useful hole-transporting materials includes
polycyclic aromatic compounds as described in EP 1 009 041. Some
hole-injecting materials described in EP 0 891 121 A1 and EP 1 029
909 A1 can also make useful hole-transporting materials. In addition,
polymeric hole-transporting materials can be used including poly(N-vinylcarbazole)
(PVK), polythiophenes, polypyrrole, polyaniline, and copolymers
including poly(34-ethylenedioxythiophene)/poly(4-styrenesulfonate)
also called PEDOT/PSS.
Light-Emitting Layer (LEL)
[0116] As more fully described in U.S. Pat. Nos. 4769292 and
5935721 each of the light-emitting layers (LEL) of the organic
EL element include a luminescent fluorescent or phosphorescent material
where electroluminescence is produced as a result of electron-hole
pair recombination in this region. The light-emitting layer can
be comprised of a single material, but more commonly contains a
host material doped with a guest emitting material or materials
where light emission comes primarily from the emitting materials
and can be of any color. This guest emitting material is often referred
to as a light emitting dopant. The host materials in the light-emitting
layer can be an electron-transporting material, as defined below,
a hole-transporting material, as defined above, or another material
or combination of materials that support hole-electron recombination.
The emitting material is typically chosen from highly fluorescent
dyes and phosphorescent compounds, e.g., transition metal complexes
as described in WO 98/55561 WO 00/18851 WO 00/57676 and WO 00/70655.
Emitting materials are typically incorporated at 0.01 to 10% by
weight of the host material.
[0117] The host and emitting materials can be small nonpolymeric
molecules or polymeric materials including polyfluorenes and polyvinylarylenes
e.g., poly(p-phenylenevinylene), PPV. In the case of polymers, small
molecule emitting materials can be molecularly dispersed into a
polymeric host, or the emitting materials can be added by copolymerizing
a minor constituent into a host polymer.
[0118] An important relationship for choosing an emitting material
is a comparison of the bandgap potential which is defined as the
energy difference between the highest occupied molecular orbital
and the lowest unoccupied molecular orbital of the molecule. For
efficient energy transfer from the host to the emitting material,
a necessary condition is that the band gap of the dopant is smaller
than that of the host material. For phosphorescent emitters (including
materials that emit from a triplet excited state, i.e., so-called
"triplet emitters") it is also important that the host
triplet energy level of the host be high enough to enable energy
transfer from host to emitting material.
[0119] Host and emitting materials known to be of use include,
but are not limited to, those disclosed in U.S. Pat. Nos. 4768292
5141671 5150006 5151629 5405709 5484922 5593788
5645948 5683823 5755999 5928802 5935720 5935721
6020078 6475648 6534199 6661023 U.S. Patent Application
Publications 2002/0127427 A1 2003/0198829 A1 2003/0203234 A1
2003/0224202 A1 and 2004/0001969 A1.
[0120] Metal complexes of 8-hydroxyquinoline (oxine) and similar
derivatives constitute one class of useful host compounds capable
of supporting electroluminescence. Illustrative of useful chelated
oxinoid compounds are the following:
[0121] CO-1: Aluminum trisoxine [alias, tris(8-quinolinolato)aluminum(III)];
[0122] CO-2: Magnesium bisoxine [alias, bis(8-quinolinolato)magnesium(II)];
[0123] CO-3: Bis[benzo{f}-8-quinolinolato]zinc (II);
[0124] CO-4: Bis(2-methyl-8-quinolinolato)aluminum(III)-R-oxo-bis(2-methyl-8-quinolino-
lato)aluminum(III);
[0125] CO-5: Indium trisoxine [alias, tris(8-quinolinolato)indium];
[0126] CO-6: Aluminum tris(5-methyloxine)[alias, tris(5-methyl-8-quinolinolato)aluminum(III)];
[0127] CO-7: Lithium oxine [alias, (8-quinolinolato)lithium(I)];
[0128] CO-8: Gallium oxine [alias, tris(8-quinolinolato)gallium(III)];
and
[0129] CO-9: Zirconium oxine [alias, tetra(8-quinolinolato)zirconium(IV)].
[0130] Another class of useful host materials includes derivatives
of anthracene, such as those described in U.S. Pat. Nos. 5935721
5972247 6465115 6534199 6713192 U.S. Patent Application
Publications 2002/0048687 A1 2003/0072966 A1 and WO 2004018587.
