KR19990077188A - Patterns of electrically conductive polymers and their use as electrodes or electrical contacts - Google Patents

Abstract

An electronic device having a patterned electrically conductive polymer providing an electrical connection and a method of manufacturing the same are described. Liquid crystal display cells are described as providing a bias across a liquid crystal material in which one or more electrodes are formed of a patterned electrically conductive polymer. Thin film transistors having a patterned electrically conductive polymer as a source electrode, a drain electrode, and a gate electrode are described. A light emitting diode having an anode and a coated area formed of a patterned electrically conductive polymer is described. Patterning using a resist mask; Patterning using the patterned metal layer; Patterning the metal layer using resist; A method consisting of directly patterning an electrically conductive polymer to form an electrode, an anode region, and a cathode region is described.

Description

Patterns of electrically conductive polymers and their use as electrodes or electrical contacts

The present application is filed on March 7, 1997, in which an electrically conductive polymer film is patterned using a resist to pattern the electrically conductive polymer layer to form electrodes and interconnect conductors on the surface. Claim priority from Provisional Application No. 60 / 040,129 entitled "Method".

This application claims priority from Provisional Application No. 60 / 030,501, entitled "Shape-Shaped Transparent Polymer, Solution-Applied as Conductive Electrode," filed Nov. 12, 1996 in the name of M. Angelopoulos et al. .

This application claims priority from Provisional Application No. 60 / 040,335, entitled "Electrically Conductive Polymers and Their Uses as Electrodes and Electrical Contacts," filed March 7, 1997 in the name of Angelo Paulos et al.

This application claims priority from Provisional Application No. 60 / 040,628, entitled "Pattern of Electrically Conductive Polymer and Use as Electrode in Field Effect Transistor," filed March 7, 1997 in the name of Angelo Paulos et al.

This application is issued from Provisional Application No. 60 / 040,159, entitled "Method for Patterning Electrically Conductive Polymer Films to Form Electrodes and Interconnect Conductors on Surfaces," filed March 7, 1997 in the name of Angelo Paulos et al. Insist on priority.

The present application is filed on March 7, 1997, entitled Provisional Application No. 60 / 040,130 entitled "Method for patterning an electrically conductive polymer film to form electrodes and interconnect conductors on a surface using a resist mask." Insist on priority.

This application claims priority from Provisional Application No. 60 / 040,132, entitled "Structure with Patterned Electrically Conductive Polymer Membrane and Method for Making It," filed March 7, 1997 in the name of Angelo Paulos et al.

This application claims priority from Provisional Application No. 60 / 040,131 entitled “Light Emitting Diode with Electrically Conductive Polymer Electrode” filed March 7, 1997, in the name of Angelo Paulos et al.

Currently electrical contacts or electrodes in electro-optical transducers and other devices are generally metal. Metals are deposited by evaporation or sputtering processes, which require expensive tools and are overall cumbersome processes.

Electrically conductive polymers are a relatively new class of electronic materials taught herein as candidates for electrode materials. Such polymers combine the electrical properties of metals with the processing advantages of polymers.

Herein we describe substituted and unsubstituted electrically conductive polyaniline, polyparaphenylene, polyparaphenylenevinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyisothianaphthene, polyphenylene sulfide, Examples of electrically conductive polymers such as polyacetylene, polypyridylvinylene, polyazine, mixtures thereof, these and other polymers, blends of copolymers of these monomers are described.

In order for these polymers to be used as electrodes of the device, it is desirable that these polymers have suitable electrical conductivity and can be easily patterned. It is also desirable that these polymers do not generate gas so that they do not contaminate the device to which they provide electrical contact. In addition, the conductive polymer is preferably capable of being patterned by lithography. Patterning preferably does not reduce the electrical conductivity of the polymer or degrade the properties of the electrically conductive polymer.

Therefore, it is desirable to develop a method of patterning these polymers so that these polymers can be used in any conductive polymer system and that the patterned electrically conductive polymer can be used in the device as electrical contacts without adversely affecting the conductive polymer. . It is also desirable to adjust the conductive polymer properties so that no gas or contamination occurs in the device.

It is an object of the present invention to provide an improved electronic device using an electrically conductive polymer.

It is an object of the present invention to provide a pattern of an electrically conductive polymer and a method of making the same. In particular, the resist is first patterned and then the resist pattern is transferred to the conductive polymer. Once the pattern is transferred to the conductive polymer, the result is removed.

It is an object of the present invention to provide a pattern of electrically conductive polymers using resists applied to the electrically conductive polymers. In particular, the metal is first patterned, then the metal pattern is transferred to the conductive polymer and then the metal is removed.

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

Another object of the present invention is to provide a pattern of electrically conductive polymers having high electrical conductivity.

Another object of the present invention is to provide a pattern of electrically conductive polymers having high light transmittance.

Another object of the present invention is to provide a pattern of electrically conductive polymers having good thermal stability.

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

Another object of the present invention is to provide an electrically conductive polymer and a pattern of electrically conductive polymers that can be used as electrical contacts or electrodes.

Another object of the present invention is to provide an electrically conductive polymer and a pattern of electrically conductive polymers that can be used as electrical contacts or electrodes in electro-optic transducers and devices.

Another object of the present invention is to provide an electrically conductive polymer and a pattern of electrically conductive polymer that can be used as an electrode in a liquid crystal display.

Another object of the present invention is to provide a liquid crystal display comprising an electrically conductive polymer electrode.

Another object of the present invention is to provide a liquid crystal display including an electrically conductive polymer electrode and a metal electrode.

Another object of the present invention is to provide a liquid crystal display comprising an electrically conductive polymer electrode and an indium tin oxide electrode.

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

It is another object of the present invention to provide a liquid crystal display comprising at least one electrically conductive polymer electrode, which exhibits excellent charge retention.

Another object of the present invention is to provide a liquid crystal display comprising at least one electrically conductive polymer electrode, which exhibits excellent transmission / voltage characteristics.

It is another object of the present invention to provide a liquid crystal display comprising at least one electrically conductive polymer electrode, which exhibits excellent phase adhesion characteristics.

Another object of the present invention is to provide an electrically conductive polymer and a pattern of electrically conductive polymers that can be used as one or more electrodes in a light emitting diode.

Another object of the present invention is to provide an organic or inorganic light emitting diode comprising at least one electrically conductive polymer electrode.

Another object of the present invention is to provide an organic or inorganic light emitting diode consisting of at least one patterned electrically conductive polymer electrode.

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

Another object of the invention is an electrical conductivity that can be used as an electrical contact for a transistor, such as one or more of a drain, source and gate electrode, and a contact for a bipolar transistor in a field effect transistor (FRT). To provide a pattern of a polymer and an electrically conductive polymer.

It is another object of the present invention to provide a pattern of electrically conductive polymers that are excellent in conductivity, good in thermal stability, free from gas evolution, and in some cases exhibit high light transmission.

Another object of the present invention is to provide a pattern of the electrically conductive polymer by exposing and developing the resist by applying the resist to the electrically conductive polymer to form a pattern in the resist. The resist pattern is transferred to the conductive polymer by etching and then removing the resist.

Another broad aspect of the present invention is to provide a pattern of electrically conductive polymers by applying a metal to the electrically conductive polymer surface. The metal is patterned by the application of resist which is exposed and developed. The resist pattern is transferred to the metal and then pattern transferred to the conductive polymer by an etching technique.

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

A more specific aspect of the present invention is to provide a TFT switch for a liquid crystal display wherein at least one of the source, drain and gate electrodes comprises an electrically conductive polymer exhibiting good conductivity and good thermal stability.

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

Another object of the present invention is to provide an electrically conductive polymer and a pattern of electrically conductive polymer that can be used as one or more electrodes in a light emitting diode.

Another object of the present invention is to provide an organic or inorganic light emitting diode composed of at least one electrically conductive polymer electrode.

Another object of the present invention is to provide an organic or inorganic light emitting diode consisting of at least one patterned electrically conductive polymer electrode.

Another object of the present invention is to provide a light emitting diode comprising a conductive polymer as a hole injection electrode or electron injection layer.

Summary of the Invention

Accordingly, a broad aspect of the present invention is to provide an electrically conductive polymer and a patterned electrically conductive polymer and to provide a method of patterning the same.

It is a broad aspect of the present invention to provide an electronic device having a patterned electrically conductive polymer that provides electrical contact to the electronic device.

A broad aspect of the present invention is to place a patterned electrically conductive polymer over an electronic device to provide electrical contact to the electronic device.

Another broad aspect of the present invention is to provide a pattern of electrically conductive polymers that are good in conductivity, good in thermal stability, no gas evolution, and in some cases exhibit high light transmission.

Another broad aspect of the present invention is applying a resist to an electrically conductive polymer, exposing and developing the resist to provide a pattern of the electrically conductive polymer, the pattern being transferred to the conductive polymer by removing the resist after etching.

Another broad aspect of the present invention is to provide a pattern of electrically conductive polymers by applying a metal to the electrically conductive polymer surface. The metal is patterned by the application of resist which is exposed and developed. The resist pattern is transferred to the electrically conductive polymer by transferring the metal and then removing the metal after etching.

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

Another broad aspect of the present invention is to provide an electrically conductive polymer and a pattern of electrically conductive polymers as electrical contacts for electro-optic converters and devices.

Another broad aspect of the present invention is to provide an electro-optic converter and device having at least one electrically conductive polymer electrode.

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

A more specific aspect of the present invention is to provide a liquid crystal display having at least one electrically conductive polymer electrode having excellent charge retention, excellent transmission / voltage characteristics, and excellent phase adhesion.

A more specific aspect of the present invention is an electronic device having an electroactive portion having a surface, the surface having a dielectric layer having an opening at which its electron active portion is exposed; The layer of electrically conductive polymer is disposed in the dielectric layer; The layer of electrically conductive polymer is contacted with the electrically active portion by overlapping through the aperture such that the perimeter of the aperture is disposed over the dielectric layer.

