WO2012033075A1 - Matériau semi-conducteur organique, transistor à effet de champ, et procédé de fabrication associé - Google Patents

Matériau semi-conducteur organique, transistor à effet de champ, et procédé de fabrication associé Download PDF

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WO2012033075A1
WO2012033075A1 PCT/JP2011/070218 JP2011070218W WO2012033075A1 WO 2012033075 A1 WO2012033075 A1 WO 2012033075A1 JP 2011070218 W JP2011070218 W JP 2011070218W WO 2012033075 A1 WO2012033075 A1 WO 2012033075A1
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effect transistor
semiconductor material
field effect
organic semiconductor
organic
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PCT/JP2011/070218
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English (en)
Japanese (ja)
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雄一 貞光
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日本化薬株式会社
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Priority to KR1020127020887A priority Critical patent/KR101462526B1/ko
Priority to CN201180010025.4A priority patent/CN102770979B/zh
Priority to JP2012532980A priority patent/JP5913108B2/ja
Publication of WO2012033075A1 publication Critical patent/WO2012033075A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0083—Solutions of dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present invention relates to a field effect transistor including an organic thin film obtained by applying or printing an organic thin film semiconductor material and drying, and a method for manufacturing the same, and an organic semiconductor material used for them. More specifically, the present invention relates to a field effect transistor obtained from a semiconductor material comprising an organic heterocyclic compound and a specific additive, and a method for producing the same.
  • Field effect transistors generally have a structure in which a semiconductor material on a substrate is provided with a source electrode, a drain electrode, and a gate electrode or the like via these electrodes and an insulator layer.
  • inorganic semiconductor materials centering on silicon are used for field-effect transistors, and thin film transistors created on substrates such as glass using amorphous silicon are used for displays, etc.
  • active studies have been made on the use of an oxide semiconductor as a semiconductor material.
  • it is necessary to process the field effect transistor at a high temperature or in a vacuum.
  • films and plastics with poor heat resistance cannot be used, and expensive capital investment and production require a lot of energy, which makes the cost very high and its application range is very Is limited to.
  • field effect transistors using organic semiconductor materials that do not require high-temperature treatment during the production of field effect transistors have been actively developed. If it can be applied to organic semiconductor materials, it becomes possible to manufacture field effect transistors by a low temperature process, and the range of usable substrate materials is expanded. As a result, it becomes possible to manufacture a field effect transistor that is more flexible, lightweight, and less likely to break. In the field effect transistor manufacturing process, a large-area field effect transistor can be manufactured at a low cost by applying a solution containing an organic semiconductor material or by a printing method such as inkjet.
  • a semiconductor element using an inorganic material such as silicon is generally an oxidizing or reducing gas such as oxygen or hydrogen, or an oxidizing or reducing liquid in an organic semiconductor layer for the purpose of increasing or decreasing the carrier density in the film. It is necessary to induce a change in properties due to oxidation or reduction. This is because by adding trace elements, atomic groups, molecules, and polymers to the semiconductor layer, the carrier density in the semiconductor layer increases and decreases, and the electrical conductivity and carrier polarity (p-type-n-type conversion) are semiconductor characteristics.
  • Fermi level, etc. for example, by contacting gas such as oxygen and hydrogen, soaking in a solution containing acid or Lewis acid, halogen atoms such as iodine, or sodium, potassium, etc.
  • a treatment method using an inorganic compound that electrochemically treats metal atoms and the like, and a method of treating in advance with an electron-accepting or electron-donating organic compound are known. These treatments are performed in processes other than the formation of the semiconductor layer before and after the production of the semiconductor layer, co-evaporated by a vacuum deposition method, mixed in the atmosphere at the time of semiconductor layer production, or ions are accelerated in vacuum. In general, a technique such as collision with a semiconductor layer is used.
  • Patent Document 1 discloses a field effect transistor using an alkyl derivative of benzoseleno [3,2-b] [1] benzoselenophene and benzothieno [3,2-b] [1] benzothiophene.
  • Patent Document 2 discloses a field effect transistor using a mixed liquid of an alkyl derivative of benzothieno [3,2-b] [1] benzothiophene and a polymer compound having a specific solubility parameter.
  • Patent Document 3 discloses a field effect transistor using a material containing an alkyl derivative of benzothieno [3,2-b] [1] benzothiophene and a polymer material.
  • Patent Document 4 discloses a technique for amplifying a current value by bringing iodine or a metal into contact with a pentacene thin film.
  • Patent Document 5 discloses a technique for improving electrical conductivity by using a thin film obtained by applying and drying a solution obtained by mixing a polyacene compound and excess iodine or butyllithium.
  • Patent Document 6 discloses a technique for changing a threshold voltage by laminating a polymer semiconductor after previously applying an electron-accepting or electron-donating compound.