Some examples include derivatives of 910-dinaphthylanthracene derivatives
and 9-naphthyl-10-phenylanthracene. Other useful classes of host
materials include distyrylarylene derivatives as described in U.S.
Pat. No. 5121029 and benzazole derivatives, for example, 22',2''-(135-phenylene)tris[1-phenyl-1H-benzimidazole].
[0131] Desirable host materials are capable of forming a continuous
film. The light-emitting layer can contain more than one host material
in order to improve the device's film morphology, electrical properties,
light emission efficiency, and lifetime. Mixtures of electron-transporting
and hole-transporting materials are known as useful hosts. In addition,
mixtures of the above listed host materials with hole-transporting
or electron-transporting materials can make suitable hosts.
[0132] Useful fluorescent dopants include, but are not limited
to, derivatives of anthracene, tetracene, xanthene, perylene, rubrene,
coumarin, rhodamine, and quinacridone, dicyanomethylenepyran compounds,
thiopyran compounds, polymethine compounds, pyrilium and thiapyrilium
compounds, fluorene derivatives, periflanthene derivatives, indenoperylene
derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane
compounds, derivatives of distryrylbenzene and distyrylbiphenyl,
and carbostyryl compounds. Among derivatives of distyrylbenzene,
particularly useful are those substituted with diarylamino groups,
informally known as distyrylamines.
[0133] Suitable host materials for phosphorescent emitters (including
materials that emit from a triplet excited state, i.e., so-called
"triplet emitters") should be selected so that the triplet
exciton can be transferred efficiently from the host material to
the phosphorescent material. For this transfer to occur, it is a
highly desirable condition that the excited state energy of the
phosphorescent material be lower than the difference in energy between
the lowest triplet state and the ground state of the host. However,
the band gap of the host should not be chosen so large as to cause
an unacceptable increase in the drive voltage of the OLED. Suitable
host materials are described in WO 00/70655 A2; WO 01/39234 A2;
WO 01/93642 A1; WO 02/074015 A2; WO 02/15645 A1 and U.S. Patent
Application Publication 2002/0117662 A1. Suitable hosts include
certain aryl amines, triazoles, indoles, and carbazole compounds.
Examples of desirable hosts are 44'-N,N'-dicarbazole-biphenyl (CBP),
22'-dimethyl-44'-N,N'-dicarbazole-biphenyl, m-(N,N'-dicarbazole)benzene,
and poly(N-vinyl-carbazole), including their derivatives.
[0134] Examples of useful phosphorescent materials that can be
used in light-emitting layers of the present invention include,
but are not limited to, those described in WO 00/57676 WO 00/70655
WO 01/41512 A1 WO 02/15645 A1 WO 01/93642 A1 WO 01/39234 A2
WO 02/071813 A1 WO 02/074015 A2 U.S. Pat. Nos. 6458475 6451455
6573651 6413656 6515298 6451415 6097147 EP 1 239
526 A2 EP 1 238 981 A2 EP 1 244 155 A2 JP 2003059667A, JP 2003073665A,
JP 2003073387A, JP 2003 073388A, U.S. Patent Application Publications
2003/0017361 A1 2002/0197511 A1 2003/0072964 A1 2003/0068528
A1 2003/0124381 A1 2003/0059646 A1 2003/0054198 A1 2002/0100906
A1 2003/0068526 A1 2003/0068535 A1 2003/0141809 A1 2003/0040627
A1 and 2002/0121638 A1.
Electron-Transporting Layer (ETL)
[0135] Preferred thin film-forming materials for use in forming
the electron-transporting layer 111 of the organic EL elements of
the present invention are metal chelated oxinoid compounds, including
chelates of oxine itself (also commonly referred to as 8-quinolinol
or 8-hydroxyquinoline). Such compounds help to inject and transport
electrons, exhibit high levels of performance, and are readily fabricated
in the form of thin films. Exemplary oxinoid compounds were listed
previously.
[0136] Other electron-transporting materials include various butadiene
derivatives as disclosed in U.S. Pat. No. 4356429 and various
heterocyclic optical brighteners as described in U.S. Pat. No. 4539507.
Benzazoles and triazines are also useful electron-transporting materials.
