WO2014043860A1

WO2014043860A1 - Soluble phthalocyanine compound and preparation method thereof, and organic thin film transistor

Info

Publication number: WO2014043860A1
Application number: PCT/CN2012/081586
Authority: WO
Inventors: 耿延候; 田洪坤; 董少强
Original assignee: 中国科学院长春应用化学研究所
Priority date: 2012-09-19
Filing date: 2012-09-19
Publication date: 2014-03-27

Abstract

A soluble phthalocyanine compound has a structure disclosed as Formula (I) or Formula (II), R being an alkyl group, alkoxy group or alkylthio group, and M being a divalent metal or a tervalent+ metal containing a ligand. In the present invention, an identical substituent group is respectively introduced to sites 2, 3, 16 and 17 of the phthalocyanine core, two benzene rings in the phthalocyanine core are kept not substituted, and besides, the central metal atom can regulate the electronic structure of the substituted phthalocyanine and can also generate a synergistic effect with the substituent group to regulate and control the accumulation mode of the substituted phthalocyanine thin film, and thus, the soluble phthalocyanine compound can be used for acquiring an organic thin film transistor with higher mobility. The present invention also provides a preparation method of the soluble phthalocyanine compound and an organic thin film transistor. The carrier mobility is up to 1cm²/V·s.

Description

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

In recent years, with the development of applications of organic thin film transistors in integrated circuits and sensors, research and development of high mobility organic conjugated semiconductor materials has been very active. Phthalocyanine compounds have a unique π-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 π - π mutual The stacked structure of action, therefore, phthalocyanine compounds are widely used as high mobility organic conjugated semiconductor materials. U.S. Patent No. 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丄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 ).

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. However, since 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.

At present, various soluble phthalocyanine compounds have been disclosed in the prior art, for example, Japanese Patent Publications JP2004149752, JP2008303383, JP2009218369, JP2010045186 and JP201120483, The Chinese patent documents of US Pat. No. 5,932, 721 and US Pat. The above prior art introduces an oleophilic or hydrophilic substituent to a substitution site of a benzene ring moiety at the periphery of a mononuclear phthalocyanine, thereby improving the solubility of the phthalocyanine compound, but using the above soluble phthalocyanine compound as a semiconductor layer for an organic thin film transistor , exhibited mobility ^{^{2 / V · s -lO 10_ 3}} cm ^ cm '/ V - s, unsubstituted lower than the mobility of phthalocyanine compound, thus limiting their applications. Summary of the invention

In order to solve the above technical problems, 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);

Wherein 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'

Preferably, 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.

Preferably, 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.

Preferably, the R is octyl, hexyl, dodecyl, hexyloxy, octyloxy or octylthio. Preferably, 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;

The filtrate is mixed with hydroquinone or sodium decoxide to obtain a soluble phthalocyanine compound having the structure of formula (I):

Wherein R is an alkyl group, an alkoxy group or an alkylthio group.

Preferably, after obtaining the soluble phthalocyanine compound having the structure of the formula (I), 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):

Wherein 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.

Preferably, 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.

Preferably, the organic solvent of the solution is trichlorodecane, trichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenylbenzene, toluene, diphenylbenzene, tetrahydronaphthalene or triterpene. .

Compared with the prior art, 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 π-π 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. In addition, 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.

Further, 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. DRAWINGS

1 is a first schematic structural view of an organic thin film transistor according to an embodiment of the present invention;

2 is a schematic view showing a second structure of an organic thin film transistor according to an embodiment of the present invention;

3 is a schematic view showing a third structure of an organic thin film transistor according to an embodiment of the present invention;

4 is a transfer curve of an organic thin film transistor according to Embodiment 42 of the present invention.

detailed description

In order to further understand the invention, the preferred embodiments of the present invention are described in the accompanying drawings.

Formula (I); Formula (II); wherein R is an alkyl group, an alkoxy group or an alkylthio group; and M is a divalent metal or a trivalent or higher metal containing a ligand.

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. In formula (I) or formula (II), 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 π-π 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.

In formula (II), 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 . In the present invention, 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;

Wherein 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:

(a) Preparation of 4,5-diiodophthalonitrile

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. The 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;

To the 4,5-diiodophthalic acid amide and 1,4-diox at a temperature of 75 ° C to 80 ° C 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.

(b) Preparation of 4,5-bis(1-alkynyl)-phthalonitrile

According to the molar ratio of 1:0.04~0.1:0.02~0.05, 4,5-diiodophthalonitrile, cuprous iodide

(Cul) and dichlorobis(triphenylphosphine palladium) (Pb(PPh ₃ ) ₂ C1 ₂ ) are added to a dry mixed solvent of triethylamine and tetrahydrofuran in a volume ratio of 1:15-20. The concentration of the compound is 0.02 mol/L to 0.1 mol/L, and then 1-alkylyne, the 4,5-diiodophthalonitrile and the 1-alkyl alkyne are added to the above system. The molar ratio is 1:2~3, and the reaction is stopped after stirring at room temperature for 24 hours to 28 hours. The 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.

(c) Preparation of 4,5-dialkyl phthalonitrile

Adding palladium carbon (Pd/C) with a weight ratio of 4,5-bis(1-alkynyl)phthalonitrile and metal palladium of 8% to 12% according to a molar ratio of 1:0.05~0.1 In absolute ethanol, the concentration of the compound is 0.1 mol/L to 0.4 mol/L. After stirring for 12 hours to 36 hours under a hydrogen atmosphere of 1 to 2 atmospheres, the palladium carbon is removed by filtration, and the solvent is distilled off. Further, silica gel column chromatography was carried out using a mixed solution of chloroform and petroleum ether as a rinsing agent to obtain 4,5-dialkyl phthalonitrile.

