CN1240537A - Patterns of electrically conducting polymers and their application as electrodes or electrical contacts - Google Patents

Abstract

Electronic devices having patterned conductive polymers that can provide electrical connections thereto and methods of making them are described. A liquid crystal display cell is described having at least one electrode that can provide bias to a liquid crystal material formed from a patterned conductive polymer. Thin-film transistors incorporating patterned conductive polymers as source, drain and gate are described. A light emitting diode is described having an anode and a coated region formed from a patterned conductive polymer. Methods are described for patterning with a resist mask; patterning with a patterned metal layer; patterning a metal layer with a resist; and patterning a conductive polymer to directly form electrodes and anodes and cathode area.

Description

Conductive polymer patterns and their use as electrodes or electrical contacts

This application requires a provisional application entitled "Method of Patterning Electrically Conductive Polymer Films To Form Electrodes And Interconnection Conductors On A Surface Using AResist To Patern A Metal Layer To Patern An Electrically Conductive Polymer Layer.60/No" filed on March 17, 1997 Priority of 040,129.

This application claims priority to Provisional Application No. 60/030,501, filed November 12, 1996, by M. Angelopoulos et al., entitled "SOLUTION APPLIED, IMAGEABLE, TRANSPARENT POLYMERS AS CONDUCTING ELECTRODES."

This application claims priority to Provisional Application No. 60/040,335, filed March 7, 1997, by M. Angelopoulos et al., entitled "PATTERNS OF ELECTRICALLY CONDUCTING POLYMERS AND THEIR APPLICATION AS ELECTRODES AND ELECTRICAL CONTACTS."

This application claims priority to Provisional Application No. 60/040,628, filed March 7, 1997, by M. Angelopoulos et al., entitled "PATTERNS OF ELECTRICALLY CONDUCTING POLYMERS AND THEIR APPLICATION AS ELECTRODES INFIELD EFFECT TRANSISTORS."

This application claims priority to Provisional Application No. 60/040,159, filed March 7, 1997, by M. Angelopoulos et al., entitled "METHODS OF PATTERNING ELECTRICALLYCONDUCTIVE POLYMER FILMS TO FORM ELECTRODES ANDINTERCONNECTION CONDUCTORS ON A SURFACE."

This application claims priority to Provisional Application No. 60/040,130, filed March 7, 1997, entitled "METHOD Of Patterning Electrically Conductive Polymer Films To Form Electrodes And Interconnection Conductors On A Surface Using AResist Mask."

This application claims priority to Provisional Application No. 60/040,132, filed March 7, 1997, by M. Angelopoulos et al., entitled "STRUCTURES HAVING PATTERNED ELECTRICALLY CONDUCTIVE POLYMER FILMS AND METHODS OFF ABRICATION THEREOF." This application claims priority to Provisional Application No. 60/040,131, filed March 7, 1997, by M. Angelopoulos et al., entitled "LIGHT EMITTING DIODES HAVING ELECTRICALLY CONDUCTIVE POLYMER ELECTRODES."

Technical Field of the Invention

The object of the present invention is a patterned conductive polymer and a method for its manufacture. More specifically, the object of the present invention is an electronic device having conducting polymers as electrode contacts and active regions and patterned electrical contacts formed from conducting polymers, in particular such polymers as electrodes or electro-optical transducers. For electrical contact applications, such transducers include liquid crystal displays, electro-optic modulators, diodes, light-emitting diodes, transistors, and others.

Background technique

The electrical contacts or electrodes of current electro-optical transducers and other devices are generally metal. Metals are deposited by evaporation or sputtering processes, which require expensive instrumentation and generally cumbersome processes.

Conductive polymers are a relatively new class of electronic materials, and here they are considered as a backup for electrode materials. These polymers combine the conductive properties of metals with the processing advantages of polymers.

Examples of conductive polymers we describe here include substituted and unsubstituted conductive polyaniline, polyparaphenylene, polyparaphenylene vinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyiso Thianthene, polyphenylene sulfide, polyacetylene, polypyridine vinylene, polyazine and their combinations and mixtures of their copolymers with other polymers and their monomers.

In order for these polymers to be used as electrodes for devices, they should preferably have suitable electrical conductivity and be easily patterned. In addition, these polymers preferably do not outgas so as not to contaminate the devices using them as electrical contacts. In addition, the conductive polymer is preferably photolithographically patternable. Preferably, the patterning neither causes a reduction in the conductivity of the polymer nor does it cause any degradation of the properties of the conductive polymer.

Therefore, it would be desirable to develop methods of patterning these polymers so that they can be applied to any conductive polymer system and do not negatively affect the conductive polymer, so that the patterned conductive polymer can be used as electrical contact of the device. It is also desirable that the properties of the conductive polymer be controllable so that the device does not outgas or foul.

Purpose of the invention

It is an object of the present invention to provide electronic devices with improved performance using conductive polymers.

It is an object of the present invention to provide patterns of conductive polymers and a method of making patterns. Specifically, the resist is patterned first, and then the resist pattern is transferred onto the conductive polymer. Once the pattern is transferred to the conductive polymer, the resist is removed.

It is an object of the present invention to provide a pattern of a conductive polymer using a resist applied to the conductive polymer. Specifically, the metal is patterned, the metal pattern is transferred to a conductive polymer, and the metal is removed.

Another object of the present invention is to provide a pattern of conductive polymers using a metal applied to the conductive polymer.

Another object of the present invention is to provide patterns of conductive polymers with high conductivity.

Another object of the present invention is to provide a pattern of a conductive polymer having high light transmission.

Another object of the present invention is to provide patterns of conductive polymers with good thermal stability.

Another object of the present invention is to provide a conductive polymer having high light transmission and high conductivity.

Another object of the present invention is to provide conductive polymers and patterns of conductive polymers that can be used as electrical contacts or electrodes.

Another object of the present invention is to provide conductive polymers and patterns of conductive polymers useful as electrical contacts or electrodes in electro-optic transducers and devices.

Another object of the present invention is to provide conductive polymers and patterns of conductive polymers useful as electrodes in liquid crystal displays.

Another object of the present invention is to provide a liquid crystal display composed of conductive polymer electrodes.

Another object of the present invention is to provide a liquid crystal display composed of conductive polymer electrodes and metal electrodes.

Another object of the present invention is to provide a liquid crystal display composed of conductive polymer electrodes and indium tin oxide electrodes.

Another object of the present invention is to provide an active matrix thin film transistor (TFT) liquid crystal display composed of one or more electrodes of a conductive polymer.

Another object of the present invention is to provide a liquid crystal display composed of one or more electrodes of a conductive polymer exhibiting good charge retention.

Another object of the present invention is to provide a liquid crystal display composed of electrodes of one or more conductive polymers exhibiting good light transmission/voltage characteristics.

Another object of the present invention is to provide a liquid crystal display composed of one or more electrodes of a conductive polymer exhibiting good image retention properties.

Another object of the present invention is to provide conductive polymers and patterns of conductive polymers that can be used as one or more electrodes in light emitting diodes.

Another object of the present invention is to provide organic or inorganic light-emitting diodes consisting of one or more electrodes of conducting polymers.

Another object of the present invention is to provide organic or inorganic light emitting diodes composed of one or more patterned electrodes of conductive polymers.

Another object of the present invention is to provide a light emitting diode having a hole injection region and/or an electron injection region formed of a conductive polymer.

Another object of the present invention is to provide conductive polymers and conductive polymers that can be used as electrical contacts of transistors, such as drain, source and gate electrodes in field effect transistor (FET) devices and contacts in bipolar transistors. graphics of objects.

Another object of the present invention is to provide patterns of conductive polymers which exhibit good electrical conductivity, good thermal stability, no outgassing and in some cases high light transmission.

Another object of the present invention is to provide a pattern of a conductive polymer obtained by applying a resist to the conductive polymer, wherein the resist is exposed and developed to form a pattern in the resist. The resist pattern is transferred to the conductive polymer by etching, and the resist is then removed.

Another broad aspect of the present invention is to provide patterns of conductive polymers obtained by applying metals to the surface of conductive polymers. The metal is patterned by applying a resist, which is exposed and developed. The resist pattern is transferred to the metal, and then the pattern is transferred to the conductive polymer by etching techniques.

Another broad aspect of the present invention is to provide the patterning of the conductive polymer by applying a patterned metal layer to the conductive polymer, etching the pattern into the conductive polymer and removing the metal.

A more specific aspect of the present invention is to provide thin film transistor switches for liquid crystal displays wherein one or more of the source, drain and gate electrodes are composed of a conductive polymer exhibiting good electrical conductivity and good thermal stability.

Another object of the present invention is to provide a light emitting diode composed of conductive polymer electrodes and metal electrodes.

Another object of the present invention is to provide conductive polymers and patterns of conductive polymers that can be used as one or more electrodes in light emitting diodes.

Another object of the present invention is to provide organic or inorganic light-emitting diodes consisting of one or more electrodes of conducting polymers.

Another object of the present invention is to provide organic or inorganic light emitting diodes composed of one or more patterned electrodes of conductive polymers.

Another object of the present invention is to provide light-emitting diodes composed of conductive polymers as hole-injecting electrodes or as electron-injecting layers.

Introduction to the invention

Accordingly, it is a broad aspect of the present invention to provide conductive polymers and patterned conductive polymers and methods of patterning the same.

A broad aspect of the present invention is to provide electronic devices having patterned conductive polymers that can provide electrical connections to the devices.

A broad aspect of the present invention is the disposition of patterned conductive polymers on electronic devices to provide electrical contacts to the devices.

Another broad aspect of the present invention is to provide patterns of conductive polymers which exhibit good electrical conductivity, good thermal stability, no outgassing and in some cases high light transmission.

Another broad aspect of the present invention is to provide a pattern of conductive polymer obtained by applying a resist to the conductive polymer, wherein the resist is exposed and developed, and the pattern is transferred to the conductive polymer by etching techniques, The resist is then removed.

Another broad aspect of the present invention is to provide patterns of conductive polymers obtained by applying metals to the surface of conductive polymers. The metal is patterned by applying a resist, where the resist is exposed and developed. The resist pattern is transferred to the metal, and then the pattern is transferred to the conductive polymer by etching techniques, and the metal is removed.

Another broad aspect of the present invention is to provide the patterning of the conductive polymer by applying a patterned metal layer to the conductive polymer, then etching the pattern into the conductive polymer and removing the metal.

