WO2016201797A1 - 一种金属酞菁纳米晶、其制备方法和晶体管应用 - Google Patents
一种金属酞菁纳米晶、其制备方法和晶体管应用 Download PDFInfo
- Publication number
- WO2016201797A1 WO2016201797A1 PCT/CN2015/089366 CN2015089366W WO2016201797A1 WO 2016201797 A1 WO2016201797 A1 WO 2016201797A1 CN 2015089366 W CN2015089366 W CN 2015089366W WO 2016201797 A1 WO2016201797 A1 WO 2016201797A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal phthalocyanine
- phthalocyanine compound
- metal
- chloride
- phthalocyanine
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title abstract description 26
- -1 phthalocyanine compound Chemical class 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000007639 printing Methods 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910001510 metal chloride Inorganic materials 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- MDXGRFMFORMPGT-UHFFFAOYSA-N 4-methylbenzene-1,2-dicarbonitrile Chemical compound CC1=CC=C(C#N)C(C#N)=C1 MDXGRFMFORMPGT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- NNTKZPQZOSKWDE-UHFFFAOYSA-N 4,5-dimethylbenzene-1,2-dicarbonitrile Chemical compound CC1=CC(C#N)=C(C#N)C=C1C NNTKZPQZOSKWDE-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005456 alcohol based solvent Substances 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- HUVXQFBFIFIDDU-UHFFFAOYSA-N aluminum phthalocyanine Chemical class [Al+3].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 HUVXQFBFIFIDDU-UHFFFAOYSA-N 0.000 description 21
- 239000000976 ink Substances 0.000 description 18
- 239000004065 semiconductor Substances 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001548 drop coating Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
Definitions
- the invention belongs to the field of metal coordination compounds, in particular to a metal phthalocyanine nanocrystal, a preparation method thereof and a transistor application.
- Phthalocyanine compounds are a class of compounds with ⁇ -bonded conjugated systems, which can improve conductivity under illumination and have excellent optoelectronic semiconductor properties.
- Today, the application of phthalocyanine compounds involves sensitive devices and electroluminescence in chemical sensors. Devices, photovoltaic materials, high mobility materials, and more.
- the hole in the center of the phthalocyanine can coordinate with more than 70 metals, and the d orbital of the central metal atom can interact with the ⁇ orbital, which facilitates the transfer of charge within or between the phthalocyanine molecules, so the phthalocyanine compound is Excellent organic semiconductor materials, and compared with traditional inorganic semiconductor materials, have the advantages of low cost, large area coverage, integration with flexible substrates, etc., and have good application prospects in organic transistors, integrated circuits and sensors. It has become a hot spot for research and development in the international academic and industrial circles. However, the conventional phthalocyanine is hardly soluble in any organic solvent, and it is impossible to prepare a photovoltaic device by a liquid phase printing process.
- phthalocyanine compounds cannot achieve high-performance transistors of phthalocyanine, or can not use non-toxic and environmentally-friendly green solvents, and find a phthalocyanine compound that can be dissolved in a non-toxic and environmentally friendly solvent and can realize high-performance transistor preparation. Very important. Due to the poor water-oxygen stability of organic semiconductor materials, the fabricated devices have poor stability in the unpackaged condition. Therefore, the development of high-stability organic semiconductor materials is also the focus of current transistor research.
- the object of the present invention is a metal phthalocyanine nanocrystal, a preparation method thereof and a transistor application.
- M is Al, Ga or In.
- the compound is the metal phthalocyanine compound nanocrystal.
- a method for preparing a metal phthalocyanine compound comprising the steps of:
- the metal chloride is aluminum chloride, gallium chloride or indium chloride.
- the molar ratio of the metal chloride, the catalyst and the 4-methylphthalonitrile is 1:(1-2):(3-4), the metal chloride, the catalyst and the 4,5-dimethyl
- the molar ratio of phthalic acid to phthalonitrile is 1: (1-2): (3-4).
- the heating reaction is carried out at 120-160 ° C for 15-40 h.
- the organic solvent is 1-chlorinated naphthalene or quinoline
- the catalyst is ammonium chloride
- An electronic ink obtained by dispersing or dissolving a metal phthalocyanine compound prepared by the above metal phthalocyanine compound or the above-described production method in an alcohol solvent.
- a printing organic transistor is prepared by coating the above electronic ink.