(d) Preparation of 5,6-dialkyl-1,3-dihydro-1,3-diimidoisoindoline

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.

(e) Preparation of 4,5-dialkoxyphthalonitrile

The 4,5-dialkoxyphthalonitrile is preferably in accordance with Liquid Crystal Magazine (Liquid Crystal, 2002,

29, 1425-1433) Preparation of the disclosed method: The catechol, the brominated alkane and the potassium carbonate are dissolved in acetone at a molar ratio of 1:4:4, so that the concentration of the reactant is 0.1 mol/L to 0.4. Mol / liter, heating under reflux for 48 hours, then the reaction liquid was poured into water, and then extracted with dichloromethane, dried over anhydrous magnesium sulfate, evaporated to remove the solvent, and chromatographed by silica gel column chromatography with dichloromethane. Get 1,2-dioxane Oxybenzene

Dissolving the 1,2-dialkoxybenzene in dichloromethane and stirring at 0 ° C, slowly adding liquid bromine to the reaction system, the 1,2-dialkoxybenzene and The molar ratio of the liquid bromine is 1:2.2, and the stirring is continued for 2 hours. Then, a saturated aqueous solution of sodium thiosulfate is added to the above reaction system, and then the mixture is extracted with dichloromethane, and the organic phase is washed with saturated brine. Drying with anhydrous magnesium sulfate and evaporating the solvent to obtain 1,2-dibromo-4,5-dialkoxybenzene;

A mixture of the 1,2-dibromo-4,5-dialkoxybenzene, cuprous cyanide and dimethylformamide was heated under reflux for 24 hours, then cooled to room temperature, and the reaction liquid was poured into a large amount of water. Then, it was extracted with diethyl ether, washed with saturated brine, dried over anhydrous magnesium sulfate, evaporated, evaporated, and evaporated, and ethyl acetate and petroleum ether as a rinse to silica gel column chromatography to obtain 4,5-dialkoxy O-phthalonitrile.

(f) Preparation of 5,6-dialkoxy-1,3-dihydro-1,3-diimidoisoindoline

Substituting 4,5-dialkoxyphthalonitrile to 4,5-dialkylphthalonitrile to obtain 5,6-dialkoxy-1,3-dihydrogen according to the procedure of U) -1,3-diimidoisoindoline.

( g ) 4,5-dialkylthio phthalonitrile

The 4,5-dialkylthio phthalonitrile is preferably in accordance with J. Org. Chem., 2010,

75, 7893-7896) Preparation of the disclosed method: Mixing a mixture of alkyl mercaptan, potassium carbonate and dimethyl sulfoxide (DMSO) at room temperature for 30 minutes to industrially produce 4,5-dichlorophthalonitrile Adding to the above mixture, and stirring at 80 ° C for 12 hours, then adding saturated brine to the reaction system, extracting with dichloromethane, washing the organic phase with saturated brine, drying over anhydrous magnesium sulfate, and steaming Separation of the solvent by a silica gel column chromatography using a mixed solution of ethyl acetate and petroleum ether was carried out to obtain 4,5-dialkylthio phthalonitrile.

(h) Preparation of 5,6-dialkylthio-1,3-dihydro-1,3-diimidoisoindoline

Substituting 4,5-dialkylthio phthalonitrile for 4,5-dialkylphthalonitrile to obtain 5,6-dialkylthio-1,3-dihydrogen according to the procedure of U) -1,3-diimidoisoindoline.

The present invention uses 1,3,3-trichloroisohydroazaindene as a raw material, which is preferably in accordance with the US patent document.

Process prepared by US2701252:

Mix phthalic acid phthalimide and phosphorus pentachloride (PC1 ₅ ) uniformly, heat to 100 ° C, then add o-dichlorobenzene, reflux for 4 hours, and then vacuum distillation under conditions of 17 mmHg to 19 mmHg. A pale yellow fraction of 160 ° C to 165 ° C gives 1,3,3-trichloroisohydroazaindole. In the present invention, 5,6-dialkyl-1,3-dihydro-1,3-diiminoisoindoline and 5,6-dialkoxy-1,3- are preferably protected under nitrogen. 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. , 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;

To the filtrate, hydroquinone and sodium decoxide were added, and the reaction was refluxed for 6 hours. After the reaction was stopped, the solvent was distilled off, and the mixed solution of chloroform and petroleum ether was used as a rinsing agent to carry out silica gel column chromatography to obtain the formula (I). A structure of a soluble phthalocyanine compound, in the formula (I), R is an alkyl group, an alkoxy group or an alkylthio group.

In the present invention, 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. Most preferably an octyloxy 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. .

After obtaining a soluble phthalocyanine compound having the structure of the formula (I), 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):

In the present invention, 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 . In the present invention, 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.

In the present invention, 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. Preferably, 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.

In the present invention, 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.

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

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. In the present invention, the organic thin film transistor (OTFT) 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. For the preparation of flexible devices, 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. For a flexible plastic substrate, the thickness is preferably 50 micrometers to 5 millimeters. For a hard substrate of silicon wafer or glass, 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. Wherein, 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 μm 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. Wherein, 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. 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. Wherein, 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. 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 For specific types, such as imide, please refer to the related description of Advanced Materials Magazine (Adv. Mater., 2005, 17, 1705-1725).