Another broad aspect of the present invention is to provide conductive polymers and patterns of conductive polymers that can be used as electrical contacts for electrical-to-optical transducers and devices.

Another broad aspect of the present invention is to provide electro-optical transducers and devices having one or more conductive polymer electrodes.

A more specific aspect of the invention is to provide a liquid crystal display having one or more conductive polymer electrodes. In one embodiment a liquid crystal display has an indium tin oxide electrode and a conductive polymer electrode.

A more specific aspect of the present invention is to provide liquid crystal displays having one or more conductive polymer electrodes exhibiting high charge retention, good light transmission/voltage characteristics and good image retention properties.

A more specific aspect of the invention is an electronic device having an electroactive portion with a surface; the surface has a dielectric layer with a window thereon, the periphery of the window exposing the electroactive portion; on the dielectric layer A conductive polymer layer is provided; this conductive polymer layer is in electrical contact with the electroactive part through the window and covers the perimeter that should be provided on the dielectric layer.

Another more specific aspect of the present invention is the following liquid crystal display structure, which comprises: a first substrate; a second substrate; a liquid crystal layer disposed between the first substrate and the second substrate; One of the 1st and 2nd substrates is provided with a conductive polymer to provide a means for applying an electric potential across the liquid crystal layer.

Another more specific aspect of the invention is a field effect transistor having source, drain and gate electrodes, at least one of which electrodes is a patterned conductive polymer.

Another more specific aspect of the present invention is the following structure, which comprises: a substrate; a patterned conductive polymer gate disposed on the substrate; the gate is a conductive polymer; a gate disposed on the patterned gate an insulating layer; a patterned source electrode disposed on the insulating layer; a patterned drain electrode disposed on the insulating layer; the patterned source electrode and the patterned drain electrode are formed of a conductive polymer; and the patterned source electrode and the patterned The drain electrode and the semiconductor material in the gate between the patterned source electrode and the patterned source electrode.

Another more specific aspect of the present invention is a light emitting diode comprising: a substrate, an anode structure, an electroluminescent region, and a cathode structure, wherein either the cathode structure or the anode structure is a conductive polymer.

Another more specific aspect of the present invention is an organic light emitting diode, which is composed of: a substrate, an anode, an organic electroluminescent layer and a cathode, and the anode or cathode in this structure is a conductive polymer.

Another more specific aspect of the invention is a method comprising: providing a substrate having a layer of conductive polymer material; disposing a resist layer on the layer of conductive polymer material; exposing the resist to an energy pattern; developing the radiation pattern patterned in the resist, which constitutes covered and uncovered areas comprising the conductive polymer; removing the conductive polymer from the uncovered areas, and removing the resist to leave areas of the conductive polymer graphics.

Another more specific aspect of the present invention is a method comprising: providing a substrate having a layer of conductive polymer material; configuring the metal layer pattern through a metal mask forming a patterned metal layer on the conductive polymer layer, forming a conductive polymer area covered by the metal pattern and an uncovered area of the conductive polymer; etching the uncovered area to remove the exposed conductive polymer area; and removing the metal to obtain the conductive polymer pattern.

Another more specific aspect of the present invention is a method comprising: providing a substrate having a conductive polymer layer; disposing a metal layer on the conductive polymer layer; disposing a resist on the metal layer; exposing the radiation pattern to an agent; developing the radiation pattern patterned in the resist to obtain covered and uncovered regions of the metal film; removing the metal layer in the uncovered regions to obtain covered regions of the conductive polymer and uncovered areas; removing the uncovered areas of the conductive polymer; removing the resist; and removing the remainder of the metal layer to obtain a pattern of the conductive polymer.

Another more specific aspect of the present invention is a method comprising: providing a substrate having a layer of conductive polymer material; wherein the conductive polymer contains an energy sensitive component; exposing the conductive polymer to energy pattern exposure; and Unexposed areas; removing the conductive polymer in one of the exposed and unexposed areas to form a pattern of the conductive polymer on the substrate.

Brief introduction to the drawings

Further object of the present invention, feature and advantage will be clear by the following description of the present invention in conjunction with accompanying drawing, in the accompanying drawing:

Figure 1 is a schematic perspective view of an embodiment of a structure comprising a patterned conductive polymer according to the present invention.

Figure 2 is a schematic side view of another embodiment of a structure comprising a patterned conductive polymer according to the present invention.

Fig. 3 is a schematic diagram of a typical liquid crystal structure.

Fig. 4 is a schematic diagram of the working condition of the twisted nematic liquid crystal cell; when a voltage is applied in (a), the light transmittance of the liquid crystal cell is the largest, and when a voltage is applied in (b), the light transmittance of the liquid crystal cell is the minimum.

FIG. 5 is a schematic diagram of a typical active matrix TFT display.

FIG. 6 shows a top view of a unit cell of a TFT/LCD (Thin Film Transistor/Liquid Crystal Display) display.

FIG. 7 shows a schematic diagram of a cross-sectional view along line AA' of FIG. 6 .

FIG. 8 shows another sectional view along line AA' of FIG. 6 .

Fig. 9 shows a part of the assembled liquid crystal display.

Figure 10 shows a schematic cross-sectional view of a thin film transistor device in which one or more of the source, drain and gate electrodes are formed from a conductive polymer. The source and drain are placed directly on top of the gate insulator and then covered with a semiconductor.

Figure 11 shows a schematic cross-sectional view of a thin film transistor device in which one or more of the source, drain and gate electrodes are formed from a conductive polymer. The substrate conducts electricity and at the same time serves as a gate electrode. The source and drain electrodes are arranged directly on top of the insulator, after which they are covered with a semiconductor.

Figure 12 shows a schematic cross-sectional view of a thin film transistor device in which one or more of the source, drain and gate electrodes are formed from a conductive polymer. Source and drain electrodes are arranged directly on top of the semiconductor.

Figure 13 shows a schematic cross-sectional view of a thin film transistor device in which one or more of the source, drain and gate electrodes are formed from a conductive polymer. The substrate conducts electricity and at the same time serves as a gate electrode. Source and drain electrodes are disposed directly on the semiconductor.

FIG. 14 shows the relationship between the current flowing between the source and the drain of the TFT device with the structure shown in the schematic diagram of FIG. 11 versus the voltage gate electrode. The channel length L of the device is 100 microns, and the channel width is 1500 microns.

Figure 15 shows a top view of a typical layout of an active matrix liquid crystal display based on thin film transistor devices. One or more of the source, drain and gate electrodes are made of polymer.

Figure 16 shows a cross-sectional view of a pixel of an active matrix liquid crystal display based on thin film transistor devices having two different thin film transistor device configurations, Figure 16(a) and Figure 16(b). One or more of the source, drain and gate electrodes are made of conductive polymer.

Figure 17 shows a via contact hole through a passivation or insulating layer. The lower part is a conductive polymer. The upper layer can be the same material or a different conductive material, such as metal, or indium tin oxide.

Fig. 18 shows the OLED (Organic Light Emitting Diode) structure in the prior art, which is fabricated on a glass substrate, the upper cathode is opaque, and light can only be emitted from the glass side.

Fig. 19 schematically shows the light emitting diode structure of the present invention with a transparent (or opaque) cathode.

Figure 20 schematically shows an array of LEDs for displaying images, Figure 20A is a passive matrix with one LED at the intersection of each row and column, and Figure 20B is a passive matrix with one LED at the intersection of each row and column The active matrix of the regulation circuit.

FIG. 21 shows a patterning process of a conductive polymer when a resist is used on the surface of the conductive polymer. The resist is exposed and developed; the image is transferred to the conductive polymer; the resist is removed.

Figure 22 shows the patterning process of a conductive polymer when a patterned metal layer is applied to the surface of the conductive polymer through a metal mask. The image is transferred to a conductive polymer, after which the metal is removed.

Figure 23 shows the patterning process of a conductive polymer when a cover metal layer is applied on the conductive polymer. The metal is patterned with resist; the image is transferred first to the metal and then to the conductive polymer by etching; the remaining resist and metal are removed.

Figure 24 shows the patterning process when exposing the conducting polymer directly to radiation; the polymer is then developed to remove easily soluble areas.

Figures 25 and 26 show conductive polyaniline wires of around 10 [mu]m formed using a resist on the conductive polymer surface.

The conductive polyaniline wires shown in Figures 27 and 28 were fabricated using metal deposited on a conductive polymer surface through a metal mask.

The conductive polyaniline wires shown in Figures 29, 30 and 31 were fabricated using a capping metal deposited on a conductive polymer surface by imaging with a resist.

Figure 32 shows the transmission spectrum of a polyaniline film at 500 Angstroms.

Fig. 33 shows a characteristic curve of light transmittance versus voltage for a liquid crystal display with two polyaniline electrodes.

Fig. 34 shows a characteristic curve of brightness (transmittance) versus voltage for a liquid crystal display with two ITO electrodes.

Figure 35 shows the voltage versus time curve for a liquid crystal display with polyaniline electrodes. Charge retention is over 95%.

41 and 42 are schematic illustrations of a junction between a non-polymeric electrical conductor and a polymeric electrical conductor.

Figure 43 is a schematic diagram of a bipolar transistor with electrodes according to the invention.

Detailed description of the invention

The object of the present invention is a device using conductive polymers including substituted and unsubstituted polyaniline, polyparaphenylene, polyparaphenylene vinylene, polythiophene, polypyrrole, polyfuran, Polyselenophenes, polyisothiadenes, polyphenylene sulfides, polyacetylenes, polypyridine vinylenes and their combinations and their copolymers with other polymers and their monomers. It has been found that these polymers can be patterned by photolithography to form conductive patterns that can be used as electrodes or electrical contacts in various electrical-to-optical transducers and devices. Still another object of the invention are electro-optic transducers and devices consisting of one or more conductive polymer electrodes.

FIG. 1 is a schematic perspective view of a substrate 200 having a patterned conductive polymer 202 deposited thereon. Conductive polymer 202 forms electrical contact to surface 204 of substrate 200 along at least a portion of interface 106 between conductive polymer 202 and surface 204 . Pattern 102 may electrically connect a number of electronic devices formed over substrate 100 .

