WO2015133372A1 - 薄膜トランジスタ - Google Patents
薄膜トランジスタ Download PDFInfo
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- WO2015133372A1 WO2015133372A1 PCT/JP2015/055704 JP2015055704W WO2015133372A1 WO 2015133372 A1 WO2015133372 A1 WO 2015133372A1 JP 2015055704 W JP2015055704 W JP 2015055704W WO 2015133372 A1 WO2015133372 A1 WO 2015133372A1
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- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- FMYXZXAKZWIOHO-UHFFFAOYSA-N trichloro(2-phenylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CCC1=CC=CC=C1 FMYXZXAKZWIOHO-UHFFFAOYSA-N 0.000 description 1
- HLWCOIUDOLYBGD-UHFFFAOYSA-N trichloro(decyl)silane Chemical compound CCCCCCCCCC[Si](Cl)(Cl)Cl HLWCOIUDOLYBGD-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical class Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 description 1
- WXKZSTUKHWTJCF-UHFFFAOYSA-N zinc;ethanolate Chemical compound [Zn+2].CC[O-].CC[O-] WXKZSTUKHWTJCF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
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- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
- H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials
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- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Definitions
- the present invention relates to a thin film transistor.
- a TFT has a structure including a gate electrode, a semiconductor layer, and a gate insulating layer provided between the gate electrode and the semiconductor layer on a substrate, and a source electrode and a drain electrode are provided in contact with the semiconductor layer. It has been.
- the TFT is driven by applying a voltage to the gate electrode. By applying a voltage to the gate electrode, the amount of carriers consisting of electrons or holes in the semiconductor is controlled, and the current flowing between the source electrode and the drain electrode is controlled.
- inorganic semiconductors such as amorphous or polycrystalline thin film silicon have been used for semiconductors used in TFTs.
- a vacuum process or a high-temperature process of 300 ° C. or higher is required, and improvement in productivity is limited.
- TFTs using organic semiconductors have become widespread. Since the organic semiconductor layer can be formed by a method such as ink jet, spin coating, flexographic printing, etc., the film forming process can be performed at a lower temperature, at a high speed and efficiently, and at a low cost.
- TFTs using an organic semiconductor as a semiconductor layer use silicon oxide obtained by thermally oxidizing silicon as a gate insulating layer.
- silicon oxide film When a silicon oxide film is used, the surface of the silicon oxide film is usually treated with hexamethyldisilazane (HMDS), octadecyltrichlorosilane (OTS), or the like in order to sufficiently extract the carrier conductivity of the organic semiconductor formed thereon. , Make the surface water-repellent.
- HMDS hexamethyldisilazane
- OTS octadecyltrichlorosilane
- HMDS and OTS may aggregate or polymerize on the surface of the gate insulating film. If it becomes so, it will become difficult for a semiconductor to carry out crystal growth and sufficient carrier mobility will not be obtained.
- a TFT in which a gate insulating film is formed of an organic polymer compound is also known.
- Patent Document 1 describes a TFT in which a gate insulating layer is formed using a cured product formed using a resin and a crosslinking agent. Yes.
- This Patent Document 1 describes that it is desirable to prevent the contamination of the organic semiconductor layer by reducing the alkali metal content of the gate insulating layer, and further describes that the amount of sodium is preferably 20 ppm or less. Has been.
- An object of the present invention is to provide a thin film transistor that achieves both excellent carrier mobility and high current amplification factor, can perform switching operation more quickly and reliably, and has a low threshold voltage and reduced power consumption. To do.
- the present inventors made extensive studies in view of the above problems. As a result, in a thin film transistor containing an organic polymer compound in the gate insulating layer, when the amount of a specific metal or a specific non-metal ionic substance contained in the gate insulating layer is within a specific range, an excellent current amplification factor is obtained. It has been found that the threshold voltage, which shows (on / off ratio) and normally has a positive correlation with the current amplification factor, is surprisingly kept low and further improves the carrier mobility. The present invention has been completed based on these findings.
- a gate electrode, a semiconductor layer, a gate insulating layer formed of an organic polymer compound provided between the gate electrode and the semiconductor layer, and a semiconductor layer provided in contact with the semiconductor layer A thin film transistor having a source electrode and a drain electrode connected via In the gate insulating layer, the total content of metals selected from Mg, Ca, Ba, Al, Sn, Pb, Cr, Mn, Fe, Ni, Cu, Zn, and Ag is 10 ppb to 1 ppm, or halogen
- the total content of metals selected from Mg, Ca, Ba, Al, Sn, Pb, Cr, Mn, Fe, Ni, Cu, Zn, and Ag is 10 ppb to 1 ppm, and halogen
- the thin film transistor according to [1], wherein the total content of nonmetallic ionic substances selected from ions, sulfate ions, nitrate ions, and phosphate ions is 1 ppm to 100 ppm.
- the thin film transistor according to [1] or [2], wherein the content of a metal selected from Mg, Ca, Al, Cr, Fe and Zn in the gate insulating layer is 10 ppb to 1 ppm in total.
- the gate insulating layer has a total content of nonmetallic ionic substances selected from chlorine ions, sulfate ions, nitrate ions and phosphate ions in a range of 1 ppm to 100 ppm.
- Thin film transistor [5] The thin film transistor according to any one of [1] to [4], wherein the gate insulating layer has a total content of nonmetallic ionic substances selected from chlorine ions and sulfate ions of 1 ppm to 100 ppm.
- the organic polymer compound is polyvinylphenol, novolac resin, polystyrene, poly (meth) acrylate, epoxy resin, epoxy (meth) acrylate resin, polyvinyl alcohol, fluororesin, polycycloolefin, polysilsesquioxane, polysiloxane,
- the organic semiconductor is represented by any one of the following general formulas (C) to (T).
- a C1 and A C2 represent an oxygen atom, a sulfur atom or a selenium atom.
- R C1 to R C6 represent a hydrogen atom or a substituent, and at least one of R C1 to R C6 is a substituent represented by the following general formula (W).
- X D1 and X D2 represent NR D9 , an oxygen atom or a sulfur atom.
- a D1 represents CR D7 or a nitrogen atom
- a D2 represents CR D8 or a nitrogen atom
- R D9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group.
- R D1 to R D8 represent a hydrogen atom or a substituent, and at least one of R D1 to R D8 is a substituent represented by the following general formula (W).
- X E1 and X E2 represent an oxygen atom, a sulfur atom or NR E7 .
- a E1 and A E2 represent CR E8 or a nitrogen atom.
- R E1 to R E8 represent a hydrogen atom or a substituent, and at least one of R E1 to R E8 is a substituent represented by the following general formula (W).
- XF1 and XF2 represent an oxygen atom, a sulfur atom, or a selenium atom.
- R F1 to R F10 , R Fa and R Fb represent a hydrogen atom or a substituent, and at least one of R F1 to R F10 , R Fa and R Fb is a substituent represented by the general formula (W). . p and q each represents an integer of 0-2.
- X G1 and X G2 represent NR G9 , an oxygen atom, or a sulfur atom.
- a G1 represents CR G7 or a nitrogen atom
- a G2 represents CR G8 or a nitrogen atom.
- R G9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group
- R G1 to R G8 represent a hydrogen atom or a substituent
- at least one of R G1 to R G8 Is a substituent represented by the following general formula (W).
- W general formula (H)
- X H1 to X H4 represent NR H7 , an oxygen atom or a sulfur atom
- R H7 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group, or a heteroaryl group.
- R H1 to R H6 represent a hydrogen atom or a substituent, and at least one of R H1 to R H6 is a substituent represented by the following general formula (W).
- X J1 and X J2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR J9 .
- X J3 and X J4 represent an oxygen atom, a sulfur atom or a selenium atom.
- R J1 to R J9 represent a hydrogen atom or a substituent, and at least one of R J1 to R J9 is a substituent represented by the following general formula (W).
- X K1 and X K2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR K9 .
- X K3 and X K4 represent an oxygen atom, a sulfur atom or a selenium atom.
- R K1 to R K9 represent a hydrogen atom or a substituent, and at least one of R K1 to R K9 is a substituent represented by the following general formula (W).
- X L1 and X L2 represent an oxygen atom, a sulfur atom or NR L11 .
- R L1 to R L11 represent a hydrogen atom or a substituent, and at least one of R L1 to R L11 is a substituent represented by the following general formula (W).
- W general formula
- X M1 and X M2 represent an oxygen atom, a sulfur atom, a selenium atom or NR M9 .
- R M1 to R M9 represent a hydrogen atom or a substituent, and at least one of R M1 to R M9 is a substituent represented by the following general formula (W).
- XN1 and XN2 represent an oxygen atom, a sulfur atom, a selenium atom, or NRN13 .
- R N1 to R N13 each represents a hydrogen atom or a substituent, and at least one of R N1 to R N13 is a substituent represented by the following general formula (W).
- W general formula
- X P1 and X P2 represent an oxygen atom, a sulfur atom, a selenium atom, or NRP13 .
- R P1 to R P13 represent a hydrogen atom or a substituent, and at least one of R P1 to R P13 is a substituent represented by the following general formula (W).
- X Q1 and X Q2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR Q13 .
- R Q1 to R Q13 represent a hydrogen atom or a substituent, and at least one of R Q1 to R Q13 is a substituent represented by the following general formula (W).
- X R1 , X R2 and X R3 represent an oxygen atom, a sulfur atom, a selenium atom or NR R9 .
- R R1 to R R9 represent a hydrogen atom or a substituent, and at least one of R R1 to R R9 is a substituent represented by the following general formula (W).
- X S1 , X S2 , X S3 and X S4 represent an oxygen atom, a sulfur atom, a selenium atom or NR S7 .
- R S1 to R S7 represent a hydrogen atom or a substituent, and at least one of R S1 to R S7 is a substituent represented by the following general formula (W).
- W general formula
- X T1 , X T2 , X T3 and X T4 represent an oxygen atom, a sulfur atom, a selenium atom or NR T7 .
- R T1 to R T7 represent a hydrogen atom or a substituent, and at least one of R T1 to R T7 is a substituent represented by the following general formula (W).
- L represents a divalent linking group represented by any one of the following general formulas (L-1) to (L-25), or two or more of the following general formulas (L-1) to (L And a divalent linking group to which the divalent linking group represented by any one of -25) is bonded.
- R W is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, a siloxane group, the number of silicon atoms is more than one It represents an oligosiloxane group or a substituted or unsubstituted trialkylsilyl group.
- the wavy line represents the bonding position with any ring forming each skeleton represented by the general formulas (C) to (T). * Shows the point of attachment to the wavy portion of the connecting position or formula with R w (L-1) ⁇ (L-25).
- M in the general formula (L-13) represents 4
- m in the general formulas (L-14) and (L-15) represents 3
- m in the general formulas (L-16) to (L-20) represents 2 and m in (L-22) represents 6.
- R LZ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L19) and (L-21) to (L-24) each independently represents a hydrogen atom Or represents a substituent.
- R N represents a hydrogen atom or a substituent, and R si each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.
- substituents when there are a plurality of substituents, linking groups, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when there are repetitions of a plurality of partial structures represented by the same indication in the formula, each partial structure or repeating unit may be the same or different. Further, unless otherwise specified, when a plurality of substituents and the like are adjacent (particularly adjacent), they may be connected to each other or condensed to form a ring.
- the term “compound” (including polymer) is used to mean not only the compound itself but also its salt and its ion. In addition, it means that a part of the structure is changed as long as the desired effect is achieved.
- a substituent that does not clearly indicate substitution or non-substitution means that the group may further have a substituent as long as the intended effect is not impaired. .
- This is also synonymous for compounds that do not specify substitution / non-substitution.
- ppm and “ppb” are based on mass.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the thin film transistor of the present invention exhibits excellent carrier mobility and has a high current amplification factor, so that switching operation can be performed more quickly and more reliably, and the threshold voltage is lower and power consumption is suppressed. It is done.
- the TFT of the present invention The mode of the thin film transistor of the present invention (hereinafter simply referred to as “the TFT of the present invention”) will be described below.
- the TFT of the present invention is provided on a substrate, in contact with the semiconductor layer, a gate electrode, a semiconductor layer, a gate insulating layer provided between the gate electrode and the semiconductor layer, and through the semiconductor. And a source electrode and a drain electrode connected to each other.
- a current channel channel is formed at the interface between the semiconductor layer between the source electrode and the drain electrode and the adjacent layer. That is, the current flowing between the source electrode and the drain electrode is controlled according to the input voltage applied to the gate electrode.
- FIGS. 1A and 1B are longitudinal sectional views each schematically showing a typical preferable embodiment of a TFT of the present invention.
- 1A to 1D 1 is a semiconductor layer
- 2 is a gate insulating layer
- 3 is a source electrode
- 4 is a drain electrode
- 5 is a gate electrode
- 6 is a substrate.
- 1A is a bottom gate / bottom contact type
- FIG. 1B is a bottom gate / top contact type
- FIG. 1C is a top gate / bottom contact type
- FIG. 1D is a top.
- a gate-top contact type TFT is shown. All of the above four forms are included in the TFT of the present invention.
- an overcoat layer may be formed on the top of each TFT in the drawing (opposite to the substrate 6).
- the substrate may be any substrate that can support the TFT and the display panel or the like produced thereon.
- the substrate is not particularly limited as long as the surface is insulative, has a sheet shape, and has a flat surface.
- An inorganic material may be used as the material for the substrate.
- a substrate made of an inorganic material for example, various glass substrates such as soda lime glass and quartz glass, various glass substrates with an insulating film formed on the surface, a quartz substrate with an insulating film formed on the surface, and an insulating film on the surface Examples thereof include a silicon substrate, a sapphire substrate, a metal substrate made of various alloys such as stainless steel, aluminum, nickel, and various metals, metal foil, and paper.
- a conductive or semiconducting material such as stainless steel sheet, aluminum foil, copper foil or silicon wafer, an insulating polymer material or metal oxide is usually applied or laminated on the surface. Used.
- an organic material may be used as the material of the substrate.
- polymethyl methacrylate polymethyl methacrylate, PMMA
- polyvinyl alcohol PVA
- polyvinyl phenol PVP
- polyethersulfone PES
- polyimide polyamide
- polyacetal polycarbonate
- PC polyethylene terephthalate
- flexible plastic substrate also referred to as a plastic film or a plastic sheet
- an organic polymer exemplified by polyethylene naphthalate (PEN), polyethyl ether ketone, polyolefin, and polycycloolefin.
- PEN polyethylene naphthalate
- PEN polyethylene naphthalate
- PEN polyethyl ether ketone
- polyolefin polycycloolefin
- the thing formed with the mica can also be mentioned. If such a flexible plastic substrate or the like is used, for example, a TFT can be incorporated or integrated into a display device or electronic device having a curved shape
- the glass transition point is preferably high and the glass transition point is preferably 40 ° C. or higher.
- the coefficient of linear expansion is small from the viewpoint that the dimensional change is hardly caused by the heat treatment at the time of manufacture and the transistor performance is stable.
- a material having a linear expansion coefficient of 25 ⁇ 10 ⁇ 5 cm / cm ⁇ ° C. or less is preferable, and a material having a coefficient of 10 ⁇ 10 ⁇ 5 cm / cm ⁇ ° C. or less is more preferable.
