WO2014043860A1 - Composé de phtalocyanine soluble et son procédé de préparation et transistor à film mince organique - Google Patents

Composé de phtalocyanine soluble et son procédé de préparation et transistor à film mince organique Download PDF

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WO2014043860A1
WO2014043860A1 PCT/CN2012/081586 CN2012081586W WO2014043860A1 WO 2014043860 A1 WO2014043860 A1 WO 2014043860A1 CN 2012081586 W CN2012081586 W CN 2012081586W WO 2014043860 A1 WO2014043860 A1 WO 2014043860A1
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phthalocyanine compound
thin film
soluble phthalocyanine
semiconductor layer
film transistor
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PCT/CN2012/081586
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English (en)
Chinese (zh)
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耿延候
田洪坤
董少强
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中国科学院长春应用化学研究所
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Priority to PCT/CN2012/081586 priority Critical patent/WO2014043860A1/fr
Publication of WO2014043860A1 publication Critical patent/WO2014043860A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions

Definitions

  • Soluble phthalocyanine compound, preparation method thereof and organic thin film transistor Soluble phthalocyanine compound, preparation method thereof and organic thin film transistor
  • the invention relates to the technical field of organic semiconductor materials, in particular to a soluble phthalocyanine compound, a preparation method thereof and an organic thin film transistor. Background technique
  • Phthalocyanine compounds have a unique ⁇ -conjugated structure, which makes them have unique physical properties and excellent environmental stability. Especially by regulating the electronic structure and the molecular packing mode in the solid state, they can form strong ⁇ - ⁇ mutual The stacked structure of action, therefore, phthalocyanine compounds are widely used as high mobility organic conjugated semiconductor materials.
  • 5,969,376 discloses a planar metal phthalocyanine which is copper phthalocyanine (CuPc), phthalocyanine (ZnPc) or phthalocyanine (SnPc), which is a hole transport organic as a semiconductor layer.
  • a thin film transistor having a hole mobility of 1 T 3 cm 2 /V ⁇ s;
  • Chinese Patent Application No. 200710055258.1 discloses an organic thin film transistor using an axially substituted phthalocyanine compound as a semiconductor layer, and carrier mobility thereof The rate is 1 (T 3 cm 2 /V ⁇ s; US Patent Publication No.
  • 2010140593 also discloses an organic thin film transistor using an axially substituted phthalocyanine, wherein indium phthalocyanine chloride (CllnPc) has a high hole mobility and can Up to 0.52 cm 2 /V . s; advanced materials (Adv. Mater., 2008, 20, 2142) and Applied Physics Letters (Appl. Phys ⁇ ett., 2008, 92, 143303) respectively disclose the use of tin phthalocyanine dichloride An electron transporting organic thin film transistor of (Cl 2 SnPc ) and tin phthalocyanine (OSnPc ).
  • Cl 2 SnPc indium phthalocyanine chloride
  • OSnPc tin phthalocyanine
  • the phthalocyanine compound reported in the above literature has poor solubility in an organic solvent, so that a vacuum evaporation method is required for preparing a semiconductor layer in an organic thin film transistor.
  • a vacuum evaporation method is required for preparing a semiconductor layer in an organic thin film transistor.
  • the vacuum evaporation method is complicated, the conditions are harsh, and the cost is high, the solution is used.
  • Processing Methods The preparation of semiconductor layers in organic thin film transistors has become a trend in the development of organic electronic devices. Therefore, the development of soluble phthalocyanine semiconductor materials enables the semiconductor layer of organic thin film transistors to be prepared by solution processing, which is one of the main directions for the development of high mobility organic semiconductors.
  • the present invention provides a soluble phthalocyanine compound, a process for preparing the same, and an organic thin film transistor, and the organic thin film transistor prepared by using the soluble phthalocyanine compound provided by the present invention has high carrier mobility.
  • the present invention provides a soluble phthalocyanine compound having the structure of formula (I) or the structure of formula (II): Formula (II);
  • R is an alkyl group, an alkoxy group or an alkylthio group
  • M is a divalent metal or a trivalent or higher metal containing a ligand'
  • R is a linear alkyl group, a branched alkyl group, a linear alkoxy group, a branched alkoxy group, a linear alkylthio group or a branched alkylthio group.
  • the R is a C 4 to C 18 linear alkyl group, a C 4 to C 18 linear alkoxy group or a C 4 to C 18 linear alkylthio group.
  • the R is octyl, hexyl, dodecyl, hexyloxy, octyloxy or octylthio.
  • the divalent metal is Cu, Zn, Ni, Co or Pb;
  • the trivalent or higher metal containing the ligand is InCl, SbCl, MnCl, GaCl, A1C1, TiCl, TiO, VO, SnO or SnCl 2 .
  • the invention provides a preparation method of a soluble phthalocyanine compound, comprising the following steps: 5,6-dialkyl-1,3-dihydro-1,3-diiminoisoindoline, 5,6- Dialkoxy-1,3-dihydro-1,3-diiminoisoindoline or 5,6-dialkylthio-1,3-dihydro-1,3-diimine
  • the porphyrin is mixed with triethylamine and 1,3,3-trichloroisohydroazaindole in an organic solvent, and filtered to obtain a filtrate;
  • R is an alkyl group, an alkoxy group or an alkylthio group.
  • the method further comprises: dissolving the soluble phthalocyanine compound having the structure of the formula (I) with a divalent or higher metal salt in n-pentanol or N-decylpyrrolidone The reaction is carried out to obtain a soluble phthalocyanine compound having the structure of formula (II):
  • M is a divalent metal or a trivalent or higher metal containing a ligand.
  • the present invention provides an organic thin film transistor including a substrate, a dielectric layer provided with a gate, and a semiconductor layer provided with a drain electrode and a source electrode at both ends, the semiconductor layer comprising the soluble phthalocyanine compound described above; Wherein the semiconductor layer is composited on the dielectric layer, and the dielectric layer is composited On the substrate; or the dielectric layer is composited on the semiconductor layer, and the semiconductor layer is composited on the substrate.
  • the method for preparing the semiconductor layer is specifically: preparing the thin film by formulating the soluble phthalocyanine compound, and annealing and depositing the electrode to obtain a semiconductor layer.