FIG. 2 is a schematic side view of a substrate 208 having a dielectric layer 210 on a surface 212 thereof. The dielectric layer 210 has a via hole 214 therein, and a patterned conductive polymer 216 disposed on the dielectric layer 110 for filling the via hole 114 so as to contact the surface 118 of the substrate 108 . Examples of some useful devices on which the present invention may be used are liquid crystal displays (LCDs), transistors (bipolar and field effect transistors), light emitting diodes, and the like.

Liquid crystal display device

Liquid crystal based electro-optical transducers are now a modern technology for the production of flat panel displays, especially for portable electronic devices. This technology is expected to continue to dominate in the future as the industry moves towards large area displays.

A typical liquid crystal (twisted nematic) cell is shown in Figure 3. In this device, nematic liquid crystals are placed between two glass plates separated by an average distance of 5-20 μm. A transparent electrode, indium tin oxide, is deposited on the surface of the glass sheet. An alignment layer is deposited on the indium tin oxide, and the alignment layer is subjected to rubbing treatment so that the alignment direction of the nematic liquid crystal is parallel to the rubbing direction. If the rubbing directions of the two alignment layers are at an angle of 90° to each other, the liquid crystal takes a twisted structure as shown in Figure 4a. If polarized light is incident on the cell, the plane of polarization will follow the twist of the molecules and turn 90° as it passes through the cell. If the second polarizer placed at the other end of the liquid crystal cell is also rotated 90° relative to the first polarizer, the light will pass through the liquid crystal cell. When a voltage is applied to the liquid crystal cell, an electric field is generated between the two ends of the liquid crystal cell. The liquid crystal molecules will be oriented according to the electric field (Fig. 4b) and destroy the twisted state. At this time, the direction of the polarizer encountered by the incident light is crossed, so no light passes through the liquid crystal cell. Liquid crystal cells are described in US Patent 5,623,514, the contents of which are incorporated herein by reference.

There are different types of liquid crystal displays, including passive and active matrix displays. Active matrix displays can be composed of two terminal devices such as diode rings, back-to-back diodes (reverse diodes) and metal-insulator-metal devices. The composition of the active matrix display can also be three terminal devices, such as thin film transistors, the materials of which are polysilicon, amorphous silicon, amorphous germanium, cadmium selenide and so on.

Another technology that is being intensively researched and developed due to its future application potential in flat-panel displays is light-emitting diodes, especially light-emitting diodes with organic materials as the electroluminescent layer. The composition of the light emitting diode includes an injection electrode, an electroluminescent layer and an electron injection electrode. The most commonly used hole injection electrode is indium tin oxide.

Today, the vast majority of flat-panel displays are manufactured using active-matrix liquid crystals based on thin-film transistors. One of the most troublesome processes in the manufacture of liquid crystal cells is the deposition and patterning of indium tin oxide electrodes. Indium tin oxide needs to be deposited first using an evaporation process. It must then be annealed at high temperature for several hours. A photoresist is then applied to pattern the indium tin oxide. The photoresist is exposed and developed. The pattern is transferred to ITO by etching. The etching solution is a strong acid mixture. Indium tin oxide is typically deposited either before or after the thin film transistor layers are deposited. In the latter case, the indium tin oxide etching solution can cause defects in thin film transistor devices.

Therefore, it would be better to develop a new electrode material that is simple to handle compared to ITO, and at the same time has high light transmission, good electrical conductivity, good environmental and thermal stability, is easy to pattern using photolithography, and It has good liquid crystal display properties, such as high charge retention, low image retention, and good light transmission/voltage characteristics. It would also be desirable to develop better electrode materials and electrical contacts for light-emitting diodes and other devices.

Conductive polymers are a relatively new class of electronic materials and can be considered as potential candidates for electrode materials. Such polymers have the potential to combine the electrical properties of metals with the usual processing advantages of polymers. Here we introduce substituted and unsubstituted conductive polyaniline, polyparaphenylene, polyazine, polyparaphenylene vinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyisothianaphne, poly Phenylene sulfide, polyacetylene, polypyridine vinylene and their combinations and mixtures of their copolymers with other polymers and their monomers.

In order to use these polymers as a substitute for ITO or as a general electrode, these polymers must have suitable electrical conductivity, easy patterning and high light transmittance in some occasions. In addition, these polymers should not outgas, which would cause device contamination. Outgassing of conductive polymers in liquid crystal display cells can significantly reduce the charge retention of the display. In addition, conductive polymers need to be easily patterned by photolithography. Patterning should not reduce the conductivity of the conductive polymer, nor should it cause any degradation in the properties of the conductive polymer. So, it would be desirable to develop a method to pattern these polymers, ideally one that can be used with any conducting polymer system and not negatively affect the performance of the conducting polymer.

One potential conductive polymer that can be used as a conductive electrode is polyaniline. Polyaniline (and other conductive polymers) are a family of polymers described in US Patents USP 5,198,153, USP 5,200,112 and USP 5,202,061, entitled "Conductive Polymer Materials and Uses Thereof", which are hereby incorporated by reference.

In order to consider using a conductive polymer such as polyaniline as a conductive electrode of, for example, a liquid crystal display, the polymer preferably exhibits certain properties. As an example, the description of the present invention will take polyaniline as an example, but the present invention is not limited to the use of polyaniline. These properties include:

1. Preferably the conductive polymer has greater than 80% transparency in the visible region, while still exhibiting sufficient electrical conductivity and contact resistance to the device metallurgy.

2. Preferably exhibit good solubility and form a uniform coating. The coating should ideally be free of grains, streaks and obvious pinholes or defects.

3. It is best to be compatible with the alignment layer deposited on the top of the conductive electrode; the solvent used to deposit the alignment layer (polyimide in most cases) should not dissolve polyaniline, and no serious interfacial mixing , and will not extract any dopant ions from polyaniline. The extraction of doping ions will cause the conductivity of polyaniline to decrease and the doping ions may be added to the alignment layer and eventually enter the liquid crystal, thereby destroying the performance of the liquid crystal cell.

4. Preferably the thermal stability of the polymer is capable of maintaining temperatures up to at least 150°C.

5. Preferably the polymer does not exhibit outgassing, as any outgassing will lead to ion contamination into the liquid crystal and damage the performance of the liquid crystal cell.

6. Preferably the polymer provides good step coverage.

7. Preferably the polymer can be patterned without strong etchant.

In addition to the above-mentioned polymer properties, it is also important that a liquid crystal cell made of polyaniline should have certain properties. These properties include:

1. Good light transmittance and voltage relationship characteristics.

2. Good charge retention at room temperature and high temperature.

3. No image residue at room temperature and high temperature.

It was not obvious that a conductive polymer, such as polyaniline, could be used in such an application and yield the above properties. Polyaniline is known to conduct electricity by reacting a non-conductive form of the polymer (the base) with an acid, such as hydrochloric acid, to form a conductive salt. This is described in the article by A.G. MacDiamid and A.J. Epstein published in Farad. Discuss. Chem. Soc., 88, 317. The structure of the conductive form contains delocalized polymeric radical cations that can be neutralized by an anionic counterion, application No. 08/370,127, filed January 9, 1995, entitled "Deaggregation of Conductive Polymers and Their Precursors" are described in the U.S. Patent, which is incorporated herein by reference.

Ions are needed for a material to be a conductor. It is well known that the presence of ions in liquid crystal panels will result in reduced charge retention and poor image retention, as described in the article "Charge Carriers and Display Parameters" published by H. Seiberle, M. Schadt in SID'92 Digest, 25 (1992). The effect on the performance of passive and actively addressable LCDs" is described. This is one of the greatest concerns when using polyaniline. The use of HCL acid as a dopant results in volatile mobile ions. The outgassing of HCL from polyaniline films was actually observed at temperatures as low as 40-50°C. This outgassing can destroy the performance of liquid crystals (LCs), as ions migrate into the liquid crystals. Surprisingly, we found here that polyaniline can be modified to obtain doped polymers. This doped polymer does not migrate into liquid crystals at room temperature or at high temperatures. As a result, liquid crystals The display can have excellent charge retention and image persistence.

Another concern about ions is that when the polyimide alignment layer is deposited on top of the polyaniline electrode, the solvent used for polyimide is usually a highly polar solvent, such as NMP (N-methylpyrrolidone) or gamma-butyrolactone, both of which are fairly highly polar solvents, will extract dopant ions from polyaniline and allow these ions to migrate into the alignment layer and liquid crystal. This in turn destroys the performance of the display. In addition, the extraction of these ions will reduce the conductivity of polyaniline. Quite surprisingly, it has been found that polyimide alignment layers are quite compatible with polyaniline and that no ion leaching occurs.

The polyaniline preferably provides good light transmission while exhibiting sufficient surface resistance and contact resistance to the underlying data metal lines. The light transmittance of polyaniline can be adjusted by reducing the thickness, but at the same time, the surface resistance of the material will increase. The materials we describe here exhibit good light transmission, good surface resistance and good contact resistance to metals.

Polyaniline is preferred to provide good step coverage. This is a big problem when using indium tin oxide. Indium tin oxide is used as a transparent conductive electrode in a typical thin film transistor device structure. Indium tin oxide is deposited by sputtering and photolithographically patterned using common photoresist systems. It is then etched using a hot solution of a mixture of concentrated nitric acid and hydrochloric acid. Generally, ITO is deposited before or after the thin film transistor layer and passivation layer are deposited. The latter is generally used to reduce the number of photolithographic masking steps. In this case, via holes are formed in the passivation layer to provide the ITO layer with a connection to the source/drain metal of the underlying thin film transistor device. If the passivation layer is too thick, there is a problem of step coverage of ITO to the via hole, because ITO is deposited by a sputtering process. On the other hand, when the passivation layer is thin, pinholes generally exist, and the ITO etchant may cause defects in TFT devices or bus lines. Polyaniline will be deposited by spin coating or roll coating process. Good step coverage is thus provided. Polyaniline also does not require strong etchants for patterning.

