WO2005064993A1

WO2005064993A1 - Flexible electroluminescent devices

Info

Publication number: WO2005064993A1
Application number: PCT/SG2003/000296
Authority: WO
Inventors: Furong Zhu; Kian Soo Ong; Xiaotao Hao
Original assignee: Agency For Science, Technology And Research
Priority date: 2003-12-30
Filing date: 2003-12-30
Publication date: 2005-07-14
Also published as: CN1895003A; JP2007536697A; AU2003288884A1; TW200522786A; EP1712109A4; US20070222370A1; EP1712109A1

Abstract

An organic light emitting diode (OLED) formed on an opaque flexible substrate is disclosed. The opaque flexible substrate is composed of one of the following: (i) a plastic layer laminated to or coated with a metal layer, (ii) a metal layer sandwiched between two plastic layers, or (iii) a metal foil. When the OLED is formed on a metal surface of the flexible substrate, the metal surface may be coated with an isolation layer. The isolation layer may be a spin-coated polymer layer or a dielectric layer. The metal in the flexible substrate serves as a barrier to minimize the permeation of oxygen and moisture to the OLED. In addition, the OLED is provided with a transparent or semi-transparent upper electrode so that light can emit through the upper electrode.

Description

FLEXIBLE ELECTROLUMINESCENT DEVICES

FIELD OF THE INVENTION

The present invention generally relates to organic electroluminescent

devices, and more particularly to flexible organic light emitting devices (OLEDs).

BACKGROUND OF THE INVENTION

Organic light emitting devices (OLEDs) have recently attracted attention as

display devices that can replace liquid crystal displays (LCDs) because OLEDs

can produce high visibility by self-luminescence, thus, they do not require back¬

lighting, which are necessary for LCDs, and they can be fabricated into lightweight,

thin and flexible displays. A typical OLED is constructed by placing an organic

light-emitting material between a cathode layer that can inject electrons and an

anode layer that can inject holes. When a voltage of proper polarity is applied

between the cathode and anode, holes injected from the anode and electrons

injected from the cathode combine to release energy as light, thereby producing

electroluminescence. Polymeric electroluminescent materials have been used for

OLEDs, which devices are referred to as PLEDs.

One conventional structure of OLED is a bottom-emitting structure, which

includes a metal or metal alloy cathode and a transparent anode on a transparent

substrate, whereby light can be emitted from the bottom of the structure. The

OLED may also have a top-emitting structure, which is formed on either an

opaque substrate or a transparent substrate. A top-emitting OLED has a relatively transparent top electrode so that light can emit from the side of the top electrode.

The top-emitting OLED has two typical structures. When the OLED structure has

a transparent anode on top of the organic layers, the structure is referred to as an

inverted OLED. The top-emitting OLED can also be made with a transparent

cathode on top of the organic layers. The OLED with a transparent anode and a

transparent cathode formed on a transparent transparent substrate is referred to

as a transparent OLED. The top-emitting OLED structures increase the flexibility

of device integration and engineering. Furthermore, the top-emitting OLEDs are

desirable for high-resolution displays.

Traditionally, OLEDs have been built on rigid glass substrates. Glass has

low permeability to oxygen and water vapors. Over the past few years, ultra thin

glass sheets and transparent plastic substrates have been considered as the

possible substrate choices for flexible OLEDs and PLEDs. Ultrathin glass sheets,

however, are very brittle and OLEDs formed on ultrathin glass sheets have limited

potential as flexible OLED displays. To make OLEDs that are lighter, thinner,

more rugged and highly flexible, plastic substrates, e.g. polyethylene terephthalate

(PET) and polyethylene naphthalate (PEN), have been used for flexible OLEDs.

However, these devices have very short lifetimes because plastics exhibit low

resistance to water and oxygen. Accordingly, efforts have been made to protect

OLEDs formed on plastic substrates from exposure to oxygen and water vapor in

order to minimize degradation of the devices.

