CA1291905C - Electronic device fabrication on non-conductive polymer substrate - Google Patents
Electronic device fabrication on non-conductive polymer substrateInfo
- Publication number
- CA1291905C CA1291905C CA 558593 CA558593A CA1291905C CA 1291905 C CA1291905 C CA 1291905C CA 558593 CA558593 CA 558593 CA 558593 A CA558593 A CA 558593A CA 1291905 C CA1291905 C CA 1291905C
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- polyaniline
- conductive polymer
- conductive
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/003—Apparatus or processes specially adapted for manufacturing resistors using lithography, e.g. photolithography
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/003—Thick film resistors
- H01C7/005—Polymer thick films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F5/00—Coils
- H01F5/003—Printed circuit coils
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Abstract
ABSTRACT OF THE DISCLOSURE
A process for fabricating an electronic device on a non-conductive polymer substrate, particularly from the family of polyaniline, comprises applying a covalent doping agent, such as an R+ donor compound, where R is an organic group, e.g., methyl iodide, to a preselected portion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, and converting such preselected portion of the polymer substrate to an electrically conductive polymer portion, by covalent linkage of the R
groups of such donor compound, to nitrogen atoms of the non-conductive polymer substrate. Electronic devices, such as resistors, capacitors, inductors, printed circuits and the like, can be provided by the invention process, in the form of light-weight polymers containing no metal, and which are stable and wherein the conductive portions are non-diffusing.
A process for fabricating an electronic device on a non-conductive polymer substrate, particularly from the family of polyaniline, comprises applying a covalent doping agent, such as an R+ donor compound, where R is an organic group, e.g., methyl iodide, to a preselected portion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, and converting such preselected portion of the polymer substrate to an electrically conductive polymer portion, by covalent linkage of the R
groups of such donor compound, to nitrogen atoms of the non-conductive polymer substrate. Electronic devices, such as resistors, capacitors, inductors, printed circuits and the like, can be provided by the invention process, in the form of light-weight polymers containing no metal, and which are stable and wherein the conductive portions are non-diffusing.
Description
12~19Q~
ELEC~RONIC DEVICE FABRICATION ON
NON-CONDUCTIVE POLYMER SUBSTRATE
BACKGROUND OF THE INV~NTION
The present invention relates to the production of electronic devices and is particularly concerned with a process for the fa~rication of electronic devices employing a non-conductive polymer substrate, portions of which can be selectively rendered conductive by suitable chemical treatment.
The free-base form of polyaniline is electrically non-conductive. Protonic acid doping of polyaniline by reaction of polyaniline with a protonic acid HX where X is, for example, Cl, to produce electrically conductive polyaniline is known, for example, as disclosed in.A. G.
MacDiarmid, et al, Mol. Cryst. Liq. Cryst., 121, 173 (1985).
Conductive polyaniline of this type has been employed in batteries, as disclosed in French Patent No. 1,519,729.
However, if a film or bulk polymer of a material, such as polyaniline, is subjected to treatment in preselected regions, as by normal protonic acid treat~lent, to form doped conductive regions, for example, to form a conductive strip, such conductive regions or strip remains conductively stable only for a very short time, after which , . . . _ . ., .. _ .. . . _ _ . _ _ _ . = _ _ _ _ ., , _ _ _ . _ _ _, . .. ... . .. . .. .. .. .
~Z91~0S
such conductive regions diffuse, causing the entire piece to have constant conductivity.
Further, base-type conductlve polymers, as represented by the protonic ac~d-doped polyaniline class of conductive polymers, are unstable and degrade when exposed to water. Stabil-ity on contact with water is extremely rare in prior art conducting polymers, such as produced by treatment of polyaniline with protonic acids.
The present invention seeks to enable the construction of polymeric electronic devices without the use of metals.
The invention also seeks to provide a process for producing electronic devices on a non-conductive polymer substrate which can be selectively converted by suitable treatment to provide conductive portions which do not tend to diffuse.
The invention also seeks the provision of novel procedure for the production of electronic devices, as noted above, wherein the conductivity of the conducting portions of such devices does not degrade if the components of the device are exposed to water.
SUMMARY OF THE INVENTION
-According to the present invention there is provided a process for producing an electronic device on a non-conductive polymer substrate which comprises applying a covalent doping agent to a preselected portion of a base-type non-conductive poly-mer substrate containing carbon-nitrogen linkages, said agent being capable of covalently binding to the nitrogens of said polymer, said covalent doping agent being an R donor compound containing :"
9~0S
an organic cation group, the R+ donor compound being selected from the group consisting of RX, R30X, R2S04, R'S02Cl, and R"3SiCl, where R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6 , SbC16 and benzene sulfonate, and wherein the base-type non-conductive polymer substrate is selected from the group consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives, and converting said preselected portion of said polymer substrate to an electrically conductive polymer portion in which such cation groups are covalently linked to the nitrogen atoms of said pre-selec~ed polymer portion.
The invention also provides a process for producing an electronic device on a polyaniline substrate, which comprises applying to a preselected region of a base-type non-conductive polymer having the general formula:
H H
( - A - N - A - N = A = N - A - N )y where A is a carbon-containing aryl group and y is an integer ranging from about 1 to about 1,000, a compound selected from the group consisting of RX, R30X, R2S04, R'S02Cl, and R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6 , SbC16 , S02~1 and benzene sulfonate, and forming an electrically conductive polymer region on said non-conductive polymer substrate.
1~91905 The invention additionally provides a process for producing an electronic device on a non-conductive polymer sub-strate which comprises applying a covalent doping agent to a preselected portion of a non-conductive polyaniline substrate, said agent being capable of covalently binding to the nitrogens of said polyaniline, and converting said preselected portion of said polyaniline substrate to an electrically conductive poly-aniline portion.
The invention also provides a process for producing an electronic device on a non-conductive polymer substrate which comprises applying a covalent doping agent to a preselected por-tion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, said agent being capable of covalently binding to the nitrogens of said polymer, and converting said ~
preselected portion of said polymer substrate to an electrically conductive polymer porticn, wherein the base-type non-conductive polymer substrate is selected from the group consisting of poly-aniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives.
The invention further provides a process for producing an electronic device on a polyaniline substrate, which comprises applying to a preselected region of a non-conductive polyaniline free-base substrate a compound selected from the group consisting of RX, R30X, R2S04, R'S02Cl, and R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, ., PF6 , SbC16 , SO2Cl and benzene sulfonate, and forming an elec-trically conductive polyaniline region on said non-conductive polyaniline substrate.
Another aspect of the invention provides an electronic device free of metal, which comprises a base-type non-conductive polymer substrate containing carbon-nitrogen linkages and having an electrically conductive polymer region comprising an organic dopant group covalently linked to nitrogen atoms of said polymer substrate.
The invention provides carbocation doping of preselec-ted portions of a base-type non-conductive polymeric substrate, particularly from the polyaniline family, to form conducting por-tions on the non-conductive substrate. This can be accomplished, e.g., according to one embodiment, by applying a mask to the non-conductive polymer substrate, leaving certain preselected areas or regions of the polymer substrate not covered by the mask exposed, and treating the exposed areas of the polymer substrate, as by spraying, with an organic material of a type which reacts with the exposed polymer regions to render them conductive, by covalent linkage of the organic group to the nitrogen atoms of the polymer.
The base-type non-conductive polymer forming the sub-strate is of the type which contains carbon-nitrogen linkages, as in polyaniline. The material which is applied, as by spraying, immersion or brushing, to the preselected exposed areas of the polymer substrate is an R donor compound, where R is an organic - 3b -c _ ~'~9~05 cation group, such R group being capable of covalently binding to the nitrogens of the polymer, and forming an electrically conductive polymer in which the R groups are covalently linked to the nitrogen atoms of the polymers, in the preselected or exposed portions - 3c -rB
of the substrate.
More partlcularly, in one embodiment, the preselected or exposed portions of the non-conductive polymer substrate containing carbon-nitrogen linkages, particularly as represented by the free-base polyaniline, can be treated and reacted with an R donor compound, such as R X or R30 X , where R is a strong donor, i.e., an organic cation, such as an alkyl group, e.g., CH3 , and X ls a stable anion, such as I , e.g., as provided by CH3I, to form a polymer salt ln which a covalent bond is formed between a nitrogen and the organic R group.
The reaction of base-type non-conductive polymers, such as polyaniline, wlth a compound or agent of the above type to produce base-type conducting polymers, is disclosed in co-pending Canadian appllcatlon, Serial No. 55~,364 Siled December 24, 1987, titled "Production of Base-Type Conducting Polymers", and assigned to the same assignee as ~he present application.