- the present invention provides a metal phthalocyanine compound, which uses aluminum, gallium or indium as a substitute metal to obtain ⁇ .
- the metal phthalocyanine compound can be dissolved in a non-toxic and environmentally friendly alcohol solvent, and ultrasonically dispersed in an alcohol solvent to obtain Organic electronic ink can realize liquid phase printing preparation of high performance organic transistor, carrier mobility is more than 1cm 2 /V ⁇ s, and the phthalocyanine compound has good water oxygen stability, and the obtained printed organic transistor can be realized in water. High stability work in an oxygen environment.
- Figure 1 is an electron micrograph of ⁇ -tetramethyl substituted aluminum phthalocyanine nanocrystal.
- Figure 2 is an ultraviolet-visible absorption spectrum of ⁇ -tetramethyl substituted aluminum phthalocyanine.
- Figure 3 is a nuclear magnetic resonance spectrum of ⁇ -tetramethyl substituted aluminum phthalocyanine.
- Figure 5 is an ultraviolet-visible absorption spectrum of ⁇ -octamethyl substituted aluminum phthalocyanine.
- Figure 6 is a nuclear magnetic resonance spectrum of ⁇ -octamethyl substituted aluminum phthalocyanine.
- Fig. 7 is an organic electronic ink prepared by metal phthalocyanine nanocrystals.
- Fig. 8 is an organic semiconductor film printed by metal phthalocyanine nanocrystalline organic electronic ink.
- Figure 9 is a schematic view showing the structure of a bottom contact transistor.
- Figure 10 is a graph of the ⁇ -octamethyl substituted aluminum phthalocyanine transistor I-V prepared by spin coating.
- Figure 11 is a graph showing the device stability test of a spin-coated preparation of an ⁇ -octamethyl substituted aluminum phthalocyanine transistor.
- Figure 12 is a graph showing the preparation of an ⁇ -octamethyl substituted aluminum phthalocyanine transistor I-V by drop coating.
- M is Al, Ga or In.
- the compound is the metal phthalocyanine compound nanocrystal.
- the invention also provides a preparation method of a metal phthalocyanine compound, comprising the steps of: 1) taking a metal chloride, a catalyst and 4-methyl phthalonitrile or 4,5-dimethylphthalonitrile, adding The organic solvent is heated under the protection of a protective gas and cooled; 2) the obtained crude product is separated, washed and separated to obtain a metal phthalocyanine compound; wherein the metal chloride is aluminum chloride, gallium chloride or indium chloride.
- the molar ratio of metal chloride, catalyst and 4-methylphthalonitrile is 1:(1-2):(3-4), metal chloride, catalyst and 4,5-dimethylphthalonitrile The molar ratio is 1: (1-2): (3-4).
- the heating reaction is carried out at 120-160 ° C for 15-40 h.
- the organic solvent is 1-chlorinated naphthalene or quinoline, and the catalyst is ammonium chloride.
- the washing and separating is ultrasonic cleaning of the obtained crude product using water and an organic solvent, and the metal phthalocyanine compound nanocrystals are collected by centrifugation.
- the invention also provides an electronic ink prepared by the above metal phthalocyanine compound or the above preparation method
- the metal phthalocyanine compound is obtained by dispersing or dissolving in an alcohol solvent.
- a printed organic transistor can be obtained by coating the above electronic ink.
- the preferred embodiment of the preparation of ⁇ -tetramethyl-substituted metal phthalocyanine nanocrystals in the present invention is as follows: 7.0 mmol of 4-methyl phthalonitrile, 2.3 mmol of anhydrous aluminum trichloride and 2.3 mmol of catalyst ammonium chloride are weighed. Transfer to a single-mouth flask, add about 1 mL of the solvent 1-chlorinated naphthalene (or quinoline), exchange nitrogen three times, heat to 150 ° C under the protection of inert nitrogen gas and keep the reaction for about 20 h, close the reaction, and naturally cool to room temperature.
- the crude product obtained by centrifugation was ultrasonically washed with water, acetone, ethanol and the like, and collected by centrifugation until the supernatant liquid was colorless after centrifugation, and ⁇ -tetramethyl-substituted aluminum phthalocyanine nanocrystals were collected.
