WO2011056903A1

WO2011056903A1 - Compositions and methods for generating conductive films and coatings of oligomers

Info

Publication number: WO2011056903A1
Application number: PCT/US2010/055339
Authority: WO
Inventors: Henry Tran; Yue Wang
Original assignee: Henry Tran; Yue Wang
Priority date: 2009-11-03
Filing date: 2010-11-03
Publication date: 2011-05-12

Abstract

In one embodiment a conductive film or coating is provided comprising a conductive oligomer and a dopant, wherein the conductivity of the conductive film is about 1 S/cm or greater, and, in another embodiment, a method of preparing the conductive film or coating is provided.

Description

COMPOSITIONS AND METHODS FOR GENERATING CONDUCTIVE FILMS AND

COATINGS OF OLIGOMERS

Priority Claim

[0001] This application claims the benefit of U.S. Provisional Application No. 61 /257,742, filed November 3, 2009, which is incorporated herein by reference in its entirety.

Background

[0002] Since the discovery of inherently conducting polymers (ICPs), a substantial amount of work has been devoted towards the development of highly conducting ICPs, particularly ICPs that are stable and can be processed from solution. By bridging the gap between the moderate conductivities typically observed for ICPs and the conductivities observed for traditional metals such as copper, a new class of materials with the combined properties of polymers and metals would result that could potentially have a substantial commercial impact.

[0003] In general, higher molecular weight polyaniline has been favored for producing higher conductivity polyaniline. Generally, oligomers have been previously reported to possess a conductivity ranging from 10^"4 to 1 S/cm. Most known strategies for producing higher conductivity in polyaniline focus on higher molecular weight species based on the assumption that longer polymer chains reduce the amount of interchain hopping of charge carriers in the film. This assumption is generally considered to be the limiting factor for achieving high conductivity in organic polymers.

70553-8002.WO00/LEGAL19530833.2 1 [0004] Post-processing of low molecular weight oligomers of aniline to achieve high conductivity has not received the same attention or success by researchers. But properties of oligomers (e.g. molecular weights, polydispersities, redox states) can be better controlled than polymers. Oligomers are also more soluble than polymers, and can be dissolved/dispersed in more solvents at generally higher concentrations.

Therefore, there exists a need to prepare conductive materials using oligomers with improved conductivities.

Summary

[0005] One aspect of the present disclosure relates to a highly conductive film comprising a conductive oligomer and a dopant, wherein the conductivity is from about 1 S/cm to about 1000S/cm.

[0006] Another aspect of the present disclosure relates to a method of preparing a highly conductive film or coating comprising:

providing a doped conductive oligomer solution/dispersion comprising the conductive oligomer, a solvent/solvent system, and the dopant; and

making the highly conductive film from the doped conductive oligomer solution.

[0007] Another aspect of the present disclosure relates to a method of preparing a highly conductive film or coating comprising:

providing an undoped conductive oligomer solution/dispersion comprising the conductive oligomer, a solvent/solvent system;

making an undoped conductive film from the undoped conductive oligomer

solution/dispersion; and

70553-8002.WO00/LEGAL19530833.2 2 making the highly conductive film by exposing the undoped conductive film to the dopant.

Brief Description of the Drawings

[0008] Figure 1 : Representative structures of aniline oligomers.

[0009] Figure 2: X-ray diffraction (XRD) of tetraaniline doped with HCI0₄ (top diffraction) and tetraaniline doped with H₂S0₄ (bottom diffraction).

[0010] Figure 3. Preparation of phenyl-capped aniline octamer.

[0011] Figure 4. MS of phenyl-capped aniline octamer

[0012] Figure 5. GPC of phenyl-capped aniline octamer.

[0013] Figure 6. UV-Vis of phenyl-capped aniline octamer in: (A) the

leucoemeraldine oxidation state; (B) the pernigraniline oxidation state; (C) emeraldine base form. and (D) doped emeraldine salt form.

[0014] Figure 7: Preparation of aniline 16-mer.

[0015] Figure 8: A block diagram illustrating a method of creation of highly conductive films, coatings and moldings of aniline oligomers and their derivatives.

Detailed Description

[0016] The following description is intended to illustrate various embodiments of the invention. As such, the specific modifications discussed are not to be construed as limitations on the scope of the invention. It will be apparent to one skilled in the art that

70553-8002.WO00/LEGAL19530833.2 3 various equivalents, changes, and modifications may be made without departing from the scope of the invention, and it is understood that such equivalent embodiments are to be included herein.

[0017] I. Highly conductive film

[0018] One aspect of the present disclosure relates to a highly conductive film comprising a conductive oligomer and a dopant.

[0019] In one embodiment, the conductivity of the highly conductive film is in the order of about 1 S/cm to about 1000 S/cm. In another embodiment, the conductivity of the highly conductive film is in the order of more than about 10 S/cm. In another embodiment, the conductivity of the highly conductive film is in the order of more than about 10 S/cm to about 1000 S/cm. In another embodiment, the conductivity of the highly conductive film is in the order of about 10 S/cm to about 100 S/cm. In another embodiment, the conductivity of the highly conductive film is greater than 100 S/cm. In another embodiment, the conductivity of the highly conductive film is greater than about 1000 S/cm.

[0020] In one embodiment, the sheet resistance of the highly conductive film is from about 0.1 to about 10⁹ ohms/sq depending on conductivity and film thickness.

[0021] In another embodiment, the enhancement of conductivity of the highly conductive film compared to the conductivity previously reported for the conductive oligomer is up to two orders of magnitude.

