GB2430438A - Method to manufacture polymer nanostructures and a polymer nanosensor manufactured therefrom - Google Patents

Method to manufacture polymer nanostructures and a polymer nanosensor manufactured therefrom Download PDF

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GB2430438A
GB2430438A GB0519542A GB0519542A GB2430438A GB 2430438 A GB2430438 A GB 2430438A GB 0519542 A GB0519542 A GB 0519542A GB 0519542 A GB0519542 A GB 0519542A GB 2430438 A GB2430438 A GB 2430438A
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polymer
substrate
polypyrrole
copolymer
layer
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GB0519542D0 (en
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Bin Dong
Harald Fuchs
Lifeng Chi
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Westfaelische Wilhelms Universitaet Muenster
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Westfaelische Wilhelms Universitaet Muenster
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Priority to PCT/EP2006/009344 priority patent/WO2007039188A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/093—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antistatic means, e.g. for charge depletion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • 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
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/221—Changing the shape of the active layer in the devices, e.g. patterning by lift-off techniques
    • 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
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A method for manufacturing a patterned layer of a polymer, preferably a conducting polymer, is described. The method comprising the following steps: depositing a layer of resist (10) on a substrate (20); patterning the layer of resist (10); copolymerizing of a first monomer of a polymer with a second monomer to form the copolymer; depositing the copolymer on the substrate (20); and finally lifting off the layer of resist (10). The method is used for the manufacturer of a device, such as a sensor.

Description

Method to Fabricate Polymer Nanostructures and a Polymer Nanosensor
manufactured therefrom
Field of the Invention
The invention relates to conducting polymers nanowires and nanosensors made therefrom.
Background to the Invention
Conducting polymers have attracted considerable attention owing to the unique combination of their electronic, optical, magnetic and mechanical properties (lightweight, easily processable, highly flexible), see for example the reviews of H. Shirakawa, Angew. Chem. mt.
Ed. 2001, 40, 2574-2580, A. 0. MacDiarmid, Angew. Chem. mt. Ed. 2001, 40, 258 1-2590 and A. J. Heeger, Angew. Chem. mt. Ed. 2001, 40, 2591-2611 The anticipated application areas of conducting polymers range from microelectronics, electro-optics and optical electronics to sensors and actuators as has been reported in the publications of J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Bums, A. B. Holmes, Nature 1990, 347, 539-541, M. Angelopoulos, IBM J. RES. & DEV. 2001, 45, 57-75 and E. W. H. Jager, B. Smela, 0. Inganas, Science 2000, 290, 1540-1545.
In recent years, a significant portion of these studies has been devoted to the fabrication of all- polymer devices (as is taught by D. Voss, Nature, 2000, 407, 442-444). All-polymer devices have been demonstrated to possess properties that may rival those of inorganic devices while still retaining their low cost, flexibility and disposable nature (see H. Sirringhaus, N. Tessler, a S.5 **S ** *5 S S * * S S S S a. S S S * S * S *.. S S S S R. H. Friend, Science, 1998, 280, 1741-1744). Although they are still at the prototype stage, different kinds of devices, such as field effect transistors (PET) (see F. Gamier, R. Hajlaoui, A. Yassar, P. Srivastava, Science, 1994, 265, 1684-1686, Z. Bao, Y. Feng, A. Dodabalapur, V. R. Raju, A. J. Lovinger, Chem. Mater. 1997, 9, 1299-1301 and M. Halik, H. Klauk, U. Zschieschang, T. Kriem, G. Schmid, W. Radlik, K. Wussow, App!. Phys. Lett. 2002, 81, 289- 291), charge storage devices (Y. Gofer, H. Sarker, J. G. Killian, T. 0. Poehier, P. C. Searson, App!. Phys. Lett. 1997, 71, 1582-1584), integrated circuits (C. J. Drury, C. M. J. Mutsaers, C. M. Hart, M. Matters, D. M. de Leeuw, App!. Phys. Lett. 1998, 73, 108-110, H. Sirringhaus, T. Kawase, R. H. Friend, T. Shimoda, M. Inbasekaran, W. Wu, E. P. Woo, Science, 2000, 290, 2 123-2126 and G. H. Gelinck, T. C. T. Geuns, D. M. de Leeuw, Appi. Phys. Lett. 2000, 77, 1487-1489) and optoelectronic devices (A. Dodabalapur, Z. Bao, A. Makhija, J. G. Laquindanum, V. R. Raju, Y, Feng, H. E. Katz, J. Rogers, App!. Phys. Lett. 1998, 73, 142-144 and P. K. H. Ho, D. S. Thomas, R. H. Friend, N. Tessler, Science, 1999, 285, 233-236) have been demonstrated.