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. For example, 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). In the present invention, 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%.

At the same time, the soluble phthalocyanine compound can improve the carrier mobility of the organic thin film transistor and is advantageous for application. Further, 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.

In the present invention, 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.

In the present invention, 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.

In the present invention, 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. In FIG. 1, 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; and a semiconductor layer 5 is composited on the modification layer 4, The modification layer 4 is composited on the dielectric layer 3, and 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.

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.

3 is a schematic view showing a third structure of an organic thin film transistor according to an embodiment of the present invention. In FIG. 3, the dielectric layer 3 is composited on the semiconductor layer 5, the semiconductor layer 5 is composited on the modification layer 4, and 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.

After obtaining an organic thin film transistor, 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.

Example 1 Preparation of 4,5-bis(1-octynyl)-phthalonitrile

Under nitrogen, 4.30 g (11. 3 mmol) of 4,5-diiodophthalonitrile, 125 mg (0.66 mmol) of CuL 154 mg (0.22 mmol) Pd ( PPh ₃ ) ₂ C1 ₂ , 7 ml of triethylamine and 100 ML tetrahydrofuran was added to the reaction flask, and 3.7 ml (24.9 mmol) of 1-octyne was slowly poured thereinto, and the reaction was carried out at room temperature with stirring. The progress of the reaction was monitored by thin layer chromatography (TLC), and found after 24 hours. 4,5-diiodophthalic acid nitrile was present. 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 spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and _3⁄4 NMR. The results were: δ (ppm) 7.73 (s, 2H), 2.50 (t, J = 7.0 Hz, 4H), 1.64 (m, 4H), 1.49 (m, 4H), 1.30 (m, 8H), 0.91 (t, J = 6.8 Hz, 6H). 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: δ (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.

Example 24 Preparation of 5-dioctyl suburbs: phthalonitrile

3.30 g ( 9.57 mmol) of 4,5-bis(1-octynyl)phthalic acid nitrile prepared in Example 1 and

1.06g (1.Ommol) of Pb/C with a weight ratio of 10% was added to 40 ml of absolute ethanol, and reacted under a hydrogen atmosphere of 2 standard atmospheres at room temperature with stirring. TLC monitoring showed After 24 hours, the reaction was completed, the Pd/C was removed by filtration, and the solvent was evaporated to dryness. The product was purified by silica gel column chromatography, and a mixture of the oil ratio of 50:1 and ethyl acetate was used as a rinse to obtain a crude product. Further distillation under reduced pressure gave 2.40 g of a white solid (yield: 71%).

The obtained white solid was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and _3⁄4 NMR. The results were: δ (ppm) 7.56 (s, 2H), 2.67 (t, J = 7.8 Hz, 4H), 1.58 (m, 4H), 1.28 (m, 20H), 0.89 (m, 6H). 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: δ (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.

EXAMPLE 35 Preparation of 6-Dioctyl-1,3-dihydro-1,3-diimidoisoindoline

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: δ (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.

Example 42, Preparation of 3,16,17-tetraoctylphthalocyanine

1.03 g (2.8 mmol) of 5,6-dioctyl-1,3-dihydro-1,3-diiminoisoindoline prepared in Example 3 under a nitrogen atmosphere and 1.2 ml (8.7 mmol) Triethylamine was dissolved in 30 ml of tetrahydrofuran, the reaction solution was lowered to 0 ° C, and 1,3,3-trichloroisohydroazaindole solution (617 mg (2.8 mmol) 1,3,3-trichloro) The iso-dihydroazaindole was dissolved in 15 ml of tetrahydrofuran. The mixture was added dropwise to the above reaction solution over 10 minutes. 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 filtrate was transferred to a reaction flask containing 308 mg (2.8 mmol) of hydroquinone and 454 mg (8.4 mmol) of sodium decoxide, and refluxed for 6 hours, and then chloroform was added to the reaction flask to obtain an organic phase. After washing three times with saturated brine, dried over anhydrous magnesium sulfate, and then, then,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, %.

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: δ 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.

Example 51 Preparation of 2-dioctyloxybenzene

3.00 g (27.20 mmol) of catechol, 15.06 g (O.llmol) of potassium carbonate and 100 ml of C The ketone was added to the reaction flask, and 21.25 g (0.1 mmol) of 1-bromooctane was added dropwise to the reaction flask. After the completion of the dropwise addition, the mixture was heated under reflux for 48 hours, and then the reaction liquid was poured into water to dichloride. The decane was extracted twice (100 ml each time), washed with saturated brine, dried over anhydrous magnesium sulfate, evaporated, and evaporated to silica Oil, yield 96%.

The obtained colorless oil was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and _3⁄4 NMR results were: δ (ppm) 6.91 (s, 4H), 4.01 (t, J = 6.58 Hz, 4H), 1.84 ( q, J = 6.58 Hz, 2H), 1.55-1.24 (m, 20H), 0.91 (t, J = 6.58 Hz, 6H). The above results indicate that the obtained product is 1,2-dioctyloxybenzene.

