Organic thin film transistor with polymeric interface

Description of equivalent WO 03041185 A2

ORGANIC THIN FILM TRANSISTOR WITH POLYMERIC INTERFACE

0002Technical Field

0003This invention relates to organic thin film transistors having improved performance. More particularly, the invention relates to organic thin film transistors having a polymeric layer between the semiconductor and gate dielectric and methods of making such transistors.

0004Background

0005Organic semiconductors are of great interest for a variety of applications involving low-cost electronics. It is believed that organics can be synthesized to incorporate the necessary electronic properties for a wide variety of devices, and also can be constructed to allow low-cost, reel-to-reel processing that is not currently possible for crystalline silicon microelectronics.

0006One area of concern in organic electronic devices is the quality of the interface formed between the organic semiconductor and another device layer. Prior work on the interface between the semiconductor and the gate dielectric has included using a silazane or silane coupling agents on silicon oxide surfaces. Silane coupling agents also require complex deposition processes.

0007EP 1041652 A2 describes the use of several surface treatments to enhance the crystalline domain size of solution-cast oligothiophenes on SiO_x for thin film transistors (TFTs), although measured charge carrier mobility values were generally lower than the untreated controls. Other work involving surface treatments in TFTs involved poly( vinyl alcohol) layers, which may be relatively thick. In rare instances, previous work has shown minor improvements in mobility. The predominant effects shown in the previous work have been no improvement and/or detrimental effects on mobility, without regard for other important aspects of device performance.

0008Summary

0009The present inventors discovered materials for and methods of improving the properties of organic thin film transistors by controlling the interface between the organic semiconductor and the dielectric material. The organic thin film transistors of the invention also are suitable for low-cost manufacturing processes.

0010Briefly, the present invention provides an organic thin film transistor (OTFT) comprising a substantially nonfluorinated polymeric layer interposed between a gate dielectric and an organic semiconductor layer, the substantially nonfluorinated polymeric layer having a thickness less than about 400A.

0011In another aspect, the present invention provides a method of making an OTFT comprising providing a substrate, forming a gate electrode on the substrate, forming a gate dielectric on the gate electrode, applying a substantially nonfluorinated polymeric layer (having a thickness less than about 400A) interposed between the gate dielectric and an organic semiconductor layer, depositing an organic semiconductor layer adjacent to the polymeric layer, and depositing a source electrode and a drain electrode contiguous to the organic semiconductor layer. The polymeric layer comprises a polymer selected from one of those described above in reference to the OTFTs of the invention, or a combination of two or more of said polymers. An integrated circuit comprising a plurality of OTFTs is also provided.

0012Any known thin film transistor configuration is possible with the invention. For example, the source and drain electrodes may be adjacent to the gate dielectric with the organic semiconductor layer over the source and drain electrodes, or the organic semiconductor layer may be interposed between the source and drain electrodes and the gate dielectric. In each option, the invention provides a polymeric layer between the organic semiconductor layer and the gate dielectric.

0013The present invention provides organic thin film transistors with one or more improvements over known devices. With the present invention, improvements in properties such as threshold voltage, subthreshold slope, on/off ratio, and charge-carrier mobility can be achieved. In addition, large improvements in at least one property, such as charge-carrier mobility, can be achieved with the invention, while maintaining other OTFT properties within desirable ranges. The improvements in device performance provided by the present invention enable the production by simpler processing conditions of complex circuits having higher operating speeds than an OTFT made without the polymer layer. This invention also enables the production of larger circuit elements having comparable performance to devices with very small features. Devices with larger feature sizes can be less expensive as they do not require expensive precision patterning methods.

0014As used herein, "a" or "an" or "the" are used interchangeably with "at least one", to mean "one or more" of the element being modified. Other features and advantages of the invention will be apparent from the following detailed description of the invention and the claims. The above summary of principles of the disclosure is not intended to describe each illustrated embodiment or every implementation of the present disclosure. The detailed description that follows more particularly exemplifies certain preferred embodiments utilizing the principles disclosed herein.

0015Detailed Description

0016Generally, a thin film transistor includes a gate electrode, a gate dielectric on the gate electrode, a source electrode and a drain electrode adjacent to the gate dielectric, and a semiconductor layer adjacent to the gate dielectric and adjacent to the source and drain electrodes. More specifically, an organic thin film transistor (OTFT) has an organic semiconductor layer. Such OTFTs are known in the art as shown, for example, in copending application USSN 09/947,845, Attorney Docket No. 56999US002, filed on September 6, 2001. The organic thin film transistor of the present invention further includes a polymeric layer interposed between the gate dielectric and the organic semiconductor layer.

0017Substrate

0018A substrate can be used to support the OTFT, e.g., during manufacturing, testing, storage, use, or any combination thereof. The gate electrode and/or gate dielectric may provide sufficient support for the intended use of the resultant OTFT such that another substrate is not required. For example, doped silicon can function as the gate electrode and support the OTFT. In another example, one substrate may be selected for testing or screening various embodiments while another substrate is selected for commercial embodiments. In another embodiment, a support may be detachably adhered or mechanically affixed to a substrate, such as when the support is desired for a temporary purpose. For example, a flexible polymeric substrate may be adhered to a rigid glass support, which support could be removed. In some embodiments, the substrate does not provide any necessary electrical function for the OTFT. This type of substrate is termed a "non-participating substrate" in this document.

0019Useful substrate materials can include organic and/or inorganic materials. For example, the substrate may comprise inorganic glasses, ceramic foils, polymeric materials, filled polymeric materials, coated metallic foils, acrylics, epoxies, polyamides, polycarbonates, polyimides, polyketones, poly (oxy-l,4-phenyleneoxy- 1,4- phenylenecarbonyl-l,4-phenylene) (sometimes referred to as poly (ether ether ketone) or PEEK), polynorbornenes, polyphenyleneoxides, poly(ethylene naphthalenedicarboxylate) (PEN), polyethylene terephthalate) (PET), poly(phenylene sulfide) (PPS), and fiber- reinforced plastics (FRP).