  • the organic solvent of the solution is trichlorodecane, trichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenylbenzene, toluene, diphenylbenzene, tetrahydronaphthalene or triterpene. .
  • the present invention provides a soluble phthalocyanine compound having the structure of formula (I) or the structure of formula (II) which is a 2,3,16,16-tetrasubstituted phthalocyanine compound.
  • the present invention introduces only one and the same substituent to each of the 2, 3, 16 and 17 positions of the phthalocyanine nucleus, while leaving the two benzene rings in the phthalocyanine nucleus unsubstituted, and adopting the selectivity to the phthalocyanine compound.
  • Substituting can improve the solubility without destroying the close ⁇ - ⁇ stacking arrangement of the phthalocyanine core, and can reduce the adverse effect of the substituent on the arrangement of the phthalocyanine nucleus in the film, thereby realizing a higher field. Effect mobility.
  • the central metal atom can modulate the electronic structure of the substituted phthalocyanine, and at the same time it can synergize with the substituent to regulate the stacking mode of the substituted phthalocyanine film. Therefore, the organic thin film transistor having higher mobility can be obtained by using the soluble phthalocyanine compound provided by the present invention.
  • the experimental results show that the organic thin film transistor can be prepared by using the soluble phthalocyanine compound provided by the invention, and the carrier mobility can reach 1 cm 2 /V - s.
  • the present invention enriches the kind of the soluble phthalocyanine compound, and further, the present invention employs a soluble phthalocyanine compound to prepare an organic thin film transistor by a solution deposition method, and the method is low in cost and low in cost.
  • FIG. 1 is a first schematic structural view of an organic thin film transistor according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing a second structure of an organic thin film transistor according to an embodiment of the present invention.
  • FIG. 3 is a schematic view showing a third structure of an organic thin film transistor according to an embodiment of the present invention.
  • the present invention provides a soluble phthalocyanine compound having the structure of formula (I) or the structure of formula (II):
  • the soluble phthalocyanine compound provided by the present invention has a structure of the formula (I) or a structure of the formula (II) which is a 2,3,16,17-tetrasubstituted phthalocyanine compound.
  • the 2, 3, 16 and 17 positions of the phthalocyanine core each have an identical substituent R, and R is an alkyl group, an alkoxy group or an alkylthio group.
  • the alkyl group may be a branched alkyl group or a linear alkyl group, preferably a C 4 to C 18 linear alkyl group, more preferably an octyl group, a hexyl group or a dodecyl group, and most preferably an octyl group.
  • the alkoxy group may be a branched alkoxy group or a linear alkoxy group, preferably a C 4 to C 18 linear alkoxy group, more preferably an octyloxy group or a hexyloxy group, most preferably It may be an octyloxy group;
  • the alkylthio group may be a branched alkylthio group, or may be a linear alkylthio group, preferably a linear alkylthio group of c 4 to c 18 , more preferably an octylthio group.
  • the present invention introduces only one and the same substituent to each of the 2, 3, 16 and 17 positions of the phthalocyanine nucleus, while leaving the two benzene rings in the phthalocyanine nucleus unsubstituted, and adopting the selectivity to the phthalocyanine compound. Substituting, can improve the solubility without destroying the close ⁇ - ⁇ stacking arrangement of the phthalocyanine core, and can reduce the adverse effect of the substituent on the arrangement of the phthalocyanine nucleus in the film, thereby realizing a higher field. Effect mobility.
  • the present invention comprehensively considers the influence of the substituent type and the substitution position on the phthalocyanine compound, and the organic thin film transistor prepared by using the phthalocyanine compound provided by the present invention has high carrier mobility and is advantageous for application.
  • the ruthenium may be a divalent metal, preferably Cu, Zn, Ni, Co or Pb, more preferably Pb; the M may also be a trivalent or higher metal containing a ligand, including three
  • the metal atom above the valence, the ligand to which it is covalently bonded, such as an oxygen atom or a halogen atom, is preferably InCl, SbCl, MnCl, GaCl, A1C1, TiCl, TiO, VO, SnO or SnCl 2 , more preferably TiO, VO Or SnCl 2 .
  • the central metal atom is capable of modulating the electronic structure of the substituted phthalocyanine, and its energy and substituent A synergistic effect is produced to regulate the manner in which the phthalocyanine film is replaced.
  • the invention provides a preparation method of a soluble phthalocyanine compound, comprising the following steps: 5,6-dialkyl-1,3-dihydro-1,3-diiminoisoindoline, 5,6 -dialkoxy-1,3-dihydro-1,3-diiminoisoindoline or 5,6-dialkylthio-1,3-dihydro-1,3-diimine
  • the isoindoline is mixed with triethylamine and 1,3,3-trichloroisohydroazaindole in an organic solvent, and filtered to obtain a filtrate;
  • R is an alkyl group, an alkoxy group or an alkylthio group.
  • the present invention is 5,6-dialkyl-1,3-dihydro-1,3-diiminoisoindoline, 5,6-dialkoxy-1,3-dihydro-1,3 - Diimidoisoindoline or 5,6-dialkylthio-1,3-dihydro-1,3-diimidoisoindoline is used as a starting material, which are preferably prepared as follows:
  • the 4,5-diiodophthalonitrile is preferably prepared according to the method disclosed in J. Org. Chem., 1996, 61, 3034-3040: o-phthalimide and elemental iodine
  • the mixture was stirred in 30% fuming sulfuric acid at 75 ° C to 80 ° C for 24 hours to obtain a reaction mixture, which was poured into ice water, filtered to obtain a precipitate, which was sequentially saturated with water, 2% aqueous potassium carbonate solution, and saturated.
  • aqueous sodium thiosulfate solution and water are washed, and dried in air, and then subjected to silica gel column chromatography using a mixed solution containing chloroform and ethyl acetate as a rinsing agent to obtain 4,5-diiodophthalimide;
  • the 4,5-diiodophthalimide was added to concentrated aqueous ammonia, and stirred at 50 ° C to 60 ° C for 1.5 hours to form a white solid, and the white solid was sequentially washed with ice water and ethanol. Washing to obtain 4,5-diiodophthalic acid amide;
  • Trifluoroacetic anhydride was added to a mixture of hexacyclohexane and pyridine. After stirring at room temperature for 12 hours, it was poured into water and extracted with ethyl acetate. The organic phase was washed successively with water, diluted hydrochloric acid, aqueous sodium carbonate and water, and then with ethanol. Crystallization gave 4,5-diiodophthalonitrile.