Example 6 Preparation of 1,2-dibromo-4,5-dioctyloxybenzene

5.00 g (0.017 mol) of the 1,2-dioctyloxybenzene prepared in Example 5 was dissolved in 10 ml of dichloromethane, and stirred at 0 ° C, and 6.00 g (0.0375 mol) of the solution was slowly added dropwise thereto. The bromine was further stirred for 2 hours, and then a saturated aqueous solution of sodium thiosulfate was added to the above-mentioned reaction mixture, and the mixture was extracted with dichloromethane, and the organic phase was washed with brine, dried over anhydrous magnesium sulfate and evaporated. 5.50 g of a colorless oil was obtained.

The obtained colorless oil was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and the Η NMR results were: δ (ppm) 7.06 (s, 2H), 3.94 (t, J = 6.58 Hz, 4H), 1.84 -1.75 (m, 2H), 1.50-1.30 (m, 20H), 0.91 (t, J = 6.9 Hz, 6H). The above results indicate that the obtained product is 1,2-dibromo-4,5-dioctyloxybenzene.

Example 7 4,5-dixin! Preparation of o-phthalonitrile

A mixture of 14.7 g (28.4 mmol) of 1,2-dibromo-4,5-dioctyloxybenzene prepared in Example 6, 10.5 g (117 mmol) of cuprous cyanide and 120 ml of dimethylformamide was heated. After refluxing for 24 hours, it was cooled to room temperature, and the reaction mixture was poured into a large amount of water, and then extracted with diethyl ether, washed with saturated brine, dried over anhydrous magnesium sulfate, evaporated, and evaporated. The rinsing agent was subjected to silica gel column chromatography to give 7.10 g of product.

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: 7.18 ( s, 2H ), 4.07 ( t, J = 7.8 Hz, 4H ), 1.84 ( m, 4H ), 1.29 ( m, 20H ), 0.89 ( m, 6H ). . 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.

Example 92 Preparation of 3,16,17-tetraoctyloxyphthalocyanine

The 5,6-dioctyloxy-1,3-dihydro-1,3-diiminoisoindoline prepared in Example 8 was substituted for 5,6-dioctyl- according to the procedure of Example 4. 1,3-Dihydro-1,3-diimidoisoindoline gave the product in 20% yield.

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: δ 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 ). Elemental analysis of the obtained product, C, 74.74, H, 8.12, N, 11.02; Calculated from C ₆₄ H ₈₂ N ₈ 0 ₄ , calculated: C, 74.82, H, 8.04, N, 10.91 . The above results indicate that the obtained product is 2,3,16,17-tetraoctyloxyphthalocyanine.

Example 104 Preparation of 5-dioctylthio-ortho-carbonitrile

A mixture of 6.0 g (50.7 mmol) of octyl-1-thiol, 14.0 g (101.3 mmol) of potassium carbonate and 200 ml of dimethyl sulfoxide was stirred at room temperature for 30 minutes to give 4.0 g (20.3 mmol) of 4,5- Dichlorophthalic acid nitrile was added to the above mixture, and stirred at 80 ° C for 12 hours, cooled to room temperature, then 100 ml of saturated brine was added to the reaction system, and extracted twice with diethyl ether, 100 ml each time. After evaporating the solvent, silica gel column chromatography was carried out using a mixture of petroleum ether and ethyl acetate in a volume ratio of 9:1 to afford 5.17 g of a colorless oil, yield 70%.

The obtained colorless oil was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and _3⁄4 NMR results were: δ (ppm) 7.38 (s, 4H), 3.00-2.97 (t, J = 15 Hz, 4H), 1.75-1.69 (q, J = 30 Hz, 4H), 1.50-1.44 (m, 8H), 1.32-1.29 (m, 12H) 0.91 (t, J = 6.58 Hz, 6H). The above results indicate that the obtained product is 4,5-dioctylthio-phthalonitrile. Example 115, Preparation of 6-dioctylthio-1,3-dihydro-1,3-diiminoisoindoline

4.17 g (10.0 mmol) of 4,5-dioctylthio-phthalonitrile was prepared in accordance with the procedure of Example 3 in place of 4,5-dioctylphthalic acid to give 3.60 g of product. , the yield was 83%.

EXAMPLES Preparation of 122,3,16,17-tetraoctyl phthalocyanine

The 5,6-dioctylthio-1,3-dihydro-1,3-diimidoisoindoline prepared in Example 11 was substituted for 5,6-dioctyl group according to the procedure of Example 4. 1,3-Dihydro-1,3-diimidoisoindoline gave the product in a yield of 25%.

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 obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz and CDC1 ₃ , and the NMR results were: δ (ppm) - 3.24 (brs, 2H), 0.91 (t, J = 7.02 Hz, 12 H), 1.78 - 1.36 ( m, 40 H ), 2.08 - 2.06 (m, 4H) , 3.44 ( t, J = 7 Hz, 8 H ) , 7.79 (br, 4H) 8.05 (br, 4H), 8.48 ( s, 4H ). Elemental analysis of the obtained product, C, 70.64, H, 7.62, N, 10.12; Calculated for C ₆₄ H ₈₂ N ₈ S ₄ : C, 70.41, H, 7.57, N, 10.26 . The above results indicate that the obtained product is 2,3,16,17-tetraoctylthiophthalocyanine.