Cathode
[0137] When light emission is viewed solely through the anode,
the cathode 113 used in the present invention can be comprised of
nearly any conductive material. Desirable materials have effective
film-forming properties to ensure effective contact with the underlying
organic layer, promote electron injection at low voltage, and have
effective stability. Useful cathode materials often contain a low
work function metal (<4.0 eV) or metal alloy. One preferred cathode
material is comprised of a Mg:Ag alloy wherein the percentage of
silver is in the range of from 1 to 20%, as described in U.S. Pat.
No. 4885221. Another suitable class of cathode materials includes
bilayers comprising a thin electron-injection layer (EIL) in contact
with the organic layer (e.g., ETL), which is capped with a thicker
layer of a conductive metal. Here, the EIL preferably includes a
low work function metal or metal salt, and if so, the thicker capping
layer does not need to have a low work function. One such cathode
is comprised of a thin layer of LiF followed by a thicker layer
of Al as described in U.S. Pat. No. 5677572. Other useful cathode
material sets include, but are not limited to, those disclosed in
U.S. Pat. Nos. 5059861 5059862 and 6140763.
[0138] A metal-doped organic layer can be used as an electron-injecting
layer. Such a layer contains an organic electron-transporting material
and a low work-function metal (<4.0 eV). For example, Kido et
al. reported in "Bright Organic Electroluminescent Devices
Having a Metal-Doped Electron-Injecting Layer", Applied Physics
Letters, 73 2866 (1998) and disclosed in U.S. Pat. No. 6013384
that an OLED can be fabricated containing a low work-function metal-doped
electron-injecting layer adjacent to a cathode. Suitable metals
for the metal-doped organic layer include alkali metals (e.g. lithium,
sodium), alkaline earth metals (e.g. barium, magnesium), or metals
from the lanthanide group (e.g. lanthanum, neodymium, lutetium),
or combinations thereof. The concentration of the low work-function
metal in the metal-doped organic layer is in the range of from 0.1%
to 30% by volume. Preferably, the concentration of the low work-function
metal in the metal-doped organic layer is in the range of from 0.2%
to 10% by volume. Preferably, the low work-function metal is provided
in a mole ratio in a range of from 1:1 with the organic electron
transporting material.
[0139] When light emission is viewed through the cathode, the cathode
should be transparent or nearly transparent. For such applications,
metals should be thin or one should use transparent conductive oxides,
or include these materials. Optically transparent cathodes have
been described in more detail in U.S. Pat. Nos. 4885211 5247190
5703436 5608287 5837391 5677572 5776622 5776623
5714838 5969474 5739545 5981306 6137223 6140763
6172459 6278236 6284393 JP 3234963 and EP 1 076 368.
Cathode materials are typically deposited by evaporation, sputtering,
or chemical vapor deposition. When needed, patterning can be achieved
through many well known methods including, but not limited to, through-mask
deposition, integral shadow masking, for example, as described in
U.S. Pat. No. 5276380 and EP 0 732 868 laser ablation, and selective
chemical vapor deposition.
Other Common Organic Layers and Device Architecture
[0140] In some instances, layers 109 and 111 can optionally be
collapsed into a single layer that serves the function of supporting
both light emission and electron transportation. It also known in
the art that emitting dopants can be added to the hole-transporting
layer, which can serve as a host. Multiple dopants can be added
to one or more layers in order to produce a white-emitting OLED,
for example, by combining blue- and yellow-emitting materials, cyan-
and red-emitting materials, or red-, green-, and blue-emitting materials.
White-emitting devices are described, for example, in EP 1 187 235
EP 1 182 244 U.S. Pat. Nos. 5683823 5503910 5405709 5283132
6627333 U.S. Patent Application Publications 2002/0186214 A1
2002/0025419 A1 and 2004/0009367 A1.
[0141] Additional layers such as exciton, electron and hole-blocking
layers as taught in the art can be employed in devices of the present
invention. Hole-blocking layers are commonly used to improve efficiency
of phosphorescent emitter devices, for example, as in U.S. Patent
Application Publications 2002/0015859 A1 2003/0068528 A1 2003/0175553
A1 WO 00/70655A2 and WO 01/93642A1.
[0142] The present invention can be used in so-called stacked device
architecture, for example, as taught in U.S. Pat. Nos. 5703436
6337492 6717358 and U.S. Patent Application Publication 2003/0170491
A1.