  • reaction solution is poured into diethyl ether, and washed with an aqueous solution of ammonium chloride until the pH of the organic layer is 7, and then saturated brine is used. It was washed, dried over anhydrous magnesium sulfate, and subjected to silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as a rinsing agent to give 4,5-di(1-alkynyl) phthalonitrile.
  • Ammonia gas was continuously introduced into a mixture of 4,5-dialkylphthalonitrile, sodium decanoate and decyl alcohol, and stirred at a temperature of 60 ° C for 12 hours, then cooled to room temperature, and filtered. A precipitate was obtained, and the precipitate was washed with cold methanol and vacuum dried to give 5,6-dialkyl-1,3-dihydro-1,3-diimidoisoindoline.
  • the 4,5-dialkoxyphthalonitrile is preferably in accordance with Liquid Crystal Magazine (Liquid Crystal, 2002,
  • the 4,5-dialkylthio phthalonitrile is preferably in accordance with J. Org. Chem., 2010,
  • the present invention uses 1,3,3-trichloroisohydroazaindene as a raw material, which is preferably in accordance with the US patent document.
  • Dihydro-1,3-diiminoisoindoline or 5,6-dialkylthio-1,3-dihydro-1,3-diimidoisoindoline is dissolved in an organic solvent such as tetrahydrofuran In (THF), the dissolution is preferably carried out under stirring, and then triethylamine is added dropwise, and preferably 1,0 or less is dissolved in an organic solvent such as tetrahydrofuran under cooling at 0 ° C as in an ice salt bath.
  • THF tetrahydrofuran In
  • the 3-trichloroiso-dihydroazepine solution is reacted, the reaction is first carried out under the condition of stirring in an ice salt bath for 1 hour, and then stirred at room temperature for 5 hours to 8 hours, and pumped. The solid was removed by filtration to give a filtrate;
  • a structure of a soluble phthalocyanine compound, in the formula (I), R is an alkyl group, an alkoxy group or an alkylthio group.
  • the alkyl group may be a branched alkyl group or a linear alkyl group, preferably a C4 to C18 linear alkyl group, more preferably an octyl group, a hexyl group or a dodecyl group, most preferably
  • the alkoxy group may be a branched alkoxy group or a linear alkoxy group, preferably a C 4 to C 18 linear alkoxy group, more preferably an octyloxy group or a hexyloxy group.
  • the alkylthio group may be a branched alkylthio group or a linear alkylthio group, preferably a C 4 to C 18 linear alkylthio group, more preferably an octylthio group.
  • the present invention introduces only one and the same substituent to each of the 2, 3, 16 and 17 positions of the phthalocyanine nucleus, while leaving the two benzene rings in the phthalocyanine nucleus unsubstituted, and adopting the selectivity to the phthalocyanine compound. Substituting, can improve the solubility without destroying the close ⁇ - ⁇ stacking arrangement of the phthalocyanine core, and can reduce the adverse effect of the substituent on the arrangement of the phthalocyanine nucleus in the film, thereby realizing a higher field. Effect mobility.
  • the present invention comprehensively considers the influence of the substituent type and the substitution position on the phthalocyanine compound, and the organic thin film transistor prepared by using the phthalocyanine compound provided by the present invention has high carrier mobility and is advantageous for application.
  • the present invention preferably further comprises: the soluble phthalocyanine compound having the structure of the formula (I) and the divalent or higher metal salt in n-pentanol or indole-pyridylpyrrolidone The reaction is carried out to obtain a soluble phthalocyanine compound having the structure of formula (II):
  • M is a divalent metal or a trivalent or higher metal containing a ligand.
  • the M may be a divalent metal, preferably Cu, Zn, Ni, Co or Pb, more preferably Pb; the M may also be a trivalent or higher metal containing a ligand, including a trivalent or higher
  • the metal atom, a ligand to which it is covalently bonded, such as an oxygen atom or a halogen atom, is preferably InCl, SbCl, MnCl, GaCl, A1C1, TiCl, TiO, VO, SnO or SnCl 2 , more preferably TiO, VO or SnCl. 2 .
  • the central metal atom can modulate the electronic structure of the substituted phthalocyanine, and at the same time, it can synergize with the substituent, thereby regulating the manner of stacking the substituted phthalocyanine film.
  • the soluble phthalocyanine compound having the structure of the formula (I) and the divalent or higher metal salt are preferably dissolved in n-pentanol or N-decylpyrrolidone under an inert atmosphere such as nitrogen or argon, and the reaction is carried out by heating under reflux.
  • the reaction mixture is poured into methanol at room temperature for 10 minutes to 12 hours, and the mixture is extracted with chloroform, dried over anhydrous magnesium sulfate, and subjected to silica gel column chromatography using chloroform as a rinse to obtain formula (II). Structure of soluble phthalocyanine compounds.
  • the divalent or higher metal salt includes, but is not limited to, acetic acid, copper acetate, lead acetate, nickel acetate, cobalt acetate, titanium tetrabutoxide, vanadyl sulfate, indium trichloride (InCl 3 ) and Tin chloride (SnCl 2 ).
  • the heating temperature is preferably from 120 ° C to 200 ° C, more preferably from 140 ° C to 190 ° C.
  • the present invention After obtaining the product soluble phthalocyanine compound, the present invention performs MALDI-TOF mass spectrometry, nuclear magnetic resonance analysis and elemental analysis, respectively.
  • the analysis results indicate that the product soluble phthalocyanine compound has the structure of the formula (I) or the structure of the formula (II).
  • the present invention also provides an organic thin film transistor comprising a substrate, a dielectric layer provided with a gate, and a semiconductor layer provided with a drain electrode and a source electrode at both ends, the semiconductor layer comprising the soluble phthalocyanine described above Compound
  • the organic thin film transistor includes a substrate.
  • the substrate is a substrate commonly used in the art and may be a silicon wafer, a glass or a plastic foil.
  • the organic thin film transistor is often made of a plastic substrate such as polyester (p 0 ly es t e r ), polycarbonate (polycarbonate) or polyimide (polyimide).
