JP2008535794A - Semiconductors containing perfluoroether acyl oligothiophene compounds - Google Patents

Abstract

  A semiconductor device is described comprising a semiconductor layer comprising a perfluoroether acyl oligothiophene compound, preferably an α, ω-bis-perfluoroether acyl oligothiophene compound. Further described is a method of manufacturing a semiconductor device, comprising depositing a semiconductor layer containing a perfluoroether acyl oligothiophene compound, preferably an α, ω-bis (2-perfluoroether acyl oligothiophene compound).

Description

  The present invention provides a semiconductor device and a method of manufacturing a semiconductor device comprising a semiconductor layer containing a perfluoroetheracyl oligothiophene compound.

  Traditionally, inorganic materials have dominated the semiconductor industry. For example, silicon arsenide and gallium arsenide are used as semiconductor materials, silicon dioxide is used as an insulating material, and metals such as aluminum and copper are used as electrode materials. However, in recent years, there have been an increasing number of research attempts aimed at using organic materials instead of conventional inorganic materials in semiconductor devices. Among other advantages, the use of organic materials may reduce the cost of manufacturing electronic devices, may allow for large area applications, and is flexible for display backplanes or integrated circuits. It may be possible to use a circuit support.

  A variety of organic semiconductor materials are contemplated, the most common being tetracene and pentacene, bis (acetyl) acetylene, and oligomeric materials containing acene-thiophene, thiophene or fluorene units, and regioregular poly (3 -Fused aromatic ring compounds exemplified by polymer materials such as alkylthiophene). At least some of these organic semiconductor materials have performance such as charge carrier mobility, on / off current ratio, and subthreshold voltage that are comparable to or better than those of amorphous silicon based devices Has characteristics.

  The chemical nature of thiophene and the chemical stability of the thiophene ring indicate the potential use of thiophene materials in molecular-based electronics and photonics. In particular, α, α'-conjugated thiophene oligomers (nT) and polymers (polythiophene-PT) are of great interest as semiconducting elements of organic thin film transistors (TFTs). To be useful in such devices and related structures, the organic material is a channel of holes or electrons (p- or n-type semiconductor, respectively) formed by a gate electrode bias that switches the device “on”. Must support. Furthermore, the charge mobility of the material must be large enough to increase source-drain on-conduction by orders of magnitude more than the “off” state. The density of charge carriers in the channel is changed by the voltage applied to the gate electrode.

US Pat. No. 6,585,914 (Marks et al.) Describes an α that can be used to produce a thin film transistor that behaves as an n-type semiconductor and has a FET mobility of about 0.01 cm ² / Vs. , Ω-diperfluoroalkyl sexithiophene deposited films are described.

  Novel perfluoroether acyl (oligo) thiophene compounds such as α, ω-bis-perfluoroether acyl oligothiophene compounds are provided. In addition, novel methods for preparing these compounds are provided. These compounds are useful, for example, as n-channel semiconductor layers for electronic devices such as thin film transistors. There are a number of problems and deficiencies associated with the prior art relating to useful organic n-type semiconductor compounds, compositions and / or materials. There is a need for related applications useful in combination with the fabrication of thin film transistors and related devices that can be incorporated into such materials, compositions, layers and / or thin film deposition composites and integrated circuits. Accordingly, it is an object of the present invention to provide new and useful n-type organic materials with one or more fabrication methods.

  Semiconductor devices and methods for manufacturing semiconductor devices are provided. More specifically, the semiconductor device comprises a semiconductor layer containing at least one perfluoroether acyl oligothiophene compound, preferably at least one α, ω-bis-perfluoroether acyl oligothiophene compound.

  New compound formula

Wherein Y is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a perfluoroether acyl group, p is at least 1, preferably at least 2, and R _f is a perfluoroether group. is there.

  Preferred compounds are those of formula II:

An α, ω-bis-perfluoroether acyl oligothiophene compound, wherein each R _f is a perfluoroether group, and n is at least 1, preferably at least 2, more preferably 3-6. Using conventional terminology, consecutive thiophene rings are connected by covalent bonds, as shown in Formulas I and II. In one aspect, a semiconductor device comprising a semiconductor layer containing an α, ω-bis-perfluoroether acyl oligothiophene compound of Formula I or II is provided.

  In another aspect, a method for making a semiconductor device is provided. This method requires the step of making a semiconductor layer containing a compound of formula II. The semiconductor layer is often formed using vapor deposition techniques.

  Some of the methods for manufacturing semiconductor devices are methods for manufacturing organic thin film transistors. One such method includes providing a gate electrode, depositing a gate dielectric layer on the surface of the gate electrode, and adjacent to the surface of the gate dielectric layer opposite the gate electrode. A step of fabricating a semiconductor layer and a step of disposing a source electrode and a drain electrode on the surface of the semiconductor layer on the opposite side of the gate dielectric layer are required. The source electrode and the drain electrode are separated from each other in a region on the surface of the semiconductor layer. The semiconductor layer contains a compound of formula I or II.

  Yet another method of fabricating an organic thin film transistor includes providing a gate electrode, depositing a gate dielectric layer on the surface of the gate electrode, and adjacent to the gate dielectric layer opposite the gate electrode. A source electrode and a drain electrode, wherein the source electrode and the drain electrode are separated by a region on the gate dielectric layer, on the source electrode, on the drain electrode, and And a step of forming a semiconductor layer in a region between the source electrode and the drain electrode. The semiconductor layer contains a compound of formula I or II.

  The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following drawings, detailed description and examples illustrate these embodiments in more detail. While the invention is susceptible to various modifications and alternative forms, the details thereof are illustrated in the drawings and will be described in detail. However, it should be understood that the invention is not limited to the specific embodiments described. On the contrary, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

  The invention may be more fully understood in view of the following detailed description of various embodiments of the invention in conjunction with the accompanying drawings.

  Novel perfluoroether acyl (oligo) thiophene compounds are provided. The novel compound has the general formula:

Wherein Y is a hydrogen atom, a halogen atom, an alkyl group, and an aryl group or a perfluoroether acyl group, p is at least 1, preferably at least 2, and R _f is a perfluoroether group.

  Preferred α, ω-bis-perfluoroether acyl oligothiophene compounds are provided. The novel compound has the general formula:

Wherein each R _f is a perfluoroether group and n is at least 2.

  The present invention provides a semiconductor device and a method for making a semiconductor device comprising a semiconductor layer containing a perfluoroetheracyl (oligo) thiophene compound. Suitable thiophene groups include thiophene groups having 2 to 6 consecutively linked thiophene rings.

Definitions As used herein, the terms “a”, “an”, and “the” are used interchangeably with “at least one” to mean one or more of the elements being described.

  “Alkyl” means a saturated monovalent hydrocarbon group having 1 to about 12 carbon atoms or a branched saturated monovalent hydrocarbon group having 3 to about 12 carbon atoms, such as methyl, ethyl, 1-propyl , 2-propyl, pentyl and the like.

  “Alkylene” means a saturated divalent hydrocarbon group having 1 to about 12 carbon atoms or a branched saturated divalent hydrocarbon group having 3 to about 12 carbon atoms, such as methylene, ethylene, propylene, 2 -Means methylpropylene, pentylene, hexylene and the like;

“Alkyleneoxy” essentially has the meaning given above for alkylene, except the alkylene group is terminated by an oxygen atom, eg, —CH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ O— _{, -CH 2 CH 2 CH 2 CH} 2 O -, - CH 2 CH (CH 3) CH 2 O- and the like.

  The term “aryl” refers to a monounsaturated aromatic carbocyclic group having a single ring such as phenyl or multiple condensed rings such as naphthyl or anthryl.

  As used herein, the term “oligothiophene” refers to an oligomer having at least two thiophene repeat units linked by covalent bonds in two consecutive positions. “(Oligo) thiophene” includes thiophene compounds having one thiophene ring and oligomeric thiophene compounds (oligothiophene) having two or more thiophene rings.

  “Perfluoroalkyl” essentially has the meaning given above for “alkyl” except that all or essentially all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms, and the number of carbon atoms Is 1 to about 12, for example, perfluoropropyl, perfluorobutyl, perfluorooctyl and the like.

  “Perfluoroalkylene” essentially has the meaning given above for “alkylene” except that all or essentially all of the hydrogen atoms of the alkylene group are replaced by fluorine atoms, eg perfluoropropylene Perfluorobutylene, perfluorooctylene and the like.

“Perfluoroalkyloxy” essentially has the meaning given above for “alkyloxy” except that all or essentially all of the hydrogen atoms of the alkoxy group are replaced by fluorine atoms. The number of carbon atoms is from 3 to about 12, for example, CF ₃ CF ₂ O—, CF ₃ CF ₂ CF ₂ CF ₂ O—, C ₃ F ₇ CF (CF ₃ ) O—, and the like.

“Perfluoroalkyleneoxy” essentially has the meaning given above for “alkyleneoxy”, except that all or essentially all of the hydrogen atoms of the alkyleneoxy group are replaced by fluorine atoms, eg _{, -CF 2 O -, - CF} 2 CF 2 O -, - CF 2 CF (CF 3) is O- and the like.

“Perfluoroether” is a saturated perfluorinated monovalent alkyl group having from 2 to about 50 carbon atoms and at least one ether oxygen atom, such as CF ₃ CF ₂ OCF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ —, CF ₃ CF (CF ₃ ) OCF ₂ CF ₂ OCF ₂ CF ₂ —, CF ₃ CF (CF ₃ ) O— [CF (CF ₃ ) —CF ₂ O] _n —CF ( CF ₃ ) − and the like. “Perfluoroether” includes perfluoromonoethers and perfluoropolyethers.