Although the invention is applicable to a wide variety of devices, it is presented by way of embodiment of active liquid crystal displays, and is particularly directed to thin film transistor liquid crystal displays. As shown in FIG. 5 , a common thin film transistor device display 10 consists of an array of liquid crystal cells or A, and each liquid crystal cell contains a thin film transistor 11 for addressing the liquid crystal cell by applying a voltage to the liquid crystal cell when the transistor is turned on. and a capacitor 12 to maintain the voltage when the transistor is off. Transistors are formed on the glass substrate 13 on the back of the display 10 and are connected between the column data electrodes 14 and the row electrodes 15 and to the transparent display electrodes 16 of each pixel, all on the back of the display 10 . The front side of the display is formed by means of a continuous transparent common electrode 17 which is separated from and parallel to the transparent display electrode 16 . Both electrode 17 and display electrode 16 are preferably formed using a thin conductive transparent material, such as indium tin oxide, carried on a glass substrate. Since the display electrode 16 of each pixel is smaller in size than the continuous common electrode 17, when a voltage is applied across the electrodes, a stray field is produced extending from the pixel or cell edge of the display electrode outward to the common electrode. The polarizing plate 19 parallel to the outer surface of the common electrode 17 and adjacent to the glass substrate 18 and the polarizing plate 20 provided in the back of the rear glass substrate 13 are properly oriented relative to each other. Alignment layers 21 and 22 are disposed on the inner surfaces of the display and common electrodes 16 and 17 respectively, and are in contact with the liquid crystal layer with twisted nematic liquid crystal molecules therein. Between the glass substrates 1 and 18 mounted in parallel. A visible light source (not shown) at the back of the display is directed onto the display 10 through a diffuser. If display 10 needs to be colored, a color filter 25 can be configured on the alignment layer side of common electrode 17, and it includes 3 primary colors (red, green and blue) groups, each of which is associated with a 3 primary colors. Groups of adjacent pixels A are connected to form a color liquid crystal cell.

The function of the patterned conductive polymer (i.e. polyaniline) in the manufactured liquid crystal cell is to be used as the transparent electrode 16 of each pixel unit in the display 10, and the function of the above-mentioned indium tin oxide is to be used as the continuous transparent electrode 17 . Furthermore, a liquid crystal cell was fabricated in which a patterned conductive polymer was used as the transparent electrode 16 and a continuous coating of the conductive polymer was used as the continuous transparent electrode 17 . A conductive polymer is also used as the continuous transparent electrode 17 and patterned indium tin oxide can be used as the pixel electrode 16 .

FIG. 6 shows a top view of a cell structure of a TFT/LCD (Thin Film Transistor/Liquid Crystal Display) display. 101 and 102 are data buses, and 103 and 104 are gate buses. 106 , 107 and 108 form a thin film transistor, wherein 108 is a protrusion of 104 , and 106 is a protrusion of 101 . 106 is a source electrode, and 107 is a drain electrode. 106 and 107 are usually made of the same conductive material, such as metal. 105 is a transparent pixel electrode, which is made of conductive polymer by means of photolithography. The pixel electrode 105, the upper electrode on the color filter side (not shown) and the liquid crystal (not shown) in between form a pixel capacitor. 130 is an extension of 105. 130 and 103 are separated by an insulator layer (not shown) and form a storage capacitor. When a suitable high voltage is applied to the gate bus 104, the thin film transistor device is turned on. Thus, the pixel capacitor and storage capacitor are charged from the data bus 101 through the thin film transistor device to the design voltage that determines the electro-optical properties of the liquid crystal in the pixel. Thus, the design image is obtained for the display. Two cross-sectional structural views along the line A-A' are shown in FIGS. 7 and 8 . In Figures 7 and 8, 106 is a source electrode, 107 is a drain electrode, 108 is a gate electrode, 109 is a gate insulating layer, 110 is an amorphous silicon layer, 111 is an n+ amorphous silicon layer, 112 is a passivation layer, and 105 is pixel electrodes. In FIG. 8, on top of the passivation layer 112 there is another layer 113 which is a low dielectric transparent polymer layer. The pixel electrode layer 105 is placed on top of 113 so that the pixel electrode can extend above the data bus to increase the aperture ratio of the pixel. In FIG. 7, a part of the pixel electrodes 105 and 107 is directly covered. In FIG. 8, this overlay is through via holes in the polymer layer 113. In FIG. Fig. 9 shows a part of the assembled liquid crystal display. 120 is a glass substrate. 121 is a color filter layer. 122 is a conductive transparent electrode layer. 122 may be an indium tin oxide layer or a transparent conductive polymer layer. 123 is a transfer pad, which is connected to the electrode sheet (not shown) used to be fixed to the driving electronic circuit through the fin. 123 is made of metal layers. 124 is conductive epoxy resin, which is electrically connected with 122 and 123. Thus, 122 can be connected via 124 and 123 to the drive electronics. 125 is a liquid crystal layer. All metallic and conductive layers in Figures 6-9 can be replaced by conductive polymers according to the invention.

thin film transistor device

The electrical contacts or electrodes in today's thin film transistor devices are metals. Metals are deposited by evaporation or sputtering processes, which require expensive instrumentation.

Suitable polymers include substituted and unsubstituted conductive polyanilines, polyparaphenylenes, polyparaphenylene vinylenes, polythiophenes, polyfurans, polypyrroles, polyselenophenes, polyisothiadenes, polyphenylenes Thioethers, polyacetylenes, polyazines, polypyridylvinylidenes and their combinations and their copolymers with other polymers and their monomers.

In order for these polymers to be used as contact electrodes of thin film transistors, they preferably have suitable conductivity and are easy to pattern. In addition, these polymers preferably do not outgas to avoid contamination of devices in use. In addition, the conductive polymer is preferably photolithographically patternable. Preferably, the patterning neither causes a reduction in the conductivity of the polymer nor does it cause any degradation of the properties of the conductive polymer.

Therefore, it would be desirable to develop a method for patterning these polymers, ideally one that can be applied to any conducting polymer system and that does not negatively impact the conducting polymer.

型共轭聚合物作为半导体层的薄膜晶体管器件中的源极和漏极之中的至少一个先前已经介绍过(H.Koezuka，A.Tsumura，T.Ando，美国专利No.5,107,308)。在本专利中栅极始终是由金属构成。此外，每当薄膜晶体管器件中的漏电极中的一个是导电聚合物薄膜时，这一薄膜就具有图形化的金属引线。所使用的导电聚合物生长法为电化学聚合。尽管上述专利的作者总地描述了另一种可用来形成导电聚合物电极的方法，他们对如何使导电聚合物层图形化成为所要求的源极和/或漏极电极的形状和在电极之间形成晶体管沟道的问题未提供任何解决办法。在本发明申请中我们提出了采用导电聚合物作为薄膜晶体管器件的一个或多个源极，漏极和栅极电极的器件及使导电聚合物层图形化的途径。Using conductive polymer electrodes as different

Type conjugated polymers as at least one of the source and drain in thin film transistor devices have been described previously (H. Koezuka, A. Tsumura, T. Ando, US Patent No. 5,107,308). In this patent the gate is always made of metal. Furthermore, whenever one of the drain electrodes in a thin film transistor device is a conductive polymer film, this film has patterned metal leads. The conductive polymer growth method used was electrochemical polymerization. Although the authors of the above patents generally describe another method that can be used to form conductive polymer electrodes, they have no idea how to pattern the conductive polymer layer into the desired shape of the source and/or drain electrodes and between the electrodes. does not provide any solution to the problem of forming transistor channels between them. In the present application we propose devices employing conductive polymers as one or more source, drain and gate electrodes of thin film transistor devices and approaches to patterning conductive polymer layers.

Another object of the present invention is a thin film transistor device in which one or more of the source, drain and gate electrodes is composed of a conductive polymer. 10 to 13 show the configuration of a thin film transistor device.

FIG. 10 shows a device fabricated on a substrate 61 . A patterned conductive polymer gate electrode 62 is disposed on the substrate 61 . The insulating layer 63 is disposed on the gate electrode 62 . Two electrodes, a source electrode 65 and a drain electrode 66 made of conductive polymer, are arranged on the gate insulating layer 63 and patterned. The semiconductor layer 64 is arranged on the source electrode 65 and the drain electrode 66 electrodes and a part of the gate insulating layer 63 .

FIG. 11 differs from FIG. 10 in that the substrate 61 is conductive and serves as the gate 61 . A specific but non-limiting example of such a structure is to use a heavily doped substrate as the substrate/gate electrodes (61 and 62) and thermally grown oxide 63 as an insulating layer thereon. Other layers are the same as those in FIG. 10 .

The difference between FIG. 12 and FIG. 10 is that the source electrode 65 and the drain electrode 66 are disposed above the semiconductor layer 64, which was previously disposed above the gate insulating layer.

The difference between FIG. 13 and FIG. 10 is that the source electrode 65 and the drain electrode 66 are disposed above the semiconductor layer 64, which was previously disposed above the gate insulating layer.

FIG. 14 shows the relationship between the current flowing between the source and the drain of the TFT device with the structure shown in the schematic diagram of FIG. 11 versus the gate electrode voltage. The channel length, L, of this device was 100 microns, and the channel width was 1500 microns.

Figure 15 shows a top view of a typical structure of an active matrix liquid crystal display based on thin film transistor devices. One or more of the source, drain and gate electrodes are made of polymer.

FIG. 16 shows a cross-sectional view of a pixel of a TFT device-based active matrix liquid crystal display having two different TFT device configurations, FIG. 16(a) and FIG. 16(b). One or more of the source, drain and gate electrodes are made of conductive polymer.

Figure 17 shows a via contact hole through a passivation or insulating layer. The lower part is a conductive polymer. The upper layer can be the same material or a different conductive material such as metal, conductive polymer or indium tin oxide.

Light Emitting Diode Devices

Patterned conductive polymers can also be used to produce electroluminescent diodes. More particularly, the present invention relates to transparent cathode and anode structures for light emitting diodes, including organic light emitting diodes, which when fabricated on transparent substrates provide at least partially transparent displays and when fabricated on a Provides a display that can be viewed from the cathode side when on an opaque substrate. The invention is applicable to light-emitting diodes with organic and inorganic electroluminescent regions. The description of the present invention will refer to organic light emitting diodes, but is not limited to organic light emitting diodes.

OLEDs described in previous work were fabricated on glass substrates and their lower electrodes were transparent conductors such as indium tin oxide. The top electrode of this device is opaque, so the light emitted from the electroluminescent region can only be observed from the glass side. An exception is the structure recently reported by V. Bulovic et al. in Nature 380, 29 (1996), in which the cathode metal was thinned and partially transparent in the middle of the subsequent indium tin oxide deposition.