- the organic material constituting the substrate is preferably a material having resistance to a solvent used at the time of TFT fabrication, and a material excellent in adhesion to the gate insulating layer and the electrode is preferable.
- a plastic substrate made of an organic polymer having a high gas barrier property. It is also preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate, or to deposit or laminate an inorganic material.
- a conductive substrate (a substrate made of a metal such as gold or aluminum, a substrate made of highly oriented graphite, a stainless steel substrate, etc.) can also be mentioned.
- a functional layer such as a buffer layer for improving adhesion and flatness, a barrier film for improving gas barrier properties, and a surface treatment layer such as an easy adhesion layer may be formed on the surface. Further, surface treatment such as corona treatment, plasma treatment, UV / ozone treatment may be performed.
- the thickness of the substrate is preferably 10 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less. On the other hand, it is preferably 0.01 mm or more, and more preferably 0.05 mm or more. In particular, in the case of a plastic substrate, the thickness is preferably about 0.05 to 0.1 mm. In the case of a substrate made of an inorganic material, the thickness is preferably about 0.1 to 10 mm.
- a conductive material (also referred to as an electrode material) constituting the gate electrode is not particularly limited.
- metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, molybdenum, titanium, magnesium, calcium, barium, sodium, palladium, iron, manganese; InO 2 , SnO 2 , indium / tin oxide (ITO ), Conductive metal oxides such as fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO); polyaniline, polypyrrole, polythiophene, polyacetylene, poly (3,4-ethylenedioxy) Conductive polymers such as thiophene) / polystyrene sulfonic acid (PEDOT / PSS); acids such as hydrochloric acid, sulfuric acid,
- the method of forming the gate electrode there is no limitation on the method of forming the gate electrode.
- a film formed by physical vapor deposition (PVD) such as vacuum vapor deposition, chemical vapor deposition (CVD), sputtering, printing (coating), transfer, sol-gel, or plating is necessary.
- PVD physical vapor deposition
- CVD chemical vapor deposition
- sputtering sputtering
- printing coating
- sol-gel sol-gel
- plating sol-gel
- a solution, paste, or dispersion of the above material can be prepared and applied, and a film can be formed or an electrode can be directly formed by drying, baking, photocuring, aging, or the like.
- patterning can be performed in combination with the following photolithography method or the like.
- Examples of the photolithography method include a method in which a patterning of a photoresist is combined with etching such as wet etching with an etchant or dry etching with reactive plasma, a lift-off method, or the like.
- etching such as wet etching with an etchant or dry etching with reactive plasma, a lift-off method, or the like.
- a method of irradiating the material with an energy beam such as a laser or an electron beam to polish the material or changing the conductivity of the material may be used.
- substrate is also mentioned.
- the thickness of the gate electrode is arbitrary, but is preferably 1 nm or more, particularly preferably 10 nm or more. Moreover, 500 nm or less is preferable and 200 nm or less is especially preferable.
- the gate insulating layer of the TFT of the present invention is formed of an organic polymer compound having insulating properties.
- the organic polymer compound is not particularly limited as long as it has insulating properties, and a thin film, for example, a film capable of forming a thin film having a thickness of 1 ⁇ m or less is preferable.
- One type of organic polymer compound may be used, or two or more types may be used in combination.
- the gate insulating layer constituting the TFT of the present invention includes Mg, Ca, Ba, Al, Sn, Pb, Cr, Mn, Fe, Ni, Cu, Zn, and Ag (hereinafter referred to as “specific metal” by combining these metals).
- specific metal by combining these metals.
- the total content of non-metallic ionic substances selected from "" is from 1 ppm to 100 ppm.
- the gate insulating layer has a total content of metals selected from specific metals of 10 ppb to 1 ppm, and a total content of nonmetallic ionic materials selected from specific nonmetallic ionic materials is 1 ppm to 100 ppm.
- the specific metal includes those existing in the form of ions.
- the TFT of the present invention since the content of the specific metal or specific non-metal ionic substance in the gate insulating layer is suppressed within a specific range, a leak path (conduction path) is hardly formed. Therefore, the TFT of the present invention exhibits a high current amplification factor with the excellent insulating property of the gate insulating layer.
- this current amplification factor is smaller than that in the case where the specific metal or specific non-metal ionic material in the gate insulating layer is lower than that defined in the present invention (that is, less material that can cause a leakage path).
- the amount of the specific metal or specific non-metal ionic substance contained in the amount specified in the present invention that is, when a certain amount of a substance that may cause a leak path is contained).
- the TFT of the present invention has a low threshold voltage.
- the insulating property of the gate insulating layer and the threshold voltage of the TFT are positively correlated. That is, when the insulating property of the gate insulating layer is high, the threshold voltage is also increased.
- the TFT of the present invention maintains the high insulating property of the gate insulating layer because the content of the specific metal or specific non-metal ionic substance in the gate insulating layer is within the specific range defined in the present invention.
- the threshold voltage can be kept low. That is, the present invention provides a TFT that can perform a switching operation more reliably with less power consumption.
- the carrier mobility is also increased when the content of the specific metal or specific non-metal ionic substance in the gate insulating layer is within a specific range defined in the present invention. Even if the amount of alkali metal in the gate insulating layer is adjusted, the above-described composite performance improvement is not recognized.
- the total content of the metal selected from the specific metal in the gate insulating layer is preferably 10 ppb to 500 ppb, more preferably 10 ppb to 200 ppb, further preferably 12 ppb to 100 ppb, and further preferably 14 ppb to 70 ppb.
- the content of the nonmetallic ionic substance selected from the specific nonmetallic ionic substances is preferably 2 ppm to 70 ppm, more preferably 3 ppm to 50 ppm, and further preferably 5 ppm to 40 ppm.
- the amount of the specific metal or specific non-metal ionic substance in the gate insulating layer can be adjusted by subjecting a material used for manufacturing the gate insulating layer to a cleaning process, a purification process, or the like.
- the total content of metals selected from Mg, Ca, Al, Cr, Fe and Zn in the gate insulating layer is preferably 10 ppb to 1 ppm, more preferably 10 ppb to 500 ppb, It is preferably 10 ppb to 200 ppb, more preferably 12 ppb to 100 ppb, and still more preferably 13 ppb to 70 ppb.
- the total content of nonmetallic ionic substances selected from chlorine ions, sulfate ions, nitrate ions and phosphate ions in the gate insulating layer is preferably 2 ppm to 70 ppm.
- the total content of non-metallic ionic substances selected from chlorine ions and sulfate ions in the gate insulating layer is preferably 2 ppm to 70 ppm, more preferably 3 ppm to 50 ppm, and still more preferably Is from 5 ppm to 40 ppm.
- the organic polymer compound used for the gate insulating layer of the TFT of the present invention include, for example, polyvinylphenol, novolac resin, polystyrene, poly (meth) acrylate, epoxy resin, epoxy (meth) acrylate resin, polyvinyl alcohol, and fluororesin. , Polycycloolefin, polysilsesquioxane, polysiloxane, polyester, popolyethersulfone, polyetherketone, and one or more selected from polyimides.
- poly (meth) acrylate polyalkyl methacrylate is preferable, and polymethyl methacrylate is more preferable.
- fluororesin examples include cyclic fluoroalkyl polymers represented by polyvinylidene fluoride, polytetrafluoroethylene, and CYTOP.
- polysiloxane dialkyl polysiloxane is preferable and polydimethylsiloxane is more preferable.
- the organic polymer compound used in the gate insulating layer of the TFT of the present invention is polyvinylphenol, polystyrene, poly (meth) acrylate, epoxy (meth) acrylate, fluororesin, polycycloolefin, polysilsesquioxane, and It is 1 type, or 2 or more types chosen from polysiloxane, More preferably, it is 1 type, or 2 or more types chosen from polyvinyl phenol, polysilsesquioxane, and a fluororesin.
- the exemplified organic polymer compound may be in the form of a copolymer having the constituent components of the exemplified organic polymer compound (polymer) as a constituent unit.
- the organic polymer compound exemplified above includes a form having a desired substituent.
- the organic polymer compound can be used in combination with a compound having a reactive substituent such as an alkoxysilyl group, a vinyl group, an acryloyloxy group, an epoxy group, or a methylol group.
- the above-described organic polymer compound included in the gate insulating layer includes a form having a crosslinked structure.
- Crosslinking is preferably carried out by generating an acid or radical using light, heat or both.
- radical generator that generates radicals by light or heat
- a radical generator that generates radicals by light or heat for example, the heat described in JP-A-2013-214649, [0182] to [0186]
- the photo-radical polymerization initiator and the like described in [0056] can be suitably used, and the contents thereof are preferably incorporated in the present specification.
- the “number average molecular weight (Mn) is 140 to 5,000 described in JP 2013-214649 A [0167] to [0177]”. Yes, it is preferred to use a compound (G) having a crosslinkable functional group and no fluorine atom, the contents of which are preferably incorporated herein.
- a photoacid generator for generating an acid by light for example, a photocation described in JP-A 2010-285518, [0033] to [0034]
- Polymerization initiators, acid generators described in JP-A-2012-163946, [0120] to [0136], particularly sulfonium salts, iodonium salts, and the like can be preferably used. Incorporated into.
- a thermal acid generator (catalyst) that generates an acid by heat
- thermal cationic polymerization initiators described in JP-A-2010-285518, [0035] to [0038] particularly onium salts, etc.
- the catalysts described in [0034] to [0035] of Kaikai 2005-354012 can be preferably used, and the contents thereof are preferably incorporated herein.
- the crosslinking agent described in JP-A-2005-354012 [0032] to [0033] particularly a bifunctional or higher functional epoxy compound, an oxetane compound
- the cross-linking agent described in [0046] to [0062] of JP-A-2006-303465 particularly having two or more cross-linking groups, wherein at least one of the cross-linking groups is a methylol group or an NH group.
- compounds having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule described in JP 2012-163946 A, [0137] to [0145] are preferably used.
- Examples of the method for forming the gate insulating layer with an organic polymer compound include a method of coating and curing an organic polymer compound.
- the coating method is not particularly limited, and includes the above printing methods. Of these, a wet coating method such as a micro gravure coating method, a dip coating method, a screen coating printing, a die coating method or a spin coating method is preferable.
- the gate insulating layer can be provided by a method in which any one of the lift-off method, the sol-gel method, the electrodeposition method, and the shadow mask method is combined with the patterning method as necessary.
- the gate insulating layer may be subjected to surface treatment such as corona treatment, plasma treatment, UV / ozone treatment, etc. In this case, it is preferable not to roughen the surface roughness due to the treatment.
- the arithmetic mean roughness of the surface of the gate insulating layer Ra or root mean square roughness R MS is 0.5nm or less.
- the gate insulating layer may contain an inorganic insulating material as long as the provisions of the present invention are satisfied.
- a self-assembled monolayer may be formed on the gate insulating layer.
- the compound that forms the self-assembled monolayer is not particularly limited as long as it is a compound that self-assembles.
- one or more compounds represented by the following formula 1S are used as the compound that self-assembles. be able to.
- R 1S represents any of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group (thienyl, pyrrolyl, pyridyl, fluorenyl, etc.).
- X S represents an adsorptive or reactive substituent, specifically, —SiX 4 X 5 X 6 group (X 4 represents a halide group or an alkoxy group, and X 5 and X 6 are each independently a halide group.
- X 4 , X 5 , and X 6 are preferably the same, more preferably a chloro group, a methoxy group, and an ethoxy group, and a phosphonic acid group (— PO 3 H 2 ), phosphinic acid group (—PRO 2 H, R is an alkyl group), phosphoric acid group, phosphorous acid group, amino group, halide group, carboxy group, sulfonic acid group, boric acid group (—B ( OH) 2 ), a hydroxy group, a thiol group, an ethynyl group, a vinyl group, a nitro group, or a cyano group.
- R 1S is preferably not branched, for example, a linear normal alkyl (n-alkyl) group, a ter-phenyl group in which three phenyl groups are arranged in series, or a para-position of the phenyl group.
- n-alkyl groups are arranged on both sides.
- the alkyl chain may have an ether bond, and may have a carbon-carbon double bond or a triple bond.
- Self-assembled monolayer layer, adsorptive or reactive substituent X S is, interacting with the reactive sites (e.g., -OH groups) of the corresponding surface of the gate insulating layer, by forming the adsorption or reaction bonded Formed on the gate insulating layer.
- the reactive sites e.g., -OH groups
- the surface of the self-assembled monolayer provides a smoother surface with a lower surface energy. Therefore, the main skeleton of the compound represented by the above formula 1S is linear. It is preferable that the molecular length is uniform.
- alkyl such as methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, octyltrichlorosilane, decyltrichlorosilane, octadecyltrichlorosilane, and phenethyltrichlorosilane
- alkyltrialkoxysilane compounds such as trichlorosilane compounds, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, alkylphosphonic acid, arylphosphonic acid, alkyl Examples thereof include carboxylic acid, arylphosphonic acid, alkylboric
- the self-assembled monolayer may be formed using a method in which the above compound is deposited on the gate insulating layer under vacuum, a method in which the gate insulating layer is immersed in a solution of the above compound, a Langmuir-Blodgett method, or the like. it can. Further, for example, the gate insulating layer can be formed by treating the alkyl chlorosilane compound or the alkylalkoxysilane compound with a solution of 1 to 10% by mass in an organic solvent. In the present invention, the method for forming the self-assembled monolayer is not limited to these. For example, as a preferable method for obtaining a denser self-assembled monolayer, Langmuir 19, 1159 (2003) and J. Org. Phys. Chem. B 110, 21101 (2006) etc. are mentioned.
- the gate insulating layer is immersed in a highly volatile dry solvent in which the above compound is dispersed to form a film, the gate insulating layer is taken out, and if necessary, the above compound such as annealing and the gate insulating layer After performing the above reaction step, it is possible to form a self-assembled monolayer by washing with a dry solvent and then drying.
- a dry solvent For example, chloroform, a trichloroethylene, anisole, diethyl ether, hexane, toluene etc. can be used individually or in mixture.
- an inert gas such as nitrogen as the dry gas.
- the organic semiconductor layer is a layer that exhibits semiconductor properties and can accumulate carriers.
- the organic semiconductor layer may be a layer containing an organic semiconductor. It does not specifically limit as an organic semiconductor, An organic polymer, its derivative (s), a low molecular weight compound, etc. are mentioned.
- the low molecular compound means a compound other than the organic polymer and its derivative. That is, it refers to a compound having no repeating unit. As long as the low molecular weight compound is such a compound, the molecular weight is not particularly limited.
- the molecular weight of the low molecular weight compound is preferably 300 to 2000, more preferably 400 to 1000.
- Examples of the low molecular weight compound include condensed polycyclic aromatic compounds.
- acene such as naphthacene, pentacene (2,3,6,7-dibenzoanthracene), hexacene, heptacene, dibenzopentacene, tetrabenzopentacene, anthradithiophene, pyrene, benzopyrene, dibenzopyrene, chrysene, perylene, coronene, terylene , Ovalene, quaterrylene, circumanthracene, and derivatives obtained by substituting a part of these carbon atoms with atoms such as N, S, O, etc., or at least one hydrogen atom bonded to the carbon atom is a functional group such as a carbonyl group Derivatives substituted with a group (dioxaanthanthrene compounds including perixanthenoxanthene and derivatives thereof, triphenodio
- metal phthalocyanines represented by copper phthalocyanine, tetrathiapentalene and derivatives thereof, naphthalene-1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethylbenzyl) naphthalene— 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (1H, 1H-perfluorooctyl), N, N′-bis (1H, 1H-perfluorobutyl), N, N′-dioctylnaphthalene -1,4,5,8-tetracarboxylic acid diimide derivatives, naphthalene tetracarboxylic acid diimides such as naphthalene-2,3,6,7-tetracarboxylic acid diimide, anthracene-2,3,6,7-tetracarboxylic acid Condensed ring tetracarboxylic acid di
- Further examples include polyanthracene, triphenylene, and quinacridone.