Another more specific aspect of the invention includes a first substrate; Second substrate; A liquid crystal display structure having a liquid crystal layer disposed between these first substrates and a second substrate, wherein at least one of the first substrate and the second substrate has an electrically conductive polymer disposed thereon to apply a potential across the liquid crystal layer. To provide.

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

Another more specific aspect of the invention is a substrate; A patterned electrically conductive polymer gate disposed over the substrate; An insulating layer disposed over the patterned gate; A patterned source electrode disposed over the insulating layer; A patterned drain electrode disposed over the insulating layer; A patterned source electrode and a patterned drain electrode formed of an electrically conductive polymer; A structure having a patterned source, a patterned drain, and a semiconducting material disposed at a gate between these patterned sources and the patterned drain.

Another more specific aspect of the invention is a light emitting diode having a substrate, an anode structure, an electroluminescent region, a cathode structure, wherein the cathode structure or anode structure is an electrically conductive polymer.

Another more specific aspect of the invention is an organic light emitting diode having a substrate, an anode, an organic electroluminescent layer and a cathode, in which the cathode or anode is an electrically conductive polymer.

Another more specific aspect of the invention is a method comprising the following steps:

(1) providing a substrate having a layer of electrically conductive polymeric material;

(Ii) disposing a layer of resist over the layer of electrically conductive polymeric material;

③ exposing the resist to an energy pattern;

④ developing a radiation pattern to form a pattern in the resist comprising a shielded area and an unshielded area of the electrically conductive polymer;

⑤ removing the electrically conductive polymer from the unshielded area;

⑥ removing the resist and leaving a pattern of electrically conductive polymer.

Another more specific aspect of the invention is a method comprising the following steps:

(1) providing a substrate having a layer of electrically conductive polymeric material;

(2) attaching a pattern of the metal layer by a metal mask forming a patterned metal layer on the layer of electrically conductive polymer, thereby forming an area of the electrically conductive polymer and an unshielded area of the electrically conductive polymer that are shielded by the metal pattern;

③ etching the unshielded region to remove the exposed electrically conductive polymer region;

④ removing the metal to obtain a pattern of the electrically conductive polymer.

Another more specific aspect of the invention is a method comprising the following steps:

(1) providing a substrate having a layer of electrically conductive polymer;

(Ii) disposing a metal layer over the layer of electrically conductive polymer;

③ placing a resist over the metal layer;

④ exposing the resist to a radiation pattern;

Developing a pattern of radiation forming a pattern in the resist to obtain a shielded area and an unshielded area of the metal layer;

⑥ removing the metal layer from the unshielded region to obtain a shielded region and an unshielded region of the electrically conductive polymer;

⑦ removing the unshielded region of the electrically conductive polymer;

⑧ removing the resist;

⑨ removing the remaining portion of the metal layer to obtain a pattern of electrically conductive polymer.

Another more specific aspect of the invention is a method comprising the following steps:

(1) providing a substrate having a layer of electrically conductive polymer material containing energy sensitive components;

(2) exposing the electrically conductive polymer to a pattern of energy to form a pattern of exposed and unexposed regions;

③ removing the electrically conductive polymer in one of the exposed and unexposed areas to form a pattern of the electrically conductive polymer on the substrate.

The present invention relates to patterned electrically conductive polymers and methods of making the same. More specifically, the present invention relates to electronic devices having electrically conductive polymers as electrode contacts and to active regions and patterned electrical contacts made of electrically conductive polymers, in particular liquid crystal displays, electro-optic modulators, diodes, light emitting It relates to the use of these polymers as electrodes or electrical contacts for electro-optic transducers such as diodes, transistors and the like.

Further objects, features and advantages of the present invention will become apparent upon consideration of the following description of the present invention in conjunction with the following drawings.

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

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

3 schematically illustrates a typical liquid crystal arrangement.

4 schematically illustrates the operation of a twisted nematic liquid crystal cell, in which the transmission of the cell is maximum when voltage is applied in (a), while in (b) the transmission of the cell is applied when voltage is applied. Is the minimum.

5 schematically illustrates a typical active matrix thin film transistor display.

6 is a top view of a unit grid of a TFT / LCD display.

FIG. 7 is a cross-sectional view taken along line AA ′ of FIG. 6.

FIG. 8 is another cross-sectional view taken along the line AA ′ of FIG. 6.

9 shows a part of the assembled liquid crystal display.

10 schematically shows a cross section of a TFT wherein at least one of the source, drain, and gate electrodes comprises a conductive polymer. The source and drain are located directly above the gate insulator and then covered by the semiconductor.

11 schematically shows a cross section of a TFT wherein at least one of the source and drain electrodes comprises a conductive polymer. The substrate is conductive and is also used as the gate electrode. The source and drain electrodes are disposed directly over the insulators and then covered with a semiconductor.

12 schematically illustrates a cross section of a TFT wherein at least one of the drain and gate electrodes comprises a conductive polymer. The source electrode and the drain electrode are disposed directly above the semiconductor.

13 schematically shows a cross section of a TFT wherein at least one of the source and drain electrodes comprises a conductive polymer. The substrate is conductive and is used as the gate electrode. The source electrode and the drain electrode are disposed directly above the semiconductor.

FIG. 14 is a diagram showing the current flow between the source and the drain of the TFT device whose structure is schematically shown in FIG. 11, with respect to the voltage gate electrode. The channel depth L of this device was 100 microns and the channel width was 1500 microns.

15 is a top view of a typical design of an active matrix liquid crystal display based on TFT. At least one of the source electrode, the drain electrode, and the gate electrode includes a polymer.

16A and 16B are cross-sectional views of pixels of an active matrix liquid crystal display device based on TFTs having two different TFT arrangements. At least one of the source electrode, the drain electrode, and the gate electrode includes a conductive polymer.

17 shows contact vias through a passivation layer or an insulating layer. The top layer can be the same metal or a different conductive material (eg metal or ITO).

18 shows a conventional OLED structure on a glass substrate having an opaque cathode on top, where light is emitted only at the glass side.

19 shows an LED structure of the present invention having a transparent (or opaque) cathode as a whole.

20A and 20B schematically show an array of LEDs for displaying an image, where FIG. 20A shows a passive matrix with LEDs at the intersection of each row and column, and FIG. 20B shows each row. Represents an active matrix with a current control circuit at the intersection of overheat.

21 illustrates patterning the conductive polymer by applying a resist on the surface of the conductive polymer. The resist is exposed and developed, the pattern is transferred to the conductive polymer, and the resist is removed.

22 illustrates patterning a conductive polymer by applying a metal layer patterned by a metal mask on top of the conductive polymer. After the pattern is transferred to the conductive polymer, the metal is removed.

FIG. 23 illustrates patterning the conductive polymer by applying a blanket metal layer over the conductive polymer. The metal is patterned by the resist, the pattern is first transferred to the metal, then transferred to the conductive polymer by etching, and the remaining resist and metal are removed.

FIG. 24 illustrates direct patterning of the conductive polymer by exposing the conductive polymer to radiation in which the polymer is subsequently developed to remove more soluble regions.

25 and 26 show conductive polyaniline lines on the order of 10 [mu] m shown using resist on the surface of the conductive polymer.

27 and 28 illustrate conductive polyaniline lines fabricated using metal deposited on the surface of the conductive polymer by a metal mask.

29, 30 and 31 illustrate conductive polyaniline lines fabricated using blanket metal deposited on the surface of a conductive polymer shaped by the use of resist.

32 shows the light transmission spectrum of a polyaniline membrane of 500 Hz.

33 shows transmittance / voltage characteristics of a liquid crystal display made of two polyaniline electrodes.

Fig. 34 shows lightness (transmittance) / voltage characteristics of a liquid crystal display made of two ITO electrodes.

35 shows the voltage vs. time curve of a liquid crystal display made of polyaniline electrode. The charge retention is over 95%.

36 and 37 schematically illustrate joints between non-polymeric and polymeric electrical conductors.

38 schematically shows a bipolar transistor with electrodes according to the invention.

The present invention relates to substituted and unsubstituted polyaniline, polyparaphenylene, polyparaphenylene vinylene, polythiophene, polypyrrole, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyacetylene, poly A device using electrically conductive polymers, including pyridyl vinylene, combinations thereof and blends of these and other polymers, copolymers of these monomers. It has been found that these polymers can be patterned by lithography to form electrically conductive patterns that can act as electrodes or electrical contacts of various electro-optic transducers and devices. The invention also relates to an electro-optical transducer and device composed of one or more electrically conductive polymer electrodes.

1 is a schematic perspective view of a substrate 200 with a patterned electrically conductive polymer 202 disposed thereon. The electrically conductive polymer 202 forms electrical contacts at the surface 204 of the substrate 200 along at least a portion of the interface 106 of the electrically conductive polymer 202 and the surface 204. The pattern 102 may electrically interconnect a plurality of electronic devices formed on the substrate 100.

2 is a schematic side view of a substrate 208 having a dielectric layer 210 on surface 212. The dielectric layer 210 has a through-hole 214 therein, wherein the patterned electrically conductive polymer 216 disposed over the dielectric layer 210 fills the through-hole 214 with the substrate 208. ) Surface 218. Some examples of devices useful in practicing the present invention are liquid crystal displays (LCDs), transistors (bipolar and field effect transistors), light emitting diodes, and the like.

LCD device

BACKGROUND OF THE INVENTION An electro-optic converter based on liquid crystal is currently a state of the art for the manufacture of flat panel displays, especially for portable electronic devices. This technology is expected to continue to dominate in the future as the industry seeks a wide range of displays.

