# Patent

## Title
Transparent electrodes

## Abstract

A cathode adapted for use in an organic optoelectronic device is provided. The cathode has an electron injection layer, an organic buffer layer, a conducting layer, and a transparent conductive oxide layer disposed, in that order, over the organic operative layers of the optoelectronic device. A method of fabricating the cathode is also provided.

## Background
The subject matter of this application is related to concurrently filed patent application Ser. No. 09/931,939, which is incorporated by reference in its entirety.
RESEARCH AGREEMENTS
The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to joint university-corporation research agreement: Princeton University, The University of Southern California and Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.


FIELD OF THE INVENTION
The present invention relates to the field of organic semiconductor devices, and more particularly to transparent electrodes used in such devices.
BACKGROUND OF THE INVENTION
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants, while it may be more difficult to tune inorganic emissive materials. As used herein, the term “organic material” includes polymers as wells as small molecule organic materials that may be used to fabricate organic opto-electronic devices.
OLEDs makes use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly popular technology for applications such as flat panel displays, illumination, and backlighting. OLED configurations include double heterostructure, single heterostructure, and single layer, and a wide variety of organic materials may be used to fabricate OLEDs. Several OLED materials and configurations are described in U.S. Pat. No. 5,707,745, which is incorporated herein by reference in its entirety.
One or more transparent electrodes may be useful in an organic opto-electronic device. For example, OLED devices are generally intended to emit light through at least one of the electrodes. For OLEDs from which the light emission is only out of the bottom of the device, that is, only through the substrate side of the device, a transparent anode material, such as indium tin oxide (ITO), may be used as the bottom electrode. Since the top electrode of such a device does not need to be transparent, such a top electrode, which is typically a cathode, may be comprised of a thick and reflective metal layer having a high electrical conductivity. In contrast, for transparent or top-emitting OLEDs, a transparent cathode such as disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745 may be used. As distinct from a bottom-emitting OLED, a top-emitting OLED is one which may have an opaque and/or reflective substrate, such that light is produced only out of the top of the device and not through the substrate. In addition, a fully transparent OLED that may emit from both the top and the bottom.
The transparent cathodes as disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745 typically comprise a thin layer of metal such as Mg:Ag with a thickness, for example, that is less than about 100 angstroms. The Mg:Ag layer is coated with a transparent, electrically-conductive, sputter-deposited, ITO layer. Such cathodes may be referred to as compound cathodes or as TOLED (“Transparent-OLED”) cathodes. The thickness of the Mg:Ag and ITO layers in such compound cathodes may each be adjusted to produce the desired combination of both high optical transmission and high electrical conductivity.
The organic materials of an opto-electronic device may be very sensitive, and may be damaged by conventional semiconductor processing. For example, any exposure to high temperature or chemical processing may damage the organic layers and adversely affect device reliability. In addition, exposure to air or moisture may also damage the sensitive organic layers. Such exposure may also damage any Mg:Ag layer that may be present, because Mg:Ag is highly reactive. The organic materials may also be damaged by the processes used to deposit transparent electrode materials. While conventional processes and structures allow for the fabrication of operational organic devices with transparent electrodes, the yield with such processes may be less than optimal. Indeed, the yield may not be great enough to fabricate commercially viable displays, for example, where the failure of only a few percent of the devices may render the display unsuitable for commercial use. There is therefore a need for a method of fabrication and/or transparent electrode structures that result in higher yields.
SUMMARY OF THE INVENTION
A cathode adapted for use in an organic optoelectronic device is provided. The cathode has an electron injection layer, an organic buffer layer, a conducting layer, and a transparent conductive oxide layer disposed, in that order, over the organic operative layers of the optoelectronic device. A method of fabricating the cathode is also provided.
A method of fabricating a device is provided. A substrate having first conductive layer disposed thereon. An organic layer is fabricated over the first conductive layer. A second conductive layer is then fabricated over the organic layer such that the second conductive layer is in electrical contact with the first conductive layer during at least a portion of the step of depositing the second conductive layer. The electrical contact between the first conductive layer and the second conductive layer is then broken.
A method of fabricating an active matrix array of organic light emitting devices is provided. A substrate is obtained, having circuitry adapted to control the current flowing through each organic light emitting device, and having a first conductive layer disposed thereon, such that the first conductive layer is electrically attached to the circuitry. An organic layer is fabricated over the first conductive layer. A second conductive layer is then fabricated over the organic layer such that the second conductive layer is in electrical contact with the circuitry, and such that the circuitry allows sufficient leakage between the first conductive layer and the second conductive layer to reduce the electrical field across the organic layer, during at least a portion of the step of fabricating the second conductive layer. The electrical contact between the circuitry and the second conductive layer is then broken.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a top-emitting organic light emitting device having a transparent multi-layer top electrode through which light may be emitted.
FIG. 2 shows a top-emitting organic light emitting device having a transparent multi-layer top electrode, having a structure different from that of FIG. 1, through which light may be emitted.
FIG. 3 shows a top-emitting organic light emitting device having a transparent multi-layer top electrode, having a structure different from that of FIGS. 1 and 2, through which light may be emitted.
FIG. 4 shows a top view of a first patterned conductive layer disposed over a substrate.
FIG. 5 shows a top view of a passive matrix display using first patterned conductive layer of FIG. 4.
FIG. 6 shows a circuit diagram of a single pixel of an active matrix OLED display
FIG. 7 shows a circuit diagram of 2×2 active matrix OLED array.
FIG. 8 shows a top schematic view of the array of FIG. 7.
FIG. 9 shows a cross section of FIG. 8 across line 9.
FIG. 10 shows a plot of current density v. voltage for two of the example devices.
FIG. 11 shows normalized luminescence v. time for these devices.