  • Non-Patent Document 1 discloses a field effect transistor using an alkyl derivative of benzothieno [3,2-b] [1] benzothiophene.
  • Non-Patent Document 2 discloses a field effect transistor prepared by a surface selective deposition method using an alkyl derivative of benzothieno [3,2-b] [1] benzothiophene.
  • the present invention provides an excellent field effect transistor having not only improved semiconductor characteristics such as a reduction in threshold voltage while maintaining high carrier mobility, but also has printability capable of forming a highly uniform thin film with fewer steps.
  • the purpose is to do.
  • the present inventors have obtained an organic semiconductor material obtained by mixing a specific organic heterocyclic compound and an electron-accepting material having a specific substituent as a semiconductor material in an organic solvent.
  • the field effect transistor used is formed, not only can the semiconductor characteristics such as the reduction of the threshold voltage be improved while maintaining high carrier mobility, but also the printability capable of forming a highly uniform thin film with fewer steps.
  • the present inventors have found that a practical field effect transistor can be provided, and have completed the present invention.
  • the present invention An organic semiconductor material obtained by dissolving and / or dispersing a compound represented by the following formula (1) and an electron-accepting compound having a cyano group in at least one organic solvent
  • R 1 and R 2 each independently represents an unsubstituted or halogeno-substituted C1-C36 aliphatic hydrocarbon group), About.
  • a field effect transistor is formed using an organic semiconductor material in which a compound represented by the above formula (1) and an electron-accepting compound having a cyano group are dissolved and / or dispersed in at least one organic solvent.
  • a practical field-effect transistor with excellent printability that can not only improve semiconductor characteristics such as threshold voltage reduction while maintaining high carrier mobility, but also can form highly uniform thin films with fewer steps. Can be provided.
  • the present invention relates to an organic semiconductor material in which a specific organic heterocyclic compound and an electron-accepting compound having a cyano group are dissolved and / or dispersed in at least one organic solvent, a field effect transistor using them, and a method for producing the same About.
  • R 1 and R 2 each independently represents an unsubstituted or halogeno-substituted C1-C36 aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group is a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group, preferably a linear or branched aliphatic hydrocarbon group, more preferably a linear It is an aliphatic hydrocarbon group.
  • the carbon number is usually C1-C36, preferably C2-C24, more preferably C4-C20, and still more preferably C6-C12.
  • linear or branched saturated aliphatic hydrocarbon group examples include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, iso-pentyl, t- Pentyl, sec-pentyl, n-hexyl, iso-hexyl, n-heptyl, sec-heptyl, n-octyl, n-nonyl, sec-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl,
  • cyclic saturated aliphatic hydrocarbon group examples include cyclohexyl, cyclopentyl, adamantyl, norbornyl and the like.
  • linear or branched unsaturated aliphatic hydrocarbon group examples include vinyl, aryl, eicosadienyl, 11,14-eicosadienyl, and geranyl (trans-3,7-dimethyl-2,6-octadien-1-yl).
  • Farnesyl trans, trans-3,7,11-trimethyl-2,6,10-dodecatrien-1-yl
  • 4-pentenyl 1-propynyl, 1-hexynyl, 1-octynyl, 1-decynyl, 1 -Undecynyl, 1-dodecynyl, 1-tetradecynyl, 1-hexadecynyl, 1-nonadecynyl and the like.
  • linear, branched and cyclic aliphatic hydrocarbon groups a linear or branched aliphatic hydrocarbon group is preferable, and a linear aliphatic hydrocarbon group is particularly preferable.
  • the saturated or unsaturated aliphatic hydrocarbon group includes a saturated alkyl group, an alkenyl group containing a carbon-carbon double bond, and an alkynyl group containing a carbon-carbon triple bond, more preferably an alkyl group or an alkynyl group. And more preferably an alkyl group.
  • the aliphatic hydrocarbon residue is a combination of these saturated or unsaturated aliphatic hydrocarbon groups, that is, a carbon-carbon double bond or a carbon-carbon triple bond at a site in the aliphatic hydrocarbon group. All cases are included at the same time.
  • the halogeno-substituted aliphatic hydrocarbon group means one in which any kind of halogen atom is substituted at any position on the above aliphatic hydrocarbon group.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned,
  • halogeno-substituted aliphatic hydrocarbon group examples include chloromethyl, bromomethyl, trifluoromethyl, pentafluoroethyl, n-perfluoropropyl, n-perfluorobutyl, n-perfluoropentyl, n-perfluorooctyl, and n-perfluorodecyl.
  • the compound represented by the above formula (1) can be synthesized by known methods described in, for example, Patent Document 1 and Non-Patent Document 1.