Semiconductor device type

A semiconductor device having a semiconductor layer containing the compound is provided, wherein each R _f is a perfluoroether group and n is at least 2, preferably 3-6. R _f may be a monoether or polyether, ie a monovalent perfluoroalkoxyalkylene group or a monovalent perfluoropolyether group.

The perfluoroheteroalkyl group R _f of the fluorinated ethers of formulas I and II is preferably of the formula:
^{_{R f 1 -O- (R f 2}} ) x - (R f 3) - (III)
Wherein R _f ¹ represents a perfluoroalkyl group having ¹ to 10 carbon atoms, preferably 1 to 6 carbon atoms, and (R _f ² ) _x is 1 to 10 carbon atoms. A perfluoropolyalkyleneoxy group consisting of a perfluoroalkyleneoxy group R _f ² having 1 to 6 carbon atoms, wherein R _f ³ is 1 to 10 perfluorinated carbon atoms Represents a perfluoroalkylene group having preferably 1 to 6 carbon atoms, and x is 0 to 25, preferably at least 1 and more preferably 1 to 4. The perfluoroalkyl and perfluoroalkylene groups of formula (III) may be linear or branched. A typical perfluoroalkyl group is CF ₃ —CF ₂ —CF ₂ —. For example, R _f ³ is —CF ₂ — or —CF (CF ₃ ) —.

Examples of the perfluoroalkyl group R _f ¹ include CF ₃ —CF ₂ —, CF ₃ —CF (CF ₃ ) —, CF ₃ —CF ₂ —CF ₂ —, CF ₃ —, CF ₃ —CF ₂ CF ₂ —. _{CF (CF 3) -, CF} 3 -CF 2 CF (C 3 F 7) -, CF 3 -CF (C 3 F 7) CF 2 -, and _{CF 3 -CF 2 -CF 2 -CF 2} - and is there.

Examples of the perfluoroalkyleneoxy group of the perfluorinated polyalkyleneoxy group R _f ² include —CF ₂ —CF ₂ —O—, —CF (CF ₃ ) —CF ₂ —O—, —CF ₂ —CF (CF _{3) -O -, - CF 2} -CF 2 -CF 2 -O -, - CF 2 -O -, - CF (CF 3) -O-, and _{-CF 2 -CF 2 -CF 2 -CF 2} - O- etc.

Examples of perfluoroalkylene group ^{_{R f 3, -CF 2 -CF 2}} -, - CF (CF 3) -CF 2 -, - CF 2 -CF (CF 3) -, - CF 2 -CF 2 -CF 2 _{-, - CF 2 -, -} CF (CF 3) -, and _{-CF 2 -CF 2 -CF 2 -CF 2} - , and the like.

The perfluoroalkyleneoxy group R _f ² may consist of the same perfluoroalkyleneoxy unit or a mixture of different perfluoroalkyleneoxy units. When the perfluoroalkyleneoxy group consists of different perfluoroalkyleneoxy units, they may be present in irregular, alternating structures, or they may be present as blocks. Typical examples of perfluoropolyalkyleneoxy groups include — [CF ₂ —CF ₂ —O] _n —, — [CF (CF ₃ ) —CF ₂ —O] _n —, — [CF ₂ CF ₂ —O _{] i - [CF 2 O]} j - and _{- [CF 2 -CF 2 -O]} l - [CF (CF 3) -CF 2 -O] m - include, n represents an integer from 1 to 25 , And i, l, m and j are each an integer of 1 to 25.

In certain embodiments, the fluorinated polyether R _f has the following formula (IV):
^{_{R f 1 -O- [CF (CF}} 3) -CF 2 O] x -CF (CF 3) - (IV)
In the above formula, R _f ¹ represents a perfluorinated alkyl group, for example, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, and x is 0 to 25, preferably Is an integer of at least 1, more preferably 1-4. A preferred perfluorinated polyether group corresponding to formula (IV) is CF ₃ —CF (CF ₃ ) —O— [CF (CF ₃ ) —CF ₂ O] _x —CF (CF ₃ ) —, Is an integer from 1 to 4. This perfluoropolyether can be derived from the oligomerization of hexafluoropropylene oxide.

Preferred perfluoroether groups R _f are dimers, trimers and tetramers derived from hexafluoropropylene oxide (HFPO) and have the structure:

It corresponds to.

  Corresponding acids, acid halides and esters may be prepared from oligomerization of hexafluoropropylene oxide or oxidative oligomerization of hexafluoropropylene, which are known in the art. Many of these compounds are commercially available from Matrix Scientific, Columbia, SC, Columbia, South Carolina.

  Compounds of formula (IV) are obtained, for example, by oligomerization of hexafluoropropylene oxide, resulting in perfluoropolyether carbonyl fluoride. The carbonyl fluoride may be converted to an acid or ester by reactions known to those skilled in the art. The carbonyl fluoride or acyl fluoride, acid, or ester derived therefrom may then be further reacted to introduce the desired perfluoroether group into the oligothiophene compound by known acylation procedures. For example, US Pat. No. 6,127,498 or US Pat. No. 3,536,710 describe methods suitable for preparing compounds of formula (IV) having the desired acyl moiety. Has been.

  For further details regarding materials and procedures for the preparation of perfluorinated polyethers, see, for example, US Pat. No. 3,242,218 (Miller), US Pat. No. 3,322,826 ( Moore), US Pat. No. 3,250,808 (Moore et al.), US Pat. No. 3,274,239 (Selman), US Pat. No. 3,293,306 (LeBleu et al.), US Pat. No. 3,810,874 (Mitsch et al.), US Pat. No. 3,544,537 (Brace), US Pat. No. 3,553. 179 (Bartlett), US Pat. No. 3,864,318 (Caporicio et al.), US Pat. No. 4,321,4 4 (Williams et al.), US Pat. No. 4,647,413 (Savu), US Pat. No. 4,818,801 (Rice et al.), US Patent No. 4,472,480 (Olson), U.S. Pat. No. 4,567,073 (Larson et al.), U.S. Pat. No. 4,830,910 (Larson) US Pat. No. 5,362,919 (Costello), US Pat. No. 5,578,278 (Fall) and US Pat. No. 5,306,758 (Pellerite). . See Patricia M. Savu, Fluorinated High Carboxylic Acids, 11 Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, 551-94 (also 4th edition, 551-94).

A perfluoroetheracyl (oligo) thiophene compound of formula I (Y is not a perfluoroetheracyl group) may be prepared as follows. Treating thiophene (Y = H) with an alkyl lithium reagent (in the presence of a Lewis acid catalyst such as BF ₃ -Et ₂ O) followed by acylation with a perfluoroether ester to produce a monoperfluoroether acyl compound Also good. The corresponding 5-alkyl or 5-aryl compound (Y = alkyl or aryl) starts from 2-alkyl or 2-arylthiophene (as is known in the art) followed by acylation and optionally It may be prepared by a similar route of bromination. The corresponding 2-bromo-5-perfluoroether acyl compound may be prepared by monoacylating 2,5-dibromothiophene to produce the 2-bromo-5-perfluoroether acyl compound directly.

  Higher thiophene compounds (Y is H, halogen, alkyl or aryl) may be prepared by Stille coupling of thienylstannane and α-bromo-ω-perfluoroether acylthiophene according to the following general scheme.

  Preferred α, ω-bis-perfluoroether acyl oligothiophene compounds of formula II may be prepared by Reaction Scheme A with a Still coupling reaction. Generally, oligothiophenes are bis (trialkylstannyl) thiophenes (eg 2,5-bis (trialkylstannyl) thiophene or 5,5′-bis (trialkylstannyl) bithiophene) 2-perfluoroether acyl 5 It may be prepared by reacting with -halothiophene (or 5-perfluoroetheracyl 5'-halobithiophene) in the presence of a palladium catalyst.

  2-halo-5-perfluoroether acylthiophene (such a compound of formula VI) or 5-halo-5′-perfluoroether acylbithiophene (such a compound of formula X) is converted to a bis (trialkylstannyl) compound (ie, the formula V or VIII, where R is an alkyl group, can be reacted to form α, ω-bis (2-perfluoroether acyl oligothiophene (ie, formula VII, IX, XI or XII). Still coupling reactions are described by Farina V. and Krishnamurthy, V., Organic Reactions, LA Packets, LA Wicket and John Wiley &.・ Sands (John Wiley and Sons, 1997, vol.50, pages 1 to 652. The reaction product may be purified to semiconductor grade material by any known method, such as by vacuum sublimation. Also good.

  Reaction Scheme A

  Bis-trialkylstannylthiophene compounds of the formulas V and VIII are known. Y. Y. Wei et al., Chem. Mater. Vol. 8, 1996, pages 2659-2666.

  A monoacyl compound of formula VI is prepared by treating 2,5-dihalothiophene with an alkyllithium compound to produce 2-bromo-5-lithiothiophene, followed by perfluorinated ether in the presence of boron trifluoride etherate. It may be prepared by reacting with an ester (or equivalent). This method yielded the desired product V in high yield and was found to be superior to other known methods such as reacting with perfluorinated acyl compounds after forming the cuprate.