A typical liquid crystal (twist nematic) cell is shown in FIG. 3. In this device, the nematic liquid crystal is placed between two glass plates on average 5-20 μm apart. Indium tin oxide (ITO), which is a transparent electrode, is deposited on the surface of the glass plate. ITO is deposited with an alignment layer which is rubbed so that the nematic liquid crystal is aligned parallel to the rubbing direction. When the two alignment layers are rubbed at 90 ° with respect to each other, the liquid crystal has a twisted structure as shown in Fig. 4A. When polarized light enters the cell, a polarization plane occurs as the molecules are twisted, and the polarization plane rotates 90 ° while passing through the cell. If the second polarizer located at the other end of the cell also rotates 90 ° with respect to the first polarizer, light will pass through the cell. When a voltage is applied to the cell, an electric field is applied across the liquid crystal cell. The liquid crystal molecules align themselves according to the electric field (see FIG. 4B), so that the twist is broken. Incident light is now directed towards the cross polarizer, so no light transmission through the cell occurs. U. S. Patent No. 5,623, 514 describes liquid crystal cells, the teachings of which are incorporated herein by reference.

There are various liquid crystal displays, including floating matrix displays and active matrix displays. The active matrix display may consist of two terminal devices such as diode rings, continuous diodes, and metal-insulator-metal devices. The active matrix display may also consist of three terminal devices such as thin film transistors whose material is polysilicon, amorphous silicon, amorphous germanium, cadmium selenide and the like.

Another technology that has been researched and developed for future potential uses in flat panel displays is light emitting diodes, especially light emitting diodes in which the electroluminescent layer is an organic material. The light emitting diode is composed of a hole injection electrode, an electroluminescent layer, and an electron injection electrode. The hole injection electrode is most commonly indium tin oxide.

Today, flat panel displays are fabricated using active matrix liquid crystals based primarily on thin film transistors. One of the most cumbersome process steps in liquid crystal cells is the deposition and patterning of ITO electrodes. ITO is first deposited by an evaporation process. It must then be annealed for several hours at high temperature. The ITO is then patterned by applying photoresist. It develops by exposing a photoresist. The pattern is transferred to ITO by etching. The etching solution consists of a mixture of strong acids. ITO is generally deposited before or after the thin film transistor layer is deposited. In the latter case, the ITO acid etching solution may cause defects in the thin film transistor device.

Thus, it provides a simpler process compared to ITO, while at the same time high light transmittance, good conductivity, good environmental stability and thermal stability, easy patterning by lithography, good liquid crystal display properties (e.g. high charge retention, low phase adhesion) It is desirable to develop new electrode materials that provide good transmission / voltage characteristics.

Electrically conductive polymers are a relatively new class of electronic materials that can be considered potential electrode material candidates. Such polymers have the potential to combine the electrical properties of metals with the processing advantages of conventional polymers. We provide substituted and unsubstituted electrically conductive polyaniline, polyparaphenylene, polyazine, polyparaphenylenevinylene, polythiophene, polyfuran, polypyrrole, polyselenophene, polyisothianaphthene, polyphenylene sulfide , Polyacetylene, polypyridylvinylene, combinations thereof, blends of these and other polymers, copolymers of these monomers are described.

In order for these polymers to be used as ITO substitutes or as general electrodes, these polymers must have suitable conductivity, can be easily patterned, and in certain cases have high light transmittance. In addition, these polymers do not produce gas evolution that can contaminate the device. In liquid crystal display cells, gas evolution by the conductive polymer can significantly reduce the charge retention of the display device. In addition, the conductive polymer should be able to be easily patterned by lithography. Patterning does not reduce the conductivity of the conductive polymer or deteriorate the properties of the conductive polymer. Therefore, it is desirable to develop a method of patterning these polymers, ideally used in any conductive polymer system and not adversely affecting the properties of the conductive polymer.

A potential conductive polymer that can be used as the conductive electrode is polyaniline. Polyaniline (and other conductive polymers) are a class of polymers described in US Pat. No. 5,198,153, US Pat. No. 5,200,112, and US Pat. No. 5,202,061, all of which are incorporated herein by reference.

In order for a conductive polymer such as polyaniline to be considered as the conductive electrode of a liquid crystal display, for example, it is preferable that the polymer exhibits certain characteristics. By way of example, the present invention will be described with reference to polyaniline, but is not limited thereto. Preferred properties are as follows:

(1) It is preferable that the light transmittance in the visible light region is greater than 80% and exhibits sufficient conductivity and contact resistance to the device metallurgy.

(2) It is preferable that the solubility is excellent and a uniform film is formed. The coating is preferably free of particles, streaks or significant pinholes or dewes.

3. The solvent used to deposit the alignment layer deposited on top of the conductive electrode, and in most cases polyimide, does not dissolve the polyaniline, causes little interfacial mixing, or removes the dopant ions from the polyaniline. It is desirable not to. The removal of dopant ions reduces the conductivity of the polyaniline, and the dopant ions are likely to enter the alignment layer and ultimately the liquid crystal and destroy the properties of the liquid crystal cell.

(4) It is preferable that the polymer exhibits thermal stability up to at least 150 ° C.

(5) It is preferable that the polymer does not generate gas because ionic contamination of the liquid crystal may occur due to gas generation, thereby destroying the characteristics of the liquid crystal battery.

(6) The polymer is preferably excellent in step coverage.

(7) The polymer is preferably patterned without the need for a strong etchant.

In addition to the polymer properties described above, it is also important for liquid crystal cells made of polyaniline to preferably exhibit the following properties:

① Excellent transmittance vs. voltage characteristics.

② Excellent charge retention at room temperature and high temperature.

③ There is no phase adhesion even at room temperature and high temperature.

It is not clear whether conductive polymers such as polyaniline can be used in such applications to exhibit the properties described above. Polyaniline is known to make conductive by reacting a nonconductive form of a polymer (base) with an acid such as hydrochloric acid to become a conductive salt. This is described by A. G. MacDiarmid and A. J. Epstein in Farad. Discuss. Chem. Soc., 88, 317. The structure of the conductive form consists of a non-localized polymer radical cation that is neutralized by counter ions, which is referred to herein as "unassembled electrically conductive polymer and its precursor," filed Jan. 9, 1995, which is incorporated herein by reference. Described in US patent application Ser. No. 08 / 370,127.

Ions are essential to making the material conductive. If ions are present in the liquid crystal plate, H. Seiberle, M. Schadt, "Influence of Charge Carriers and Display Parameters on the Performance of Dynamically Active Addressed LCDs", SID ' 92 Digest, 25 (1992), is known for poor charge retention and phase adhesion. This is one of the biggest reasons for using polyaniline as an electrode. The use of HCl acid as a dopant generates volatile mobile ions. In fact, it is observed that HCl generates gas from a thin film of polyaniline at a temperature of about 40 to 50 ° C. This gas evolution will destroy the properties of the LC as ions migrate to the liquid crystal (LC). Here, the inventors have surprisingly found that polyaniline is deformed so that ion migration does not occur with LC even at room temperature or at high temperatures, and as a result, a doped polymer is obtained which produces an LCD having excellent charge retention and phase adhesion properties.

Another problem with ions is that while depositing a polyimide alignment layer on top of the polyaniline electrode, they are generally used for polyimides, which are very polar solvents, such as NMP or gamma-butyrolactone, both of which are very polar solvents. The solvent will remove the dopant ions from the polyaniline and transfer these ions to the alignment layer and the LC. This will also destroy the characteristics of the display. In addition, removal of ions will reduce the conductivity of the polyaniline. Very surprisingly, it has been found that the polyimide alignment layer is very compatible with polyaniline and no removal of ions occurs.

Polyaniline preferably has good light transmittance and sufficient surface resistance and contact resistance to the underlying data metal line. By reducing the thickness of the polyaniline, the light transmittance of the polyaniline can be modified, but the surface resistance of the material is increased during this process. Here, the inventors describe a material which is excellent in light transmittance and excellent in surface resistance and contact resistance to metals.

Polyaniline is preferably excellent in short coatability. This is a major problem when using ITO. In a typical TFT arrangement, indium tin oxide (ITO) is used as the transparent conductive electrode. ITO is deposited by sputtering with conventional photoresist systems and patterning by lithography. It is then etched using a hot solution of a mixture of concentrated nitric acid and hydrochloric acid. In general, ITO is deposited before or after the thin film transistor (TFT) layer and passivation layer are deposited. To reduce the number of photolithography mask steps, the latter is used. In this case, via holes are formed in the passivation layer to connect the ITO layer to the source / drain metal of the TFT device underneath. If the passivation layer is too thick, there is a problem of short coating of via holes with ITO because ITO is deposited by the sputtering process. Conversely, if the passivation layer is thin, pinholes are generally present, and the ITO acidic etching solution can cause defects in the TFT device or bus line. Polyaniline will be deposited by spin-coating or roller coating processes. Therefore, excellent short coatability can be provided. Polyaniline has also been found to be patterned without the need for a strong etchant.