  • the purification method of the compound represented by the above formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be employed. Moreover, you may use combining these methods as needed.
  • the electron-accepting compound having a cyano group is an additive for doping an organic semiconductor material, and is not particularly limited, but includes tetracyanoquinodimethane (hereinafter abbreviated as TCNQ) or a derivative thereof, specifically, TCNQ, 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinodimethane (hereinafter abbreviated as F4-TCNQ), trifluoromethyltetracyanoquinodimethane (CF3TCNQ), 2,5-difluorotetracyanoquino Dimethane (F2TCNQ), fluorotetracyanoquinodimethane (FTCNQ), tetracyanoethylene (TCNE), 11,11,12,12-tetracyanonaphth-2,6-quinodimethane (TNAP) and Japanese published patent publication “ Quinodimethanes having a cyano group described in JP-A-2008-530773 It is preferably used. Of these, TCNQ
  • the organic semiconductor material of the present invention is formed by dissolving or dispersing at least a compound represented by the formula (1) and an electron-accepting compound having a cyano group in an organic solvent, and represented by the formula (1). Even if each of the compound and the electron-accepting compound having a cyano group is contained, one or both of the compound represented by the formula (1) and the electron-accepting compound having a cyano group are mixed. May be used.
  • the content of the electron-accepting compound having a cyano group with respect to the compound represented by the formula (1) Is usually in the range of 0.1 to 40% by mass, preferably 0.1 to 20% by mass, and more preferably 0.1 to 10% by mass. If the content exceeds 40% by mass, the characteristic value decreases due to an increase in OFF current.
  • the content is particularly preferably 10% by mass or less.
  • the organic semiconductor material of the present invention is mixed with other organic semiconductor materials and various additives as necessary in order to improve the characteristics of the field effect transistor and to impart other characteristics. You may do it.
  • additives include viscosity modifiers, surface tension modifiers, leveling agents, penetrants, rheology modifiers, alignment agents, and dispersants.
  • the content of these additives is 0 to 30% by mass, preferably 0 to 20% by mass, and more preferably 0 to 10% by mass with respect to the total amount of the organic semiconductor material of the present invention.
  • the organic semiconductor material of the present invention is obtained by dissolving or dispersing the compound represented by the formula (1) and the electron-accepting compound in a solvent to improve the adaptability of the organic semiconductor material for coating and printing processes.
  • the solvent that can be used is not particularly limited as long as the compound can form a film on the substrate.
  • an organic solvent is preferable, and a single organic solvent or a mixture of a plurality of organic solvents can be used.
  • halogeno hydrocarbon solvents such as chloroform, methylene chloride and dichloroethane
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol
  • fluorinated alcohol solvents such as octafluoropentanol and pentafluoropropanol
  • ethyl acetate Ester solvents such as butyl acetate, ethyl benzoate and diethyl carbonate
  • aromatics such as toluene, xylene, benzene, chlorobenzene, mesitylene, ethylbenzene, diethylbenzene, triethylbenzene, dichlorobenzene, chloronaphthalene, tetrahydronaphthalene, decalin and cyclohexylbenzene Hydrocarbon solvents
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobut
  • the concentration of the compound represented by the formula (1) and the electron-accepting compound varies depending on the type of the solvent and the thickness of the semiconductor layer to be produced. %, Preferably 0.01 to 20% by mass.
  • the semiconductor material of the present invention may be dissolved or dispersed in the above organic solvent, but it is preferable that the semiconductor material is dissolved as a uniform solution in order to form a more uniform thin film.
  • the field effect transistor (Field effect transistor, hereinafter sometimes abbreviated as FET) of the present invention has two electrodes, a source electrode and a drain electrode, in contact with a semiconductor layer, and a current flowing between the two electrodes is gated. It is controlled by a voltage applied to another electrode called a gate electrode through an insulator layer.
  • the field effect transistor includes the organic thin film.
  • FIG. 1 shows some aspects of the field effect transistor of the present invention, and the arrangement of each layer and electrode can be appropriately selected depending on the use of the element.
  • the same numbers are assigned to the same names.
  • the substrate 1 needs to be able to hold each layer formed thereon without peeling off.
  • insulating material such as resin plate, resin film, paper, glass, quartz, ceramic, etc .; formed by coating an insulating layer on a conductive substrate such as metal or alloy; and various combinations of resin and inorganic material Materials can be used.
  • the resin film generally used includes, for example, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, polyetherimide and the like.
  • the thickness of the substrate is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 3 mm.
  • a conductive material is used for the source electrode 2, the drain electrode 3, and the gate electrode 6.
  • metals such as platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, barium, lithium, potassium, sodium, etc.
  • Conductive polymer compounds and semiconductors may be doped.