  Monoacylbithiophene compound X is prepared by first producing (in situ generated) 5-lithio-2,2′-bithiophene in the presence of a perfluorinated ether ester (or equivalent) and boron trifluoride etherate) It may be prepared by a two-step synthesis including a reaction step and subsequent bromination with N-bromosuccinimide or the like.

  With respect to compounds VI and X, 5-halo-5'-perfluoroether acylthiophene compounds are useful in the preparation of the bis-perfluoroetherthiophene compounds of the present invention. Such novel compounds have the general formula:

Wherein Y is H, a halogen, an aryl or an alkyl group, R _f is a perfluoroether group, and p is 1-6. A compound wherein p is 2 or more is obtained by reacting a compound of formula VI or X with a mono-trialkylstannylthiophene or mono-trialkylstannylbithiophene, followed by a ω-5 position of the terminal thiophene ring. May be prepared by halogenation.

  Bithiophene compounds of formula XIII are described in Portnoy, J. et al. Org. Chem, vol. 32, 1967, pp 233-4, may be prepared by coupling 5-bromo-2-thienylmagnesium bromide and perfluoroether acid halide. The Ullman coupling reaction may also be useful.

Asymmetric α, ω-bis-perfluoroether acyl oligothiophenes (ie, oligothiophenes having different perfluoroether acyl groups) use, for example, a mixture of compounds of formula VI or X having different R _f groups May result in a mixture of products. For each of the reaction schemes, preferred bromo-substituted thiophenes are shown, but other halides may be used.

Other synthetic methods can be used to prepare α, ω-bis-perfluoroether acyl oligothiophene compounds. For example, thiophene-2-aldehyde may be reacted with a perfluoroether organometallic compound (such as R _f -Li generated in situ) to produce the indicated alcohol. This may be brominated at the 5 position, followed by oxidation of the hydroxyl group to a ketone. Reference may be made to the general methods described in US Pat. No. 6,608,323 and US Pat. No. 6,585,914 (Marks et al.).

The compounds of the present invention may be used as n-channel semiconductors. A semiconductor layer containing an α, ω-bis-perfluoroether acyl oligothiophene compound may be included in any type of semiconductor device. The semiconductor device is, for example, S.I. M.M. By S. M. Sze, Physics of Semiconductor Devices , 2nd edition, John Wiley and Sons, New York (1981). Such devices include rectifiers, transistors (many types such as pnp, npn, and thin film transistors), photoconductors, current limiters, thermistors, pn junctions, field effect diodes. A Schottky diode or the like may be provided.

  A semiconductor device can include components such as transistors, transistor arrays, diodes, capacitors, embedded capacitors, and resistors used to form a circuit. The semiconductor device can also include an array of circuits that perform electronic functions. Examples of these arrays, or integrated circuits, are inverters, oscillators, shift registers, and logic. Applications of these semiconductor devices and arrays include radio frequency identification devices (RFID), smart cards, display backplanes, sensors, memory devices, and the like.

Each semiconductor device contains a semiconductor layer having a compound of formula I or II. The semiconductor layer can be combined with a conductive layer, a dielectric layer, or a combination thereof to form a semiconductor device. Semiconductor devices can be made or manufactured by known methods, such as those described by Peter Van Zant, Microchip Fabrication , 4th edition, McGraw-Hill, New York (2000). .

  Some of the semiconductor devices are organic thin film transistors. One embodiment of the organic thin film transistor 10 is shown in FIG. 1A. An organic thin film transistor (OTFT) 10 is disposed on an arbitrary substrate 12, a gate electrode 14 disposed on the arbitrary substrate 12, a gate dielectric material 16 disposed on the gate electrode 14, and a gate dielectric layer 16. An optional surface treatment layer 18, a source electrode 22, a drain electrode 24, and a semiconductor layer 20 in contact with both the source electrode 22 and the drain electrode 24 are provided. The source electrode 22 and the drain electrode 24 are separated from each other in the region on the surface of the semiconductor layer 20 (that is, the source electrode 22 does not contact the drain electrode 24). A part of the semiconductor layer disposed between the source electrode and the drain electrode is referred to as a channel 21. The channel is disposed on the gate electrode 14, the gate dielectric layer 16, and the optional surface treatment layer 18. The semiconductor layer 20 is in contact with the gate dielectric layer 16 or the surface treatment layer 18.

  A second embodiment of the organic thin film transistor is shown in FIG. 1B. The OTFT 100 includes a gate electrode 14 disposed on an arbitrary substrate 12, a gate dielectric layer 16 disposed on the gate electrode 14, an arbitrary surface treatment layer 18 disposed on the gate dielectric layer 16, a semiconductor layer. 20, and a source electrode 22 and a drain electrode 24 disposed on the semiconductor layer 20. In this embodiment, the semiconductor layer 20 is between the gate dielectric layer 16 and both the source electrode 22 and the drain electrode 24. The semiconductor layer 20 can be in contact with the gate dielectric layer 16 or any surface treatment layer 18. The source electrode 22 and the drain electrode 24 are separated from each other in a region on the surface of the semiconductor layer 20 (that is, the source electrode 22 does not contact the drain electrode 24). The channel 21 is a part of a semiconductor layer disposed between the source electrode 22 and the drain electrode 24. Channel 21 is disposed on gate electrode 14, gate dielectric layer 16, and optional surface treatment layer 18.

  In operation of the semiconductor device structure shown in FIGS. 1A and 1B, a voltage can be applied to the drain electrode 24. However, if a positive voltage is not applied to the gate electrode 14 with respect to the source electrode 22, no electric charge (that is, current) flows through the source electrode 22. That is, if no voltage is applied to the gate electrode 14, the channel 21 of the semiconductor layer 20 remains in a non-conductive state. When a voltage is applied to the gate electrode 14, the channel 21 becomes conductive and charge flows from the source electrode 22 to the drain electrode 24 through the channel 21.

  The substrate 12 often supports the OTFT during manufacturing, testing, and / or use. In some cases, the substrate can provide the electrical function of the OTFT. For example, the back side of the substrate can provide electrical contact. Useful support materials include inorganic glass, ceramic materials, polymeric materials, filled polymeric materials (eg, fiber reinforced polymeric materials), metal, paper, woven or non-woven, coated or uncoated metal foil, or combinations thereof There are, but are not limited to them. Suitable polymer substrates include acrylic derivatives, epoxy, polyamide, polycarbonate, polyimide, polyketone, polynorbornene, polyphenylene oxide, poly (ethylene naphthalate), poly (ethylene terephthalate), poly (phenylene sulfide), poly (ether ether) Ketone), such as poly (oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene).

  The gate electrode 14 can contain one or more layers of conductive material. For example, the gate electrode can contain doped silicon materials, metals, alloys, conductive polymers, or combinations thereof. Suitable metals and alloys include, but are not limited to, aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, titanium, indium tin oxide (ITO) or combinations thereof. Typical conductive polymers include, but are not limited to, polyaniline or poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonate). In some organic thin film transistors, the same material can provide both gate electrode function and substrate support function. For example, doped silicon can function as both a gate electrode and a substrate.

  A gate dielectric layer 16 is disposed on the gate electrode 14. This gate dielectric layer 16 electrically insulates the gate electrode 14 from the rest of the OTFT device. Useful materials for the gate dielectric include, for example, inorganic dielectric materials, polymeric dielectric materials, or combinations thereof. The gate dielectric may be a single layer or multiple layers of suitable materials. Each layer of a single or multi-layer dielectric can contain one or more dielectric materials.

  Typical inorganic dielectric materials include strontate, tantalate, titanate, zirconate, aluminum oxide, silicon oxide, tantalum oxide, titanium oxide, silicon nitride, barium titanate, strontium barium titanate, barium zirconate titanate, Examples include zinc selenide, zinc sulfide, and hafnium oxide. In addition, alloys, combinations, and multilayers of these materials can be used for the gate dielectric layer 16.

Typical polymeric dielectric materials include polyimide, parylene C, crosslinked benzocyclobutene, cyanoethyl pullulan, polyvinyl alcohol, and the like. For example, C.I. D. C. D. Sheraw et al., “Spin-on polymer gate dielectric for high performance organic thin film transducers, Materials Research Society Society . 558, pages 403-408 (2000), Materials Research Society, Warrendale, PA, USA, and US Pat. No. 5,347,144 (Garnier).

  Other exemplary organic polymer dielectrics include cyano-functional, such as cyano-functional styrene copolymers as disclosed in US patent application Ser. No. 10 / 434,377, filed May 8, 2003. There is a functional polymer. Some of these polymeric materials may be coated from solution, cross-linked, photopatterned, and have high thermal stability (eg, stable to a temperature of about 250 ° C. May have a low processing temperature (eg, less than about 150 ° C. or less than about 100 ° C.), may be compatible with a flexible substrate, or a combination thereof.

  Typical cyano-functional polymers that can be used as organic dielectric materials include styrene maleic anhydride copolymers modified by adding methacrylate functional groups for crosslinking purposes and by attaching cyano functional groups Reaction product of bis (2-cyanoethyl) acrylamide and acrylated polystyrene macromer, polymer formed from 4-vinylbenzylcyanide, polymer formed from 4- (2,2′-dicyanopropyl) styrene, 4 Polymers formed from-(1,1 ', 2-tricyanoethyl) styrene, and polymers formed from 4- (bis- (cyanoethyl) aminoethyl) styrene, and 4-vinylbenzyl cyanide and 4-vinylbenzyl Such as copolymers formed from acrylates. But it is not limited to these.