Various approaches have been proposed for forming barrier protection on

plastic substrates. See for example WO O2/065558, WO 02/091064, US Pat. No. 5,757,126, US Pub. No. 2002/0022156. US Pat. No. 5,757,126 discloses a

multilayer barrier coating composed of organic and inorganic materials. US Pub.

No. 2002/0022156 proposes a multilayer barrier composite formed over a plastic

substrate, which composite includes a thin transparent metal oxide or metal nitride

and one or more additional layers selected from the group of a thin transparent

metallic film, an organic polymer, a thin transparent dielectric, and a thin

transparent conductive oxide. WO O2/065558 discloses a transparent polymerized

organosilicon protective layer over a transparent polymeric substrate. WO

02/091064 discloses a multilayer barrier that includes organic layers and inorganic

layers. These approaches, however, require numerous deposition steps and

potentially produce some adverse effects on the optical and mechanical

performance of the OLEDs. Thus, these approaches cannot resolve the

permeation problem in a cost-effective way.

There remains a need for a flexible OLED that can be easily fabricated in a

cost-effective way.

SUMMARY OF THE INVENTION

The present invention is directed to a flexible organic light emitting diode

(OLED), and more specifically, a polymer light emitting diode (PLED), which is

formed on an opaque flexible substrate. The opaque flexible substrate is

composed of one of the following: (i) a plastic layer laminated to or coated with a

metal layer, (ii) a metal layer sandwiched between two plastic layers, or (iii) a

metal foil. When the OLED is formed on a metal surface of the flexible substrate, the metal surface may be coated with an isolation layer. The isolation

layer may be a spin-coated polymer layer or a dielectric layer. The metal in the

flexible substrate serves as a barrier to minimize the permeation of oxygen and

moisture to the OLED. In addition, the OLED of the present invention is provided

with a transparent or semi-transparent upper electrode so that light can be emitted

through the upper electrode. The novel design of the present invention yields an

OLED having superior barrier properties and high flexibility, which can be easily

fabricated by mass production.

The advantages and novel features of the present invention will become

apparent from the following detailed description of the invention when considered

in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross-sectional view of a representative OLED formed on a

plastic/metal substrate according to the present invention.

FIG. 2 shows a cross-sectional view of the OLED formed on a metal/plastic

substrate with an isolation layer according to the present invention.

FIG. 3 shows a cross-sectional view of the OLED formed on a

plastic/metal/plastic substrate according to the present invention.

FIG. 4 shows a cross-sectional view of the OLED formed on a metal foil

according to the present invention.

FIG. 5 shows an example of an OLED with a transparent multilayer cathode

according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIG. 1 , the representative OLED of the present invention

comprises a flexible opaque substrate 1 , a lower electrode 2 on top of the substrate, an organic stack 3 on top of the lower electrode, and a semi-transparent

or transparent upper electrode 4 on top of the organic stack. In one embodiment, the flexible opaque substrate 1 is composed of a plastic layer 1a laminated to or coated with a metal layer 1b as shown in FIG. 1. Alternatively, it is also feasible to form the OLED on the metal side of the substrate 1 as shown in FIG. 2. In such a

case, it may be desirable to form an isolation layer 5 between the metal layer 1 b and the lower electrode 2. In another embodiment shown in FIG. 3, the flexible

substrate 1 is composed of a metal layer 1d sandwiched between two plastic

layers 1c and 1e. The metallic material used for the substrate 1 includes

aluminum and other highly reflective metals. Aluminum is preferred because it is

an excellent barrier against water and oxygen. The plastic material used for the

flexible substrate 1 includes polyethylene terephthalate (PET), polyethylene

naphthalate (PEN), polyether sulfone (PES), and other plastics known in the art to

provide the suitable characteristics for flexible OLEDs. The isolation layer 5 may be a spin-coated polymer layer or a dielectric layer, e.g. inorganic oxide or spin-

on-glass (SOG). This isolation layer 5 also functions as a planarizing layer. In yet another embodiment shown in FIG. 4, the flexible substrate 1 is a

metal foil, which is coated with an isolation layer 5. The metal foil may be made of aluminum, copper or stainless steel. The isolation layer 5 is as described previously for FIG. 2. The metal foil in this case functions as a barrier layer and a

mirror-like surface that reflects the emitted light back to the relatively transparent

upper electrode 4 to enhance the light output.