OLED displays on opaque substrates or OLED displays on transparent substrates require the upper electrode structure to meet the following criteria: (1) be transparent to the LED emission, (2) provide low series resistance to the LED active region current injection, (3) providing sufficiently high electrode plane lateral conductivity when such diodes form a two-dimensional array self-emissive display, (4) serving as a protective film to the underlying organic film that is susceptible to chemical and physical damage, and ( 5) It can be deposited in a benign manner without causing damage to the organic layer where it is deposited, so the integrity of the layer/electrode interface can be protected. The commonly used transparent electrode material that is often used as the anode of OLEDs is indium tin oxide, which can meet requirements 1-4, but because it is usually in an oxygen plasma environment that can damage the organic regions in the OLED device structure middle deposition, so (5) cannot be satisfied. The same is true for GaN used as an electrode. Criterion (5) is actually the most decisive, since although there are several transparent conductive materials, almost all of them involve plasma or high processing temperatures that cause irreversible damage to the organic light-emitting material.

What is needed is a transparent cathode and/or anode structure that is easy to fabricate and meets all of the above requirements.

Therefore, it would be desirable to develop new electrode materials that are simpler to process than ITO, but at the same time provide high light transmission, good electrical conductivity, environmental and thermal stability, and are easy to pattern by photolithography .

A typical light-emitting diode consists of a hole injection electrode, an electroluminescence layer, and an electron injection electrode. This is a basic structure. Sometimes a hole transport layer can be combined between the injection electrode and the electroluminescent layer to improve the mobility of holes and isolate holes. Also, an electron transport layer may also be included between the electroluminescence layer and the electron injection electrode.

The electroluminescence layer can be organic conjugated polymer, organic small molecule, such as AlQ material, or inorganic material, such as gallium arsenide. A typical hole injection electrode comprises indium tin oxide. Typical electron injection electrodes contain aluminum, calcium, etc.

The P-doped conducting polymers according to the invention can be used as hole-injection layers, and the M-doped conducting polymers according to the invention can be used as electron-injecting layers.

The structure of a prior art organic light emitting diode 300 is shown in FIG. 18 . The substrate 312 is glass, and a thin film of indium tin oxide 314 is deposited directly on the glass and forms the anode. In order to work efficiently, the organic region usually includes multiple layers, shown in FIG. The EL layer 320 is a metal chelate tris(8-quinolinolato)aluminum, (sometimes abbreviated as S or Alq3). The hole transport layer in this structure is an aromatic diamine. The metal alloy MgAg is deposited on the organic to form the cathode 322, which is opaque at a thickness greater than about 10 nm. Not shown is the hermetic seal that is sometimes used to protect the cathode from moisture.

The EL layer of the Figure 18 structure is a member of a group of organic materials known as molecular organics. These are sequentially deposited using an evaporation process. Polymers form another group of organic materials that exhibit electroluminescence and are usually applied by spin coating. Polymer OLEDs are also typically fabricated on a glass substrate with an indium tin oxide anode and have an opaque cathode (usually a low work function metal such as calcium), with the result that light can only be emitted from one side. They are also available with multiple layers of polymers to increase work efficiency.

One embodiment of the light emitting diode of the present invention is an organic light emitting diode with a transparent cathode 340 , the general structure of which is shown in FIG. 19 . If the OLED is formed on a glass substrate 332 or a plastic substrate with an indium tin oxide (or conductive polymer) anode 334, then light is emitted from both sides and the OLED is at least partially transparent . When a viewer looks at a display composed of such OLED arrays, he can not only focus on the image presented on the display, but also see the scene behind through the display. On the other hand, a display formed on an opaque substrate such as silicon and utilizing OLEDs with a transparent cathode would be viewable by looking at the light emitted from the cathode side. Fabrication of OLED displays on silicon is advantageous because devices and circuits can be formed before OLEDs are deposited on silicon, and devices and circuits can be used to fabricate active matrix displays with integrated driver circuits.

According to the present invention, the anode or cathode of a light emitting diode may be formed or covered by a protective layer of an abrasion and scratch resistant conductive polymer, as incorporated herein by reference. Light emitted from an OLED having a cross-section as shown in FIG. 19 is emitted from the top and bottom (ie, from both sides of the diode) because both the anode and the cathode are transparent.

The conductive polymers described here provide satisfactory cathode electrodes by meeting the requirements for transparency, vertical conductivity for low series resistance, formation of a protective film, and a damage-free deposition process. Application No. 08/193,926, both titled "Electrically Conductive and Abrasion/Scratch Resistant Polymeric Materials, Methods of Making and Using Themselves", on February 9 , 1994 and Application No. 08/476,141, filed June 7, 1995 in two US patent applications, the contents of which are incorporated herein by reference. Each requirement is considered separately below.

A display device is formed by fabricating a plurality of identical organic light emitting diodes on a monolithic substrate, and wherein the organic light emitting diodes are arranged in a two-dimensional array with means to control the light emission from each diode. Generally speaking, the image is formed by one wire on Fig. 20A (passive matrix approach), for example, with the selected row wire 490 at a positive voltage Vr, while all unselected row wires 492 are kept at ground potential . A voltage is applied to each column conductor 494, 496, where i is the column conductor index and up to the maximum column number. The forward bias on the OLEDs 498, 400 along the selected row conductor 490 is then equal to Vr-Vci and this voltage determines the amount of light emitted. All other OLEDs 402, 404 are reverse biased and therefore do not emit light.

For the array shown in Figure 20A, the OLEDs will only emit light when the row of wires is addressed, producing a flicker in high information content displays. This can be remedied by the array shown in Figure 20B (active matrix approach), where circuitry is included at each cross point to sample the column conductor voltage and hold the other row conductors being addressed. In this case, all diodes share a common cathode. Because these circuits need to be small and fast, it is most convenient to make them from single crystal silicon. In this second case, the substrate is opaque and a transparent cathode is required to view the image.

References cited herein are hereby incorporated by reference. US Patent Application No. 08/794,072, filed February 4, 1997, assigned to the assignee of the present invention, describes the structure and method of fabrication of organic light emitting diodes, the contents of which are incorporated herein by reference.

graphical method

In order to be able to serve as electrodes or electrical contacts, the conductive polymer is preferably patterned. Various methods are described here that can be used to pattern various conductive polymers.

These methods include applying a resist material to the surface of a conductive polymer. Resists can be negative or positive working and can be developed in aqueous or organic solvents. Examples of negative resists are polymethyl methacrylates, novolak/diazonaphthoquinone systems, tert-butoxycarbonyl-protected styrene polymers and their copolymers, tert-butyl-protected styrene Polymers and their copolymers, tert-butyl protected styrene polymers and their copolymers, other acrylate polymers and their copolymers that are easily deprotected by acids. These are just examples and are not limited to these. Examples of positive resists are epoxy-containing polymers, hydroxystyrene polymers with crosslinkers, and silicone polymers. These are just examples and are not limited to these. Expose the resist to given radiation such as UV/visible light, electron beam, X-ray and ion beam, and then develop it with a developer such as tetramethylammonium hydroxide aqueous solution, NaOH aqueous solution, KOH aqueous solution , Methyl isobutyl ketone, tetraethyl ammonium hydroxide aqueous solution, isopropanol, propylene, ethylene glycol methyl ether acetate, diglyme, methyl ethyl ketone and so on. These are just examples and are not limited to these. This resist image is then transferred to a conductive polymer by reactive ion etching (RIE), for example using oxygen, _CO2 , _SO2 , fluorine, etc. Once the image has been transferred to the conductive polymer, the remaining resist is removed, preferably with a solvent wash such as acetone, diglyme, isopropanol, etc. This scheme is shown in Figure 21. It is preferable that the solvent used to apply the resist and the developer of the resist and the developing conditions of the resist, and the solvent used to remove the resist do not degrade the properties of the conductive polymer, such as conductivity, transparency, etc. Photonity, thermal stability, etc., deterioration.

The second method of patterning the conductive polymer is to use the method of depositing metal on the surface of the conductive polymer, and the metal used includes aluminum, gold and the like. A patterned metal layer is deposited on the conductive polymer through a metal mask. This pattern is then transferred to a conductive polymer by reactive ion etching (RIE), such as oxygen, CO ₂ , SO ₂ , fluorine, etc. The metal is then etched away using acid solutions such as hydrochloric acid, hydrofluoric acid, acetic acid, sulfuric acid, perchloric acid, phosphoric acid, nitric acid, and any combination thereof. This scheme is shown in Figure 22. Preferably, the conditions during metal deposition and etching do not adversely affect the properties of the conductive polymer.

A third method for patterning conductive polymers is to deposit a capping metal on the surface of the conductive polymer, such as aluminum, gold, and the like. The metal is patterned with the aid of a resist. exposing the resist to radiation such as ultraviolet light, visible light, electron beam, x-ray, ion beam and developing with a developer similar to that described above, and by, for example, treating the metal with an acid solution as described above. Etching transfers the pattern onto the metal layer. This pattern is then transferred to a conductive polymer by reactive ion etching, such as oxygen, CO ₂ , SO ₂ , fluorine, etc. The resist is then removed using a solvent, followed by an acid etchant similar to that described above to remove the metal. This scheme is shown in Figure 23. It is desirable that the above-mentioned processing steps and the solvents used in these processing steps do not impair the properties of the conductive polymer.

A fourth method of patterning conductive polymers is direct exposure to radiation. Conductive polymers are radiation sensitive, so irradiation produces a difference in solubility between exposed and unexposed areas. The radiation can be electron beams, ion beams, and electromagnetic radiation (such as x-rays and light rays). In this case, the exposed areas of higher solubility can be removed by solvent washing, resulting in a directly conductive polymer pattern. Such an arrangement is shown in Figure 24 and, as described in US Patent No. 5,198,153, the contents of which are incorporated herein by reference.

In all of the above cases, radiation exposure can include electromagnetic radiation, such as X-rays and light of various wavelengths, and can include charged and uncharged particle beams, such as electron beams, ion beams and elementary particle beams.