  The organic thin film transistor can include an optional surface treatment layer 18 disposed between the gate dielectric layer 16 and at least a portion of the organic semiconductor layer 20. In some embodiments, the optional surface treatment layer 18 serves as an interface between the gate dielectric layer and the semiconductor layer. The surface treatment layer may be a self-assembled monolayer or a polymer material.

  Suitable self-assembled monolayer surface treatment layers are disclosed, for example, in US Pat. No. 6,433,359 B1 (Kelly et al.). Typical self-assembled monolayers are 1-phosphono-2-ethylhexane, 1-phosphono-2,4,4-trimethylpentane, 1-phosphono-3,5,5-trimethylhexane, 1-phosphonooctane, It can be formed from phosphonohexane, 1-phosphonohexadecane, 1-phosphono-3,7,11,5-tetramethylhexadecane and the like.

Useful polymers and copolymers for the surface treatment layer are usually nonpolar, glassy solids at room temperature. The polymeric material of this layer typically has a glass transition temperature (T _g ) measured in bulk of at least 25 ° C., at least 50 ° C., or at least 100 ° C. Suitable polymeric surface treatment layers are described, for example, in US 2003/0104471 A1 (Kelly et al.) And US Pat. No. 6,617,609 (Kelly et al.).

  Typical polymer surface treatment layers are polystyrene, polyfluorene, polynorbornene, poly (1-hexene), poly (methyl methacrylate), poly (acenaphthylene), poly (vinyl naphthalene), poly (butadiene), and poly (vinyl). Acetate). Other typical polymer surface treatment layers are α-methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4- (phosphonomethyl) styrene, divinylbenzene, and Polymers or copolymers derived from combinations of these can be included. Examples of other useful polymeric materials for the surface treatment layer include poly (dimethylsiloxane), poly (dimethylsiloxane-co-diphenylsiloxane), poly (methylphenylsiloxane-co-diphenylsiloxane), poly (dimethyl Siloxane-co-methylphenylsiloxane).

  Surface treatment layers often have a maximum thickness of less than 400 angstroms (Å). For example, the surface treatment layer may be smaller than 200 mm, smaller than 100 mm, or smaller than 50 mm. The surface treatment layer generally has a thickness of at least about 5 mm, at least about 10 mm, or at least 20 mm. The thickness can be quantified by a known method such as ellipsometry.

  The source electrode 22 and the drain electrode 24 are made of metal, alloy, metal compound, conductive metal oxide, conductive ceramic, conductive dispersion, and conductive polymer such as gold, silver, nickel, chromium, barium, platinum, Palladium, aluminum, calcium, titanium, indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), indium zinc oxide (IZO), poly (3,4-ethylenedioxythiophene ) / Poly (styrene sulfonate), polyaniline, other conductive polymers, alloys thereof, combinations thereof, and multilayers thereof. Some of these materials are suitable for use with n-type semiconductor materials, and others are suitable for use with p-type semiconductor materials, as is known in the art.

  Thin film electrodes (eg, gate electrode, source electrode, and drain electrode) can be provided by any means known in the art, such as physical vapor deposition (eg, thermal evaporation or sputtering), ink jet printing, and the like. These electrodes can be patterned by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, and pattern coating.

Semiconductor devices containing perfluoroetheracyl oligothiophene compounds tend to have performance characteristics such as charge carrier mobility and current on / off ratio that are equivalent to known organic semiconductor devices such as semiconductor devices containing pentacene. For example, a semiconductor device having an n-channel mobility of about 1 cm ² / volt-second and an on / off ratio greater than about 10 ⁵ can be fabricated.

  In another aspect, a method for making a semiconductor device is provided. The method requires the step of making a semiconductor layer containing a perfluoroetheracyl oligothiophene compound of formula I or II, where n is preferably 3-6. The semiconductor layer is usually formed using a vapor deposition method.

  In some exemplary methods of making a semiconductor device, the method includes the steps of making a semiconductor layer containing a perfluoroether acyl oligothiophene compound of Formula I or II, and a dielectric layer adjacent to the semiconductor layer, conductive Depositing layers, or combinations thereof. As used herein, the term “adjacent” refers to a first layer disposed near a second layer. The first layer often contacts the second layer, but another layer can be placed between the first and second layers. A specific order of fabrication or deposition is not required, however, semiconductor layers are often fabricated on the surface of another layer, such as a dielectric layer, a conductive layer, or a combination thereof.

  One exemplary method of making a semiconductor device provides an organic thin film transistor. The method includes the steps of making a semiconductor layer containing a perfluoroetheracyl oligothiophene compound of Formula I or II, and the source and drain electrodes are separated in a region on the surface of the semiconductor layer (ie, the source electrode is drained). And a step of disposing a source electrode and a drain electrode on the surface of the semiconductor layer so as not to be in contact with the electrode. The method can further include providing a gate dielectric layer, a gate electrode, and an optional surface treatment layer.

  More specifically, the organic thin film transistor includes a step of providing a gate electrode, a step of depositing a gate dielectric layer on the surface of the gate electrode, and a step of fabricating a semiconductor layer adjacent to the gate dielectric layer ( That is, a gate dielectric is disposed between the gate electrode and the semiconductive layer), and a step of disposing a source electrode and a drain electrode on the surface of the semiconductor layer opposite the gate dielectric layer. can do. The source electrode and the drain electrode are separated from each other in a region on the surface of the semiconductor layer.

  In one embodiment of this method, the various layers of the semiconductor device are arranged in the following order: a gate electrode, a gate dielectric layer, a semiconductor layer, and a layer containing source and drain electrodes. In another embodiment, the various layers of the semiconductor device are arranged in the following order: a gate electrode, a gate dielectric layer, a surface treatment layer, a semiconductor layer, and a layer containing source and drain electrodes. The source electrode is not in contact with the drain electrode in these embodiments. That is, the source electrode and the drain electrode are separated from each other in a region on the surface of the semiconductor device. One surface of the semiconductor layer is in contact with both the source and drain electrodes, and the opposite surface of the semiconductor layer is in contact with the gate dielectric layer or the surface treatment layer.

  The organic thin film transistor illustrated in FIG. 1B includes a step of providing a substrate, a step of depositing a gate electrode on the substrate, and a gate dielectric such that the gate electrode is disposed between the substrate and a gate dielectric layer. Depositing a body layer on the surface of the gate electrode; applying a surface treatment layer to the surface of the gate dielectric layer opposite the gate electrode; and It can be produced by a step of producing a semiconductor layer on the surface of the surface treatment layer and a step of disposing a source electrode and a drain electrode on the surface of the semiconductor layer on the opposite side of the polymer treatment layer. The source electrode and the drain electrode are separated from each other in a region on the surface of the semiconductor layer. An isolation region between the source electrode and the drain electrode may define a channel in the semiconductor layer.

  Another organic thin film transistor includes providing a gate electrode, depositing a gate dielectric layer on the surface of the gate electrode, and a source electrode and a drain electrode separated from each other in a region above the gate dielectric layer. Arranging the source and drain electrodes adjacent to the gate dielectric material, and producing a semiconductor layer deposited on the source electrode, on the drain electrode, and in a region between the source and drain electrodes, Can be produced. The semiconductor layer is in contact with both the source electrode and the drain electrode. A portion of the semiconductor layer disposed in a region between the source electrode and the drain electrode defines a channel.

  In one embodiment of this method, the various layers of the semiconductor device are arranged in the following order: a gate electrode, a gate dielectric layer, a layer containing a source electrode and a drain electrode, and a semiconductor layer. In another embodiment, the various layers of the semiconductor device are arranged in the following order: a gate electrode, a gate dielectric layer, a surface treatment layer, a layer containing source and drain electrodes, and a semiconductor layer. In these embodiments, the source electrode does not contact the drain electrode. A portion of the semiconductor layer can extend between the source electrode and the drain electrode.

  The organic thin film transistor illustrated in FIG. 1A includes a step of providing a substrate, a step of depositing a gate electrode on the substrate, and a gate such that the gate electrode is disposed between the substrate and a gate dielectric layer. Depositing a dielectric layer on the surface of the gate electrode, applying a surface treatment layer to the surface of the gate dielectric layer opposite the gate electrode, and separating the two electrodes from each other in the region The source electrode and the drain electrode are formed on the surface of the polymer treatment layer, and the semiconductor layer is formed on the source electrode, the drain electrode, and a region between the source electrode and the drain electrode. be able to. The semiconductor layer contacts both the source electrode and the drain electrode. A portion of the semiconductor layer disposed in a region between the source electrode and the drain electrode defines a channel of the semiconductor layer.

  Other semiconductor devices such as organic thin film transistors or integrated circuits can be fabricated using flexible repositionable polymer aperture masks. This technique requires the sequential deposition of material through a number of polymer aperture masks formed in a pattern that defines a layer of a semiconductor device, or a portion of a layer. The use of such a polymer aperture mask is disclosed in U.S. Patent Application Publication No. 2003 / 0094959-A1, U.S. Patent Application Publication No. 2003 / 0150384-A1, U.S. Patent Application Publication No. 2003 / 0152691-A1. And U.S. Patent Application Publication No. 2003 / 0151118-A1.