0020A flexible substrate is used in some embodiments of the present invention. This allows for roll processing, which may be continuous, providing economy of scale and economy of manufacturing over some flat and/or rigid substrates. The flexible substrate chosen preferably is capable of wrapping around the circumference of a cylinder of less than about 50 cm diameter without distorting or breaking. The substrate chosen more preferably is capable of wrapping around the circumference of a cylinder of less than about 25 cm diameter without distorting or breaking the substrate. In some embodiments, the substrate chosen most preferably is capable of wrapping around the circumference of a cylinder of less than about 10 cm diameter, or even about 5 cm diameter, without distorting or breaking the substrate. The force used to wrap the flexible substrate of the invention around a particular cylinder typically is low, such as by unassisted hand, i.e., without the aid of levers, machines, hydraulics, and the like. The preferred flexible substrate may be rolled upon itself. Gate Electrode

0021The gate electrode can be any useful conductive material. For example, the gate electrode may comprise doped silicon, or a metal, such as aluminum, chromium, copper, gold, silver, nickel, palladium, platinum, tantalum, and titanium. Conductive polymers also can be used, for example polyaniline, poly (3, 4-ethylenedioxythiophene)/poly (styrene sulfonate) (PEDOT:PSS). In addition, alloys, combinations, and multilayers of these materials may be useful. Gate Dielectric

0022The gate dielectric is provided on the gate electrode, for example, through a deposition process. This gate dielectric electrically insulates the gate electrode under the operating conditions of the OTFT device from the balance of the device. Thus, the gate dielectric comprises an electrically insulating material. The gate dielectric should have a dielectric constant above about 2, more preferably above about 5. The dielectric constant of the gate dielectric also can be very high, for example, 80 to 100 or even higher. Useful materials for the gate dielectric may comprise, for example, an organic or inorganic electrically insulating material, or combinations thereof. The gate dielectric may comprise a polymeric material, such as polyvinylidenefluoride (PNDF), cyanocelluloses, polyimides, epoxies, etc. In some embodiments, an inorganic capping layer comprises the outer layer of an otherwise polymeric gate dielectric for improved bonding to the polymeric layer and/or improved dielectric properties. Specific examples of inorganic materials useful for the gate dielectric include strontiates, tantalates, titanates, zirconates, aluminum oxides, silicon oxides, tantalum oxides, titanium oxides, silicon nitrides, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, and zinc sulfide. In addition, alloys, combinations, and multilayers of these can be used for the gate dielectric. Of these materials, aluminum oxides, silicon oxides, silicon nitrides, and zinc selenide are preferred.

0023The gate dielectric can be deposited in the OTFT as a separate layer, or formed on the gate such as by oxidizing, including anodizing, the gate material to form the gate dielectric.

0024Source and Drain Electrodes The source electrode and drain electrode are separated from the gate electrode by the gate dielectric, while the organic semiconductor layer can be over or under the source electrode and drain electrode. The source and drain electrodes can be any useful conductive material. Useful materials include those described above for the gate electrode, for example, aluminum, barium, calcium, chromium, copper, gold, silver, nickel, palladium, platinum, titanium, polyaniline, PEDOT:PSS, other conducting polymers, alloys thereof, combinations thereof, and multilayers thereof. The thin film electrodes (e.g., gate electrode, source electrode, and drain electrode) can be provided by any useful means such as physical vapor deposition (e.g., thermal evaporation, sputtering), plating, or ink jet printing. The patterning of these electrodes can be accomplished by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, transfer printing, and pattern coating.

0025Organic Semiconductors

0026Useful materials for the organic semiconductor layer include acenes, such as anthracene, tetracene, pentacene, and substituted pentacenes. Substituted pentacene compounds that are useful as organic semiconductors in the present invention comprise at least one substituent selected from the group consisting of electron-donating substituents (for example, alkyl, alkoxy, or thioalkoxy), halogen substituents, and combinations thereof. Useful substituted pentacenes include but are not limited to 2,9-dialkylpentacenes and 2,10-dialkylpentacenes, wherein the alkyl group has from 1 to 12 carbons; 2,10- dialkoxypentacenes; and 1,4,8,11-tetraalkoxypentacenes. Such substituted pentacenes are taught in copending applications USSN 09/966,954, Attorney Docket No. 57087US002, and USSN 09/966,961, Attorney Docket No. 57088US002, both filed on September 26, 2001.

0027Examples of other useful organic semiconductors include perylenes, fullerenes, phthalocyanines, oligothiophenes, and substituted derivatives thereof. Particular organic semiconductor compounds include sexithiophene, α,ω-dihexylsexithiophene, quinquethiophene, quaterthiophene, α,ω-dihexylquaterthiophene, α,ω- dihexylquinquethiophene, poly(3-hexylthiophene), bis(dithienothiophene), anthradithiophene, dihexylanthradithiophene, polyacetylene, polythienylenevinylene, C₆₀, copper(II) hexadecafluorophthalocyanine, and

0028N,N'-bis(pentadecafluoroheptylmethyl)naphthalene-l,4,5,8-tetracarboxylic diimide.

0029The organic semiconductor layer can be provided by any useful means, such as for example, vapor deposition, solution deposition, spin coating, and printing techniques.

0030Polymeric Layer The polymeric layer of the invention has a maximum thickness less than about

0031400 Angstroms (A), more preferably less than about 200 A, and most preferably less than about 100 A. The polymeric layer of the invention generally has a thickness of at least about 5 A, more preferably at least about 10 A. The thickness can be determined through known methods, e.g., ellipsometry.

0032The polymeric layer is selected from many options. For example, a substantially nonfluorinated polymeric layer having a thickness within the range set forth above may be used. In this document, "substantially nonfluorinated" means that less than about 5%

0033(more preferably less than about 1% and even more preferably 0%) of the carbons in the polymeric layer have fluorine substituents.