In another embodlment, such preselected portions of the non-conductive polymer 6ubstrate containing carbon-nitrogen linkages can be treated with an R+ donor compound, such as R2S04, R'S02Cl, or R3SiCl, where R , R'S02+ or R3Si is a strong donor or organic cation, and RS0; or the Cl is a stable anion, to form a polymer salt in which a covalent bond is formed between the nitrogen of the polymer and such donor cation.
T~e reaction oi base-type non-conductive polymers, such as polyanlline, with a compound, such as R2S04, R'S02C1, or R3SiCl, to produce base-type conductin~ po~ymers, is disclosed in r,~
12~ 05 ~S Patent No. 4,806,27 issued February 21, 1989, by Stuart I.
Yaniyer, et a1, titled "Preparation of Base--'rype Conductive Po1ymers", and assiyned to the same assignee as the present application.
The resulting polymer substrate, following treatment with one of the above compounds, has electrically conductive portions in pre-selested areas surrounded by the non-conductive polymer substrate. In the exposed conductive, e.g., non-masked, areas wherein there is a covalent linkage between the above-noted donor cation groups and nitrogens in the polymer, this results in pinning the conductive region, so that the region to which the treating agent has been applied, e.g., in the form of a strip, remains conductive, with substantially no diffusion taking place to other regions of the substrate. In addition, the preselected conductive regions on the polymer substrate do not lose conductivity on contact with water.
Utilizing the above concept, various electronic components which do not contain metal can be fabricated according to the invention, which are stable, and have the advantages of light we1ght and flexibility, provided by the 1291~305 use of polymers, as substrate, and which can be fabricated at relatively low cost. Electronic devices which can be fabricated by the invention process include resistors, capacitors, inductors, printed circuits, electronic devices with components having conductivity gradients, etc.
/ / /
/ / /
-- 5.1 --1~91~5 BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more clearly unders~ood by reference to the detailed description of the invention, set forth hereinafter, taken in conjunction with the acco~panying drawings wherein:
Fig. 1 illustrates the steps of the procedure according to the invention, for fabricating a resistor;
Fig. 2 illustrates the steps of the invention process for producing a capacitor;
Fig. 3 is an enlarged cross-section of the capacitor produced by the process of Fig. 2, taken on line 3-3 of Fig. 2(c);
Fig. 4 illustrates the steps of the invention procedure for producing an electronic component having conductivity gradients;
Fig. 5 illustrates the procedure for producing an inductor by the invention procedure; and Fig. 6 illustrates production of an electronic device having a conductive loop formed on a non-conductive ~0 polymeric substrate.
/
/ / /
?()5 DETAILED DESCRIPTION OF THE INVENTION
AND PREFERRED EMBODIMENTS
According to the invention, covalent doping of base-type non-conductive polymers, e.g., polyaniline free-base substrates, in preselected regions, yields non-diffusing conductive regions surrounded by insulating polymer substrate. Thus, a passive electronic component can be fabricated by exposure of preselected regions of the substrate base polymer to chemical reactants, such as the above-noted R donor compound, which cause the above-noted chemical reaction.
Referring to Fig. 1 of the drawing, illustrating a mode of procedure for producing a resistor according to the invention, numeral 10 illustrates a base-type non-conductive polymer substrate to which a conductive region is to be applied. A preferred form of non-conductive base-type polymer emploved as substrate are those of the polyaniline family, including polyaniline and derivatives thereof containing naphthyl or biphenyl groups or other aromatic groups, in place of the phenyl groups of polyaniline. Such polymers can include alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenvl derivatives, e.g., 2-methyl biphenyl, butyl naphthalene, 2-methyl aniline derivatives, beta phenyl naphthalene and be~a tolyl naphthalene. Such polymeric substrates also can l~91~(~S
include other base-type polymers containing carbon atoms linked to nitrogen, such as cyanogen polymer of the type:
~N~ ~N~
Another type of polvmer substrate can include mixtures and blends of the above non-conductive homopolymers and copolymers of the above polymers and other polymers, such as a blend of polyaniline and polymethylmethacrylate, and polymer alloys, such as polybenzinidazole-polyimide alloys, containing carbon-nitrogen groups.
Thus, the term "non-conductive polymer substrate"
as employed herein is intended to denote any of the above homopolymer or copolvmer materials.
The invention will be described hereinafter, however mostly in terms of the use of the preferred non-conductive free-base polyaniline as non-conductive polymeric substrate. In the case of polyaniline free-base, this is a high polymer having a molecular weight of the order of 50,000 to 80,000. Lower molecular weight polyaniline, such as emeraldine, can be employed, which is an oligomer of polyaniline containing eight (8) subunits and having a molecular weight of about 800 to 900.
$here is applied to the surface of the non-conductive polymer substrate 10 a mask 12 having a cut-out strip 14 therein. For this purpose, any conventional maskant which is inert to the reactant or 1~9~905 treating agent can be employed. The maskant composition should also be inert with respect to the hase polymer of the substrate. For this purpose, metal masks, such as stainless steel, can be employed. Other metals which can be emploved as maskant include platinum, gold, nickel, and the like.
The metal mask can be suitably adhered to the polymer substrate as by pressure contact, adhesive, and the like, but can be readily removed following chemical treatment.
Alternatively, organic maskants containing as an essential ingredient thereof an organic polymer, such as a chloroprene polymer resin, or a styrene butadiene or a styrene ethylene buty,ene co-polymer, can be employed.
The masked polymeric substrate 12, as seen in Fig.
l(b), is treated, as by spraying, to contact the exposed surface of the pol~er substrate within the cut-out area 14 of the mask, with the treating agent. The treating agent with which the exposed area 16 of the polymer suhstrate is contacted is an R+ donor compound, such as RX, R30X, R2S04, R'S02Cl, or R3SiCl, where R, R'S02 or R3Si is a group which readily forms a covalent bond with nitrogen, and wherein R, R' and R" each can be alkyl, e.g., methyl, ethyl and the like, and aryl, e.g., p-toluene sulfonyl (tos~
benzyl, tolyl, xylyl, and other aromatic moieties, and X is an anion such as halogen, e.~., Cl , I or Br ; PF6 , SbC16 , and substituted and unsubstituted benzene sulfonate, and the like. The above reaction forms a conductive polymer salt.
. _ .. _, . . _ ._ . . . .. ~ . _ _ _ . _ . , :~291~05 Thus; the reactant which forms a covalent chemical bond with the nitrogen of the polyaniline free-ba~e or equivalent polymer noted above, can be, for exam~le, one of the above R+ donor compounds, ~uch as an alkyl halide, wherein the alkvl group can contain from 1 to 20 carbon atoms, such as methyl iodide, or d~methyl~ulfate, (CH3CH2)30 SbC16 , (CH3)2CHI, p-CX3-C6~4S02Cl, (CH3)30 PF6 , (CH3)30S03C6~4C~3 and (CH3)3SiCl. Al~o, multifunctional reagents, e.g., ClS02-C6~4-C6H4-S02Cl can be employed. ~owever, R, R' or R~ al~o can be an oligomeric or polymeric group, e.q., containing from about 20 to about 100,000 carbon atom~, e.q., polyvinyl iodide.
~he reaction for converting the ba~e-type non-conductive polymer portion in the expo~ed area 16 of the sub~trate to a conductive polymer can be repre~ented a~
follows, where RX or R30X i~ the R+ donor compound:
( A - ~ - A - N ~ A - N - A - 5 - ) RX or P30X
IIA ( A - ~ - A - ~ - A - ~ - A - N )y or IIB ( A - ~ - A - ~ - A - ~+ - A - ~ - )y or IIC ~ A - ~+- A - ~ - A - ~ - A - ~ - )y X X X X
~`t~
.,~
OS
where A is a carbon-containing qroup, such as aryl, particularly the benzene ring, and including naphthyl and biphenyl, and substituted benzene, naphthyl or biphenyl groups, such as the alkyl and aryl derivatives described above; R and X are as defined above, and y is an integer ranging from about 1 to about 1,000, e.g., about 10 to about 100. When y is in the lower end of the above range, e.g., when y is 1 or 2, the materials are known as oligomers and are intended to be included within the term "polymer"
employed herein.
Where the preferred non-conductive polvmer employed as the base substrate is polyaniline free-base (PFB), the general reaction scheme for producinq conductive polymer portions when employing the reactant RX or R30X is represented below:
~Z9190~
III ( - ~ - N - ~ - N = ~ = N - ~ - N - ) RX or R30X
X ~ / X
IV ( - ~ - N - ~ - ~ - ~ - N - )~
X~ 1 X~
V ~ R ~ 'NR ~ Y
VI ( ~ ~ ~ ~ ~ ~ R ~
X X X X
where R, X and y have the values noted above.