DETAILED DESCRIPTION
In an embodiment of the invention, a multi-layer transparent cathode structure is provided. The structure includes a layer of conductive oxide, such as indium tin oxide (ITO), zinc indium tin oxide, or aluminum zinc oxide. The structure may also include an electron injection layer that enhances the injection of electrons from the cathode into the organic layers of the device. The structure may also include an organic buffer layer that protects underlying organic layers during the subsequent deposition of ITO. The structure may also include a conductive layer that enhances the injection of electrons from the ITO layer into other layers of the electrode.
FIG. 1 shows a top-emitting organic light emitting device 100 having a transparent multi-layer top electrode 140 through which light may be emitted. Device 100 is disposed over substrate 110, and includes a bottom electrode 120, an organic operative layer 130, and a top electrode 140, deposited in that sequence over substrate 110. Top electrode 140 further includes an electron injection layer 150, an organic buffer layer 160, a conducting layer 170, and a transparent conductive oxide layer 180, deposited in that sequence over organic operative layer 130.
Substrate 110 may be made of any conventional substrate material. Glass, plastic, metal foil, and ceramic substrates are known to the art. Substrate 110 may be rigid or flexible. Substrate 110 may be transparent or opaque. Substrate 110 may be a semiconductor such as silicon, which may facilitate the fabrication of circuitry connected to device 100 onn substrate 110.
Bottom electrode 120 may be made of any conventional electrode material. In the embodiment of FIG. 1, bottom electrode 120 is an anode. Indium tin oxide (ITO) and metal anodes are known to the art. Bottom electrode 120 may be transparent or opaque.
Organic operative layer 130 may be any organic layer known to the art that may be incorporated into an opto-electronic device between the electrodes of that device. In one embodiment, device 100 is an OLED, and operative organic layer 130 may include any conventional OLED organic materials. The word “operative” is intended to distinguish organic operative layer 130, i.e., the organic layer between the electrodes of an optoelectronic device, from any organic layer that may be a part of the cathode, such as organic buffer layer 160, but is not intended to otherwise limit the layer. Organic operative layer 130 may be a single layer, or may include the multiple layers of conventional OLED structures, such as a single or double heterostructure, or one or more layers containing a mixture of OLED organic materials. In other embodiments, organic operative layer 120 may be the one or more organic layers of a photodetector, photovoltaic cell, phototransistor, or other opto-electronic device.
Top electrode 140 further includes an electron injection layer 150, an organic buffer layer 160, a conducting layer 170, and a transparent conductive oxide layer 180, deposited in that sequence over organic operative layer 130. In one embodiment, it is contemplated that top electrode 140 may also include other layers. In such an embodiment, each layer may be described as “disposed over” an underlying layer. For example, organic buffer layer 160 may be described as “disposed over” electron injection layer 150 to allow for the possibility that there is one or more additional layers deposited between organic buffer layer 160 and electron injection layer 150. In another embodiment, it is contemplated that there are no layers other than those described, in which case the layers may be described as “disposed over and in physical contact with” the underlying layer. However, even in this embodiment it is contemplated that interfacial effects may occur between the layers described.
Electron injection layer 150 may improve the injection of electrons from organic buffer layer 160 into organic operative layer 130. A preferred electron injection layer 150 further comprising two layers, a layer of LiF disposed over organic operative layer 130, and a layer of Al disposed over the layer of LiF. Another preferred electron injection layer material is LiF co-evaporated with Al. Other preferred electron injection layer materials include Li2O, CsF, alkali metal halides, and alkaline earth metal halides. The electron injection layer thickness is preferably as thin as possible, while still retaining electron injection capabilities. For example, the thickness is preferably about 5-25 Å, and more preferably about 25 Å. At these thicknesses, it is possible that the layers are not contiguous, and may form islands. It is also possible that much of the material, for example LiF, may dissociate and that the resultant Li may diffuse into other layers, such as organic buffer layer 160. Even if the layers are not contiguous and if there is significant dissociation and diffusion, the term “layer” is intended to describe the result of depositing the electron injection material.
Organic buffer layer 160 may reduce damage to underlying organic operative layer 130 during the fabrication of subsequently deposited layers. In particular, the processes used to deposit transparent conductive oxide layer 180 may damage organic operative layer in the absence of a buffer layer. Preferably, organic buffer layer has a high electron mobility, such that it does not significantly increase the operating voltage of device 100. Preferably, the electron mobility of organic buffer layer 160 is higher than that of any electron transport layer that may be included in organic operative layer 130. Preferably, organic buffer layer 160 does not increase the operating voltage of device 100 more than about 25% relative to a similar device with no organic buffer layer. More preferably, this increase is not more than about 10%. Preferred materials for organic buffer layer 160 include copper phthalocyanine (CuPc), and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Other preferred materials include various metal phthalocyanines, such as ZnPc, MgPc, and PbPc. The thickness of organic buffer layer 160 is preferably thick enough that there is little or no damage to organic operative layer 130 due to fabrication processes that occur after organic buffer layer 160 is deposited, yet not so thick as to significantly increase the operating voltage of device 100. Preferably, buffer layer 160 is about 50-500 Å thick, and more preferably about 400 Å thick. Buffer layer 160 may be doped to increase its conductivity. For example, a CuPc or BCP buffer layer 160 may be doped with Li.