0034As used in this document, "substituted" means substituted by substituents that do not interfere with the desired performance of the OTFT. Examples of suitable substituents include halogen (e.g., CI, Br, I), cyano, C C₂o aliphatic, aryl, and arylalkyl groups, and the like. As used in this document, "heteroatom" means a non-carbon atom such as O, P, S, N and Si.

0035The polymeric layer may comprise a polymer having interpolymerized units according to the formula: R¹

0036-CH- ( I ]

0037R² R²

0038in an amount from about 50 to 100% of interpolymerized units according to Formula I, and from 0 to about 50% of said interpolymerized units according to the formula:

X

0040I — C — CH — ( II ) .

0041I I R² R²

0042In these formulas, each R and R" comprises, independently, a group selected from hydrogen; d-C₂₀ aliphatic; chloro; bromo; carboxy; acyloxy; nitrile; amido; alkoxy; carboalkoxy; aryloxy; chlorinated aliphatic; brominated aliphatic; C₆-C₂o aryl; C₇-C₂o arylalkyl; hydroxy when Rι and X are different; and combinations thereof which may contain one or more heteroatom(s) and/or one or more functional group(s). Each X, independently, comprises a functional group capable of bonding to the gate dielectric. In addition, any combination of at least two R¹, R², and/or X groups may together form a cyclic or polycyclic, aliphatic or aromatic group. Particular selections for R¹ and/or R² include groups selected from hydrogen, Ci- C₂o aliphatics, which may be linear or branched, saturated or unsaturated; C₆-C₂₀ aryl; and C -C₂o arylalkyl which also may contain linear or branched, and saturated or unsaturated segments. Specific polymers may be derived from precursor monomers such as methyl (mefh)acrylate, straight-chain or branched C₂-C₁₈ aliphatic or arylalkyl (meth)acrylates,

0043(meth)acrylic acid, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, vinyl chloride, vinyl acetate, ethylene, straight-chain or branched C₃-C₁₈ α-olefins, isoprene, chloroprene, 1,3-butadiene, diethyl fumarate, allyl acetate, methyl vinyl ketone, and styrene.

0044The functional group capable of bonding to the gate dielectric includes groups known to form chemical bonds to the selected gate dielectric. Particular selections for X groups include -PO₃R₂ or -OPO₃R₂ wherein each R is, independently, hydrogen or a Q- C₁₂ aliphatic group or a C₆-C₁₈ aryl or arylalkyl group; -SO₃H; alkoxysilyl; chlorosilyl; acetoxysilyl; benzotriazolyl (-C₆H₄N₃); -CONHOH; -COOH; -OH; -SH; -COSH; -COSeH; -C₅H N; -SeH; -NC; amino; and phosphinyl. Benzotriazolyls include, for example, benzotriazolylcarbonyloxy (-OC(=O)C₆H N₃), benzotriazolyloxy (-O- HφNs), and benzotriazolylamino (-NH-C₆H₄N₃) groups. Specific preferred groups include -PO₃H₂, -OPO₃H₂, and trimethoxysilyl.

0045Combinations of at least two R¹, R², and/or X groups may together form a cyclic or polycyclic group that can be aliphatic or aromatic. Specific examples are copolymers incorporating comonomers such as norbornene and substituted norbornenes, maleic anhydride, acenaphthylene, and itaconic anhydride. Also useful are polymers and copolymers which can form crosslinked networks by vinyl-type polymerizations, including those derived from divinylbenzenes, and (mefh)acrylate-derived cinnamates. Thus, the polymeric layer having interpolymerized units of Formula I and, optionally, Formula π, includes a broad array of materials. Specific examples include homopolymers such as polystyrene, poly(l-hexene), poly(methyl methacrylate), poly (acenaphthylene), poly(vinylnaphthalene), poly(butadiene), poly(vinyl acetate), and those derived from α-methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3- methylstyrene, and 4-methylstyrene. In such homopolymer examples, the polymeric layer comprises 0% of said interpolymerized units according to Formula II.

0046A preferred polymeric layer is comprised of a polymer having styrenic interpolymerized units. Styrenic interpolymerized units include those derived from styrene and substituted styrenes, such as α-methylstyrene, 4-tert-butylstyrene, 2- methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-(phosphonomethyl)styrene, and divinyl benzene.

0047Copolymers, such as block, random, and alternating, are also useful in the polymeric layer described in this invention. Useful copolymers comprise interpolymerized units of Formula I and optionally Formula π. Preferred examples include copolymers of at least two different monomers selected from styrene, α- methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, and 4- methylstyrene. Other preferred examples include those materials having units of Formula π. Specific examples of monomers useful to form Formula π units include vinylphosphonic acid and other phosphonic acid-containing comonomers such as 4- (phosphonomethyl)styrene, and trialkoxysilane-containing comonomers such as 3- (trimethoxysilyl)propyl methacrylate. Preferred examples include a variety of copolymers of styrene and vinylphosphonic acid, copolymers of styrene and other phosphonic acid- containing comonomers, copolymers of styrene and phosphonate-containing comonomers, copolymers of styrene and phosphate-containing comonomers, a copolymer of styrene and 4-(phosphonomethyl)styrene, a copolymer of styrene and trimethoxysilylpropyl methacrylate, and copolymers of styrene and silyl-containing comonomers.