- the equation of the reaction process is as follows:
- a preferred embodiment of the preparation of the ⁇ -octamethyl-substituted metal phthalocyanine nanocrystal in the present invention is as follows: 6.4 mmol of 4,5-dimethylphthalonitrile, 2.1 mmol of anhydrous aluminum trichloride and 2.1 mmol of a catalyst are weighed. Ammonium chloride was transferred into a one-necked flask, and about 5 mL of a solvent of 1-chlorinated naphthalene (or quinoline) was added thereto, and nitrogen gas was distilled off three times, heated to 160 ° C under the protection of an inert nitrogen gas, and the reaction was maintained for about 20 hours. The reaction was turned off and allowed to cool to room temperature.
- the crude product obtained by centrifugation was ultrasonically washed with water, acetone, ethanol and the like, and collected by centrifugation until the supernatant liquid was colorless after centrifugation, and ⁇ -octamethyl substituted aluminum phthalocyanine nanocrystals were collected.
- the equation of the reaction process is as follows:
- the yield of the product obtained by the above reaction is 92%, and the obtained ⁇ -octamethyl substituted aluminum phthalocyanine (AlMe 2 Pc) nanocrystal has a rod shape and a length of about 20 nm, and the electron micrograph is as shown in Fig. 4; The spectrum was characterized to obtain Figure 5; the product was characterized by NMR spectroscopy to obtain Figure 6.
- Nuclear magnetic H spectrum data 1H NMR (400 MHz, CD3OD): ⁇ (ppm) 9.48 (s, 8H), 2.99 (s, 24H).
- a preferred embodiment of the preparation of the organic electronic ink in the present invention is as follows: the above metal phthalocyanine compound or the ⁇ -tetramethyl-substituted aluminum phthalocyanine nanocrystal and the ⁇ -octamethyl-substituted aluminum phthalocyanine prepared by the above preparation method are used.
- Nanocrystalline, dry, poured into ethanol or other alcohol solvent according to the ratio of 20mg/mL, fully ultrasonically dispersed, can get organic electronic ink, the specific form of electronic ink is shown in Figure 7, in the left bottle is ⁇ -eight An electronic ink prepared by methyl-substituted aluminum phthalocyanine (AlMe 2 Pc) nanocrystals, and an electronic ink prepared by ⁇ -tetramethyl-substituted aluminum phthalocyanine (AlMePc) nanocrystals in the right bottle.
- AlMe 2 Pc methyl-substituted aluminum phthalocyanine
- AlMePc ⁇ -tetramethyl-substituted aluminum phthalocyanine
- a preferred embodiment of the preparation of the organic semiconductor thin film of the present invention is as follows: the organic electronic ink prepared by the above method is used, and the organic semiconductor film is printed by spin coating, drop coating, blade coating, ink jet printing, etc. to obtain an organic semiconductor film.
- the left side of the figure is an ⁇ -tetramethyl substituted aluminum phthalocyanine (AlMePc) nanocrystalline electronic ink printing film, and the right side is ⁇ -octamethyl substituted aluminum phthalocyanine (AlMe 2 Pc) nanocrystalline electron.
- AlMePc ⁇ -tetramethyl substituted aluminum phthalocyanine
- AlMe 2 Pc ⁇ -octamethyl substituted aluminum phthalocyanine
- a preferred embodiment of the preparation of the organic transistor in the present invention is as follows: an organic transistor substrate uses silicon as a substrate as a gate electrode, silicon oxide as a dielectric layer, and gold as a gate and a drain, and the device is fabricated by a bottom contact method. A schematic diagram of the structure of the contact transistor is shown in FIG.
- the organic light-emitting ink prepared by using the above ⁇ -octamethyl-substituted aluminum phthalocyanine nanocrystal was subjected to a rotary coating apparatus at an acceleration of 200 rpm at room temperature under exposure to air.
- the rotation speed is 2000 rpm, spin coating for 60 seconds, and the obtained sample is heated by a heating plate at 60 degrees Celsius for 5 minutes to obtain a transistor device, and the transistor device is tested by a probe station semiconductor analyzer, and the transistor IV curve is obtained as shown in FIG.
- the hole mobility can reach 5 ⁇ 10 -2 cm 2 /V ⁇ s.
- the device stability test is carried out, and the result is shown in Fig. 11.
- the device In the environment where the humidity is greater than 70% in the air environment, the device is tested at a gate voltage of -40 volts and a gate voltage of -40 volts, and the channel current rapidly reaches a steady state;
- the device performance was basically unchanged after being placed in a humidity of more than 70% air environment for two months without packaging, indicating that the ink-printing transistor device has high stability against water and oxygen.