The emerging field of nanosensors offers the prospect of high sensitivity and rapid detection of the analyte (K. C. Persaud, S. M. Khaffaf, J. S. Payne, A. M. Pisanelli, D. H. Lee, H. G. Byun, Sen. Actuators. B 1996, 3536, 267-273, M. H. Yun, N. V. Myung, R. P. Vasquez, C. Lee, E. Menke, R. M. Penner, Nano Lett. 2004, 4, 4 19-422, K. Ramanathan, M. A. Bangar, M. H. Yun, W. Chen, A. Muichandani, N. V. Myung, Nano Lett. 2004, 4, 12371239 and D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537-2574). For instance, Craighead et al. , Nano lett. 2004, 4, 67 1-675, have reported a polyaniline nanowire chemical sensor 30 times more sensitive than the traditional film-based sensors to ammonium gas.
Huang et aL, J. Am. Chem. Soc. 2003, 125, 314-315, reported a nanofiber film sensor that responds much faster than the conventional film sensor to HC1 gas. Apart from the detection of chemical vapors, the improved sensing behavior is also observed for detecting biological * * *h : : . *0 * * * * S S S S * * S b I 4 a * molecules, such as glucose E. S. Forzani, H. Q, Zhang, L. A. Nagahara, I. Amlani, R. Tsui, N. J. Tao, Nano Lett. 2004, 4, 1785-1788) and biotin (K. Ramanathan, M. A. Bangar, M. H. Yun, W. Chen, N. V. Myung, A. Mulchandanj, J. Am. Chem. Soc. 2005, 127, 496-497).
A sensor which uses an immobilized affinity component capable of interacting with an analyte species and associated with a conducting poiymer is known from US Patent No. 6,300,123 (Vadgama et a!, assigned to the Victoria University of Manchester). In this patent, a conducting polymer of poly (3- methylthiophene) or poly(pyrrole)bridges two gold electrodes. The affinity component is immobilized with the conducting polymer layer.
Another sensor using conductor polymer compositions is known from US patent application number US 2004/0040841.
This prior art all has in common that an all-polymer concept has currently not yet been applied to nano sensors. This is possibly due to the limitation in the resolution and integration of the conducting polymer lines.
The term "nanosensor", "nanowire" and "nanoscale" as used in this patent application imply that at least one dimension of the object has a size which is in the "nanoregion", i.e. less than around lOOnm.
There are basically two approaches to the construction of nanoscale conducting polymeric structures: the synthesis and post assembly method (see, for examples, Y. Huang, X. F. Duan, Q. Q. Wei, C. M. Lieber, Science, 2001, 291, 630-633, P. A. Smith, C. D. Nordquist, T. N. Jackson, T. S. Mayer, B. R. Martin, J. Mbindyo, T. E. Mallouk, App!. Phys. Lett. 2000, 77, 1399-1401) or the microfabrication method (taught in J. Y. Bai, C. M. Snively, W. N. a a I II.
: *1e3.,1 I * * * a a * * a * a * I a. I 4 Delgass, J. Lauterbach, Adv. Mater. 2002, 14, 1546-1549, F. Shi, B. Dong, D. L. Qiu, J. Q. Sun, 1. Wu, X. Zhang, Adv. Mater. 2002, 14, 805-809, Y. N. Xia, 0. M. Whitesides, Angew.
Chem. mt. Ed. 1998, 37, 550-575, C. B. Gorman, H. A. Biebuyck, G. M. Whitesides, Chem. Mater. 1995, 7, 526-529, Z. Y. Huang, P. C. Wang, A. G. MacDiarmid, Y. N. Xia, G. M. Whitesides, Langmuir 1997, 13, 6480-6484, K. M. Vaeth, R. J. Jackman, A. J. Black, G. M. Whitesides, K. F. Jensen, Langmuir 2000, 16, 8495-8500, B. W. Maynor, S. F. Filocamo, M. W. Grinstaff, J. Liu, J. Am. Soc. Chem. 2002, 124, 522-523, J. H. Lim, C. A. Mirkin, Adv.