[0022] A) The conductive oligomer

70553-8002.WO00/LEGAL19530833.2 4 [0023] In one embodiment the conductive oligomer is a homooligomer. In another embodiment, the conductive oligomer is a co-oligomer.

[0024] The conductive oligomer can be any conductive oligomer known in the art, and derivatives thereof. Examples of monomers of the conductive oligomer include, without limitation, aniline, aniline derivatives (e.g. substituted and/or unsubstituted aniline such as phenyl-capped aniline) (Figure 1 ), pyrrole, pyrrole derivatives (e.g.

substituted and/or unsubstituted pyrrole), thiophene, and thiophene derivatives (e.g. substituted and/or unsubstituted thiophene such as hexyl-capped

ethylenedioxythiophene).

[0025] In one embodiment, the degree of oligomerization of the conductive oligomer is from 2 to 100. In one embodiment, the degree of oligomerization of the conductive oligomer is an integer selected from 2 to 100. In another embodiment, the degree of oligomerization of the conductive oligomer is from 4 to 64. In another embodiment, the degree of oligomerization of the conductive oligomer is 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, or 64.

[0026] Compared to polymers, oligomers can be prepared with better controlled molecular weights and with lower polydispersities. The conductive oligomers in the present disclosure have a low polydispersity of less than about 2, less than about 1 .40, less than about 1 .10, less than aboutl .05, about 1 .00, or 1 .00.

70553-8002.WO00/LEGAL19530833.2 5 [0027] In another aspect, the conductive oligomer has been processed to its preferred conductive state. In one embodiment, the conductive oligomer is oligoaniline or oligoaniline derivative, the preferred conductive state is emeraldine oxidation state. In one embodiment, the emeraldine oxidation state of oligoaniline or oligoaniline derivative can be achieved by first reducing the oligoaniline or oligoaniline derivative to it reductive state, and then oxidize to the emeraldine oxidation state. In another embodiment, the emeraldine oxidation state of oligoaniline or oligoaniline derivative can be achieved by first oxidizing the oligoaniline or oligoaniline derivative to it most oxidative state, and then reduce to the emeraldine oxidation state.

[0028] In another embodiment, the conductive oligomer is oligoparrole or oligoparrole derivative, and the preferred conductive state is the oxidized state. In another embodiment, the conductive oligomer is oligothiophene or oligothiophene derivative, and the preferred conductive state is the oxidized state.

[0029] B) The dopant

[0030] Examples of dopants include protonic acids and redox active agents.

[0031] Examples of redox active agent include, without limitation, iodine, bromine, and chlorine. Examples of protonic acids include, without limitation, inorganic acids (e.g. HCI, H₂S0₄, perchloric acid), organic acids (e.g. sulfonic acid such as camphor sulfonic acid (CSA), toluene sulfonic acid, dodecylbenzenesulfonic acid) and polymeric acids (e.g. polymeric sulfonic acid such as polystyrenesulfonic acid, and polyacrylic acid).

70553-8002.WO00/LEGAL19530833.2 6 [0032] In one embodiment, the conductive oligomer is oligoaniline or oligoaniline derivative, and the suitable dopant can be a protonic acid. The protonic acid makes the doped oligoaniline or oligoaniline derivative more conductive, and provides

counteranion for the doped oligomer.

[0033] In another embodiment, the conductive oligomer is oligothiophene, or oligothiophene derivative, and the suitable dopant can be a redox active agent or a protonic acid.

[0034] In another embodiment, the conductive oligomer is oligopyrrole, or oligopyrrole derivative, and the suitable dopant can be a redox active agent or a protonic acid.

[0035] In another embodiment, the oligomer is electrochemically doped with the dopant.

[0036] C) Solvent

[0037] In one embodiment, a single solvent is used to dissolve or disperse the conductive oligomer. In another embodiment, a solvent system comprising more than one solvent is used to dissolve or disperse the conductive oligomer.

[0038] Examples of suitable solvents include, without limitation, high boiling point solvents, highly polar solvents, aromatic solvents and aqueous solvents.

[0039] In one embodiment, high boiling point solvents having boiling point higher than about 100 °C can be used to dissolve or disperse a doped conductive oligomer or

70553-8002.WO00/LEGAL19530833.2 7 an undoped conductive oligomer. Examples of high boiling point solvents include, without limitation, dimethylforamide (DMF), N-Methyl-2-pyrrolidone (NMP), m-cresol, dichloroacetic acid, and dimethylsulfoxide (DMSO).

[0040] In another embodiment, highly polar solvents (Polarity Index > 6.0) can be used to dissolve or disperse a doped conductive oligomer or an undoped conductive oligomer. In certain embodiments, the dopant is an organic acid (e.g. sulfonic acids such as camphorsulfonic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid). Examples of highly polar solvents include, without limitation, m-cresol,

hexafluoroisopropanol (HFIP) and acetone, chloroform, THF, acetonitrile, and alcohol (e.g. methanol, ethanol, trifluoroisopropanol).

[0041] In another embodiment, aromatic solvents can be used to dissolve or disperse a doped conductive oligomer or an undoped conductive oligomer. In certain embodiments, the dopant comprises a hydrophobic structure (e.g. long hydrocarbon such as dodecylbenzenesulfonic acid, or a polymeric acid such as polystyrenesulfonic and polyacrylic acid). Examples of aromatic solvents include, without limitation, benzene, toluene, dicholorobenzene, and xylene.