  Repositionable polymer aperture masks often have a thickness of 5-50 micrometers or 15-35 micrometers. The various deposition apertures of the aperture mask typically have a width of less than 1000 micrometers, less than 50 micrometers, less than 20 micrometers, less than 10 micrometers, or even less than 5 micrometers. These size apertures are particularly useful in forming small circuit elements for integrated circuits. In addition, the gap or gaps between the deposition apertures are typically less than 1000 micrometers, less than 50 micrometers, less than 20 micrometers, or less than 10 micrometers, and are also useful for forming small circuit elements. is there. The aperture mask can have a pattern with a width greater than 1 centimeter, 25 centimeter, 100 centimeter, or even 500 centimeters. Patterns with these widths can be useful in forming various circuits over the surface area.

  Various laser ablation techniques can be used to facilitate the formation of a polymer aperture mask having a pattern of deposition apertures. In addition, stretching techniques and other techniques can be used to facilitate alignment of the flexible polymer aperture mask. In addition, a method for controlling the sag of the aperture mask that may be particularly useful for using a mask with a pattern that extends over a large width may be used.

  Semiconductor devices can be fabricated using other methods known in the art. These methods include, for example, metal shadow masks, photolithography and / or etching, and printing methods such as inkjet, screen printing, and gravure printing.

  In some methods that require the use of aperture masks, semiconductor devices (eg, integrated circuits) do not require any of the etching or photolithography steps typically used to form such devices. It can be formed using only an aperture mask deposition technique. Such techniques may be particularly useful in forming circuit elements for electronic displays such as liquid crystal displays and low cost integrated circuits such as radio frequency identification (RFID) circuits. Moreover, such techniques may be advantageous in the manufacture of integrated circuits that incorporate organic semiconductors and are typically incompatible with photolithography or other wet chemical methods.

  Objects and advantages of the present invention will be further illustrated in the following non-limiting examples, although the specific materials and their amounts described in these examples, as well as other conditions and details, are unreasonable. Should not be construed as limiting.

All reactions were performed under nitrogen. The melting point is quantified by DSC analysis under N ₂ at an increase rate of 20 ° C./min and is recorded as the range between the onset temperature and the peak maximum. Combustion analysis was performed using a LECO 932 CHNS elemental analyzer (LECO Corporation, St. Joseph, Michigan). Infrared spectra were recorded using pellets pressurized with KBr. Cation mass spectrometry was performed using a DE / STRMALDI / TOF mass spectrometer (Applied Biosystems, Foster City, Calif.) From Applied Biosystems Inc. (Applied Biosystems Inc.). A diluted CHCl ₃ solution of the sample was deposited directly on the probe tip without using a matrix. ¹ H and ¹⁹ F NMR spectra were collected in d ₆ -acetone at 200 MHz and 188 MHz, respectively, unless otherwise noted. Internal tetramethylsilane and fluorotrichloromethane were based on 0.0 ppm. Silica gel for column chromatography was purchased from Aldrich (Milwaukee, WI, Merck, Brand 9385, 230-400 mesh, 60Å). Tetrahydrofuran (THF) and diethyl ether (Et ₂ O) were distilled from sodium / benzophenone ketyl. N, N-dimethylformamide (DMF) is vacuum distilled from MgSO ₄ under nitrogen and purchased as an anhydrous brand from Aldrich. All other solvents were used as obtained. Bithiophene, 2,5-dibromothiophene, 3-bromothiophene, boron trifluoride diethyl etherate, aluminum trichloride, n-butyllithium (1.6M or 2.5M in hexane), N-bromosuccinimide (NBS), and dimethyl Amine borane was purchased from Aldrich. NBS was recrystallized from warm water and dried under vacuum before use. Perfluoro (2,5-dimethyl-3,6-dioxanonane) acid methyl ester (HFPO trimercarbomethoxylate), methyl 3,6-dioxadecanoate, and methyl 3,6,9-trioxadecanoate Was purchased from Matrix Scientific (Columbia, SC) and used as received. Tetrakis (triphenylphosphine) palladium (0) was purchased from Strem Chemicals, Newburyport, Mass., Newburyport, Massachusetts. 5,5′-bis (tri-n-butylstannyl) -2,2′-bithiophene and 5,5′-bis (tri-n-butylstannyl) thiophene were prepared according to Y. Wei, Y. Y. Yand, and J. -By J.-M Yeh, Chem. Synthesized using the procedure published by Mater, 8, 2659-2666 (1996).

Example 1
5-Perfluoro (3,6,9-trioxadecanoyl) -2,2'-bithiophene

BuLi in hexane (10.18 mL, 16.3 mmol) was added dropwise to a low temperature (-70 ° C.) THF solution (250 mL) of bithiophene (2.71 g, 16.3 mmol). After 30 minutes, CF ₃ (OC ₂ F ₄ ) ₂ OCF ₂ CO ₂ Me (7.66 g, 16.4 mmol) and BF ₃ .OEt ₂ (2.5 mL, 19.6 mmol, 1.2 eq) were successively added. And the mixture was stirred at -70 ° C. for 90 minutes. A few mL of saturated NH ₄ Cl (aq) was charged, the mixture was warmed to room temperature, and volatile materials were removed under reduced pressure. Et ₂ O (400 mL) and brine (250 mL) were charged and the reaction was stirred vigorously.

The mixture was filtered through a celite pad and the amber organic was washed with 2 × 100 mL brine, dried over MgSO ₄ and filtered. The solvent was stripped and the material was adsorbed onto silica gel. The crude product was purified by column chromatography (hexane / EtOAc, 0% -3%) to yield 6.38 g (70%) of yellow product. Mp (ΔH): 50-53 ° C. (51 J / g). IR: 1684 (ν _CO ), 1505 w, 1450 m, 1423 w, 1229 s, 1193 s, 1139 s, 1103 s, 1077 s, 906 m, 869 m, 842 m, 803 m, 741 m, 706 s, 682 m, 619 w, 546 w, 522 w, 508 w, 453 wcm ⁻¹ . ¹ H NMR: δ 7.22 (dd, J = 5.1 Hz, 3.8 Hz, 5′-H), 7.56 (d, J = 4.3 Hz, 3-H), 7.67 (dd, J = 3.7 Hz, 1.1 Hz, 4′-H), 7.73 (dd, J = 5.1 Hz, 1.1 Hz, 3′-H), 8.01 (dt, J = 4.3 Hz, 1 .7 Hz, 4-H). ¹⁹ F NMR: δ-55.03 (t, J = 9.0 Hz, CF ₃ ), −74.43 (m, 8-line, COCF ₂ ), −87.50 (m, 5 line, CF ₂ ) , −88.16 (br, 2CF ₂ group), −90.19 (q, J = 9.4 Hz, CF ₂ OCF ₃ ). Analytical calculated values for C ₁₅ H ₅ F ₁₃ O ₄ S ₂ : C, 32.15, H, 0.90, S, 11.45. Measured value: C, 32.2, H, 0.9, S, 11.6.

Example 2
5-Perfluoro (3,6-dioxadecanoyl) -2,2'-bithiophene

This compound was prepared as in Example 1. The reaction of BuLi (36.75 mL, 58.8 mmol) and bithiophene (9.75 g, 58.6 mmol) in cold THF (250 mL, −70 ° C.) was stirred for 30 minutes, after which C ₄ F ₉ OC ₂ F ₄ OCF ₂ CO ₂ Me (30.2 g, 65.7 mmol) and BF ₃ OEt ₂ (9.0 mL, 71 mmol) were added sequentially.

The material was purified by chromatography to yield 18.7 g (54%) of yellow product. Mp (ΔH): 50-53 ° C. (45 J / g). IR: 1666 m (ν _CO ), 1504 w, 1448 m, 1309 m, 1233 s, 1202 s, 1153 s, 1081 m, 1027 m, 993 m, 851 w, 837 w, 802 m, 763 w, 752 w, 802 m, 763 w, 752 w, 721 m, 710 m, 654 w, 616 w, 532 w, 460 wcm ⁻¹ . ¹ H NMR: δ 7.20 (dd, J = 5.17 Hz, 3.8 Hz, 5′-H), 7.53 (d, J = 4 Hz, 3-H), 7.64 (dd, J = 4 Hz) 1 Hz, 4′-H), 7.69 (dd, J = 5.1 Hz, 1.1 Hz, 3′-H), 7.98 (dt, J = 4.2 Hz, 1.6 Hz, 4-H ). ¹⁹ F NMR: δ-74.46 (t, J = 12.2 Hz, CF ₃ ), −80.88 (br, COCF ₂ O), −83.08 (br, OCF ₂ CF ₂ O), −87 .60 ('t', J = 12.0 Hz, -OCF ₂ CF ₂ O), -88.05 ('t', J = 12.7 Hz, OCF ₂ C ₃ F ₇ ), -126.14 (m , CF ₂ CF ₂ CF ₂ CF ₃ ). Calculated for C ₁₆ H ₅ F ₁₅ O ₃ S ₂ : C, 32.33, H, 0.85, S, 10.79. Measured value: C, 32.1, H, 0.8, S, 10.9.