0048A class of polymers useful in the present invention includes hydrocarbon olefin homo- and co-polymers of ethylene, propylene, and higher α-olefins. These olefins can be represented by the general structure CH₂CHR, wherein R is hydrogen or a Ci-Cio (preferably - ) aliphatic radical. Copolymers may comprise one or more ethylenically- unsaturated comonomers which are copolymerizable with such olefins. These include vinyl esters, such as vinyl acetate; acrylic and α-alkyl acrylic acids and their alkyl esters, amides, and nitriles, such as methyl methacrylate and acrylonitrile; vinyl aromatics, such as styrene and vinylnaphthalene; anhydrides and alkyl esters of maleic and fumaric acids; vinyl alkyl ethers; vinylpyridine; N-vinylcarbazole; and dienes, such as 1,3-butadiene. Polymers useful for this invention may also be prepared by the introduction of functional groups. These can be provided through the use of a variety of materials, typically referred to as functional initiators, functional chain transfer agents, or functional chain terminators. Examples of these materials include phosphorus oxychloride, mercaptopropyltrialkoxysilanes, chlorotrialkoxysilanes, and tetrachlorosilane. The introduction of these species typically introduces a functional group at the end or midpoint of a polymer chain. Examples of useful polymeric species prepared using these reactants include α-(triethoxysilyl)propylthio polystyrene, and ω-(phosphonic acid) polystyrene. The polymer layer may be derived from a ring-opening polymerization. A wide variety of monomers may be used in this embodiment. Examples of suitable monomers include cyclic ethers, cyclic amides, cyclic amines, cyclic sulphides, and inorganic ring compounds such as phosphonitrilic chlorides. The repeat units of the polymer in these materials are joined by links similar to those found in the monomer, but rearranged to provide a linear rather than cyclic chain. These polymerizations may proceed by a variety of mechanisms. One specific type of ring-opening polymerization is a ring-opening metathesis polymerization, or ROMP. Suitable monomers that can be polymerized in this fashion include norbornenes, C₄-C₁₀ cyclic alkenes, and C -C₁₀ cyclic non-conjugated dienes. These ROMP monomers may be substituted with one or more CrC₂₀ straight- chain or branched aliphatic groups, aromatic groups, or arylalkyl groups, any of which may include one or more heteroatoms. As is known, aliphatic groups may be saturated or may contain one or more carbon-carbon multiple bonds, while arylalkyl groups contain both aliphatic and aromatic structures. Specific materials useful in this aspect of the invention include straight-chain or branched Cι-Cι₈ alkyl-substituted norbornenes, trialkoxysilyl-substituted norbornenes, esters of 5-norbornene-2-carboxylic acid, esters of 2-phosphono-5-norbornene, 1,4-cyclooctadiene, and dicyclopentadiene.

0049The polymeric layer may be derived from monomeric precursors, monomers, and oligomers comprising an aromatic-functional segment. Such polymeric materials are found in the class of aromatic thermosets. A preferred class of aromatic thermosets is the polyarylenes, for example, polyphenylene and polynaphthalene. Such polyarylenes include polymers containing heteroatoms, for example, polyarylene ethers. Polyarylenes can be prepared in a variety of ways. One useful means of preparing polyarylene compositions is by applying suitable monomeric or oligomeric precursors to the dielectric layer and subsequently polymerizing these materials through exposure to an energy source, such as by heating or irradiation. A preferred class of oligomer is a low molecular weight aromatic thermosetting composition comprised of cyclopentadienone and acetylene-substituted materials. The molecular weight is sufficiently low to permit spin coating of these oligomers. Such materials are commerically available as SiLK™ resin from Dow Chemical Co., Midland, MI. The SiLK™ resin is more fully described in "Development of a Low-Dielectric-Constant Polymer for the Fabrication of Integrated Circuit Interconnect", Martin, J.P., et al, Adv. Mater. 2000, 12(23), 1769-1778 and references therein, and U.S. Patent Nos. 5,956,679 and 6,288,188. The SiLK™ resin can be spin-coated onto surfaces and then subsequently cured by heating to form an insoluble polyarylene film.

0050Other useful oligomeric compositions are polyfunctional o-phenylethynyl- substituted aromatic monomers which crosslink upon exposure to an energy source, especially thermal radiation, to form polynaphthalenes. Other examples of classes of monomeric precursors that form aromatic thermoset polymers include: cinnamates, divinylbenzenes, diacetylenes, benzocyclobutenes, and substituted derivatives thereof. Other preferred classes of polyarylenes are the parylenes (i.e., poly(p-xylylene) polymers) and the polyfluorenes. The parylenes are semicrystalline polymers prepared by simultaneous adsorption and polymerization of reactive p-xylylene monomers from their vapor onto a surface. The vapor deposition of the monomer and its polymerization results in the formation of a thin film of uniform thickness conformal to the substrate surface that is effectively free of pinholes. Useful parylenes include parylene N, parylene C, and parylene D.

0051In another aspect, useful polymers and copolymers of this invention are substantially non-polar, glassy solids at room temperature. Preferably, the polymer comprises 80 mole % or more of alkyl, aryl, or arylalkyl monomer units, wherein said monomer units are substantially free of heteroatoms. The polymer has fewer than about 20 mole % of monomer units containing heteroatoms (more preferably, fewer than about 10 mole %). Furthermore, said polymer preferably has a glass transition temperature (T_g) measured in the bulk of at least about 25 °C, more preferably of at least about 50 °C, and most preferably at least about 100 °C. Examples of these types of polymers include many of those described above, including linear and thermoset materials. Specific examples include polystyrene, polyfluorene, polynorbornene, poly(acenapthylene), and alkyl- substituted derivatives thereof, and functionalized copolymers. In addition, blends of two or more polymeric or copolymeric materials may be used. In another aspect, the OTFT of the invention has a substantially nonfluorinated polymeric layer having a thickness less than about 400A and the OTFT has a charge carrier mobility at least 50% greater than the charge carrier mobility of a similar OTFT lacking the polymeric layer. In another aspect of the invention, the OTFT has a charge carrier mobility at least 0.02 cm /Ns, preferably at least 0.10 cm /Ns, more preferably at least 1.0 cm²/Ns, greater than the charge carrier mobility of a similar OTFT lacking the polymeric layer. In this document, all charge carrier mobility values are room temperature values.

0052The polymers and copolymers useful in the invention can be prepared by any known means, for example, by free-radical, ring-opening, anionic, cationic, or coordination polymerization of monomers such as those described above. The polymer may also be modified by subsequent reactions to introduce functional groups.

0053The polymeric layer is provided on the gate dielectric by any known method. For example, the polymeric layer can be provided through a coating process such as spray, spin, dip, knife, gravure, microcontact printing, ink jet printing, stamping, transfer printing, and vapor deposition. The polymeric layer can be provided on the gate dielectric via a solvent-based or solventless method. Presently preferred routes to the polymeric layer include solvent-based methods. When a solution of a polymeric layer precursor is provided on the gate dielectric layer, the solvent is removed by a method compatible with the materials involved, for example by heating.

