WO2018209927A1 - Polyphthalocyanine compound, compound of double-layer sandwiched structure and preparation method therefor, organic field-effect transistor and preparation method therefor, and display device - Google Patents

Polyphthalocyanine compound, compound of double-layer sandwiched structure and preparation method therefor, organic field-effect transistor and preparation method therefor, and display device Download PDF

Info

Publication number
WO2018209927A1
WO2018209927A1 PCT/CN2017/115273 CN2017115273W WO2018209927A1 WO 2018209927 A1 WO2018209927 A1 WO 2018209927A1 CN 2017115273 W CN2017115273 W CN 2017115273W WO 2018209927 A1 WO2018209927 A1 WO 2018209927A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
mol
compound
double
semiconductor material
Prior art date
Application number
PCT/CN2017/115273
Other languages
French (fr)
Chinese (zh)
Inventor
高雪
刘飞
赵合彬
石广东
Original Assignee
京东方科技集团股份有限公司
北京京东方显示技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京东方科技集团股份有限公司, 北京京东方显示技术有限公司 filed Critical 京东方科技集团股份有限公司
Publication of WO2018209927A1 publication Critical patent/WO2018209927A1/en

Links

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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms

Definitions

  • the present disclosure belongs to the technical field of organic compound synthesis, and in particular relates to a polyphthalocyanine compound, a double-layer sandwich structure compound, a preparation method thereof, an organic field effect transistor, a preparation method thereof, and a display device.
  • phthalocyanine Due to the diversity of its compounds, phthalocyanine has high chemical stability (no obvious decomposition when heated at 400-500 ° C in air), and unique optical, electrical, magnetic and other ⁇ - ⁇ interactions with its molecular macrocycles.
  • the physical properties related to the role have received widespread attention and have been applied as semiconductor materials to the study of OFETs.
  • the inventors have found that at least the following problems exist in the prior art: compared with the monomeric phthalocyanine, the synthesis and separation of the polyphthalocyanine compound are difficult due to the expansion of the conjugated system, and the polypyrene is limited due to the limitation of the synthesis technique. Cyanine compounds are difficult to apply to OFETs.
  • the present disclosure provides a polyphthalocyanine compound having a molecular structural formula as follows:
  • the present disclosure provides a compound that also provides a two-layer sandwich structure having the following structure:
  • M is a rare earth element
  • the present disclosure also provides a method for preparing a compound of the above double-layer sandwich structure, comprising:
  • reaction temperature is from 100 to 120 °C.
  • the molar ratio of the 4,5-dicarbonylbutyoxy-o-dicyanobenzene to diisoindole and acetylacetone rare earth complex M(AcAc) 3 is 1-1.5 mmol: 0.125-1.135 mmol. 0.45-0.50 mmol.
  • the preparation method further comprises the following steps:
  • the first solvent comprises dichloromethane and the reducing agent comprises iron powder.
  • the catalyst comprises tetraoctyl ammonium bromide.
  • the reaction temperature of the step (2) is 100-120 ° C; the reaction temperature of the step (3) is 100-120 ° C; and the reaction temperature of the step (4) is 100 ° C.
  • the molar ratio of the o-xylene, iodine, reducing agent, liquid bromine is 0.2-0.3 mol: 10-11 mmol: 10-11 mmol: 0.4-0.5 mol;
  • the molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.025-0.030 mol: 0.1-0.15 mol;
  • the molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.01-0.015 mol: 0.01-0.015 mol: 0.02-0.025 mol;
  • the molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is from 0.01 to 0.015 mol: 0.02 to 0.025 mol.
  • the present disclosure also provides an organic field effect transistor comprising a layer of semiconductor material comprised of a compound of the double layer sandwich structure described above.
  • the layer of semiconductor material has an electron mobility of 1.0-1.5 cm 2 /(V ⁇ s).
  • the method further includes: a substrate, a gate layer, a gate insulating layer, a source and a drain; wherein the gate layer is over the substrate; and the gate insulating layer is located at the gate layer The semiconductor material layer is over the gate insulating layer; the source drain is above the semiconductor material layer.
  • the present disclosure also provides a method for fabricating the above-described organic field effect transistor, comprising the following steps:
  • a source drain is simultaneously fabricated on the layer of semiconductor material.