  • Examples of the dopant include acids such as hydrochloric acid, sulfuric acid and sulfonic acid; Lewis acids such as PF 5 , AsF 5 and FeCl 3 ; iodine and the like
  • a halogen atom, a metal atom such as lithium, sodium, potassium, or the like is used.
  • a method of doping with molybdenum oxide or a metal may be treated with thiol or the like.
  • a conductive composite material in which metal particles such as carbon black, gold, platinum, silver, and copper are dispersed in the above material is also used.
  • a wiring is connected to each electrode 2, 3, 6, and the wiring is also made of substantially the same material as the electrode.
  • the film thickness of the source electrode 2, drain electrode 3, and gate electrode 6 varies depending on the material, but is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 10 ⁇ m, more preferably 1 nm to 5 ⁇ m.
  • the gate insulator layer 5 is an insulating material such as polyparaxylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinylphenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, Polymers such as polysulfone, epoxy resin, phenol resin, and copolymers thereof; oxides such as silicon dioxide, aluminum oxide, titanium oxide, and tantalum oxide; ferroelectric oxides such as SrTiO 3 and BaTiO 3 ; silicon nitride And nitrides such as aluminum nitride; sulfides; dielectrics such as fluorides; or polymers in which particles of these dielectrics are dispersed.
  • the film thickness of the gate insulator layer 5 varies depending on the material, but is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 50 ⁇ m, more preferably 5 nm to 10 ⁇ m.
  • the organic semiconductor material contained in the semiconductor layer 4 is composed of at least the above-described formula (1) and an electron-accepting compound having a cyano group, and several kinds of each of these derivatives may be mixed and used. On the other hand, it is necessary to contain 50% by mass or more, preferably 80% by mass or more, more preferably 95% by mass or more. At this time, in order to improve the characteristics of the field effect transistor and to provide other characteristics, other organic semiconductor materials and various additives may be mixed as necessary.
  • the semiconductor layer 4 may be composed of a plurality of layers. The thickness of the semiconductor layer 4 is preferably as thin as possible without losing necessary functions.
  • the film thickness of the semiconductor layer for exhibiting the functions required by the semiconductor is usually 0.1 nm to 10 ⁇ m, preferably 0.5 nm to 5 ⁇ m, more preferably 1 nm to 3 ⁇ m.
  • membrane which consists of various resins, such as acrylic resins, such as an epoxy resin and a polymethylmethacrylate, a polyurethane, a polyimide, polyvinyl alcohol, a fluororesin, polyolefin, silicon oxide, aluminum oxide
  • a protective material developed for organic EL displays can also be used.
  • the protective layer can have any thickness depending on the purpose, but is usually 100 nm to 1 mm. Forming the protective layer has the advantage of stabilizing the electrical characteristics, such as reducing the influence of outside air such as humidity and increasing the ON / OFF ratio of the device.
  • the field effect transistor of the present invention is a substrate surface cleaning treatment, such as acid treatment with hydrochloric acid, sulfuric acid, acetic acid, etc., alkali treatment with sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc., ozone treatment, fluorination treatment, oxygen Excellent print suitability by performing plasma processing such as argon and argon, Langmuir / Blodgett film forming process, other insulator and semiconductor thin film forming process, mechanical process, corona discharge and other electrical processes
  • plasma processing such as argon and argon, Langmuir / Blodgett film forming process, other insulator and semiconductor thin film forming process, mechanical process, corona discharge and other electrical processes
  • other layers may be provided between the above layers or on the outer surface of the semiconductor element as necessary.
  • an electrode By improving the properties such as carrier mobility by reducing trap sites on the interface and insulator layer, and adjusting the hydrophilic / hydrophobic balance of the substrate surface, It is possible to further improve the uniformity of the device by improving the paintability to the substrate.
  • a substrate treatment include a silane coupling treatment with phenylethyltrichlorosilane and the like, a thiol treatment, a rubbing treatment using fibers, and the like.
  • a vacuum deposition method for example, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method and the like can be used as appropriate. preferable.
  • the field effect transistor of the present invention is produced by providing necessary electrodes and various layers on the substrate 1 (see FIG. 1). It is also possible to perform the above-described surface treatment on this substrate.
  • the thickness of the substrate 1 is preferably as thin as possible without interfering with necessary functions. Although it varies depending on the material, it is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 3 mm.
  • a source electrode 2 and a drain electrode 3 are formed on the substrate 1 using the above electrode material or the like.
  • the material of the source electrode 2 and the drain electrode 3 may be the same or different.
  • Examples of the method for forming the electrode include a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, and a sol-gel method. It is preferable to perform patterning as necessary so as to obtain a desired shape during or after film formation.