Conductive layer 170 may improve electron injection from transparent conductive oxide layer 180 into organic buffer layer 160. The injection of electrons from some transparent conductive oxides, such as ITO, into some organic buffer layers, such as CuPc, may be less than optimal. Conductive layer 170 may improve such injection. Preferred materials for conductive layer 170 include Mg:Ag, other metals, Ca, and LiF/Al, and any materials described above as preferred materials for electron injection layer 150. Conductive layer 170 is preferably very thin, because very little thickness is needed to improve electron injection, and any additional thickness may reduce the transparency of device 100. Where Mg:Ag is used, the thickness may preferably be up to about 125 Å, and more preferably about 100 Å or less. Where Mg:Ag is used, the ratio of Mg to Ag is preferable about 10:1 to 30:1. Where LiF/Al is used, conductive layer 170 is preferably similar to the LiF/Al layer described above as a potential electron injection layer 150.
Transparent conductive oxide layer 180 may be responsible for most of the conductivity of electrode 140 in the plane parallel to substrate 110. The material and thickness of transparent conductive oxide layer 180 may be chosen to achieve a desired combination of conductivity and transparency. Preferred materials for transparent conductive oxide layer include ITO, zinc indium tin oxide, and aluminum zinc oxide. Preferably, transparent conductive oxide layer is about 100-2000 Å thick, and more preferably about 500-1000 Å thick.
The materials and thicknesses of each of the layers of top electrode 140 may be selected in combination to control the optical properties of top electrode 140. For example, the materials and thicknesses may be selected to obtain a desired transparency. For applications where a high transparency is desirable, a transparency of greater than about 90% may be obtained. For other applications, a lower transparency may be desirable, and such transparencies may also be readily achieved through selection of materials and thicknesses. For example, a transparency of about 30% may be satisfactory for certain applications, and an electrode having such a transparency is considered “transparent” for such applications. Other optical properties may also be controlled by material selection and dopants. For example, CuPc may act as a blue filter, reducing the amplitude of visible light in the red region. Various dopants may be added to the layers of top electrode 140 to modify their optical properties.
Top electrode 140 may be used as the cathode of a device 100 that emits light through top electrode 140, but not through bottom electrode 120 and substrate 110. In such a device, the materials and thicknesses of bottom electrode 120 and substrate 110 are preferably selected to maximize back reflection, for example, a thick, highly reflective metal layer. Top electrode 140 may also be used as the cathode of a device 100 that emits light through both top electrode 140 and bottom electrode 120. In such a device, the materials and thicknesses of all layers may be selected to achieve a desired level of transparency.
FIG. 2 shows a top-emitting organic light emitting device 200 having a transparent multi-layer top electrode 240 through which light may be emitted. Device 200 is disposed over substrate 210, and includes a bottom electrode 220, an organic operative layer 230, and a top electrode 240, deposited in that sequence over substrate 210. Top electrode 240 further includes an electron injection layer 250, a conducting layer 270, and a transparent conductive oxide layer 280, deposited in that sequence over organic operative layer 230.
The materials and thicknesses of substrate 210, bottom electrode 220, organic operative layer 230, electron injection layer 250, conducting layer 270, and transparent conductive oxide layer 280 of device 200 may be similar to those of substrate 110, bottom electrode 120, organic operative layer 130, electron injection layer 150, conducting layer 170, and transparent conductive oxide layer 180, respectively, of device 100.
The embodiment of FIG. 2 involves a trade-off when compared to that of FIG. 1. The absence of a buffer layer results in a simpler structure, with less manufacturing steps. However, the process used to deposit the conductive oxide layer, such as ITO, may be more restricted due to the absence of the protective buffer layer and the need to minimize damage to the operative organic layers. For example, a lower ITO deposition rate and different partial pressures of the various gases involved may be used in the embodiment of FIG. 2 as compared to the embodiment of FIG. 1.
FIG. 3 shows a top-emitting organic light emitting device 300 having a transparent multi-layer top electrode 340 through which light may be emitted. Device 300 is disposed over substrate 310, and includes a bottom electrode 320, an organic operative layer 330, and a top electrode 340, deposited in that sequence over substrate 310. Top electrode 340 further includes an electron injection layer 350, a buffer layer 360, and a transparent conductive oxide layer 380, deposited in that sequence over organic operative layer 330.
The materials and thicknesses of substrate 310, bottom electrode 320, organic operative layer 330, electron injection layer 350, buffer layer 360, and transparent conductive oxide layer 380 of device 300 may be similar to those of substrate 110, bottom electrode 120, organic operative layer 130, electron injection layer 150, buffer layer 160, and transparent conductive oxide layer 180, respectively, of device 100.