In the above representative reactions, it will be understood that the R+ donor reactant can alternatively be R2S04, R'S02Cl or R3'SiQ, where Q is a halogen, such as Cl or Br. If the reaction is carred out using R2S04, R+ is the organic cation which is covalently linked to the N atoms of the polymer and X is the stable RS04 anion. When R'S02Cl is the reactant, the organic cation is the R'S02+ group, which is covalently linked to the N atoms of the polymer through the S atom of such group, and X is the stable Cl anion. When R'3SiCl is the reactant, the organic cation is the R'3Si group, which is covalently linked to .. .. . ~
129~91)5 the N atoms of the polymer through the Si atom of such group, and X is the stable Cl anion. When R3SiCl is the reactant, the organic cation is the R3Si+ group, which is covalently linked to the N atoms of the polymer through the Si atom of such aroup, and X is the stable Cl anion.
The reaction can be carried out as a heterogenuous reaction wherein the reactant, e.g., RX, per se, is reacted with the exposed polymer substrate portion, such as polyaniline free-base, or the reactant can be dissolved in a suitable solvent which does not irreversibly react with the R+ donor, such as, e.g., methylene chloride, tetrahydrofuran (THF), acetonitrile, pyridine, dimethylsulfoxide (DMS~) and dimethylformamide (DMF).
However, when employing an R30X donor compound, such as (CH3)30X , and acetonitrile as solvent, the ~CH3)30+ group can react with the CH3C=N solvent to form CH3C=N -CH3 which can also function as a methyl cation donor~
The rate of reaction can range widely, dependinq on the particular R+ donor or reactant employed, and the period of exposure of the exposed polymer substrate portion 16 to the reactant. If the reaction between the exposed polymer, e.g., polyaniline, substrate portion and the R donor compound is carried to completion, the cation or R group can be substituted for every hydrogen on the polymeric chain to form the conductive polymer, as represented by Formula V above. Further reaction results in all amine-like nitrogens forming quaternary ammonium groups, as illustrated by Formula VI above. If the reaction is not carried to completion, only a portion of the hydrogen atoms on the polymer will be substituted by catlon or R groups, as illustrated by Formu:la IV above.
Whele the "R " donor is an "R30X" donor, an ether, R2Q, e.g., dimethyl ether, is given off in the reaction.
The above reactions of an R donor compound with a base-type polymer, particularly polyaniline, for produ~ing base-type conductive polymers are disclosed in Canadian application, Serial No. 555,364 filed on December 24, 1987.
Following treatment of the exposed portion 16 of the substrate with the spray 1~3 of chemical treating agent, the mask 12 is removed, leaving a conducti~re and resistive polyaniline region 20 surrounded by the polyaniline non-conductive or insulating region 22, thus forming a resistor element 24.
Now referring to Fig. 2 of the drawings a non-conductive sheet 26 formed of a base-type polymer, such as polyaniline free-base, has attached to the surfaces on opposite sides 28 thereof a metal, e.g., steel, mask in the form of a peripheral frame 30 around all four sides of the sheet, leaving an ex~?osed central surface portion 32 of non-conductive polymer on each side of the sheet.
A spray of a treating agent 27 in the form of an R
donor compound, such as RX, as described above, is applied to opposite sides 28 of the non-conductive polymer `; 14 ~2gl~0S
sheet 26 and contacting the exposed portions 32 on opposite sides of the sheet. As a result of the reaction of the treating agent with the exposed portions 32 of the polymer sheet 26, there are formed central conductive regions 34 of conductive polymer or conductive polyaniline on opposite sides 28 of the non-conductive polymer sheet, with a non-conductive or insulating border portion 36 around the conductive central portions 34, and a non-conductive or insulating interior portion 38 (see Fig. 3) between the two conductive regions 34. The resulting non-conductive polymer substrate containing the separated conductive regions 34 can function as a capacitor.
If desired, the treating agent can be painted unto the exposed regions 32 on both sides of the non-conductive polymer sheet 26. Further, if desired, the mask 30 can be omitted, and the entire area on both sides of the non-conductive polymeric sheet 26 can be treated, as by spraying or painting, with the treating agent to form conductive regions over the entire area on opposite surfaces of the polymeric sheet, separated by the interior non-conductive region 38. The thickness of the conductive regions 34 depends on the particular treating or doping agent employed and the period of time of exposure of the surfaces of the polymer sheet to the treating agent. Thus, the capacitance of the resulting capacitor can be controlled - lS -lZ91~05 by varying the thickness of the conducting regions 34.
In the processes illustrated in Figs. 1 to 3, the non-conductive polymer substrate is treated in preselected surface portions with a doping agent molecule that S covalently attaches to the polymer base site to form conductive regions surrounded or separated by dielectric or insulating regions.
Conductive regions formed on a dielectric or insulating substrate, such as polyaniline free-base, can be made to have conductivity gradients by reacting different parts of the substrate with a covalent doping agent for different lengths of time, or by selective diffusion into a bulk body of the base insulating polymer.
Thus, referring to Fig. 4, a block of base-type non-conductive polymer, such as polyaniline, at 40 can be immersed in a bath of covalent doping agent or R+ donor compound 42, to a predetermined depth, as shown in Fig.
ELEC~RONIC DEVICE FABRICATION ON
NON-CONDUCTIVE POLYMER SUBSTRATE
BACKGROUND OF THE INV~NTION
The present invention relates to the production of electronic devices and is particularly concerned with a process for the fa~rication of electronic devices employing a non-conductive polymer substrate, portions of which can be selectively rendered conductive by suitable chemical treatment.
The free-base form of polyaniline is electrically non-conductive. Protonic acid doping of polyaniline by reaction of polyaniline with a protonic acid HX where X is, for example, Cl, to produce electrically conductive polyaniline is known, for example, as disclosed in.A. G.
MacDiarmid, et al, Mol. Cryst. Liq. Cryst., 121, 173 (1985).
Conductive polyaniline of this type has been employed in batteries, as disclosed in French Patent No. 1,519,729.
However, if a film or bulk polymer of a material, such as polyaniline, is subjected to treatment in preselected regions, as by normal protonic acid treat~lent, to form doped conductive regions, for example, to form a conductive strip, such conductive regions or strip remains conductively stable only for a very short time, after which , . . . _ . ., .. _ .. . . _ _ . _ _ _ . = _ _ _ _ ., , _ _ _ . _ _ _, . .. ... . .. . .. .. .. .
~Z91~0S
such conductive regions diffuse, causing the entire piece to have constant conductivity.
Further, base-type conductlve polymers, as represented by the protonic ac~d-doped polyaniline class of conductive polymers, are unstable and degrade when exposed to water. Stabil-ity on contact with water is extremely rare in prior art conducting polymers, such as produced by treatment of polyaniline with protonic acids.
The present invention seeks to enable the construction of polymeric electronic devices without the use of metals.
The invention also seeks to provide a process for producing electronic devices on a non-conductive polymer substrate which can be selectively converted by suitable treatment to provide conductive portions which do not tend to diffuse.
The invention also seeks the provision of novel procedure for the production of electronic devices, as noted above, wherein the conductivity of the conducting portions of such devices does not degrade if the components of the device are exposed to water.
SUMMARY OF THE INVENTION
-According to the present invention there is provided a process for producing an electronic device on a non-conductive polymer substrate which comprises applying a covalent doping agent to a preselected portion of a base-type non-conductive poly-mer substrate containing carbon-nitrogen linkages, said agent being capable of covalently binding to the nitrogens of said polymer, said covalent doping agent being an R donor compound containing :"
9~0S
an organic cation group, the R+ donor compound being selected from the group consisting of RX, R30X, R2S04, R'S02Cl, and R"3SiCl, where R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6 , SbC16 and benzene sulfonate, and wherein the base-type non-conductive polymer substrate is selected from the group consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives, and converting said preselected portion of said polymer substrate to an electrically conductive polymer portion in which such cation groups are covalently linked to the nitrogen atoms of said pre-selec~ed polymer portion.
The invention also provides a process for producing an electronic device on a polyaniline substrate, which comprises applying to a preselected region of a base-type non-conductive polymer having the general formula:
H H
( - A - N - A - N = A = N - A - N )y where A is a carbon-containing aryl group and y is an integer ranging from about 1 to about 1,000, a compound selected from the group consisting of RX, R30X, R2S04, R'S02Cl, and R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6 , SbC16 , S02~1 and benzene sulfonate, and forming an electrically conductive polymer region on said non-conductive polymer substrate.