- the transistor was prepared by a drop coating method, and the same substrate was used as a substrate, and the electronic ink prepared by using the above ⁇ -octamethyl substituted aluminum phthalocyanine nanocrystal was directly dropped onto the substrate by a dropper, and air was taken at room temperature. In the middle, waiting for the ethanol solvent to naturally evaporate, the obtained sample is heated by a heating plate at 60 degrees Celsius for 5 minutes to obtain a transistor device, and the transistor device is tested by a probe station semiconductor analyzer, and the transistor IV curve is obtained as shown in FIG. 12, and the device is p-type.
- the hole mobility is 1.2 cm 2 /V ⁇ s or more.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Thin Film Transistor (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
针对目前酞菁化合物用于有机晶体管的制备,存在制备工艺需要使用有毒溶剂或制备所得晶体管性能不佳的问题,本发明公开了金属酞菁化合物,采用铝、镓或铟为取代金属,得到α-四甲基取代金属酞菁纳米晶或α-八甲基取代金属酞菁纳米晶,该金属酞菁化合物可以溶解于无毒环保的醇类溶剂中,在醇类溶剂中超声分散即可得到有机电子墨水,可以实现高性能有机晶体管的液相打印制备,载流子迁移速率大于1.2cm2/V·s,且该酞菁化合物水氧稳定性好,制得的打印有机晶体管可以实现在水氧环境下的高稳定性工作。
Description
本发明属于金属配位化合物领域,尤其涉及一种金属酞菁纳米晶、其制备方法和晶体管应用。
酞菁化合物是一类具有π键共轭体系的化合物,在光照下可以提高电导率,具有优异的光电半导体性能,现今酞菁化合物的应用领域已涉及到化学传感器中的灵敏器件、电致发光器件、光伏材料、高迁移率材料等等。酞菁中心的空穴可以与七十多钟金属相配位,中心金属原子的d轨道能与π轨道发生相互作用,有利于电荷在酞菁分子内部或分子之间的转移,因此酞菁化合物是优良的有机半导体材料,且相比传统的无机半导体材料,具有成本低、可实现大面积覆盖、可与柔性基底集成等优势,在有机晶体管、集成电路和传感器等方面具有很好的应用前景,已成为国际学术界和产业界研究和开发的热点领域。但是传统酞菁几乎不溶于任何有机溶剂,无法实现液相打印工艺制备光电器件。因此对酞菁进行功能化修饰,制备酞菁打印墨水受到广大科研工作者关注。中科院长春应化所合成了一系列可溶性酞菁,酞菁材料的有机溶解性提高了,并成功打印制备了晶体管,器件载流子迁移率达到1cm2/V·s,是迄今可溶性酞菁打印有机晶体管的最高报道,但是该酞菁也只能溶解于三氯甲烷、三氯乙烷、氯苯、二氯苯、三氯苯、氯代甲苯等有毒溶剂,制备工艺采用有毒溶剂,会对环境造成污染,无法达到环保要求。关于水溶性酞菁的合成也有报道,捷克科学家利用磺化钠修饰了铝酞菁,合成了具有水溶性的酞菁,同时也制备了晶体管,但是器件性能差,晶体管载流子迁移速率达到0.2cm2/V·s,产品质量无法满足需求。目前关于酞菁化合物的研究要么无法实现酞菁的高性能晶体管,要么无法采用无毒环保的绿色溶剂,寻找一种能溶于无毒环保的溶剂,且能够实现高性能晶体管制备的酞菁化合物具有非常重要的意义。有机半导体材料由于水氧稳定性差,其制备的器件在未封装情况下稳定性差,因此开发高稳定性的有机半导体材料也是目前晶体管研究的重点。
发明内容
本发明的目的在于一种金属酞菁纳米晶、其制备方法和晶体管应用。
本发明所采取的技术方案是:
一种金属酞菁化合物,该化合物具有式(I)或式(II)结构:
其中,M为Al、Ga或In。
作为发明的进一步改进,所述的化合物是所述金属酞菁化合物纳米晶。
一种金属酞菁化合物的制备方法,包括以下步骤:
1)取金属氯化物、催化剂和4-甲基邻苯二腈或4,5-二甲基邻苯二腈,加入有机溶剂,保护气保护下加热反应,冷却;
2)分离所得粗产物,清洗并分离,得到金属酞菁化合物;
其中,金属氯化物为氯化铝、氯化镓或氯化铟。
作为发明的进一步改进,金属氯化物、催化剂和4-甲基邻苯二腈的摩尔比为1∶(1-2)∶(3-4),金属氯化物、催化剂和4,5-二甲基邻苯二腈的摩尔比为1∶(1-2)∶(3-4)。