- low molecular weight compound examples include 4,4′-biphenyldithiol (BPDT), 4,4′-diisocyanobiphenyl, 4,4′-diisocyano-p-terphenyl, 2,5-bis (5 '-Thioacetyl-2'-thiophenyl) thiophene, 2,5-bis (5'-thioacetoxyl-2'-thiophenyl) thiophene, 4,4'-diisocyanophenyl, benzidine (biphenyl-4,4'- Diamine), TCNQ (tetracyanoquinodimethane), tetrathiafulvalene (TTF) and its derivatives, tetrathiafulvalene (TTF) -TCNQ complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTF-iodine complex , A charge transfer complex represented by TCNQ-iod
- the organic semiconductor is preferably a low molecular compound, and among them, a condensed polycyclic aromatic compound is preferable.
- the condensed polycyclic aromatic compound has a high effect of improving carrier mobility and durability, and also exhibits an excellent threshold voltage reduction effect.
- the condensed polycyclic aromatic compound is preferably an acene represented by any one of formulas (A1) to (A4) and a compound represented by any one of the following general formulas (C) to (T).
- a compound represented by any one of formulas (C) to (T) is more preferred.
- a preferable acene as the condensed polycyclic aromatic compound is represented by the following formula (A1) or (A2).
- R A1 to R A6 , X A1 and X A2 represent a hydrogen atom or a substituent.
- Z A1 and Z A2 represent S, O, Se, or Te.
- nA1 and nA2 represent an integer of 0 to 3. However, nA1 and nA2 are not 0 at the same time.
- R A1 to R A6 , X A1 and X A2 are not particularly limited, but are alkyl groups (eg, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, tert-pentyl, hexyl).
- R A7 , R A8 , X A1 and X A2 represent a hydrogen atom or a substituent.
- R A7 , R A8 , X A1 and X A2 may be the same or different.
- the substituents represented by R A7 and R A8 are preferably those listed above as substituents that can be employed as R A1 to R A6 in formulas (A1) and (A2).
- Z A1 and Z A2 represent S, O, Se, or Te.
- nA1 and nA2 represent an integer of 0 to 3. However, nA1 and nA2 are not 0 simultaneously.
- R A7 and R A8 are preferably those represented by the following formula (SG1).
- R A9 to R A11 represent substituents.
- X A represents Si, Ge or Sn.
- the substituents represented by R A9 to R A11 are preferably those listed above as substituents that can be employed as R A1 to R A6 in formulas (A1) and (A2).
- acene or acene derivative represented by formulas (A1) to (A4) are shown below, but are not limited thereto.
- a C1 and A C2 represent an oxygen atom, a sulfur atom or a selenium atom.
- both A C1 and A C2 represent an oxygen atom and a sulfur atom, more preferably a sulfur atom.
- R C1 to R C6 represent a hydrogen atom or a substituent. At least one of R C1 to R C6 is a substituent represented by the following general formula (W).
- X D1 and X D2 represent NR D9 , an oxygen atom or a sulfur atom.
- a D1 represents CR D7 or N atom
- a D2 represents CR D8 or N atom
- R D9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an acyl group.
- R D1 to R D8 represent a hydrogen atom or a substituent
- at least one of R D1 to R D8 is a substituent represented by the following general formula (W).
- X E1 and X E2 represent an oxygen atom, a sulfur atom or NR E7 .
- a E1 and A E2 represent CR E8 or a nitrogen atom.
- R E1 to R E8 represent a hydrogen atom or a substituent. At least one of R E1 to R E8 is a substituent represented by the following general formula (W).
- XF1 and XF2 represent an oxygen atom, a sulfur atom, or a selenium atom.
- X F1 and X F2 preferably represent an oxygen atom or a sulfur atom, and more preferably represent a sulfur atom.
- R F1 to R F10 , R Fa and R Fb represent a hydrogen atom or a substituent. At least one of R F1 to R F10 , R Fa and R Fb is a substituent represented by the general formula (W).
- p and q each represents an integer of 0-2.
- X G1 and X G2 represent NR G9 , an oxygen atom, or a sulfur atom.
- a G1 represents CR G7 or an N atom.
- a G2 represents CR G8 or an N atom.
- R G9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group.
- R G1 to R G8 represent a hydrogen atom or a substituent. At least one of R G1 to R G8 is a substituent represented by the following general formula (W).
- X H1 to X H4 represent NR H7 , an oxygen atom or a sulfur atom.
- X H1 to X H4 preferably represent a sulfur atom.
- R H7 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an acyl group, an aryl group or a heteroaryl group.
- R H1 to R H6 each represents a hydrogen atom or a substituent. At least one of R H1 to R H6 is a substituent represented by the following general formula (W).
- X J1 and X J2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR J9 .
- X J3 and X J4 represent an oxygen atom, a sulfur atom or a selenium atom.
- X J1 , X J2 , X J3 and X J4 preferably represent a sulfur atom.
- R J1 to R J9 represent a hydrogen atom or a substituent. At least one of R J1 to R J9 is a substituent represented by the following general formula (W).
- X K1 and X K2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR K9 .
- X K3 and X K4 represent an oxygen atom, a sulfur atom or a selenium atom.
- X K1 , X K2 , X K3 and X K4 preferably represent a sulfur atom.
- R K1 to R K9 represent a hydrogen atom or a substituent.
- At least one of R K1 to R K9 is a substituent represented by the following general formula (W).
- X L1 and X L2 represent an oxygen atom, a sulfur atom or NR L11 .
- X L1 and X L2 preferably represent an oxygen atom or a sulfur atom.
- R L1 to R L11 represent a hydrogen atom or a substituent, and at least one of R L1 to R L11 is a substituent represented by the following general formula (W).
- X M1 and X M2 represent an oxygen atom, a sulfur atom, a selenium atom or NR M9 .
- X M1 and X M2 preferably represent a sulfur atom.
- R M1 to R M9 represent a hydrogen atom or a substituent.
- At least one of R M1 to R M9 is a substituent represented by the following general formula (W).
- XN1 and XN2 represent an oxygen atom, a sulfur atom, a selenium atom, or NRN13 .
- X N1 and X N2 preferably represent a sulfur atom.
- R N1 to R N13 each represent a hydrogen atom or a substituent.
- At least one of R N1 to R N13 is a substituent represented by the following general formula (W).
- X P1 and X P2 represent an oxygen atom, a sulfur atom, a selenium atom, or NRP13 .
- X P1 and X P2 preferably represent a sulfur atom.
- R P1 to R P13 each represents a hydrogen atom or a substituent.
- At least one of R P1 to R P13 is a substituent represented by the following general formula (W).
- X Q1 and X Q2 represent an oxygen atom, a sulfur atom, a selenium atom, or NR Q13 .
- X Q1 and X Q2 preferably represent a sulfur atom.
- R Q1 to R Q13 each represents a hydrogen atom or a substituent.
- At least one of R Q1 to R Q13 is a substituent represented by the following general formula (W).
- X R1 , X R2 and X R3 represent an oxygen atom, a sulfur atom, a selenium atom or NR R9 .
- X R1 , X R2 and X R3 preferably represent a sulfur atom.
- R R1 to R R9 represent a hydrogen atom or a substituent.
- At least one of R R1 to R R9 is a substituent represented by the following general formula (W).
- X S1 , X S2 , X S3 and X S4 represent an oxygen atom, a sulfur atom, a selenium atom or NR S7 .
- X S1 , X S2 , X S3 and X S4 preferably represent a sulfur atom.
- R S1 to R S7 represent a hydrogen atom or a substituent. At least one of R S1 to R S7 is a substituent represented by the following general formula (W).
- X T1 , X T2 , X T3 , and X T4 represent an oxygen atom, a sulfur atom, a selenium atom, or NR T7 .
- X T1 , X T2 , X T3 and X T4 preferably represent a sulfur atom.
- R T1 to R T7 each represents a hydrogen atom or a substituent. At least one of R T1 to R T7 is a substituent represented by the following general formula (W).
- Substituents R C to R T can be a halogen atom, alkyl group (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Alkyl groups having 1 to 40 carbon atoms such as 2,6-dimethyloctyl, 2-decyltetradecyl, 2-hexyldecyl, 2-ethyloctyl, 2-decyltetradecyl, 2-butyldecyl, 1-octylnonyl , 2-ethyloctyl, 2-octyltetradecyl, 2-ethylhexyl, cycloalkyl, bicycloalkyl, tricycloalkyl, etc.), al
- the substituents that the substituents R C to R T can take include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an alkylthio group, and a general formula (W) described later.
- the alkyl group, alkenyl group, alkynyl group, acyl group, and aryl group of R D9 , R G9, and R H7 are the alkyl groups and alkenyl groups described above for the substituents that R C to R T can take.
- the heteroaryl group has the same meaning as the heteroaryl group described for the substituents of R A1 to R A6 .
- L represents a divalent linking group represented by any one of the following general formulas (L-1) to (L-25), or the following general formulas (L-1) to (L-25).
- R W is a substituted or unsubstituted alkyl group, a cyano group, a vinyl group, an ethynyl group, an oxyethylene group, repetition number v of oxyethylene units is more than one oligo oxyethylene group, a siloxane group, the number of silicon atoms is more than one It represents an oligosiloxane group or a substituted or unsubstituted trialkylsilyl group.
- the wavy line represents the bonding position with any ring forming each skeleton represented by the general formulas (C) to (T).
- L represents a divalent linking group in which two or more divalent linking groups represented by any of the general formulas (L-1) to (L-25) are bonded
- the moiety is a bonding position with any ring forming each skeleton represented by the general formulas (C) to (T) and a divalent group represented by the general formulas (L-1) to (L-25).
- R LZ is independently It represents a hydrogen atom or a substituent, formula (L-1) and (L-2) R LZ may form a condensed ring by combining with R W adjacent L respectively in.
- R N represents a hydrogen atom or a substituent
- R si each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group.
- the divalent linking groups represented by the general formulas (L-17) to (L-21), (L-23) and (L-24) are represented by the following general formulas (L-17A) to (L It is more preferably a divalent linking group represented by -21A), (L-23A) and (L-24A).
- a substituted or unsubstituted alkyl group an oxyethylene group, an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted group. If a trialkylsilyl group substitutions present on the end of the substituent of the general formula (W) -R W alone and can also be interpreted in, be interpreted as -L-R W in the general formula (W) it can.
- two (2) R LZ is a hydrogen atom (L-1) and n-heptyl having 7 carbon atoms.
- the substituent represented by the general formula (W) is an alkoxy group having 8 carbon atoms
- one linking group represented by the general formula (L-4) which is —O— and two R This is interpreted as a substituent in which one linking group represented by (L-1), in which LZ is a hydrogen atom, and an n-heptyl group having 7 carbon atoms are bonded.
- an oxyethylene group an oligooxyethylene group having a repeating number v of 2 or more, a siloxane group, an oligosiloxane group having 2 or more silicon atoms, or a substituted or unsubstituted trialkylsilyl group. If a group is present at the end of the substituents on including a linking group as possible from the end of the substituent, it is interpreted as R W alone in the general formula (W).
- the substituent R LZ in the general formulas (L-1), (L-2), (L-6) and (L-13) to (L-24) is represented by the general formulas (C) to (T). It may be mentioned those exemplified as the substituents of the substituents R C ⁇ R T can be taken.
- substituents R LZ in that in any general formula (L-6) is an alkyl group if (L-6) in the R LZ is an alkyl group has a carbon number of the alkyl group of 1 to It is preferably 9, more preferably 4 to 9 from the viewpoint of chemical stability and carrier transport properties, and further preferably 5 to 9.
- R LZ in (L-6) is an alkyl group
- the alkyl group is preferably a linear alkyl group from the viewpoint of increasing carrier mobility.
- the R N may be mentioned those exemplified as the substituents which may take the substituents R C ⁇ R T. Among them a hydrogen atom or a methyl group is preferable as also R N.
- R si is preferably an alkyl group. There are no particular limitations on the alkyl group R si can take, the preferred range of the alkyl group R si can take is the same as the preferred ranges of the alkyl group can take the silyl group when R W is a silyl group .
- the alkenyl group that R si can take is not particularly limited, but is preferably a substituted or unsubstituted alkenyl group, more preferably a branched alkenyl group, and the alkenyl group preferably has 2 to 3 carbon atoms.
- the alkynyl group that R si can take is not particularly limited, but is preferably a substituted or unsubstituted alkynyl group, more preferably a branched alkynyl group, and the alkynyl group has 2 to 3 carbon atoms. preferable.
- L is a divalent linking group represented by any one of the general formulas (L-1) to (L-5), (L-13), (L-17) or (L-18), or A divalent linkage in which two or more divalent linking groups represented by any one of (L-1) to (L-5), (L-13), (L-17) or (L-18) are bonded.
- divalent divalent linking group represented by the linking group and formula (L-1) of that is a divalent linking group attached is particularly preferred.
- There divalent linking group bonded is preferably a divalent linking group represented by formula (L-1) binds to R W side.
- a divalent linking group including a divalent linking group represented by the general formula (L-1) is particularly preferred, represented by the general formula (L-1).
- L is a divalent linking group represented by the general formulas (L-18) and (L-1), and (L-1) bonded to R W, more particularly preferably more that R W is a substituted or unsubstituted alkyl group, a divalent linking group L is represented by the general formula (L-18A) and (L-1) Yes, (L-1) via bonded to R W, it is even more particularly preferred R W is a substituted or unsubstituted alkyl group.
- R W may be a substituted or unsubstituted alkyl group.
- R W represents a substituted or unsubstituted alkyl group, an oxyethylene group, It is preferably an oligooxyethylene group having 2 or more repeating oxyethylene units, a siloxane group, or an oligosiloxane group having 2 or more silicon atoms, more preferably a substituted or unsubstituted alkyl group.
- R W when L adjacent to R W is a divalent linking group represented by formula (L-2) and (L-4) ⁇ (L -25) is, R W is It is more preferably a substituted or unsubstituted alkyl group.
- R W when L adjacent to R W is a divalent linking group represented by the general formula (L-3) is, R W represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted The silyl group is preferable.
- R W is a substituted or unsubstituted alkyl group, it preferably has a carbon number of 4-17, it is chemically stable is 6 to 14, more preferably from the viewpoint of carrier transportability, 6-12 More preferably it is.
- R W are long-chain alkyl group having the above-mentioned range, and particularly a straight-chain alkyl group of chain increases the linearity of the molecule, from the viewpoint of capable of enhancing the carrier mobility. If R W represents an alkyl group, a straight-chain alkyl group, even branched alkyl group, it may be a cyclic alkyl group, a straight-chain alkyl groups, increases the linearity of the molecules, to increase the carrier mobility It is preferable from the viewpoint that can be achieved.