Mater. 2002, 14, 1474-1477 and M. Su, M. Aslam, L. Fu, N. Q. Wu, V. P. Dravid App!. Phys. Lett. 2004, 84, 4200-4202 (photolithography, soft lithography, etc). In the former approach, the sub 100 nm structures can be readily obtained by either template synthesis (taught in Z. H.Cai, C. R. Martin, J. Am. Chem. Soc. 1989, 111, 4138-4139, W. B. Liang, C. R. Martin, J. Am. Chem. Soc. 1990, 112, 9666-9668, C. R. Martin, Science 1994, 266, 1961-1966) or electrospinning (taught in D. H. Reneker, I. Chun, Nanotechnology, 1996, 7, 2 16-223, D. H. Reneker, A. L. Yarin, H. Fong, S. Koombhongse, J. App!. Phys. 2000, 87, 453 1-4547, I. D. Norris, M. M. Shaker, F. K. Ko, A. G. MacDiarmid, Synth. Met. 2000, 114, 109-114, A. G. MacDiarmid, W. E. Jones, I. D. Norris, J. Gao, A. T. Johnson, N. J. Pinto, J. Hone, B. Han, F. K. Ko, H. Okuzaki, M. Llaguno, Synth. Met. 2001, 119, 27-30, D. Li, Y. L. Wang, Y. N. Xia, Nano Lett. 2003, 3, 11671171, D. Li, Y. N. Xia, Nano Lett. 2004, 4, 933-938). However, manipulation and positioning of these synthesized nano-objects with respect to the microelectrodes is rather difficult and not precise. In the latter case, the microfabrication techniques provide conducting polymer microstructures, but these techniques possess significant limitation for patterning structures of sub 100 nm dimensions.
Summary of the Invention
* * ass 51 5 *s S I * a S S S S.. I S S * I 8S5 5 4 S S It is therefore an object of the invention to provide a method of fabrication which overcomes the above limitations.
It is furthermore an object of the invention to fabricate a polymer nanosensor with a resolution of less than 100 rim, In the present work, fabrication of an all-polymer nano sensor by a copolymer strategy with a resolution less than 100 rim is described. Copolymerization of a conducting polymer with another components is known to be an effective way to improve the solubility and processability of conducting polymers (as has been show in several papers: J. R. Reynolds, P. A. Poropatic, R. L. Toyooka, Macromolecules 1987, 20, 958-961, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 72, 89-94, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 72, 167-171, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 73, 26 1-266, F. Fusalba, D. Belanger, J. Phys. Chem. B 1999, 103, 9044-9054, C. J. Xia, X. W. Fan, M. Park, R. C. Advincula, Langmuir, 2001, 17, 7893-7898, and P. Taranekar, X. W. Fan, R. Advincula, Langmuir, 2002, 18, 7943-7952.
By adjusting the fraction of the two monomers in the resulting copolymer, the properties of the conducting polymer such as conductivity and adhesion, can also be tuned. Adhesion has been demonstrated to be quintessential for the microfabrication techniques that involve lift off processes, e.g. the deposition of metals (see S. Y. Chou, P. R. Krauss, P. J. Renstrom, Appl.
Phys. Lett. 1995, 67, 3114-3116, S. Y. Chou, P. R. Krauss, P. J. Renstrom, Science 1996, 272, 85-87and S. Y. Chou, P. R. Krauss, P. J. Renstrom, J. Vac. Sci. Technol. B 1996, 14, 4129- 4133). Conducting polymers are usually not amenable to the lift off process because their films do not adhere to the substrate. As a result, they can be easily peeled off from the substrate to give freestanding films. Various methods have been established in order to S.: * 1. *. *.. S. * *S * * S S I I * S * S S I I * S S S 555 5 5 5 S improve the adhesion of conducting polymer films, e.g. surface anchoring (R. A. Simon, A. J. Ricco, M. S. Wrighton, J. Am. Chem. Soc. 1982, 104, 203 1-2034, R. J. Willicut, R. L. McCarley, J. Am. Chem. Soc. 1994, 116, 10823-10824, and C. 0. Noble, R. L. McCarley, J. Am. Chem. Soc. 2000, 122, 6518-6519), addition of additives (E. L. Kupila, J. Kankare, Synth. Met. 1995, 74, 241-249) etc. By utilizing both silane groups and a surfactant as glue molecules, the fabrication of sub-micron polypyrrole wires through a lift off process was reported (B. Dong, M. Krutscbke, X. Zhang, L. F. Chi, H. Fuchs, Small 2005, 1, 520-524).