The upper electrode 4 may be a cathode or an anode. When the upper

electrode 4 is the anode, the lower electrode 2 serves as the cathode, and the

OLED is referred to as an inverted OLED. The lower electrode 2 may be

transparent or opaque, and reflective or light absorbing. The upper electrode 4

should be semi-transparent or transparent (hereinafter referred to as "relatively

transparent"). Suitable materials for the upper electrode 4 and the lower electrode

2 include conductive polymeric materials, conductive organic materials,

transparent conductive oxides (TCOs), metals or metal alloys. Examples of TCO

include indium-tin-oxide (ITO), zinc-indium-oxide (ZIO), aluminum-doped ZnO, Ga-

In-Sn-O (GITO), Sn0₂, Zn-ln-Sn-0 (ZITO), and Ga-ln-O (GIO). Suitable metals

include gold (Au), silver (Ag), aluminum (Al), iridium (Ir), nickel (Ni) and chromium

(Cr). Either of the lower electrode 2 or the upper electrode 4 may be a single layer

structure made of one of the materials mentioned above or a multilayer structure

made of a combination of these materials. When metals are used as the electrode

materials, the interfacial surface of the metal electrode (i.e., the boundary surface

between the metal electrode and the organic stack 3) may be modified in order to

enhance charge carrier injection in the OLED. TCO (e.g. ITO) has been found to

be effective for modifying the metal surface. The materials to be used for

modifying the metal surface of the electrode are not limited to TCOs, however,

other inorganic materials, as well as organic materials, may also be used for the same purpose. When a metal electrode has been modified, the interfacial

modification layer is positioned between the organic stack 3 and the metal

electrode. The relatively transparent upper electrode 4 may be comprised of a single

relatively transparent conductive layer, or a multilayer structure containing at least

one relatively transparent conductive layer. A multilayer upper electrode may be

comprise a relatively transparent conductive layer covered with an index-matching

layer in order to enhance the light output. The index-matching layer is made of an

organic or inorganic material having a refractive index that is effective for

enhancing the light output. Examples of the materials for the index-matching layer

are tris-(8-hydroxyquinoline) aluminum (Alq3), N,N'-di(naphthalene-1 -yl)-N,N'-

diphenylbenzidine (NPB), MgF₂, SiO₂, MgO, ITO, ZnO, Ti0₂. In some cases, a

TCO layer, e.g. ITO, serve as both a relatively transparent upper electrode and an

index-matching layer for enhancing the light output. The index-matching layer also

serves as a barrier or an encapsulation layer. The index-matching layer may have

a thickness of 1 to 500 nm, depending on the reflective index of the materials

being used. The multilayer upper electrode may further include at least one thin,

charge carrier injection layer, which is formed between the relatively transparent

conductive layer and the organic stack 3. When the multilayer upper electrode is a

cathode, the charge carrier injection layer is an electron injection layer. Suitable

materials for the electron injection layer include low work function metals such as

rare earth metals. When the multilayer upper electrode is an anode, the charge

carrier injection layer is a hole injection layer. The hole injection layer may be made of a high work function metal, e.g. Au or Ag, or TCO. Various inorganic

materials, organic materials, or combinations of inorganic and organic materials

are also feasible as materials for the hole injection layer so long as these materials

are effective for hole injection. The charge carrier injection layer may have a

thickness of up to 50 nm. The thickness of a single relatively transparent

conductive layer may be from 1 to 150 nm. The total thickness of a multilayer

electrode structure may be 30nm or thicker.

It should be understood by one skilled in the art that various materials and

multilayer structures are feasible for the upper electrode 4 and the lower electrode

2 so long as they can provide lateral conductivity and interfacial properties

required for efficient charge carrier injection.