Although the present invention is suitable for many devices, it will be described as an embodiment of an active liquid crystal display, in particular a thin film transistor (TFT) liquid crystal display. As shown in Fig. 5, the conventional TFT display device 10 includes an array of cells or A, each of which is a thin film transistor that addresses a battery by applying a voltage to the battery when the transistor is in operation. (11) and a capacitor (12) which retains the voltage even after the transistor is turned off. This transistor is formed on the glass substrate 13 on the back side of the display device 10, and is connected between the row data electrode 14 and the column electrode 15 to the transparent display electrode 16 of each pixel, and all the pixels. Is on the back of the display device 10. The front surface of the display device includes a continuous common transparent electrode 17 spaced apart from and parallel to the transparent display electrode 16. Electrode 17 and display electrode 16 are preferably made of a thin transparent conductive material such as indium tin oxide (ITO) 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 electrode, a fringe electric field spreading from the pixel or battery edge of the display electrode to the common electrode is present. Occurs. The polarizer 19 suitably oriented with respect to the polarizer 20 provided behind the rear glass substrate 13 is parallel to the outer surface of the common electrode 17 and is adjacent to the glass substrate 18. The alignment layers 21 and 22 are disposed on the inner surfaces of the display device, the common electrodes 16 and 17, respectively, and are in contact with the liquid crystal layer, wherein the twisted nematic liquid crystal molecules are aligned with the alignment layer 21. It is sealed between two glass substrates 1 and 18 provided in parallel with (22). On the back of the display device is a visible light source (not shown) that irradiates the display device 10 through a diffuser. If the display device 10 wants to display color, a color filter 25 is used as a common electrode. Placed on the alignment layer side of (17), the color filter contains a group of three primary colors (red, green, blue), each of which combines with one of three adjacent groups of pixels A to form a color battery.

The liquid crystal cell was fabricated such that the patterned electrically conductive polymer (ie, polyaniline), which acted as the transparent electrode 16 of each pixel element of the display device 10 on ITO, acts as the continuous transparent electrode 17. In addition, the liquid crystal cell was fabricated such that the patterned electrically conductive polymer acted as the transparent electrode 16 and the continuous coating of the electrically conductive polymer acted as the continuous transparent electrode 17. The electrically conductive polymer can also serve as the transparent conductive electrode 17 and the patterned ITO can serve as the pixel electrode 16.

6 is a top view of the unit cell structure of the TFT / LCD display. Reference numerals 101 and 102 are data bus lines, and 103 and 104 are gate bus lines. 106, 107, and 108 form a thin film transistor (TFT), where 108 is the protrusion of 104 and 106 is the protrusion of 101. Reference numeral 106 denotes a source electrode, and 107 denotes a drain electrode. 106 and 107 are typically made of the same electrically conductive material, such as a metal. 105 is a transparent pixel electrode made of a conductive polymer by photolithography. The pixel electrode 105, an upper electrode (not shown) on the color filter surface, and a liquid crystal (not shown) between these two electrodes form a pixel capacitor. 130 is an extension of 105. 130 and 103 are separated by a layer of insulator (not shown), forming a storage capacitor. When a suitable high voltage is applied to the gate bus line 104, the TFT is turned on. Thus, the pixel capacitor and the storage capacitor are charged from the data bus line 101 across the TFT to a designed voltage that determines the electrooptic properties of the liquid crystal in the pixel. In this way, the designed image is displayed. Two cross-sectional structures taken along A-A 'are shown in FIGS. 7 and 8. 7 and 8, 106 is a source electrode, 107 is a drain electrode, 108 is a gate electrode, 109 is a gate insulator layer, 110 is an amorphous silicon layer, ( 111 is an n + amorphous silicon layer, 112 is a passivation layer, and 105 is a pixel electrode. In FIG. 8, there is another layer 113 on top of passivation layer 112, which is a low dielectric transparent polymer layer. The calcination electrode layer 105 is positioned above 113, so that the pixel electrode extends over the data bus line to increase the pixel aperture ratio. In Fig. 7, the pixel electrodes 105 and 107 directly overlap. In FIG. 8, this overlap passes through the via holes on the polymer layer 113. 9 shows a part of the assembled liquid crystal display. 120 is a glass substrate. Reference numeral 121 is a color filter layer. 122 is a conductive transparent electrode layer. 122 is an indium tin oxide (ITO) layer or transparent conductive polymer layer. 123 is a transfer pad connected to an electrode leaf (not shown) for tab bonding to driving electronics. 123 is made of a metal layer. 124 is a conductive epoxy that electrically connects 122 and 123. Thus, 122 may be connected to the driving electronics through 124 and 123. Reference numeral 125 is a liquid crystal layer. All metal layers and electrically conductive layers of FIGS. 6-9 can be replaced with electrically conductive polymers according to the invention.

Thin film transistor device

The electrical contacts or electrodes of current thin film transistor (TFT) devices are metal. Metals are deposited by evaporation or sputtering processes which require expensive equipment.

Suitable polymers include substituted and unsubstituted electrically conductive polyaniline, polyparaphenylene, polyparaphenylenevinylene, polythiophene, polyfuran, polyrilol, polyselenophene, polyisothianaphthene, polyphenylene sulfide, Polyacetylene, polyazine, polypyridylvinylene, combinations thereof and blends thereof with other polymers, copolymers of these monomers.

In order for such a polymer to be used as a contact electrode in a TFT, it is desirable to have suitable electrical conductivity and be easily patterned. In addition, these polymers should be free of gas evolution that contaminates the device. In addition, it is preferred that the conductive polymer can be patterned by lithography. Patterning preferably does not reduce the conductivity of the polymer or deteriorate the properties of the conductive polymer.

Therefore, it is desirable to develop a method of patterning such polymers, ideally that can be used in any conductive polymer system and does not adversely affect the properties of the conductive polymer.

The use of a conductive polymer electrode as at least one of a source and a drain in a TFT having a different i-type bonded polymer as a semiconductor layer is known as H. Koezuka, A. Tsumura, and T. Ando. Has already been described in US Pat. No. 5,107,308. In this patent, the gate is always made of metal. In addition, when one of the drain electrodes of the TFT is a film of a conductive polymer, the film has a patterned metal lead. The method used for the growth of conductive polymers is electrochemical polymerization. The inventors of the patent have generally described different methods that can be used to form conductive polymer electrodes, but patterning the conductive polymer layer into source and / or drain electrodes of desired shape and forming transistor channels between the electrodes It does not provide a solution to the problem of the method. In the present invention, the present inventors present a method of using a conductive polymer in at least one of a source electrode, a drain electrode and a gate electrode of a TFT and a method of patterning the conductive polymer layer.

The invention also relates to a TFT device in which at least one of the source electrode, the drain electrode, and the gate electrode comprises an electrically conductive polymer. 10 to 13 show the arrangement of the TFT device.

10 shows an apparatus fabricated on a substrate 61. A patterned conductive polymer gate electrode 62 is disposed over the substrate 61. An insulating layer 63 is disposed over the gate electrode 62. A source electrode 65 and a drain electrode 66 comprising a conductive polymer were disposed and patterned over the gate insulator 63. The semiconductor layer 64 is disposed over the source electrode 65, the drain electrode 66 and a portion of the gate insulator 63.

FIG. 11 differs from FIG. 10 in that the substrate 61 is conductive and acts as the gate 61. A specific, non-limiting example of this structure is the use of thermally grown oxide 63 with a heavily doped wafer as substrate / gate electrodes 61 and 62, and as an insulator thereon. The remaining layers are as shown in FIG.

FIG. 12 differs from FIG. 10 in that the source electrode 65 and the drain electrode 66 are disposed over the semiconductor layer 64 which is first disposed over the gate insulator.

FIG. 13 differs from FIG. 10 in that the source electrode 65 and the drain electrode 66 are disposed over the semiconductor layer 64 which is first disposed on the gate insulator.

FIG. 14 shows a current flow versus voltage gate electrode between a source and a drain of the TFT device, and the structure of the TFT device is schematically shown in FIG. The channel length L of this apparatus was 100 micrometers and the channel width was 1500 micrometers.

15 is a top view of a typical design of an active matrix liquid crystal display based on TFT. At least one of the source electrode, the drain electrode, and the gate electrode includes a polymer.

16A and 16B are cross-sectional views of pixels of an active matrix liquid crystal display device based on TFTs having two different TFT arrangements. At least one of the source electrode, the drain electrode, and the gate electrode includes a conductive polymer.

17 shows contact vias through a passivation layer or an insulating layer. The top layer can be the same metal or different conductive material (eg metal, conductive polymer or ITO).

LED device

Patterned electrically conductive polymers are also useful for making electroluminescent diodes. More specifically, the present invention provides a display device that is at least partially transparent when fabricated on a transparent substrate, and a light emitting diode (organic) which allows the display device to be viewed from the cathode side when fabricated on a circuit containing a device containing an opaque substrate. Transparent cathode and anode structure). The invention also relates to LEDs having organic and inorganic electroluminescent regions. Although the present invention will be described with respect to OLEDs, it is not limited thereto.

Prior art organic light emitting diodes (OLEDs) are fabricated on a glass substrate, the lower electrode of which is indium tin oxide (ITO), which is a transparent conductor. The top electrode of this device was opaque so that light from the electroluminescent region could only be seen from the glass side. One exception is the structure recently reported in V. Bulovic et al., Nature, 380, 29 (1996), in which the cathode metal becomes thin and partially transparent during subsequent ITO deposition.

OLED displays on opaque substrates or transparent OLED displays on transparent substrates require top electrode structures that meet the following criteria:

① Transparent to LED light emission.

② Provides low resistance current to the LED active area.

(3) provides sufficiently high lateral conductivity in the plane of the electrode when forming the diodes as a self-emitting display of a two-dimensional array.

④ acts as a protective film on the organic film below it, chemically and physically fragile.

⑤ Must be deposited in a gentle manner that does not damage the deposited organic layer to preserve the integrity of the layer / electrode interface.

A typical transparent electrode material is indium tin oxide (ITO), which is often used as an anode of an OLED, which satisfies the conditions of 1 to 4 above, but is typically deposited in an oxygen plasma, thereby damaging the organic region of the OLED device structure. It does not satisfy the condition. The same applies to GaN as an electrode. (5) The condition is actually the most important because there are some transparent conductive materials, but almost all require plasma or high processing temperatures that irreversibly damage the organic light emitting material.

What is needed is a transparent cathode and / or anode structure that is convenient to satisfy all of the above conditions.