Specific examples are as follows:

1. Polyaniline doped with acrylamidopropanesulfonic acid as described in U.S. Patent Application No. 08/595,853, filed February 2, 1996, which is incorporated herein by reference On the substrate, suitable solutions for use include n-methylpyrrolidone, m-cresol, dimethylpropyleneurea, dimethylsulfodimethylformamide, and the like. The thickness of the coating can be controlled by the concentration of the polymer in the solution and the spin speed. Typically 0.1% to 5% polymer solutions in a given solvent are used. The thickness of the coating is between 500 and 1000 Angstroms. The conductivity of the film is 1 to 150 S/cm (S/cm). The coated film was baked in an oven at 85°C for 5 minutes to remove remaining solvent. On this polyaniline surface a usual Shipley photolithographic resist (MP1808) was applied. The resist was baked at 85°C for 30 minutes. The resist-coated polyaniline substrate was then exposed to UV light at a dose of 70 mj. It was then developed in an aqueous alkaline Micropos CD-30 developer solution. Since alkaline developers can dedope polyaniline and make it less conductive, it is best to closely control the developer and development time. In this case, the developer concentration may be diluted 50% with deionized water. The resist was developed for 30 seconds followed by rinsing with water. The developed resist was then cured at 1 °C for 30 minutes to harden the resist prior to image transfer. The resist image was then transferred onto the polyaniline by means of oxygen reactive ion etching. Etching of polyaniline was carried out in a reactive ion etcher using an RF (radio frequency) power load of 150 watts at a pressure of 100 millitorr and 20 sccm (standard cubic centimeters per minute) of oxygen in a reactive ion etcher. After image transfer, the remaining photolithographic resist was washed away with acetone. A 10 micron conductive polyaniline wire made in this manner is shown in FIGS. 25 and 26 . After measurement, it was found that the conductivity of the polyaniline pattern was similar to the initial conductivity. In other words, this process results in no appreciable reduction in conductivity. Other properties including light transmission, thermal stability and overall environmental chemical stability were also evaluated and are discussed below.

2. Dissolve poly(3-butylthiophene-2,5-diyl) in an appropriate solvent (such as tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, etc.) and spin coat it on a glass plate . The film was then exposed to an iodine chamber to dope the polythiophene. The doped sample is then pumped under dynamic vacuum. The resulting conductivity was 1000 to 2000 S/cm. This film was patterned using Shipley photoresist MP1808 as used above for polyaniline.

3. Poly(3-hexylthiophene-2,5-diyl) was dissolved, coated and doped as above and patterned as in Example 1 above.

4. The poly(3-octylthiophene-2,5-diyl) was processed and patterned as above.

5. Polypyrrole was deposited on a glass plate as follows. Pyrrole monomer (0.045M) was dissolved in 500 ml of water. In a second beaker dissolve the oxidant _FeCl3 (.015M) in 500 mL of water. Then (.015M) 5-sulfosalicylic acid and (.015M) 5-anthraquinone-2-sulfonic acid sodium salt were added to the oxidizer solution. Immerse the masked glass plate on one side into the monomer solution. The oxidant solution is then added to the monomer solution. The solution was allowed to react for 10 to 30 minutes to allow the monomer to polymerize and deposit on the glass plate. The thickness of the conductive polypyrrole deposited on the glass plate depends on the time the glass plate is left in the polymerization bath. Polypyrrole has an electrical conductivity of about 200 S/m. The polypyrrole deposited on the glass plate was then patterned by means of the above-mentioned resist.

6. Spin-coat polyaniline doped with acrylamidopropanesulfonic acid onto a glass plate. Evaporate a 300 angstrom layer of capping aluminum on the polyaniline. A 2.0 micron thick resist based on Shipley polypropylene glycol ether acetate solvent was applied to the aluminum. This resist was exposed to a dose of 150 mj of UV light and developed with a 50/50 mixture of Microposit developer concentrate and deionized water. After development, the resist was baked at 85°C for 30 minutes. The patterns were then transferred to the aluminum by etching the aluminum at room temperature with a Transene aluminum etch solution consisting of 80% phosphoric acid, 5% acetic acid, 5% nitric acid and 10% water. The etch rate was 4.19 Angstroms/sec. The pattern was in turn transferred to the polyaniline by oxygen reactive ion etching at a rate of 39 angstroms/second by applying a power load of 150 watts at a pressure of 100 mTorr and 20 sccm (standard cubic centimeters per minute) of oxygen. Another way to transfer graphics to polyaniline is to etch aluminum at 30°C. Both aluminum and polyaniline were etched by the acid solution at elevated temperatures with an etch rate of 37 Angstroms/sec. The remaining resist was removed by washing with acetone. The remaining aluminum can be removed by diluting 25% dilute hydrochloric acid solution. Figures 27, 28 and 29 show conductive polyaniline patterned in this way.

7. The substituted polythiophenes and in situ polymerized polypyrroles described above were also patterned with aluminum covering metal as described above for polyaniline.

8. Polyaniline acrylamidopropanesulfonic acid deposited on one side of the glass. On this surface an aluminum wiring pattern is deposited through a metal mask. This pattern was transferred to polyaniline by means of oxygen reactive ion etching. The rest of the aluminum is then etched away with dilute hydrochloric acid solution. This approach is ideal due to its sizeable nature. In this way a 50 micron polyaniline wire as shown in Figures 30 and 31 can be fabricated.

9. Substituted thiophenes and polypyrroles polymerized in situ can also be patterned in this way.

10. Polyaniline acrylamidopropanesulfonic acid can be directly patterned by exposing the film to radiation such as electron beam. After irradiation, the polymer becomes insoluble by crosslinking. The unexposed areas can be washed out with a solvent to form a pattern of conductive polyaniline.

Conductive polymers can be applied to the substrate by spin coating, dip coating, roll coating, spray coating, or can be chemically or electrochemically polymerized on the surface in situ.

In order to make the conductive polymer applicable to liquid crystal displays, the light transmittance of the film is preferably greater than 80% in the visible region. Figure 32 shows the light transmission of polyaniline acrylamidopropanesulfonic acid (overlay and patterned wires). As can be seen from the figure, as a 500 Angstrom film, the polymer exhibits greater than 90% transmittance throughout the visible region. This is consistent with the typical light transmission of annealed ITO. The electrical conductivity of the polyaniline wire is about 100 S/m, preferably greater than 100 S/m. The material exhibits environmental stability, with no change in electrical conductivity over time in air. The material exhibits thermal stability at 150 °C.

Because the performance of the material is good, a liquid crystal cell is assembled. One of the two electrodes of the liquid crystal cell is made of conductive polymer such as polyaniline, while the other uses polyaniline for one electrode and indium tin oxide for the other electrode. Where polyaniline is used for both electrodes, one electrode consists of a patterned wire and the second electrode consists of a cover film. An alignment layer of polyimide (Nissan SE5210) was spin-coated on the polyaniline. The polyimide was cured at 125°C for 1 hour. The thickness of the film was 500 angstroms. The polyimide layer is then mechanically rubbed. The experimental liquid crystal cell was filled with Merck liquid crystal containing left-chiral reagent. The polarizer is attached to the outside of the glass with its transmission axis parallel to the rubbing direction. Thus, the right-hand 90° twisted nematic phase test plate was completed. The performance of this liquid crystal cell was measured. Fig. 33 shows the light transmittance/voltage characteristic curve of a liquid crystal cell composed of two polyaniline electrodes. This curve is consistent with the light transmittance/voltage characteristic curve ( FIG. 34 ) of the crystal composed of the indium tin oxide electrode. The degree of charge retention of the liquid crystal comprising polyaniline electrodes was 95% at room temperature (FIG. 35). This is also consistent with the degree of charge retention exhibited by liquid crystal cells composed of indium tin oxide electrodes. The image sticking properties of the liquid crystal cells were also well consistent.

41 shows a surface 411 of a substrate 413 with a material layer 415 arranged thereon and a material layer 417 arranged on the surface 411 in such a way that the material layer 417 covers the material layer 415 on a footprint 419 . Material 417 may be a conducting polymer according to the invention, while material 415 may be a non-polymer conducting material such as a metal or a semiconductor. Also, both regions 417 and 415 may also be conductive polymers.

FIG. 42 shows a surface 423 of a substrate 421 with material layers 425 and 427 , which adjoin with an interface 429 . Materials 425 and 427 may be conductive polymers or one of layers 425 and 427 may be a conductive polymer while the other is a non-polymer conductive material such as a metal or a semiconductor.

The structures of Figures 41 and 42 are readily fabricated using the patterning methods for conducting polymers described herein and using methods for patterning non-polymeric conductors known in the art.

Figure 43 schematically shows a bipolar transistor consisting of a substrate 802, a buried sub-collector 804, a lightly doped region 896, a base region 808, an emitter region 810, a dielectric layer 812 and an access sub-collector Highly doped region 814 of electrode 804 . The dielectric layer has a window 816 for connecting the emitter; a window 818 for connecting the base region and a window 820 for connecting the region 814 to connect the sub-collector 804 . Patterned conductors or electrodes 822, 824 and 826 provide contacts to the emitter, base and collector regions, respectively.

Electrodes 822, 824 and 826 may be formed from a conductive polymer according to the invention. The conductive polymer forms ohmic contacts connecting the active device regions 810 , 808 and 814 .

Examples of conductive polymers that can be used to realize the present invention are substituted and unsubstituted conductive polyparaphenylenes, polyparaphenylene vinylenes, polyanilines, polyazines, polythiophenes, polyphenylenes formed from their soluble precursors. P-phenylene sulfide, polyfuran, polypyrrole, polyselenophene, polyacetylene and their compositions and copolymers of monomers. The general molecular formulas of these polymers, the structures made using them, and their methods of use can be found in U.S. Patent No. 5,198,153 and 1994, filed February 9, pending application No. 08/193,926, to Angelopoulos et al. US Patent Application and copending US Patent Application No. 08/476,141, filed June 7, 1995, the contents of which are incorporated herein by reference.

Polyaniline-based conductive polymers have been introduced as the most promising and most suitable conductive polymers for wide commercial applications. The polymers have excellent environmental stability and offer simple one-step synthesis. A large number of soluble derivatives can be prepared. For example, we have previously disclosed a new family of water-soluble conductive polyanilines in US Patent 5,370,825, the contents of which are incorporated herein by reference.