  • Various methods can be used as the patterning method, and examples thereof include a photolithography method in which patterning and etching of a photoresist are combined.
  • the film thickness of the source electrode 2 and the drain electrode 3 varies depending on the material, but is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 10 ⁇ m, more preferably 1 nm to 5 ⁇ m.
  • the film thickness of the source electrode 2 and the drain electrode 3 may be the same or different.
  • the semiconductor layer is an organic thin film formed by a coating printing process using the organic semiconductor material described above.
  • an organic thin film can be referred to as an organic semiconductor thin film.
  • the coating printing process was obtained by dissolving or dispersing in advance an organic semiconductor material having solvent solubility, for example, a compound represented by the above formula (1) of the present invention and an electron-accepting compound having a cyano group in an organic solvent. It refers to a method for manufacturing a semiconductor layer, in which a semiconductor layer having excellent semiconductor characteristics can be easily formed by applying or printing a solution of an organic semiconductor material and drying.
  • the manufacturing method by coating or printing that is, the coating printing process is industrially advantageous because a large area field effect transistor can be manufactured at a low cost without the need for making the environment during device manufacturing vacuum or high temperature.
  • the methods for manufacturing a semiconductor layer it is particularly preferable.
  • the organic semiconductor material of the present invention is prepared by dissolving or dispersing a compound represented by the above formula (1) and an electron-accepting compound having a cyano group in a solvent.
  • the compound represented by the formula (1) and the electron-accepting compound having a cyano group may be dissolved or dispersed at the same time, or may be prepared by individually dissolving or dispersing in a solvent and then mixing.
  • the concentration of the compound represented by the formula (1) and the electron-accepting compound having a cyano group in the organic semiconductor material of the present invention is Depending on the type of solvent and the thickness of the semiconductor layer to be produced, it is usually 0.001 to 50% by mass, preferably 0.01 to 20% by mass, based on the total amount of the solution.
  • the field effect transistor characteristics, and other characteristics, additives and other types of semiconductor materials can be mixed.
  • the organic semiconductor material In order to prepare the organic semiconductor material, it is necessary to dissolve or disperse the compound represented by the above formula (1) and the electron-accepting compound having a cyano group in a solvent. Good. Further, the obtained organic semiconductor material may be filtered using a filter to remove impurities and the like. When this is coated on a substrate, the film-forming property of the semiconductor layer is improved and can be suitably used.
  • the organic semiconductor material prepared as described above is applied to the substrate (exposed portions of the source electrode and the drain electrode).
  • Coating methods such as casting, spin coating, dip coating, blade coating, wire bar coating, spray coating, etc .; inkjet printing, screen printing, offset printing, letterpress printing, gravure printing, etc .; microcontact printing method
  • a soft lithography method such as the above, and a method combining a plurality of these methods can be employed.
  • the Langmuir-Blodgett method in which a monomolecular film of a semiconductor layer produced by dropping the above organic semiconductor material onto the water surface is transferred to a substrate and laminated, a material in a liquid crystal or melt state It is also possible to adopt a method of sandwiching between two substrates and introducing them between the substrates by capillary action.
  • the thickness of the semiconductor layer manufactured by these methods is preferably thin as long as the function is not impaired. As the film thickness increases, the leakage current may increase.
  • the film thickness of the semiconductor layer is the same as that of the semiconductor layer 4 described above.
  • the semiconductor layer thus manufactured can improve the semiconductor characteristics by post-processing. For example, by heat-treating the substrate after forming the semiconductor layer, the distortion in the film generated during film formation is alleviated, and the alignment and orientation in the film can be controlled, so that the semiconductor characteristics can be improved and stabilized. And pinholes can be reduced.
  • the heat treatment may be performed at any stage as long as the semiconductor layer is formed.
  • the temperature of the heat treatment is not particularly limited, but is usually room temperature to 150 ° C., preferably 40 to 120 ° C., more preferably 45 to 100 ° C.
  • the heat treatment time is not particularly limited, but is usually 1 second to 24 hours, preferably 1 minute to 1 hour.
  • the atmosphere during the heat treatment may be in the air, but may be an inert atmosphere such as nitrogen or argon.
  • a gate insulator layer 5 is formed on the semiconductor layer 4 using the above insulator material or the like (see FIG. 1).
  • Examples of the method for forming the gate insulator layer 5 include spin coating, spray coating, dip coating, casting, bar coating, blade coating, and the like; screen printing, offset printing, inkjet printing, and the like; vacuum deposition, molecular Examples thereof include a line epitaxial growth method, an ion cluster beam method, an ion plating method, a sputtering method, an atmospheric pressure plasma method, a dry process method such as a CVD method, and the like. Further, a method of forming an oxide film on the metal surface such as a sol-gel method or anodized on aluminum can also be used.