0054In one embodiment, the source and drain electrodes are deposited adjacent to the gate dielectric before providing the polymeric layer. Then, the polymeric layer is applied. After the layer comprising a polymer is complete, the organic semiconductor layer is deposited over the source and drain electrodes and over the polymeric layer adjacent to the gate dielectric. Before deposition of the semiconductor, the material deposited on the gate dielectric to provide the polymeric layer may be rinsed so the source and drain electrodes are essentially free of the polymeric layer. That is, less than about 5 A of polymeric layer, more preferably less than 1 A and most preferably no polymeric layer, is present on the source and drain electrodes. OTFT Methods

0055The present invention also provides a method of making a thin film transistor comprising the steps of: (a) providing a substrate; (b) depositing a gate electrode material on the substrate; (c) providing a gate dielectric on the gate electrode material; (d) applying a substantially nonfluorinated polymeric layer adjacent to the gate dielectric, the polymeric layer having a thickness less than about 400A; (e) providing an organic semiconductor layer adjacent to the polymeric layer; and (f) depositing a source electrode and a drain electrode contiguous to the organic semiconductor layer. The polymeric layer is selected from those described above, including combinations of two or more such polymeric layer materials. These steps can be performed in the order listed or in another order so long as the polymeric layer is interposed between the gate dielectric and the organic semiconductor layer. For example, the organic semiconductor layer can be provided over or under the source and drain electrodes.

0056Additional steps are useful in certain embodiments of the present invention. For example, rinsing may be performed after applying the polymeric layer. The polymeric layer may be applied via deposition of a polymer solution or a monomer solution which is then polymerized. The applied material may be exposed to an energy source, such as thermal radiation, UV or visible light, to remove solvent and/or crosslink the material to form the polymeric layer on the gate dielectric surface. Any combination of rinsing and/or energy-exposure may be used for particular embodiments, such as rinsing before or after heating, rinsing only, or heating without rinsing.

0057The present invention also provides an integrated circuit comprising a plurality of OTFTs made by the process described above and a method of making an integrated circuit comprising providing a plurality of OTFTs of the invention. Thus, the present invention is embodied in an article that comprises one or more of the OTFTs described. Such articles include, for example, radio-frequency identification tags, backplanes for active matrix displays, smart cards, memory devices, and the like. In devices containing the OTFTs of the present invention, such OTFTs are operatively connected by means known in the art.

0058The entire process of making the thin film transistor or integrated circuit of the present invention can be carried out below a maximum substrate temperature of about 450°C, preferably below about 250°C, more preferably below about 150°C. In another aspect, temperatures below about 70°C, such as temperatures around room temperature (about 25°C) can be used. The temperature selection generally depends on the substrate and processing parameters known in the art, once one is armed with the knowledge of the present invention contained herein. These temperatures are well below traditional integrated circuit and semiconductor processing temperatures, which enables the use of any of a variety of relatively inexpensive substrates, such as flexible polymeric substrates. Thus, the invention enables production of relatively inexpensive integrated circuits containing organic thin film transistors with significantly improved performance. The OTFT of the present invention has one or more advantages over known organic thin film transistors. These advantages are apparent, for example, in charge- carrier mobility. The present invention provides OTFTs having a charge-carrier mobility greater than a comparison OTFT lacking the polymeric layer of the present invention. The OTFTs of the invention preferably have a charge-carrier mobility at least about 25% greater, more preferably at least about 50% greater, even more preferably at least about

005975% greater, and in some embodiments at least about 100% greater, than the charge- carrier mobility of a comparison OTFT not made according to the present invention. Such improvements in charge-carrier mobility are provided while maintaining OTFT properties within desirable ranges. For example, the above-described improvements are obtained while providing a threshold voltage between about 25 and -25 N, a subthreshold slope below about 10 N/decade (absolute value), an on/off ratio of at least about 10⁴, and a charge-carrier mobility at least about 10^"2 cmVVs when the semiconductor layer comprises a p-type semiconductor or at least about 10^"4 cm²/Vs when the semiconductor layer comprises an n-type semiconductor. Various embodiments of the invention provide OTFTs with two, three, or more of these properties.

0060The invention provides a p-type semiconductor OTFT having a threshold voltage of between about -25 and 25 N, preferably a threshold voltage of between about 0 and -IO N, more preferably between about 0 and -5 N. The invention provides an n-type semiconductor OTFT having a threshold voltage of between about -25 and 25 V, preferably a threshold voltage of between about 10 and 0 N, more preferably between about 5 and 0 N. The invention provides an OTFT with a subthreshold slope below about 10 N/decade (absolute value), preferably a subthreshold slope below about 5 N/decade (absolute value), more preferably below about 2 V/decade (absolute value). The invention provides an OTFT with an on/off ratio of at least about 10⁴, preferably at least about 10⁵, more preferably at least about 5xl0⁵, and even more preferably at least about 10⁶.

0061More specifically, in an embodiment having pentacene or a substituted pentacene as the organic semiconductor, the invention provides an OTFT with a charge-carrier 9 9 mobility at least about 0.1 cm /Ns, more preferably at least 0.2 cm /Ns, and even more preferably at least about 0.5 cm²/Ns. In some embodiments of the present invention, the charge-carrier mobility is above 1.0, or even above 2.0 cm /Vs. Particular embodiments of the present invention have shown a charge-carrier mobility greater than that reported for bulk single crystals of pentacene. In another embodiment of the invention, a pentacene

0062OTFT has a charge-carrier mobility of at least about 2 cm /Ns, a negative threshold voltage, a subthreshold slope below about 3 N/decade, and an on/off ratio at least about 5xl0⁵.

0063In another embodiment of the invention, a tetracene OTFT has shown a charge- carrier mobility above 0.05 cmVVs.

0064Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.