The following U.S. patents describe resists useful in the practice of the present invention, the contents of which are incorporated herein by reference:

5,580,694，5,554,485，5,545,409，5,492,793，5,401,614，5,296,332，5,240,812，5,071,730，4,491,628，5,583,620，5,561,194，5,547,812，5,498,765，5,486,267，5,482,817，5,464,726，5,380,621，5,374,500，5,372,912，5,342,727，5,304,457，5,300,402，5,278,010，5,272,042，5,266,444， 5,198,153，5,164,278，5,102,772，5,098,816，5,059,512，5,055,439，5,047,568，5,045,431，5,026,624，5,019,481，4,940,651，4,939,070，4,931,379，4,822,245，4,800,152，4,760,013，4,551,418，5,338,818，5,322,765，5,250,395，4,613,398，4,552,833，5,457,005，5,422,223，5,338,818， 5,322,765，5,312,717，5,229,256，5,286,599，5,270,151，5,250,395，5,238,773，5,229,256，5,229,251，5,215,861，5,204,226，5,115,095，5,110,711，5,059,512，5,048,358，5,023,164，4,999,280，4,981,909，4,908,298，4,867,838，4,816,112，4,810,601，4,808,511，4,782,008，4,770,974， 4,693,960，4,692,205，4,665,006，4,657,845，4,613,398，4,603,195，4,601,913，4,599,243，4,552,833，4,507,331，4,493,855，4,464,460，4,430,153，4,307,179，4,307,178，5,362,599，4,397,937，5,567,569，5,342,727，5,294,680，5,273,856，4,980,264，4,942,108，4,880,722，4,853,315， 4,601,969，4,568,631，4,564,575，4,552,831，4,522,911，4,464,458，4,409,319，4,377,633，4,339,522，4,259,430，5,209,815，4,211,843，5,260,172，5,282,264，5,227,280，5,024,896，4,904,564，4,828,964，4,745,045，4,692,405，4,606,998，4,600,683，4,449,243，4,567,132，4,564,484， 4,562,091，4,539,222，4,493,855，4,456,675，4,359,522，4,289,573，4,284,706，4,238,559，4,224,361，4,212,935，4,204,009，5,091,103，5,124,927，5,378,511，5,366,757，4,590,094，4,886,727，5,268,260，5,391,464，5,115,090，5,114,826，4,886,734，4,568,601，4,678,850，4,543,319， 4,524,126, 4,497,891, 4,414,314, 4,414,059, 4,398,001, 4,389,482, 4,379,826, 4,379,833, 4,187,331.

Although the present invention has been described with respect to preferred embodiments, various modifications, changes and improvements can be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (131)