- a divalent linking group L in formula (C) ⁇ (T) is represented by formula (L-1), and either an alkyl group R W is 1-4 carbon atoms, straight-chain 17; or, L is the general formula (L-3), any one Tsudehyo of (L-13) or (L-18) a divalent divalent divalent linking group linking group is attached, which is represented by the linking group and formula (L-1) that are, and that R W is a straight chain alkyl group, This is preferable from the viewpoint of increasing carrier mobility.
- L is a divalent linking group represented by formula (L-1), and, if R W is an alkyl group having a carbon number of 4 to 17 linear, carbon atoms R W is a linear 6 From the viewpoint of increasing carrier mobility, a linear alkyl group having 6 to 12 carbon atoms is particularly preferable.
- L is a divalent linking group represented by any one of general formulas (L-3), (L-13) or (L-18) and a divalent linking group represented by general formula (L-1).
- a divalent linking group of the linking group is bonded, and, if R W is a straight chain alkyl group, more preferably R W is an alkyl group having a carbon number of 4 to 17 linear, straight-chain
- the alkyl group having 6 to 14 carbon atoms is more preferable from the viewpoints of chemical stability and carrier transport properties, and the straight chain alkyl group having 6 to 12 carbon atoms is particularly preferable from the viewpoint of increasing carrier mobility. preferable.
- R W is a branched alkyl group.
- R W is an alkyl group having a substituent
- substituents when R W is an alkyl group having a substituent include a halogen atom, a fluorine atom is preferred. It is also possible if R W is an alkyl group having a fluorine atom is substituted with any hydrogen atom of the alkyl group a fluorine atom to form a perfluoroalkyl group. However, it is preferred that R W is an unsubstituted alkyl group.
- R W is ethylene group or an oligo ethylene group, and represented by R W "oligooxyethylene group" herein, - (OCH 2 CH 2) v refers to the group represented by OY (
- the repeating number v of the oxyethylene unit represents an integer of 2 or more, and Y at the terminal represents a hydrogen atom or a substituent.
- Y at the terminal of the oligooxyethylene group is a hydrogen atom, it becomes a hydroxy group.
- the number of repeating oxyethylene units v is preferably 2 to 4, and more preferably 2 to 3.
- the terminal hydroxy group of the oligooxyethylene group is preferably sealed, that is, Y represents a substituent.
- the hydroxy group is preferably sealed with an alkyl group having 1 to 3 carbon atoms, that is, Y is preferably an alkyl group having 1 to 3 carbon atoms, and Y is a methyl group or an ethyl group. Is more preferable, and a methyl group is particularly preferable.
- R W is, for siloxane group or an oligosiloxane groups, the number of repetitions of the siloxane units is preferably from 2 to 4, more preferably 2-3. Further, it is preferable that a hydrogen atom or an alkyl group is bonded to the Si atom. When an alkyl group is bonded to the Si atom, the alkyl group preferably has 1 to 3 carbon atoms, and for example, a methyl group or an ethyl group is preferably bonded. The same alkyl group may be bonded to the Si atom, or different alkyl groups or hydrogen atoms may be bonded thereto. Moreover, although all the siloxane units which comprise an oligosiloxane group may be the same or different, it is preferable that all are the same.
- R W is a substituted or unsubstituted silyl group. If R W is a substituted or unsubstituted silyl group Among them, it is preferred that R W is a substituted silyl group. Although there is no restriction
- R W is a trialkylsilyl group
- the carbon number of the alkyl group bonded to the Si atom is 1-3, for example, it is preferable to bind a methyl group or an ethyl group or an isopropyl group.
- the same alkyl group may be bonded to the Si atom, or different alkyl groups may be bonded thereto. Examples of the substituents when R W is a trialkylsilyl group having a substituent on the alkyl group is not particularly limited.
- the total number of carbon atoms contained in L and R W is 5 to 18. If the total number of carbon atoms contained in L and R W is at least the lower limit within the above range, the carrier mobility is high, lower the driving voltage. If the total number of carbon atoms contained in L and R W is not more than the upper limit of the above range, solubility in an organic solvent is increased. Preferably the total number of carbon atoms contained in L and R W is 5 to 14, more preferably 6 to 14, particularly preferably from 6 to 12, in particular more to be 8-12 preferable.
- the number of the groups represented by the general formula (W) is 1 to 4, and the carrier mobility is It is preferable from the viewpoint of increasing the solubility in an organic solvent, more preferably 1 or 2, and particularly preferably 2.
- the position of the group represented by the general formula (W) is not particularly limited.
- any one of R C1 , R C2 , R C3 and R C6 is preferably a group represented by the general formula (W), and R C1 and R C2 It is more preferable that both or both R C3 and R C6 are groups represented by the general formula (W).
- R D6 is preferably a group represented by the general formula (W), and both R D5 and R D6 are represented by the general formula (W). More preferably, it is a group.
- R E6 is preferably a group represented by the general formula (W), and both R E5 and R E6 are represented by the general formula (W). More preferably, it is a group. Further, when R E5 and R E6 are substituents other than the group represented by the general formula (W), it is also preferable that two R E7 are groups represented by the general formula (W).
- R F2 , R F3 , R F8 and R F9 is a substituent represented by the general formula (W).
- R G5 or R G6 is a group represented by the general formula (W) from the viewpoint of increasing carrier mobility and increasing solubility in an organic solvent. preferable.
- R H4 or R H6 is preferably a group represented by the general formula (W), and R H4 or R H6 and R H3 or R H5 are generally used. The group represented by the formula (W) is more preferable.
- R J8 is preferably a group represented by the general formula (W), and both R J8 and R J4 are represented by the general formula (W). More preferably, it is a group.
- R K7 is preferably a group represented by the general formula (W), and both R K7 and R K3 are represented by the general formula (W). More preferably, it is a group.
- R L2 , R L3 , R L6 and R L7 is a group represented by the general formula (W).
- R M2 is preferably a group represented by the general formula (W), and both R M2 and R M6 are represented by the general formula (W). More preferably, it is a group.
- R N3 is represented by the general formula (W)
- both R N3 and R N9 are represented by formula (W) More preferably, it is a group.
- R P2 or R P3 is preferably a group represented by the general formula (W), and both R P2 and R P8 or both R P3 and R P9 It is more preferable that both are groups represented by the general formula (W).
- R Q3 is preferably a group represented by the general formula (W), and both R Q3 and R Q9 are represented by the general formula (W). More preferably, it is a group.
- R R2 is preferably a group represented by the general formula (W), and both R R2 and R R7 are represented by the general formula (W). More preferably, it is a group.
- R S2 is preferably a group represented by the general formula (W), and both R S2 and R S5 are represented by the general formula (W). More preferably, it is a group.
- R T2 is preferably a group represented by the general formula (W), and both R T2 and R T5 are represented by the general formula (W). More preferably, it is a group.
- the number of substituents other than the group represented by the general formula (W) is preferably 0 to 4, more preferably 0 to 2.
- the compound represented by the general formula (C) preferably has a molecular weight of 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and particularly preferably 850 or less.
- the molecular weight is within the above range, solubility in a solvent can be enhanced.
- the molecular weight is preferably 300 or more, more preferably 350 or more, and further preferably 400 or more.
- the molecular weight of the compound represented by the general formula (D) is preferably the same as that of the compound represented by the general formula (C) because the solubility in a solvent can be increased.
- the molecular weight is preferably 400 or more, more preferably 450 or more, and further preferably 500 or more.
- the molecular weights of the compound E, the compound F, the compound G, and the compound H are preferably the same as the compound C whose upper limit is represented by the general formula (C), so that the solubility in a solvent can be improved. .
- the lower limit of the molecular weight is the same as the compound represented by the general formula (D).
- the upper limit of the molecular weights of the compound J and the compound K is the same as that of the compound C represented by the general formula (C), so that the solubility in a solvent can be improved.
- the lower limit of the molecular weight is the same as the compound represented by the general formula (D).
- the molecular weights of the compound L, the compound M, the compound N, the compound P, and the compound Q are the same as those of the compound C represented by the general formula (C) in the upper limit, which increases the solubility in a solvent. It is possible and preferable.
- the lower limit of the molecular weight is the same as the compound represented by the general formula (D).
- the molecular weights of the compound R, the compound S, and the compound T are preferably the same as those of the compound C represented by the general formula (C), because the solubility in the solvent can be improved.
- the lower limit of the molecular weight is the same as the compound represented by the general formula (D).
- organic polymer and derivatives thereof examples include polypyrrole and substituted products thereof, polydiketopyrrole and substituted products thereof, polythiophene and derivatives thereof, isothianaphthene such as polyisothianaphthene, thienylene vinylene such as polythienylene vinylene, poly Poly (p-phenylene vinylene) such as (p-phenylene vinylene), polyaniline and its derivatives, polyacetylene, polydiacetylene, polyazulene, polypyrene, polycarbazole, polyselenophene, polyfuran, poly (p-phenylene), polyindole, poly Examples thereof include polymers such as pyridazine, polytellurophene, polynaphthalene, polyvinylcarbazole, polyphenylene sulfide, and polyvinylene sulfide, and polymers of condensed polycyclic aromatic compounds.
- the polythiophene and derivatives thereof are not particularly limited.
- poly-3-hexylthiophene (P3HT) in which hexyl group is introduced into polythiophene, polyethylenedioxythiophene, poly (3,4-ethylenedioxythiophene) / polystyrenesulfone An acid (PEDOT / PSS) etc. are mentioned.
- the oligomer for example, oligothiophene which has the same repeating unit as these polymers can also be mentioned.
- Examples of the organic polymer include polymer compounds in which compounds represented by the following general formulas (C) to (T) have a repeating structure.
- a compound represented by the general formulas (C) to (T) has a ⁇ -conjugated structure in which a repeating structure is formed via at least one arylene group or heteroarylene group (thiophene, bithiophene, etc.).
- Examples thereof include a polymer and a pendant polymer in which compounds represented by the general formulas (C) to (T) are bonded to a polymer main chain via a side chain.
- the polymer main chain is preferably polyacrylate, polyvinyl, polysiloxane or the like, and the side chain is preferably an alkylene group or a polyethylene oxide group.
- the polymer main chain may be formed by polymerizing at least one of the substituents R C to R T having a group derived from a polymerizable group.
- These organic polymers preferably have a weight average molecular weight of 30,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more.
- the weight average molecular weight is not less than the above lower limit value, the intermolecular interaction can be enhanced and high mobility can be obtained.
- the inorganic semiconductor material for forming the semiconductor layer is not particularly limited, but a coating type semiconductor is preferable, and an oxide semiconductor is given as a preferable example.
- the oxide semiconductor is not particularly limited as long as it is made of a metal oxide.
- the semiconductor layer made of an oxide semiconductor is preferably formed using an oxide semiconductor precursor, that is, a material that is converted into a semiconductor material made of a metal oxide by a conversion process such as thermal oxidation.
- the oxide semiconductor is not particularly limited.
- InGaZnO x , InGaO x , InSnZnO x , GaZnO x , InSnO x , InZnO x , SnZnO x (all x> 0), ZnO, and SnO 2 can be given.
- oxide semiconductor precursor examples include metal nitrates, metal halides, and alkoxides.
- metal contained in the oxide semiconductor precursor include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr, Examples thereof include at least one selected from the group consisting of Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- oxide semiconductor precursor examples include, for example, indium nitrate, zinc nitrate, gallium nitrate, tin nitrate, aluminum nitrate, indium chloride, zinc chloride, tin chloride (divalent), tin chloride (tetravalent), and gallium chloride.
- Aluminum chloride tri-i-propoxy indium, diethoxy zinc, bis (dipivaloylmethanato) zinc, tetraethoxy tin, tetra-i-propoxy tin, tri-i-propoxy gallium, tri-i-propoxy aluminum It is done.
- the source electrode is an electrode through which current flows from the outside through the wiring.
- the drain electrode is an electrode that sends current to the outside through wiring, and is usually provided in contact with the semiconductor layer.
- a conductive material used in a conventional thin film transistor can be used, and examples thereof include the conductive material described for the gate electrode.
- the source electrode and the drain electrode can be formed by a method similar to the method for forming the gate electrode, respectively.
- a lift-off method or an etching method can be employed.
- the source electrode and the drain electrode can be preferably formed by an etching method.
- the etching method is a method of removing unnecessary portions by etching after forming a conductive material.
- the conductive material remaining on the base when the resist is removed can be peeled off, and the resist residue or the removed conductive material can be prevented from reattaching to the base, and the shape of the electrode edge portion is excellent. This is preferable to the lift-off method.
- a resist is applied to a part of the base, a conductive material is formed thereon, and the resist is removed together with the solvent by elution or peeling with a solvent.
- This is a method of forming a film of a conductive material only on a portion where no is applied.
- a source electrode and a drain electrode is arbitrary, 1 nm or more is preferable respectively and 10 nm or more is especially preferable. Moreover, 500 nm or less is preferable and 300 nm or less is especially preferable.
- the interval (channel length) between the source electrode and the drain electrode is arbitrary, but is preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
- the channel width is preferably 5000 ⁇ m or less, and particularly preferably 1000 ⁇ m or less.
- the TFT of the present invention may have an overcoat layer.
- the overcoat layer is usually a layer formed as a protective layer on the surface of the TFT.
- a single layer structure or a multilayer structure may be used.
- the overcoat layer may be an organic overcoat layer or an inorganic overcoat layer.
- the material for forming the organic overcoat layer is not particularly limited, and examples thereof include organic polymers such as polystyrene, acrylic resin, polyvinyl alcohol, polyolefin, polyimide, polyurethane, polyacetylene, and epoxy resin, and these organic polymers. Derivatives in which a crosslinkable group or a water repellent group is introduced may be mentioned.
- organic polymers and derivatives thereof can be used in combination with a crosslinking component, a fluorine compound, a silicon compound, and the like.
- the material for forming the inorganic overcoat layer is not particularly limited, and examples thereof include metal oxides such as silicon oxide and aluminum oxide, and metal nitrides such as silicon nitride. These materials may be used alone or in combination of two or more in any combination and ratio.
- the organic overcoat layer is, for example, a solution containing a material to be an overcoat layer is applied and dried on the underlying layer, a solution containing a material to be an overcoat layer is applied, and exposure is performed after drying. It can be formed by a method such as development and patterning. The patterning of the overcoat layer can also be directly formed by a printing method, an inkjet method, or the like. The overcoat layer may be crosslinked by exposure or heating after the patterning of the overcoat layer.
- the inorganic overcoat layer can be formed by a dry method such as a sputtering method or a vapor deposition method or a wet method such as a sol-gel method.
- the TFT of the present invention may be provided with layers and members other than those described above.
- Examples of other layers or members include banks.
- the bank is used for the purpose of blocking the discharge liquid at a predetermined position when a semiconductor layer, an overcoat layer, or the like is formed by an inkjet method or the like. For this reason, the bank usually has liquid repellency.
- Examples of the bank forming method include a method of performing liquid repellency treatment such as a fluorine plasma method after patterning by a photolithography method or the like, a method of curing a photosensitive composition containing a liquid repellent component such as a fluorine compound, and the like.
- the method of curing the photosensitive composition containing the latter liquid repellent component does not cause the gate insulating layer to be affected by the liquid repellent treatment. ,preferable.
- a technique may be used in which a liquid repellent contrast is given to the base without using the bank so as to have the same role as the bank.