0065Examples

0066Test Methods A. Film Thickness

0067Single wavelength ellipsometry was employed to obtain estimates of polymeric layer thickness. Substrate values of Psi and Delta (ψ_s and Δ_s) were obtained from the cleaned substrates (described below) at an angle of incidence of 70° and a wavelength of

0068632.8 nm using a Gaertner Dual Mode Automatic Ellipsometer, model LI 16A (Gaertner Co., Skokie, Illinois). The polymeric layer was applied to the substrates, and values were measured (ψ_f and Δ_f).

0069Ellipsometry modeling software, WVASE32 (from J. A. Woollam, Inc., Lincoln, Nebraska) was used to construct optical models appropriate to the specific polymer and substrate investigated. Material optical constants included with the program were used unless specified otherwise.

0070For thermal oxide on silicon substrates, the optical model consisted of 1000 A of SiO₂ on 50 A of an intermix layer (a Bruggeman effective medium approximation consisting of 50% SiO and 50% Si) on top of a silicon substrate. The floating variables in the fit were the SiO₂ thickness, the intermix layer thickness and the intermix layer SiO₂ percentage (where the Si percentage is adjusted to make up the balance of the interlayer composition). Typical fit values were 950 - 990 A SiO₂, 40 - 60 A intermix consisting of 20 - 60 % SiO₂.

0071For alumina layers on silicon substrates, the optical model was 1500 A of Al₂O₃ on Si. The floating variables in the fit were the thickness in Angstroms (d) and refractive index (n) of the Al₂O₃. Seed values of d = 1500 and n = 1.77 were used. Typical final fit values were between 140θA and 170θA with n between 1.56 and 1.60.

0072For silicon nitride layers, an optical model of 1500 A Si₃N on Si was used, in which both the thickness and refractive index of the Si₃N₄ were allowed to vary. A seed value of 2.02 was used for the refractive index of Si₃N₄. Typical final fit values were 1450 to 1480 A for the thickness and 2.04 to 2.05 for the refractive index of the Si₃N₄.

0073Once the substrate parameters were determined by modeling ψ_s and Δ_s, they were fixed and a polymer layer was added to the optical model, between the air and dielectric layers. This layer had a variable thickness, but its refractive index was fixed at a value typical of that polymer in its bulk state. The refractive index of copolymer samples was estimated. The polymeric layer thickness was then varied to achieve the best fit to ψf and

0074Δ_f. Each thickness reported in Table 1 (below) was the average of four measurements on each sample.

0075B. Water Contact Angle (WCA) Static, advancing, and receding water contact angles were measured with a video contact angle apparatus (Model NCA-2500XE, from AST Products, Billerica, Massachusetts). Values reported were averages of measurements on both sides of at least three drops on each tested surface. Estimated uncertainties in these measurements were +/- 1 degree in static and advancing measurements and +/- 2 degrees in receding measurements. Surface characterization data are summarized in Table 1 (below).

0076C. Thin Film Transistor Performance

0077Transistor performance was tested at room temperature in air using techniques known in the art, for example as shown in S.M. Sze, Physics of Semiconductor Devices, page 442, John Wiley & Sons, New York, 1981. A Semiconductor Parameter Analyzer

0078(model 4145 A from Hewlett-Packard, Palo Alto, California) was used to obtain the results below. For p-type semiconductors, the square root of the drain current (I_d) was plotted as a function of gate-source bias (N_g), from +10N to -40N for a constant source-drain bias (N_d) of -40N. For n-type semiconductors, the square root of the drain current (I_d) was plotted as a function of gate-source bias (N_g), from -ION to +40 V for a constant source-drain bias (Nd) of +40N. The saturation field effect mobility was calculated from the straight line portion of the curve using the specific capacitance of the gate dielectric, the channel width and the channel length. The x-axis extrapolation of this straight-line fit was taken as the threshold voltage (N_t). In addition, plotting I_d as a function of N_g yielded a curve where a straight line fit was drawn along a portion of the curve containing N_t. The inverse of the slope of this line was the subthreshold slope (S). The on-off ratio was taken as the difference between the minimum and maximum drain current (I_d) values of the I_d-N_g curve.

0079Substrates Single crystal <100> orientation heavily-doped silicon wafers were obtained from

0080Silicon Valley Microelectronics, San Jose, California. A 150θA layer of alumina (Wafer A), or a lOOOA layer of high temperature thermal silicon oxide (Wafer B) was deposited on each wafer front via chemical vapor deposition methods. Alternatively, a 1500 A layer of silicon nitride (Wafer C) was deposited on each wafer front via physical vapor deposition methods. A 5000 A layer of aluminum metal' was vapor deposited onto the backside of each wafer. In this demonstration, the doped wafer capped with aluminum served as the gate electrode and the aluminum oxide, silicon oxide, or silicon nitride functioned as the gate dielectric when organic thin film transistors were prepared.

0081Wafer Preparation and Polymer Coating

0082Wafer substrates were quartered and cleaned by 5 min exposure in a UV/ozone chamber. The material of choice was applied by spin coating (300 rpm/5 s then 2000 rpm/15 s) a solution of the polymer in toluene as named in the particular example and allowed to dry in air and without rinsing, unless otherwise noted. Ellipsometric film thickness and water contact angles were measured using the procedures outlined above.

0083Results appear in the tables below. Semiconductor Coating

0084Pentacene (available from Aldrich Chemical) was purified in a 3-zone furnace (Thermolyne 79500 tube furnace, from Bamstead Thermolyne, Dubuque, Iowa) at reduced pressure under a constant flow of nitrogen gas. The purified pentacene was deposited by sublimation under vacuum

0085(approximately 10^"6 Torr (or 1.33 x 10^"4 Pa)) onto the polymeric surface at a rate of 0.5A per second to reach a thickness of 50θA as measured by a quartz crystal microbalance.

0086Final Steps for Device Preparation and Testing

0087Palladium or gold source and drain electrodes were shadow masked onto the p- type semiconductor layer, while aluminum source and drain electrodes were shadow masked onto the n-type semiconductor layer. The device dimensions were 40μm to 60μm channel length x lOOOμm channel width.