Therefore, it is desirable to develop a novel material which provides a simpler process than ITO, has a high light transmittance, excellent conductivity, environmental stability and thermal stability, and is easy to pattern by lithography.

A typical light emitting diode arrangement consists of a hole injection electrode, an electroluminescent layer and an electron injection electrode. This is a basic arrangement. Occasionally, a hole transport layer can be incorporated between the injection electrode and the electroluminescent layer to improve hole mobility and to isolate the hole. In addition, an electron transport layer can be included between the electroluminescent layer and the electron injection electrode.

The electroluminescent layer can be an organic binding polymer, an organic small molecule (eg AlQ material), or an inorganic material such as gallium arsenide. Typical hole injection electrodes include ITO. Typical electron injection electrodes include aluminum, calcium and the like.

The P-doped electrically conductive polymer according to the present invention can be used as the hole injection layer, and the M-doped electrically conductive polymer according to the present invention can be used as the electron injection layer.

An example of a prior art OLED 300 structure is shown in FIG. 18. The substrate 312 is glass, and the ITO film 314 is deposited directly on the glass to form the anode. For efficient operation, the organic region generally consists of a hole injection layer 315, a hole transport layer 318, and an electroluminescent (EL) layer 320 as shown in FIG. 18. EL layer 320 is a metal chelate tris (8-hydroxyquinoline) aluminum—sometimes referred to by the abbreviation S or Alq3. In this arrangement the hole transport layer is aromatic diamine. The metal alloy MgAg is deposited on the organic to form an opaque cathode 322 because of a thickness greater than about 10 nm. Although not shown, an airtight sealing method is sometimes used to protect the negative electrode from moisture.

In the structure of Fig. 18, the EL layer is one of a class of organic materials known as molecular organics. These are in turn deposited by an evaporation process. The polymers constitute another class of organic materials that exhibit electroluminescence and are typically applied by spin coating. Polymer OLEDs are also generally made on glass substrates using ITO anodes and have an opaque cathode (typically a low workability metal such as calcium) so that light is emitted from only one side. They may also use multiple polymer layers to improve work efficiency.

An exemplary embodiment of the LED of the present invention is an OLED having a transparent cathode 340 shown as the general structure of FIG. An OLED is formed over the glass substrate 332 with an ITO (or electrically conductive polymer) anode 334, light is emitted from both sides, and the OLED is at least partially transparent. An observer looking at a display device composed of such an array of OLEDs can either focus the image presented on the display device or see the rear view past the display device. In contrast, a display device formed using an OLED together with a transparent cathode on an opaque substrate (eg, silicon) can be seen by looking at the light emitted from the cathode side. It is advantageous to fabricate OLED displays on silicon, because devices and circuits can be formed in silicon prior to depositing OLEDs on silicon, and the devices and circuits can be fabricated with active matrix displays having integrated drivers. Because it can be used to make.

In accordance with the present invention, the anode or cathode of an LED may be formed from or covered with a protective layer of wear resistant, endogenous electrically conductive polymer, as incorporated herein by reference. Light emission from the OLED having the cross section shown in FIG. 19 takes place at the top and bottom (ie, both sides of the diode) because both the anode and the cathode are transparent.

The electrically conductive polymers described herein provide a satisfactory cathode electrode by satisfying the conditions of transparency, low resistance to vertical resistance to conduction, formation of a protective film and deposition process without damage. Abrasion resistant, isotropic electrically conductive polymers are filed in the U.S. Patent Application, filed Feb. 9, 1994, entitled "Conductive Abrasion Resistant Phosphorus Polymer Material, Methods for Making and Uses thereof," the disclosure of which is incorporated herein by reference. No. 08 / 193,926 and US patent application Ser. No. 08 / 476,141 filed June 7, 1995. Each condition is considered individually below.

A display device is formed by fabricating a plurality of identical OLEDs on a monolithic substrate in a two dimensional array and providing means for controlling the light emission from each diode. Generally, in forming the line of FIG. 20A (floating matrix method), for example, the selected column 490 becomes positive voltage Vr, and all unselected columns 492 remain grounded. If a voltage is applied to the lines 494 and 496 of each row—where I is the column line index—the voltage flows beyond the maximum number of row lines. The net bias of the OLEDs 498, 400 along the selected heat line 490 is Vr-Vci, and this voltage determines the amount of emission. All other OLEDs 402 and 404 are reverse biased and no light is emitted.

In the arrangement shown in FIG. 20A, the OLED emits light only when the heat line approaches, which can cause flicker in the multi-information display. This can be healed by the array shown in Fig. 20B (active matrix method) in which the line voltages are sampled using circuits introduced at each intersection and other column lines are approached. In this case, all diodes have a common cathode. Since these circuits must be small and fast, it is convenient to fabricate one crystalline silicon. In this case, the substrate should be opaque and the transparent cathode should exhibit a phase.

References cited herein are hereby incorporated by reference. US patent application Ser. No. 08 / 794,072, filed Feb. 4, 1997, assigned to the assignee of the present invention, describes an OLED structure and its fabrication method.

Patterning method

In order for the electrically conductive polymer to be used as an electrode or an electrical contact, it is preferably patterned. A number of methods have been described that can be used to pattern various electrically conductive polymers.

These methods include applying a resist material to the surface of the conductive polymer. The resist can be negative or positive and can be developed in an aqueous or organic solvent. Examples of negative resists include polymethylmethacrylate type, novolak / diazonaphtaquinone systems, t-boc protected styrene polymers and copolymers thereof, t-butyl protected styrene polymers and copolymers thereof, t-butyl protected Styrene polymers and copolymers thereof, and other acid-deprotected acrylate ester polymers and copolymers thereof. These are only examples, but are not limited to these. Examples of positive resists are epoxy containing polymers, hydroxystyrene polymers with crosslinking agents, siloxane polymers. These are only examples, but are not limited to these. The resist can be given radiation such as infrared / visible electron beam, x-ray, ion beam, aqueous tetramethyl ammonium hydroxide, aqueous tetramethyl ammonium hydroxide, aqueous NaOH, aqueous KOH, methylisobutyl ketone, aqueous tetraethylammonium hydroxide Side, isopropanol, propylene, glycol methyl ether acetate, diglyme, methyl ethyl ketone. These are only examples, but are not limited to these. The resist phase is then transferred to the conductive polymer by etching (RIE) with reactive ions such as oxygen gas, CO ₂ , SO ₂ , fluorine and the like. Once the phase is transferred to the conductive polymer, the remaining resist is preferably removed by solvent washing with acetone, diglyme, isopropanol and the like. This process is shown schematically in FIG. The solvent used to apply the resist, as well as the developer of the resist, the conditions under which the resist is developed and the solvent used to remove the resist, preferably do not deteriorate characteristics such as conductivity, transmittance, thermal stability, and the like of the conductive polymer.

The second method of patterning conductive polymers is by deposition of metals such as aluminum, gold and the like. The patterned metal layer is deposited on the conductive polymer by depositing the metal with a metal mask. The pattern is then transferred to the conductive polymer by etching with oxygen gas, CO ₂ , SO ₂ , fluorine or the like. The metal is then removed by etching with an acid solution such as hydrochloric acid, hydrofluoric acid, acetic acid, sulfuric acid, perchloric acid, phosphoric acid, nitric acid, combinations thereof. This process is depicted in FIG. The conditions under which the metal is deposited and etched preferably do not adversely affect the properties of the conductive polymer.

A third method of patterning conductive polymers is by deposition of blanket metals such as aluminum, gold, and the like on the surface of the conductive polymer. The metal is patterned by the application of resist. The resist is exposed to radiation such as infrared, visible, electron beam, x-ray, ion beam, etc., developed using a developer similar to that described above, and transferred to the metal layer by etching the metal, for example, with an acid solution as described above. . The pattern is then transferred to the conductive polymer by, for example, reactive ion etching of oxygen, CO ₂ , SO ₂ , fluorine and the like. The resist is then removed by solvent and the metal is removed by acid etching, similar to that described above. This process is illustrated in FIG. The above process steps and the solvents used in these steps preferably do not adversely affect the properties of the conductive polymer.

A fourth way of patterning conductive polymers is to expose them directly to radiation. Conductive polymers are sensitive to radiation, resulting in differences in solubility between exposed and unexposed areas upon irradiation. The radiation may be an electron beam, an ion beam, an electron beam (eg x-ray, light). In this case, more of the soluble exposed area is removed by the solvent to obtain a direct conductive polymer pattern. This process is depicted in FIG. 24, which is described in US Pat. No. 5,198,153, the teachings of which are incorporated herein by reference.

In all of these cases, exposure to radiation may include electron beams (eg x-rays) and light of various wavelengths, and may include charged and uncharged particle beams such as electron beams, ion beams, and elemental particle beams. .

1. A polyaniline doped with acrylamidopropanesulfonic acid described in US patent application Ser. No. 08 / 595,853, filed Feb. 2, 1996, the disclosure of which is incorporated herein by reference, N-methylpyrroli Spin applications were made on glass substrates from suitable solutions including dinon, m-cresol, dimethylpropylene urea, dimethylsulfodimethylformamide and the like. The thickness of the coating can be controlled by the polymer concentration in the solution and the spin rate. In general, 0.1-5% solution of the polymer in a given solvent was used. The thickness of the film was 500-1000 kPa. The conductivity of the membrane was 1 to 150 S / cm. The coated membrane was heated in an oven at 85 ° C. for 5 minutes to remove residual solvent. A conventional Shipley photoresist (MP 1808) was applied to this polyaniline surface. The resist was heated at 85 ° C. for 30 minutes. The resist coated polyaniline substrate was then exposed to infrared radiation at a dose of 70mj. The resist was then developed in an aqueous alkaline Micropos CD-30 developer. Since the developer which is alkaline can undo the polyaniline to make polyaniline less conductive, the developer and the development time are preferably controlled precisely. In this case, the developer concentration is diluted 50% with deionized water. The resist was developed for 30 seconds and then rinsed with water. The developed resist is cured at 1 ° C. for 30 minutes to cure the resist before phase transfer. The resist phase was then transferred to polyaniline by oxygen reactive ion etching. The polyaniline was etched using 150 watts RF power, 100 millitorr pressure and 20 sccm oxygen gas in a reactive ion etch chamber for 2 minutes. After the phase was transferred, the remaining photoresist was removed by washing with acetone. 10 μm conductive polyaniline lines shaped in this manner are shown in FIGS. 25 and 26. The conductivity of the polyaniline pattern was measured and found to be similar to the initial conductivity. In other words, there is little reduction in conductivity as a result of this process. The light transmittance, thermal stability and other characteristics and overall environmental chemical stability were evaluated and discussed below.