However, due to the lack of control over the film thickness during deposition, this method is not suitable for high resolution (< 100 rim) fabrication.
Description of the Figures
Fig. 1 shows a schematic representation of the fabrication process.
Fig. 2 shows the molecular formula of the copolymer.
Fig. 3a shows an AFM image of an 80 rim wide polypyrrole wire (size: 11 j. tmxll jim).
Fig. 3b shows optical images of six pairs of polypyrrole microelectrode shaped structures (size: 475 j.tmx390 jim).
Fig. 3c shows an enlarged AFM image of the area inside the black box of Figure 3b, showing one 100 rim wide polypyrrole wire that bridges the end of two polypyrrole microelectrodes (size: 9 jimxlO jim).
Fig. 4a shows the I-V characteristics of a 100 rim all-polypyrrole nanodevice as shown in Figure 3c.
Fig. 4b show a real time response of this 100 rim nanowire sensor (Figure 3c) to a 240 ppm NH3 stream (40 s on /40 s off).
Fig. 4c shows the sensitivity dependence on the width of the wire between the electrodes (at constant thickness).
* age,6 * : * * * *. *8. 8$ S S. * S * S S * * S S S S S S S * S S 8S. S S S * Fig. 5a shows optical images of five pairs of polyaniline microelectrode shaped structures on silicon substrate with 100 nm Si02 layer (size: 350 jimx200 jim).
Fig. 5a inset shows an AFM image of one all-polyaniline device containing 200 nm wire, size: 3.5 jimx3.5 jim).
Fig. 5b shows the I-V characteristics of the structure shown in Figure 5a inset.
Detailed Description of the Invention
The present invention is based on using a copolymer strategy to control the thickness, adhesive and electrical properties of conducting polymer by incorporating a surface active monomer into the main chains of the conducting poiymer, thus make the conducting poiymer suitable for the fabrication of devices exclusively based on conducting polymers with a sub mn resolution through a lift off process. Due to the generality of the copolymerization process, the method is applicable to a wide range of species of conducting polymers. Two different types of all-polymer nanostructures consisting exclusively of polypyrrole or polyaniline are fabricated and their use as nanosensors are demonstrated. The invention is not limited to these types of conducting polymers but could also be used by other polymers, such as light-emitting polymers.
Fig. 1 depicts the fabrication process comprising three steps. In the first step, a resist layer 10 is deposited on the surface of a substrate 20 and a resist pattern 30 is defined on the photoresist using e-bearn lithography as is known in the art. In the second step, a copolymer film 40 thinner than the resist layer 10 is deposited by oxidizing pyrrole (or aniline) and N-(3- trimethoxysilylpropyl)pyrrole (abbreviated as py-silane) with iron chloride. Finally, the resist layer 10 is lifted off in acetone by sonication.
* S ** ** S..
: Pae.:. s.
S. S A S S S * * S S S S S S S * * *8. * * S Figure 2 depicts the structure of the copolymers used for the copolymer film 40. In order to realize the successful fabrication of conducting polymer structures by the lift off process and the further application as sensors, conductivity and adhesion as well as their combination are the parameters that should be taken into account. In this work, the two-point measurement method and the adhesion tape test (as taught in Z. Y. Huang, P. C. Wang, A. G. MacDiarmid, Y. N. Xia, G. M. Whitesides, Langmuir 1997, 13, 6480-6484) was respectively used to estimate the electrical and adhesive properties of the copolymer film 40, respectively. Taking polypyrrole as an example, the introduction of py-silane has a significant influence on the properties of polypyrrole as is shown in Table 1.
Table 1. Influence of copolymer composition on the properties of the resulting polypyrrole film.