  • the thickness of the substrate is not particularly limited, and is generally 10 micrometers to 10 millimeters.
  • the thickness is preferably 50 micrometers to 5 millimeters.
  • the thickness is preferably 0.5. Mm ⁇ 10 mm.
  • the organic thin film transistor includes a dielectric layer provided with a gate.
  • the gate electrode is formed of a conductive material, and may be a metal film, a conductive polymer film, a conductive film formed of a conductive ink or a conductive paste, or a substrate itself such as a heavily doped silicon wafer.
  • the metal film may be aluminum, gold, silver, chromium or indium tin oxide (ITO);
  • the conductive polymer film may be poly(p-phenate) doped poly(3,4-two) Oxyethane thiophene) (PEDOT: PSS);
  • the conductive ink may be carbon black;
  • the conductive paste may be silver colloid.
  • the thickness of the gate electrode may be determined according to the material used, and the thickness of the gate electrode formed of the metal thin film is generally 10 nm to 100 nm; for the gate electrode formed of the conductive polymer, the thickness is generally 0.5 ⁇ m to 10 Micron.
  • the dielectric layer is typically formed of an inorganic material, an organic polymer, or a thin film of an organic polymer and an inorganic material hybrid material.
  • the inorganic material is silicon dioxide, silicon nitride, aluminum oxide, barium titanate, strontium zirconate or bismuth pentoxide;
  • the organic polymer is decyl acrylate (PMMA), polyvinyl Phenol (PVP), polyvinyl alcohol (PVA), polystyrene (PS), polyvinyl chloride (PVC) or polyimide.
  • PMMA decyl acrylate
  • PVP polyvinyl Phenol
  • PVA polyvinyl alcohol
  • PS polystyrene
  • PVC polyvinyl chloride
  • the thickness of the dielectric layer depends on the dielectric constant of the material used, and is generally from 10 nm to 500 nm.
  • the present invention can selectively modify the dielectric layer with a modifying agent to form a modifying layer to change the interface property between the dielectric layer and the semiconductor layer, which is beneficial to improve the performance of the organic thin film transistor device.
  • the modifier includes a silicon-containing compound, a phosphoric acid-containing compound, a high dielectric constant polymer, and the like.
  • the silicon-containing compound can chemically react with a free hydroxyl group on the dielectric layer, and is widely applied to self-assemble monolayer modification of the dielectric layer; commonly used silicon-containing compounds include octadecyl three Chlorosilane (ODTS), phenyltrichlorosilane and fluorine-containing alkyltrichlorosilane, etc., specific silicon-containing compound modifiers and modification methods can be found in the Journal of Applied Physics (J. Appl. Phys., 2004, 96, 6431) 6438) related description.
  • ODTS octadecyl three Chlorosilane
  • phenyltrichlorosilane phenyltrichlorosilane
  • fluorine-containing alkyltrichlorosilane etc.
  • the phosphoric acid-containing compound can also be applied to self-assembled monolayer modification of a dielectric layer;
  • the phosphoric acid-containing compound includes a phosphoric acid having a carbon chain length of 12 to 16 and a phenyl-substituted phosphoric acid.
  • the specific phosphoric acid-containing compound modifier and modification method can be referred to the Journal of Physical Chemistry B (J. Phys. Chem. B, 2003, 107). , 5877-5881) related description.
  • the high dielectric constant polymer includes polydecyl methacrylate (PMMA), polyglycol phenol (PVP), polyvinyl alcohol (PVA), polystyrene (PS), polyvinyl chloride (PVC), and poly
  • PMMA polydecyl methacrylate
  • PVP polyglycol phenol
  • PVA polyvinyl alcohol
  • PS polystyrene
  • PVC polyvinyl chloride
  • the organic thin film transistor includes a semiconductor layer, and a drain electrode and a source electrode are respectively disposed at both ends thereof. Both the source electrode and the drain electrode may be made of the same material as the gate electrode, but a small contact resistance between the electrode material and the semiconductor layer material is ensured.
  • the thickness of the drain electrode and the source electrode and the like are not particularly limited, and the thickness thereof is preferably from 40 nm to 100 nm, and the width to length ratio of the formed conductive channel is preferably 30.
  • the semiconductor layer comprises the above-described soluble phthalocyanine compound having the structure of the formula (I) or the formula (II), the soluble phthalocyanine compound having good solubility in an organic solvent, and the solution method is easy
  • the film is processed to form a method of preparing the organic thin film transistor.
  • the solubility of the soluble phthalocyanine compound having the structure of the formula (I) of the present invention is at least 100% higher than that of copper phthalocyanine (CuPc).
  • the organic solvent may be trichlorodecane, trichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorinated benzene, toluene, diphenylbenzene, tetrahydronaphthalene or triterpene.
  • benzene Among them, trichloromethane, trichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, and chlorinated benzene are among the chlorinated solvents, and the solubility of the soluble phthalocyanine compound in a chlorinated solvent is generally 0.01 wt. % ⁇ 20wt%.
  • the soluble phthalocyanine compound can improve the carrier mobility of the organic thin film transistor and is advantageous for application.
  • another advantage of the soluble phthalocyanine compound having the structure of the formula (II) of the present invention is that a semiconductor material having a hole transporting property and an electron transporting property can be obtained by selecting a different central ligand structure. For example, hole transport can be achieved with a vanadium oxide ligand, while electron transport can be achieved with a tin dichloride ligand.
  • the semiconductor layer preferably further comprises a polymer, i.e., the soluble phthalocyanine compound is blended with the polymer to form a semiconductor layer.
  • the polymer includes a polyarylamine-containing polymer (poly(triarylamine)), polycarbazole, polyfluorene, polythiophene, polyethylene, polystyrene, polydecyl methacrylate, polyglycol phenol, and polycarbonate. Wait.
  • the method for preparing the semiconductor layer is preferably specifically: the soluble phthalocyanine compound After the solution is prepared, a film is prepared, and an electrode is annealed and deposited to obtain a semiconductor layer.
  • processing techniques for preparing a film by formulating the soluble phthalocyanine compound into a solution include spin-coating, dip-coating, blade-coating, and screen printing ( Screening-printing), inkjet printing (inkjet-printing) and other common solution film forming techniques.