Example 3
5-perfluoro (2,5-dimethyl-3,6-dioxanonanoyl) -2,2'-bithiophene

This compound was prepared as in Example 1. Bithiophene (7.90 g, 47.5 mmol), BuLi (47.6 mmol), HFPO trimer carbomethoxylate (26.7 g, 52.2 mmol), and BF ₃ OEt ₂ (7.0 mL, in 250 mL cold THF) Reaction) yielded 24.8 g (81%) of product. Mp (ΔH): 37-40 ° C. 37 (J / g). IR: 1666s (ν _CO ), 1504w, 1449s, 1310s, 1233s, 1202vs, 1153s, 1081m, 1027m, 993s, 897w, 850m, 837m, 802s, 763m, 752m, 721m, 710s, 654m, 616m, 532m, 456wcm ^{− 1} . ¹ H NMR: δ 7.23 (dd, J = 4.0 Hz, 5.0 Hz, 5′-H), 7.59 (d, J = 4.4 Hz, 3-H), 7.70 (dd, J = 3.8 Hz, 1.2 Hz, 4'-H), 7.74 (dd, J = 5.2 Hz, 1.2 Hz, 3'-H), 8.16 ('t', J = 4.0 Hz) 4-H). ¹⁹ F NMR: δ-76.8 to-82.1 (m, 4FOCF ₂ CF (CF ₃ ) OCF ₂ —), −79.8 (s, 3F, CF ₂ CFCF ₃ ), −81.1 (s, 6F, COCFCF ₃ and CF ₂ CF ₃ ), −129.2 (brm, 1F, COCFCF ₃ ), −129.2 (s, 2F, OCF ₂ CF ₂ CF ₃ ), −144.6 (brm, 1F, OCF ₂ CFCF ₃ O). Numerous resonances in the ¹⁹ F NMR data are observed as pairs due to the asymmetric center of the fluorinated group. Calculated value for C ₁₇ H ₅ F ₁₇ O ₃ S ₂ : C, 31.69, H, 0.78, S, 9.95. Measured value: C, 31.3, H, 0.8, S, 9.9.

Example 4
5-Bromo-5'-perfluoro (3,6,9-trioxadecanoyl) -2,2'-bithiophene

NBS (2.50 g, 13.32 mmol) between DMF (250 mL) and 5-perfluoro (3,6,9-trioxadecanoyl) -2,2′-bithiophene (6.22 g, 11.1 mmol). Added to the stirred mixture and covered with aluminum foil. The solution was stirred overnight, poured into 500 mL brine and extracted with Et ₂ O (500 mL) and hexane (250 mL). The yellow extract was separated, washed with 100 mL brine, 100 mL water, dried over MgSO ₄ and filtered.

After the filtrate was concentrated, it was cooled at -15 ° C. overnight resulting in 5.32 g (75%) of a bright yellow product. Mp (ΔH): 78-81 ° C. (47 J / g). IR: 1677 s (ν _CO ), 1509 w, 1452 m, 1421 m, 1231 s, 1191 s, 1153 s, 1104 s, 1076 s, 906 m, 891 m, 861 m, 837 w, 791 m, 740 m, 714 m, 683 m, 648 w, 545 w, 523 w, 510 w, 457 wcm ^{− 1} . ¹ H NMR: δ 7.30 (d, J = 4.0 Hz, 3′-H), 7.51 (d, J = 4.0 Hz, 4-H), 7.56 (d, J = 4.3 Hz) , 3-H), 8.02 (dt, J = 4.3 Hz, 1.4 Hz, 4′-H). ¹⁹ F NMR: δ-55.03 (t, J = 9.2 Hz, CF ₃ ), −74.49 (m, COCF ₂ ), −87.49 (m, CF ₂ ), −88.15 (br ₂ CF ₂ group), - 90.19 (q, J = 8.1Hz, CF 2 OCF 3). Calculated value for C ₁₅ H ₄ BrF ₁₃ O ₄ S ₂ : C, 28.19, H, 0.63, S, 10.03. Actual value: C, 28.2, H, 0.4, S, 10.1.

Example 5
5-Bromo-5'-perfluoro (3,6-dioxadecanoyl) -2,2'-bithiophene

NBS (6.70 g, 37.6 mmol) was placed in a DMF solution (200 mL) of 5-perfluoro (3,6-dioxadecanoyl) -2,2′-bithiophene (17.20 g, 28.94 mmol) and a foil. And stirred overnight. The orange crystals of the product are the solution. Precipitate from Et ₂ O (200 mL) and brine (200 mL) was added to the reaction and the solution was washed in a separatory funnel. The organic layer was separated and washed with 3 × 200 mL brine.

The organic layer was dried over MgSO ₄ , filtered, and volatile material was removed under reduced pressure to yield 18.63 g (96%) of yellow product. The crude product was cleaned by NMR spectroscopy and used directly in further reactions. Mp (ΔH): 86-89 ° C. (49 J / g), endothermic transition at 82 ° C. was present only in the first scan. IR: 1671s, 1508w, 1446s, 1420w, 1337w, 1312m, 1290w, 1219s, 1192s, 1144s, 1114m, 1082m, 975w, 954w, 901w, 891w, 860w, 821w, 788m, 736w, 714w, 693w, 684w, 649w 597w, 543w, 509w, 457w, 409wcm ⁻¹ . ¹ H NMR: δ 7.30 (d, J = 4.0 Hz, 3′-H), 7.51 (d, J = 4.0 Hz, 4-H), 7.56 (d, J = 4.3 Hz) , 3-H), 8.02 (dt, J = 4.3 Hz, 1.6 Hz, 4′H). ¹⁹ F NMR: δ-74.20 (t, J = 12 Hz, CF ₃ ), −80.76 (m, COCF ₂ O), −82.99 (m, OCF ₂ CF ₂ O), −87.52 _{(m, OCF 2 CF 2 O} ), - 87.97, (m, OCF 2 C 3 F 7), - 126.09 (brm, OCF 2 C 2 F 4 CF 3).

Example 6
5-Bromo-5'-perfluoro (2,5-dimethyl-3,6-dioxanonanoyl) -2,2'-bithiophene

This compound was prepared using the same procedure as used in Example 5, yielding 16.1 g (94%) of a yellow product. Mp (ΔH): 51-55 ° C. (34 J / g). IR: 1661s (ν _CO ), 1505w, 1448s, 1421m, 1299s, 1237vs, 1203s, 1149s, 1081s, 1029s, 994s, 884m, 835m, 814m, 790s, 752w, 743w, 723m, 705m, 651m, 615m, 532m, 458 mcm ^-1 . ₁ H NMR: δ 7.30 (d, J = 3.8 Hz, 3′-H), 7.53 (d, J = 4.0 Hz, 4-H), 7.57 (d, J = 4, 4 Hz) , 3-H), 8.15 ('t', J = 4.0 Hz, 4'-H). ^{19 F NMR: δ-76.7~-} 82.1 (m, 4F, OCF2), - 79.4 (s, 3F, CF 3), - 81.1 (s, 6F, CF 3), - 129 .0 (m, 1F, CF), -129.2 (m, 2F, CF ₂ CF ₂ CF ₃ ), -144.7 (m, 1F, CF). ^{In the 19} F data, multiple resonances are observed as pairs due to the two asymmetric centers of the fluorinated end groups. Calculated value of C ₁₇ H ₄ BrF ₁₇ O ₃ S ₂ : C, 28.23, H, 0.56, S, 8.87. Actual value: 28.6, H, 1.1, 9.1.

Example 7
2-Bromo-5-perfluoro (3,6-dioxadecanoyl) -thiophene

BuLi (3.7 mL, 9.3 mmol) was added dropwise to a cold (−70 ° C.) mixture of THF (40 mL) and 2,5-dibromothiophene (1.0 mL, 8.9 mmol). After 40 minutes at -70 ° C., C ₄ F ₉ OC ₂ F ₄ OCF ₂ CO ₂ Me (4.1 g, 8.9 mmol) and BF ₃ OEt ₂ (1.3 mL, 10.3 mmol) were added continuously. The clear colorless mixture turned light yellow. After stirring overnight, volatile materials were removed under reduced pressure.

The remaining liquid was extracted with 100 mL ether, washed with 2 × 100 mL brine, dried over MgSO ₄ and stripped into a clear orange liquid. Purification by column chromatography on silica gel yielded a yellow liquid that was dried under vacuum to yield 3.80 g (73%). A larger scale preparation (71 g theoretical yield) yielded 37.8 g (53%) of clear product after purification by distillation (bp 55-56 ° C., 0.1 mm Torr), 7.7 g precut Was collected from 50-55 ° C., which was about 63% product / 37% C ₄ H ₃ SCOR _f , 1.1 g postcut was 91% product and 9% C ₄ HBr _2. SCOR _f . IR (neat, KBr plate): 1701 cm ₋₁ (s, ν _CO ). ¹ H NMR: δ 7.52 (d, J = 4.4 Hz, 3-H), 7.91 (dt, J = 4.4, 1.4 Hz, 4-H). ¹⁹ F NMR: δ-74.79 (m, CF ₃ ), −80.87 (m, COCF ₂ O), −83.07 (m, OCF ₂ CF ₂ O), −87.61 (m, OCF ₂ CF ₂ O), −88.05 (m, OCF ₂ C ₃ F ₇ ), −126.1 (m, CF ₂ CF ₂ CF ₂ CF ₃ ).

Example 8
2-Perfluoro (3,6-dioxadecanoyl) -thiophene

BuLi (7.8 mL, 12.5 mmol) was added to a cold (−65 ° C.) mixture of THF (50 mL) and thiophene (1.0 mL, 12.5 mmol). The clear colorless solution was warmed to room temperature, cooled to −65 ° C., C ₄ F ₉ OC ₂ F ₄ OCF ₂ CO ₂ Me (5.84 g, 12.7 mmol) and BF ₃ (OEt ₂ ) (1 .9 mL, 15 mmol) was added continuously. This yellow solution was stirred at low temperature for 2 hours and then mixed with 2 mL of saturated NH ₄ Cl (aq). Volatile material was removed under reduced pressure and the residue was extracted with 50 mL hexane.