2. Poly (3-butylthiophene-2,5-diyl) was dissolved in a suitable solvent such as tetrahydrofuran, methyl ethyl ketone, N-methyl pyrrolidinone and the like and spin coated onto a glass plate. The polythiophene was then doped by exposing the membrane to an iodine chamber. Doped samples were pumped under dynamic vacuum. Conductivity of 1000 to 2000 S / cm was obtained. The film was patterned by applying Shipley Photoresist MP1808 as described above for polyanilene.

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

4. Poly (3-octylthiophene-2,5-diyl) was treated and patterned as described above.

5. Polypyrrole was deposited on the glass plate as follows. Pyrrole monomer (0,045 M) was dissolved in 500 ml of water. In another beaker the oxidant FeCl ₃ (0.105M) was dissolved in 500 ml of water. 0.105 M of 5-sulfosalicylic acid and 0.105 M of atlaquinone-2-sulfonic acid sodium salt are added to the oxidizer solution. One side of the shielded glass plate was immersed in the monomer solution. The oxidant solution is then added to the monomer solution. The solution is left for 10 to 30 minutes so that polymerization of the monomer proceeds and is deposited on the glass plate. The thickness of the conductive polypyrrole deposited on the glass plate is time dependent and the glass plate is left in the polymerization bath. The polypyrrole had a conductivity of about 200 S / cm. Polypyrrole deposited on the glass plate was patterned by applying a resist as described above.

6. Polyaniline doped with acrylamidopropanesulfonic acid was spin applied onto a glass plate. 300 μs of blanket aluminum was evaporated over polyanilene and a 2.0 μm thick Shipley polypropylene glycol ether acetate solvent based resist was applied over the aluminum. The resist was exposed to infrared radiation at a dose of 150mj, followed by a 50/50 mixture of Microposit developer concentrate and deionized water. After development, the resist is heated at 85 ° C. for 30 minutes. The pattern is then transferred to aluminum by etching aluminum at room temperature using a Transcene aluminum etching solution consisting of 80% phosphoric acid, 5% acetic acid, 5% nitric acid and 10% water. The etching rate is 4.19 kPa / sec. The pattern is transferred to polyanilene by oxygen reactive ion etching using a power of 150 watts at 20 cc of oxygen at a pressure of 100 millitorr and an etching rate of 39 kW / sec. Another method of transferring the pattern to polyaniline is to perform aluminum etching at 30 ° C. At high temperatures, aluminum and polyaniline are etched with the acid solution at a rate of 37 ms / sec. The remaining resist is removed by acetone cleaning. The remaining aluminum is etched away using dilute 25% hydrochloric acid solution. 27, 28, 29 depict conductive polyaniline patterned in this manner.

7. Aluminum blanket metals such as those described above for polyaniline were also patterned with polythiophene substituted and polypyrrole polymerized in situ.

8. Polyaniline acrylamidopropanesulfonic acid was deposited on a glass slide. The pattern of the aluminum line was deposited on this surface by the metal mask. The pattern was transferred to polyaniline by oxygen reactive ion etching. The remaining aluminum was then etched with dilute hydrochloric acid solution. This method is ideal for relatively large features. As shown in FIGS. 30 and 31, a polyaniline line of 50 μm was produced in this manner.

9. Polypyrrole polymerized in situ with substituted polythiophenes was also patterned in this manner.

10. The polyaniline acrylamidopropanesulfonic acid film can be directly patterned by exposure to radiation such as an electron beam. Upon irradiation, the polymer crosslinks and becomes insoluble. The unexposed areas are removed by solvent washing to obtain a pattern of conductive polyaniline.

The conductive polymer can be spin applied, immersed, roll coated, spray coated, or spray coated on the substrate, or polymerized in situ chemically or electrochemically at the surface.

In order for the conductive polymer to be used in the liquid crystal display, it is preferable that the light transmittance of the film exceeds 80% in the visible region. 32 depicts the light transmittance of polyaniline acrylamidopropanesulfonic acid (blanket and patterned lines). As can be seen from the graph, the polymer as a film of 500 Hz has a transmittance of greater than 90% over the entire visible region. This is consistent with typical light transmittance of annealed indium tin oxide. The conductivity of the polyaniline wire is about 100 S / cm, preferably greater than 100 S / cm. This material is environmentally stable in that its conductivity does not change over time in air. This material is thermally stable up to about 150 ° C.

Since the properties of this material are considered to be excellent, a liquid crystal battery was assembled using a conductive polymer such as polyaniline as a positive electrode, a polyaniline as one electrode, and indium tin oxide as another electrode. When polyaniline was used as the positive electrode, one electrode consisted of patterned lines and the other electrode consisted of a blanket film. An alignment layer of polyimide (Nissan SE5210) was spin coated onto polyaniline. The polyimide was cured at 125 ° C. for 1 hour. This film was 500 mm thick. The polyimide layer was then mechanically rubbed. Test cells were filled with Merck liquid crystals containing a leftward chiral agent. The polarizer was attached to the outside of the glass so that the transmission axis of the polarizer was parallel to the friction direction. In this way, the nematic test plate twisted 90 degrees to the right was completed. Then, the performance of the liquid crystal battery was measured. 33 depicts the transmittance / voltage characteristics of a liquid crystal cell consisting of two polyaniline electrodes. This is consistent with the transmittance / voltage characteristic exhibited by the crystal composed of indium tin oxide electrode (FIG. 34). The charge retention of the liquid crystal containing the polyaniline electrode was 95% at room temperature (FIG. 35). This also coincides with the charge retention rate indicated by the liquid crystal battery composed of the ITO electrode. The phase adhesion of the liquid crystal battery was also in good agreement.

36 shows a surface 411 of the substrate 413 with a layer of material 415 disposed thereon and a material disposed on the surface 411 such that the material 417 overlaps the material 415 in the overlap region 419. The layer of 417 is shown. Material 417 may be an electrically conductive polymer according to the present invention, and material 415 may be a nonpolymeric electrically conductive material such as a metal or a semiconductor. In addition, the two regions 417 and 415 can be electrically conductive polymers.

FIG. 37 shows surface 423 of substrate 421 with layers of materials 425 and 427 abutting at interface 429. Materials 425 and 427 may be electrically conductive polymers, or one layer of 425 and 427 may be electrically conductive polymers, and the other may be a nonpolymeric electrically conductive material such as a metal or a semiconductor.

Methods of patterning the electrically conductive polymers taught herein and methods of patterning nonpolymeric electrical conductors known in the art can be used to facilitate the structures of FIGS. 36 and 37.

38 shows substrate 802, buried electrons 804, lightly doped region 896, base region 808, emitter region 810, dielectric layer 812, electron collecting electrons A bipolar transistor is schematically depicted with region 814 highly doped to contact region 804. The dielectric layer has an opening 816 for contacting the emitter, an opening 818 for contacting the base region and an opening 820 for contacting the region 814 for contacting the small electrons 804. Patterned electrical conductors or electrodes 822, 824, and 826 provide electrical contact to the emitter, base, and current collector regions, respectively.

The electrodes 822, 824 and 826 can be made of an electrically conductive polymer according to the present invention. The electrically conductive polymer is ohmic in contact with the active device regions 810, 808 and 814.

Examples of electrically conductive polymers that can be used to practice the invention include substituted and unsubstituted polyparaphenylenes, polyparaphenylenevinylenes, polyanilines, polyazines, polythiophenes, poly-p-phenylene sulfides, polyfurans , Polypyrrole, polyselenophene, polyacetylene formed from soluble precursors, combinations thereof and copolymers of these monomers. The general formulas of these polymers, the structures made from them, and methods of use thereof are described in US Patent No. 5,198,153, filed Feb. 9, 1994 to Angelo Paulos et al., The teachings of which are incorporated herein by reference. Pending US patent application Ser. No. 08 / 193,926 and co-pending US patent application Ser. No. 08 / 476,141 filed June 7, 1995.

The polyaniline class of conductive polymers has been shown to be one of the most promising and most suitable for a wide range of commercial applications. The polymer has good environmental stability and provides a simple one step synthesis. Many soluble derivatives can be prepared. For example, we have already disclosed a new class of water soluble conductive polyaniline in US Pat. No. 5,370,825, the teachings of which are incorporated herein by reference.