作为发明的进一步改进,所述加热反应是在120-160℃下反应15-40h。
作为发明的进一步改进,所述有机溶剂为1-氯化萘或喹啉,所述催化剂为氯化铵。
一种电子墨水,由上述的金属酞菁化合物或者上述的制备方法制备得到的金属酞菁化合物分散或溶解于醇类溶剂得到。
一种打印有机晶体管,由上述的电子墨水涂布制备得到。
本发明的有益效果是:
针对目前酞菁化合物用于有机晶体管的制备,存在制备工艺需要使用有毒溶剂或制备所得晶体管性能不佳的问题,本发明提供了金属酞菁化合物,采用铝、镓或铟为取代金属,得到α-四甲基取代金属酞菁纳米晶或α-八甲基取代金属酞菁纳米晶,该金属酞菁化合物可以溶解于无毒环保的醇类溶剂中,在醇类溶剂中超声分散即可得到有机电子墨水,可以实现高性能有机晶体管的液相打印制备,载流子迁移速率大于1cm2/V·s,且该酞菁化合物水氧稳定性好,制得的打印有机晶体管可以实现在水氧环境下的高稳定性工作。
图1为α-四甲基取代铝酞菁纳米晶电镜图。
图2为α-四甲基取代铝酞菁紫外可见吸收光谱。
图3为α-四甲基取代铝酞菁核磁共振图谱。
图4为α-八甲基取代铝酞菁纳米晶电镜图。
图5为α-八甲基取代铝酞菁紫外可见吸收光谱。
图6为α-八甲基取代铝酞菁核磁共振图谱。
图7为金属酞菁纳米晶制备的有机电子墨水。
图8为金属酞菁纳米晶有机电子墨水打印的有机半导体薄膜。
图9为底接触晶体管结构示意图。
图10为旋转涂布制备α-八甲基取代铝酞菁晶体管I-V曲线。
图11为旋转涂布制备α-八甲基取代铝酞菁晶体管的器件稳定测试曲线图。
图12为滴涂制备α-八甲基取代铝酞菁晶体管I-V曲线。
一种金属酞菁化合物,该化合物具有式(I)或式(II)结构:
其中,M为Al、Ga或In。
所述的化合物是所述金属酞菁化合物纳米晶。
本发明还提供了一种金属酞菁化合物的制备方法,包括以下步骤:1)取金属氯化物、催化剂和4-甲基邻苯二腈或4,5-二甲基邻苯二腈,加入有机溶剂,保护气保护下加热反应,冷却;2)分离所得粗产物,清洗并分离,得到金属酞菁化合物;其中,金属氯化物为氯化铝、氯化镓或氯化铟。金属氯化物、催化剂和4-甲基邻苯二腈的摩尔比为1∶(1-2)∶(3-4),金属氯化物、催化剂和4,5-二甲基邻苯二腈的摩尔比为1∶(1-2)∶(3-4)。所述加热反应是在120-160℃下反应15-40h。所述有机溶剂为1-氯化萘或喹啉,所述催化剂为氯化铵。所述清洗并分离是使用水和有机溶剂超声清洗所得粗产物,离心分离收集得到金属酞菁化合物纳米晶。
本发明还提供了一种电子墨水,由上述的金属酞菁化合物或者上述的制备方法制备得到
的金属酞菁化合物分散或溶解于醇类溶剂得到。由上述电子墨水涂布制备可以得到一种打印有机晶体管。
本发明中的α-四甲基取代金属酞菁纳米晶的制备优选实施方式如下:称取7.0mmol 4-甲基邻苯二腈、2.3mmol无水三氯化铝和2.3mmol催化剂氯化铵,转移入单口烧瓶,加入溶剂1-氯化萘(或喹啉)约5mL,抽换氮气三次,惰性氮气体保护下加热到150℃并保持反应约20h,关闭反应,自然冷却到室温。通过离心分离所得到的粗产物分别使用水、丙酮、乙醇等溶剂超声清洗并离心收集,直到离心后上层清液显无色,收集得到α-四甲基取代铝酞菁纳米晶。反应过程方程式如下:
通过上述反应制取产物的得率为89%,得到的α-四甲基取代铝酞菁(AlMePc)纳米晶形态为棒状,长度为200nm左右,电镜图如图1;采用紫外可见吸收光谱进行表征,得到图2;采用核磁共振波谱法对产物进行表征,得到图3,核磁H谱数据:1H NMR(400MHz,CD3OD):δ(ppm)9.59(dd,J=7.4Hz,4H),9.54(s,4H),8.30(d,J=7.6Hz,4H),3.09(s,12H)。
本发明中的α-八甲基取代金属酞菁纳米晶的制备的优选实施方式如下:称取6.4mmol4,5-二甲基邻苯二腈、2.1mmol无水三氯化铝和2.1mmol催化剂氯化铵,转移入单口烧瓶,加入溶剂1-氯化萘(或喹啉)约5mL,抽换氮气三次,惰性氮气体保护下加热到160℃并保持反应约20h。关闭反应,自然冷却到室温。通过离心分离所得到的粗产物分别使用水、丙酮、乙醇等溶剂超声清洗并离心收集,直到离心后上层清液显无色,收集得到α-八甲基取代铝酞菁纳米晶。反应过程方程式如下:
通过上述反应制取产物的得率为92%,得到的α-八甲基取代铝酞菁(AlMe2Pc)纳米
晶形态为棒状,长度为20nm左右,电镜图如图4;采用紫外可见吸收光谱进行表征,得到图5;采用核磁共振波谱法对产物进行表征,得到图6,核磁H谱数据:1H NMR(400MHz,CD3OD):δ(ppm)9.48(s,8H),2.99(s,24H)。
本发明中的有机电子墨水的制备的优选实施方式如下:取上述金属酞菁化合物或采用上述制备方法制备得到的α-四甲基取代铝酞菁纳米晶和α-八甲基取代铝酞菁纳米晶,干燥,按照20mg/mL的比例倒入乙醇或其他醇类溶剂中,充分超声分散,即可得到有机电子墨水,电子墨水具体形态如图7,图中左瓶中为由α-八甲基取代铝酞菁(AlMe2Pc)纳米晶制备得到的电子墨水,右瓶中为由α-四甲基取代铝酞菁(AlMePc)纳米晶制备得到的电子墨水。