The organic stack 3 may be a single layer or a multilayer stack comprising a

plurality of organic sub-layers adaptable for light emission. The organic materials

for the organic stack 3 include electroluminescent and phosphorescent organic

materials that are conventional in the art for light emitting devices. More

specifically, the organic stack 3 may be made of electroluminescent and/or

phosphorescent polymeric materials conventionally used for PLEDs. The organic

stack may be a single layer of an emissive material or a bi-layer comprised of a

hole transporting layer and a light-emitting layer. Yet another possibility is a three-

layer organic stack comprising a hole transporting layer, an electron transporting

layer, and an emissive layer between the hole transporting layer and the electron

transporting layer. The device having such three-layer organic stack is referred to

as a double heterostructure. The hole transporting layer should be next to the anode because the holes are injected from the anode. When an electron

transporting layer is used, it should be next to the cathode. The total thickness of

the organic stack 3 may range from 50 to 1000 nm.

AN EXAMPLE OF THE PRESENT INVENTION One example of a top-emitting PLED according to the present invention is

shown in FIG. 5. The flexible substrate 1 is composed of a 125 microns thick PET sheet 1a laminated to a 25 microns thick Al foil 1b. A 120 nm thick transparent ITO

anode 2 is formed on the plastic side of the flexible substrate 1. Forming on the ITO anode 2 is a bi-layer organic stack 3 composed of an 80 nm thick emissive

layer 3a made of polyphenylene vinylene (Ph-PPV), and a 30 nm thick hole

transport layer 3b made of polyethylene dioxythiophene (PEDOT). The relatively

transparent cathode 4 is a multilayer structure composed of, in order from the top,

a 52 nm thick tris-(δ-hydroxyquinoline) aluminum (Alq3) layer 4a, a 15 nm thick

semitransparent Ag layer 4b, a 1.0 nm thick calcium (Ca) layer 4c, and a 0.6 nm

thick lithium fluoride (LiF) layer 4d. In this case, Alq3 serves as the index- matching layer, Ag serves as the conducting layer for lateral conductivity, and the

combination of LiF/Ca serves as the electron injector. The multilayer cathode can

be formed by thermal evaporation, thereby avoiding the damaging effect of the

sputter deposition process. The Al foil 1b serves as an excellent barrier for the

PET substrate, thereby improving the lifetime of the device. This example of the present invention could be considered as a convenient and cost-effective approach for fabricating top-emitting PLEDs. The present invention offers a flexible OLED on an opaque and flexible

substrate that can be bent to a substantial extent without breaking. Thus, the

flexible OLED of the present invention has the ability to conform, bend or roll into

any shape. This flexibility will enable the fabrication of display devices by

continuous roll processing, thereby providing a cost-effective approach for mass

production. The flexible substrates disclosed in this invention may also be used

for organice photo-detectors, organic thin film transistors, organic photovoltaic

cells, organic memories, organic integrated circuits, and other organic or inorganic

optoelectronic devices that require flexible substrate with good barrier properties

and mechanical flexibility.

The OLED of the present invention has a variety of applications, including

mobile phones, PDA and other hand-held devices, computer monitors, digital

audio devices, video cameras, lighting devices, decorative devices, and

advertising devices.

While the invention has been described with respect to the preferred

embodiments, it will be understood by those skilled in the art that modifications

may be made in the invention without departing from the spirit and scope of the

appended claims.

Claims

1. A flexible organic light emitting device comprising: a flexible substrate; a lower electrode layer on said flexible substrate; an upper electrode layer that is at least semi-transparent; an organic region between said lower electrode layer and said upper

electrode layer, in which electroluminescence can take place when a voltage is

applied between said lower electrode layer and said upper electrode layer, wherein said flexible substrate is comprised of one of the following:

(i) a plastic layer laminated to or coated with a metal layer, (ii) a metal layer

sandwiched between two plastic layers, and (iii) a metal foil.