The solution was filtered, dried over MgSO ₄ , filtered again and stripped to yield 5.53 g (86%) of a clear orange liquid that was clean by NMR spectroscopy. IR: 1700 cm ⁻¹ (s, ν _CO ). ¹ H NMR: δ 7.41 (dd, J = 6.0 Hz, 4.0 Hz, 5-H), 8.08 (m, 3-H), 8.33 (dd, J = 4.9 Hz, 1. 1 Hz, 4-H). ¹⁹ F NMR: δ-74.93 (m, CF ₃ ), −80.91 (m, COCF ₂ O), −83.12 (m, OCF ₂ CF ₂ O), −87.67 (m, OCF ₂ CF ₂ O), −88.11 (m, OCF ₂ C ₃ F ₇ ), −126.18 (m, CF ₂ CF ₂ CF ₂ CF ₃ ).

Example 9
5-perfluoro (3,6,9-trioxadecanoyl) -2,2 ′: 5 ′, 2 ″ -terthiophene

Under nitrogen, the vessel was charged with 2,2 ′: 5 ′, 2 ″ -terthiophene (878 mg, 3.53 mmol) and anhydrous THF (75 mL). The solution was cooled to −78 ° C. and ⁿ BuLi (2.2 mL, 3.5 mmol) was added slowly by syringe. The mixture was stirred at low temperature for 30 minutes, then methyl 3,6,9-trioxadecanoate (1.0 mL, 3.8 mmol, 1.1 eq) and BF ₃ OEt ₂ (0.54 mL, 4.3 mmol, 1.2 eq) was added continuously. After an additional 90 minutes at -78 ° C., saturated NH ₄ Cl (aq) (20 mL) was added and the mixture was warmed to ambient temperature and further diluted with ether (100 mL) and water (50 mL). The aqueous phase was separated and the yellow-green organic phase was washed with 2 × 100 mL brine, dried over MgSO ₄ and filtered.

Analysis by TLC (SiO ₂ on glass) with 5% EtOAc / residue hexane showed the main reaction product with R _f = 0.45. The organic solution was concentrated, adsorbed onto silica gel and purified by column chromatography (silica gel / hexane, 1.25 in × 10 in) using hexane eluent to yield 1.03 g (45%) of a bright orange product Brought about. ¹ H NMR: d 7.15 (dd, J = 5.2 Hz, 3.6 Hz), 7.37 (d, J = 4.0 Hz), 7.44 (dd, J = 3.6 Hz, 1.2 Hz) 7.55 (dd, J = 5.2 Hz, 1.2 Hz), 7.59 (d, J = 4.0 Hz), 7.65 (d, J = 4.0 Hz), 8.02 (dt, ³ J _HH = 4.0 Hz, ⁵ J _HF = 1.6 Hz). ¹⁹ F NMR: d-54.9 (t, J = 9.4 Hz, CF ₃ ), −74.3 (m, COCF ₂ ), −87.4 (m, CF ₂ ), −88.1 (br , 2CF ₂ - group), - 90.1 (q, J = 9.4Hz, CF 2 OCF 3).

Example 10
Synthesis of 5,5 ′ ″-bis [perfluoro (3,6-dioxadecanoyl)]-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″-quaterthiophene

Under a nitrogen atmosphere, continuously add 2-bromo-5-perfluoro (3,6-dioxadecanoyl) thiophene (3.24 g, 5.48 mmol), dry DMF (30 mL), 5,5′-bis in a container. (Tri-n-butylstannyl) -2,2′-bithiophene (2.04 g, 2.74 mmol) and Pd (PPh ₃ ) ₄ (63 mg, 0.055 mmol) were added. The mixture was bubbled with nitrogen for 20 minutes and then stirred at 85 ° C. overnight. The reaction mixture was transferred to a mixture of EtOAc (100 mL) and CH ₂ Cl ₂ (100 mL), stirred, and then poured into a 10-20 μm glass filter frit to isolate the product. The red solid was washed on the frit with methanol (100 mL) and air dried overnight to yield 2.28 g (70%).

The material used in OTFT was sublimed at least twice. In a typical experiment, 1.01 g was loaded into a continuous sublimation system. P = 3 × 10 ⁻⁶ Torr, the source region was raised to 240 ° C. and the product region was 180 ° C. The product was melted into the source at this point but was not mobile. The source and product regions were raised to 280 ° C. and 220 ° C., respectively, and sublimation was performed in 30 minutes. Only a very small amount of film remained in the source. 884 mg (87% input) was isolated from the product area. TGA: 1% wt loss at 271 ° C., 5% wt loss at 285 ° C., no residue at 988 ° C. DSC (20 ° C./min): 185 ° C. (−71 J / g), reversible melting point. MALDI-TOF mass spectrometry contains an abundant peak at m / z 11861200 (M ⁺ ) and peaks at M + 1 (76%), M + 2 (55%), M + 3 (22%), and M + 4 (8%) Molecular ion isotope clusters are shown.

Example 11
5,5 ″ ″-bis [perfluoro (3,6,9-trioxadecanoyl)]-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″: 5 ′ ″ , 2 ''''-Synthesis of quinkethiophene

Under nitrogen, Pd (PPh ₃ ) ₄ (65 mg, 0.056 mmol, 0.5 mol% / conjugate site), 5-bromo-5′-perfluoro (3,6,9-trioxadecanoyl)- 2,2′-bithiophene (3.54 g, 5.54 mmol), DMF (40 mL), and 5,5′-bis (tri-n-butylstannyl) thiophene (1.83 g, 2.76 mmol) were added. . The mixture was bubbled with nitrogen for 20 minutes and then stirred at 90 ° C. for 20 hours. The red mixture was cooled to room temperature and the solid was collected on a 10-20 μm filter frit, washed with 2 × 60 mL isopropanol, and air dried overnight to give 2.34 g (71%) of crude red purple The product resulted.

The material was continuously sublimed at P = 4 × 10 ⁻⁶ torr at a source temperature of 315 ° C. (the material was melted) and a product collection area of 180 ° C. to obtain 2.23 g (67%) of red-purple The product resulted. The product was sublimated once more before making the device. ¹ H NMR (600 MHz, d ₄ -o-dichlorobenzene, 100 ° C.): Due to the high temperature used during data collection (the material has a very low solubility), a broad singlet of 5 chemicals Observed for each proton not equivalent to d 7.79, 7.16, 7.10, 7.06, 7.04. ¹⁹ F NMR (564 MHz, d ₄ -o-dichlorobenzene, 100 ° C.): Data were the same as those described in Preparative Examples 1 and 4. MALDI-TOF mass spectrometry contains an abundant peak at m / z 1200 (M ⁺ ) and peaks at M + 1 (65%), M + 2 (45%), M + 3 (20%), and M + 4 (10%) Molecular ion isotope clusters are shown.

Example 12
5,5 ′ ″ ″-bis [perfluoro (2,5-dimethyl-3,6-
Dioxanonanoyl)]-2, 2 ': 5', 2 ": 5", 2 '": 5'", 2 "": 5 "", 2 "" Synthesis of '-sexithiophene

Under a nitrogen atmosphere, continuously put 5-bromo-5′-perfluoro (2,5-dimethyl-3,6-dioxanonanoyl) -2,2′-bithiophene (3.49 g, 4.83 mmol) in a container. , Dry DMF (75 mL), 5,5′-bis (tri-n-butylstannyl) -2,2′-bithiophene (1.80 g, 2.42 mmol), and Pd (PPh ₃ ) ₄ (30 mg, 0 .026 mmol). The mixture was bubbled with nitrogen for 30 minutes and then stirred at 100 ° C. for 5 hours. A red ppt formed in the mixture. The solution was cooled to room temperature and then further cooled in an ice water bath. The solution was poured into a 10-20 μm glass filter frit and the red solid was washed with methanol (100 mL), hexane (100 mL) and then air dried overnight. Yield: 2.79 g, 80%. The material used in OTFT was sublimed at least twice.

In one experiment, 994 mg of material was loaded into a continuous sublimation system and sublimed in the product region with P = 2 × 10 ⁻⁶ Torr, source temperature 320 ° C., and 240 ° C. The material melted in the source before volatilizing and moving to the product area. 918 mg (92% of the input) was isolated.

IR spectroscopy (KBr pellets, v _CO = 1663 cm ₋₁ ), combustion analysis, and high resolution mass spectrometry were consistent with the proposed structure. ¹ H NMR (400 MHz, d ₆ -acetone, internal TMS is based on 0 pm): δ 8.18 (m, 1H), 7.71 (d, J = 4 Hz, 1H), 7.62 (d, J = 4 Hz, 1H), 7.44 ('d', J = 4 Hz, 2H), 7.38 (d, J = 4 Hz, 1H). TGA: 1% wt loss at 365 ° C., 5% wt loss at 381 ° C., no residue at 988 ° C. DSC (20 ° C./min): 150 ° C. (−17 J / g), 218 ° C. (−2 J / g), reversible melting point. ^{The 19} F NMR data was substantially the same as that of Preparative Examples 3 and 6. Numerous resonances in the ¹⁹ F data are observed as pairs due to the two asymmetric centers of the fluorinated end groups. IR (KBr): 1663 s (ν _CO ), 1436 s, 1236 vs, 1202 s, 1151 s, 1079 m, 1029 m, 994 s, 981 m, 790 mcm ⁻¹ .