  • the thickness of the gate insulator layer 5 is preferably as thin as possible without impairing its function, and is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 50 ⁇ m, more preferably 5 nm to 10 ⁇ m.
  • the gate electrode 6 can be formed by the same method as the method for forming the source electrode 2 and the drain electrode 3.
  • the film thickness varies depending on the material, but is usually 1 nm to 100 ⁇ m, preferably 0.5 nm to 10 ⁇ m, more preferably 1 nm to 5 ⁇ m.
  • the protective layer 7 may have any thickness depending on the purpose, but is usually 100 nm to 1 mm.
  • Various methods can be employed to form the protective layer.
  • the protective layer is made of a resin, for example, a method of drying a resin-containing solution after application to form a resin film, or applying or depositing a resin monomer The method of superposing
  • the protective layer is made of an inorganic material, for example, a forming method in a vacuum process such as a sputtering method or a vapor deposition method or a forming method in a coating printing process such as a sol-gel method can be used.
  • a protective layer can be provided between the layers as needed in addition to the surface of the semiconductor layer. The installed protective layer may help to stabilize the electrical characteristics of the field effect transistor.
  • the operating characteristics of a field effect transistor are determined by the carrier mobility of a semiconductor layer, conductivity, capacitance of an insulating layer, element configuration (distance and width between source and drain electrodes, film thickness of the insulating layer, etc.), and the like.
  • the organic material used for the semiconductor layer of the field effect transistor requires high carrier mobility, but the compound represented by the above formula (1) of the present invention that can be manufactured at low cost is high in carrier mobility as an organic semiconductor material. Express degree.
  • the field effect transistor of the present invention can be manufactured by a relatively low temperature process, and a flexible material such as a plastic plate or a plastic film that cannot be used under high temperature conditions can be used as the substrate.
  • the display include a liquid crystal display, a polymer dispersion type liquid crystal display, an electrophoretic display, an EL display, an electrochromic display, a particle rotation type display, and the like.
  • the field effect transistor of the present invention since the field effect transistor of the present invention has good film formability, it can be manufactured by a coating printing process such as coating, and the field effect for a large area display application at a very low cost compared to a conventional vacuum deposition process. It can also be applied to the manufacture of transistors.
  • the field effect transistor of the present invention can be used as a digital element or an analog element such as a memory circuit element, a signal driver circuit element, or a signal processing circuit element, and an IC card or an IC tag can be manufactured by combining these elements. Furthermore, since the field effect transistor of the present invention can change its characteristics by an external stimulus such as a chemical substance, it can be expected to be used as an FET sensor.
  • the present invention includes the following forms (2) to (7).
  • Example 1 preparation of semiconductor materials 100 parts of the stock solution of compound (11), 20 parts of TCNQ stock solution, and 80 parts of chloroform were mixed, respectively, and chloroform-acetonitrile (9: 1) containing 1% of compound (11) and 0.02% of TCNQ A mixed solution 1 of organic semiconductor materials was prepared.
  • a mixed solution 1 containing the compound (11) and TCNQ prepared in advance on a 300 nm UV-ozone-treated n-doped silicon wafer with a SiO 2 thermal oxide film was applied by spin coating, and then the substrate was placed on a hot plate at 80 After heating at 0 ° C. for 10 minutes, the organic thin film was formed by drying at 120 ° C. for 1 minute.
  • Gold was deposited on the organic thin film as a source electrode and a drain electrode (channel length 50 ⁇ m, channel width 2 mm) by a vacuum deposition method using a metal mask, and a bottom gate-top contact element was produced.
  • the four semiconductor characteristics on one substrate were changed under the condition that the drain voltage was changed to ⁇ 60V and the gate voltage Vg was changed from +20 to ⁇ 80V. evaluated.
  • the average value of the mobility of the four electrodes on the calculated standard deviation is an index showing the variation of 0.31 cm 2 / Vs
  • the substrate was 0.02 cm 2 / Vs.
  • the threshold voltage is the average -29V
  • ON current is 2.3 ⁇ 10 -4 A
  • standard deviation 2.6 ⁇ 10 -5 A high semiconductor characteristics and uniformity in the substrate showed that.
  • the OFF current was on the order of 10 ⁇ 11 A, and no increase in OFF current was observed when an electron accepting material was added. Furthermore, even when exposed to the atmosphere for 1 week, the mobility was 0.32 cm 2 / Vs, the threshold voltage was ⁇ 31 V, the ON current was 2.2 ⁇ 10 ⁇ 4 A, and excellent semiconductor characteristics were maintained.