0088Multiple OTFTs were prepared and a representative sample of at least six pentacene OTFTs was tested for each of at least two deposition runs. For the other semiconductors, between three and twelve OTFTs were tested. Averaged results appear below in Table 2.

0089Examples 1-3

0090Samples of Wafers A, B, and C were quartered and cleaned using the procedure described above. A solution of 0.1 wt% polystyrene (secondary standard with a weight average molecular weight of 239,700 and a number average molecular weight of 119,628, available from Aldrich Chemicals, Milwaukee Wisconsin) in toluene was applied to each wafer using the Polymer Coating Procedure described above, except that the spin coating conditions were 500 rpm for 20 seconds then 2000 rpm for 40 seconds, followed by 5 minutes dry time in air and 5 minutes in an oven set at 110°C. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below.

0091Example 4

0092Wafers were quartered and cleaned using the procedure described above. A solution of 0.1 wt% poly(methyl methacrylate) (available from Aldrich, having a weight average molecular weight of approximately 70,000 g/mol as determined by GPC using polystyrene standards) in toluene was applied to Wafer B samples using the Polymer Coating Procedure described above. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Example 5-6

0093Wafers were quartered and cleaned using the procedure described above. A solution of 0.1 wt% poly(acenaphthylene) (Aldrich) in toluene was applied to Wafer A samples (Example 5) and Wafer B samples (Example 6) using the Polymer Coating Procedure described above. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Examples 7-8 Poly(styrene-co-vinylphosphonic acid) was synthesized by free radical polymerization in solution. The starting materials were commercially available, e.g., from Aldrich Chemicals, Milwaukee, WI. To a solution of styrene (4.04 g, 39 mmol) in ethyl acetate (16 g) were added vinylphosphonic acid (0.45 g, 4.2 mmol) and benzoyl peroxide (0.0295 g, 0.12 mmol). The resulting solution was sparged with nitrogen for 15 minutes, sealed, and heated at 85°C for 16 h. After cooling to room temperature, the solution was precipitated into 200 mL of heptane. The precipitate was separated by filtration and dried under vacuum at 40°C overnight to obtain the polymer. This material was approximately 92.3 mole % styrene and 7.7 mole % vinylphosphonic acid, as obtained from ^!H/³¹P NMR cross-integration, and had a weight-average molecular weight of 17.5 kg/mol from gel permeation chromatography in tetrahydrofuran against polystyrene standards.

0094A 0.1 wt% solution of the polymer in toluene was applied to Wafer A samples (Example 7) and Wafer B samples (Example 8) using the described Polymer Coating Procedure. The spin-coated sample was then baked on a hot plate in air at 150°C for 3 minutes and rinsed with fresh toluene. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below.

0095Example 9

0096A phosphonic acid end-functional polystyrene was synthesized by anionic polymerization in solution. The starting materials were obtained from Aldrich Chemicals. The styrene and cyclohexane were purified by passage through basic alumina, followed by sparging with dry nitrogen for 30 minutes. The sec-butyllithium and POCl₃ were used as received. A 3-neck reactor was evacuated and dried, then filled with dry nitrogen. To this reactor was added 100 mL of cyclohexane by cannula, followed by 0.5 mL (4 mmol) of styrene by syringe. To the reactor was then added 0.7 mL of sec-butyllithium (1.3 mol/L in cyclohexane), followed by 9.5 mL (83 mmol) of styrene. The polymerization was allowed to proceed for 4 h at room temperature, at which point 3 mL (32 mmol) of phosphorus oxy chloride was added. The reaction mixture was stirred for 12 h, after which 10 mL of deionized water was added, and stirring was continued for an additional 4 h.

0097The resulting polymer was precipitated into methanol, yielding a material with a weight average molecular weight of 131 kg/mol by gel permeation chromatography (GPC) against polystyrene standards. A 0.1 wt% solution of the polymer in toluene was applied to Wafer A samples using the described Polymer Coating Procedure. The sample was baked on a hot plate at 150°C for 3 minutes and then rinsed in fresh toluene. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below: Example 10

0098A trimethoxysilyl end-functional polystyrene was synthesized by free radical polymerization in solution. The starting materials were commercially available from

0099Aldrich Chemicals, with the exception of VAZO 67, an azo compound which was commercially available from Dupont Chemical, Wilmington, DE. To a solution of styrene (15.0 g, 144 mmol) in 35 g of ethyl acetate was added 0.0300 g (0.16 mmol) of VAZO 67 and 0.08 g (0.41 mmol) of (3-mercaptopropyl)trimethoxysilane. The resulting solution was sparged with nitrogen for 20 minutes, and heated with agitation for 16 hours at 60 °C.

0100The resulting polymers were precipitated into 250 mL of methanol, recovered by filtration, and dried in a vacuum oven at 40 °C for 12 hours. The resulting polymer had a weight average molecular weight of 195 kg/mol by GPC against polystyrene standards. A 0.1 wt% solution of the polymer in toluene was applied to Wafer B samples using the Polymer Coating Procedure described above. The samples were baked on a hot plate at 150°C for 3 minutes and then rinsed with fresh toluene. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Example 11 A trimethoxysilyl-functional polystyrene was synthesized by free radical polymerization in solution. The starting materials were obtained from Aldrich Chemicals, with the exception of (methacryloxypropyl)trimethoxysilane (MAPTMS), which was commercially available from Gelest, Inc., Tullytown PA. To a solution of styrene (7.2 g, 69 mmol) in 35 mL of ethyl acetate was added MAPTMS (0.79 g, 3.2 mmol) and benzoyl peroxide (0.0608 g, 0.25 mmol). The resulting solution was sparged with nitrogen for 15 minutes, sealed, and heated at 85 °C for 10 h. After cooling to room temperature, the polymer was precipitated in 200 mL of heptane, collected, and dried overnight under vacuum at 40 °C. The resulting polymer was 94 mole % styrene and 6 mole % MAPTMS based on 1H NMR, and had a weight-average molecular weight of 791 kg/mol from gel permeation chromatography against polystyrene standards. A 0.1 wt% solution of the polymer in toluene was applied to Wafer B samples using the described Polymer Coating Procedure. The samples were baked on a hot plate at 150°C for 3 minutes and then rinsed in fresh toluene. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Example 12