  High performance liquid chromatography (HPLC) of the product in THF was performed using an Agilent Model LC / MSD quadrupole mass spectrometer equipped with an atmospheric pressure chemical ionization (APCI) source. The sample solution was injected into a mobile phase of THF / water (1: 1) and data was collected for a mass range of 1,000 to 2,000 daltons at a scan rate of about 2 scans / second. The only significant ions in the spectrum were found at m / z 1451, m / z 1452, and m / z 1453, corresponding to a compound with a molecular weight of 1,450, consistent with the proposed product.

Example 13
On the back side preparation and testing of an OTFT having a Al ₂ O ₃ sputtered in 1.5kÅ aluminum and the front side of 5KA, Silicon Valley Microelectronics (Silicon Valley Microelectronics) (San Jose, California (San Jose, CA)) OTFTs were fabricated on doped silicon <100> wafers obtained from A 0.1 wt% solution of poly (α-methylstyrene) (average Mw about 100,300 by GPC) was applied to the surface from toluene by spin coating (500 rpm for 20 seconds, then 2000 rpm for 40 seconds). The sample was placed in a 110 ° C. oven and baked for 30 minutes after spin coating. The resulting polymer layer was approximately 100 mm as measured by single beam elliptical polarization. A thin film of perfluoroacylthiophene described above (approximately 600 Å) was deposited by physical vapor deposition at a pressure of ≦ 5 × 10 ⁻⁶ Torr. The sample was then moved to another vacuum chamber where gold source-drain contacts (600 Å) were deposited on the organic film through a polymer shadow mask.

FIG. 2 shows 5,5 ′ ″-bis [perfluoro (3,6-dioxadecanoyl)]-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ ″ − in the semiconductor layer. FIG. 6 shows characterization data (I _D ^1/2 vs. V _G curve calculated from I _D -V _G transfer curve) of a thin film transistor (Example 10) fabricated with quarterthiophene. The data is in saturation, and in each case the drain voltage (V _D ) is equal to the maximum gate voltage (V _G ). The device was measured under a vacuum of ^10-6 torr. Data is plotted for both negative to positive (-/ +) and positive to negative (+/-) scans of the gate voltage. Saturated electron mobility (μ _e ) is calculated from the standard metal oxide semiconductor field effect transistor (MOSFET) equation (SE, SM (Sze, SM), Physics of Semiconductor Devices, 2nd edition, John Wiley & Sons (John Wiley & Sons): New York (New York), was calculated from the slope of the I _D ^1/2 vs. V _G trace at a point indicated using a see 1981). For the device shown in FIG. 2, the mobility is 1.8 cm ² / Vs for the positive V _G scanned from negative, the negative scan positive was 2.6 cm ² / Vs. Additional data for other devices on the same wafer is shown in Table 1.

FIG. 3 shows 5,5 ″ ″-bis [perfluoro (3,6,9-trioxadecanoyl)]-2,2 ′: 5 ′, 2 ″: 5 ″, 2 ′ in the semiconductor layer. '': 5 ′ ″, 2 ″ ″ — I _D ^1/2 vs. V _G curve of a thin film transistor (Example 11) produced using kinkethiophene. Devices were manufactured and tested as described above. Table 2 lists additional data for other devices on the same wafer.

  For the thin film transistor using the n-channel semiconductor oligothiophene of the present invention, the mobility value obtained is the highest recorded so far for n-channel organic semiconductor materials, and in performance with p-channel semiconductors such as pentacene. It is equivalent.

It is sectional drawing of a typical organic thin-film transistor. It is sectional drawing of a typical organic thin-film transistor. 10 is a graph of the performance of a semiconductor device using the oligothiophene semiconductor of Example 10. 10 is a graph of the performance of a semiconductor device using the oligothiophene semiconductor of Example 11.

Claims (27)

formula:

Wherein Y is a hydrogen atom, a halogen atom, an alkyl group, and an aryl group or a perfluoroether acyl group, p is at least 1, and R _f is a perfluoroether group. formula:

The compound according to claim 1, wherein each R _f is independently a perfluoroether group and n is at least 1. The compound according to claim 2, wherein each R _f is a perfluoroalkoxyalkylene group or a perfluoropolyether group. Each R _f has the formula:
^{_{R f 1 -O- (R f 2}} ) x - (R f 3) -
Wherein R ¹ _f represents a perfluoroalkyl group, and R _f ² represents from a perfluoroalkyleneoxy group having 1 to 4 perfluorinated carbon atoms or a mixture of such perfluoroalkyleneoxy groups. consisting represents perfluorinated polyalkyleneoxy group, R _f ³ represents a perfluoroalkylene group, x is from 0 to 25, a compound according to claim 2. Each R _f ² is _{independently, -CF 2 -CF 2 -O -,} - CF (CF 3) -CF 2 -O -, - CF 2 -CF (CF 3) -O -, - CF 2 -CF 2 _{-CF 2 -O -, - CF 2} -O -, - CF (CF 3) -O-, and -CF ₂ -CF ₂ -CF ₂ are selected from -CF ₂ -O-, claim 4 Compound. Each R _f ³ is _{independently, -CF 2 -CF 2 -, -} CF (CF 3) -CF 2 -, - CF 2 -CF (CF 3) -, - CF 2 -CF 2 -CF 2 -, - _{CF 2 -O -, - CF (} CF 3) -, and _{-CF 2 -CF 2 -CF 2 -CF 2} - is selected from a compound according to claim 4.   The compound according to claim 4, wherein x is 1-4. Each R _f is ^{_{R f 1 -O- [CF (CF}} 3) -CF 2 O] x -CF (CF 3) - and is, in the formula, R _f ¹ is a perfluoroalkyl group, x is from at least 1 The compound of claim 2, wherein R _f ¹ represents a perfluorinated alkyl group having 1 to 6 carbon atoms The compound of claim 4.   The compound according to claim 2, wherein n is 3-6. R _f is

The compound of claim 2, wherein a. Bis-trialkylstannyl (oligo) thiophene b. 2-halo-5-perfluoroether acylthiophene or 5-halo-5′-perfluoroether acyl oligothiophene;
c. A process for preparing a compound according to claim 2 comprising reacting in the presence of a palladium catalyst. formula

A bis-trialkylstannylthiophene wherein each R is selected from a lower alkyl group

2-halo-5-perfluoroether acylthiophene [wherein m is 1 to 3 and R _f is a perfluoroether group]
The process according to claim 12, comprising the step of c) reacting in the presence of a palladium catalyst. formula

The compound of
formula:

14. A process according to claim 13, which is prepared by brominating a compound of the following: each m is 2-3 and _Rf is a perfluoroether group. formula

In the presence of a Lewis acid catalyst:

Is treated with an alkyllithium compound, after which the thienyl anion is converted to a perfluorinated compound of the formula R _f —CO—OR where R _f is a perfluorinated ether group and R is an alkyl group. 15. The method of claim 14, wherein the method is prepared by quenching with a fluorinated ether ester, wherein m is 1-3.   The method of claim 15, wherein the Lewis acid catalyst is boron trifluoride etherate. formula

In the presence of a Lewis acid catalyst, 2,5-dihalothiophene is treated with an alkyllithium compound, after which the thienyl anion is converted to the formula R _f —CO—OR where R _f is a perfluorinated ether. 15. The method of claim 14, wherein the method is prepared by quenching with a perfluorinated ether ester of the group wherein R is an alkyl group, wherein m is 1-3.   An n-channel semiconductor device, wherein the semiconductor layer comprises a compound of the formula according to any one of claims 1-11.   The semiconductor device of claim 18, further comprising a conductive layer, a dielectric layer, or a combination thereof adjacent to the semiconductor layer.   The semiconductor device of claim 18, wherein the semiconductor device comprises an organic thin film transistor.   The semiconductor device according to claim 18, further comprising a source electrode and a drain electrode in contact with the semiconductor layer, wherein the source electrode and the drain electrode are separated by a region of a surface of the semiconductor layer.   19. The semiconductor device of claim 18, further comprising a conductive layer adjacent to one surface of the semiconductive layer and a dielectric layer adjacent to an opposite surface of the semiconductive layer. Providing a gate electrode;
Depositing a gate dielectric layer on the surface of the gate electrode;
Forming a semiconductor layer comprising a compound of the formula according to any one of claims 1 to 11 adjacent to the gate dielectric layer on the opposite side of the gate electrode. .   Arranging a source electrode and a drain electrode on a surface of the semiconductor layer opposite to the gate dielectric layer, wherein the source electrode and the drain electrode are separated from each other in a region on the surface of the semiconductor layer; 24. The method of claim 23, further comprising:   24. The method of claim 23, further comprising depositing a surface treatment layer between the gate dielectric layer and the semiconductor layer. Providing a gate electrode;
Depositing a gate dielectric layer on the surface of the gate electrode;
Disposing a source electrode and a drain electrode adjacent to the gate dielectric layer opposite the gate electrode, wherein the source electrode and the drain electrode are separated by a region above the gate dielectric layer;
A semiconductor layer containing the compound according to claim 1 on the surface of the source electrode, on the surface of the drain electrode, and in a region between the source electrode and the drain electrode. A method of manufacturing an organic thin film transistor.   The Schottky diode comprising the device of claim 18, wherein a first metal is in contact with the first surface of the semiconductor and a second metal is in contact with the second surface of the semiconductor layer.

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