Deposition of Organic Layers
[0143] The organic materials mentioned above are suitably deposited
through a vapor phase method such as sublimation, but can be deposited
from a fluid, for example, from a solvent with an optional binder
to improve film formation. If the material is a polymer, solvent
deposition is useful but other methods can be used, such as sputtering
or thermal transfer from a donor sheet. The material to be deposited
by sublimation can be vaporized from a sublimation "boat"
often comprised of a tantalum material, e.g., as described in U.S.
Pat. No. 6237529 or can be first coated onto a donor sheet and
then sublimed in closer proximity to the substrate. Layers with
a mixture of materials can use separate sublimation boats or the
materials can be pre-mixed and coated from a single boat or donor
sheet. Patterned deposition can be achieved using shadow masks,
integral shadow masks (U.S. Pat. No. 5294870), spatially-defined
thermal dye transfer from a donor sheet (U.S. Pat. Nos. 5688551
5851709 and 6066357), and inkjet method (U.S. Pat. No. 6066357).
Optical Optimization
[0144] OLED devices of the present invention can employ various
well known optical effects in order to enhance its properties if
desired. This includes optimizing layer thicknesses to yield maximum
light transmission, providing dielectric mirror structures, replacing
reflective electrodes with light-absorbing electrodes, providing
anti glare or anti-reflection coatings over the display, providing
a polarizing medium over the display, or providing colored, neutral
density, or color conversion filters in functional relationship
with the light emitting areas of the display. Filters, polarizers,
and anti-glare or anti-reflection coatings can also be provided
over a cover or as part of a cover. It will be understood that color
filters can formed on the cover glass or internally within the device
itself, for example, over the inorganic barrier layer discussed
later.
[0145] The OLED device can have a microcavity structure. In one
useful example, one of the metallic electrodes is essentially opaque
and reflective; the other one is reflective and semitransparent.
The reflective electrode is preferably selected from Au, Ag, Mg,
Ca, or alloys thereof. Because of the presence of the two reflecting
metal electrodes, the device has a microcavity structure. The strong
optical interference in this structure results in a resonance condition.
Emission near the resonance wavelength is enhanced and emission
away from the resonance wavelength is depressed. The optical path
length can be tuned by selecting the thickness of the organic layers
or by placing a transparent optical spacer between the electrodes.
For example, an OLED device of the present invention can have ITO
spacer layer placed between a reflective anode and the organic EL
media, with a semitransparent cathode over the organic EL media.
Encapsulation
[0146] As stated, OLED devices are sensitive to moisture or oxygen,
or both, so they are commonly sealed in an inert atmosphere such
as nitrogen or argon. In sealing an OLED device in an inert environment,
a protective cover can be attached using an organic adhesive, a
metal solder, or a low melting temperature glass. The desiccant
is also provided within the sealed space over the OLED and in the
path of light emission. The desiccant film of the present invention
can be used in combination with other getters and desiccants including,
for example, alkali and alkaline metals, alumina, bauxite, calcium
sulfate, clays, silica gel, zeolites, alkaline metal oxides, alkaline
earth metal oxides, sulfates, or metal halides and perchlorates.
In addition, the desiccant film can be used in combination with
barrier layers such as SiOx, Teflon, and alternating inorganic/polymeric
layers as known in the art. Barrier layers can be provided over
the OLED, between the OLED and a flexible substrate, or both. Barrier
layers provided in association with the desiccant film in areas
of light emission should be transparent.
[0147] Some non-limiting examples of inorganic barrier layer materials
include metal oxides such as silicon oxides and aluminum oxides,
and metal nitrides such as silicon nitride. Suitable examples of
inorganic barrier layer materials include aluminum oxide, silicon
dioxide, silicon nitride, silicon oxynitride, and diamond-like carbon.
In some circumstances it is useful if the inorganic barrier layer
material can be electronically conductive, such as a conductive
metal oxide, a metal or metal alloy. In this case, the conductive
inorganic barrier layer can carry current to one or more device
electrodes, serve as the electrode, or provide a way for discharging
static electricity. Metals such as Al, Ag, Au, Mo, Cr, Pd, or Cu,
or alloys containing these metals can be useful inorganic barrier
layers. Multiple layers of metal can be used to fabricate a conductive
inorganic barrier layer. Where unwanted shorting can occur, conductive
barrier layers should not be used, or they should be patterned,
e.g., with a shadow mask, such that they do not cause shorting.