2. The flexible organic light emitting device of claim 1 , wherein said flexible

substrate is comprised of a plastic layer laminated to or coated with an aluminum

layer, the plastic layer being positioned between the lower electrode layer and the

aluminum layer.

3. The flexible organic light emitting device of claim 1 , wherein said flexible

substrate is comprised of a steel foil.

4. The flexible organic light emitting device of claim 1 further comprising an

isolation layer between said flexible substrate and said lower electrode layer.

5. The flexible organic light emitting device of claim 4, wherein said isolation

layer is a spin-coated polymeric layer or a dielectric layer.

6. The flexible organic light emitting device of claim 3 further comprising an

isolation layer between said steel foil and said lower electrode layer.

7. The flexible organic light emitting device of claim 1 , wherein said upper

electrode layer is transparent.

8. The flexible organic light emitting device of claim 1 , wherein said upper

electrode layer is a semitransparent or transparent anode.

9. The flexible organic light emitting device of claim 1 , wherein said upper

electrode layer is a semitransparent or transparent cathode.

10. The flexible organic light emitting device of claim 1 , wherein said upper

electrode layer is a multilayer structure comprising at least one semitransparent or

transparent conductive film.

11. The flexible organic light emitting device of claim 10, wherein said multilayer

structure comprises an index-matching layer and a charge carrier injection layer.

12. The flexible organic light emitting device of claim 11 , wherein said index- matching layer comprises an organic or inorganic material having a refractive

index effective for enhancing light output.

13. The flexible organic light emitting device of claim 11 , wherein said index-

matching layer comprises a combination of organic and inorganic materials that are effective for enhancing light output.

14. The flexible organic light emitting device of claim 11 , wherein said multilayer structure is an anode and said charge carrier injection layer is a hole injection

layer.

15. The flexible organic light emitting device of claim 14, wherein said hole

injection layer comprises a high work function metal or a transparent conductive oxide (TCO).

16. The flexible organic light emitting device of claim 15, wherein said high work function metal is gold or silver.

17. The flexible organic light emitting device of claim 15, wherein said TCO is metal oxide.

18. The flexible organic light emitting device of claim 15, wherein said TCO is

selected from the group consisting of indium-tin-oxide (ITO), zinc-indium-oxide, aluminum-doped zinc oxide, Ga-ln-Sn-O, SnO₂, Zn-ln-Sn-O, and Ga-ln-O.

19. The flexible organic light emitting device of claim 14, wherein said hole injection layer comprises an organic material effective for hole injection or a combination of inorganic and organic materials that are effective for hole injection.

20. The flexible organic light emitting device of claim 14, wherein said hole injection layer comprises an inorganic material effective for hole injection or a

combination of inorganic and organic materials that are effective for hole injection.

21. The flexible organic light emitting device of claim 11 , wherein said multilayer

structure is a cathode and said charge carrier injection layer is an electron injection layer.

22. The flexible organic light emitting device of claim 21 , wherein said electron

injection layer comprises a low work function metal .

23. The flexible organic light emitting device of claim 22, wherein said low work function metal is a rare earth metal.

24. The flexible organic light emitting device of claim 21 , wherein said index- matching layer comprises tris-(8-hydroxyquinoline) aluminum (Alq3) or N,N'- di(naphthalene-1-yl)-N,N'-diphenylbenzidine (NPB).

25. The flexible organic light emitting device of claim 21 , wherein said cathode

comprises a silver layer and said electron injection layer is comprised of a calcium

sub-layer over a lithium fluoride sub-layer, the silver layer being formed over the

calcium layer.

26. The flexible organic light emitting device of claim 1 , wherein at least one of

the lower electrode layer and the upper electrode layer is modified to enhance

charge carrier injection.

27. The flexible organic light emitting device of claim 1 , wherein said organic

region comprises (i) a hole transporting layer and (ii) an emissive layer or an

electron transporting layer.

28. The flexible organic light emitting device of claim 1 , wherein said organic

region comprises (i) a hole transporting layer, (ii) an emissive layer, and (iii) an

electron transporting layer.