Pyrrole: Film Film Withstand py-silane conductivity thickness adhesion (v%:v%) (S/cm) (nm) tape test (yes/no) 100:0 32 5 60 10 no 91:9 20 4 50 10 yes 73:27 5.5 1.5 40 10 yes 55:45 0.45 0.2 34 10 yes 36:64 0.013 0.005 26 10 yes 22:78 2.6xl05 lx105 17 10 yes 0:100 <106 <10 yes Notably, copolymers that contain only a small amount of py-silane (9% volume percent) can successfully withstand the adhesion tape test whereas pure polypyrrole cannot. Moreover, upon increasing the fraction of py-silane, the electrical conductivity and film thickness of the copolymer film 40 decreases (as described in J. R. Reynolds, P. A. Poropatic, R. L. Toyooka, Macromolecules 1987, 20, 958-961, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met.
1995, 72, 89-94, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 72, 167-171, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 73, 26 1-266 F. Fusalba, D. * S *S *SS : Pae8 *:.
*S S S S S S S S * * S S S S S S S S 5. S S i3elanger, J. Phys. Chem. B 1999, 103, 9044-9054 C. J. Xia, X. W. Fan, M. Park, R. C. Advincula, Langmuir, 2001, 17, 7893- 7898 P. Taranekar, X. W. Fan, R. Advincula, Langmuir, 2002, 18, 7943-7952) The thickness of the copolymer film 40 can be well controlled by the deposition time (as is shown in Z. Y. Huang, P. C. Wang, A. G. MacDiarmid, Y. N. Xia, 0. M. Whitesides, Langmuir 1997, 13, 6480-6484), thus the copolymer film 40 can be kept thinner than the resist layer 10, thereby facilitating the lift off process. In order to obtain a strongly adherent copolymer film 40 that retained as high an electrical conductivity as possible, depositions were carried out at a pyrrole to py-silane volume ratio of 91:9 unless mentioned otherwise. Under these conditions, the actual copolymer composition is estimated to be roughly 97:3 (pyrrole to py-silane) based on XPS measurements (Table 2). See also J. R. Reynolds, P. A. Poropatic, R. L. Toyooka, Macromolecules 1987, 20, 958-961, D. Stanke, M. L. Hallensleben, L. Toppare, Synt/z. Met.
1995, 72, 89-94, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 72, 167-171, D. Stanke, M. L. Hallensleben, L. Toppare, Synth. Met. 1995, 73, 261-266, F. Fusalba, D. Belanger, J. Phys. Chem. B 1999, 103, 9044-9054, C. J. Xia, X. W. Fan, M. Park, R. C. Advincula, Langmuir, 2001, 17, 7893-7898, P. Taranekar, X. W. Fan, R. Advincula, Langmuir, 2002, 18, 7943-7952.
Table 2. Binding energies and relative contribution of different elements present in the copolymer deposited at a pyrrole to py-silane ratio of 91:9 as determined by XPS.
Binding Contribution Assignment energy(ev) (%) Cis 284.92 78.6 Cl 284.75 C-C C2 286.83 C-O/C-N C3 288.45 C=O Nls 399.88 13.5 Ni 397.65 C=N N2 399. 74 N-H, Pyrrole iage19,.
* * * ** S.. St *. * . . . S S S * S S S S S * S S S *55 S * . N3 400.76 C-N Ols 531.85 7. 4 Si2p 101.97 0.4 Simon et al., J. Am. Chem. Soc. 1982, 104, 203 1-2034, have previously reported that a py- silane modified electrode with a small coverage of < 5 xl (I mol/cm2 can dramatically improve the adhesion of the electrochemically deposited polypyrrole overlayer. The results are thus in agreement with the observation of Simon et a!, that is, the existence of a small amount of py-silane is sufficient to promote adhesion of the polypyrrole film. The appearance of a C=O peak and a C-Nt peak in the previously reported high resolution Cis and Nis XPS spectra (as shown in Table 2), can be ascribed to over-oxidation phenomena and doped structures, respectively (F. Fusalba, D. Belanger, J. Phys. Chem. B 1999, 103, 9044-9054, C. J. Xia, X. W. Fan, M. Park, R. C. Advincula, Langmuir, 2001, 17, 7893-7898, P. Taranekar, X. W. Fan, R. Advincula, Langmuir, 2002, 18, 7943-7952).