The embodiment of FIG. 3 involves a trade-off when compared to that of FIG. 1. The absence of a conductive layer results in a simpler structure, with less manufacturing steps. Also, the absence of a conductive layer may result in an electrode having a higher transparency. However, while not intending to be limited as to any theory of how the invention works, it is believed that there is a difference between the embodiments of FIGS. 1 and 3 in the mechanism by which electrons are injected from the conductive oxide into the buffer layer, which may result in a slightly higher operating voltage for the embodiment of FIG. 3. In particular, it is believed that the electron injection from the conductive oxide into the buffer layer in the embodiment of FIG. 3 is facilitated by damage states in the buffer layer. This mechanism is described in more detail in U.S. Pat. No. 6,420,031, issued to Parthasarathy et al. entitled “Highly Transparent Non-Metallic Cathodes,” which is incorporated by reference in its entirety. In addition, the cathode of FIG. 3 may be slightly less conductive than that of FIG. 1 in lateral directions, i.e., directions parallel to the substrate.
Top electrodes 140, 240 and 340 of FIGS. 1, 2 and 3 may advantageously be used as the cathode of an opto-electronic device, because of the electron injection layers included therein. By replacing the electron injection layer with an appropriate hole injection layer, the structures may advantageously be used as the anode of an opto-electronic device. Top electrodes 140 and 340 may advantageously be used as top electrodes, because of the buffer layer included therein. The structure of top electrode 240 may be advantageously used as a top electrode (cathode) or as a bottom electrode (cathode).
In addition, the organic materials of organic opto-electronic devices may sustain “charging damage” during fabrication. Charging damage is the result of a voltage applied across the device during fabrication, generally due to secondary electrons generated during the processes used to deposit electrodes after the organic layers are already present. Charging damage may occur during e-beam processes or plasma related processes, such as sputtering, plasma-enhanced chemical vapor deposition, and reactive ion etching. Unfortunately, many of the most desirable transparent electrode materials, such as indium tin oxide (ITO), are generally deposited using processes such as sputtering that generate secondary electrons. Again, conventional methods may be utilized to fabricate operational devices, but the yield may be less than optimal.
In an embodiment of the invention, a method of fabricating an opto-electronic device is provided that reduces charging damage. After a first electrode and an organic layer are fabricated, a second electrode is fabricated such that the second electrode is in electrical contact with the first electrode during at least a portion of the step of depositing the second electrode. This electrical contact may be through a direct conductive path, or it may be indirect, through circuitry that allows for enough leakage to reduce charging damage. Because the first and second electrode are in electrical contact during the fabrication of the second electrode, a significant voltage difference between the first and second electrodes is not sustainable, and charging damage is reduced. In order to create a functional device, the electrical contact between the first and second electrodes is broken after the second electrode is fabricated.
In one embodiment, the second electrode may be electrically connected to ground instead of to the first electrode during at least a portion of the step of depositing the second electrode. However, this embodiment is less preferable than electrically connecting the second electrode to the first electrode, because there may be a voltage difference between ground and the first electrode, which may have floating voltage. Even so, this embodiment may reduce the voltage difference between the first and second electrodes during fabrication of the second electrode. A connection to “ground” may be established, for example, by an electrical connection to a conductive wall of the chamber in which the device is being fabricated.
FIG. 4 shows a first patterned conductive layer 420 disposed over a substrate 410. The particular pattern shown in FIG. 4 is designed for use in a passive matrix display. The materials and thicknesses of substrate 410 and first patterned conductive layer 420 may be any suitable substrate and electrode materials, respectively. Indium tin oxide (ITO) is a preferred material for first patterned conductive layer 420.
FIG. 5 shows a passive matrix display using first patterned conductive layer 420 of FIG. 4, which is disposed over substrate 410. First patterned conductive layer 420 includes three first electrodes 525, as well as residual portions 523. Scribe lines 550 define the boundary between first electrodes 525 and residual portions 523. An organic layer 530 is disposed over first electrode 525. A second patterned conductive layer 540 is disposed over organic layer 530. Second patterned conductive layer 540 includes three second electrodes 545, as well as residual portions 543. Scribe lines 550 define the boundary between second electrodes 545 and residual portions 543. Scribe lines 550 also define the boundary between a portion 515 of substrate 410, and residual portions 513 of substrate 410.
Organic layer 530 may comprise any suitable organic layer. Organic layer 530 may also comprise multiple organic layers, such as the multiple layers of a double heterostructure or single heterostructure OLED. Organic layer 530 may be the operative layer of any organic optoelectronic device, including an OLED, a photovoltaic cell, a photodetector, a phototransistor, etc.