1~91905 The invention additionally provides a process for producing an electronic device on a non-conductive polymer sub-strate which comprises applying a covalent doping agent to a preselected portion of a non-conductive polyaniline substrate, said agent being capable of covalently binding to the nitrogens of said polyaniline, and converting said preselected portion of said polyaniline substrate to an electrically conductive poly-aniline portion.
The invention also provides a process for producing an electronic device on a non-conductive polymer substrate which comprises applying a covalent doping agent to a preselected por-tion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, said agent being capable of covalently binding to the nitrogens of said polymer, and converting said ~
preselected portion of said polymer substrate to an electrically conductive polymer porticn, wherein the base-type non-conductive polymer substrate is selected from the group consisting of poly-aniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives.
The invention further provides a process for producing an electronic device on a polyaniline substrate, which comprises applying to a preselected region of a non-conductive polyaniline free-base substrate a compound selected from the group consisting of RX, R30X, R2S04, R'S02Cl, and R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, ., PF6 , SbC16 , SO2Cl and benzene sulfonate, and forming an elec-trically conductive polyaniline region on said non-conductive polyaniline substrate.
Another aspect of the invention provides an electronic device free of metal, which comprises a base-type non-conductive polymer substrate containing carbon-nitrogen linkages and having an electrically conductive polymer region comprising an organic dopant group covalently linked to nitrogen atoms of said polymer substrate.
The invention provides carbocation doping of preselec-ted portions of a base-type non-conductive polymeric substrate, particularly from the polyaniline family, to form conducting por-tions on the non-conductive substrate. This can be accomplished, e.g., according to one embodiment, by applying a mask to the non-conductive polymer substrate, leaving certain preselected areas or regions of the polymer substrate not covered by the mask exposed, and treating the exposed areas of the polymer substrate, as by spraying, with an organic material of a type which reacts with the exposed polymer regions to render them conductive, by covalent linkage of the organic group to the nitrogen atoms of the polymer.
The base-type non-conductive polymer forming the sub-strate is of the type which contains carbon-nitrogen linkages, as in polyaniline. The material which is applied, as by spraying, immersion or brushing, to the preselected exposed areas of the polymer substrate is an R donor compound, where R is an organic - 3b -c _ ~'~9~05 cation group, such R group being capable of covalently binding to the nitrogens of the polymer, and forming an electrically conductive polymer in which the R groups are covalently linked to the nitrogen atoms of the polymers, in the preselected or exposed portions - 3c -rB
of the substrate.
More partlcularly, in one embodiment, the preselected or exposed portions of the non-conductive polymer substrate containing carbon-nitrogen linkages, particularly as represented by the free-base polyaniline, can be treated and reacted with an R donor compound, such as R X or R30 X , where R is a strong donor, i.e., an organic cation, such as an alkyl group, e.g., CH3 , and X ls a stable anion, such as I , e.g., as provided by CH3I, to form a polymer salt ln which a covalent bond is formed between a nitrogen and the organic R group.
The reaction of base-type non-conductive polymers, such as polyaniline, wlth a compound or agent of the above type to produce base-type conducting polymers, is disclosed in co-pending Canadian appllcatlon, Serial No. 55~,364 Siled December 24, 1987, titled "Production of Base-Type Conducting Polymers", and assigned to the same assignee as ~he present application.
In another embodlment, such preselected portions of the non-conductive polymer 6ubstrate containing carbon-nitrogen linkages can be treated with an R+ donor compound, such as R2S04, R'S02Cl, or R3SiCl, where R , R'S02+ or R3Si is a strong donor or organic cation, and RS0; or the Cl is a stable anion, to form a polymer salt in which a covalent bond is formed between the nitrogen of the polymer and such donor cation.
T~e reaction oi base-type non-conductive polymers, such as polyanlline, with a compound, such as R2S04, R'S02C1, or R3SiCl, to produce base-type conductin~ po~ymers, is disclosed in r,~
12~ 05 ~S Patent No. 4,806,27 issued February 21, 1989, by Stuart I.
Yaniyer, et a1, titled "Preparation of Base--'rype Conductive Po1ymers", and assiyned to the same assignee as the present application.
The resulting polymer substrate, following treatment with one of the above compounds, has electrically conductive portions in pre-selested areas surrounded by the non-conductive polymer substrate. In the exposed conductive, e.g., non-masked, areas wherein there is a covalent linkage between the above-noted donor cation groups and nitrogens in the polymer, this results in pinning the conductive region, so that the region to which the treating agent has been applied, e.g., in the form of a strip, remains conductive, with substantially no diffusion taking place to other regions of the substrate. In addition, the preselected conductive regions on the polymer substrate do not lose conductivity on contact with water.
Utilizing the above concept, various electronic components which do not contain metal can be fabricated according to the invention, which are stable, and have the advantages of light we1ght and flexibility, provided by the 1291~305 use of polymers, as substrate, and which can be fabricated at relatively low cost. Electronic devices which can be fabricated by the invention process include resistors, capacitors, inductors, printed circuits, electronic devices with components having conductivity gradients, etc.
/ / /
/ / /
-- 5.1 --1~91~5 BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more clearly unders~ood by reference to the detailed description of the invention, set forth hereinafter, taken in conjunction with the acco~panying drawings wherein:
Fig. 1 illustrates the steps of the procedure according to the invention, for fabricating a resistor;
Fig. 2 illustrates the steps of the invention process for producing a capacitor;
Fig. 3 is an enlarged cross-section of the capacitor produced by the process of Fig. 2, taken on line 3-3 of Fig. 2(c);
Fig. 4 illustrates the steps of the invention procedure for producing an electronic component having conductivity gradients;
Fig. 5 illustrates the procedure for producing an inductor by the invention procedure; and Fig. 6 illustrates production of an electronic device having a conductive loop formed on a non-conductive ~0 polymeric substrate.
/
/ / /
?()5 DETAILED DESCRIPTION OF THE INVENTION
AND PREFERRED EMBODIMENTS
According to the invention, covalent doping of base-type non-conductive polymers, e.g., polyaniline free-base substrates, in preselected regions, yields non-diffusing conductive regions surrounded by insulating polymer substrate. Thus, a passive electronic component can be fabricated by exposure of preselected regions of the substrate base polymer to chemical reactants, such as the above-noted R donor compound, which cause the above-noted chemical reaction.
Referring to Fig. 1 of the drawing, illustrating a mode of procedure for producing a resistor according to the invention, numeral 10 illustrates a base-type non-conductive polymer substrate to which a conductive region is to be applied. A preferred form of non-conductive base-type polymer emploved as substrate are those of the polyaniline family, including polyaniline and derivatives thereof containing naphthyl or biphenyl groups or other aromatic groups, in place of the phenyl groups of polyaniline. Such polymers can include alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and biphenvl derivatives, e.g., 2-methyl biphenyl, butyl naphthalene, 2-methyl aniline derivatives, beta phenyl naphthalene and be~a tolyl naphthalene. Such polymeric substrates also can l~91~(~S
include other base-type polymers containing carbon atoms linked to nitrogen, such as cyanogen polymer of the type:
~N~ ~N~
Another type of polvmer substrate can include mixtures and blends of the above non-conductive homopolymers and copolymers of the above polymers and other polymers, such as a blend of polyaniline and polymethylmethacrylate, and polymer alloys, such as polybenzinidazole-polyimide alloys, containing carbon-nitrogen groups.
Thus, the term "non-conductive polymer substrate"
as employed herein is intended to denote any of the above homopolymer or copolvmer materials.
The invention will be described hereinafter, however mostly in terms of the use of the preferred non-conductive free-base polyaniline as non-conductive polymeric substrate. In the case of polyaniline free-base, this is a high polymer having a molecular weight of the order of 50,000 to 80,000. Lower molecular weight polyaniline, such as emeraldine, can be employed, which is an oligomer of polyaniline containing eight (8) subunits and having a molecular weight of about 800 to 900.
$here is applied to the surface of the non-conductive polymer substrate 10 a mask 12 having a cut-out strip 14 therein. For this purpose, any conventional maskant which is inert to the reactant or 1~9~905 treating agent can be employed. The maskant composition should also be inert with respect to the hase polymer of the substrate. For this purpose, metal masks, such as stainless steel, can be employed. Other metals which can be emploved as maskant include platinum, gold, nickel, and the like.
The metal mask can be suitably adhered to the polymer substrate as by pressure contact, adhesive, and the like, but can be readily removed following chemical treatment.
Alternatively, organic maskants containing as an essential ingredient thereof an organic polymer, such as a chloroprene polymer resin, or a styrene butadiene or a styrene ethylene buty,ene co-polymer, can be employed.