  • the thickness of the film is preferably controlled to be from 10 nm to 100 nm, more preferably from 30 nm to 60 nm.
  • the annealing temperature is preferably from 50 ° C to 150 ° C, more preferably from 80 ° C to 120 ° C; and the annealing time is preferably from 10 minutes to 50 minutes, more preferably from 20 minutes to 40 minutes.
  • the semiconductor layer is composited on the dielectric layer, the dielectric layer is composited on the substrate; or the dielectric layer is composited on the semiconductor layer, and the semiconductor layer is compounded on On the substrate. Additionally, the dielectric layer selectively includes a finishing layer.
  • FIG. 1 is a first schematic structural view of an organic thin film transistor according to an embodiment of the present invention.
  • 1 is a substrate
  • 2 is a gate
  • 3 is a dielectric layer
  • 4 is a modified layer
  • 5 is a semiconductor layer
  • 6 is a source electrode
  • 7 is a drain electrode
  • a semiconductor layer 5 is composited on the modification layer 4
  • the modification layer 4 is composited on the dielectric layer 3
  • the dielectric layer 3 is composited on the substrate 1.
  • the gate electrode 2 is disposed on the dielectric layer 3, and the source electrode 6 and the drain electrode 7 are respectively disposed on the upper surfaces of both ends of the semiconductor layer 5.
  • FIG. 2 is a schematic view showing a second structure of an organic thin film transistor according to an embodiment of the present invention. 2 differs from FIG. 1 only in that the source electrode 6 and the drain electrode 7 are respectively disposed on the lower surfaces of both ends of the semiconductor layer 5.
  • FIG. 3 is a schematic view showing a third structure of an organic thin film transistor according to an embodiment of the present invention.
  • the dielectric layer 3 is composited on the semiconductor layer 5
  • the semiconductor layer 5 is composited on the modification layer 4
  • the modification layer 4 is composited on the substrate 1.
  • the gate electrode 2 is disposed on the dielectric layer 3
  • the source electrode 6 and The drain electrodes 7 are respectively disposed on the lower surfaces of both ends of the semiconductor layer 5.
  • the present invention measures the transfer curve and compares the carrier mobility, the switching current ratio and the like.
  • the experimental results show that the organic thin film transistor can be prepared by using the soluble phthalocyanine compound provided by the invention, and the carrier mobility can reach 1 cm 2 /V ⁇ s, and the performance is good.
  • the material, the preparation method thereof and the organic thin film transistor are specifically described.
  • the reaction solution was poured into 200 ml of diethyl ether and extracted with distilled water three times.
  • the obtained diethyl ether layer was washed with a saturated aqueous solution of ammonium chloride.
  • the ether layer was washed three times with saturated brine, dried over magnesium sulfate, and evaporated to ethyl ether.
  • the product was purified by silica gel column chromatography, and a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1 was used as a rinsing agent to obtain 3.30. g yellow liquid, yield 85%.
  • the obtained yellow liquid was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, CDC1 3 , and 13 C NMR results: ⁇ (ppm) 136.3, 131.7, 114.8, 113.3, 102.4, 77.3, 31.3, 28.5, 28.2, 22.5, 19.8, 14.0 .
  • the above results indicate that the obtained product is 4,5-bis(1-octynyl)-phthalonitrile.
  • the obtained white solid was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, CDC1 3 , and 13 C NMR results: ⁇ (ppm) 147.3, 133.9, 115.8, 112.8, 32.5, 31.8, 30.3, 29.6, 29.4, 29.3, 22.6, 14.0 .
  • the above results indicate that the obtained product is 4,5-dioctyl phthalonitrile.
  • Ammonia gas was continuously introduced into a mixture of 2.50 g (7.1 mmol) of 4,5-dioctylphthalic acid nitrile prepared in Example 2, 80 mg (1.4 mmol) sodium decoxide and 40 ml of decyl alcohol at a temperature. Bar for 60 °C After stirring for 5 hours, it was cooled to -20 ° C, and a precipitate was obtained by filtration. The precipitate was washed with cold methanol to recrystallize and dried in vacuo to give 2.1 g of pale yellow solid.
  • the obtained pale yellow solid was subjected to MALDI-TOF mass spectrometry to have a nucleus-to-mass ratio (m/z) of 370.3 [M+H] + (theoretical molecular weight: 369.3) and a melting point of from 109 ° C to 110 ° C.
  • the obtained pale yellow solid was subjected to nuclear magnetic resonance spectroscopy.
  • the NMR results were: ⁇ (ppm) 7.48 (br, 2H), 2.70 (m, 4H), 1.61 (m, 4H), 1.28 (m, 20H), 0.89 (m, 6H). The results showed that the obtained product was 5,6-dioctyl-1,3-dihydro-1,3-diiminoisoindoline.
  • the reaction mixture was further stirred at 0 ° C for 1 hour, then slowly warmed to room temperature, and the reaction was continued for 8 hours.
  • the initial yellow color turns yellow-green, and the solid triethylamine hydrochloride formed in the reaction is removed by suction filtration to obtain a filtrate;
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 963.6 [M+H] + (theoretical molecular weight was 962.7).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy.
  • the NMR results were: ⁇ 8.61 (br, 4H), 8.05 (br, 4H), 7.79 (br, 4H), 2.75 (br, 8H), 1.83 (m, 8H) , 1.61-1,45 (br, 40H), 1.02 ( m, 12H), -3.41 (br, 2H ).
  • the resulting product was subjected to elemental analysis, measured value: C, 79.74; H, 8.54 ; N, 11.72; to C 64 H 82 N 8 is calculated, the calculated value: C, 79.79; H, 8.58 ; N, 11.63.
  • the above results indicate that the obtained product is 2,3,16,17-tetraoctylphthalocyanine.
  • the above results indicate that the obtained product is 1,2-dioctyloxybenzene.
  • the above results indicate that the obtained product is 1,2-dibromo-4,5-dioctyloxybenzene.
  • the above results indicate that the obtained product is 4,5-dioctyloxyphthalonitrile.