Although organic layer 530 is shown as patterned into strips parallel to second electrode 540, other configurations may be used. For example, organic layer 530 may be a blanket layer, or organic layer 530 may be patterned into strips parallel to first electrode 420, or other configurations may be used.
The array of FIG. 5 may be fabricated as follows. A substrate 410 having thereon a first patterned conductive layer 420 is obtained or fabricated using any suitable technique, including techniques known to the art. Organic layer 530 is fabricated over first patterned conductive layer 420 using any suitable technique, including techniques known to the art. Second patterned conductive layer 540 is fabricated over organic layer 530 using any suitable technique, including techniques known to the art, such that there is electrical contact between first patterned conductive layer 420 and second patterned conductive layer 540 over residual portions 513 of substrate 410 during at least a portion of the step of depositing second patterned conductive layer 540. The electrical connection between first electrode 525 and second electrode 545 is then broken, for example by scribing and breaking substrate 410 along scribe lines 550, such that residual portions 513 are removed along with any layers deposited thereon.
The electrical contact between first patterned conductive layer 420 and second patterned conductive layer 540 advantageously reduces “charging damage” during the deposition of second patterned conductive layer 540 that might otherwise occur. The terminology “during at least a portion” is used to indicate that electrical contact may not yet be formed at the very beginning of the step. For example, if second patterned conductive layer is a single layer of ITO, the very first particles deposited may not be in electrical contact with each other, let alone first patterned conductive layer 420. However, at some point, second patterned conductive layer 540 becomes sufficiently contiguous that is may be considered in electrical contact with first patterned conductive layer 420. Preferably, second patterned layer 540 is in electrical contact with first patterned conductive layer 420 substantially throughout the deposition process.
In a preferred embodiment, second patterned conductive layer 540, and second electrode 545, are multi-layer structures that include a layer of metal deposited over organic layer 530, and a layer of ITO deposited over the layer of metal. Using conventional fabrication techniques, it is believed that most charging damage occurs during the deposition of ITO, which is generally deposited using a technique such as sputtering that involves secondary electrons. In this preferred embodiment, second patterned conductive layer 540 is in electrical contact with first patterned conductive layer 420 via the layer of metal during the entire deposition of the ITO. The layer of metal may be deposited using techniques such as subliminal evaporation that do not tend to cause charging damage.
In a preferred embodiment, the multilayer top electrode of FIG. 1, 2 or 3 is used as top electrode 540 of FIG. 5.
The electrical contact between first patterned conductive layer 420 and second patterned conductive layer 540 during at least a portion of the step of fabricating second patterned conductive layer 540 may be achieved in a number of different ways. One is by direct physical contact between the two layers, as illustrated in FIG. 5.
Another is by contact through a conductive medium, such as a conductive paste or tape present on residual portions 513 of substrate 410. In this alternative, the parts of patterned conductive layers 420 and 540 extending onto residual portions 513 of substrate 410, i.e., residual portions 523 and 543, may be much smaller than depicted in FIG. 5. Any other suitable means of achieving this electrical contact may also be used.
The breaking of electrical contact between first electrode 525 and second electrode 545 may also be achieved in a number of ways. One is by scribing and breaking substrate 410 along scribe lines 550, as illustrated in FIG. 5.
Another way of breaking the electrical contact between first electrodes 525 and second electrodes 545 is through a subtractive etching process, during which the region of substrate 410 occupied by first electrodes 525 and second electrodes 545 is protected by a mask or a passivation layer selectively deposited prior to the subtractive etching process. Suitable subtractive processes include reactive ion etching and oxygen plasma etching.
Another way of breaking the electrical contact between first electrodes 525 and second electrode 545 is lift-off. In particular, a photoresist or other material that may be readily and selectively removed may be deposited onto residual portions 513 of substrate 410 prior to the fabrication of first electrodes 525. After second electrodes 545 have been fabricated, the photoresist may be removed, along with any layers deposited thereon, breaking the electrical contact.
Another way of breaking the electrical contact between first electrodes 525 and second electrodes 545 is by using a conductive paste, tape or film to achieve the contact, and then removing the conductive paste, tape or film by wiping, peeling, or a similar method. Any other suitable method of breaking the electrical contact may be used, in addition to those specifically described herein.
FIG. 6 shows a circuit diagram of a single pixel of an active matrix OLED display. Organic light emitting device 610 has an anode 620 and a cathode 630. Power is provided though power line 650 (Vdd). Cathode 630 is connected to ground, or a fixed reference voltage, though line 660. The voltage at anode 620 is determined by control circuitry 640 based on input from data lines 670 and 680. Control circuitry 640 may include various configurations for controlling a pixel, including those known to the art, and is not limited to the specific circuit illustrated in FIG. 6. For example, two transistors in series may be disposed between power line Vdd and anode 620.