The masked polymeric substrate 12, as seen in Fig.
l(b), is treated, as by spraying, to contact the exposed surface of the pol~er substrate within the cut-out area 14 of the mask, with the treating agent. The treating agent with which the exposed area 16 of the polymer suhstrate is contacted is an R+ donor compound, such as RX, R30X, R2S04, R'S02Cl, or R3SiCl, where R, R'S02 or R3Si is a group which readily forms a covalent bond with nitrogen, and wherein R, R' and R" each can be alkyl, e.g., methyl, ethyl and the like, and aryl, e.g., p-toluene sulfonyl (tos~
benzyl, tolyl, xylyl, and other aromatic moieties, and X is an anion such as halogen, e.~., Cl , I or Br ; PF6 , SbC16 , and substituted and unsubstituted benzene sulfonate, and the like. The above reaction forms a conductive polymer salt.
. _ .. _, . . _ ._ . . . .. ~ . _ _ _ . _ . , :~291~05 Thus; the reactant which forms a covalent chemical bond with the nitrogen of the polyaniline free-ba~e or equivalent polymer noted above, can be, for exam~le, one of the above R+ donor compounds, ~uch as an alkyl halide, wherein the alkvl group can contain from 1 to 20 carbon atoms, such as methyl iodide, or d~methyl~ulfate, (CH3CH2)30 SbC16 , (CH3)2CHI, p-CX3-C6~4S02Cl, (CH3)30 PF6 , (CH3)30S03C6~4C~3 and (CH3)3SiCl. Al~o, multifunctional reagents, e.g., ClS02-C6~4-C6H4-S02Cl can be employed. ~owever, R, R' or R~ al~o can be an oligomeric or polymeric group, e.q., containing from about 20 to about 100,000 carbon atom~, e.q., polyvinyl iodide.
~he reaction for converting the ba~e-type non-conductive polymer portion in the expo~ed area 16 of the sub~trate to a conductive polymer can be repre~ented a~
follows, where RX or R30X i~ the R+ donor compound:
( A - ~ - A - N ~ A - N - A - 5 - ) RX or P30X
IIA ( A - ~ - A - ~ - A - ~ - A - N )y or IIB ( A - ~ - A - ~ - A - ~+ - A - ~ - )y or IIC ~ A - ~+- A - ~ - A - ~ - A - ~ - )y X X X X
~`t~
.,~
OS
where A is a carbon-containing qroup, such as aryl, particularly the benzene ring, and including naphthyl and biphenyl, and substituted benzene, naphthyl or biphenyl groups, such as the alkyl and aryl derivatives described above; R and X are as defined above, and y is an integer ranging from about 1 to about 1,000, e.g., about 10 to about 100. When y is in the lower end of the above range, e.g., when y is 1 or 2, the materials are known as oligomers and are intended to be included within the term "polymer"
employed herein.
Where the preferred non-conductive polvmer employed as the base substrate is polyaniline free-base (PFB), the general reaction scheme for producinq conductive polymer portions when employing the reactant RX or R30X is represented below:
~Z9190~
III ( - ~ - N - ~ - N = ~ = N - ~ - N - ) RX or R30X
X ~ / X
IV ( - ~ - N - ~ - ~ - ~ - N - )~
X~ 1 X~
V ~ R ~ 'NR ~ Y
VI ( ~ ~ ~ ~ ~ ~ R ~
X X X X
where R, X and y have the values noted above.
In the above representative reactions, it will be understood that the R+ donor reactant can alternatively be R2S04, R'S02Cl or R3'SiQ, where Q is a halogen, such as Cl or Br. If the reaction is carred out using R2S04, R+ is the organic cation which is covalently linked to the N atoms of the polymer and X is the stable RS04 anion. When R'S02Cl is the reactant, the organic cation is the R'S02+ group, which is covalently linked to the N atoms of the polymer through the S atom of such group, and X is the stable Cl anion. When R'3SiCl is the reactant, the organic cation is the R'3Si group, which is covalently linked to .. .. . ~
129~91)5 the N atoms of the polymer through the Si atom of such group, and X is the stable Cl anion. When R3SiCl is the reactant, the organic cation is the R3Si+ group, which is covalently linked to the N atoms of the polymer through the Si atom of such aroup, and X is the stable Cl anion.
The reaction can be carried out as a heterogenuous reaction wherein the reactant, e.g., RX, per se, is reacted with the exposed polymer substrate portion, such as polyaniline free-base, or the reactant can be dissolved in a suitable solvent which does not irreversibly react with the R+ donor, such as, e.g., methylene chloride, tetrahydrofuran (THF), acetonitrile, pyridine, dimethylsulfoxide (DMS~) and dimethylformamide (DMF).
However, when employing an R30X donor compound, such as (CH3)30X , and acetonitrile as solvent, the ~CH3)30+ group can react with the CH3C=N solvent to form CH3C=N -CH3 which can also function as a methyl cation donor~
The rate of reaction can range widely, dependinq on the particular R+ donor or reactant employed, and the period of exposure of the exposed polymer substrate portion 16 to the reactant. If the reaction between the exposed polymer, e.g., polyaniline, substrate portion and the R donor compound is carried to completion, the cation or R group can be substituted for every hydrogen on the polymeric chain to form the conductive polymer, as represented by Formula V above. Further reaction results in all amine-like nitrogens forming quaternary ammonium groups, as illustrated by Formula VI above. If the reaction is not carried to completion, only a portion of the hydrogen atoms on the polymer will be substituted by catlon or R groups, as illustrated by Formu:la IV above.
Whele the "R " donor is an "R30X" donor, an ether, R2Q, e.g., dimethyl ether, is given off in the reaction.
The above reactions of an R donor compound with a base-type polymer, particularly polyaniline, for produ~ing base-type conductive polymers are disclosed in Canadian application, Serial No. 555,364 filed on December 24, 1987.
Following treatment of the exposed portion 16 of the substrate with the spray 1~3 of chemical treating agent, the mask 12 is removed, leaving a conducti~re and resistive polyaniline region 20 surrounded by the polyaniline non-conductive or insulating region 22, thus forming a resistor element 24.
Now referring to Fig. 2 of the drawings a non-conductive sheet 26 formed of a base-type polymer, such as polyaniline free-base, has attached to the surfaces on opposite sides 28 thereof a metal, e.g., steel, mask in the form of a peripheral frame 30 around all four sides of the sheet, leaving an ex~?osed central surface portion 32 of non-conductive polymer on each side of the sheet.
A spray of a treating agent 27 in the form of an R
donor compound, such as RX, as described above, is applied to opposite sides 28 of the non-conductive polymer `; 14 ~2gl~0S
sheet 26 and contacting the exposed portions 32 on opposite sides of the sheet. As a result of the reaction of the treating agent with the exposed portions 32 of the polymer sheet 26, there are formed central conductive regions 34 of conductive polymer or conductive polyaniline on opposite sides 28 of the non-conductive polymer sheet, with a non-conductive or insulating border portion 36 around the conductive central portions 34, and a non-conductive or insulating interior portion 38 (see Fig. 3) between the two conductive regions 34. The resulting non-conductive polymer substrate containing the separated conductive regions 34 can function as a capacitor.
If desired, the treating agent can be painted unto the exposed regions 32 on both sides of the non-conductive polymer sheet 26. Further, if desired, the mask 30 can be omitted, and the entire area on both sides of the non-conductive polymeric sheet 26 can be treated, as by spraying or painting, with the treating agent to form conductive regions over the entire area on opposite surfaces of the polymeric sheet, separated by the interior non-conductive region 38. The thickness of the conductive regions 34 depends on the particular treating or doping agent employed and the period of time of exposure of the surfaces of the polymer sheet to the treating agent. Thus, the capacitance of the resulting capacitor can be controlled - lS -lZ91~05 by varying the thickness of the conducting regions 34.
In the processes illustrated in Figs. 1 to 3, the non-conductive polymer substrate is treated in preselected surface portions with a doping agent molecule that S covalently attaches to the polymer base site to form conductive regions surrounded or separated by dielectric or insulating regions.
Conductive regions formed on a dielectric or insulating substrate, such as polyaniline free-base, can be made to have conductivity gradients by reacting different parts of the substrate with a covalent doping agent for different lengths of time, or by selective diffusion into a bulk body of the base insulating polymer.
Thus, referring to Fig. 4, a block of base-type non-conductive polymer, such as polyaniline, at 40 can be immersed in a bath of covalent doping agent or R+ donor compound 42, to a predetermined depth, as shown in Fig.
4(a), and by pulling the block of polymer 40 gradually from the treating bath or solution until it is completely withdrawn, as indicated in Fig. 4(b), the resulting polymer block 40, shown in Fig. 4(c), will have a gradient of conductivity ranging from high conductivity at 44 adjacent the bottom of the block to low conductivity at 46 adjacent the upper end of the polymer block. This is due to the fact that the region 46 near the top of the polymer block has .