The invention provides a method of fabrication of conducting polymers structures with a resolution of less than 100 nm. For example, using the invention an 80 nm wide, 11 j.tm long polypyrrole nanowire was produced on a silicon substrate with a 100 nm Si02 layer (as shown in Figure 3a).. Other substrates can be used which include, but are not limited to, glass, and other OH functional group terminated plastic surfaces. The structure of the polypryrrole wire is initially defined on the resist by e-beam lithography. Since an inexpensive technique to pattern the resist at a sub 100 nm scale has already been established (e.g. nanoimprinting - see S. Y. Chou, P. R. Krauss, P. J. Renstrom, Appl. Phys. Lett. 1995, 67, 3114-3116, S. Y. Chou, P. R. Krauss, P. J. Renstrom, Science 1996, 272, 85-87 and S. Y. Chou, P. R. Krauss, P. J. Renstrom, J. Vac. Sci. Technol. B 1996, 14, 4129-4133), the method of the invention opens an opportunity for large scale patterning of conducting polymer nanostructures in a single step, which may be useful in many different application fields. ag. l0
* C * .. *.. ** S ** * S S S * * * S * S * * * . . * S 55. . . . . Precise manipulation and placement of the nanostructures at desired locations and their integration with larger scale systems has long been a challenge and has set a serious hindrance for the further development of nanoelectronics (see, for example, Y. Huang, X. F. Duan, Q. Q. Wei, C. M. Lieber, Science, 2001, 291, 630-633 and P. A. Smith, C. D. Nordquist, T. N. Jackson, T. S. Mayer, B. R. Martin, J. Mbindyo, 1. E. Mallouk, Appi. Phys. Lett. 2000, 77, 1399-140 1). Exploiting advantages of the method of the invention, the nanowires can be integrated in between the conducting polymer microelectrodes in one deposition step. This facilitates, in particular, the fabrication of an all-polymer nanosensor. Fig. 3b shows an optical image of six pairs of polypyrrole microelectrodes on a silicon substrate with a 100 nm Si02 layer (structures defined by e-beam lithography). The polypyrrole wires situated in between the polypyrrole microelectrodes are not visible at the magnification of Fig. 3b. The overall electrodes consist of homogeneous, closely packed, globular shaped polypyrrole structures (see, for example, Figure 3c, electrode part). It has been reported by T. Silk, Q. Hong, J. Tamm, R. G. Compton, Synth. Met. 1998, 93, 59-64, that the surface morphology of polypyrrole films is globular at film thicknesses below 1000 nm and is independent of the dopant. Since the thicknesses of polypyrrole structures fabricated using the inventive method are all well below 100 nm (see Table 1), the measured morphology of this polypyrrole nanodevice (Figure 3c) is consistent with the observations in the literature. The densely packed, defect free nature of this polypyrrole film indicates that it can serve as a suitable substitute for metals as the electrode material (see, for example, M. Angelopoulos, IBM J. RES. & DEV. 2001, 45, 57-75). All six pairs of electrodes were successfully connected with the polypyrrole nanowires, proving the reliability of this strategy. in Figure 3c one of the six junctions, consisting of one single polypyrrole nanowire (100 nm wide, 1. 25 j.tm long) bridging the ends of two polypyrrole microelectrodes, is shown.
:êJ.. .:. .: :: I I S * S * * I S I S I * S S
S S
fo demonstrate the functionality of the structure, a current vs. potential study was carried out.
A linear dependence of the current on the applied potential was observed (as is shown in Fig. 4a), confirming the ohmic behavior of the material. The sensing performance of the device was evaluated by exposing it to a 240 ppm NH3 stream. The detection of NH3 in air is of interest from an environmental point of view because of the high toxicity of this gas. The sensing principle is based on the fact that the electron-donating molecule (in this case NH3) can reduce the charge carrier concentration of polypyrrole (a p-type conducting polymer or electron acceptor) and decrease its conductivity (see J. P. Blanc, N. Derouiche, A. El Hadri, J. P. Germain, C. Maleysson, H. Robert, Sen. Actuators. B 1990, 1, 130-133 and J. Janata, M. Josowicz, D. M. DeVaney, Anal. Chem. 1994, 66, 207R-228R). The device shown in Fig. 3c exhibits a reversible response upon the addition of NH3 with a sensitivity (defined as R/Ft0- 1, where R0 is the initial resistance, while R is the resistance after exposure to NH3) of 0.8 (Fig. 4b), which is of the same order of magnitude as reported for polypyrrole- based sensors (as discussed in H. Nagase, K. Wakabayashi, T. Imanaka, Sen. Actuators. B 1993, 14, 596-597 and M. Brie, R. Turcu, C. Neamtu, S. Pruneanu, Sen. Actuators. B 1996, 37, 119-122).