FIG. 7 shows a circuit diagram of 2×2 active matrix OLED array. Each pixel 710 of the array may further include the circuit diagram of FIG. 6.
FIG. 8 shows a top schematic view of the array of FIG. 7. FIG. 9 shows a cross section of FIG. 8 across line 9. The array is fabricated on a substrate 605. Control circuitry 640 (not shown) may be on substrate 605. Preferably, substrate 605 may be made of a material similar to those described for substrate 110 of FIG. 1. Anode 620 is disposed over substrate 605, and may be on substrate 605, with an exposed surface, as illustrated. An organic layer 625 (only shown in FIG. 9, not shown in FIG. 8) is disposed over anode 620. Cathode 630, a large conductive sheet spanning the entire array, is disposed over organic layer 605. The voltage at each anode 610 may be individually controlled by signals applied through data lines 670 and 680 (not shown in FIGS. 8 and 9). Power line 650 and data lines 670 and 680 may be on substrate 605, with exposed contacts as illustrated in FIG. 8.
The embodiment of FIGS. 6 through 9 may be fabricated as follows. Substrate 605, control circuitry 640, power lines 650, data lines 670 and 680, and anodes 620 may be fabricated using any suitable technique, including techniques known to the art. Organic layer 625 is then deposited over anodes 620. Cathode 630 is then deposited over organic layer 625, such that cathode 630 is in electrical contact with power lines 650 during at least a portion of the step of depositing cathode 630. This electrical contact is preferably implemented by electrically connecting cathode 630 to the exposed contact of power lines 650 as illustrated in FIG. 9. Any of the techniques described with respect to the embodiment of FIGS. 4 and 5 may be used to achieve this electrical contact. Although power line 650 is not necessarily in direct electrical contact with anodes 610 during the deposition of cathode 630, control circuitry 640 should allow sufficient leakage, such that the field strength between anode 620 and cathode 630 should not exceed about 106 V/cm, corresponding to a voltage of about 10 V across a 1000 Å thick device, during the deposition of cathode 630 using most conventional deposition methods for conductive oxide materials.
This leakage may be obtained in several ways. The characteristics of the transistors, generally thin film transistors, may such that the leakage occurs. For example, for an average pixel size, the capacitance is less than about 10 pF. A field of 106 V/cm corresponds to about 10 V across a 1000 Å device. A rough estimate of sufficient leakage is that the voltage discharges in about 1 second, which is much less than an expected deposition time of about 100 seconds. Using the equation C*V=I*T, where C=10−11, V=10, and T=1, the result is I=10−10 A. If the leakage of the transistors is insufficient, several options exist. First, the transistor controlling the OLED may be designed to increase its leakage, for example by reducing the channel length, or adjusting the threshold voltage to increase leakage when no bias is applied. Although leakage in transistors is generally viewed as undesirable, the reduction in charging damage may justify a higher leakage for this application. Second, an electrical bias may be applied to the control circuitry, for example through data lines 670 and 680, during the deposition of the second conductive layer such that the transistor conducts.
Preferred materials and thicknesses of organic layer 625 and cathode 630 are similar to those for the embodiment of FIGS. 4 and 5.
Preferably, the embodiment of FIGS. 6 through 9 uses as a cathode one of the embodiments described in FIGS. 1 through 5.
It is to be understood that the present invention may be used to fabricate much larger arrays of organic devices than those specifically described herein. For example, although FIG. 5 shows a 3×3 array of devices, and FIG. 7 shows a 2×2 array, much larger arrays may be fabricated.
Although many of the embodiments are not specifically described with respect to multicolor displays, it is understood that all embodiments may be readily adapted for use in a multicolor display by one of ordinary skill in the art. For example, a multi-color display may be fabricated by depositing various down-conversion layers known to the art, or using different organic materials in different devices. A multi-color array may also be fabricated by a number of other methods, such as using an array of white-emitting OLEDs in combination with color filters or a distributed Bragg reflector.
It is also to be understood that the present invention is not limited to the specific illustrated embodiments, and may be used to in a wide variety of other embodiments.
The present invention may be used to fabricate a number of products incorporating organic opto-electronic devices, including flat panel displays, organic photodetectors, organic phototransistors, organic photovoltaic cells, and organic photodiodes, both in arrays and as individual devices.
EXAMPLES
The following structures were fabricated on a 6′′ OLED deposition tool having an island cluster tool, obtained from the Kurt Lesker company of Pittsburgh, Pa. Each structure was fabricated on a Rel-4-Regular substrate, which is an ITO coated soda lime glass obtained from Applied Films Corp. of Colorado. Prior to fabricating each structure, the substrate was preheated to 100 degrees C. for 2 minutes, and then subjected to an oxygen plasma treatment, 50 W, 100 mTorr for 2 minutes.
Example 1
For comparative purposes, an array of OLEDs similar to the prior art was fabricated by depositing the following layers, in sequence, through appropriate masks. The deposition of all material was by thermal evaporation, except for ITO (which was only deposited in examples 2, 3 and 4), which was deposited by sputtering. Due to the use of different feedback mechanisms to monitor the deposition sources, the source parameter that was controlled may be either a temperature or a voltage. The MgAg layer was co-deposited from separate Mg and Ag targets to the total thickness shown (1000 Å in example 1).