.. . _ .. _. .. . _. ... . _ ... . . _ . _ 1~3190S
been withdrawn first and exposed to the treating agent 42 for the shortest time period, whereas the region 44 adjacent the bottom of the block 40 has been exposed to the treating bath for the longest time period and subjected to the greater amount of diffusion of the liquid treating agent into the block polymer. Thus, a non-conductive polymer, such as polyaniline, can be rendered conductive over a broad range of conductivity, for example, along its length, by selective diffusion, whereas such varying conductivity cannot be imparted to a metal or to a conventional plastic material.
Another electronic device which can be produced according to the invention by covalent doping of certain portions of a non-conductive base-type polymer, such as polyaniline, is an inductor or induction coil. This can be accomplished by a lathe-type process. Thus, as seen in Fig.
.. . _ .. _. .. . _. ... . _ ... . . _ . _ 1~3190S
been withdrawn first and exposed to the treating agent 42 for the shortest time period, whereas the region 44 adjacent the bottom of the block 40 has been exposed to the treating bath for the longest time period and subjected to the greater amount of diffusion of the liquid treating agent into the block polymer. Thus, a non-conductive polymer, such as polyaniline, can be rendered conductive over a broad range of conductivity, for example, along its length, by selective diffusion, whereas such varying conductivity cannot be imparted to a metal or to a conventional plastic material.
Another electronic device which can be produced according to the invention by covalent doping of certain portions of a non-conductive base-type polymer, such as polyaniline, is an inductor or induction coil. This can be accomplished by a lathe-type process. Thus, as seen in Fig.
5, to a rod of base polymer 48 there is applied, from a suitable spray gun 50 a spray of cationic doping agent or R+
donor compound of the above types. The rod of base polymer 48 is rotated as in a clockwise direction, viewing Fig. 5, and the spray gun 50 is moved or translated in a horizontal direction at a constant rate, parallel to the axis of the rod, as indicated by the arrow ~4. This results in the formation of a helical line or coil of conductive polymer, indicated by dotted lines 56, around the outer periphery of 1~905 the non-conductive rod 48, defined by the line of impingement of the spray 52 on the outer surface of the rod 48.
Instead of employing a lathe-type process for fabricating an inductor according to the invention, as seen in Fig. 6, an inductor 58 can also be produced by utilizing a sheet or block 60 of non-conductive base-type polymer, such as polyaniline, and, for example, by means of a paint brush having a liquid covalent doping agent thereon, according to the invention, painting a conductive loop 62 or any other desired shape, on a configuration of such loop or shape formed on the insulating sheet 60, by reaction of the covalent doping agent applied by the paint brush, with the non-conductive base-type polymer.
Also, employing one of the procedures noted above, e.g., the masking procedure illustrated in Fig. l(b), or bv the painting procedure illustrated in Fig. 6, a printed c~rcuit board can be made by applying a covalent doping agent as described above to predetermined portions of a base-type non-conductive polymeric substrate, such as polyaniline, to provide an entirely plastic printed circuit board which does not employ a metal, such as copper, as the conductor.
_ _ ~ . . . .. . . _.. _ ~9~
The following are examples of practice of the invention:
Example I
To a surface of a sheet of polyaniline free-base was applied a stainless steel mask, as illustrated in Fig.
l(b). A 1 molar solution of triethyloxonium hexachloroantimonate in methylene chloride was applied by spraying over the exposed area 16 of the polyaniline substrate. The mask was removed, providing a conductive trace or region 20 on the insulating polymer, to form a resistor. The conductive trace 20 remains non-diffusing over an extended time period, and the conductivity thereof is not degraded by exposure to water.
Example II
A polyaniline free-base block polymer was exposed by spraying on oppoaite sides thereof, generally according to the procedure illustrated in Fig. 2, with pure dimethylsulfate. The resulting polymer substrate had conductive areas on opposite sides thereof, as illustrated at 38 in Fig. 3, and functions as a capacitor.
/ /
/ / /
..
. ~
Example III
A polyaniline free-base block polymer was immersed in a solution of 1 molar methyl iodide in T~F and the block was gradually completely withdrawn from the treating solution, as illustrated in Fig. 4. The resulting bloc~
polymer had a conduc'ivity gradient ranging from high conductivity at the lower end of the block to low conductivity adjacent the upper end of the block, as illustrated in Fig. 4(c).
Example IV
An inductor was made according to the procedure illustrated in Fig. 5, by impinging a spray of trimethyloxonium hex2fluorophosphate in methylene chloride on a rotating cylindrical rod of polyaniline free-base, while the spray was moved transversely of the rod and parallel to the axis thereof. A helical conductor was formed around the outer periphery of the rod.
From the foregoing, it is seen that the invention provides novel procedure for fabricating novel electronic devices without employing metal and resulting in light-weight, reliable devices formed entirely of polymeric material, and having stable conductivity and free of conductivity degradation on contact with water.
~9190~
While particular embodiments of the invention have been described for purposes of illustration, it will be understood that various changes and modifications within the spirit of the invention can be made, and the invention is not to be taken as limited except by the scope of the appended claims.
. _ . . , , . . _ _ _ _ ~ .. . ... . ...... ... . . . . . . .. .
donor compound of the above types. The rod of base polymer 48 is rotated as in a clockwise direction, viewing Fig. 5, and the spray gun 50 is moved or translated in a horizontal direction at a constant rate, parallel to the axis of the rod, as indicated by the arrow ~4. This results in the formation of a helical line or coil of conductive polymer, indicated by dotted lines 56, around the outer periphery of 1~905 the non-conductive rod 48, defined by the line of impingement of the spray 52 on the outer surface of the rod 48.
Instead of employing a lathe-type process for fabricating an inductor according to the invention, as seen in Fig. 6, an inductor 58 can also be produced by utilizing a sheet or block 60 of non-conductive base-type polymer, such as polyaniline, and, for example, by means of a paint brush having a liquid covalent doping agent thereon, according to the invention, painting a conductive loop 62 or any other desired shape, on a configuration of such loop or shape formed on the insulating sheet 60, by reaction of the covalent doping agent applied by the paint brush, with the non-conductive base-type polymer.
Also, employing one of the procedures noted above, e.g., the masking procedure illustrated in Fig. l(b), or bv the painting procedure illustrated in Fig. 6, a printed c~rcuit board can be made by applying a covalent doping agent as described above to predetermined portions of a base-type non-conductive polymeric substrate, such as polyaniline, to provide an entirely plastic printed circuit board which does not employ a metal, such as copper, as the conductor.
_ _ ~ . . . .. . . _.. _ ~9~
The following are examples of practice of the invention:
Example I
To a surface of a sheet of polyaniline free-base was applied a stainless steel mask, as illustrated in Fig.
l(b). A 1 molar solution of triethyloxonium hexachloroantimonate in methylene chloride was applied by spraying over the exposed area 16 of the polyaniline substrate. The mask was removed, providing a conductive trace or region 20 on the insulating polymer, to form a resistor. The conductive trace 20 remains non-diffusing over an extended time period, and the conductivity thereof is not degraded by exposure to water.
Example II
A polyaniline free-base block polymer was exposed by spraying on oppoaite sides thereof, generally according to the procedure illustrated in Fig. 2, with pure dimethylsulfate. The resulting polymer substrate had conductive areas on opposite sides thereof, as illustrated at 38 in Fig. 3, and functions as a capacitor.
/ /
/ / /
..
. ~
Example III
A polyaniline free-base block polymer was immersed in a solution of 1 molar methyl iodide in T~F and the block was gradually completely withdrawn from the treating solution, as illustrated in Fig. 4. The resulting bloc~
polymer had a conduc'ivity gradient ranging from high conductivity at the lower end of the block to low conductivity adjacent the upper end of the block, as illustrated in Fig. 4(c).
Example IV
An inductor was made according to the procedure illustrated in Fig. 5, by impinging a spray of trimethyloxonium hex2fluorophosphate in methylene chloride on a rotating cylindrical rod of polyaniline free-base, while the spray was moved transversely of the rod and parallel to the axis thereof. A helical conductor was formed around the outer periphery of the rod.
From the foregoing, it is seen that the invention provides novel procedure for fabricating novel electronic devices without employing metal and resulting in light-weight, reliable devices formed entirely of polymeric material, and having stable conductivity and free of conductivity degradation on contact with water.
~9190~
While particular embodiments of the invention have been described for purposes of illustration, it will be understood that various changes and modifications within the spirit of the invention can be made, and the invention is not to be taken as limited except by the scope of the appended claims.
. _ . . , , . . _ _ _ _ ~ .. . ... . ...... ... . . . . . . .. .