EXAMPLES Preparation of 132,3,16,17-tetraoctyl zinc phthalocyanine

Under a nitrogen atmosphere, 192 mg (0.20 mmol) of 2,3,16,17-tetraoctylphthalocyanine prepared in Example 4 and 150 mg (0.80 mmol) of acetic acid were dissolved in 10 ml of N-decylpyrrolidone and 10 ml of hydrazine. In the mixed solution of benzene, the mixture was heated to reflux at 140 ° C, stirred at 7 'J, and then cooled to room temperature. The reaction solution was allowed to settle in 300 ml of decyl alcohol, and a precipitate was obtained by filtration. 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: δ 8.24 (br, 4H ), 7.56 (br, 4H), 7.14 (br, 4H), 2.24 (br, 8H), 1.39 (48H), 1.0 (t, 12H). Elemental analysis of the obtained product: C, 73.41, H, 7.01, N, 11.95; Calculated from C ₆₄ H ₈₂ N ₈ Zn, calculated: C, 73.55, H, 7.05, N, 12.25. The above results indicate that the obtained product is 2,3,16,17-tetraoctylphthalocyanine. Example 142, Preparation of 3,16,17-tetraoctylphthalocyanine lead

125 mg (0.13 mmol) of 2,3,16,17-tetraoctylphthalocyanine prepared in Example 4 and 100 mg (0.26 mmol) of lead acetate trihydrate were dissolved in 7 ml of n-pentanol under an argon atmosphere, and heated to 160 The reaction was refluxed at ° C, stirred for 12 hours, and then cooled to room temperature. The reaction solution was poured into 150 ml of decyl alcohol, and the precipitate was obtained by filtration. The precipitate was purified by silica gel column chromatography and purified by silica gel column chromatography. Recrystallization from a mixed solution of an alcohol and chloroform afforded 119 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 1169.6 [M+H]+ (theoretical molecular weight was 1168.63). The obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and the NMR results were: 9.20 (dd, J = 2.88 Hz, J = 5.11 Hz, 4H), 8.95 (s, 4H), 8.08 (dd, J = 2.65 Hz, J = 5.42 Hz, 4H), 3.14 (m, 8H), 1.96 (m, 8H), 1.65 (m, 8H), 1.40 (br, 24H), 0.96 (t, 12H). 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.

EXAMPLES Preparation of 152,3,16,17-tetraoctylphthalocyanine titanate

241 mg (0.25 mmol) of 2,3,16,17-tetraoctylphthalocyanine prepared in Example 4 was dissolved in 20 ml of N-decylpyrrolidone under an argon atmosphere, and heated to 190 ° C to 0.34 ml ( l.Ommol) Titanium butoxide was added dropwise to carry out the reaction, and after stirring for 0.5 hour, it was cooled to room temperature, and the reaction liquid was sedimented in 300 ml of methanol, and a precipitate was obtained by filtration, and the precipitate was 50:1 by volume. The mixed solution of chloroform and decyl alcohol was eluted with silica gel column chromatography, and recrystallized from cyclohexane and chloroform to give 120 mg of product (yield: 47%).

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 nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, and the CDC1 ₃ , ^NMR results were: δ 9.26 ( dd, 4H, J = 2.95 Hz, J = 5.42 Hz ), 8.67 (s, 4H), 8.24 ( dd , 4H, J=2.72 Hz, J=5.65 Hz), 3.06 ( br, 8H), 1.98 (m, 8H), 1.71 (m, 8H), 1.60 ( m, 8H), 1.53 ( m, 8H), 1.44 (br, 16H), 0.99 (t, 12H). The resulting product was subjected to elemental analysis, measured value: C, 74.66, H, 7.82 , N, 10.70; to C ₆₄ H _8. Calculated for N ₈ OTi, calculated as C, 74.98, H, 7.87, N, 10.93. The above results indicate that the obtained product is 2,3,16,17-tetraoctylphthalocyanine. Example 16 Preparation of 2,3,16,17-tetraoctylphthalocyanine vanadyl

231 mg (0.24 mmol) of 2,3,16,17-tetraoctylphthalocyanine prepared in Example 4, 200 mg (1.2 mmol) of vanadyl sulfate, and 1.4 g (24 mmol) of urea were dissolved in 15 ml under an argon atmosphere. In N-decylpyrrolidone, the reaction was carried out by heating to 200 ° C, and after stirring for 8 hours, it was cooled to room temperature, and the reaction liquid was settled in 250 ml of methanol, and a precipitate was obtained by filtration, and the precipitate was treated with chloroform as a rinse. Purification by silica gel column chromatography gave 124 mg ofyield.

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.

Example 17 Preparation of 2,3,16,17-tetraoctylphthalocyanine indium chloride

According to the procedure of Example 16, 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.

Example 18 2,3,16,17-tetraoctyltinphthalocyanine dichloride

According to the procedure of Example 14, tin dichloride (SnCl ₂ ) was replaced by lead acetate trihydrate to obtain a product in a yield of 60%.

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). The obtained product was subjected to nuclear magnetic resonance spectroscopy under the conditions of 300 MHz, CDC1 ₃ , and the NMR results were: δ (ppm) 9.46 (dd, 4H, J = 3.05 Hz, J = 5.20 Hz), 8.47 (s, 4H), 8.04 ( dd, 4H, J=2.90 Hz, J=5.30 Hz ), 3.16 ( br, 8 H ), 2.05 ( m, 8H ), 1.78 ( m, 8 H ), 1.60 ( m, 8H ), 1.53 ( m , 8H ), 1.40 ( br, 16H ), 0.99 ( t, 12H ). Elemental analysis of the obtained product, C, 66.66, H, 7.07, N, 9.82; Calculated by C ₆₄ H ₈₀ Cl ₂ N ₈ Sn, calculated: C, 66.78, H, 7.01, N, 9.74. The above results indicate that the obtained product is 2,3,16,17-tetraoctyltinphthalocyanine dichloride.