The inorganic barrier layer is typically provided in a thickness
of 10 to several hundreds of nanometers.
[0148] Useful techniques of forming layers of inorganic barrier
layer material from a vapor phase include, but are not limited to,
thermal physical vapor deposition, sputter deposition, electron
beam deposition, chemical vapor deposition (CVD), plasma-enhanced
chemical vapor deposition, laser-induced chemical vapor deposition,
and atomic layer deposition (ALD). CVD and ALD are particularly
useful. In some instances, said materials can be deposited from
a solution or another fluidized matrix, e.g., from a super critical
solution of CO.sub.2. Care should be taken to choose a solvent or
fluid matrix does not negatively affect the performance of the device.
Patterning of said materials can be achieved through many way including
but not limited to photolithography, lift-off techniques, laser
ablation, and more preferably, through shadow mask technology.
[0149] The organic barrier layer material can be monomeric or polymeric,
and can be deposited using vapor deposition or from solution. If
cast from solution, it is important that the deposition solution
does not negatively affect the OLED device.
[0150] Conveniently, the organic barrier layer is made of a polymeric
materials such as parylene materials, which can be deposited from
a vapor phase to provide a polymer layer having excellent adhesion
to, and step coverage over, topological features of the OLED devices,
including defects such as particulate defects. The organic barrier
layer is typically formed in a thickness range of from 0.01 to 5
micrometer. However, by their very nature, the organic materials
in the organic barrier layer exhibit more moisture permeability
than a layer formed of an inorganic dielectric material or a layer
formed of a metal. Thus, it is often desirable to encase the organic
barrier layer with an inorganic material.
Embodiments
[0151] As a first embodiment, FIGS. 2-4B illustrate various stages
of the fabrication of an OLED device 200A. Turning first to FIG.
2 a top view of an OLED substrate 202 is shown. A predetermined
seal area 210 is represented by the space between the dotted lines
in FIG. 2. The inner dotted line further represents the sealed region
of the OLED device. Over OLED substrate 202 are provided a first
electrode 204 a first electrical contact pad 208 and a first interconnect
line 206 that provides an electrical connection between the first
electrode 204 and the first electrical contact pad 208. The first
interconnect line 206 extends through the seal area. As discussed
later, the first electrode 204 can be the anode or cathode, and
can be any number of well known conductive materials, as discussed
above. The conductive material used for each of the first electrode
204 the first interconnect line 206 and the first electrical contact
pad 208 can be the same or different. In addition, each of the first
electrode 204 the first interconnect line 206 and the first electrical
contact pad 208 can contain two or more layers of different conductive
materials.
[0152] A second interconnect line 216 and a second contact pad
218 are provided over the OLED substrate 202 to provide a way for
making electrical contact to a second electrode that is formed in
a later step. The conductive material used for the second contact
pad 218 and second interconnect line 216 can be the same or different,
and can also be the same or different from the material(s) used
as the first electrical contact pad 208 and first interconnect line
206.
[0153] The conductive materials for forming the first electrode
204 the first and second interconnect lines, and the first and
second contact pads can be deposited by vacuum methods such as thermal
physical vapor deposition, sputter deposition, plasma-enhanced chemical
vapor deposition, electron-beam assisted vapor deposition, and other
methods known in the art. In addition, so-called "wet"
chemical processes can be used such as electroless and electrolytic
plating. The first electrode 204 the first interconnect line 206
the first electrical contact pad 208 the second interconnect line
216 and the second contact pad 218 can be provided in the same
patterning step or different patterning steps. Patterning can be
achieved by deposition through a shadow mask, photolithographic
methods, laser ablation, selective electroless plating, electrochemical
etching, and other well known patterning techniques.
[0154] The first electrode 204 interconnect lines 206 and 216
and contact pads 208 and 218 are made from aluminum. In this arrangement,
the first electrode functions as the anode, is reflective and opaque.
In order to provide a high work function surface for effective hole
injection, a layer of indium-doped tin oxide (ITO) is provided over
the anode (not shown). The second contact pad 218 and second interconnect
line 216 are made from aluminum in this arrangement.