The following US patents describe resists useful in practicing the present invention, which are incorporated herein by reference: 5,580,694, 5,554,485, 5,545,509, 5,492, 793, 5,401,614, 5,296,332 5,240,812, 5,071,730, 4,491,628, 5,585,220, 5,561,194, 5,547,812, 5,498,765, 5,486,267, 5,482,817, 5,464,726, 5,380,500, 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, 5,459,512,5,059,512 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, 5,053,418,818 5,322,765, 5,250,395, 1st 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, 29,5,5,238,5,5,238 , 5,229,251, 5,215,861, 5,204,226, 5,115,095, 5,110,711, 5,059,512, 5,041,358, 5,023,164, 4,999,280, 4,981,909, 4,908,4,8,838,286, 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, 4,603,195, 4,4,601,913 4,552,833, 4,507,331, 4,493,855, 4,464,460, 4,430,153, 4,307,179, 4,307,178, 5,362,599, 4,397,939, 5,567,569, 5,342,727, 5,342,727 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, 4,552,911, 4,464,458, 4,409,319, 4,377,633, 4,339,522,430,430,430,430 5,209,815, 4,211,834, 5,260,172, 5,258,264, 5,227,280, 5,024,896, 4,904,564, 4,828,964, 4,745,045, 4,692,205, 4,606,998, 4,600,684,4,600,684 4,567,132, 4,564,584, 4,562,091, 4,539,222, 4,493,855, 4,456,675, 4,359,522, 4,289,573, 4,284,706, 4,238,559, 4,224,36212, 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, 5,114,734,601, 4,886,601 , 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.

While the present invention has been described in terms of preferred embodiments, those skilled in the art will be able to make numerous modifications, changes, and improvements without departing from the spirit and scope of the invention.

Claims (131)