Claims (32)
1. A process for producing an electronic device on a non-conductive polymer substrate which comprises applying a co-valent doping agent to a preselected portion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, said agent being capable of covalently binding to the nitrogens of said polymer, said covalent doping agent being an R+ donor compound containing an organic cation group, the R+ donor compound being selected from the group consisting of RX, R3OX, R2SO4, R'SO2Cl, and R"3SiCl, where R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6-, SbCl6- and benzene sulfonate, and wherein the base-type non-conductive polymer substrate is selected from the group consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted poly-aniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives, and converting said preselected portion of said polymer substrate to an electrically conductive polymer portion in which such cation groups are covalently linked to the nitrogen atoms of said preselected polymer portion.
2. The process of claim 1, said R donor compound being dissolved in a solvent which does not react irreversibly with said R donor compound.
3. The process of claim 1, said R+ donor compound being dissolved in a solvent selected from the group consisting of methylene chloride, tetrahydrofuran, acetonitrile, pyridine, dimethylsulfoxide and dimethylformamide.
4. The process of claim 1, said covalent doping agent being applied to said preselected portion of said polymer sub-strate by spraying, immersion or brushing.
5. The process of claim 1, including applying a suitable mask to said polymer substrate and exposing said preselected por-tion of said polymer substrate to said covalent doping agent.
6. The process of claim 1, said base-type non-conductive polymer having the general formula:
where A is a carbon-containing group and y is an integer ranging from about 1 to about 1,000.
where A is a carbon-containing group and y is an integer ranging from about 1 to about 1,000.
7. The process of claim 1, said base-type non-conductive polymer substrate including homopolymer mixtures and blends, copolymers and polymer alloys, containing carbon-nitrogen groups.
8. The process of claim 1, wherein said non-conductive polymer substrate is polyaniline.
9. A process for producing an electronic device on a polyaniline substrate, which comprises applying to a preselected region of a base-type non-conductive polymer having the general formula:
where A is a carbon-containing aryl group and y is an integer ranging from about 1 to about 1,000, a compound selected from the group consisting of RX, R3OX, R2SO4, R'SO2Cl, and R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6-, SbCl6-, SO2Cl- and benzene sulfonate, and forming an electrically conductive polymer region on said non-conductive polymer substrate.
where A is a carbon-containing aryl group and y is an integer ranging from about 1 to about 1,000, a compound selected from the group consisting of RX, R3OX, R2SO4, R'SO2Cl, and R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6-, SbCl6-, SO2Cl- and benzene sulfonate, and forming an electrically conductive polymer region on said non-conductive polymer substrate.
10. A process for producing an electronic device on a non-conductive polymer substrate which comprises applying a co-valent doping agent to a preselected portion of a non-conductive polyaniline substrate, said agent being capable of covalently binding to the nitrogens of said polyaniline, and converting said preselected portion of said polyaniline substrate to an electri-cally conductive polyaniline portion.
11. A process for producing an electronic device on a non-conductive polymer substrate which comprises applying a covalent doping agent to a preselected portion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, said agent being capable of covalently binding to the nitrogens of said polymer, and converting said preselected portion of said polymer substrate to an electrically conductive polymer portion, wherein the base-type non-conductive polymer substrate is selected from the group consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted polyaniline and its alkyl and aryl substituted naphthyl and diphenyl derivatives.
12. A process for producing an electronic device on a polyaniline substrate, which comprises applying to a preselected region of a non-conductive polyaniline free-base substrate a compound selected from the group consisting of RX, R3OX, R2SO4, R'SO2C1, R3"SiQ, where Q is a halogen, R, R' and R" are each selected from the group consisting of alkyl and aryl, and X is selected from the group consisting of halogen, PF6-, SbCl6-, SO2Cl- and benzene sulfonate, and forming an electrically conduc-tive polyaniline region on said non-conductive polyaniline sub-strate.
13. The process of claim 12, said compound being in liquid form and applied to said preselected region by spraying or brush-ing, or by immersion of said substrate in said liquid compound for a predetermined time.
14. The process of claim 12, including applying a suitable mask to said polymer substrate and exposing said preselected region of said polymer substrate to said compound.
15. The process of claim 12 for producing a resistor, wherein said conductive polyaniline region is in the form of a resistive strip surrounded by non-conductive polyaniline.
16. The process of claim 12 for producing a capacitor, wherein said non-conductive polyaniline free-base substrate is in the form of a block having substantially parallel opposite sides and applying said compound to preselected regions on said opposite sides of said polyaniline substrate, and forming a conductive polyaniline region on said opposite sides separated by a thickness of non-conductive polyaniline.
17. The process of claim 12 for producing a device having a conductivity gradient, wherein said compound is applied to said preselected region of said substrate by immersing said polyaniline substrate in a liquid bath of said compound, and gradually with-drawing said substrate from said bath, thereby exposing said preselected region of said substrate to said bath for different times, and forming a region of varying conductivity on said substrate.
18. The process of claim 12 for producing an inductor, where-in said polyaniline substrate is in the form of a cylinder, and said compound in liquid form is applied as a spray on said cylinder substrate while rotating same and moving said spray along a line parallel to the axis of said cylinder, and forming a helical coil of conductive polyaniline on said non-conductive polyaniline cylindrical substrate.
19. The process of claim 12 for producing an inductor, wherein said polyaniline substrate is in the form of a sheet, and said compound in liquid form is applied to said preselected region in the form of a loop, and forming a conductive polyaniline loop on said non-conductive polyaniline sheet.
20. The process of claim 12 wherein Q is chlorine.
21. The process of claim 12, wherein said compound is RX, where R is alkyl and X is halogen.
22. An electronic device free of metal, which comprises a base-type non-conductive polymer substrate containing carbon-nitrogen linkages and having an electrically conductive polymer region comprising an organic dopant group covalently linked to nitrogen atoms of said polymer substrate.
23. The device of claim 22, wherein said dopant group is selected from the class consisting of alkyl, aryl, R'SO2, and R3"Si, where R' and R" are alkyl or aryl, and including an anion also linked to said nitrogen atoms, said anion being selected from the group consisting of halogen, PF6-, SbCl6- and benzene sulfonate.
24. The device of claim 23 wherein said electrically conductive polymer region has the formula IIA or IIB or IIC where R is said dopant group, X is said anion, and y is an integer ranging from about 1 to about 1,000.
25. The device of claim 23, wherein said polymer substrate is selected from the group consisting of polyaniline, its naphthyl and biphenyl derivatives, and alkyl and aryl substituted poly-aniline and its alkyl and aryl substituted naphthyl and biphenyl derivatives.
26. The device of claim 25, wherein said polymer substrate is polyaniline.
27. The device of claim 26, wherein said electrically conductive polymer region has the formula IV or V or VI where R is said dopant group, X is said anion, and y is an integer ranging from about 1 to about 1,000.
28. The device of claim 25, wherein said conductive polymer region is in the form of a resistive strip surrounded by non-conductive polymer substrate, and forming a resistor.
29. The device of claim 25, wherein said non-conductive polymer substrate is in the form of a block having substantially parallel sides, and containing conductive polymer regions on opposite sides of said substrate separated by a thickness of non-conductive polymer substrate, and forming a capacitor.
30. The device of claim 25, wherein said conductive polymer region has varying conductivity.
31. The device of claim 25, wherein said non-conductive polymer substrate is in the form of a cylinder, and said conduc-tive polymer region is in the form of a helical conductive polymer coil on said non-conductive polymer substrate, and forming an inductor.