[0155] Turning now to FIG. 3 an insulation layer 244 is provided
in a pattern over the OLED substrate 202. The insulation layer 244
extends over a portion of the first electrode 204 and over at least
a portion of the first and second interconnects, 206 and 216. A
via 246 is provided over the second interconnect line 216 that is
located inside the sealed region. The insulation layer 244 does
not extend through the predetermined seal area 210 in this arrangement.
[0156] The insulation layer 244 can be any number of organic or
inorganic materials provided that the material has low electrical
conductivity and provides effective adhesion with the surfaces over
which it is applied. The insulation layer 244 acts to reduce shorting
that can occur between first and second electrodes, and can provide
planarization. Insulation layer 244 is typically provided in a thickness
of from a few nanometers to a few microns. Many of the same materials
and deposition methods can be used to form the insulation layer
244 as described above for barrier layer materials.
[0157] Some examples of organic materials that are useful for the
insulation layer 244 include polyimides, parylene, and acrylate-based
photoresist materials. Some examples of inorganic materials that
are useful for the insulation layer 244 include metal oxides such
as silicon oxides and aluminum oxides, and metal nitrides such as
silicon nitride and ceramic composites. In addition, the materials
can be provided from a solution, such as a sol-gel. For the purposes
of discussion, a sol-gel material that has high planarizing ability
is used as the insulation layer 244 in this arrangement.
[0158] As shown in FIG. 4A, the organic EL media layer 212 and
second electrode 214 are then deposited to make OLED device 200A.
To illustrate the layer order, the lower right corner of first electrode
area is pictorially cut away to show the first electrode 104. A
cross-sectional view taken along lines 4B is shown in FIG. 4B. The
second electrode is the cathode and is semitransparent. It is made
from a thin layer of Li (e.g., 1 nm) in contact with the organic
EL media, a thin layer of Al (e.g., 10 nm) over the lithium, and
a thicker layer of ITO (e.g. 100 nm) over the Al. The cathode makes
contact to the second interconnect line 216 in the via.
[0159] To illustrate the layer order, the lower right corner of
first electrode area is pictorially cut away to show the first electrode
204. The organic EL media layer 212 is described in more detail
below, but it can contain one or several layers of different materials.
The organic EL media layer 212 is provided over the entire first
electrode 204 and over a portion of the insulation layer 244. The
organic EL media layer does not extend into the via 246 or through
the predetermined seal area 210. The second electrode 214 is patterned
over the first electrode and into the via 246 but does not contact
the first interconnect line 206. The light-emitting area (pixel)
is defined by the area of overlap of the first electrode 204 with
the second electrode 214 wherein there is organic EL media sandwiched
there between. Because the first electrode is reflective and opaque,
and the second electrode is semitransparent, this light will emit
in a direction away from OLED substrate 202. This is referred to
as a "top-emitting" OLED. The second electrode 214 can
be deposited and patterned using methods previously described.
[0160] Turning now to FIG. 5 a top-emitting, encapsulated OLED
device 200 is shown. Where elements correspond to those in FIG.
4B, the same reference numerals will be used. A light transmissive
desiccating film 260 is provided over the second electrode of the
OLED device, which includes a host and molecularly dispersed desiccant
material previously discussed. Although not necessary, it can be
advantageous for the light transmissive desiccating film 260 to
be deposited by vapor deposition in order to avoid subjecting the
organic EL media to possible contamination by solvents. If desiccant
is deposited from solution, the second electrode and the insulating
layer should be selected so that they are compatible with the solvent
and do not permit transmission of desiccant solution into the organic
EL media layer.
[0161] A cover 223 is made of glass and provided having deposited
thereon a seal material 224 in a pattern corresponding to the predetermined
seal area 210. The cover 223 with the patterned seal material 224
is provided over the OLED device 200A in alignment with the predetermined
seal area 210. Pressure is applied between the OLED substrate 202
and cover 223 while the seal material is cured or fused. The sealing
step is preferably done under inert conditions such as under vacuum
or under a dry nitrogen or argon atmosphere. The nitrogen or argon
atmosphere can be at a pressure lower than atmospheric pressure.
If the sealing step is done under nitrogen or argon, this space
is filled with these gasses. If the pressure in space 240 is slightly
reduced relative to atmospheric pressure, there can be an advantage
of maintaining a pressure between the cover and the OLED substrate
to ensure an effective seal. Further, if the space 240 is under
slightly reduced pressure, then there is less chance of seal failure
if the encapsulated OLED device is exposed to low pressures (e.g.,
transportation in the cargo bay of an airplane).