[0042] In another embodiment, aqueous solvents can be used to dissolve or disperse a doped conductive oligomer or an undoped conductive oligomer. In certain embodiments, the dopant is a polymeric dopant such as polystyrenesulfonic acid or polyacrylic acid. The aqueous solvents can be water, aqueous acids solutions, or aqueous salt solutions.

70553-8002.WO00/LEGAL19530833.2 8 [0043] In one embodiment, the concentration (w/w) of the conductive oligomer in a solvent or a solvent system can be as high as the oligomer up to about 20%, from about 0.1 % to about 10%, from about 1 % to about 10%, or from about 0.5 % to about 1 %, about 10%, or about 5%.

[0044] D) Oligoaniline and oligothiophene.

[0045] In one embodiment, the conductive oligomer is aniline tetramer, and the dopant can be CSA, HCI0₄ and/or H₂S0₄. A solvent such as water, DMF, and/or HDIP can be used to dissolve/disperse the doped or undoped oligomer to a concentration (w/w) of up to about 20%, from about 0.1 % to about 10%, from about 1 % to about 10%, or from about 0.5 % to about 1 %, about 10%, or about 5%. The polydispersity of the tetramer is less than about 2, less than about 1 .40, less than about 1 .10, less than abouti .05, about 1 .00, or 1 .00. A highly conductive film comprising an aniline tetramer doped with CSA, HCI0₄ and/or H₂S0₄ can have a conductivity of about 1 to about 10 S/cm.

[0046] In another embodiment, the conductive oligomer is phenyl-capped aniline octamer, and the dopant can be CSA, HCI, H₂S0₄ and/or toluenesolfonic acid. A solvent such as m-cresol and/or DMF can be used to dissolve/disperse the doped or undoped oligomer to a concentration (w/w) of up to about 20%, from about 0.1 % to about 10%, from about 1 % to about 10%, or from about 0.5 % to about 1 %, about 10%, or about 5%. The polydispersity of the octamer is less than about 2, less than about 1 .40, less than about 1 .10, less than abouti .05, about 1 .00, or 1 .00. A highly

70553-8002.WO00/LEGAL19530833.2 9 conductive film comprising a phenyl-capped aniline octamer doped with CSA, HCI, H₂S0₄ and/or toluenesolfonic acid can have a conductivity of about 500 S/cm.

[0047] In another embodiment, the conductive oligomer is aniline 16-mer, and the dopant can be CSA, and/or polystyrenesulfonic acid. A solvent such as m-cresol, DMF and/or water can be used to dissolve/disperse the doped or undoped oligomer to a concentration (w/w) of up to about 20%, from about 0.1 % to about 10%, from about 1 % to about 10%, or from about 0.5 % to about 1 %, about 10%, or about 5%. The polydispersity of the 16-mer is less than about 2, less than about 1 .40, less than about 1 .10, less than aboutl .05, about 1 .00, or 1 .00. A highly conductive film comprising an aniline 16-mer doped with CSA, and/or polystyrenesulfonic acid can have a conductivity of about 1000 S/cm.

[0048] In another embodiment, the conductive oligomer is thiophene octamer, and the dopant can be polystyrenesulfonic acid. A solvent such as dichlorobenzene and/or acetonitrile can be used to dissolve/disperse the doped or undoped oligomer to a concentration (w/w) of up to about 20%, from about 0.1 % to about 10%, from about 1 % to about 10%, or from about 0.5 % to about 1 %, about 10%, or about 5%. The polydispersity of the octamer is less than about 2, less than about 1 .40, less than about 1 .10, less than aboutl .05, about 1 .00, or 1 .00. A highly conductive film comprising a thiophene octamer doped with polystyrenesulfonic acid can have a conductivity of about 80 S/cm.

[0049] In another embodiment, the conductive oligomer is hexyl-capped ethylenedioxythiophene octamer, and the dopant can be polystyrenesulfonic acid. A

70553-8002.WO00/LEGAL19530833.2 10 solvent such as water can be used to dissolve/disperse the doped or undoped oligomer to a concentration (w/w) of up to about 20%, from about 0.1 % to about 10%, from about 1 % to about 10%, or from about 0.5 % to about 1 %, about 10%, or about 5%. The polydispersity of the octamer is less than about 2, less than about 1 .40, less than about 1 .10, less than aboutl .05, about 1 .00, or 1 .00. A highly conductive film comprising a hexyl-capped ethylenedioxythiophene octamer doped with polystyrenesulfonic acid can have a conductivity of about 1 10 S/cm.

[0050] II. Method of preparing the highly conductive film

[0051] Another aspect of the present disclosure relates to a method of preparing a highly conductive film comprising a conductive oligomer and a dopant.

[0052] In one embodiment, the method comprises: preparing a solution/dispersion of a doped conductive oligomer; and

creating the highly conductive film.

[0053] In certain embodiments, preparation of the solution/dispersion of the doped conductive oligomer comprises:

preparing the conductive oligomer;

dissolving/dispersing the conductive oligomer in a solvent/solvent system; and reducing and/or oxidizing the conductive oligomer to a preferred oxidative state.

[0054] Conductive oligomers can be prepared using synthetic procedures known in the art, such as condensation reactions, radical oxidation, and metal cross-coupling

70553-8002.WO00/LEGAL19530833.2 1 1 reactions. For example, oligoaniline or a derivative thereof can be prepared by condensation reactions between an amine and a diacid, radical oxidation, and metal cross-coupling reactions.