0101Poly(5-hexylnorbornene-co-5-(triethoxysilyl)norbornene) was synthesized as follows. All materials were obtained from Aldrich, except tris(perfluorophenyl)boron

0102(from Strem Chemicals, Newburyport, MA), 5-(triethoxysilyl)norbornene (from Gelest Inc., Tullytown, PA), and 5-hexylnorbornene, which was synthesized as described in U.S. Patent 3,557,072. Toluene and 1,2-dichloroethane were purified by passage over a 30 cm column filled with activated 4A molecular sieves and neutral alumina. 5-(Triethoxysilyl)norbornene was vacuum distilled from CaH₂. 5-Hexylnorbornene was vacuum distilled and passed over a 30 cm column filled with activated 4A molecular sieves and neutral alumina.

0103To a clean, dry 100 mL serum vial with cap under an inert atmosphere was added 8.52 g (47.79 mmol) 5-hexylnorbornene, 30 ml toluene (dried and degassed), 1.36 g (5.31 mmol) of 5-(triethoxysilyl)norbornene, 0.26 ml (26 μmol) of a 0.10 M solution of Ni(II)- bis(2,2,6,6-tetramethyl-3,5-heptanedionate) in toluene, 0.26 ml (260 μmol) of triethylaluminum (1.0 M in hexanes), and 2.34 ml (234 μmol) of a 0.1 M solution in 1,2- dichlorethane of tris(perfluorophenyl) boron. Upon addition of the triethylaluminum, the solution went from a light purple color to brown. The solution was stirred in the drybox overnight, whereupon it was removed. To the contents of the vial were added 0.50 g

01048-hydroxyquinoline dissolved in 150 mL cyclohexane. After stirring a further 24 hours, the solution was filtered through a fine glass frit (15 - 20 μm) followed directly by filtration through a 0.1 μm filter. The polymer was then precipitated in 900 mL of rapidly stirred acetone. Filtration on a fine glass frit, followed by washing with two 100 mL portions of fresh acetone afforded the polymer as a white solid. The resulting polymer was then dried under vacuum overnight. Wafer B samples were quartered and cleaned using the procedure described above.

0105A 0.1 wt% solution of silylated norbornene in toluene was applied to the wafer samples.

0106The solution was applied via the Polymer Coating Procedure described above, then the samples were baked on a hotplate at 150°C for 3 min., then rinsed with fresh toluene.

0107Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below.

0108Comparative Examples 1-3 (CE1, CE2, and CE3)

0109Wafers were quartered and cleaned immediately before use using consecutive rinses in acetone, methanol, 2-propanol and water, baked on a hot plate at 100°C for 3 minutes and exposed to UV/ozone in a home built chamber for 15 minutes. Wafer A was used for CE1, Wafer B was used for CE2, and Wafer C was used for CE3. Pentacene was applied as described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below.

0110Example 13

0111Wafer B samples were quartered and cleaned using the procedure described above. A 0.1 wt% solution of polystyrene in toluene was applied to the samples as in Example 2.

0112Copper(II) hexadecafluorophthalocyanine was used as received (copper(U)

01131 ,2,3,4,8,9, 10,11,15,16,17, 18,22,23,24,25-hexadecafluoro-29H, 3 IH-phthalocyanine from

0114Aldrich). The unpurified semiconductor was vapor-deposited by the pentacene method described above. OTFTs were prepared and tested as described above. Results are shown in Tables

01151 and 2 below.

0116Comparative Example 4 (CE4)

0117OTFT samples were prepared and tested as in Comparative Example 2 except that copper(JJ) hexadecafluorophthalocyanine was used rather than pentacene. Results are shown in Tables 1 and 2 below. Example 14

0118Wafer B samples were quartered and cleaned using the procedure described above. A 0.1 wt% solution of polystyrene in toluene was applied as in Example 2.

0119Tetracene, available as 2,3-benzanthracene from Aldrich, was purified in the furnace described above under reduced pressure and flowing forming gas (Ar with 2-6%

0120H₂) at a temperature about 230°C. The purified tetracene was vapor-deposited by the pentacene method described above.

0121OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Comparative Example 5 (CE5)

0122OTFT samples were prepared and tested as in Comparative Example 2 except that purified tetracene was used rather than pentacene. Results are shown in Tables 1 and 2 below.

0123Examples 15-17 Wafers were quartered and cleaned using the procedure described above. A 0.1 wt% solution of polystyrene in toluene was applied as in Examples 1-3 to samples of Wafer A (Example 15), Wafer B (Example 16), and Wafer C (Example 17), respectively.

0124Sexithiophene (obtained from Syncom, BV, The Netherlands) was purified in the Barnstead/Thermolyne furnace under reduced pressure and flowing nitrogen at a temperature of ~260°C. The purified sexithiophene was vapor-deposited by the pentacene method described above. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Comparative Examples 6-8 (CE6, CE7, and CE8)

0125Wafers were prepared as in Comparative Examples 1-3 except with purified sexithiophene rather than pentacene. Wafer A was used for CE6, Wafer B was used for

0126CE7, and Wafer C was used for CE8. OTFTs were prepared and tested as described above. Results are shown in Tables 1 and 2 below. Table 1: Thickness and Water Contact Angles (WCA)

0127<img file="WO03041185A2_D0001.tif" />

0128The thickness measurement was not applicable to the Comparative Examples, which all had advancing, static, and receding water contact angles of less than 20 degrees.

0129Table 2: OTFT Performance

0130<img file="WO03041185A2_D0002.tif" />

0131, no transistor behavior was observed. In CE6, only one OTFT was tested. Various modifications and alterations of this invention will be apparent to those skilled in the art in view of the foregoing description, without departing from the scope and principles of this invention. Accordingly, it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth hereinabove.