  • Example 8 Preparation of 5,6-dioctyloxy-1,3-dihydro-1,3-diiminoisoindoline 6.92 g (18.0 mmol) of the 4,5-dioctyloxyphthalonitrile prepared in Example 7 was replaced by 4,5-dioctylphthalonitrile in the procedure of Example 3 to give 6.10 g of product. , the yield was 84.3%.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 401.2 [M+H]+ (theoretical molecular weight was 401.3).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy.
  • the NMR results were: 57.48 (br, 2H), 3.86 (m, 4H), 1.61 (m, 4H), 1.28 (m, 20H), 0.89 (m, 6H).
  • the above results indicate that the obtained product is 5,6-dioctyloxy-1,3-dihydro-1,3-diimidoisoindoline.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1027.7 [M+H]+ (theoretical molecular weight was 1026.7).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy.
  • the NMR results were: ⁇ 8.61 (br, 4H), 8.05 (br, 4H), 7.79 (br, 4H), 2.75 (br, 8H), 1.83 (m, 8H) , 1.61-1,45 (br, 40H), 1.02 ( m, 12H), -3.41 ( br, 2H ).
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1091.6 [M+H]+ (theoretical molecular weight was 1090.6).
  • the precipitate was obtained in a volume ratio of 3:
  • the chloroform and THF of 1 were eluted with a silica gel column, and then recrystallized from cyclohexane and chloroform to give 160 mg of product, yield 78%.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 913.4 [M+H] + (theoretical molecular weight was 912.4).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz and CDC1 3 , and the NMR results were: ⁇ 8.24 (br, 4H ), 7.56 (br, 4H), 7.14 (br, 4H), 2.24 (br, 8H), 1.39 (48H), 1.0 (t, 12H).
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1169.6 [M+H]+ (theoretical molecular weight was 1168.63).
  • the resulting product was subjected to elemental analysis, measured value: C, 65.57, H, 7.01 , N, 9.75; calculated to be C 64 H 82 N 8 Pb, calcd: C, 65.78, H, 6.90 , N, 9.59.
  • the above results indicate that the obtained product is lead 2,3,16,17-tetraoctylphthalocyanine.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1025.6 [M+H] + (theoretical molecular weight was 1024.59).
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1028.6 [M+H]+ (theoretical molecular weight was 1027.6).
  • the resulting product was subjected to elemental analysis, measured value: C, 74.56, H, 7.79 , N, 10.75; to C 64 H 8. Calculated for N 8 OV, calculated as: C, 74.75, H, 7.84, N, 10.90.
  • the above results indicate that the obtained product is 2,3,16,17-tetraoctyl phthalocyanine vanadyl.
  • indium trichloride (InCl 3 ) was substituted for vanadyl sulfate to obtain a product in a yield of 80%.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its nucleus to mass ratio (m/z) was 1111.5 [M+H] + (theoretical molecular weight was 1110.5).
  • the resulting product was subjected to elemental analysis, measured value: C, 69.26, H, 7.37 , N, 10.15; to C 64 H 8. Calculated by ClInN 8 , the calculated values are: C, 69.15, H, 7.25, N, 10.08.
  • the above results indicate that the obtained product is 2,3,16,17-tetraoctyl indium phthalocyanine chloride.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1151.5 [M+H] + (theoretical molecular weight was 1150.5).
  • Example 19 Preparation of 2,3,16,17-tetraoctyloxyphthalocyanine Titanium Oxide
  • the 2,3,16,17-tetraoctyloxyphthalocyanine prepared in Example 9 was replaced by 2,3,16,17-tetraoctylphthalocyanine according to the procedure of Example 15 to give the product in a yield of 56%. .
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1089.6 [M+H] + (theoretical molecular weight was 1088.6).
  • the resulting product was subjected to elemental analysis, measured value: C, 70.66, H, 7.57 , N, 10.42; to C 64 H 8. Calculated for N 8 0 5 Ti, calculated as: C, 70.57, H, 7.40, N, 10.29.
  • the above results indicate that the obtained product is 2,3,16,17-tetraoctyloxyphthalocyanine.
  • Example 9 The 2,3,16,17-tetraoctyloxyphthalocyanine prepared in Example 9 was replaced by 2,3,16,17-tetraoctylphthalocyanine according to the procedure of Example 18 to give the product in a yield of 65%. .
  • the obtained product was subjected to MALDI-TOF mass spectrometry and its nuclear-to-mass ratio (m/z) was 1215.6 [M+H] +
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1153.5 [M+H] + (theoretical molecular weight was 1152.5).
  • the resulting product was subjected to elemental analysis, measured value: C, 66.76, H, 7.07 , N, 9.78; to C 64 H 8. Calculated for N 8 OS 4 Ti, calculated as: C, 66.64, H, 6.99, N, 9.71.
  • the above results indicate that the obtained product is 2,3,16,17-tetraoctylthiophthalocyanine.
  • Example 12 The 2,3,16,17-tetraoctylthiophthalocyanine prepared in Example 12 was replaced by 2,3,16,17-tetraoctylphthalocyanine according to the procedure of Example 18 to give the product in a yield of 63%. .
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1279.4 [M+H] + (theoretical molecular weight was 1278.4).
  • the resulting product was subjected to elemental analysis, measured value: C, 60.16, H, 6.09 , N, 8.68; to C 64 H 8. Calculated for Cl 2 N 8 S 4 Sn, calculated as C, 60.09, H, 6.30, N, 8.76.
  • the above results indicate that the obtained product is 2,3,16,17-tetraoctylthiophthalocyanine dichloride.
  • the obtained product was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, CDC1 3 , and 13 C NMR results: ⁇ (ppm) 136.7, 132.1, 115.2, 113.8, 102.7, 77.0, 30.7, 22.3, 19.9, 14.0. The above results indicate that the obtained product is 4,5-bis(1-hexynyl)phthalonitrile.
  • the obtained product was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, CDC1 3 , and 13 C NMR results: ⁇ (ppm) 147.3, 133.9, 115.8, 112.8, 32.5, 31.5, 30.3, 29.1, 22.5, 14.0schreib
  • the product obtained was 4,5-dihexyl phthalonitrile.
  • the obtained solid was subjected to MALDI-TOF mass spectrometry and had a nucleus to mass ratio (m/z) of 314.3 [M+H]+ (theoretical molecular weight: 313.3) and a melting point of from 102 ° C to 104 ° C.