- the TFT of the present invention is preferably used by being mounted on a display panel.
- the display panel include a liquid crystal panel, an organic EL panel, and an electronic paper panel.
- the above compound L9 is a compound represented by the general formula (L), Journal of Organic Physics / Bioelectronics, 2011, 22, 9-12. And synthesized according to the method described in International Publication No. 2009/148016 pamphlet and the like.
- the compound C16 is a compound represented by the general formula (C), and was synthesized according to the following synthesis method of the following compound C1.
- FIG. 1 Production of bottom-gate TFT-1 A bottom-gate / bottom-contact TFT shown in FIG. A doped silicon substrate (also serving as the gate electrode 5) having a thickness of 1 mm was used as the substrate 6, and the gate insulating layer 2 was formed thereon.
- Diphenyliodonium hexafluorophosphate salt as an acid catalyst was added to the obtained filtrate so that it might become 0.1 wt%, it apply
- Production of bottom gate TFT-3 In Production Example 1 above, a commercially available polysilsesquioxane was used instead of poly (4-vinylphenol) in the formation of the gate insulating layer, tetrahydrofuran was used as the solvent, and no cross-linking agent and acid catalyst were added. A TFT was produced in the same manner as in Production Example 1 except that.
- TFTs of Examples 1 to 3 and Comparative Examples 1 to 3 were obtained. More specifically, the TFTs of Examples 1 to 3 below are the ones obtained by washing the polymer used for forming the gate insulating layer or the mixture of the polymer and the cross-linking agent once with pure water and drying in Production Examples 1 to 3. Was used to form the gate insulating layer.
- the polymers used in forming the gate insulating layer or the mixture of the polymer and the crosslinking agent in Production Examples 1 to 3 were washed three times with pure water, and after ultrafiltration, What was refine
- the content of the specific metal in the gate insulating layer is the same as the polymer used for forming the gate insulating layer, or a mixture of the polymer and the crosslinking agent (after washing once with the above pure water and drying, or the above purification) It was determined by quantifying using ICP-MS HP7700 (manufactured by Agilent) after ashing and acid-dissolving after treatment.
- the content of the specific metal in the gate insulating layer is the content of the specific metal in the solid content of the polymer used for forming the gate insulating layer or the mixture of the polymer and the crosslinking agent.
- the content of the specific non-metallic ionic substance in the gate insulating layer is the polymer used for forming the gate insulating layer or a mixture of the polymer and the crosslinking agent (after washing once with the above pure water and drying, Or after the above purification treatment) is dissolved in an organic solvent, and separated with ultrapure water, and the aqueous phase is analyzed by a gradient method using an ICS-2000 type IC device (manufactured by Dionex). Determined.
- the content of the specific nonmetallic ionic substance in the gate insulating layer is the content of the specific nonmetallic ionic substance in the solid content of the polymer used for forming the gate insulating layer or the mixture of the polymer and the crosslinking agent. is there.
- Table 1 below shows the measurement results of the specific metal and specific non-metal ionic substances in the gate insulating layer for the bottom gate TFTs of Examples 1 to 3 and Comparative Examples 1 to 3.
- metals or non-metal ionic substances below the detection limit are not considered in the calculation of the total amount.
- TFT performance evaluation For the bottom gate TFTs obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the threshold voltage, carrier mobility, and on / off ratio were evaluated by the following method. The performance of was investigated.
- Id (w / 2L) ⁇ Ci (Vg ⁇ Vth) 2 (Where L is the gate length, w is the gate width, Ci is the capacitance per unit area of the insulating layer, Vg is the gate voltage, and Vth is the threshold voltage)
- On / Off ratio is (maximum value of
- Example 1 as the organic semiconductor, A26, A27, C1, C4, C7, D1, E2, F2, F5, F10, G12, G14, H10, H11, J2, J3, K2, K3, L2,
- the TFTs shown in FIG. 1A were manufactured in the same manner as in Example 1 except that L5, L6, L8, L15, M8, N4, P3, Q3, R1, S1, or T1 was used.
- the carrier mobility ⁇ , the On / Off ratio, and the threshold voltage Vth were evaluated in the same manner as in Test Example 3.
- the results were superior in performance as compared with the case where the amount of the specific metal and non-metal ionic substance in the gate insulating layer was outside the range defined in the present invention.
- top gate TFT-1 A top gate / bottom contact TFT shown in FIG. 1C was manufactured.
- a glass substrate manufactured by NEC Corning, OA10 washed with water and dried was used as the substrate 6.
- a chromium / gold electrode as a source electrode and a drain electrode was formed on the glass substrate by vacuum deposition using a mask. Thereby, a source electrode 3 and a drain electrode 4 having a thickness of 100 nm were provided.
- the gate width W was 100 mm and the gate length L was 100 ⁇ m.
- Diphenyliodonium hexafluorophosphate salt as an acid catalyst was added to the obtained filtrate so that it might become 0.1 wt%, it apply
- an Ag fine particle aqueous dispersion was applied onto the gate insulating layer by an inkjet method and dried to form a gate electrode having a thickness of 200 nm.
- TFTs of Examples 4 to 6 and Comparative Examples 4 to 6 were obtained.
- the TFTs of Examples 4 to 6 below were obtained by washing the polymer used for forming the gate insulating layer or the mixture of the polymer and the cross-linking agent once with pure water and drying in Production Examples 4 to 6. Was used to form the gate insulating layer.
- the polymers used for forming the gate insulating layer or the mixture of the polymer and the crosslinking agent in Production Examples 4 to 6 were washed with pure water three times, and after ultrafiltration treatment, What was refine
- Example 4 as the organic semiconductor, A26, A27, C1, C4, C7, D1, E2, F2, F5, F10, G12, G14, H10, H11, J2, J3, K2, K3, L2,
- the TFTs shown in FIG. 1C were manufactured in the same manner as in Example 4 except that L5, L6, L8, L15, M8, N4, P3, Q3, R1, S1, or T1 was used.
- the carrier mobility ⁇ , the On / Off ratio, and the threshold voltage Vth were evaluated in the same manner as in Test Example 3.
- the performance of the gate insulating layer was superior to that in which the amount of the specific metal and non-metal ionic substance was outside the range defined in the present invention.
- the dielectric constant of the gate insulating layer in which the content of the specific metal and the specific non-metal ionic substance is within the range defined in the present invention increases while maintaining the insulating property (volume resistivity), As a result, the threshold voltage of the TFT could be lowered.
- the TFT having the gate insulating layer defined in the present invention has a carrier transporting property as compared with the TFT of the comparative example in which the content of the specific metal and specific non-metal ionic substance in the gate insulating layer is less than that defined in the present invention. It was also found that both the degree and the on / off ratio showed high values. That is, it was shown that the TFT of the present invention is a TFT that has both excellent carrier mobility and current amplification factor, low threshold voltage, and low power consumption.
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Abstract
Description
これに対し近年では、有機半導体を用いたTFTも普及してきている。有機半導体層は、インクジェット、スピンコート、フレキソ印刷等の方法により成膜できるため、成膜プロセスをより低温で、高速・効率的に、低コストで行うことができる。
また、ゲート絶縁膜を有機高分子化合物で形成したTFTも知られており、例えば特許文献1には、樹脂と架橋剤を用いて形成した硬化物でゲート絶縁層を形成したTFTが記載されている。この特許文献1には、ゲート絶縁層のアルカリ金属の含有量を少なくして有機半導体層の汚染を防ぐことが望ましいことが記載され、さらにナトリウムの量を20ppm以下とすることが好ましいことが記載されている。
〔1〕
基板上に、ゲート電極と、半導体層と、該ゲート電極と該半導体層との間に設けられた、有機高分子化合物で形成されたゲート絶縁層と、半導体層に接して設けられ、半導体層を介して連結されたソース電極及びドレイン電極とを有する薄膜トランジスタであって、
ゲート絶縁層中、Mg、Ca、Ba、Al、Sn、Pb、Cr、Mn、Fe、Ni、Cu、Zn及びAgから選ばれる金属の含有量が総量で10ppb~1ppmであるか、又は、ハロゲンイオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、薄膜トランジスタ。
〔2〕