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 20 Preparation of 2,3,16,17-tetraoctyloxyphthalocyanine Dichloride

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] ⁺

(Theoretical molecular weight is 1214.5). The resulting product was subjected to elemental analysis, measured value: C, 63.24, H, 6.54 , N, 9.32; to C ₆₄ H _8. Calculated for Cl ₂ N ₈ 0 ₄ Sn, calculated as C, 63.27, H, 6.64, N, 9.22. The above results indicate that the obtained product is 2,3,16,17-tetraoctyloxyphthalocyanine dichloride.

Example 21 2,3,16,17-tetraoctylthiophthalocyanine

The 2,3,16,17-tetraoctylthiophthalocyanine prepared in Example 12 was replaced by the procedure of Example 15.

2,3,16,17-Tetraoctylphthalocyanine gave 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 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 22 2,3,16,17-tetraoctylthiophthalocyanine dichloride

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.

Example 23 Preparation of 2,3,16,17-tetrahexylphthalocyanine

Following the procedure of Example 1, 1-hexyne was substituted for 1-octyne to give the product 4,5-di(1-hexynyl). O-phthalonitrile, yield 97%.

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: δ (ppm) 7.73 (s, 2H), 2.51 (t, J = 6.9 Hz, 4H), 1.63 (m, 4H) ), 1.53 (m, 4H), 0.96 (t, J = 7.2 Hz, 6H). 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: δ (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 4,5-bis(1-hexynyl)phthalic acid nitrile was replaced by 4,5-bis(1-octynyl)phthalic acid nitrile according to the procedure of Example 2 to obtain 4,5. - Dihexyl 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: δ (ppm) 7.56 (s, 2H), 2.67 (t, J = 6.8 Hz, 4H), 1.36 (m, 4H) ), 1.33 ( m, 12H ) , 0.90 ( t, J = 6.8 Hz, 6H ). 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: δ (ppm) 147.3, 133.9, 115.8, 112.8, 32.5, 31.5, 30.3, 29.1, 22.5, 14.0 „ The product obtained was 4,5-dihexyl phthalonitrile.

The obtained 4,5-dihexylphthalonitrile was replaced by 4,5-dioctylphthalonitrile in the procedure of Example 3 to obtain 5,6-dihexyl-1,3-dihydro- 1,3-diimidoisoindoline.

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: δ (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 5,6-dihexyl-1,3-dihydro-1,3-diimidoisoindoline was substituted for 5,6-dioctyl-1,3-di according to the procedure of Example 4. Hydrogen-1,3-diimidoisoindoline gives 2,3,16,17-tetrahexylphthalocyanine.

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: δ7·73 (ppm) (s, 2H), 2.50 (t, J = 7.0 Hz, 4H), 1.64 (m, 4H), 1.49 (m, 4H), 1.30 (m, 8H), 0.91 (t, J = 6.8 Hz, 6H). 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: δ (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.

Example 24 Preparation of 2,3,16,17-tetrahexyloxyphthalocyanine

Substituting 1-bromohexane for 1-bromooctane according to the procedure of Example 5 gave 1,2-dihexyloxybenzene. The 1,2-dihexyloxybenzene obtained was replaced by 1,2-dioctyloxybenzene according to the procedure of Example 6 to give 1,2-dibromo-4,5-dihexyloxybenzene.

The obtained 1,2-dibromo-4,5-dihexyloxybenzene was replaced by 1,2-dibromo-4,5-dioctyloxybenzene according to the procedure of Example 7, to obtain 4,5-di. Hexyloxyphthalonitrile.

The obtained 4,5-dihexyloxyphthalonitrile was replaced by 4,5-dioctylphthalonitrile to obtain 5,6-dihexyloxy-1,3 according to the procedure of Example 3. - Dihydro-1,3-diimidoisoindoline.

The obtained 5,6-dihexyloxy-1,3-dihydro-1,3-diimidoisoindoline was substituted for 5,6-dioctyl-1,3 according to the procedure of Example 4. -Dihydro-1,3-diimidoisoindoline gives 2,3,16,17-tetrahexyloxyphthalocyanine.

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: δ 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 ). Elemental analysis of the obtained product, C, 73.74, H, 7.12, N, 12.02; Calculated for C ₅₆ H ₆₆ N ₈ 0 ₄ , calculated: C, 73.49, H, 7.27, N, 12.24 . The above results indicate that the obtained product is 2,3,16,17-tetraoctyloxyphthalocyanine.

Example 25 Preparation of 2,3,16,17-tetrahexylphthalocyanine copper

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: δ 8.20 (br, 4H), 7.46 (br, 4H), 7.04 (br, 4H), 2.24 (br, 8H), 1.39 ( 32H ), 1.0 ( t, 12H ). The resulting product was subjected to elemental analysis, measured value: C, 73.81, H, 7.11 , N, 12.15; to C ₅₆ H ₆₄ CuN ₈ calculated calcd: C, 73.69, H, 7.07 , N, 12.28. The above results indicate that the obtained product is 2,3,16,17-tetrahexylphthalocyanine. Copper.

Example 26 Preparation of 2,3,16,17-tetrahexylphthalocyanine vanadyl

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.