  • the obtained solid was subjected to nuclear magnetic resonance spectroscopy.
  • the NMR results were: ⁇ (ppm) 7.49 (br, 3H), 2.71 (m, 4H), 1.61 (m, 4H), 1.34 (m, 12H), 0.90 (m) , 6H).
  • the results showed that the obtained product was 5,6-dioctyl-1,3-dihydro-1,3-diimidoisoindoline.
  • the obtained product was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, and the CDC1 3 , 13 C NMR results were: ⁇ (ppm ) 136.3 . 131.7, 114.8, 113.3, 102.4, 77.3, 31.3, 28.5, 28.2, 22.5, 19.8, 14.0.
  • the above results indicate that the obtained product is 2,3,16,17-tetrahexylphthalocyanine.
  • the obtained product was subjected to MALDI-TOF mass spectrometry to have a nucleus to mass ratio (m/z) of 915.5 [M+H] + (theoretical molecular weight was 914.5).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy.
  • the 3 ⁇ 4 NMR results were: ⁇ 8.62 ( br, 4H ), 8.06 ( br, 4H ), 7.80 ( br, 4H ), 2.73 ( br, 8H ), 1.83 ( m, 8H ) , 1.61-1,45 ( br, 24H ), 1.02 ( m, 12H ), -3.41 ( br, 2H ).
  • Example 23 The 2,3,16,17-tetrahexylphthalocyanine obtained in Example 23 was replaced by 2,3,16,17-tetraoctylphthalocyanine according to the procedure of Example 13, and copper chloride was used instead of acetic acid to obtain 2 , 3,16,17-tetrahexylphthalocyanine copper.
  • the obtained product was subjected to MALDI-TOF mass spectrometry to have a nucleus to mass ratio (m/z) of 912.5 [M+H] + (theoretical molecular weight: 911.5).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz and CDC1 3 , and the NMR results were: ⁇ 8.20 (br, 4H), 7.46 (br, 4H), 7.04 (br, 4H), 2.24 (br, 8H), 1.39 ( 32H ), 1.0 ( t, 12H ).
  • Example 23 The 2,3,16,17-tetrahexylphthalocyanine prepared in Example 23 was replaced by 2,3,16,17-tetraoctylphthalocyanine according to the procedure of Example 16 to obtain 2,3,16,17-tetra. Hexyl phthalocyanine vanadate.
  • the obtained product was subjected to MALDI-TOF mass spectrometry and its nuclear-to-mass ratio (m/z) was 916.5 [M+H] +
  • Theoretical molecular weight is 915.5.
  • the resulting product was subjected to elemental analysis, measured value: C, 73.56, H, 7.19 , N, 12.15; calculated to C 56 H 64 N 8 OV, calcd: C, 73.42, H, 7.04 , N, 12.23.
  • the above results indicate that the obtained product is 2,3,16,17-tetrahexyl phthalocyanine vanadyl.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its ratio of nucleus to mass (m/z) was 1121.5 [M+H] + (theoretical molecular weight was 1120.5). Elemental analysis of the obtained product was carried out in C, 60.16, H, 5.69, N, 10.15. Calculated from C 56 H 64 N 8 Pb: C, 60.03, H, 5.76, N, 10.00. The above results indicate that the obtained product is lead 2,3,16,17-tetrahexyloxyphthalocyanine.
  • the obtained product was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, CDC1 3 , and 13 C NMR results: ⁇ (ppm) 136.3, 131.7, 114.8, 113.3, 102.4, 77.4, 31.9, 29.6, 29.5, 29.3, 29.1, 28.9 , 28.3, 22.6, 19.8, 14.0.
  • the above results indicate that the obtained product is 4,5-bis(1-dodecynyl)-phthalonitrile.
  • Nuclear magnetic resonance carbon spectrum analysis of the obtained product The conditions were 75 MHz, CDC1 3 , 13 C NMR results were: ⁇ (ppm) 147.3, 133.9, 115.8, 112.8, 32.5, 31.8, 30.4, 29.7, 29.4, 29.3, 29.1, 22.6, 14.0. The above results indicate that the obtained product is 4,5-di(1-dodecyl)phthalonitrile.
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 3 , and 3 ⁇ 4 NMR. The results were: ⁇ (ppm) 7.48 ( br, 2H ) , 2.70 ( m, 4H ) , 1.61 ( m, 4H ) , 1.28 ( m , 20H), 0.89 (m, 6H).
  • the obtained product was subjected to nuclear magnetic resonance carbon spectrum analysis under the conditions of 75 MHz, CDC1 3 , 13 C NMR results: ⁇ (ppm) 164.5, 145.1, 131.3, 121.6, 33.2, 31.9, 31.1, 29.7 (br), 29.6, 29.5, 29.4 22.7, 14. K The above results indicate that the obtained product is 5,6-di(dodecyl)-1,3-dihydro-1,3-diiminoisoindoline.
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 400 MHz, CDC1 3 , and 3 ⁇ 4 NMR. The results were: ⁇ (ppm) 8.82 (br, 4H), 8.39 (br, 4H), 7.90 (br, 4H), 2.92 (br , 8H), 1.92 (m, 8H), 1.63-1.34 (br, 48H), 1.01 (m, 12H), -2.78 (br, 2H).
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its nucleus to mass ratio (m/z) was 1188.0 [M+H] + (theoretical molecular weight was 1186.9).
  • Example 28 The 2,3,16,17-tetrakis(dodecyl)phthalocyanine prepared in Example 28 was replaced by 2,3,16,17-tetraoctylphthalocyanine according to the procedure of Example 13, to obtain 2,3. 16,17-tetrakis(dodecyl) phthalocyanine.
  • the obtained product was subjected to MALDI-TOF mass spectrometry, and its nucleus to mass ratio (m/z) was 1249.8 [M+H] + (theoretical molecular weight was 1248.8).
  • the obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz and CDC1 3 , and the NMR results were: ⁇ 8.24 (br, 4H ), 7.56 (br, 4H), 7.14 (br, 4H), 2.24 (br, 8H), 1.39 ( 80H), 1.0 (t, 12H ). Elemental analysis of the obtained product, measured value For: C, 76.91, H, 9.11, N, 8.75; to C 8 . H 112 N 8 Zn was calculated and calculated as C, 76.80, H, 9.02, N, 8.96. The above results indicate that the obtained product is 2,3,16,17-tetrakis(dodecyl)phthalocyanine.