This value can be further improved by the introduction of other anionic dopants (see H. Nagase, K. Wakabayashi, T. Imanaka, Sen. Actuators. B 1993, 14, 596-597 and M. Brie, R. Turcu, C. Neamtu, S. Pruneanu, Sen. Actuators. B 1996, 37, 119-122). The sensitivity of this all-polymer nanosensor was compared with a polypyrrole nanowire sensor with metal electrode contact and no difference was observed. This indicates that the nanowire is the key element that determines the sensitivity. By increasing the width of the wire from nanometer regime to micrometer (e.g. 2 tm in width) or even into a bulk film, a decrease in sensitivity was observed (see Fig. 4c), proving the superiority of the nanoscale device. This is likely to be due to the high surface area to volume ratio of the nanowire. A conductivity enhancement trend was also observed with decreased wire width which is in agreement with the results 2agi2
: : :. : . . . S S * * S S S S S *.S S S S reported in literature (Z. H. Cai, C. R. Martin, J. Am. Chem. Soc. 1989, 111, 4138-4139, W. B. Liang, C. R. Martin, J. Am. Chem. Soc. 1990, 112, 9666-9668, C. R. Martin, Science 1994, 266, 1961-1966). ..DTD: This method of the invention can be readily extended from polypyrrole to other systems. Fig. shows an example of the all-polymer nanodevices consisting exclusively of polyaniline and the corresponding I-V characteristic of one 200 nm all-polyaniline nanodevice. Since the copolymerization is highly applicable to a wide range of monomers such as pyrrole, thiophene, aniline and their substituted derivatives, one could easily obtain conductive nanostructures comprising different components with this method, making it useful in fabricating all-polymer nanosensor arrays and other organic nanoelectronic devices.
Although the fabricating all-polymer nanosensor was demonstrated on silicon surface, the concept can be easily extended to other surfaces such as glass and OH functional group terminated plastic surfaces, , which can chemically bind with silian molecule.
Examples
Materials and fabrication methods: Iron chloride (FeC13, 97%), pyrrole and aniline were purchased from Sigma- Aldrich. N-(3trimethoxysilylpropyl)pyrrole was purchased from ABCR GmbH. Poly (methyl methacrylate) (PMMA), 950K and 50K, was purchased from All Resist GmbH. All chemicals were used without further purification. The silicon wafers with a 100 nm thermally oxidized 5i02 layer were purchased from Si-mat Company.
*IageJ3 [ . * S * ** 5*0 0* * S. S * S S S S S S *.: . . *S.
One example of a polypyrrole copolymer deposition process is as follows: 0.72 g (or 0.08 g) FeC!3 was dissolved in 7 ml purified water. Another solution containing 300 l pyrrole, 30.tl py-silane, 2 ml isopropanol (absent in those cases where 0.08 g FeC!3 was used) and 12 ml purified water was added to initiate polymerization at room temperature (21 C). The substrate was patterned with the resist was placed vertically into the resulting solution for 10 mm in order to deposit the copolymer films. The deposition process of polyaniline copolymer resembles the above one: 0.72 g FeCI3 was dissolved in 7 ml purified water. Another solution containing I ml aniline, 30 p1 py-silane, and 7 ml purified water was added to initiate polymerization (21 C). The substrate with the patterned resist was immersed into this solution for 1 h to deposit polyaniline copolymer.
It should be noted that substituted analogues of pyrrole and aniline (such as poiy (substituted) pyrrole or poly-pyrrole-aniline) can also be used in the co-polymer deposition process.