上記ゲート絶縁層中、Mg、Ca、Ba、Al、Sn、Pb、Cr、Mn、Fe、Ni、Cu、Zn及びAgから選ばれる金属の含有量が総量で10ppb~1ppmであり、且つ、ハロゲンイオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、〔1〕に記載の薄膜トランジスタ。
〔3〕
上記ゲート絶縁層中、Mg、Ca、Al、Cr、Fe及びZnから選ばれる金属の含有量が総量で10ppb~1ppmである、〔1〕又は〔2〕に記載の薄膜トランジスタ。
〔4〕
上記ゲート絶縁層中、塩素イオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、〔1〕~〔3〕のいずれかに記載の薄膜トランジスタ。
〔5〕
上記ゲート絶縁層中、塩素イオン及び硫酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、〔1〕~〔4〕のいずれかに記載の薄膜トランジスタ。
〔6〕
上記有機高分子化合物が、ポリビニルフェノール、ノボラック樹脂、ポリスチレン、ポリ(メタ)アクリレート、エポキシ樹脂、エポキシ(メタ)アクリレート樹脂、ポリビニルアルコール、フッ素樹脂、ポリシクロオレフィン、ポリシルセスキオキサン、ポリシロキサン、ポリエステル、ポリエーテルスルホン、ポリエーテルケトン、及びポリイミドから選ばれる有機高分子化合物である、〔1〕~〔5〕のいずれかに記載の薄膜トランジスタ。
〔7〕
上記半導体層が有機半導体を含む、〔1〕~〔6〕のいずれかに記載の薄膜トランジスタ。
〔8〕
上記有機半導体が、下記一般式(C)~(T)のいずれかで表される、〔7〕に記載の薄膜トランジスタ。
一般式(D)中、XD1及びXD2はNRD9、酸素原子又は硫黄原子を表す。AD1はCRD7又は窒素原子を表し、AD2はCRD8又は窒素原子を表し、RD9は水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基を表す。RD1~RD8は水素原子又は置換基を表し、RD1~RD8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(E)中、XE1及びXE2は酸素原子、硫黄原子又はNRE7を表す。AE1及びAE2はCRE8又は窒素原子を表す。RE1~RE8は水素原子又は置換基を表し、RE1~RE8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(F)中、XF1及びXF2は酸素原子、硫黄原子又はセレン原子を表す。RF1~RF10、RFa及びRFbは水素原子又は置換基を表し、RF1~RF10、RFa及びRFbのうち少なくとも一つは一般式(W)で表される置換基である。p及びqは0~2の整数を表す。
一般式(G)中、XG1及びXG2はNRG9、酸素原子又は硫黄原子を表す。AG1はCRG7又は窒素原子を表し、AG2はCRG8又は窒素原子を表す。RG9は水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表し、RG1~RG8は水素原子又は置換基を表し、RG1~RG8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(H)中、XH1~XH4はNRH7、酸素原子又は硫黄原子を表し、RH7は水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表す。RH1~RH6は水素原子又は置換基を表し、RH1~RH6のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(J)中、XJ1及びXJ2は酸素原子、硫黄原子、セレン原子又はNRJ9を表す。XJ3及びXJ4は酸素原子、硫黄原子又はセレン原子を表す。RJ1~RJ9は水素原子又は置換基を表し、RJ1~RJ9のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(K)中、XK1及びXK2は酸素原子、硫黄原子、セレン原子又はNRK9を表す。XK3及びXK4は酸素原子、硫黄原子又はセレン原子を表す。RK1~RK9は水素原子又は置換基を表し、RK1~RK9のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(L)中、XL1及びXL2は酸素原子、硫黄原子又はNRL11を表す。RL1~RL11は水素原子又は置換基を表し、RL1~RL11のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(M)中、XM1及びXM2は酸素原子、硫黄原子、セレン原子又はNRM9を表す。RM1~RM9は水素原子又は置換基を表し、RM1~RM9のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(N)中、XN1及びXN2は酸素原子、硫黄原子、セレン原子又はNRN13を表す。RN1~RN13は水素原子又は置換基を表し、RN1~RN13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(P)中、XP1及びXP2は酸素原子、硫黄原子、セレン原子又はNRP13を表す。RP1~RP13は水素原子又は置換基を表し、RP1~RP13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(Q)中、XQ1及びXQ2は酸素原子、硫黄原子、セレン原子又はNRQ13を表す。RQ1~RQ13は水素原子又は置換基を表し、RQ1~RQ13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(R)中、XR1、XR2及びXR3は酸素原子、硫黄原子、セレン原子又はNRR9を表す。RR1~RR9は水素原子又は置換基を表し、RR1~RR9のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(S)中、XS1、XS2、XS3及びXS4は酸素原子、硫黄原子、セレン原子又はNRS7を表す。RS1~RS7は水素原子又は置換基を表し、RS1~RS7のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(T)中、XT1、XT2、XT3及びXT4は酸素原子、硫黄原子、セレン原子又はNRT7を表す。RT1~RT7は水素原子又は置換基を表し、RT1~RT7のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(W): -L-RW
一般式(W)中、Lは下記一般式(L-1)~(L-25)のいずれかで表される2価の連結基又は2以上の下記一般式(L-1)~(L-25)のいずれかで表される2価の連結基が結合した2価の連結基を表す。
RWは置換又は無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、オキシエチレン単位の繰り返し数vが2以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が2以上のオリゴシロキサン基、あるいは、置換又は無置換のトリアルキルシリル基を表す。
一般式(L-13)におけるmは4を表し、一般式(L-14)及び(L-15)におけるmは3を表し、一般式(L-16)~(L-20)におけるmは2を表し、(L-22)におけるmは6を表す。
一般式(L-1)、(L-2)、(L-6)及び(L-13)~(L19)及び(L-21)~(L-24)におけるRLZはそれぞれ独立に水素原子又は置換基を表す。
RNは水素原子又は置換基を表し、Rsiはそれぞれ独立に水素原子、アルキル基、アルケニル基又はアルキニル基を表す。
〔9〕
上記有機半導体が、一般式(C)、(F)、(J)及び(L)のいずれかで表される、〔8〕に記載の薄膜トランジスタ。
なお、本明細書において「~」を用いて表される数値範囲は、「~」前後に記載される数値を下限値および上限値として含む範囲を意味する。
本発明の薄膜トランジスタ(以下、単に「本発明のTFT」という。)の形態を以下に説明する。
図1(A)~(D)は、各々、本発明のTFTの代表的な好ましい形態を模式的に表わす縦断面図である。図1(A)~(D)において、1は半導体層、2はゲート絶縁層、3はソース電極、4はドレイン電極、5はゲート電極、6は基板を示す。
また、図1(A)は、ボトムゲート・ボトムコンタクト型、図1(B)は、ボトムゲート・トップコンタクト型、図1(C)はトップゲート・ボトムコンタクト型、図1(D)はトップゲート・トップコンタクト型のTFTを示している。本発明のTFTには上記4つの形態のすべてが包含される。図示を省略するが、各TFTの図面最上部(基板6に対して反対側)には、オーバーコート層が形成されている場合もある。
基板は、TFT及びその上に作製される表示パネル等を支持できるものであればよい。基板は、表面に絶縁性があり、シート状で、表面が平坦であれば特に限定されない。
基板がステンレスシート、アルミ箔、銅箔又はシリコンウェハ等の導電性あるいは半導体性の材料で形成されている場合、通常は、表面に絶縁性の高分子材料あるいは金属酸化物等を塗布又は積層して用いられる。
このような可撓性を有するプラスチック基板等を使用すれば、例えば曲面形状を有するディスプレイ装置や電子機器へのTFTの組込みあるいは一体化が可能となる。
また、基板を構成する有機材料は、TFT作製時に用いる溶媒に対する耐性を有する材料が好ましく、また、ゲート絶縁層及び電極との密着性に優れる材料が好ましい。
さらに、ガスバリア性の高い有機ポリマーからなるプラスチック基板を用いることも好ましい。
基板の少なくとも片面に緻密なシリコン酸化膜等を設けたり、無機材料を蒸着又は積層したりすることも好ましい。
ゲート電極は、TFTのゲート電極として用いられている従来公知の電極を用いることができる。ゲート電極を構成する導電性材料(電極材料ともいう)としては、特に限定されない。例えば、白金、金、銀、アルミニウム、クロム、ニッケル、銅、モリブデン、チタン、マグネシウム、カルシウム、バリウム、ナトリウム、パラジウム、鉄、マンガン等の金属;InO2、SnO2、インジウム・錫酸化物(ITO)、フッ素ドープ酸化錫(FTO)、アルミニウムドープ酸化亜鉛(AZO)、ガリウムドープ酸化亜鉛(GZO)等の導電性金属酸化物;ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリ(3,4-エチレンジオキシチオフェン)/ポリスチレンスルホン酸(PEDOT/PSS)等の導電性高分子;塩酸、硫酸、スルホン酸等の酸、PF6、AsF5、FeCl3等のルイス酸、ヨウ素等のハロゲン原子、ナトリウム、カリウム等の金属原子等のドーパントを添加した上記導電性高分子、並びに、カーボンブラック、グラファイト粉、金属微粒子等を分散した導電性の複合材料等が挙げられる。これらの材料は、1種のみを用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
また、ゲート電極は、上記導電性材料からなる1層でもよく、2層以上を積層してもよい。
塗布法では、上記材料の溶液、ペースト又は分散液を調製、塗布し、乾燥、焼成、光硬化又はエージング等により、膜を形成し、又は直接電極を形成できる。
また、インクジェット印刷、スクリーン印刷、(反転)オフセット印刷、凸版印刷、凹版印刷、平版印刷、熱転写印刷、マイクロコンタクトプリンティング法等は、所望のパターニングが可能であり、工程の簡素化、コスト低減、高速化の点で好ましい。
スピンコート法、ダイコート法、マイクログラビアコート法、ディップコート法を採用する場合も、下記フォトリソグラフィー法等と組み合わせてパターニングすることができる。
他のパターニング方法として、上記材料に、レーザーや電子線等のエネルギー線を照射して、研磨し、又は材料の導電性を変化させる方法も挙げられる。
さらに、基板以外の支持体に印刷したゲート電極用組成物を基板等の下地層の上に転写させる方法も挙げられる。
本発明のTFTのゲート絶縁層は、絶縁性を有する有機高分子化合物で形成される。有機高分子化合物は、絶縁性を有するものであれば特に限定されず、薄膜、例えば厚み1μm以下の薄膜を形成できるものが好ましい。
有機高分子化合物は、ぞれぞれ、1種を用いても、2種以上を併用してもよい。
本発明のTFTは、そのゲート絶縁層中の特定金属又は特定非金属イオン性物質の含有量が特定の範囲内に抑えられているためにリークパス(伝導パス)が形成されにくい。そのため、本発明のTFTはゲート絶縁層の優れた絶縁性に伴い高い電流増幅率を示す。しかも意外なことに、この電流増幅率は、ゲート絶縁層中の特定金属又は特定非金属イオン性物質が本発明で規定するよりも低い場合に比べて(すなわちリークパスの原因となりうる物質をより少なくした場合に比べて)、特定金属又は特定非金属イオン性物質を本発明で規定する量含有する場合(すなわちリークパスの原因となりうる物質を一定程度含有する場合)において高まる。さらに、本発明のTFTは閾値電圧が低い。通常、ゲート絶縁層の絶縁性とTFTの閾値電圧とは正に相関する。すなわち、ゲート絶縁層の絶縁性が高いと閾値電圧も高くなる。しかし、本発明のTFTは、ゲート絶縁層中の特定金属又は特定非金属イオン性物質の含有量が本発明で規定する特定の範囲内にあることで、ゲート絶縁層の高い絶縁性を維持しながら閾値電圧は低く抑えられる。すなわち、本発明により、少ない消費電力でより確実にスイッチング動作を行うことができるTFTが提供される。さらに本発明のTFTは、ゲート絶縁層中の特定金属又は特定非金属イオン性物質の含有量が本発明で規定する特定の範囲内にあることでキャリア移動度も高められる。なお、ゲート絶縁層中のアルカリ金属の量を調節しても上記のような複合的な性能向上は認められない。
本発明のTFTにおいて、ゲート絶縁層中、特定金属から選ばれる金属の含有量は総量で10ppb~500ppbが好ましく、10ppb~200ppbがより好ましく、12ppb~100ppbがさらに好ましく、14ppb~70ppbがさらに好ましい。また、ゲート絶縁層中、特定非金属イオン性物質から選ばれる非金属イオン性物質の含有量は2ppm~70ppmが好ましく、3ppm~50ppmがより好ましく、5ppm~40ppmがさらに好ましい。
ゲート絶縁層の特定金属や特定非金属イオン性物質の量は、ゲート絶縁層の製造に用いる材料を、洗浄処理や精製処理等に付することで調整することができる。
また、本発明のTFTは、そのゲート絶縁層中における塩素イオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で2ppm~70ppmであることが好ましく、より好ましくは3ppm~50ppm、さらに好ましくは5ppm~40ppmである。さらに本発明のTFTは、そのゲート絶縁層中における塩素イオン及び硫酸イオンから選ばれる非金属イオン性物質の含有量が総量で2ppm~70ppmであることが好ましく、より好ましくは3ppm~50ppm、さらに好ましくは5ppm~40ppmである。
上記ポリ(メタ)アクリレートとしては、ポリアルキルメタクリレートが好ましく、ポリメチルメタクリレートがより好ましい。上記フッ素樹脂としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、CYTOPに代表される環状フルオロアルキルポリマーを挙げることができる。上記ポリシロキサンとしては、ジアルキルポリシロキサンが好ましく、ポリジメチルシロキサンがより好ましい。
また、ラジカルを発生させて高分子化合物に架橋構造を導入する場合、特開2013-214649号公報の[0167]~[0177]に記載の「数平均分子量(Mn)が140~5,000であり、架橋性官能基を有し、フッ素原子を有さない化合物(G)」を用いるのが好ましく、これらの内容は好ましくは本願明細書に組み込まれる。
また、酸を発生させて高分子化合物に架橋構造を導入する場合、特開2005-354012号公報の[0032]~[0033]に記載の架橋剤、特に二官能以上のエポキシ化合物、オキセタン化合物、特開2006-303465号公報の[0046]~[0062]に記載の架橋剤、特に2個以上の架橋基を有し、該架橋基の少なくとも一つがメチロール基もしくはNH基であることを特徴とする化合物、及び、特開2012-163946号公報の[0137]~[0145]に記載の、ヒドロキシメチル基又はアルコキシメチル基を分子内に2個以上有する化合物を用いるのが好ましく、これらの内容は好ましくは本願明細書に組み込まれる。
ゲート絶縁層上には、自己組織化単分子膜層を形成することもできる。
自己組織化単分子膜層を形成する化合物としては、自己組織化する化合物であれば特に限定されず、例えば、自己組織化する化合物として、下記式1Sで表される一種類以上の化合物を用いることができる。
式1S:R1S-XS
XSは吸着性又は反応性置換基を表し、具体的には、-SiX4X5X6基(X4は、ハライド基又はアルコキシ基を表し、X5、X6はそれぞれ独立にハライド基、アルコキシ基、アルキル基、アリール基を表す。X4、X5、X6はそれぞれ同じであることが好ましく、クロロ基、メトキシ基、エトキシ基であることがより好ましい)、ホスホン酸基(-PO3H2)、ホスフィン酸基(-PRO2H、Rはアルキル基)、リン酸基、亜リン酸基、アミノ基、ハライド基、カルボキシ基、スルホン酸基、ホウ酸基(-B(OH)2)、ヒドロキシ基、チオール基、エチニル基、ビニル基、ニトロ基又はシアノ基のいずれかを表す。
例えば、より緻密な自己組織化単分子膜層を得る好ましい方法として、Langmuir 19, 1159 (2003)及びJ. Phys. Chem. B 110, 21101 (2006)等に記載の方法が挙げられる。
乾燥溶媒としては、特に限定されないが、例えば、クロロホルム、トリクロロエチレン、アニソール、ジエチルエーテル、ヘキサン、トルエン等を単独又は混合して用いることかできる。
さらに、乾燥雰囲気中又は乾燥気体の噴きつけによって、膜を乾燥させることが好ましい。乾燥気体には窒素等の不活性気体を用いるのが好ましい。このような自己組織化単分子膜層の製造方法を用いることにより、緻密で凝集や欠損のない自己組織化単分子膜層が形成されることから、自己組織化単分子膜層の表面粗さを0.3nm以下に抑えることができる。
<有機半導体層>
有機半導体層は、半導体性を示し、キャリアを蓄積可能な層である。
有機半導体層は、有機半導体を含有する層であればよい。
有機半導体としては、特に限定されず、有機ポリマー及びその誘導体、低分子化合物等が挙げられる。
本発明において、低分子化合物は、有機ポリマー及びその誘導体以外の化合物を意味する。すなわち、繰り返し単位を有さない化合物をいう。低分子化合物は、このような化合物である限り、分子量は特に限定されるものではない。低分子化合物の分子量は、好ましくは300~2000であり、さらに好ましくは400~1000である。
ZA1及びZA2は、S、O、Se又はTeを表す。
nA1及びnA2は0~3の整数を表す。ただし、nA1及びnA2が同時に0になることはない。
これらの置換基は、さらに置換基を複数有していてもよい。複数有していてもよい置換基としては、上記、RA1~RA6で表される置換基が挙げられる。