本发明中的有机半导体薄膜的制备的优选实施方式如下:取上述方法制备得到的有机电子墨水,采用旋转涂布、滴涂、刮涂、喷墨打印等方式打印有机半导体薄膜,得到有机半导体薄膜如图8所示,图中左侧为α-四甲基取代铝酞菁(AlMePc)纳米晶电子墨水打印薄膜,右侧为α-八甲基取代铝酞菁(AlMe2Pc)纳米晶电子墨水打印薄膜。
本发明中的有机晶体管的制备的优选实施方式如下:有机晶体管基材以硅为衬底作为门电极,氧化硅为介电层,金为栅极和漏极,采用底接触方式制备器件,底接触晶体管结构示意图如图9所示。对于旋转涂布方法打印制备晶体管,采用上述α-八甲基取代铝酞菁纳米晶制备的有机电子墨水,在暴露于空气的室温条件下,利用旋转涂布仪,以加速度为200转/秒,转速为2000转,旋转涂布60秒,将所得样品用加热板60摄氏度加热5分钟即可得到晶体管器件,采用探针台半导体分析仪测试晶体管器件,测试得到晶体管I-V曲线如图10,器件为p型,空穴迁移率可达到5×10-2cm2/V·s。进行器件稳定测试,得到结果如图11,在空气环境为湿度大于70%环境中,器件在门电压-40伏,栅极电压-40伏下测试,沟道电流快速达到稳定状态;而器件在不封装情况下放置于湿度大于70%空气环境中两个月,器件性能基本保持不变,显示了该墨水打印晶体管器件具有抗水氧影响的高稳定性。
采用滴涂方法制备晶体管,以同样的基材为衬底,采用上述α-八甲基取代铝酞菁纳米晶制备的电子墨水,利用滴管直接将溶液滴到基材上,在室温下空气中,等待乙醇溶剂自然挥发,将所得样品用加热板60摄氏度加热5分钟即可得到晶体管器件,采用探针台半导体分析仪测试晶体管器件,测试得到晶体管I-V曲线如图12,器件为p型,空穴迁移率达到1.2cm2/V·s以上。
Claims (8)
- 根据权利要求1所述的金属酞菁化合物,其特征在于,所述的化合物是所述金属酞菁化合物纳米晶。
- 一种金属酞菁化合物的制备方法,包括以下步骤:1)取金属氯化物、催化剂和4-甲基邻苯二腈或4,5-二甲基邻苯二腈,加入有机溶剂,保护气保护下加热反应,冷却;2)分离所得粗产物,清洗并分离,得到金属酞菁化合物;其中,金属氯化物为氯化铝、氯化镓或氯化铟。
- 根据权利要求3所述的制备方法,其特征在于,金属氯化物、催化剂和4-甲基邻苯二腈的摩尔比为1∶(1-2)∶(3-4),金属氯化物、催化剂和4,5-二甲基邻苯二腈的摩尔比为1∶(1-2)∶(3-4)。
- 根据权利要求3所述的制备方法,其特征在于,所述加热反应是在120-160℃下反应15-40h。
- 根据权利要求3所述的制备方法,其特征在于,所述有机溶剂为1-氯化萘或喹啉,所述催化剂为氯化铵。
- 一种电子墨水,其特征在于,由权利要求1-2任一项所述的金属酞菁化合物或者权利要求3-6任一项所述的制备方法制备得到的金属酞菁化合物分散或溶解于醇类溶剂得到。
- 一种打印有机晶体管,其特征在于,由权利要求7所述的电子墨水涂布制备得到。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510334411.9A CN105017263B (zh) | 2015-06-16 | 2015-06-16 | 一种金属酞菁纳米晶、其制备方法和晶体管应用 |
CN201510334411.9 | 2015-06-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016201797A1 true WO2016201797A1 (zh) | 2016-12-22 |
Family
ID=54407610
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2015/089366 WO2016201797A1 (zh) | 2015-06-16 | 2015-09-10 | 一种金属酞菁纳米晶、其制备方法和晶体管应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN105017263B (zh) |
WO (1) | WO2016201797A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2564425A (en) * | 2017-07-07 | 2019-01-16 | Wuhan Xinqu Chuangrou Optoelectronics Tech Co Ltd | Formulation and layer |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105330667B (zh) * | 2015-12-07 | 2017-12-19 | 南方科技大学 | 金属酞菁凝胶及其应用 |
CN106098946B (zh) * | 2016-08-24 | 2019-09-10 | 南方科技大学 | 太阳能电池及其制备方法 |
CN110078739B (zh) * | 2019-05-13 | 2020-10-30 | 南方科技大学 | 一种空穴传输材料及其制备方法、钙钛矿太阳能电池 |