Example 27 Preparation of lead 2,3,16,17-tetrahexyloxyphthalocyanine

The 2,3,16,17-tetrahexyloxyphthalocyanine prepared in Example 24 was replaced by the procedure of Example 14.

2,3,16,17-tetraoctylphthalocyanine gives lead 2,3,16,17-tetrahexyloxyphthalocyanine.

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.

Example 28 Preparation of 2,3,16,17-tetrakis(dodecyl)phthalocyanine

Following the procedure of Example 1, 1-dodecyne was replaced by 1-octyne to give the product 4,5-bis(1-dodecynyl)-phthalic acid nitrile in a yield of 83%.

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: δ (ppm) 7.73 ( s, 2H ) , 2.49 ( t, J = 7.0 Hz, 4H ) , 1.63 ( m, 4H ), 1.46 (m, 4H), 1.27 (m, 24H), 0.91 (t, J = 6.8 Hz, 6H). 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: δ (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.

The obtained 4,5-bis(1-dodecynyl)phthalic acid nitrile was replaced by 4,5-bis(1-octynyl)phthalic acid nitrile according to the procedure of Example 2 to obtain 4, 5-bis(dodecyl) phthalic acid nitrile, yield 83%.

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: δ (ppm) 7.56 ( s, 2H ) , 2.67 ( t, J = 7.9 Hz, 4H ) , 1.57 ( m, 4H ), 1.26 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H). Nuclear magnetic resonance carbon spectrum analysis of the obtained product The conditions were 75 MHz, CDC1 ₃ , ¹³ C NMR results were: δ (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 4,5-di(dodecyl)phthalonitrile was replaced by 4,5-dioctylphthalonitrile in the procedure of Example 3 to obtain 5,6-di(dodecane). -1,3-dihydro-1,3-diimidoisoindoline, yield 74%.

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: δ (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: δ (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 5,6-di(dodecyl)-1,3-dihydro-1,3-diiminoisoindoline was substituted for 5,6-dioctyl group according to the procedure of Example 4. 1,3-Dihydro-1,3-diimidoisoindoline gave 2,3,16,17-tetrakis(dodecyl)phthalocyanine in a yield of 22%.

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: δ (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). The resulting product was subjected to elemental analysis, measured value: C, 80.86, H, 9.63 , N, 9.25; to C _8. H ₁₁₄ N ₈ was calculated and calculated as: C, 80.89, H, 9.67, N, 9.43. The above results indicate that the obtained product is 2,3,16,17-tetrakis(dodecyl)phthalocyanine.

EXAMPLES Preparation of 292,3,16,17-tetrakis(dodecyl)phthalocyanine

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: δ 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

Using a heavily doped n-type silicon wafer as a substrate;

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. After annealing, gold having a thickness of 50 nm is deposited as a source electrode and a drain electrode, and a conductive channel having a width to length ratio of 30 (W/L = 3000 μm / 100 μm = 30) is formed to obtain a semiconductor layer, and finally an organic layer is formed. Thin film transistor.

After obtaining the organic thin film transistor, 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.

Table 1 Inventive Examples 30 to 38 Process Parameters and Properties of Organic Thin Film Transistors Organic Thin Film Charge Transfer Annealing Temperature / Time Mobility Switching Electrical Semiconductor Layer

Transistor input type (.C/min) (cm ² /Vs ) ratio

2,3,16,17 -tetrakis

Example 30 Cavity 80/40 0.03 10 ⁵ based) zinc phthalocyanine

2,3,16,17 -tetrahexyl

Example 31 Hole 120/30 0.04 10 ⁵ copper

2,3,16,17 - tetraoctyl

Example 32 Hole 100/20 0.08 10 ⁵ Lead

Example 33 2,3,16,17-tetraoctylfluorene cavity 100/30 0.15 10 ⁶ Indium chloride

2,3,16,17 -tetrahexyl

Example 34 Hole 100/20 0. 4 10 ⁶ Vanadium Oxide

2,3,16,17 - tetraoctyl

Example 35 Hole 100/20 1.0 10 ⁶ Crystalline Titanium Oxide

2,3,16,17 -tetraoctyloxy

Example 36 Hole 80/20 0.85 10 ⁶ Phthalocyanine

2,3,16,17 - tetraoctyl

Example 37 Electron 80/30 0.20 10 ⁶ Cyanine Dichloride

2,3,16,17 _tetraoctylthio

Example 38 Electron 100/20 0.35 10 ⁶ phthalocyanine dichloride

It can be seen from Table 1 that 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.

Example 39 to Example 41 Preparation of Glass Substrate Organic Thin Film Transistor

Using Corning7059 glass as a substrate;

Magnetron sputtering a layer of aluminum oxide (A1 ₂ 0 ₃ ) having a thickness of 200 nm as a dielectric layer on the substrate, the dielectric layer is provided with a gate, and the gate is a method of RF magnetron sputtering a plated and photolithographic metal chromium (Cr) film having a thickness of 100 nm;

Self-assembling monolayer modification with dodecylphosphoric acid on the surface of the dielectric layer to form a modified layer; the modified layer is covered with a semiconductor layer having a thickness of 30 nm to 60 nm, and the preparation process of the semiconductor layer is respectively The following were used: The soluble phthalocyanine compound obtained in Example 27, Example 15, and Example 20 was used as a semiconductor material, and each was prepared into 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 was formed and then annealed. The temperature and time of the annealing are shown in Table 2. Table 2 shows the main process parameters and properties of the organic thin film transistor provided in Examples 39 to 41 of the present invention. After annealing, gold having a thickness of 50 nm is deposited as a source electrode and a drain electrode, and a conductive channel having a width to length ratio of 30 (W/L = 3000 μm / 100 μm = 30) is formed to obtain a semiconductor layer, and finally an organic layer is formed. Thin film transistor.