[0055] The conductive oligomer in the present disclosure has been processed to its preferred conductive state.

[0056] In one embodiment, the conductive oligomer is oligoaniline or oligoaniline derivative, the preferred conductive state is emeraldine oxidation state. In one embodiment, the emeraldine oxidation state of oligoaniline or oligoaniline derivative can be achieved by first reducing the oligoaniline or oligoaniline derivative to it reductive state, and then oxidize to the emeraldine oxidation state. In another embodiment, the emeraldine oxidation state of oligoaniline or oligoaniline derivative can be achieved by first oxidizing the oligoaniline or oligoaniline derivative to its most oxidative state, and then reduce to the emeraldine oxidation state.

[0057] In another embodiment, the conductive oligomer is oligoparrole or oligoparrole derivative, the preferred conductive state is the most oxidative state. In another embodiment, the conductive oligomer is oligothiophene or oligothiophene derivative, the preferred conductive state is the most oxidative state.

[0058] The preferred oxidative state of the conductive oligomer can be obtained by suitable oxidation and/or reduction methods known in the art. Examples of reducing agents include, without limitation, phenylhydrazine, hydrazine, sodium borohydride, lithium aluminium hydride, sodium amalgam, and hydrogen. Examples of oxidizing agents include, without limitation, APS, FeCI₃, and inorganic and organic acids

70553-8002.WO00/LEGAL19530833.2 12 [0059] In certain embodiments, reduction/oxidation of the conductive oligomer is provided comprising: dissolved/dispersed in a solvent/solvent system; and then adding one or more reducing/oxidizing agents. In certain embodiments, the

reducing/oxidizing agents are added neat. In certain embodiments, the reducing agents are dissolved in a solvent/solvent system, wherein the solvent/solvent system for the reducing/oxidizing agents can be the same or different from the solvent/solvent system used to dissolve/disperse the conductive oligomer.

[0060] In certain embodiments, the oxidizing agents are dissolved/dispersed in water or aqueous acid solution. The acid can be inorganic acid (e.g. HCI, H₂S0₄, perchloric acid), organic acid (e.g. sulfonic acid such as camphor sulfonic acid (CSA), toluene sulfonic acid, dodecylbenzenesulfonic acid) and polymeric acid (e.g. polymeric sulfonic acid such as polystyrenesulfonic acid, and polyacrylic acid). In certain embodiments, the aqueous acid solution has a concentration of from about 0.01 M to about 6 M. In certain embodiments, the aqueous acid solution is 1 M HCI.

[0061] In certain embodiments, the oxidizing agents can also be used as dopants. Any know methods in the art can be used for doping. In one embodiment, doping can be performed by bringing the oligomer in contact with the dopant. The oligomer can be in a solid or liquid phase, and the dopant can be in a solid, liquid or gas phase. For example, in one embodiment, the conductive oligomer dissolved/dispersed in a first solvent can be mixed with the dopant dissolved/dispersed in a second solvent. The first solvent and the second solvent can be the same or different. In another embodiment, the dopant can be added into a solution/dispersion of the conductive

70553-8002.WO00/LEGAL19530833.2 13 oligomer. In another embodiment, the dopant and the conductive oligomer can be mixed at solid state and then dissolved/dispersed in a solvent/solvent system. In another embodiment, the dopant can be dissolved in a solvent/solvent system, and the solid conductive oligomer is added into the dopant solution. In another embodiment, the dopant may be volatile (e.g. HCI, H₂S0₄) and the conductive oligomer can be doped by exposure to the volatile dopant.

[0062] In one embodiment, the doped or un-doped conductive oligomer can be dissolved/dispersed in the solvent/solvent system at ambient temperature. In another embodiment, the doped or un-doped conductive oligomer can be dissolved/dispersed in the solvent/solvent system at an elevated temperature. In certain embodiments, the elevated temperature is up to about 100 °C. In certain embodiments, the elevated temperature is up to about 60 °C.

[0063] The conductive film comprising a doped conductive oligomer can by prepared using standard deposition techniques (e.g. spin-coating, drop-casting, spraying, printing, sputtering, and other evaporation deposition techniques known in the art). In one embodiment, the doped conductive oligomer solution/dispersion is deposited at ambient temperature first and then cured at an elevated temperature to expedite the evaporation of the solvent. In another embodiment, the doped conductive oligomer solution/dispersion is deposited at an elevated temperature of up to about 60 °C, or up to about 120 °C.

[0064] In another embodiment, the method comprises:

preparing a solution/dispersion of an un-doped conductive oligomer;

70553-8002.WO00/LEGAL19530833.2 14 creating an un-doped conductive film using the solution/dispersion of the un-doped conductive oligomer; and

doping the un-doped conductive film to create the highly conductive film.

[0065] The solution/dispersion of an un-doped conductive oligomer is prepared by:

preparing the conductive oligomer (as described supra); and

dissolving/dispersing the conductive oligomer into a solvent/solvent system (as described supra).

[0066] The un-doped conductive film can be created using the same standard deposition techniques as described supra.

[0067] Doping of the un-doped conductive film comprises contacting the un- doped conductive film with the dopant

[0068] In one embodiment, the un-doped conductive film is doped by exposure to vapor of a volatile dopant such as HCI or H₂S0₄.

[0069] In another embodiment, the un-doped conductive film is doped by washing the film with a dopant solution. Examples of dopant are the same as described supra. Examples of solvent that can be used to dissolve the dopant include, without limitation, water, various alcohols, DMF, NMP, and other low boiling point solvents.