(1) an electronic device having an electrically active portion having a surface, wherein the surface has a dielectric layer with an opening having a periphery to which the electrically active portion is exposed; ② an electrically conductive polymer layer disposed over the dielectric layer And wherein the electrically conductive polymer layer is in electrical contact with the electrically active portion through the opening, and wherein the periphery is disposed over the dielectric layer. The method of claim 1, The electronic device has a plurality of openings that expose the plurality of active regions in the dielectric layer, the electrically conductive polymer electrically contacts the plurality of electrically active regions, and the electrically conductive polymer connects the electrical contacts with the exposed plurality of electrically active regions. Structure with parts. The method of claim 1, A structure in which an electrically conductive polymer layer is patterned. The method of claim 1, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof and blends of these and other polymers, copolymers of these monomers. ① surface; ② comprises an electrically conductive polymer layer patterned on this surface, At least one portion of the electrically conductive polymer layer is in electrical contact with the surface, and the other portion of the electrically conductive polymer layer is not in electrical contact with the surface. The method of claim 5, And further comprising a dielectric material disposed between the other portion of the electrically conductive polymer layer and the surface of the structure. The method of claim 5, A structure wherein the surface is selected from the group consisting of electrical conductors and semiconductors. The method of claim 7, wherein A structure in which a semiconductor is formed of a material selected from the group consisting of organic and inorganic materials. The method of claim 7, wherein A structure in which the electrical conductor is formed of a material selected from the group consisting of metals and polymers. The method of claim 1, A structure wherein the electronic device is selected from the group consisting of liquid crystal devices, transistor devices, light emitting devices, and light absorbing devices. The method of claim 10, A structure wherein the transistor is selected from the group consisting of bipolar transistors and field effect transistors. The method of claim 10, A structure in which the light emitting device is a light emitting diode. The method of claim 10, A structure in which the light absorbing device is a charge coupling device. ① an electrically conductive surface with a peripheral edge; ② comprises an electrically conductive polymer layer having a peripheral edge, A structure having an area where the peripheral edge of the electrically conductive surface is not aligned with the peripheral edge of the electrically conductive polymer layer. ① first description; ② second base material; (3) a liquid crystal layer disposed between these first and second substrates, At least one of the first substrate and the second substrate has an electrically conductive polymer disposed thereon, providing a means for applying a potential across the liquid crystal layer. The method of claim 15, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. The method of claim 15, A structure having a first electrically conductive polymer layer disposed thereon and a first substrate having a second electrically conductive polymer layer disposed thereon. The method of claim 15, A structure wherein the electrically conductive polymer layer is a continuous membrane. The method of claim 15, Structures with electrically conductive polymers patterned. The method of claim 17, The structure in which the first electrically conductive polymer layer is a continuous membrane and the second electrically conductive polymer layer is patterned. The method of claim 15, Wherein one of the first substrate and the second substrate has an electrically conductive polymer disposed thereon, and the other of the first substrate and the second substrate has an indium tin oxide (ITO) layer thereon. The method of claim 15, A structure in which the electrically conductive polymer contains a dopant. The method of claim 15, A structure that is a transmissive structure. The method of claim 15, Reflective structures. The method of claim 15, At least one polarizing layer, at least one liquid crystal alignment layer in contact with the liquid crystal layer. The method of claim 23, The structure wherein both the first substrate and the second substrate are transparent to the electron beam. The method of claim 15, A structure wherein one of the first substrate and the second substrate is transparent to the electron beam and the other reflects the electron beam. The method of claim 15, A structure in which the first substrate and the second substrate are made of a material selected from the group consisting of glass, semiconductors, and ceramics. The method of claim 15, The structure wherein the first substrate is glass and the second substrate is a semiconductor. The method of claim 15, Structures in which the electrically conductive polymer is transparent. The method of claim 27, The structure wherein the reflective substrate further comprises a circuit pattern thereon. The method of claim 31, wherein A structure wherein the circuit pattern comprises a patterned electrically conductive polymer. Liquid crystal display comprising a patterned electrically conductive polymer. A first substrate having opposing first and second surfaces, the first substrate having a first electrically conductive layer disposed on the first surface; A first alignment layer disposed over the first electrically conductive layer; A second substrate having opposing first and second surfaces, wherein a second electrically conductive layer is disposed on the first surface, and an alignment layer is disposed on the second electrically conductive layer; ④ a first polarizer layer disposed on the second surface of the first substrate; A second polarizer layer disposed on the second surface of the second substrate; (6) a sealed spacer between the first substrate and the second substrate, wherein a cavity is formed between the first substrate, the second substrate, and the sealed spacer- Wherein the first substrate is disposed adjacent to the second substrate such that the first alignment layer is opposite the second alignment layer, the cavity is filled with a liquid crystal material, and one of the first electrically conductive layer and the second electrically conductive layer The structure is an electrically conductive polymer layer. The method of claim 12, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A liquid crystal display structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. (1) a semiconductor substrate having a first surface and a second surface; A reflective layer on at least a portion of the first surface; (3) a transparent surface disposed spaced apart from the semiconductor substrate; (4) a liquid crystal material disposed between the semiconductor substrate and the transparent substrate; ⑤ an electrically conductive polymer layer disposed on at least one of the transparent substrate and the semiconductor substrate Liquid crystal display structure comprising a. The method of claim 36, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. ① description; A patterned gate formed from a patterned electrically conductive material disposed over the substrate; An insulating layer disposed over the patterned gate; A patterned source electrode disposed over the insulating layer; A patterned drain electrode disposed over the insulating layer; ⑥ a semiconductor material disposed over an insulating layer between these patterned sources and patterned drains And wherein at least one of the patterned source electrode, the patterned drain electrode, and the patterned gate is formed of an electrically conductive polymer. The method of claim 38, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. The method of claim 38, A structure wherein the semiconductor material is selected from the group consisting of organic and inorganic materials. (1) an electrically conductive substrate that is a gate electrode; An insulating layer disposed on the substrate; A patterned source electrode disposed over the insulating layer; A patterned drain electrode disposed over the insulating layer; A semiconductor material disposed over the gate between the patterned source and the patterned drain And wherein at least one of the source electrode and the drain electrode is formed of an electrically conductive polymer. 42. The method of claim 41 wherein At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. 42. The method of claim 41 wherein A structure wherein the semiconductor material is selected from the group consisting of organic and inorganic materials. 42. The method of claim 41 wherein A structure wherein the substrate is formed of a material selected from the group consisting of silicon, germanium, gallium arsenide. ① description; A patterned gate that is an electrically conductive material disposed over the substrate; An insulating layer disposed over the patterned gate; ④ a semiconductor layer disposed over the insulating layer; A patterned source disposed over the semiconductor layer; ⑥ patterned drain disposed over semiconductor layer And wherein at least one of the patterned gate, patterned source, and patterned drain is an electrically conductive polymer. The method of claim 45, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. The method of claim 45, A structure wherein the semiconductor material is selected from the group consisting of organic and inorganic materials. The method of claim 47, Wherein the semiconductor layer is selected from the group consisting of Si, Ge, G, Ar, and combinations thereof. (1) an electrically conductive substrate that is a gate electrode; An insulating layer disposed over the gate; A semiconductor layer disposed over the insulating layer; ④ a patterned source disposed over the semiconductor layer; A patterned drain disposed over the semiconductor layer And wherein at least one of the gate, patterned source, and patterned drain is an electrically conductive polymer. The method of claim 49, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. The method of claim 49, A structure wherein the semiconductor material is selected from the group consisting of organic and inorganic materials. ① an insulating layer having a first side and a second side; A gate disposed on the first surface of the insulating layer; A semiconductor layer disposed on the second surface; A patterned source electrode disposed in electrical contact with the semiconductor layer; A patterned drain electrode disposed in electrical contact with the semiconductor layer And wherein at least one of the patterned gate, the patterned source and the patterned drain is an electrically conductive polymer. The method of claim 52, wherein At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. The method of claim 53, wherein A structure wherein the semiconductor material is selected from the group consisting of organic and inorganic materials. A semiconductor layer selected from the group consisting of organic and inorganic materials; A patterned electrically conductive polymer disposed over the semiconductor layer And the patterned electrically conductive layer forming ohmic contacts in the semiconductor layer. The method of claim 55, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. ① electroluminescent area; ② anode; A structure comprising a cathode, wherein at least one of the anode and the cathode is an electrically conductive polymer. The method of claim 57, The structure wherein the electrically conductive polymer is selected from the group consisting of hole injection materials and electron injection materials. The method of claim 58, Structures with electrically conductive polymers patterned. ① electroluminescent area; ② hole injection region; A structure comprising an electron injection region, wherein the electrically conductive polymer provides electrical contact to at least one of the hole injection region and the electron injection region. ① description; ② anode structure; ③ electroluminescent area; ④ cathode structure; (5) An organic light emitting diode comprising a patterned electrically conductive polymer electrically coupled to at least one of the cathode region and the anode region and covered by a protective layer of a wear resistant, phosphorous resistant electrically conductive polymer. The method of claim 57, A structure in which the electroluminescent region is formed of a material selected from the group consisting of organic and inorganic materials. The method of claim 57, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, A structure selected from the group consisting of polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. The method of claim 60, A diode wherein the electroluminescent region is formed from a material selected from the group consisting of organic and inorganic materials. 62. The method of claim 61, A diode wherein the electroluminescent region is formed of a material selected from the group consisting of organic and inorganic materials. A light emitting diode comprising a patterned electrically conductive polymer. The method of claim 57, A diode further comprising indium tin oxide. The method of claim 57, Diode whose anode is a transparent conductor. The method of claim 57, Diodes whose conductor is indium tin oxide. The method of claim 57, A diode in which the emitting region is one organic electroluminescent layer. The method of claim 57, A diode wherein the electroluminescent region comprises an organic layer stack comprising at least one of an electroluminescent layer and an electron transport layer, wherein the thin metal layer is a direct contact electron transport layer. The method of claim 57, A diode further comprising a transparent substrate. The method of claim 72, Diode wherein the substrate is translucent. The method of claim 72, Diode opaque substrate. The method of claim 74, wherein A diode wherein the material of the substrate is selected from the group consisting of glass, plastic and silicon. The method of claim 72, Structures in which the substrate is flexible. 60. An array comprising at least one organic light emitting diode according to claim 57. 78. The method of claim 77 wherein And an array further comprising a single crystal substrate comprising an electronic circuit. The method of claim 78, An array in which circuits control the light emitted from the array. ① providing a substrate having a layer of electrically conductive polymeric material; ② placing a layer of energy sensitive material over the layer of electrically conductive polymer material; (3) exposing a resist to a pattern of energy to form a pattern in the layer of energy sensitive material; ④ developing the pattern to form a pattern in the layer, thereby forming exposed and unexposed regions of the electrically conductive polymer; ⑤ removing the electrically conductive polymer of the exposed area; ⑥ removing the resist leaving a pattern of electrically conductive polymer on the substrate How to include. 81. The method of claim 80, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, Polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. 81. The method of claim 80, Energy is selected from the group consisting of electron beams, heat, and particle beams. 81. The method of claim 80, A method of performing a developing step by removing areas of resist exposed to energy. 81. The method of claim 80, A method of performing a development step by removing areas of resist that are not exposed to energy. 84. The method of claim 83 wherein Method of carrying out the removal step by chemical dissolution. 87. The method of claim 84, Method of carrying out the removal step by chemical dissolution. 81. The method of claim 80, A method of performing a removal step by reactive ion etching. ① providing a substrate having an electrically conductive polymeric material; (2) depositing a pattern of the metal layer on the layer of electrically conductive polymer by a metal mask forming a patterned metal layer, and forming an area covered by the metal pattern and an exposed area of the electrically conductive polymer; (3) etching the exposed area to remove the exposed area; ④ Step of removing metal How to include. 89. The method of claim 88 wherein At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, Polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. 92. The method of claim 89, The mask is a molybdenum mask and the metal is platinum. 92. The method of claim 89, Wherein the etching is reactive ion etching. 92. The method of claim 89, How exposed areas are removed with acid. ① providing a substrate having an electrically conductive polymer layer; ② placing a metal layer over the electrically conductive polymer layer; ③ placing an energy sensitive material over the metal layer; ④ exposing the energy sensitive material to a radiation pattern; Developing the pattern to form a pattern in the energy sensitive material, thereby forming exposed and unexposed regions of the metal layer; ⑥ removing the metal layer from the exposed areas to form exposed and unexposed areas of the electrically conductive polymer; ⑦ removing the exposed areas of the electrically conductive polymer; ⑧ removing the energy sensitive material; ⑨ Removing the rest of the metal layer How to include. 94. The method of claim 93, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, Polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. 94. The method of claim 93, The metal layer is selected from the group consisting of Al. 94. The method of claim 93, The radiation is an electron beam. 94. The method of claim 93, Removing the metal layer by acid etching in the exposed area. 94. The method of claim 93, A method for removing electrically conductive polymers by reactive ion etching in exposed areas. 94. The method of claim 93, Removing the remainder of the metal layer with an acid etchant. 1. providing a substrate having a layer of electrically conductive polymeric material containing an energy sensitive agent; (2) exposing the electrically conductive polymer to a pattern of energy to form a pattern of unexposed regions; ③ removing the electrically conductive polymer in one of the exposed and unexposed areas, thereby forming a pattern of the electrically conductive polymer on the substrate How to include. 101. The method of claim 100, At least one substituted and unsubstituted polyparaphenylene vinylene, polyparaphenylene, polyaniline, polythiophene, polyazine, polyfuran, polypyrrole, polyselenophene, poly-p-phenylene sulfide, Polyacetylene, combinations thereof, these and other polymers, blends of copolymers of these monomers. 101. The method of claim 100, Energy is selected from the group consisting of electron beams, heat, and particle beams. 101. The method of claim 100, A method of performing a developing step by removing areas of resist exposed to energy. 101. The method of claim 100, A method of performing a developing step by removing areas of resist exposed to energy. 103. The method of claim 103, Method of carrying out the removal step by chemical dissolution. 105. The method of claim 104, Method of carrying out the removal step by chemical dissolution. 101. The method of claim 100, A method of performing the removal step by reactive ion etching. 101. The method of claim 100, The energy sensitive agent is a component of an electrically conductive polymer. 101. The method of claim 100, The energy sensitive agent is an additive to the electrically conductive polymer. 109. The method of claim 108, Wherein the electrically conductive polymer comprises a precursor and a dopant of the electrically conductive polymer. 113. The method of claim 110, Wherein said component is above said precursor. 113. The method of claim 110, Wherein said component is above said dopant. A structure comprising ohmic contacts between an electrically conductive polymer and a semiconductor. 113. The method of claim 113, A structure wherein the semiconductor is selected from the group consisting of organic semiconductors and inorganic semiconductors. A structure comprising a low contact resistance electrical joint between a nonpolymeric electrical conductor and an electrically conductive polymer. (1) providing a field effect transistor having a source region, a drain region, and a gate region; ② forming a source electrode, a drain electrode, a gate electrode And wherein at least one of the source electrode, the drain electrode, and the gate electrode is formed by patterning the electrically conductive polymer. Providing a bipolar transistor having an emitter region, a base region and a current collector region; ② forming an emitter electrode, a base electrode, and a collector electrode And wherein at least one of the emitter electrode, the base electrode, and the current collector electrode is formed by patterning the electrically conductive polymer. A bipolar transistor having at least one of an emitter region, a base region and a current collector region; ② emitter electrode, base electrode, current collector electrode And wherein at least one of the emitter electrode, base electrode, current collector electrode is a patterned electrically conductive polymer. (1) providing a light emitting diode having an electroluminescent region, an anode region and a cathode region; ② forming a positive electrode and a negative electrode Wherein the at least one of the positive electrode and the negative electrode is formed by patterning an electrically conductive polymer layer. (1) providing a light emitting diode having an electroluminescent region, an anode region and a cathode region; ② forming a positive electrode and a negative electrode And wherein at least one of the anode region and the cathode region is formed of an electrically conductive polymer. 121. The method of claim 120, wherein At least one of the anode region and the cathode region is formed by patterning the electrically conductive polymer. ① providing an electronic device having an electrically active area; ② forming an electrical contact in the electrically active region by patterning the electrically conductive polymer. ① a layer of non-electrical material; (2) a dielectric material layer having an edge, having a first surface and a second surface disposed over the non-electrical material layer; A structure comprising an electrically conductive polymer layer disposed over the second surface beyond the edge of the non-electrical material layer. ① a semiconductor layer having a first side and a second side; A dielectric layer on the first side; A first patterned electrically conductive layer over the dielectric layer; ④ a second patterned electrically conductive layer on the second side And wherein at least one of the first, second, third patterned electrically conductive layers is an electrically conductive polymer. A field effect transistor comprising a source electrode, a drain electrode and a gate electrode, at least one of which is a patterned electrically conductive polymer. ① an insulating layer having a first side and a second side; A gate disposed on the first surface of the insulating layer; A semiconductor layer disposed on a second surface above the patterned source electrode and the patterned drain electrode; ④ patterned source electrode disposed on the second side And wherein at least one of the patterned gate, patterned source, and patterned drain is an electrically conductive polymer. A semiconductor layer selected from the group consisting of organic and inorganic semiconductors; A patterned electrically conductive polymer layer disposed over the semiconductor layer Structure comprising a. ① semiconductor layer; A first opening in the dielectric layer, exposing the semiconductor layer in the first region; A second opening in the dielectric layer, exposing the semiconductor layer in the second region; ④ a first pattern of electrical conductors arranged to be in electrical contact with the first region; A second pattern of electrical conductors arranged to be in electrical contact with the second region; ⑥ an electrical conductor of a third pattern disposed over the dielectric layer between the first and second patterns; ⑦ The structure wherein at least one of the first, second, and third patterns of the electrical conductor is a patterned electrically conductive polymer. ① electroluminescent area; ② hole injection region; ③ electron injection region; ④ anode contact; A structure comprising a cathode contact, wherein at least one of the hole injection region and the electron injection region is an electrically conductive polymer. A field effect transistor having a gate electrode, a source electrode, and a drain electrode, at least one of which is a patterned electrically conductive polymer. A bipolar transistor having an emitter electrode, a base electrode, and a collector electrode, at least one of which is a patterned electrically conductive polymer.