  • Example 30 Example 38 Preparation of Silicon Thin Film Organic Thin Film Transistor
  • the substrate is covered with a silicon dioxide dielectric layer having a thickness of 300 nm and provided with a gate, and the gate is extremely heavily doped n-type silicon wafer;
  • the silicon dioxide dielectric layer is modified with octyltrichlorosilane to form a modified layer
  • the modified layer is covered with a semiconductor layer having a thickness of 30 nm to 60 nm.
  • the preparation process of the semiconductor layer is as follows: Embodiment 29, Embodiment 25, Embodiment 14, Example 17, Example 26, and implementation are selected.
  • the soluble phthalocyanine compounds obtained in Example 15, Example 19, Example 18, and Example 22 were each prepared as a semiconductor material in a chloroform solution having a concentration of 0.5 wt%, respectively, at a rotation speed of 1000 rpm and a rotation time of 60 seconds.
  • the film is formed and then annealed. The temperature and time of the annealing are shown in Table 1.
  • Table 1 shows the main process parameters and properties of the organic thin film transistor provided in Examples 30 to 38 of the present invention.
  • the present invention separately measured the transfer curve, and the results of the carrier mobility and the switching current ratio are shown in Table 1.
  • Example 30 Cavity 80/40 0.03 10 5 based) zinc phthalocyanine
  • the organic thin film transistor is prepared by using the soluble phthalocyanine compound provided by the embodiment of the present invention, and the carrier mobility can reach 1 cm 2 /V ⁇ s, and the performance is good.
  • the organic thin film transistor is prepared by using the soluble phthalocyanine compound provided by the embodiment of the present invention, and the carrier mobility is almost lcm 2 /V ⁇ s, and the performance is good.
  • Magnetron sputtering has been performed on the substrate to form a dielectric layer of aluminum oxide (A1 2 0 3 ) having a thickness of 200 nm, the dielectric layer is provided with a gate, and the gate is subjected to RF magnetron sputtering.
  • the modified layer is covered with a semiconductor layer having a thickness of 30 nm to 60 nm.
  • the preparation process of the semiconductor layer is as follows: The 2,3,16,17-tetraoctylphthalocyanine titanate obtained by the embodiment 15 is selected from the PMMA. The mixture was mixed at a weight ratio of 95:5 to obtain a mixture, and the mixture was formulated into a chloroform solution having a concentration of 0.5% by weight, and a film was formed at a rotation speed of 1000 rpm and a rotation time of 60 seconds, followed by annealing at a temperature of 100. °C, the time is 20 minutes.
  • Fig. 4 is a transfer curve of the organic thin film transistor according to Example 42 of the present invention. As can be seen from Fig. 4, the organic thin film transistor has a mobility of 0.8 cm 2 /V - s.
  • the soluble phthalocyanine compound provided by the present invention can be obtained with High mobility organic thin film transistor.
  • the invention is not limited to the above embodiments.
  • the disclosed organic thin film transistors can be processed to form components in two-dimensional and three-dimensional integrated devices. These integrated devices can be used in flexible integrated circuits, active matrix displays, and more.
  • the organic thin film transistor device based on the present invention can be processed in a low temperature solution.

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Abstract

L'invention concerne un composé de phtalocyanine soluble présentant une structure décrite dans la formule (I) ou la formule (II), R représentant un groupe alkyle, un groupe alcoxy ou un groupe alkylthio et M représentant un métal divalent ou un métal trivalent contenant un ligand. Dans la présente invention, un groupe substituant identique est respectivement introduit sur les sites 2, 3, 16 et 17 du noyau de phtalocyanine, deux cycles benzène dans le noyau phtalocyanine restent non substitués et, en plus, l'atome métallique central peut réguler la structure électronique de la phtalocyanine substituée et peut également générer un effet synergique avec le groupe substituant pour réguler et commander le mode d'accumulation du film mince en phtalocyanine substituée et, donc, le composé de phtalocyanine soluble peut être utilisé pour obtenir un transistor à film mince organique doté d'une mobilité supérieure. La présente invention concerne également un procédé de préparation du composé de phtalocyanine soluble et d'un transistor à film mince organique. La mobilité du support vaut jusqu'à 1 cm2/V·s.
PCT/CN2012/081586 2012-09-19 2012-09-19 Composé de phtalocyanine soluble et son procédé de préparation et transistor à film mince organique WO2014043860A1 (fr)

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WO2016201797A1 (fr) * 2015-06-16 2016-12-22 南方科技大学 Nanocristal de phtalocyanine de métal, son procédé de préparation et applications de celui-ci dans des transistors
CN111045293A (zh) * 2019-12-03 2020-04-21 Tcl华星光电技术有限公司 彩色光刻胶组合物及液晶显示面板

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WO2008037695A2 (fr) * 2006-09-26 2008-04-03 Daehan Solvay Special Chemicals Co., Ltd Dérivés de phtalocyanine solubles pour dispositifs à piles solaires
CN101262041A (zh) * 2008-04-28 2008-09-10 中国科学院长春应用化学研究所 可溶性四烷基轴向取代酞菁化合物在制备有机薄膜晶体管中的应用
CN102002047A (zh) * 2010-10-27 2011-04-06 中国科学院长春应用化学研究所 酞菁化合物及有机薄膜晶体管
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WO2008037695A2 (fr) * 2006-09-26 2008-04-03 Daehan Solvay Special Chemicals Co., Ltd Dérivés de phtalocyanine solubles pour dispositifs à piles solaires
CN101005115A (zh) * 2007-01-23 2007-07-25 中国科学院长春应用化学研究所 轴向取代酞菁化合物用于制备有机薄膜晶体管的应用
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* Cited by examiner, † Cited by third party
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WO2016201797A1 (fr) * 2015-06-16 2016-12-22 南方科技大学 Nanocristal de phtalocyanine de métal, son procédé de préparation et applications de celui-ci dans des transistors
CN111045293A (zh) * 2019-12-03 2020-04-21 Tcl华星光电技术有限公司 彩色光刻胶组合物及液晶显示面板

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