[0070] The same method can be used to produce conductive coatings having similar conductivities.

70553-8002.WO00/LEGAL19530833.2 15 [0071] The range of conductivities and sheet resistances of these materials makes them very effective materials for conductive coatings or films. These coating or films can be used for many different purposes. In some embodiments, the material for conductive coatings or films can be used as a stand alone material in applications such as electrostatics, wherein the film or coating may be used as an anti-static coating. These films possess the necessary electrical properties to function as an anti-static coating and electrode.

[0072] In certain embodiments, the conductive films and coatings may be integrated as a component into larger devices that include, but are not limited to, antistatic elements, electrical contacts, electrostatics, electrochromics, actuators, photovoltaics, sensors, batteries, capacitors, electrodes, displays, and electromagnetic shielding.

[0073] The methods described herein may be further refined to improve conductivity of resulting films, coatings and moldings. Further improvements to conductivity would allow the material to function in additional applications such as transparent electrodes and would further improve applications that are currently be explored such as anti-static coatings or electromagnetic interference (EMI) shielding. Processing parameters may also be refined and optimized.

[0074] Most known processes for producing highly conducting organic materials focus on the processing of polymers, not oligomers. A few examples for producing conducting oligomers exist, but typically represent non-ordered oligomers that possess low conductivity (less than 1 S/cm). The methods described herein provide conductive

70553-8002.WO00/LEGAL19530833.2 16 materials of oligomers that possess significantly higher conductivity as compared to previously known oligomers. Thus, an important aspect to the present disclosure is the processing of oligomers in a way to create ordered thin films that possess conductivity that is one or more orders of magnitude higher than previously reported.

[0075] In addition, the use of aniline oligomers and their derivatives produced by the methods described herein has many advantages over the use of polymers. First, oligomers having low dispersities (< about 1 .4, < about 1 .10, < about1 .05, about 1 .00, or 1 .00) facilitate interchain packing more efficiently than polydisperse polymers, resulting in higher conductivity (Figures 2 and 4). Second, the redox chemistry of oligomers (e.g. oligoaniline) can be finely tuned, wherein that of polymers cannot be finely tuned (see Figures 6C and 6D). Third, oligomers are more solution processable than their polymer counterparts, as oligomers can be dispersed in more solvents and at a higher

concentration. For example, stable solutions with concentrations as high as about 20% (w/w) have been obtained with doped aniline tetramer which is typically not possible with the polymeric counterpart. For example, doping aniline tetramer with CSA and dissolving this mixture with HFIP, one can obtain stable solutions with concentrations as high as about 20% (w/w). Doped polyaniline can only be dispersed in a limited number of solvents such as m-cresol or HFIP. However, doped oligoanilines can be dispersed in several solvents that include, but are not limited to, m-cresol, HFIP, xylenes, DMF, acetone, THF, acetonitrile, and a variety of alcohols. Because oligoanilines can be processed from a greater variety of solvents than the polymer, the processing of these materials is easier and the production of high quality thin films is facilitated.

70553-8002.WO00/LEGAL19530833.2 17 [0076] Although the invention has been described with respect to specific embodiments and examples, it will be readily appreciated by those skilled in the art that modifications and adaptations of the invention are possible without deviation from the spirit and scope of the invention. Accordingly, the scope of the present invention is limited only by the following claims.

[0077] The following examples are provided to better illustrate the embodiments and are not to be interpreted as limiting the scope of any claimed embodiment. The extent that specific materials are mentioned, it is merely for purposes of illustration and is not intended to limit the invention. One skilled in the art may develop equivalent means or reactants without the exercise of inventive capacity and without departing from the scope of the invention. It will be understood that many variations can be made in the procedures herein described while still remaining within the bounds of the present invention. It is the intention of the inventors that such variations are included within the scope of the invention.

Examples

[0078] Example 1 . Doped aniline tetramer film. [0079] 1 A. Preparation of aniline tetramer.

[0080] Aniline tetramer was synthesized by known procedures. In brief, p-aniline dimer was oxidatively coupled into aniline tetramer by suspending the dimer in a solution of 1 M HCI. The solution was cooled to 0 °C and 2 equivalence of FeCI₃ dissolved in a separate solution of 1 M HCI was rapidly mixed with the suspension

70553-8002.WO00/LEGAL19530833.2 18 containing dimer. The reaction mixture was stirred at 0 °C for 4 hours after which time the product was filtered and dedoped by washing with NH₄OH. The crude product was recrystallized three times in order to obtain the pure aniline tetramer in its undoped state.

[0081] 1 B. Preparation of tetraaniline doped with HCI0₄.

[0082] Undoped aniline tetramer was dissolved in a solution of ethanol. The obtained solution was slowly dripped into a solution of 1 M HCI0₄. Green and doped aniline tetramer precipitated out of the solution which was then filtered to obtain the pure HCI0₄ doped aniline tetramer.

[0083] Alternatively, aniline tetramer was dissolved in a solvent mixture of ethanol and 1 M HCI0₄. The obtained solution was left unagitated for several days, and then the HCI0₄ doped aniline tetramer precipitated and was collected by filtration.

[0084] 1 C. Preparation of tetraaniline doped with H₂S0_4.

[0085] Aniline tetramer doped with H₂S0₄ was prepared in an identical fashion as described for the preparation of HCI0₄ doped aniline tetramer, except 1 M HCI0₄ was substituted by 1 M H₂S0₄.