Material
Dep. Rate (Å/s)
Thickness
Source Temperature (C.) or Power



















CuPc
1.2
100
345.1
C.


NPD
3
500
254.4
C.


Alq
3
500
266.7
C.


LiF
1-2
14
41.2
V


Al
2
10
88.9
V


CuPc
2
400
387.4
C.


MgAg
  3 (Mg)
1000
40.5
V



1.2 (Ag)
—
43.5
V









Although an Ag deposition rate of 1.2 was read on the dial, it is expected that the deposition rate was actually about 0.3 due to a tooling factor in this and in the other examples.
Example 2
An array of OLEDs similar to the device shown in FIG. 1 was fabricated by depositing the following layers, in sequence. The equipment and masks used were the same as for example 1:













Material
Dep. Rate (Å/s)
Thickness
Source Temperature (C.)/Power



















CuPc
1.2
100
345.1
C.


NPD
3
500
257-258
C.


Alq
3
500
304-331
C.


LiF
1-2
14
40.9-41.4
V


Al
2
10
88.9
V


CuPc
2
400
347-396
C.


MgAg
  3 (Mg)
100
41.5
V



1.2 (Ag)
—
43.5
V









A layer of ITO was then deposited by sputtering. The chamber contained 3 mTorr of an Ar/O2 mixture, and the power applied to the chamber was about 250 W. The power applied to the target was about 1.25-1.26 A at 1.98.6-197 V. The substrate was passed over the target 3 times at a speed of 17 inches per minute. With these parameters, it is expected that the thickness of ITO deposited was about 500 Å.
Example 3
An array of OLEDs similar to the device shown in FIG. 3 was fabricated by depositing the following layers, in sequence. The equipment and masks used were the same as for example 1:













Material
Dep. Rate (Å/s)
Thickness
Source Temperature (C.)/Power



















CuPc
1.2
100
345.1
C.


NPD
3
500
249
C.


Alq
3
500
263
C.


LiF
1-2
14
40.0-40.7
V


Al
2
10
88.9
V


CuPc
2
400
348
C.









A layer of ITO about 500 Å thick was deposited by sputtering using parameters similar to those given for example 2, and the power applied to the target was 1.26 A at 198.3-197.5 V.
Example 4
For comparative purposes, an array of OLEDs was fabricated by depositing the following layers, in sequence. The equipment and masks used were the same as for example 1:













Material
Dep. Rate (Å/s)
Thickness
Source Temperature (C.)/Power



















CuPc
1.2
100
336.2
C.


NPD
3
500
257.4
C.


Alq
3
500
257.8
C.


MgAg
  3 (Mg)
100
38.8
V



1.2 (Ag)
—
43.7
V









A layer of ITO about 500 Å thick was deposited by sputtering using parameters similar to those given for example 2, and the power applied to the target was 1.26 A at 197.1-197.2 V.
FIG. 10 shows a plot of current density v. voltage for two of the example devices. Plot 1010, illustrated by diamonds, shows the current density v. voltage for a device fabricated as described in example 2. Plot 1020, illustrated by squares, shows the current density v. voltage for a device fabricated as described in example 1. The plots show that the device of example 2 has a significantly higher current density than the device of example 1.
Without intending to be limited as to any theory as to how the invention works, it is believed that the ITO deposition process may knock some Mg from the previously deposited Mg:Ag layer into the CuPc layer, thereby improving electron injection and lowering the operating voltage.
Lifetime tests were performed on devices fabricated per examples 2 and 4. The devices were run with a constant current of 10 mA/cm2 for about 1400 hours. FIG. 11 shows normalized luminescence v. time for these devices. Plot 1110 shows the normalized luminescence v. time for a device fabricated according to example 4, illustrated by dark squares. Plot 1120 shows the normalized luminescence v. time for a device fabricated according to example 2, illustrated by triangles. The plots show that the device of example 2 retains its ability over time to luminesce much better than the device of example 4.
Without intending to be limited to any theory as to why the invention works, it is believed that the improved electron injection of the devices of Example 2 leads to a better balance of carriers in the OLED, which improves the OLED lifetime.
While the present invention is described with respect to particular examples and preferred embodiments, it is understood that the present invention is not limited to these examples and embodiments. In particular, the present invention is not limited to OLEDs, and may be applied to a wide variety of opto-electronic devices. The present invention as claimed therefore includes variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art.

## Claims

1. An optoelectronic device, comprising:
(a) an electron injection layer disposed over an organic operative layer of the optoelectronic device; 
(b) an organic buffer layer disposed over the electron injection layer; 
(c) a conducting layer disposed over the organic buffer layer; 
(d) a transparent conductive oxide layer disposed over the conducting layer.

2. The device of claim 1, wherein the device is an organic light emitting device, and the electron injection layer comprises a layer of LiF adapted to be electrically connected to an organic emissive layer of the device, and a layer of Al electrically connected to the layer of LiF.