CN111048692A (zh) * | 2019-12-05 | 2020-04-21 | 南方科技大学 | 聚合物发光二极管及其制备方法 |
CN111763213B (zh) * | 2020-06-01 | 2021-07-06 | 南方科技大学 | 金属酞菁-MXene复合材料、超级电容器及其制备方法 |
CN112159518A (zh) * | 2020-09-24 | 2021-01-01 | 中国科学院长春光学精密机械与物理研究所 | 一种具有共轭微孔结构的聚酞菁类光限幅材料及其制备方法 |
CN113135926A (zh) * | 2021-04-23 | 2021-07-20 | 昆明学院 | 新晶体结构酞菁铟纳米线及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002052307A1 (fr) * | 2000-12-22 | 2002-07-04 | Mitsubishi Chemical Corporation | Composition pour filtres colores et filtres colores |
CN101255163A (zh) * | 2008-03-14 | 2008-09-03 | 中国科学院长春应用化学研究所 | 可溶性四烷基酞菁化合物及其制备方法 |
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 |
CN102863448A (zh) * | 2012-09-19 | 2013-01-09 | 中国科学院长春应用化学研究所 | 一种可溶性酞菁化合物、其制备方法及一种有机薄膜晶体管 |
WO2014043860A1 (zh) * | 2012-09-19 | 2014-03-27 | 中国科学院长春应用化学研究所 | 一种可溶性酞菁化合物、其制备方法及一种有机薄膜晶体管 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA98525B (en) * | 1997-01-24 | 1998-07-29 | Procter & Gamble | Photobleaching compositions effective on dingy fabric |
CN100491604C (zh) * | 2005-10-17 | 2009-05-27 | 中国科学院化学研究所 | 稠环芳香族有机半导体单晶微/纳米材料及其制备方法与应用 |
-
2015
- 2015-06-16 CN CN201510334411.9A patent/CN105017263B/zh active Active
- 2015-09-10 WO PCT/CN2015/089366 patent/WO2016201797A1/zh active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002052307A1 (fr) * | 2000-12-22 | 2002-07-04 | Mitsubishi Chemical Corporation | Composition pour filtres colores et filtres colores |
CN101255163A (zh) * | 2008-03-14 | 2008-09-03 | 中国科学院长春应用化学研究所 | 可溶性四烷基酞菁化合物及其制备方法 |
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 |
CN102863448A (zh) * | 2012-09-19 | 2013-01-09 | 中国科学院长春应用化学研究所 | 一种可溶性酞菁化合物、其制备方法及一种有机薄膜晶体管 |
WO2014043860A1 (zh) * | 2012-09-19 | 2014-03-27 | 中国科学院长春应用化学研究所 | 一种可溶性酞菁化合物、其制备方法及一种有机薄膜晶体管 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2564425A (en) * | 2017-07-07 | 2019-01-16 | Wuhan Xinqu Chuangrou Optoelectronics Tech Co Ltd | Formulation and layer |
Also Published As
Publication number | Publication date |
---|---|
CN105017263B (zh) | 2017-10-10 |
CN105017263A (zh) | 2015-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016201797A1 (zh) | 一种金属酞菁纳米晶、其制备方法和晶体管应用 | |