1. A structure comprising: Electronic devices having an electroactive portion with a surface; The surface has a dielectric layer with a window exposing the electroactive portion; the window has a perimeter; a conductive polymer layer disposed on the dielectric layer; The conductive polymer layer passes through the window and covers the perimeter disposed on the dielectric layer in electrical contact with the electroactive portion 2. The structure of claim 1, wherein said electronic device has a plurality of windows on said dielectric layer exposing a plurality of electroactive regions, said conductive polymer electrically contacting said plurality of electroactive regions; said A conductive polymer has portions that couple the contacts to the exposed plurality of electroactive regions. 3. The structure of claim 1, wherein said conductive polymer layer has a pattern. 4. The structure of claim 1, wherein said conductive material is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine , polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 5. A structure comprising: surface; a patterned conductive polymer layer deposited on said surface; at least a portion of the conductive polymer layer is in electrical contact with the surface; Other portions of the conductive polymer layer are not in electrical contact with the surface. 6. The structure of claim 5 further comprising a dielectric material disposed between said other portion and said surface. 7. The structure of claim 5, wherein said surface is selected from the group consisting of electrical conductors and semiconductors. 8. The structure of claim 7, wherein said semiconductor is formed of a material selected from the group consisting of organic materials and inorganic materials. 9. The structure of claim 7, wherein said electrical conductor is formed of a material selected from the group consisting of metal and polymer. 10. The structure of claim 1, wherein said electronic device is selected from the group consisting of a liquid crystal device, a transistor device, a light emitting device and a light absorbing device. 11. The structure of claim 10, wherein said transistors are selected from the group consisting of bipolar transistors and field effect transistors. 12. The structure of claim 10, wherein the light emitting device is a light emitting diode. 13. The structure of claim 10, wherein the light absorbing device is a charge coupled device. 14. A structure comprising: a conductive surface having a perimeter; a conductive polymer layer having a perimeter; The perimeter of the conductive surface has regions that are not aligned with the perimeter of the conductive polymer layer. 15. A liquid crystal display structure, comprising: 1st substrate; 2nd substrate; a liquid crystal layer disposed between the first substrate and the second substrate; At least one of said first and second substrates having a conductive polymer disposed thereon provides means for applying an electric potential across said liquid crystal layer. 16. The structure of claim 15, wherein said conductive material is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine , polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 17. The structure of claim 15, wherein said first substrate has a first conductive polymer layer disposed thereon and said second substrate has a second conductive polymer layer disposed thereon. 18. The structure of claim 15, wherein said conductive polymer layer is a continuous film. 19. The structure of claim 15, wherein said conductive polymer layer is patterned. 20. The structure of claim 17, wherein said first conductive polymer layer is a continuous film and said second conductive polymer layer is patterned. 21. The structure of claim 15, wherein one of said first substrate and said second substrate has a conductive polymer layer disposed thereon, and the other of said first substrate and second substrate It has an indium tin oxide layer disposed thereon. 22. The structure of claim 15, wherein said conductive polymer has a dopant. 23. The structure of claim 15, wherein said structure is a transparent structure. 24. The structure of claim 15, wherein said structure is a reflective structure. 25. The structure of claim 15, formed further comprising at least one polarizing layer and at least one liquid crystal alignment layer in contact with the liquid crystal layer. 26. The structure of claim 23, wherein both said first substrate and said second substrate are transparent to electromagnetic radiation. 27. The structure of claim 15, wherein one of said substrates is transparent to electromagnetic radiation and the other of said substrates is reflective of electromagnetic radiation. 28. The structure of claim 15, wherein said first substrate and said second substrate are formed of a material selected from the group consisting of glass, semiconductor and ceramic. 29. The structure of claim 15 wherein said first substrate is glass and said second substrate is a semiconductor. 30. The structure of claim 15, wherein said conductive polymer is transparent. 31. The structure of claim 27, wherein said reflective substrate further includes a circuit pattern thereon. 32. The structure of claim 31, wherein said circuit pattern comprises a patterned conductive polymer. 33. A liquid crystal display device, the composition of which comprises a conductive polymer. 34. A structure comprising: a first substrate having first and second opposing surfaces having a first conductive polymer layer disposed on said first surface thereof; a first alignment layer disposed on the conductive layer; a second substrate having first and second opposing surfaces, the surface having a second conductive polymer layer disposed on said first surface thereof, an alignment layer disposed on said second conductive layer; a first polarizing layer disposed on the second surface of the first substrate; a second polarizing layer disposed on the second surface of the second substrate; The first substrate is disposed adjacent to the second substrate such that the first alignment layer faces the second alignment layer; The sealing spacer between the first substrate and the second substrate forms a cavity between the sealing spacer and the first substrate and between the second substrate and the sealing spacer; The cavity is filled with liquid crystal material; At least one of the first and second conductive layers is a conductive polymer layer. 35. The liquid crystal display structure of claim 12, wherein the conductive material is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine , polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 36. A liquid crystal display structure comprising: A semiconductor substrate having a first surface and a second surface; a reflective layer on at least a portion of said first surface; a transparent surface disposed separately from said semiconductor substrate; a liquid crystal material disposed between the semiconductor and the transparent substrate; A conductive polymer layer disposed on at least one of the transparent substrate and the semiconductor substrate. 37. The structure of claim 36, wherein the conductive material is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, poly Furan, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 38. A structure comprising: Substrate; a patterned gate formed from a patterned conductive material disposed on the substrate; an insulating layer disposed on the patterned gate; a patterned source electrode disposed on the insulating layer; a patterned drain electrode disposed on the insulating layer; At least one of the patterned gate, the patterned source electrode and the patterned drain electrode is formed of a conductive polymer; The semiconductor material disposed between the patterned source electrode and the patterned drain electrode and disposed on the insulating layer. 39. The structure of claim 38, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 40. The structure of claim 38, wherein said semiconductor material is selected from the group consisting of organic materials and inorganic materials. 41. A structure comprising: conductive substrate; The substrate is a gate electrode; an insulating layer disposed on the substrate; a patterned source electrode disposed on the insulating layer; a patterned drain electrode disposed on the insulating layer; at least one of the source electrode and the drain electrode is formed of a conductive polymer; A semiconductor material disposed between the patterned source electrode and the patterned drain electrode and disposed on the gate. 42. The structure of claim 41, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 43. The structure of claim 41, wherein said semiconductor material is selected from the group consisting of organic materials and inorganic materials. 44. The structure of claim 41 wherein said substrate is selected from the group consisting of silicon, germanium and gallium arsenide. 45. A structure comprising: Substrate; a patterned gate configured on the substrate; The gate is a conductive material; an insulating layer disposed on the patterned gate; a semiconductor layer disposed on the insulating layer; a patterned source disposed on the semiconductor layer; a patterned drain disposed on the semiconductor layer; At least one of the patterned gate, the patterned source and the patterned drain is a conductive polymer. 46. The structure of claim 45, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 47. The structure of claim 45, wherein said semiconductor material is selected from the group consisting of organic materials and inorganic materials. 48. The structure of claim 47, wherein said semiconductor layer is selected from Si, Ge, G, Ar, and combinations thereof. 49. A structure comprising: conductive substrate; The substrate is a gate electrode; an insulating layer disposed on the gate; a semiconductor layer disposed on the insulating layer; a patterned source electrode disposed on the semiconductor layer; a patterned drain electrode disposed on the semiconductor layer; At least one of the gate, the patterned source and the patterned drain is a conductive polymer. 50. The structure of claim 49, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 51. The structure of claim 49, wherein said semiconductor material is selected from the group consisting of organic materials and inorganic materials. 52. A structure comprising: having an insulating layer on a side 1 and a side 2; a gate disposed on the first side of the insulating layer; a semiconductor layer disposed on the second side; a patterned source electrode configured in electrical contact with the semiconductor layer; a patterned drain electrode configured to contact the semiconductor layer; At least one of the patterned gate, the patterned source and the patterned drain is a conductive polymer. 53. The structure of claim 52, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 54. The structure of claim 53, wherein said semiconductor material is selected from the group consisting of organic materials and inorganic materials. 55. A structure comprising: a semiconductor layer selected from the group consisting of organic and inorganic semiconductors; a patterned conductive polymer layer disposed on the semiconductor layer; The patterned conductive layer forms an ohmic contact to the semiconductor layer. 56. The structure of claim 55, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 57. A structure comprising: Electroluminescence area; anode; cathode; At least one of the anode and cathode is a conductive polymer. 58. The structure of claim 58, wherein said conductive polymer is selected from the group consisting of hole injecting materials and electron injecting materials. 59. The structure of claim 58, wherein said conductive polymer is patterned. 60. A structure comprising: Electroluminescence area; hole injection region; Electron injection area; A conductive polymer providing electrical contact to at least one of the hole injection region and the electron injection region. 61. An organic light emitting diode comprising: a substrate, an anode structure, an electroluminescent region, and a cathode structure electrically coupled to at least one of said anode region and cathode region and protected by a wear and scratch resistant conductive polymer layer covered patterned conductive polymer. 62. The structure of claim 57, wherein said electroluminescent region is formed of a material selected from the group consisting of organic materials and inorganic materials. 63. The diode of claim 57, wherein the conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, Polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and mixtures of their copolymers with other polymers and their monomers are selected from a group of materials. 64. The diode of claim 60, wherein said electroluminescent region is formed of a material selected from the group consisting of organic materials and inorganic materials. 65. The diode of claim 61, wherein said electroluminescent region is formed of a material selected from the group consisting of organic materials and inorganic materials. 66. A light emitting diode comprised of a patterned conductive polymer. 67. The diode of claim 57 further comprising indium tin oxide. 68. The diode of claim 57, wherein said anode is a transparent conductor. 69. The diode of claim 57, wherein said conductor is indium tin oxide. 70. The diode of claim 57, wherein said electroluminescent region is formed from a single organic electroluminescent layer. 71. The diode of claim 57, wherein said electroluminescent region is formed from an organic stack comprising at least an electroluminescent layer and an electron transport layer, wherein said thin metal layer is in direct contact with the electron transport layer. 72. The diode of claim 57, further comprising a transparent substrate. 73. The diode of claim 72, wherein said substrate is translucent. 74. The diode of claim 72, wherein said substrate is opaque. 75. The diode of claim 74, wherein said material of said substrate is selected from the group consisting of glass, plastic and silicon. 76. The structure of claim 72, wherein said substrate is flexible. 77. An array of one or more organic light emitting diodes according to claim 57. 78. The array of claim 77 further comprising a single crystal substrate with electronic circuitry. 79. The array of claim 78, wherein said circuitry controls light emitted from said array. 80. A method comprising: providing a substrate having a layer of conductive polymer material; depositing a layer of energy sensitive material on said layer of conductive polymer material; exposing said resist to an energy pattern to form a pattern on said layer of energy sensitive material; developing said pattern patterned on said layer to obtain exposed and unexposed regions of said conductive polymer; removing the conductive polymer in the exposed areas; The resist is removed leaving the conductive polymer pattern on the substrate. 81. The method of claim 80, wherein said conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyacridine selected from a group of materials such as oxazine, polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and their mixtures with other polymers and their copolymers. 82. The method of claim 80, wherein said energy is selected from the group consisting of electromagnetic radiation, heat and particle beam. 83. The method of claim 80, wherein said developing is accomplished by removing regions of said resist exposed to said energy. 84. The method of claim 80, wherein said developing is accomplished by removing regions of said resist that were not exposed to said energy. 85. The method of claim 83, wherein said removing is accomplished by chemical dissolution. 86. The method of claim 84, wherein said removing is accomplished by chemical dissolution. 87. The method of claim 80, wherein said removing is accomplished by reactive ion etching. 88. A method comprising: providing a substrate having a layer of conductive polymer material; Depositing a pattern of a metal layer through a metal mask to form a patterned metal layer on the conductive polymer layer, forming an area of the conductive polymer covered by the metal pattern and an exposed area; etching the exposed area to remove the exposed area; The metal is removed. 89. The method of claim 88, wherein said conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyacridine selected from a group of materials such as oxazine, polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and their mixtures with other polymers and their copolymers. 90. The method of claim 89, wherein said mask is molybdenum and said metal is platinum. 91. The method of claim 89, wherein said etching is reactive ion etching. 92. The method of claim 89, wherein said exposed areas are removed using an acid. 93. A method comprising: providing a substrate having a layer of conductive polymer material; disposing a metal layer on the conductive polymer layer; disposing an energy sensitive material on the metal layer; exposing the energy-sensitive material to a pattern of radiation: developing said pattern patterned on said energy sensitive material to obtain exposed and unexposed regions of said metal layer; removing the metal layer in the exposed area to obtain an exposed area and an unexposed area of the conductive polymer; removing the exposed regions of the conductive polymer; removing said energy sensitive material; The remainder of the metal layer is removed. 94. The method of claim 93, wherein said conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyacridine selected from a group of materials such as oxazine, polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and their mixtures with other polymers and their copolymers. 95. The method of claim 93, wherein said metal layer is selected from the group consisting of Al. 96. The method of claim 93, wherein said radiation is electromagnetic radiation. 97. The method of claim 93, wherein removing said metal layer in said exposed regions is by acid etching. 98. The method of claim 93, wherein said removing said conductive polymer in said exposed regions utilizes reactive ion etching. 99. The method of claim 93, wherein removing the remainder of the metal layer is with an acid etchant. 100. A method comprising: providing a substrate having a layer of conductive polymer material; the conductive polymer comprises an energy sensitive agent; Exposing the conductive polymer to an energy pattern to form a pattern of unexposed areas: The conductive polymer is removed in one of the exposed and unexposed areas to form a pattern of the conductive polymer on the substrate. 101. The method of claim 100, wherein said conductive polymer is selected from the group consisting of one or more substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyacrylamide selected from a group of materials such as oxazine, polyfuran, polypyrrole, polyselenophene, polyparaphenylene sulfide, polyacetylene and their combinations and their mixtures with other polymers and their copolymers. 102. The method of claim 100, wherein said energy is selected from the group consisting of electromagnetic radiation, heat and particle beam. 103. The method of claim 100, wherein said developing is accomplished by removing regions of said resist exposed to said energy. 104. The method of claim 100, wherein said developing is accomplished by removing regions of said resist that were not exposed to said energy. 105. The method of claim 103, wherein said removing is accomplished by chemical dissolution. 106. The method of claim 104, wherein said removing is accomplished by chemical dissolution. 107. The method of claim 100, wherein said removing is accomplished by reactive ion etching. 108. The method of claim 100, wherein said energy sensitive agent is a component of said conductive polymer. 109. The method of claim 100, wherein said energy sensitive agent is an additive to said conductive polymer. 110. The method of claim 108, wherein the composition of the conductive polymer comprises a precursor of the conductive polymer and a dopant. 111. The method of claim 110, wherein said component is said precursor. 112. The method of claim 110, wherein said constituent is said dopant. 113. A structure comprising: Ohmic contacts between conducting polymers and semiconductors. 114. The structure of claim 113, wherein said semiconductor is selected from the group consisting of organic semiconductors and inorganic semiconductors. 115. A structure comprising: A low contact resistance electrical junction between a non-polymer conductor and a conducting polymer. 116. A method comprising: providing a field effect transistor having a source region, a drain region and a gate region; Forming source electrodes, drain electrodes and gate electrodes; At least one of the source electrode, drain electrode and gate electrode is formed by patterning a conductive polymer. 117. A method comprising: Provide bipolar transistors with emitter, base and collector regions; Form the emitter electrode, base electrode and collector electrode; At least one of the emitter electrode, the base electrode and the collector electrode is formed by patterning a conductive polymer. 118. A structure comprising: Bipolar transistors with emitter, base and collector regions; emitter electrode, base electrode and collector electrode; At least one of the emitter electrode, the base electrode and the collector electrode is a patterned conductive polymer. 119. A method comprising: providing a light emitting diode having an electroluminescent region, an anode region and a cathode region; forming an anode electrode and a cathode electrode; At least one of the anode electrode and the cathode electrode is formed by patterning a conductive polymer. 120. A method comprising: providing a light emitting diode having an electroluminescent region, an anode region and a cathode region; forming an anode electrode and a cathode electrode; At least one of the anode region and the cathode region is formed from a conductive polymer. 121. The method of claim 120, wherein at least one of said anode region and said cathode region is formed by patterning a conductive polymer. 122. A method comprising: providing an electronic device having an electrically active region; Electrical contact to the electroactive region is formed by patterning a conductive polymer. 123. A structure comprising: Surfaces of non-dielectric materials; having a first surface disposed on said surface of non-dielectric material and a layer of dielectric material having a second surface; said layer of said dielectric material has an edge; A conductive polymer layer disposed on the second surface and beyond the edge to the surface of the non-dielectric material. 124. A structure comprising: a semiconductor layer having a first side and a second side; a dielectric layer on said first side; a first patterned conductive layer on the dielectric layer; a second patterned conductive layer on the second side; At least one of the first, the second and the third patterned conductive layers is a conductive polymer. 125. A field effect transistor comprising a source electrode, a drain electrode and a gate electrode, at least one of which is a patterned conductive polymer. 126. A structure comprising: having an insulating layer on a side 1 and a side 2; a gate disposed on the first side of the insulating layer; a semiconductor layer disposed on the second side across the patterned source electrode and the patterned drain electrode; a patterned source electrode disposed on the second side; At least one of the patterned gate, the patterned source and the patterned drain is a conductive polymer. 127. A structure comprising: a semiconductor layer selected from the group consisting of organic and inorganic semiconductors; A patterned conductive polymer layer disposed on the semiconductor layer. 128. A structure comprising: semiconductor layer; a first window in the dielectric layer exposing the semiconductor layer in the first region; a second window in the dielectric layer exposing the semiconductor layer in the second region; a first pattern of conductors configured in electrical contact with the first region; a second pattern of conductors configured in electrical contact with said second region; a third pattern of conductors disposed on the dielectric layer between the first pattern and the second pattern; At least one of said first, second and third patterns of conductors is a patterned conductive polymer. 129. A structure comprising: Electroluminescence area; hole injection region; Electron injection area; anode contact; cathode contact; At least one of the hole injection region and the electron injection region is a conductive polymer. 130. A field effect transistor having a gate electrode, a source electrode and a drain electrode, at least one of which is a patterned conductive polymer. 131. A bipolar transistor having an emitter electrode, a base electrode and a collector electrode, at least one of which is a patterned conductive polymer.

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