3. The device of claim 1, wherein the electron injection layer further comprises a layer of Li2O.

4. The device of claim 1, wherein the electron injection layer further comprises a layer of CsF.

5. The device of claim 1, wherein the electron injection layer further comprises a layer of alkali metal halide.

6. The device of claim 1, wherein the electron injection layer further comprises a layer of alkaline earth metal halide.

7. The device of claim 1, wherein the buffer layer further comprises a layer of CuPc.

8. The device of claim 7, wherein the buffer layer further comprises a layer of CuPc doped with Li.

9. The device of claim 1, wherein the buffer layer further comprises a layer of BCP.

10. The device of claim 9, wherein the buffer layer further comprises a layer of BCP doped with Li.

11. The device of claim 1, wherein the conducting layer further comprises a layer of MgAg.

12. The device of claim 1, wherein the conducting layer further comprises a layer of Ca.

13. The device of claim 1, wherein the conducting layer further comprises a layer of LiF and a layer of Al.

14. The device of claim 1, wherein the transparent conductive oxide layer further comprises a layer of indium tin oxide.

15. The device of claim 1, wherein the transparent conductive oxide layer further comprises a layer of zinc indium tin oxide.

16. The device of claim 1, wherein the transparent conductive oxide layer further comprises a layer of aluminum zinc oxide.

17. The device of claim 1, wherein, the electron injection layer, the organic buffer layer, the conducting layer and the transparent conductive oxide layer in combination have transparency of at least 90%.

18. The device of claim 1, wherein the buffer layer does not increase the operating voltage of the device more than about 25% compared to a device having no buffer layer.

19. The device of claim 18, wherein the buffer layer does not increase the operating voltage of the device more than about 10% compared to a device having no buffer layer.

20. The device of claim 1, wherein the optoelectronic device is an organic light emitting device having an electron transport layer, and wherein the buffer layer has an electron mobility higher than that of the electron transport layer.

21. The device of claim 1, wherein the optoelectronic device is an organic light emitting device.

22. The device of claim 1, wherein:
(a) the electron injection layer is in physical contact with the organic operative layer of the optoelectronic device; 
(b) the organic buffer layer is in physical contact with the electron injection layer; 
(c) the conducting layer is in physical contact with the organic buffer layer; 
(d) the transparent conductive oxide layer is in physical contact with the conducting layer.

23. An organic light emitting device, comprising:
(a) a layer of LiF adapted to be physically and electrically connected to an organic operative layer of the organic light emitting device; 
(b) a layer of Al physically and electrically connected to the layer of LiF; 
(c) a layer of CuPc physically and electrically connected to the layer of Al; 
(d) a layer of MgAg physically and electrically connected to the layer of CuPc; 
(e) a layer of ITO physically and electrically connected to the layer of CuPc.

24. A device, comprising:
(a) an anode disposed over a substrate; 
(b) an organic operative layer disposed over and electrically connected to the anode; 
(c) an electron injection layer physically and electrically connected to the organic operative layer; 
(d) an organic buffer layer physically and electrically connected to the electron injection layer; 
(e) a conductive layer physically and electrically connected to the organic buffer layer; 
(f) a transparent conductive oxide layer physically and electrically connected to the conductive layer.

25. A method of fabricating an optoelectronic device having a transparent cathode, comprising the steps of:
(a) depositing an electron injection layer over an organic operative layer of the organic optoelectronic device; 
(b) depositing an organic buffer layer over the electron injection layer; 
(c) depositing a conductive layer over the organic buffer layer; 
(d) depositing a transparent conductive oxide layer over the conductive layer.

26. The method of claim 25, wherein the electron injection layer includes LiF and Al.

27. The method of claim 25, wherein the electron injection layer includes Li2O.

28. The method of claim 25, wherein the electron injection layer includes CsF.

29. The method of claim 25, wherein the electron injection layer includes an alkali metal halide.

30. The method of claim 25, wherein the electron injection layer includes an alkaline earth metal halide.

31. The method of claim 25, wherein the buffer layer includes CuPc.

32. The method of claim 31, wherein the buffer layer further includes Li.

33. The method of claim 25, wherein the buffer layer includes BCP.

34. The method of claim 33, wherein the buffer layer further inludes Li.

35. The method of claim 25, wherein the conducting layer includes Mg and Ag.

36. The method of claim 25, wherein the conducting layer includes Ca.

37. The method of claim 25, wherein the conducting layer includes LiF and Al.

38. The method of claim 25, wherein the conductive oxide layer includes indium tin oxide.

39. The method of claim 25, wherein the conductive oxide layer includes zinc indium tin oxide.

40. The method of claim 25, wherein the conductive oxide layer includes aluminum zinc oxide.

41. An organic optoelectronic device having a transparent cathode fabricated by the steps of:
(a) depositing an electron injection layer over an organic operative layer of the organic optoelectronic device; 
(b) depositing an organic buffer layer over the electron injection layer; 
(c) depositing a conductive layer over the organic buffer layer; 
(d) depositing a transparent conductive oxide layer over the conductive layer.