  • Example 2 (Preparation of semiconductor materials) 100 parts of the stock solution of compound (11), 10 parts of the stock solution of TCNQ, 80 parts of chloroform and 10 parts of acetonitrile were mixed, respectively, and chloroform-acetonitrile (1% of compound (11) and 0.01% of TCNQ ( 9: 1) mixed solution 2 of organic semiconductor materials was prepared.
  • a bottom gate-top contact element was fabricated in the same manner as in Example 1 except that the semiconductor material was changed from the mixed solution 1 to the mixed solution 2.
  • the semiconductor characteristics were evaluated under the same conditions as in Example 1.
  • Mean value of the mobility of the four electrodes is the standard deviation is an index showing 0.58cm 2 / Vs, the variation in the substrate was 0.038 cm 2 / Vs.
  • the threshold voltage is -26V on average, 0.9V standard deviation, the ON current is 4.5 ⁇ 10 ⁇ 4 A, and 3.7 ⁇ 10 ⁇ 6 A standard deviation. It showed uniformity.
  • the OFF current was on the order of 10 ⁇ 11 A, and the OFF current did not increase even when the electron-accepting material was added.
  • the mobility was 0.59 cm 2 / Vs
  • the threshold voltage was ⁇ 30 V
  • the ON current was 4.1 ⁇ 10 ⁇ 4 A, and excellent semiconductor characteristics were maintained.
  • Example 3 (Preparation of semiconductor materials) 100 parts of the stock solution of compound (11), 20 parts of the stock solution of F4-TCNQ, and 80 parts of chloroform were mixed, respectively, and chloroform-acetonitrile (1% of compound (11) and 0.02% of F4-TCNQ ( 9: 1) mixed solution 2 of organic semiconductor materials was prepared.
  • a bottom gate-top contact element was fabricated in the same manner as in Example 1 except that the semiconductor material was changed from the mixed solution 1 to the mixed solution 3.
  • the semiconductor characteristics were evaluated under the same conditions as in Example 1.
  • the average value of the mobility of the four electrodes was 0.42 cm 2 / Vs, and the standard deviation as an index indicating the variation in the substrate was 0.007 cm 2 / Vs.
  • the threshold voltage is the average -20 V, the standard deviation 0.3V, ON current is 4.0 ⁇ 10 -4 A, standard deviation 9.1 ⁇ 10 -6 A, high semiconductor characteristics and in the substrate It showed uniformity.
  • the OFF current was on the order of 10 ⁇ 11 A, and the OFF current did not increase even when the electron-accepting material was added.
  • the mobility was 0.42 cm 2 / Vs
  • the threshold voltage was ⁇ 20 V
  • the ON current was 3.9 ⁇ 10 ⁇ 4 A, and excellent semiconductor characteristics were maintained.
  • a bottom gate-top contact element was fabricated in the same manner as in Example 1 except that the semiconductor material was changed from the mixed solution 1 to the mixed solution 4.
  • Example 2 The semiconductor characteristics were evaluated under the same conditions as in Example 1.
  • the average value of the mobility of the four electrodes was 0.22 cm 2 / Vs, and the standard deviation, which is an index indicating variations in the substrate, was 0.062 cm 2 / Vs.
  • the threshold voltage is -44V on average, the standard deviation is 1.5V, the ON current is 8.3 ⁇ 10 -5 A, the standard deviation is 2.9 ⁇ 10 -5 A, and the mobility and ON current are implemented. Compared with Examples 1 and 2, the threshold voltage was higher. Further, it was shown that the standard deviation indicating the variation of each characteristic was larger than that of the example.
  • the field effect transistor made of the organic semiconductor material of the present invention operates stably in the atmosphere and has high semiconductor characteristics and durability. Further, it was found that not only the semiconductor characteristics of mobility, threshold voltage, and ON current can be improved, but also the in-plane uniformity can be improved as compared with the comparative example not including the electron accepting material. Furthermore, when the semiconductor layer is manufactured, not only does it need to use a vacuum deposition method that requires special equipment, but also the purpose is to perform complicated operations such as patterning in substrate surface treatment and functions such as trap reduction. It was confirmed that a semiconductor layer can be easily and inexpensively produced by a coating method or the like without requiring a layer forming step, and the semiconductor characteristics can be improved. Therefore, it can be said that the field effect transistor using the organic semiconductor material of the present invention is extremely useful having excellent transistor performance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Thin Film Transistor (AREA)

Abstract

L'invention concerne un matériau semi-conducteur organique comprenant un composé accepteur d'électrons qui contient un groupe représenté par la formule (1) et un groupe cyano, dissous et/ou dispersé dans au moins un solvant organique. (1) Dans la formule (1), R1 et R2 représentent chacun indépendamment un groupe hydrocarboné aliphatique en C1-36 non substitué ou substitué par des halogènes.