[0086] 1 D. XRD of HCI0₄ doped and H₂S0₄ doped tetraaniline

[0087] XRD data of the oligomers were obtained by casting doped films of the oligomers onto a substrate. Powder x-ray diffraction patterns of the oligomers were then taken on a Panalytical X'Pert Pro X-ray powder diffractometer with a scan rate of 2

70553-8002.WO00/LEGAL19530833.2 19 deg/min. Sodium chloride was used as an internal standard for the crystallite size calculations using the Scherrer equation.

[0088] X-ray diffraction (XRD) of tetraaniline doped with HCIO₄ (Figure 2, top diffraction) and tetraaniline doped with H₂SO₄ (Figure 2, bottom diffraction) were obtained. Both XRD shows a high amount of structural order within doped aniline tetramer which is difficult to observe with the polymeric counterpart.

[0089] Example 2. Preparation of doped phenyl-capped aniline octamer.

[0090] 2A. Preparation of phenyl-capped aniline octamer

[0091] Tetraaniline (4.6 g, 12.55 mmol) was condensed with succinosuccinic acid (1 .25 g, 6.245 mmol) in 130 ml_ of m-cresol to produce phenyl-capped aniline octamer (Figure 3). This reaction was typically performed under an inert atmosphere at elevated temperatures ranging from 30 °C to 90 °C for 2-3 days. Subsequent purification by filtration and recrystallization affords the pure phenyl-capped octamer in yields ranging from 40-90%.

[0092] The molecular weight of phenyl-capped aniline octamer was determined by mass spectrometry (MALDI-TOF, Figure 4). The aniline oligomer was mixed with a matrix such as 2,5-dihydroxybenzoic acid (DHB) and the molecular weight of the sample was analyzed with an Applied Biosystems Voyager-DE-STR MALDI-TOF. One distinct peak at 806 m/z shows that the desired aniline oligomers were synthesized as opposed to the polyaniline which typically produces a Gaussian distribution of chain lengths.

70553-8002.WO00/LEGAL19530833.2 20 [0093] The molecular weight distribution of phenyl-capped aniline octamer was further characterized by GPC (Figure 5). Molecular weight distributions of the aniline oligomers were obtained by gel permeation chromatography (GPC) using a Waters 2690 HPLC pump with a Waters 996 photodiode array (PDA) detector. The gel permeation chromatography column used was a Waters Styragel HR 5E and the temperature of the column was held at 60 °C. HPLC grade NMP containing 0.01 M LiBF₄ was used as the eluent. A flow rate of 0.35 cm³min^"1 was used for the eluent with an injection volume of 50 μΙ_. Polystyrene (PS) standards with ten narrowly distributed M_w values (Polymer Laboratories Easical PS-1 and PS-2) were used to calibrate the columns. Samples were prepared by dissolving 0.02 mass% of dedoped aniline oligomers in a LiBF₄/NMP solution, filtered with a 0.45 μιτι Teflon syringe filter, and then allowed to equilibrate overnight under ambient conditions.

[0094] 2B. Preparation/characterization of doped phenyl-capped aniline octamer.

[0095] Phenyl-capped aniline octamer (1 .6 g, 2 mmol) was fully reduced to the leucoemeraldine oxidation state (Figure 6A) by the addition of a large excess of a reducing agent such as phenylhydrazine or hydrazine in a solvent such as DMF (20 mL). The fully reduced leucoemeraldine oligomers were oxidized to the ideal emeraldine base form (Figure 6C) by oxidizing the oligomers with one or more equivalents of an oxidizing agent such as APS or FeCI₃ in water or 1 M HCI and/or a variety of other inorganic and organic acids such as CSA, HCI0₄, H₂S0₄, or TSA, and were then further doped to their hoped emeraldine salt form (Figure 6D).

70553-8002.WO00/LEGAL19530833.2 21 [0096] The absorption spectrum of the oligomers were obtained on an HP 8452 spectrometer by dissolving the oligomer samples in N-methylpyrrolidone (NMP) in a quartz cuvette that had a 1 mm light path length. Figure 6A shows the leucoemeraldine oxidation state, Figure 6B shows the pernigraniline oxidation state Figure 6C shows the emeraldine base form and Figure 6D shows the doped emeraldine salt form of a phenyl- capped aniline octamer.

[0097] Example 2C. Preparation of CSA doped phenyl-capped aniline octamer solution.

[0098] Phenyl-capped aniline octamer in the emeraldine oxidation state (0.1 g, 0.125 mmol) was mixed in 20 mL of m-cresol along with camphorsulfonic acid (59 mg, 0.25 mmol). This dispersion/solution was stirred for one day. The stirring process was performed at room temperature or at elevated temperatures such as 60 °C in order to facilitate the dissolution process. The concentration of the final doped oligomer in solution was approximately -0.7% (w/w).

[0099] Example 3. Preparation of doped aniline 16-mers.

[00100] 3A. Preparation of aniline 16-mer

[00101] Tetraaniline (0.203 g, 3.3 mmol) in the leucoemeraldine oxidation state was suspended in 70 mL of 0.1 M HCI. Ammonium peroxydisulfate (1 .141 g, 5 mmol) in 20 mL of 0.1 M HCI was then rapidly mixed with the tetraaniline solution and stirred for 2 hours (Figure 4). Subsequent purification by filtration and multiple washing steps

70553-8002.WO00/LEGAL19530833.2 22 afforded the pure aniline 16-mer. The crude product can also be purified by a Soxhiet extractor to obtain the pure 16-mer.