JP5380296B2 (ja) | ジイミド系半導体材料ならびにジイミド系半導体材料を調製および使用する方法 | |
CN101952988B (zh) | 苝半导体及其制备方法和用途 | |
JP5591229B2 (ja) | 半導体材料並びにその製造方法およびその使用 | |
EP2683718B1 (en) | Thiocyanato substituted naphthalene diimide compounds and their use as n-type semiconductors | |
TWI416721B (zh) | 作為n型半導體材料之經n,n’-二環烷基取代之以萘為主的四羧酸二醯亞胺 | |
CN102057015B (zh) | 氯化萘四甲酸衍生物、其制备及其在有机电子部件中的用途 | |
JP2010510228A5 (zh) | ||
Centore et al. | Perylene diimides functionalized with N-thiadiazole substituents: Synthesis and electronic properties in OFET devices | |
CN101657458A (zh) | 甲硅烷基乙炔化杂并苯和由其制造的电子器件 | |
WO2007128774A1 (en) | Method for producing organic field-effect transistors | |
WO2009037283A1 (de) | Verfahren zur herstellung von mit rylentetracarbonsäurediimiden beschichteten substraten | |
CN101485007A (zh) | 生产有机场效应晶体管的方法 | |
He et al. | Molecular phase engineering of organic semiconductors based on a [1] benzothieno [3, 2-b][1] benzothiophene core | |
EP2686322B1 (en) | Tetraazaperopyrene compounds and their use as n-type semiconductors | |
Kim et al. | Synthesis and characterization of quinoxaline derivative as organic semiconductors for organic thin-film transistors | |
Kong et al. | Controlled morphology of self-assembled microstructures via solvent-vapor annealing temperature and ambipolar OFET performance based on a tris (phthalocyaninato) europium derivative | |
US9518224B2 (en) | Organic semiconductor particulate material, organic semiconductor thin-film, dispersion liquid for forming organic semiconductor film, method for producing organic semiconductor thin-film, and organic thin-film transistor | |
CN104638202B (zh) | 一种有机薄膜晶体管及其制备方法 | |
CN107619409B (zh) | 联薁二酰亚胺衍生物、其制备方法和应用 | |
TWI542591B (zh) | 四氮雜靴二蒽化合物及其作為n-型半導體之用途 | |
CN105949041A (zh) | 一种各向同性的氧原子取代基团的蒽基化合物、制备方法和应用 | |
CN104638105B (zh) | 一种有机薄膜晶体管及其制备方法 | |
CN104638106B (zh) | 一种有机薄膜晶体管及其制备方法 | |
Khan et al. | Synthesis and optoelectronic properties of an anthracene derivative |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15895370 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 03/05/2018) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15895370 Country of ref document: EP Kind code of ref document: A1 |