ZA1及びZA2は、S、O、Se又はTeを表す。
nA1及びnA2は0~3の整数を表す。ただし、nA1とnA2が同時に0になることはない。
一般式(D)中、XD1及びXD2はNRD9、酸素原子又は硫黄原子を表す。AD1はCRD7又はN原子を表し、AD2はCRD8又はN原子を表し、RD9は水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基を表す。RD1~RD8は水素原子又は置換基を表し、RD1~RD8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(E)中、XE1及びXE2は酸素原子、硫黄原子又はNRE7を表す。AE1及びAE2はCRE8又は窒素原子を表す。RE1~RE8は水素原子又は置換基を表す。RE1~RE8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(G)中、XG1及びXG2はNRG9、酸素原子又は硫黄原子を表す。AG1はCRG7又はN原子を表す。AG2はCRG8又はN原子を表す。RG9は水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表す。RG1~RG8は水素原子又は置換基を表す。RG1~RG8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(K)中、XK1及びXK2は酸素原子、硫黄原子、セレン原子又はNRK9を表す。XK3及びXK4は酸素原子、硫黄原子又はセレン原子を表す。XK1、XK2、XK3及びXK4は好ましくは硫黄原子を表す。RK1~RK9は水素原子又は置換基を表す。RK1~RK9のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(L)中、XL1及びXL2は酸素原子、硫黄原子又はNRL11を表す。XL1及びXL2は好ましくは酸素原子又は硫黄原子を表す。RL1~RL11は水素原子又は置換基を表し、RL1~RL11のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(N)中、XN1及びXN2は酸素原子、硫黄原子、セレン原子又はNRN13を表す。XN1及びXN2は好ましくは硫黄原子を表す。RN1~RN13は水素原子又は置換基を表す。RN1~RN13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(P)中、XP1及びXP2は酸素原子、硫黄原子、セレン原子又はNRP13を表す。XP1及びXP2は好ましくは硫黄原子を表す。RP1~RP13は水素原子又は置換基を表す。RP1~RP13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(R)中、XR1、XR2及びXR3は酸素原子、硫黄原子、セレン原子又はNRR9を表す。XR1、XR2及びXR3は好ましくは硫黄原子を表す。RR1~RR9は水素原子又は置換基を表す。RR1~RR9のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(T)中、XT1、XT2、XT3、及びXT4は酸素原子、硫黄原子、セレン原子又はNRT7を表す。XT1、XT2、XT3及びXT4は好ましくは硫黄原子を表す。RT1~RT7は水素原子又は置換基を表す。RT1~RT7のうち少なくとも1つは下記一般式(W)で表される置換基である。
また、ヘテロアリール基は、RA1~RA6の置換基で説明したヘテロアリール基と同義である。
*はRwとの結合位置または一般式(L-1)~(L-25)の波線部分との結合位置を表す。
一般式(L-13)におけるmは4を表し、一般式(L-14)及び(L-15)におけるmは3を表し、一般式(L-16)~(L-20)におけるmは2を表し、(L-22)におけるmは6を表す。
一般式(L-1)、(L-2)、(L-6)及び(L-13)~(L-19)及び(L-21)~(L-24)におけるRLZはそれぞれ独立に水素原子又は置換基を表し、一般式(L-1)及び(L-2)中のRLZはそれぞれLに隣接するRWと結合して縮合環を形成してもよい。
RNは水素原子又は置換基を表し、Rsiはそれぞれ独立に水素原子、アルキル基、アルケニル基又はアルキニル基を表す。
本発明では、主鎖が炭素数N個の置換又は無置換のアルキル基が置換基の末端に存在する場合は、置換基の末端から可能な限りの連結基を含めた上で一般式(W)における-L-RWと解釈することとし、一般式(W)における-RW単独とは解釈しない。具体的には「一般式(W)におけるLに相当する(L-1)1個」と「一般式(W)におけるRWに相当する主鎖が炭素数N-1個の置換又は無置換のアルキル基」とが結合した置換基として解釈する。例えば、炭素数8のアルキル基であるn-オクチル基が置換基の末端に存在する場合、2個のRLZが水素原子である(L-1)1個と、炭素数7のn-ヘプチル基とが結合した置換基として解釈する。また、一般式(W)で表される置換基が炭素数8のアルコキシ基である場合、-O-である一般式(L-4)で表される連結基1個と、2個のRLZが水素原子である(L-1)で表される連結基1個と、炭素数7のn-ヘプチル基とが結合した置換基として解釈する。
一方、本発明では、オキシエチレン基、オキシエチレン単位の繰り返し数vが2以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が2以上のオリゴシロキサン基、あるいは、置換又は無置換のトリアルキルシリル基が置換基の末端に存在する場合は、置換基の末端から可能な限りの連結基を含めた上で、一般式(W)におけるRW単独と解釈する。例えば、-(OCH2CH2)-(OCH2CH2)-(OCH2CH2)-OCH3基が置換基の末端に存在する場合、オキシエチレン単位の繰り返し数vが3のオリゴオキシエチレン基単独の置換基として解釈する。
RNとしては、置換基RC~RTが採りうる置換基として例示したものを挙げることができる。その中でもRNとしては水素原子又はメチル基が好ましい。
Rsiは、アルキル基であることが好ましい。Rsiがとり得るアルキル基としては特に制限はないが、Rsiがとり得るアルキル基の好ましい範囲はRWがシリル基である場合に該シリル基がとり得るアルキル基の好ましい範囲と同様である。Rsiがとり得るアルケニル基としては特に制限はないが、置換又は無置換のアルケニル基が好ましく、分枝アルケニル基であることがより好ましく、該アルケニル基の炭素数は2~3であることが好ましい。Rsiがとり得るアルキニル基としては特に制限はないが、置換又は無置換のアルキニル基が好ましく、分枝アルキニル基であることがより好ましく、該アルキニル基の炭素数は2~3であることが好ましい。
化学的安定性、キャリア輸送性の観点から一般式(L-1)で表される2価の連結基を含む2価の連結基であることが特に好ましく、一般式(L-1)で表される2価の連結基であることがより特に好ましく、Lが一般式(L-18)及び(L-1)で表される2価の連結基であり、(L-1)を介してRWと結合し、RWが置換又は無置換のアルキル基であることがさらにより特に好ましく、Lが一般式(L-18A)及び(L-1)で表される2価の連結基であり、(L-1)を介してRWと結合し、RWが置換又は無置換のアルキル基であることがさらにより特に好ましい。
一般式(W)において、RWに隣接するLが一般式(L-2)及び(L-4)~(L-25)で表される2価の連結基である場合は、RWは置換又は無置換のアルキル基であることがより好ましい。
一般式(W)において、RWに隣接するLが一般式(L-3)で表される2価の連結基である場合は、RWは置換又は無置換のアルキル基、置換又は無置換のシリル基であることが好ましい。
RWがアルキル基を表す場合、直鎖アルキル基でも、分枝アルキル基でも、環状アルキル基でもよいが、直鎖アルキル基であることが、分子の直線性が高まり、キャリア移動度を高めることができる観点から好ましい。
これらの中でも、一般式(W)におけるRWとLの組み合わせとしては、一般式(C)~(T)のLが一般式(L-1)で表される2価の連結基であり、かつ、RWが直鎖の炭素数4~17のアルキル基であるか;あるいは、Lが一般式(L-3)、(L-13)又は(L-18)のいずれか1つで表される2価の連結基と一般式(L-1)で表される2価の連結基が結合した2価の連結基であり、かつ、RWが直鎖のアルキル基であることが、キャリア移動度を高める観点から好ましい。
一方、有機溶媒への溶解度を高める観点からは、RWが分枝アルキル基であることが好ましい。
L及びRWに含まれる炭素数の合計は5~14であることが好ましく、6~14であることがより好ましく、6~12であることが特に好ましく、8~12であることがより特に好ましい。
一般式(C)で表される化合物においては、RC1、RC2、RC3、RC6のいずれかが一般式(W)で表される基であることが好ましく、RC1とRC2との両方又はRC3とRC6の両方が一般式(W)で表される基であることがより好ましい。
一般式(D)で表される化合物においては、RD6が一般式(W)で表される基であることが好ましく、RD5とRD6との両方が一般式(W)で表される基であることがより好ましい。
一般式(E)で表される化合物においては、RE6が一般式(W)で表される基であることが好ましく、RE5とRE6との両方が一般式(W)で表される基であることがより好ましい。また、RE5及びRE6が一般式(W)で表される基以外の置換基である場合、2つのRE7が一般式(W)で表される基であるのも好ましい。
一般式(G)で表される化合物においては、RG5又はRG6が一般式(W)で表される基であることが、キャリア移動度を高め、有機溶媒への溶解性を高める観点から好ましい。
一般式(H)で表される化合物においては、RH4又はRH6が一般式(W)で表される基であるのが好ましく、RH4又はRH6、及び、RH3又はRH5が一般式(W)で表される基であるのがより好ましい。
一般式(K)で表される化合物においては、RK7が一般式(W)で表される基であるのが好ましく、RK7とRK3との両方が一般式(W)で表される基であるのがより好ましい。
一般式(L)で表される化合物においては、RL2、RL3、RL6及びRL7のうち少なくとも一つが一般式(W)で表される基であるのがより好ましい。
一般式(N)で表される化合物においては、RN3が一般式(W)で表される基であるのが好ましく、RN3とRN9との両方が一般式(W)で表される基であるのがより好ましい。
一般式(P)で表される化合物においては、RP2又はRP3が一般式(W)で表される基であるのが好ましく、RP2とRP8との両方又はRP3とRP9との両方が一般式(W)で表される基であるのがより好ましい。
一般式(R)で表される化合物においては、RR2が一般式(W)で表される基であるのが好ましく、RR2とRR7との両方が一般式(W)で表される基であるのがより好ましい。
一般式(T)で表される化合物においては、RT2が一般式(W)で表される基であるのが好ましく、RT2とRT5との両方が一般式(W)で表される基であるのがより好ましい。
一方で、薄膜の膜質安定性の観点からは、分子量は300以上であることが好ましく、350以上であることがより好ましく、400以上であることがさらに好ましい。
ポリチオフェン及びその誘導体としては、特に限定されないが、例えば、ポリチオフェンにヘキシル基を導入したポリ-3-ヘキシルチオフェン(P3HT)、ポリエチレンジオキシチオフェン、ポリ(3,4-エチレンジオキシチオフェン)/ポリスチレンスルホン酸(PEDOT/PSS)等が挙げられる。
また、これらのポリマーと同じ繰返し単位を有するオリゴマー(例えば、オリゴチオフェン)を挙げることもできる。
このような高分子化合物としては、一般式(C)~(T)で表される化合物が少なくとも1つ以上のアリーレン基、ヘテロアリーレン基(チオフェン、ビチオフェン等)を介して繰り返し構造を示すπ共役ポリマーや、一般式(C)~(T)で表される化合物が高分子主鎖に側鎖を介して結合したペンダント型ポリマーが挙げられる。高分子主鎖としては、ポリアクリレート、ポリビニル、ポリシロキサン等が好ましく、側鎖としては、アルキレン基、ポリエチレンオキシド基等が好ましい。ペンダント型ポリマーの場合、高分子主鎖は置換基RC~RTの少なくとも1つが重合性基由来の基を有し、これが重合してなるものであってもよい。
半導体層を形成する無機半導体材料としては、特に限定されないが、塗布型半導体が好ましく、その好ましい例として酸化物半導体が挙げられる。
酸化物半導体としては、金属酸化物からなるものであれば特に限定されない。酸化物半導体からなる半導体層は、酸化物半導体前駆体、すなわち熱酸化等の変換処理によって金属酸化物からなる半導体材料に変換される材料を用いて形成するのが好ましい。
酸化物半導体は特に限定されるものではないが、例えば、酸化インジウムガリウム亜鉛、酸化インジウムガリウム、酸化インジウムスズ亜鉛、酸化ガリウム亜鉛、酸化インジウムスズ、酸化インジウム亜鉛、酸化スズ亜鉛、酸化亜鉛、酸化スズ、例えば、InGaZnOx、InGaOx、InSnZnOx、GaZnOx、InSnOx、InZnOx、SnZnOx(いずれもx>0)、ZnO、SnO2が挙げられる。
酸化物半導体前駆体の具体例としては、例えば、硝酸インジウム、硝酸亜鉛、硝酸ガリウム、硝酸スズ、硝酸アルミニウム、塩化インジウム、塩化亜鉛、塩化スズ(2価)、塩化スズ(4価)、塩化ガリウム、塩化アルミニウム、トリ-i-プロポキシインジウム、ジエトキシ亜鉛、ビス(ジピバロイルメタナト)亜鉛、テトラエトキシスズ、テトラ-i-プロポキシスズ、トリ-i-プロポキシガリウム、トリ-i-プロポキシアルミニウムが挙げられる。
本発明のTFTにおいて、ソース電極は、配線を通じて外部から電流が流入する電極である。また、ドレイン電極は、配線を通じて外部に電流を送り出す電極であり、通常、上記半導体層に接して設けられる。
ソース電極及びドレイン電極の材料としては、従来の薄膜トランジスタに用いられている導電性材料を用いることができ、例えば、上記ゲート電極で説明した導電性材料等が挙げられる。
特に、ゲート絶縁層がエッチング液や剥離液に対する耐性に優れていることから、ソース電極及びドレイン電極はエッチング法でも好適に形成することができる。エッチング法は、導電性材料を成膜した後に不要部分をエッチングにより除去する方法である。エッチング法によりパターニングすると、レジスト除去時に下地に残った導電性材料の剥がれ、レジスト残渣や除去された導電性材料の下地への再付着を防止でき、電極エッジ部の形状に優れる。この点で、リフトオフ法よりも好ましい。
ソース電極とドレイン電極との間の間隔(チャネル長)は、任意であるが、100μm以下が好ましく、50μm以下が特に好ましい。また、チャネル幅は、5000μm以下が好ましく、1000μm以下が特に好ましい。
本発明のTFTは、オーバーコート層を有していてもよい。オーバーコート層は、通常、TFTの表面に保護層として形成される層である。単層構造でも多層構造でもよい。
オーバーコート層は、有機系のオーバーコート層でも無機系のオーバーコート層でもよい。
有機系のオーバーコート層を形成する材料としては、特に限定されないが、例えば、ポリスチレン、アクリル樹脂、ポリビニルアルコール、ポリオレフィン、ポリイミド、ポリウレタン、ポリアセナチレン、エポキシ樹脂等の有機ポリマー、及び、これらの有機ポリマーに架橋性基や撥水基等を導入した誘導体等が挙げられる。これらの有機ポリマーやその誘導体は、架橋成分、フッ素化合物、シリコン化合物等と併用することもできる。
無機系のオーバーコート層を形成する材料としては、特に限定されないが、酸化ケイ素、酸化アルミニウム等の金属酸化物、窒化ケイ素等の金属窒化物等が挙げられる。
これらの材料は、1種を用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
例えば、有機系のオーバーコート層は、例えば、その下地となる層に、オーバーコート層となる材料を含む溶液を塗布後に乾燥させる、オーバーコート層となる材料を含む溶液を塗布、乾燥後に露光、現像してパターニングする等の方法により形成することができる。なお、オーバーコート層のパターニングは、印刷法やインクジェット法等により直接形成することもできる。また、オーバーコート層のパターニング後に、露光や加熱することにより、オーバーコート層を架橋させてもよい。
一方、無機系のオーバーコート層は、スパッタリング法、蒸着法等の乾式法やゾルゲル法のような湿式法により形成することができる。
本発明のTFTは、上記以外の層や部材を設けてもよい。
その他の層又は部材としては、例えば、バンク等が挙げられる。バンクは、インクジェット法等により半導体層やオーバーコート層等を形成するときに、吐出液を所定の位置に塞き止める目的等で用いられる。このため、バンクには、通常、撥液性がある。バンクの形成方法としては、フォトリソグラフィー法等によりパターニングした後にフッ素プラズマ法等の撥液処理を施す方法、フッ素化合物等の撥液成分を含む感光性組成物等を硬化させる方法等が挙げられる。
本発明の薄膜トランジスタの場合、ゲート絶縁層が有機層であることから、後者の撥液成分を含む感光性組成物を硬化させる方法が、ゲート絶縁層が撥液処理の影響を受ける可能性がなく、好ましい。なお、バンクを用いずに下地に撥液性のコントラストを持たせてバンクと同じ役割を持たせる技術を用いてもよい。
本発明のTFTは好ましくは表示パネルに搭載して使用される。表示パネルとしては、例えば、液晶パネル、有機ELパネル、電子ペーパーパネル等が挙げられる。
各例に用いた有機半導体としての化合物を以下に示す。
1,5-ジアミノナフタレン(10g)のピリジン溶液(125mL)に、p-トルエンスルホニルクロリド(34g)をゆっくりと添加し、室温で2時間撹拌した。反応液を氷水に注ぎ、析出物を減圧濾過した。得られた粗結晶をメタノールで洗浄し、化合物C1a(29g)を得た。
化合物C1a(10g)の氷酢酸溶液を95℃で加熱撹拌し、そこに氷酢酸10mLで希釈した臭素(2mL)をゆっくりと滴下した。10分間反応させ、放冷後にろ過することで粗結晶を灰色固体として得た。粗結晶をニトロベンゼン中で再結晶することで化合物C1b(6.8g)を得た。
化合物C1b(5g)の濃硫酸溶液を室温で24時間撹拌した。反応液を氷水に注ぎ、析出している固体をろ過して回収した。その固体を氷水中に再度分散し、アンモニア水で中和し、化合物C1c(0.5g)を得た。
室温下、化合物C1c(2g)のピリジン溶液にペンタノイルクロリド(バレリン酸クロリド)(2.6mL)を滴下して2時間撹拌した。氷水に反応液を注ぎ、固体を減圧濾過した。メタノール中に分散し1時間撹拌した後、固体をろ過することで化合物C1d(1.39g)を得た。
THF(360mL)及びトルエン(72mL)の混合溶液中に化合物C1d(1.2g)とローソン試薬(1.48g)を添加した後、加熱還流しながら3時間撹拌した。エバポレーションでTHFのみ除去してトルエン溶液とした後、60℃で1時間撹拌した。その後、不溶物をろ過することで化合物C1e(0.5g)を得た。
化合物C1e(0.4g)と炭酸セシウム(1.33g)をジメチルアセトアミド中、120℃で2時間反応させた。反応液を水に注ぎ析出物をろ過した。ろ過した固体をTHF中で再結晶を繰返し、目的化合物C1(0.12g)を合成した。得られた化合物C1の同定は、1H-NMR及びMassスペクトルにより行った。