[00102] The molecular weight of the aniline 16-mer was determined by mass spectrometry, and further characterized by GPC.

[00103] 3B. Preparation doped aniline 16-mers

[00104] Undoped aniline 16-mer was dissolved in a solution of ethanol. The obtained solution was slowly dripped into a solution of 1 M HCI0₄. Green and doped aniline 16-mer precipitated out of the solution which was then filtered to obtain the pure HCI0₄ doped aniline 16-mer.

[00105] Alternatively, aniline 16-mer was dissolved in a solvent mixture of ethanol and 1 M HCI0₄. The obtained solution was left unagitated for several days, and then the HCI0₄ doped aniline 16-mer precipitated and was collected by filtration.

[00106] Example 4. Conductivity of doped phenyl-capped aniline octamer, aniline 16-mer and tetraaniline. (Table 1 ).

[00107] The conductivity of the films was determined by using the equation: σ = 1 /[(Sheet resistance) ^* (film thickness)].

[00108] The thickness of the oligomer films was determined by depositing an oligomer film onto a flat surface by using a VEECO Dektak 8 Surface Profiler. Film thickness data were obtained by applying a pressure with the Profiler's stylus and measuring the vertical displacement of the stylus.

70553-8002.WO00/LEGAL19530833.2 23 [00109] The sheet resistance of oligomer films was obtained using the standard 4- pt probe technique with a Keithley 2420 source meter.

Table 1 . Representative aniline oligomers in the emeraldine oxidation state and their conductivities when doped and processed with the listed solvents and dopants

[00110] Example 5. Conductive films of oligothiophene.

[00111 ] Thiophene octamer was prepared by treatment of 2,2' : 5,2" : 5", 2" quaterthiophene with FeCI₃ in benzene. The precipitates were collected by filtration,

70553-8002.WO00/LEGAL19530833.2 24 washed with methanol, and purified recrystallization. The crude product was then further purified by sublimation in order to obtain the pure thiophene octamer.

[00112] Thiophene octamer (0.1 g, 0.152 mmol) was dissolved in 10 mL of dichlorobenzene. To this solution was added a solution of 10 mL acetonitrile containing 0.1 1 g of polystyrenesulfonic acid. The solution was rigorously sonicated for 3 hours and then stirred at room temperature for 3 days. Films cast from this solution possessed a conductivity of -80 S/cm.

[00113] Hexyl-capped ethylenedioxythiophene (EDOT) octamer was prepared by reacting hexyl-substituted bis-EDOT with Bu₃SnCI in order to produce the tin substituted hexyl bis-EDOT. Following purification, the obtained dimer was subsequently cross- coupled with dibromo ter-EDOT using Pd(PPh₃)₄ in a Stille-type coupling. The dibromo ter-EDOT itself was synthesized from brominated bis-EDOT and EDOT monomers in a Stille-type coupling. Following purification by recrystallization and sublimation, the pure product was obtained and subsequently stored at 0 °C under vacuum in a closed container that did not allow light inside.

[00114] A derivative of thiophene octamer, hexyl-capped ethylenedioxythiophene octamer (0.1 g, 0.0784 mmol), was added to a solution of 20 mL of water containing 0.1 1 g of polystyrenesulfonic acid. The solution was sonicated for 3 hours and then stirred for 4 days at -40 °C. One mL of DMF was then added to this solution and the resulting solution was stirred for 1 day at room temperature. Films cast from this solution possessed a conductivity of -1 10 S/cm.

70553-8002.WO00/LEGAL19530833.2 25 [00115] Example 6. Preparation of highly conductive films comprising doped oligoanilines. (Figure 8)

[00116] Figure 8 illustrates a method of preparing highly conductive films comprising doped oligoanilines.

[00117] First, oligoanilines were synthesized (100).

[00118] Second, the oligoanilines were reduced/oxidized to the preferred emeraldine oxidation state (1 10).

[00119] Third, the oligoanilines at the preferred oxidation state can be doped with acid and dissolved in solvent (120) and then cast into films (130).

[00120] Alternatively, the third step can be to dissolve the oligoanilines at the preferred oxidation state and cast the films (140) and then dope the films by exposure to dopant (e.g. acid) (150).

70553-8002.WO00/LEGAL19530833.2 26 REFERENCES

All patents or other references referred to above or listed below are hereby incorporated by reference in their entirety as if fully set forth herein.

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70553-8002.WO00/LEGAL19530833.2 30

Claims

1 . A conductive film comprising:

a conductive oligomer and a dopant;

the conductive oligomer comprising one or more types of monomers selected from the group consisting of aniline, aniline derivatives, pyrrole, pyrrole derivatives, thiophene, and thiophene derivatives and having a polydispersity of less than about 1 .40,

wherein the conductivity of the conductive film is about 10 S/cm or greater.

2. The conductive film according to claim 1 , wherein:

the conductive oligomer is aniline tetramer; and

the dopant is selected from the group consisting of CSA, HCI0₄ and H₂S0₄.

3. The conductive film according to claim 1 , wherein:

the conductive oligomer is phenyl-capped aniline octamer;

the dopant is selected from the group consisting of HCI, H₂S0₄, camphorsulfonic acid and toluenesolfonic acid; and

the conductivity of the conductive film is more than about 100 S/cm.