Furthermore, it is noted that thiophene (and analogues) could also be used Instruments and characterization: E-beam lithography was performed by a LEO VP 1530 field emission scanning electron microscope (SEM) with a Raith Elphy Plus lithography attachment system. Atomic Force Microscopy (AFM) measurements were carried out on a Multimode Nanoscope lila instrument (Digital Instrument) operating in tapping mode with silicon cantilevers (resonance frequency in the range of 280-340 kHz). Electrical measurements were performed with a Keith!ey 6430 sub-femtoamp remote Source Meter. X-ray Photoelectron Spectroscopy (XPS) measurements were carried out using a VG ESCALAB 250 imaging XPS spectrometer. The samples deposited on gold were irradiated with monochromatic Al Ka X-rays (15 kV, 150W, 500 Jtm spot size). The real time gas-sensing experiment was carried out by exposing the conducting polymer wire or film to a 240 ppm NH3 stream applied with a flow rate of 4.4 Lfh age.l4/ * a S SI t** 4. S : : : : : * : : : *IS * S * S via a gas tubing source held at a fixed distance of 0.5 cm above the sample. The resistance change was monitored and recorded while supplying a constant potential of 100 mV.
:: ::: ::: : . Reference Numbers Resist Layer I Substrate Resist Pattern Copolymer Film :16l

Claims (12)

  1. Claims 1. A method for manufacturing a patterned layer of a polymer
    comprising the following steps: - depositing a layer of resist (10) on a substrate (20); - patterning the layer of resist (10); - copolymerizing of a first monomer of a polymer with a second monomer to form a copolymer; depositing the copolymer on the substrate (20); and lifting off the layer of resist (10).
  2. 2. The method of claim 1 wherein the conducting copolymer is selected from the group consisting of polypyrrole, polythiophene or polyaniline and their substituted analogues.
  3. 3. The method of any of the above claims wherein the substrate is immersed into a copolymerizing solution.
  4. 4. The method of claim 3 wherein the copolymerization solution comprises aniline (or substituted analogues thereof), py-silane, FeC13 and purified water.
  5. 5. The method of claim 3 wherein the copolymerization solution comprises pyrrole (or substituted analogues thereof), py-silane, FeC!3 and purified water.
    Lag.l7 * * * *1 * IS S ** . S S I * S S S * S S S 5 4 5 5 S.. 5 5 5
  6. 6. The method of claim 5, wherein the copolymerization solution additionally comprises isopropanol.
  7. 7. The method of claim 1 or 2 wherein the substrate (20) is made of silicon with a Si02 surface layer, glass or plastic with surface OH functional groups..
  8. 8. A device for the detection of the presence of analytes comprising: a first electrode and a second electrode made of a conducting polymer on a substrate (20) ; and a wire integrated between the first electrode and the second electrode and made of the same conducting polymer.
  9. 9. The device of claim 8 wherein the conducting copolymer is polypyrrole, polythiophene, polyaniline and derivative thereof.
  10. 10. The device of claim 8 or 9 wherein the substrate (20) is made of silicon with a Si02 surface layer glass or plastic with surface OH functional groups
  11. 11. The device of any of claims 8 to 10 wherein the wire is between 50 nm and 150 run wide.
  12. 12. The device of any of claims 8 to 11 wherein the wire is between 1 and 15 tm long.
    a. *a* ag.18 a S S 5$ 5.5 5* S a. * S * S S S 5 5 * . . 5 5 $ 5.
    5*. S * a.
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JPS60100669A (en) * 1983-11-02 1985-06-04 Mitsubishi Electric Corp Apparatus for producing thin compound film
WO1995005937A1 (en) * 1993-08-25 1995-03-02 Polaroid Corporation Electroluminescent devices and processes using polythiophenes
JPH07249317A (en) * 1994-03-11 1995-09-26 Shin Etsu Chem Co Ltd Substrate with conductive polymer pattern and manufacture thereof
WO1997004464A1 (en) * 1995-07-19 1997-02-06 University Of Warwick Conducting polymer films

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60100669A (en) * 1983-11-02 1985-06-04 Mitsubishi Electric Corp Apparatus for producing thin compound film
WO1995005937A1 (en) * 1993-08-25 1995-03-02 Polaroid Corporation Electroluminescent devices and processes using polythiophenes
JPH07249317A (en) * 1994-03-11 1995-09-26 Shin Etsu Chem Co Ltd Substrate with conductive polymer pattern and manufacture thereof
WO1997004464A1 (en) * 1995-07-19 1997-02-06 University Of Warwick Conducting polymer films

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