32. The device of claim 25, wherein said non-condcutive polymer substrate is in the form of a sheet, and said conductive region is in the form of a conductive polymer loop on said non-conductive polymer substrate, and forming an inductor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13,306 | 1987-02-11 | ||
| US07/013,306 US4822638A (en) | 1987-02-11 | 1987-02-11 | Electronic device fabrication on non-conductive polymer substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1291905C true CA1291905C (en) | 1991-11-12 |
Family
ID=21759283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 558593 Expired - Lifetime CA1291905C (en) | 1987-02-11 | 1988-02-10 | Electronic device fabrication on non-conductive polymer substrate |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4822638A (en) |
| EP (1) | EP0417074A4 (en) |
| JP (1) | JPH02502233A (en) |
| CA (1) | CA1291905C (en) |
| WO (1) | WO1988006064A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220488A (en) * | 1985-09-04 | 1993-06-15 | Ufe Incorporated | Injection molded printed circuits |
| US4798685A (en) * | 1986-10-20 | 1989-01-17 | Lockheed Corporation | Production of base-type conducting polymers |
| US5006278A (en) * | 1987-01-12 | 1991-04-09 | Allied-Signal | Solution processible forms of electrically conductive polyaniline and the method of manufacture of electroconductive articles therefrom |
| US4983322A (en) * | 1987-01-12 | 1991-01-08 | Allied-Signal Inc. | Solution processible forms of electrically conductive polyaniline |
| US5160457A (en) * | 1987-08-07 | 1992-11-03 | Allied-Signal Inc. | Thermally stable forms of electrically conductive polyaniline |
| JPH0180974U (en) * | 1987-11-20 | 1989-05-30 | ||
| US5208301A (en) * | 1988-05-13 | 1993-05-04 | Ohio State University Research Foundation | Sulfonated polyaniline compositions, ammonium salts thereof, process for their preparation and uses thereof |
| US5159031A (en) * | 1988-05-13 | 1992-10-27 | Ohio State University Research Foundation | Sulfonated polyaniline salt compositions and uses thereof |
| US5137991A (en) * | 1988-05-13 | 1992-08-11 | The Ohio State University Research Foundation | Polyaniline compositions, processes for their preparation and uses thereof |
| US5164465A (en) * | 1988-05-13 | 1992-11-17 | Ohio State University Research Foundation | Sulfonated polyaniline salt compositions, processes for their preparation and uses thereof |
| US5300208A (en) * | 1989-08-14 | 1994-04-05 | International Business Machines Corporation | Fabrication of printed circuit boards using conducting polymer |
| GB8920745D0 (en) * | 1989-09-13 | 1989-10-25 | Ici Plc | Thick film resistor/integrated circuit substrate and method of manufacture |
| US5109070A (en) * | 1989-10-19 | 1992-04-28 | Ohio State University Research Foundation | Compositions of insulating polymers and sulfonated polyaniline compositions and uses thereof |
| US5093439A (en) * | 1989-10-19 | 1992-03-03 | Ohio State University Research Foundation | Processes for preparation of sulfonated polyaniline compositions and uses thereof |
| US5135696A (en) * | 1989-10-19 | 1992-08-04 | Ohio State University Research Foundation | Process for forming fibers of sulfonated polyaniline compositions and uses thereof |
| US5008041A (en) * | 1990-01-30 | 1991-04-16 | Lockheed Corporation | Preparation of conductive polyaniline having controlled molecular weight |
| US5096586A (en) * | 1990-08-28 | 1992-03-17 | Regents Of The University Of California | Membranes having selective permeability |
| US5176851A (en) * | 1990-09-04 | 1993-01-05 | Milliken Research Corporation | Method for enhancing polyaniline conductivity |
| US5262195A (en) * | 1990-11-05 | 1993-11-16 | Brewer Science | Soluble conducting polymers and their use in manufacturing electronic devices |
| US5171478A (en) * | 1991-03-05 | 1992-12-15 | Allied-Signal Inc. | Thermally induced chain coupling in solid state polyaniline |
| US5378404A (en) * | 1991-04-22 | 1995-01-03 | Alliedsignal Inc. | Process for forming dispersions or solutions of electrically conductive conjugated polymers in a polymeric or liquid phase |
| US5278213A (en) * | 1991-04-22 | 1994-01-11 | Allied Signal Inc. | Method of processing neutral polyanilines in solvent and solvent mixtures |
| US5266617A (en) * | 1991-04-22 | 1993-11-30 | Allied-Signal Inc. | Lewis base catalyzed phase transfer coating process for polyanilines |
| US5281363A (en) * | 1991-04-22 | 1994-01-25 | Allied-Signal Inc. | Polyaniline compositions having a surface/core dopant arrangement |
| US5254633A (en) * | 1991-07-10 | 1993-10-19 | Allied Signal Inc. | Process for the preparation of conductive polymer blends |
| US5227092A (en) * | 1991-07-10 | 1993-07-13 | Allied-Signal Inc. | Process for forming conjugated backbone block copolymers |
| US5911918A (en) * | 1992-06-03 | 1999-06-15 | Monsanto Company | Surface dopants as blend compatibilizers in conjugated polymers |
| US6132645A (en) * | 1992-08-14 | 2000-10-17 | Eeonyx Corporation | Electrically conductive compositions of carbon particles and methods for their production |
| US5498372A (en) * | 1992-08-14 | 1996-03-12 | Hexcel Corporation | Electrically conductive polymeric compositions |
| FR2696043B1 (en) * | 1992-09-18 | 1994-10-14 | Commissariat Energie Atomique | Support for a network of resistive elements made of conductive polymer and its manufacturing process. |
| EP1271669A3 (en) * | 1994-09-06 | 2005-01-26 | Koninklijke Philips Electronics N.V. | Electroluminescent device comprising a transparent structured electrode layer made from a conductive polymer |
| EP0721194B1 (en) * | 1995-01-09 | 2004-03-10 | International Business Machines Corporation | Deaggregated electrically conductive polymers and precursors thereof |
| KR100283545B1 (en) * | 1996-07-25 | 2001-03-02 | 포만 제프리 엘 | Vibrational methods of deaggregation of electrically conductive polymers and precursors thereof |
| US5972518A (en) * | 1996-07-30 | 1999-10-26 | The Ohio State University | Corrosion protection of iron/steel by emeraldine base polyaniline |
| US7404981B2 (en) * | 2003-04-21 | 2008-07-29 | Hewlett-Packard Development Company, L.P. | Printing electronic and opto-electronic circuits |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3346444A (en) * | 1964-08-24 | 1967-10-10 | Gen Electric | Electrically conductive polymers and process of producing the same |
| US3536781A (en) * | 1968-02-01 | 1970-10-27 | Union Carbide Corp | Charge-transfer polymer blends |
| JPS4825041A (en) * | 1971-08-04 | 1973-04-02 | ||
| US3813264A (en) * | 1972-03-22 | 1974-05-28 | Calgon Corp | Electroconductive paper |
| US4025342A (en) * | 1974-06-25 | 1977-05-24 | Eastman Kodak Company | Organic semiconductors used in photoconductor element |
| US4025691A (en) * | 1974-06-25 | 1977-05-24 | Eastman Kodak Company | Organic semiconductor element |
| US4237194A (en) * | 1979-02-16 | 1980-12-02 | Eastman Kodak Company | Conductive polyanaline salt-latex compositions, elements and processes |
| WO1984002030A1 (en) * | 1982-11-17 | 1984-05-24 | Chevron Res | Electroactive polymers |
| US4522745A (en) * | 1982-11-17 | 1985-06-11 | Chevron Research Company | Fused 5,6,5-membered heterocyclic electroactive polymers |
| US4505844A (en) * | 1982-11-17 | 1985-03-19 | Chevron Research Company | P-Type polyphenoxazine electroactive polymers |
| US4609971A (en) * | 1983-08-11 | 1986-09-02 | North American Philips Corporation | Electrolytic capacitor with polymer conductor |
| US4559112A (en) * | 1983-10-07 | 1985-12-17 | Nippon Telegraph & Telephone | Electrically conducting polymer film and method of manufacturing the same |
| US4540620A (en) * | 1983-10-19 | 1985-09-10 | Phillips Petroleum Company | Conductive patterns in polymeric films |
| US4497727A (en) * | 1984-02-13 | 1985-02-05 | W. R. Grace & Co. | Poly(dipropargylamine)and derivatives thereof per se and _p-doped and processes for preparing same |
| US4565860A (en) * | 1984-04-09 | 1986-01-21 | Nissan Motor Co., Ltd. | Polymer of triphenylamine |
| US4604427A (en) * | 1984-12-24 | 1986-08-05 | W. R. Grace & Co. | Method of forming electrically conductive polymer blends |
| US4692225A (en) * | 1986-07-08 | 1987-09-08 | Rockwell International Corporation | Method of stabilizing conductive polymers |
| US4730239A (en) * | 1986-10-29 | 1988-03-08 | Stemcor Corporation | Double layer capacitors with polymeric electrolyte |
-
1987
- 1987-02-11 US US07/013,306 patent/US4822638A/en not_active Expired - Fee Related
-
1988
- 1988-02-10 CA CA 558593 patent/CA1291905C/en not_active Expired - Lifetime
- 1988-02-10 WO PCT/US1988/000377 patent/WO1988006064A1/en not_active Application Discontinuation
- 1988-02-10 EP EP19880902297 patent/EP0417074A4/en not_active Withdrawn
- 1988-02-10 JP JP63502142A patent/JPH02502233A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0417074A1 (en) | 1991-03-20 |
| US4822638A (en) | 1989-04-18 |
| WO1988006064A1 (en) | 1988-08-25 |
| EP0417074A4 (en) | 1991-05-08 |
| JPH02502233A (en) | 1990-07-19 |
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