図1(A)に示すボトムゲート・ボトムコンタクト型のTFTを作製した。基板6として厚さ1mmのドープシリコン基板(ゲート電極5を兼ねる)を用い、その上にゲート絶縁層2を形成した。
ゲート絶縁層2は以下のように形成した。
市販のポリ(4-ビニルフェノール)6.3gと、架橋剤として2,2-ビス(3,5-ジヒドロキシメチル-4-ヒドロキシ)プロパン2.7gとを、91gの1-ブタノール/エタノール=1/1の混合溶媒に室温で完全に溶解した。この溶解液をφ0.2μmのPTFE製メンブランフィルタでろ過した。得られたろ液に酸触媒としてジフェニルヨードニウムヘキサフルオロホスフェート塩を0.1wt%となるように加え、基板6上に塗布し、乾燥して成膜した。その後、100℃に加熱して架橋構造を形成させ、厚さ0.7μmのゲート絶縁層2を形成した。
続いて、ソース電極及びドレイン電極を覆うように、下記表1に示す有機半導体5mgをトルエン1mLに溶解した溶液をスピンコートして成膜し、図1(A)に示される形態のTFTを作製した。有機半導体層の厚さは150nmとした。
上記製造例1において、ゲート絶縁層の形成の際に架橋剤及び酸触媒を添加しなかったこと以外は製造例1と同様にしてTFTを製造した。
上記製造例1において、ゲート絶縁層の形成の際にポリ(4-ビニルフェノール)に代えて市販のポリシルセスキオキサンを用い、さらに溶媒としてテトラヒドロフランを用い、架橋剤及び酸触媒を添加しなかったこと以外は製造例1と同様にしてTFTを製造した。
上記製造例1~3により実施例1~3及び比較例1~3のTFTを得た。より詳細には、下記実施例1~3のTFTは、製造例1~3において、ゲート絶縁層の形成に用いるポリマー、又はポリマーと架橋剤の混合物を純水で1回洗浄し、乾燥したものをゲート絶縁層の形成に用いた。また、下記比較例1~3のTFTは、製造例1~3において、ゲート絶縁層の形成に用いるポリマー、又はポリマーと架橋剤の混合物を純水で3回洗浄し、限外ろ過処理後、イオン交換樹脂に通して精製したものをゲート絶縁層の形成に用いた。
ゲート絶縁層中の特定金属の含有量は、ゲート絶縁層の形成に用いたポリマー、又はポリマーと架橋剤の混合物(上記の純水で1回洗浄し、乾燥した後のもの、又は上記の精製処理した後のもの)を灰化し、酸溶解した後、ICP-MS HP7700(アジレント社製)を用いて定量することで決定した。ゲート絶縁層中の特定金属の含有量は、すなわちゲート絶縁層の形成に用いたポリマー、又はポリマーと架橋剤の混合物の、固形分中の特定金属の含有量である。
ゲート絶縁層中の特定非金属イオン性物質の含有量は、ゲート絶縁層の形成に用いたポリマー、又はポリマーと架橋剤の混合物(上記の純水で1回洗浄し、乾燥した後のもの、又は上記の精製処理した後のもの)を有機溶剤に溶解した後、超純水で分液し、水相を、ICS-2000型IC装置(Dionex社製)を用いたグラジエント法により分析することで決定した。ゲート絶縁層中の特定非金属イオン性物質の含有量は、すなわちゲート絶縁層の形成に用いたポリマー、又はポリマーと架橋剤の混合物の、固形分中の特定非金属イオン性物質の含有量である。
実施例1~3及び比較例1~3のボトムゲート型TFTについて、ゲート絶縁層中の特定金属及び特定非金属イオン性物質の測定結果を下記表1に示す。なお、下記表1において検出限界以下の金属ないし非金属イオン性物質は、総量の計算において考慮しないものとする。
上記実施例1~3、比較例1~3と全く同じにゲート絶縁層を形成後、その上に厚さ100nmの金電極を真空蒸着により形成した。これをサンプルとして、ソースメジャーユニット237(Keithley社製)を用いて、体積抵抗率(Ω・cm)を測定した。
上記実施例1~3、比較例1~3と全く同じにゲート絶縁層を形成後、その上に厚さ100nmの金電極を真空蒸着により形成した。これをサンプルとして、誘電体測定システム126096W型(ソーラトロン社製)を用いて、比誘電率を測定した。
実施例1~3、比較例1~3で得られたボトムゲート型TFTについて、閾値電圧、キャリア移動度とon/off比を下記方法により評価することでTFTの性能を調べた。
ソース電極-ドレイン電極間に-40Vの電圧を印加し、ゲート電圧を40V~-40Vの範囲で変化させ、閾値電圧を測定した。
ソース電極-ドレイン電極間に-40Vの電圧を印加し、ゲート電圧を40V~-40Vの範囲で変化させ、ドレイン電流Idを表わす下記式を用いてキャリア移動度μを算出した。
Id=(w/2L)μCi(Vg-Vth)2
(式中、Lはゲート長、wはゲート幅、Ciは絶縁層の単位面積当たりの容量、Vgはゲート電圧、Vthは閾値電圧)
ソース電極-ドレイン電極間にかかる電圧を-40Vに固定し、Vgを40Vから-40Vまでスイープさせた時の(|Id|の最大値)/(|Id|の最小値)をOn/Off比とした。
製造したTFTそれぞれについて、試験例3と同様にして、キャリア移動度μ、On/Off比及び閾値電圧Vthを評価した。その結果、いずれも実施例1と同様に、ゲート絶縁層の特定金属及び非金属イオン性物質の量が本発明で規定する範囲外にあるものに比べて、性能に優れる結果となった。
図1(C)に示すトップゲート・ボトムコンタクト型のTFTを作製した。ガラス基板(NECコーニング社製、OA10)を水で洗浄し、乾燥したものを基板6として用いた。このガラス基板上にソース電極及びドレイン電極としてクロム/金電極を、マスクを用いて真空蒸着により形成した。これにより厚さ100nmのソース電極3及びドレイン電極4を設けた。ゲート幅Wは100mm、ゲート長Lは100μmとした。
上記製造例4において、ゲート絶縁層の形成の際に架橋剤及び酸触媒を添加しなかったこと以外は製造例4と同様にしてTFTを製造した。
上記製造例4において、ゲート絶縁層の形成の際にポリ(4-ビニルフェノール)に代えて市販のポリシルセスキオキサンを用い、さらに溶媒としてテトラヒドロフランを用い、架橋剤及び酸触媒を添加しなかったこと以外は製造例4と同様にしてTFTを製造した。
上記製造例4~6により実施例4~6及び比較例4~6のTFTを得た。より詳細には、下記実施例4~6のTFTは、製造例4~6において、ゲート絶縁層の形成に用いるポリマー、又はポリマーと架橋剤の混合物を純水で1回洗浄し、乾燥したものをゲート絶縁層の形成に用いた。また、下記比較例4~6のTFTは、製造例4~6において、ゲート絶縁層の形成に用いるポリマー、又はポリマーと架橋剤の混合物を純水で3回洗浄し、限外ろ過処理後、イオン交換樹脂に通して精製したものをゲート絶縁層の形成に用いた。
実施例4~6及び比較例4~6のトップゲート型TFTについて、上記ボトムゲート型TFTの場合と同様にして、ゲート絶縁層中の特定金属及び特定非金属イオン性物質の量を測定した。結果を下記表3に示す。
製造したTFTそれぞれについて、試験例3と同様にして、キャリア移動度μ、On/Off比及び閾値電圧Vthを評価した。その結果、いずれも実施例4と同様に、ゲート絶縁層の特定金属及び非金属イオン性物質の量が本発明で規定する範囲外にあるものに比べて、性能に優れる結果となった。
2 ゲート絶縁層
3 ソース電極
4 ドレイン電極
5 ゲート電極
6 基板
Claims (9)
- 基板上に、ゲート電極と、半導体層と、該ゲート電極と該半導体層との間に設けられた、有機高分子化合物で形成されたゲート絶縁層と、該半導体層に接して設けられ、該半導体層を介して連結されたソース電極及びドレイン電極とを有する薄膜トランジスタであって、
前記ゲート絶縁層中、Mg、Ca、Ba、Al、Sn、Pb、Cr、Mn、Fe、Ni、Cu、Zn及びAgから選ばれる金属の含有量が総量で10ppb~1ppmであるか、又は、ハロゲンイオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、薄膜トランジスタ。 - 前記ゲート絶縁層中、Mg、Ca、Ba、Al、Sn、Pb、Cr、Mn、Fe、Ni、Cu、Zn及びAgから選ばれる金属の含有量が総量で10ppb~1ppmであり、且つ、ハロゲンイオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、請求項1に記載の薄膜トランジスタ。
- 前記ゲート絶縁層中、Mg、Ca、Al、Cr、Fe及びZnから選ばれる金属の含有量が総量で10ppb~1ppmである、請求項1又は2に記載の薄膜トランジスタ。
- 前記ゲート絶縁層中、塩素イオン、硫酸イオン、硝酸イオン及びリン酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、請求項1~3のいずれか1項に記載の薄膜トランジスタ。
- 前記ゲート絶縁層中、塩素イオン及び硫酸イオンから選ばれる非金属イオン性物質の含有量が総量で1ppm~100ppmである、請求項1~4のいずれか1項に記載の薄膜トランジスタ。
- 前記有機高分子化合物が、ポリビニルフェノール、ノボラック樹脂、ポリスチレン、ポリ(メタ)アクリレート、エポキシ樹脂、エポキシ(メタ)アクリレート樹脂、ポリビニルアルコール、フッ素樹脂、ポリシクロオレフィン、ポリシルセスキオキサン、ポリシロキサン、ポリエステル、ポリエーテルスルホン、ポリエーテルケトン、及びポリイミドから選ばれる有機高分子化合物である、請求項1~5のいずれか1項に記載の薄膜トランジスタ。
- 前記半導体層が有機半導体を含む、請求項1~6のいずれか1項に記載の薄膜トランジスタ。
- 前記有機半導体が、下記一般式(C)~(T)のいずれかで表される、請求項7に記載の薄膜トランジスタ。
一般式(D)中、XD1及びXD2はNRD9、酸素原子又は硫黄原子を表す。AD1はCRD7又は窒素原子を表し、AD2はCRD8又は窒素原子を表し、RD9は水素原子、アルキル基、アルケニル基、アルキニル基又はアシル基を表す。RD1~RD8は水素原子又は置換基を表し、RD1~RD8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(E)中、XE1及びXE2は酸素原子、硫黄原子又はNRE7を表す。AE1及びAE2はCRE8又は窒素原子を表す。RE1~RE8は水素原子又は置換基を表し、RE1~RE8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(F)中、XF1及びXF2は酸素原子、硫黄原子又はセレン原子を表す。RF1~RF10、RFa及びRFbは水素原子又は置換基を表し、RF1~RF10、RFa及びRFbのうち少なくとも一つは一般式(W)で表される置換基である。p及びqは0~2の整数を表す。
一般式(G)中、XG1及びXG2はNRG9、酸素原子又は硫黄原子を表す。AG1はCRG7又は窒素原子を表し、AG2はCRG8又は窒素原子を表す。RG9は水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表し、RG1~RG8は水素原子又は置換基を表し、RG1~RG8のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(H)中、XH1~XH4はNRH7、酸素原子又は硫黄原子を表し、RH7は水素原子、アルキル基、アルケニル基、アルキニル基、アシル基、アリール基又はヘテロアリール基を表す。RH1~RH6は水素原子又は置換基を表し、RH1~RH6のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(J)中、XJ1及びXJ2は酸素原子、硫黄原子、セレン原子又はNRJ9を表す。XJ3及びXJ4は酸素原子、硫黄原子又はセレン原子を表す。RJ1~RJ9は水素原子又は置換基を表し、RJ1~RJ9のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(K)中、XK1及びXK2は酸素原子、硫黄原子、セレン原子又はNRK9を表す。XK3及びXK4は酸素原子、硫黄原子又はセレン原子を表す。RK1~RK9は水素原子又は置換基を表し、RK1~RK9のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(L)中、XL1及びXL2は酸素原子、硫黄原子又はNRL11を表す。RL1~RL11は水素原子又は置換基を表し、RL1~RL11のうち少なくとも1つが下記一般式(W)で表される置換基である。
一般式(M)中、XM1及びXM2は酸素原子、硫黄原子、セレン原子又はNRM9を表す。RM1~RM9は水素原子又は置換基を表し、RM1~RM9のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(N)中、XN1及びXN2は酸素原子、硫黄原子、セレン原子又はNRN13を表す。RN1~RN13は水素原子又は置換基を表し、RN1~RN13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(P)中、XP1及びXP2は酸素原子、硫黄原子、セレン原子又はNRP13を表す。RP1~RP13は水素原子又は置換基を表し、RP1~RP13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(Q)中、XQ1及びXQ2は酸素原子、硫黄原子、セレン原子又はNRQ13を表す。RQ1~RQ13は水素原子又は置換基を表し、RQ1~RQ13のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(R)中、XR1、XR2及びXR3は酸素原子、硫黄原子、セレン原子又はNRR9を表す。RR1~RR9は水素原子又は置換基を表し、RR1~RR9のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(S)中、XS1、XS2、XS3及びXS4は酸素原子、硫黄原子、セレン原子又はNRS7を表す。RS1~RS7は水素原子又は置換基を表し、RS1~RS7のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(T)中、XT1、XT2、XT3及びXT4は酸素原子、硫黄原子、セレン原子又はNRT7を表す。RT1~RT7は水素原子又は置換基を表し、RT1~RT7のうち少なくとも1つは下記一般式(W)で表される置換基である。
一般式(W): -L-RW
一般式(W)中、Lは下記一般式(L-1)~(L-25)のいずれかで表される2価の連結基又は2以上の下記一般式(L-1)~(L-25)のいずれかで表される2価の連結基が結合した2価の連結基を表す。
RWは置換又は無置換のアルキル基、シアノ基、ビニル基、エチニル基、オキシエチレン基、オキシエチレン単位の繰り返し数vが2以上のオリゴオキシエチレン基、シロキサン基、ケイ素原子数が2以上のオリゴシロキサン基、あるいは、置換又は無置換のトリアルキルシリル基を表す。
一般式(L-13)におけるmは4を表し、一般式(L-14)及び(L-15)におけるmは3を表し、一般式(L-16)~(L-20)におけるmは2を表し、(L-22)におけるmは6を表す。
一般式(L-1)、(L-2)、(L-6)及び(L-13)~(L19)及び(L-21)~(L-24)におけるRLZはそれぞれ独立に水素原子又は置換基を表す。
RNは水素原子又は置換基を表し、Rsiはそれぞれ独立に水素原子、アルキル基、アルケニル基又はアルキニル基を表す。 - 前記有機半導体が、一般式(C)、(F)、(J)及び(L)のいずれかで表される、請求項8に記載の薄膜トランジスタ。
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CN201580009803.6A CN106030823B (zh) | 2014-03-07 | 2015-02-26 | 薄膜晶体管 |
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EP15758615.7A EP3116033B1 (en) | 2014-03-07 | 2015-02-26 | Thin-film transistor |
US15/236,914 US9755160B2 (en) | 2014-03-07 | 2016-08-15 | Thin film transistor |
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CN109716491A (zh) * | 2016-09-16 | 2019-05-03 | 东丽株式会社 | 场效应晶体管的制造方法及无线通信设备的制造方法 |
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US9882023B2 (en) * | 2016-02-29 | 2018-01-30 | Taiwan Semiconductor Manufacturing Co., Ltd. | Sidewall spacers for self-aligned contacts |
JP7070826B2 (ja) * | 2017-02-28 | 2022-05-18 | 国立大学法人東海国立大学機構 | 半導体ナノ粒子およびその製造方法ならびに発光デバイス |
CN115612484A (zh) * | 2017-02-28 | 2023-01-17 | 国立大学法人东海国立大学机构 | 半导体纳米粒子及其制造方法、以及发光器件 |
TWI702186B (zh) * | 2018-03-19 | 2020-08-21 | 日商理光股份有限公司 | 形成氧化物用的塗佈液、製造氧化物薄膜的方法及製造場效電晶體的方法 |
CN109037031B (zh) * | 2018-07-11 | 2021-11-19 | 华东师范大学 | 一种掺镍氧化铜薄膜晶体管及制备方法 |
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CN109716491B (zh) * | 2016-09-16 | 2023-06-09 | 东丽株式会社 | 场效应晶体管的制造方法及无线通信设备的制造方法 |
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EP3116033A1 (en) | 2017-01-11 |
EP3116033B1 (en) | 2020-03-25 |
US9755160B2 (en) | 2017-09-05 |
CN106030823A (zh) | 2016-10-12 |
JP6255651B2 (ja) | 2018-01-10 |
KR20160105524A (ko) | 2016-09-06 |
JP2015170759A (ja) | 2015-09-28 |
KR101931863B1 (ko) | 2019-03-13 |
EP3116033A4 (en) | 2017-03-22 |
US20160351824A1 (en) | 2016-12-01 |
CN106030823B (zh) | 2019-02-15 |
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