PCT/JP2011/070218 2010-09-07 2011-09-06 Matériau semi-conducteur organique, transistor à effet de champ, et procédé de fabrication associé WO2012033075A1 (fr)

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CN201180010025.4A CN102770979B (zh) 2010-09-07 2011-09-06 有机半导体材料和场效应晶体管以及场效应晶体管的制造方法
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015156412A (ja) * 2014-02-20 2015-08-27 富士フイルム株式会社 有機薄膜トランジスタ、有機半導体薄膜および有機半導体材料
WO2017001473A1 (fr) * 2015-06-29 2017-01-05 Flexenable Limited Dispositifs électroniques/optoélectroniques organiques
EP3258509A1 (fr) * 2016-06-14 2017-12-20 Solvay SA 9,9-disubstitué 9,10-dihydroacridines et leurs utilisation pour doper des semi-conducteur organiques critsllines

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016152889A1 (fr) * 2015-03-23 2016-09-29 日本化薬株式会社 Composé organique, matériau organique semi-conducteur, film organique mince et son procédé de production, composition organique semi-conductrice et dispositif organique semi-conducteur
JP6465978B2 (ja) * 2015-08-04 2019-02-06 富士フイルム株式会社 有機薄膜トランジスタ、有機薄膜トランジスタの製造方法、有機薄膜トランジスタ用材料、有機薄膜トランジスタ用組成物、有機半導体膜、化合物
CN115448473B (zh) * 2022-08-29 2023-06-20 常熟金陵海虞热电有限公司 一种用于热电厂循环冷却水的阻垢剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009000683A1 (fr) * 2007-06-22 2008-12-31 Cambridge Display Technology Ltd Transistors à couches minces organiques, dispositifs électroluminescents organiques et affichages électroluminescents organiques
JP2010100621A (ja) * 2008-10-23 2010-05-06 Novaled Ag ラジアレン化合物およびその使用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4581062B2 (ja) * 2006-10-20 2010-11-17 日本化薬株式会社 電界効果トランジスタ、半導体デバイス作製用インク、電界効果トランジスタの製造方法、および有機複素環化合物
JP2009152355A (ja) * 2007-12-20 2009-07-09 Konica Minolta Holdings Inc 有機薄膜トランジスタの製造方法、及び有機薄膜トランジスタ

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009000683A1 (fr) * 2007-06-22 2008-12-31 Cambridge Display Technology Ltd Transistors à couches minces organiques, dispositifs électroluminescents organiques et affichages électroluminescents organiques
JP2010100621A (ja) * 2008-10-23 2010-05-06 Novaled Ag ラジアレン化合物およびその使用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
H. EBATA ET AL.: "Highly Soluble [1]Benzothieno [3,2-b]benzothiophene (BTBT) Derivatives for High-Performance, Solution-Processed Organic Field-Effect Transistors", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 129, 29 November 2007 (2007-11-29), pages 15732 - 15733 *
L. MA ET AL.: "High performance polythiophene thin-film transistors doped with very small amounts of an electron acceptor", APPLIED PHYSICS LETTERS, vol. 92, 15 February 2008 (2008-02-15), pages 063310-1 - 063310-3 *
T. MINARI ET AL.: "Surface selective deposition of molecular semiconductors for solution-based integration of organic field-effect transistors", APPLIED PHYSICS LETTERS, vol. 94, 6 March 2009 (2009-03-06), pages 093307-1 - 093307-3 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015156412A (ja) * 2014-02-20 2015-08-27 富士フイルム株式会社 有機薄膜トランジスタ、有機半導体薄膜および有機半導体材料
WO2017001473A1 (fr) * 2015-06-29 2017-01-05 Flexenable Limited Dispositifs électroniques/optoélectroniques organiques
JP2018521510A (ja) * 2015-06-29 2018-08-02 フレックスエネーブル リミティッド 有機電子／光電子デバイス
US10476015B2 (en) 2015-06-29 2019-11-12 Flexenable Limited Organic electronic/optoelectronic devices
GB2539895B (en) * 2015-06-29 2020-10-07 Flexenable Ltd Organic electronic/optoelectronic devices
JP7077019B2 (ja) 2015-06-29 2022-05-30 フレックスエネーブル リミティッド 有機電子スイッチングデバイス、デバイスを動作させることを含む方法、および電子スイッチングデバイスの製造方法
EP3258509A1 (fr) * 2016-06-14 2017-12-20 Solvay SA 9,9-disubstitué 9,10-dihydroacridines et leurs utilisation pour doper des semi-conducteur organiques critsllines
WO2017216167A1 (fr) * 2016-06-14 2017-12-21 Solvay Sa Composition semi-conductrice organique et couche semi-conductrice obtenue à partir de celle-ci

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TW201221519A (en) 2012-06-01
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