After obtaining the organic thin film transistor, the present invention separately measured the transfer curve, and the results of the carrier mobility and the switching current ratio are shown in Table 2. Table 2 Process parameters and performance of the organic thin film transistor provided by Embodiments 39 to 41 of the present invention; organic film charge transfer annealing temperature/time mobility switching electric semiconductor layer

Transistor type (.C/min) (cm ² /Vs ) ratio

2,3,16,17-tetrahexyloxy

Example 39 Hole 150/30 0.08 10 ⁵ Phthalocyanine

2,3,16,17 - tetraoctyl

Example 40 Hole 100/20 0.9 10 ⁶ Crystalline Titanium Oxide

2,3,16,17 -tetraoctyloxy

Example 41 Electron 80/40 0.2 10 ⁶ tin dichloride

It can be seen from Table 2 that 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.

Example 42 Preparation of Plastic Substrate Organic Thin Film Transistor

Using a plastic sheet as a substrate;

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. a method of plating and photolithography of a metal chromium (Cr) film having a thickness of 100 nm;

Preparing a modified layer with a 3 wt% PMMA solution of methyl ethyl ketone on the surface of the dielectric layer, the thickness of which is 50 nm;

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. After annealing, gold having a thickness of 50 nm is deposited as a source electrode and a drain electrode, and a conductive channel having a width to length ratio of 30 (W/L = 3000 μm / 100 μm = 30) is formed to obtain a semiconductor layer, and finally an organic layer is formed. Thin film transistor.

After obtaining an organic thin film transistor, the present invention measures the transfer curve, and the measurement result is shown in Fig. 4. 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.

It can be seen from the above examples that 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. In general, 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.

The above description of the embodiments is merely to assist in understanding the method of the present invention and its core idea. It is to be understood that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

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Claims

Claims A soluble phthalocyanine compound having a structure of formula (I) or a structure of formula (II):

Among them, 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.

2. The soluble phthalocyanine compound according to claim 1, wherein R is a linear alkyl group, a branched alkyl group, a linear alkoxy group, a branched alkoxy group, a linear alkylthio group or Branched alkylthio.

3. The soluble phthalocyanine compound according to claim 2, wherein R is a linear alkyl group of C ₄ to Ci8, a linear alkoxy group of C ₄ to Ci8, or a linear alkoxy group of C ₄ to C ₁₈ . Alkyl.

4. The soluble phthalocyanine compound according to claim 3, wherein R is octyl, hexyl, dodecyl, hexyloxy, octyloxy or octylthio.

5. The soluble phthalocyanine compound according to claim 1, wherein the divalent metal is Cu, Zn, Ni, Co or Pb;

The ligand-containing trivalent or higher metals are InCl, SbCl, MnCl, GaCl, A1C1, TiCl,

TiO, VO, SnO or SnCl ₂ .

6. A method for preparing a soluble phthalocyanine compound, including the following steps:

5,6-dialkyl-1,3-dihydro-1,3-diiminoisoindoline, 5,6-dialkoxy-1,3-dihydro-1,3-di Iminoisoindoline or 5,6-dialkylthio-1,3-dihydro-1,3-diiminoisoindoline and triethylamine, 1,3,3-trichloroisoindoline The dihydroazaindene is mixed in an organic solvent for reaction, and the filtrate is obtained after filtration;

The filtrate is mixed with hydroquinone and sodium methoxide, and after the reaction, a soluble phthalocyanine compound with a structure of formula (I) is obtained:

Formula (I); wherein, R is an alkyl group, an alkoxy group or an alkylthio group.

7. The preparation method according to claim 6, characterized in that, after obtaining the soluble phthalocyanine compound having the structure of formula (I), it further includes:

The soluble phthalocyanine compound having the structure of formula (I) is reacted with a divalent or higher metal salt in n-pentyl alcohol or N-methylpyrrolidone to obtain a soluble phthalocyanine compound having the structure of formula (II):

Among them, M is a divalent metal or a trivalent or higher metal containing ligands.

8. An organic thin film transistor, including a substrate, a dielectric layer provided with a gate electrode, and a semiconductor layer provided with a drain electrode and a source electrode at both ends, the semiconductor layer comprising any one of claims 1 to 5 A soluble phthalocyanine compound or a soluble phthalocyanine compound obtained by the preparation method according to any one of claims 6 to 7;

Wherein, the semiconductor layer is compounded on the dielectric layer, and the dielectric layer is compounded on the substrate; or the dielectric layer is compounded on the semiconductor layer, and the semiconductor layer is compounded on the substrate. superior.

9. The organic thin film transistor according to claim 8, wherein the preparation method of the semiconductor layer is specifically: The soluble phthalocyanine compound is prepared into a solution and a thin film is prepared. After annealing and electrode deposition, a semiconductor layer is obtained.

10. The organic thin film transistor according to claim 9, wherein the organic solvent of the solution is chloromethane, trichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene, Toluene, xylene, tetralin or triphenyl.

-μ