[0162] Alternatively, the seal material 224 can be provided on
the OLED device 200A in the predetermined seal area 210 and then
the cover is applied and sealed. The cover is preferably transparent
glass in this arrangement. A transparent polymer cover can also
be used if it is provided with a water impermeable layer(s) adjacent
to the interface with the seal material.
[0163] The seal material 224 can be an organic adhesive such as
UV or heat cured epoxy resin, acrylates, or pressure sensitive adhesive.
Alternatively, the seal material can be a glass frit seal material
or a metal solder. Such seals are activated by heating, for example
with a laser, to cause the material to flow. A seal is formed when
the seal material re-solidifies. It is desirable to maintain the
sealing temperature as low as possible because OLED devices have
thermally sensitive parts and coatings. Glass frit seal material
can be lead-based, e.g., based on PbO--ZnO--B.sub.2O.sub.3. Preferably,
the glass frit seal material is lead-free, e.g., based on ZnO--SnO--P.sub.2O.sub.5.
The seal material should also provide a coefficient of thermal expansion
(CTE) that is compatible with the CTE of the substrate.
[0164] A second embodiment of the present invention is shown in
FIG. 6. The device of FIG. 6 is analogous to that of FIG. 5 except
that a transparent barrier layer 270 is provided over the light
transmissive desiccating film 260. As described previously, the
barrier layer can be a single layer or a plurality of sublayers,
for example, alternating inorganic/organic sublayers. In a preferred
arrangement, the transparent barrier layer 270 has three sublayers
(not shown) made of Al.sub.2O.sub.3/parylene/Al.sub.2O.sub.3.
[0165] A third embodiment of the present invention is shown in
FIG. 7. The device of FIG. 7 is analogous to that of FIG. 6 except
that a transparent barrier layer 271 is provided over the OLED device
first, and the light transmissive desiccating film 260 is provided
over the transparent barrier layer 271. In addition to producing
an additional barrier to moisture penetration, transparent barrier
layer 271 can protect the OLED from solvents or chemical reactions
associated with the light transmissive desiccating film.
[0166] A fourth embodiment of the present invention is shown in
FIG. 8. The device of FIG. 8 is analogous to that of FIG. 7 except
that a transparent second barrier layer 272 has been provided over
light transmissive desiccating film 260. FIG. 8 shows a transparent
polymer buffer layer 242 provided in a fashion analogous to that
shown in FIG. 7. All of the embodiments mentioned above can use
this polymer buffer layer.
[0167] The transparent polymer buffer layer 242 is selected to
be transparent or nearly transparent, and having this layer between
the cathode and the cover can improve optical out-coupling. The
transparent polymer buffer layer 242 can be any number of materials
including UV or heat cured epoxy resin, acrylates, or pressure sensitive
adhesive. An example of a useful UV-curable epoxy resin is Optocast
3505 from Electronic Materials Inc. An example of useful pressure
sensitive adhesive is Optically Clear Laminating Adhesive 8142 from
3M. The polymer buffer layer can also serve a dual role as the light
transmissive desiccating film.
[0168] The invention has been described in detail with particular
reference to certain preferred embodiments thereof, but it will
be understood that variations and modifications can be effected
within the spirit and scope of the invention.
PARTS LIST
[0169] 101 substrate [0170] 103 anode [0171] 105 hole-injecting
layer [0172] 107 hole-transporting layer [0173] 109 light-emitting
layer [0174] 111 electron-transporting layer [0175] 113 cathode
[0176] 150 voltage/current source [0177] 160 electrical conductors
[0178] 200 encapsulated OLED device [0179] 200A OLED device [0180]
202 OLED substrate [0181] 204 first electrode [0182] 206 first interconnect
line [0183] 208 first electrical contact pad [0184] 210 seal area
[0185] 212 organic EL media layer [0186] 214 second electrode [0187]
216 second interconnect line [0188] 218 second contact pad [0189]
223 cover [0190] 224 seal material [0191] 240 space [0192] 242 transparent
polymer buffer layer [0193] 244 insulation layer [0194] 246 via
[0195] 260 light transmissive desiccating film [0196] 270 transparent
barrier layer [0197] 271 transparent barrier layer [0198] 272 transparent
second barrier layer |