4. The conductive film according to claim 1 , wherein:

the conductive oligomer is aniline 16-mer;

the dopant is selected from the group consisting of camphorsulfonic acid and toluenesolfonic acid; and

the conductivity of the conductive film is more than about 100 S/cm.

70553-8002.WO00/LEGAL19530833.2 31

5. The conductive film according to claim 1 , wherein:

the conductive oligomer is thiophene octamer;

the dopant is polystyrenesulfonic acid; and

the conductivity of the conductive film is more than about 80 S/cm.

6. The composition according to claim 1 , wherein:

the conductive oligomer is hexyl-capped ethylenedioxythiophene octamer;

the dopant is polystyrenesulfonic acid; and

the conductivity of the conductive film is more than about 100 S/cm.

7. A conductive film comprising:

a conductive oligomer and a dopant; and

having a conductivity of about 10 S/cm or greater.

8. The conductive film according to claim 7, wherein:

the conductive oligomer is a homooligomer or a co-oligomer; and

the conductive oligomer comprises one or more types of monomers selected from the group consisting of aniline, aniline derivatives, pyrrole, pyrrole derivatives, thiophene, and thiophene derivatives.

9. The conductive film according to claim 8, wherein the aniline derivative is phenyl- capped aniline, and the thiophene derivative is 3,4-ethylenedioxythiophene or hexyl-capped ethylenedioxythiophene.

10. The conductive film according to claim 7, wherein the degree of oligomerization of the conductive oligomer is an integer selected from 4 to 100.

70553-8002.WO00/LEGAL19530833.2 32

1 1 . The conductive film according to claim 8, wherein the degree of oligomerization of the conductive oligomer is 4, 8, 16, or 64.

12. The conductive film according to claim 7, wherein the polydispersity of the

oligomer is less than about 1 .40.

13. The conductive film according to claim 12, wherein the conductive oligomer is selected from the group consisting of tetraaniline, phenyl-capped aniline octamer, aniline 16-mer, thiophene octamer, and hexyl-capped ethylenedioxythiophene octamer.

14. The composition according to claim 7, wherein the dopant is an acid or an redox active agent.

15. The composition according to claim 14, wherein the acid is selected from the

group consisting of HCI, HCI0₄, H₂S0₄, sulfonic acid, camphor sulfonic acid (CSA), toluene sulfonic acid, dodecylbenzenesulfonic acid, polymeric sulfonic acid, polystyrenesulfonic acid, and polyacrylic acid.

16. The composition according to claim 14, wherein the redox active agent is

selected from the group consisting of iodine, bromine, and chlorine.

17. A method of making the conductive film according to claim 7 comprising making the conductive film from a first conductive oligomer solution comprising the conductive oligomer and a first solvent/solvent system, wherein the

solvent/solvent system comprises one or more solvents selected from the group consisting of inorganic solvent and organic solvent.

70553-8002.WO00/LEGAL19530833.2 33

18. The method according to claim 17, wherein the organic solvent is selected from the group consisting of m-cresol, hexafluoroisopropanol (HFIP), dichloroacetic acid, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP),

dimethylsulfoxide (DMSO), acetone, chloroform, THF, acetonitrile, alcohol, methanol, ethanol, isopropanol, butanol, trifluoroisopropanol, aromatic organic solvent, toluene, xylene dicholorobenzene and benzene.

19. The method according to claim 17, wherein the inorganic solvent is water,

aqueous acid solution, or aqueous salt solution.

20. A method of making the conductive film according to claim 7, comprising:

providing a first conductive oligomer solution comprising the conductive oligomer, a first solvent/solvent system, and the dopant; and

making the conductive film from the first conductive oligomer solution.

21 . The method according to claim 20, wherein the first solvent/solvent system

comprises one or more solvents selected from the group consisting of inorganic solvent and organic solvent.

22. The method according to claim 21 , wherein the organic solvent is selected from the group consisting of m-cresol, hexafluoroisopropanol (HFIP), dichloroacetic acid, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP),

70553-8002.WO00/LEGAL19530833.2 34

23. The method according to claim 22, wherein the inorganic solvent is water, aqueous acid solution, or aqueous salt solution.

24. The method according to claim 20, wherein the polydispersity of the conductive oligomer is less than about 1 .4, and the degree of oligomerization is from 4 to 100.

25. The method according to claim 24, wherein:

the conductive oligomer is a homooligomer or a co-oligomer; and

the conductive oligomer comprises one or more types of monomers selected from the group consisting of aniline, aniline derivatives, pyrrole, pyrrole

derivatives, thiophene, and thiophene derivatives.

26. A method of preparing the conductive film according to claim 7, comprising:

providing a first conductive oligomer solution comprising the conductive oligomer, the first solvent/solvent system;

making an undoped conductive film from the first conductive oligomer solution; and

making the conductive film by exposing the undoped conductive film to the dopant.

27. The method according to claim 25, wherein the first solvent/solvent system

70553-8002.WO00/LEGAL19530833.2 35

28. The method according to claim 26, wherein the organic solvent is selected from the group consisting of m-cresol, hexafluoroisopropanol (HFIP), dichloroacetic acid, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP),

29. The method according to claim 26, wherein the inorganic solvent is water, aqueous acid solution, or aqueous salt solution.

30. The method according to claim 25, wherein the polydispersity of the conductive oligomer is less than about 1 .4, and the degree of oligomerization is from 4 to 100.

31 . The method according to claim 30, wherein:

the conductive oligomer is a homooligomer or a co-oligomer; and

70553-8002.WO00/LEGAL19530833.2 36