  • the layer of semiconductor material is formed by a phase transfer method.
  • the present disclosure also provides a display device including the above-described organic field effect transistor.
  • FIG. 1 is a schematic structural view of an organic field effect transistor according to Embodiment 4 of the present disclosure.
  • the reference numerals are: 1, the gate layer; 2, the gate insulating layer; 3, the semiconductor material layer; 4, the source and drain; 10, the substrate.
  • the present disclosure is difficult to synthesize and separate existing polyphthalocyanine compounds, and is difficult to apply to problems in OFETs, and provides a polyphthalocyanine compound, a double-layer sandwich structure compound, a preparation method thereof, and an airport. Effect transistor, its preparation method, and display device.
  • the present disclosure proposes a planar-based dinuclear phthalocyanine double-layer sandwich structure compound and a preparation method thereof.
  • the compound of the double-layer sandwich structure of the present disclosure is simple in preparation method and is suitable for use as a semiconductor material having an organic field effect transistor. After being used in an OFET, the electron mobility of the semiconductor material layer reaches 1.0-1.5 cm 2 /(V ⁇ s ).
  • a method of preparing a compound of a two-layer sandwich structure may include the following steps:
  • M is a rare earth element
  • the polyphthalocyanine compound of claim 1 is The polyphthalocyanine compound of claim 1.
  • each side can represent an isoindole structure in compound A
  • the midpoint on each side represents the nitrogen element N coordinated to metal M
  • the four vertices represent nitrogen elements that do not coordinate with M. N.
  • This formula represents a two-layer sandwich structure based on the phthalocyanine compound of Example 1.
  • the double-layered sandwich structure compound of the present embodiment is a planar-based dinuclear phthalocyanine double-layer sandwich compound, and the double-layer sandwich structure compound is simple to prepare, and is suitable for use as a semiconductor material for organic field effect transistors, and is used in an OFET. Thereafter, the electron mobility of the semiconductor material layer reaches 1.0-1.5 cm 2 /(V ⁇ s).
  • This embodiment provides a method for preparing a compound having a double-layer sandwich structure, comprising the following preparation steps:
  • the reaction mixture was washed with 5% sodium hydroxide solution until colorless.
  • the organic layer was separated, and then washed with 5% sodium hydrogensulfite solution until neutral.
  • the organic layer was separated and dried over anhydrous sodium sulfate. After standing overnight, it was suction filtered, and the filtrate was evaporated under reduced pressure on a rotary evaporator to give a pale brown oily liquid. 8-10 volumes of methanol were added to the liquid, stirred and heated to boiling, then the stirring was stopped, and the temperature was reduced to zero to recrystallize. A transparent needle crystal was obtained in an amount of 32.7 g, and the yield was 62%.
  • the obtained 4,5-dibromo-o-xylene has a melting point of 88 ° C;
  • MALDI.TOF mass spectrometry molecular ion peak 264.0;
  • the reaction mixture was suction filtered with a Buchner funnel to give a colorless, crude filtrate, which was a solution of potassium 4,5-dibromophthalate.
  • the filter residue was washed twice with a 1% KOH solution, and the washing liquid was combined into a filtrate.
  • Concentrated hydrochloric acid (18 M) was slowly added dropwise to the filtrate to acidify to a pH of about 2, and a large amount of white flocculent 4,5-dibromophthalic acid precipitated. It was suction filtered with a Buchner funnel, and the filter cake was washed with a small amount of 1% hydrochloric acid solution, and then dried in a desiccator in which discoloration silica gel was placed. A white glossy solid 7.3 g was obtained with a yield of 90%.
  • test product 4,5-dibromophthalic acid was tested and analyzed as follows:
  • the product 4,5-dibromophthalic acid has a melting point of 300 ° C or more;
  • the product was purified by silica gel column chromatography with a 1:1 ratio of chloroform/n-hexane mixed solution as the eluent. First, the first ultraviolet color band is collected under the ultraviolet light of 254 lun, which is the incomplete reaction of 4-bromo-5-cyanophthalic acid butyl ester; then the second ultraviolet color band is collected, which is the target product 4 , 5 dicarbonylbutanoxy-o-dicyanobenzene. After two purifications, the solution was evaporated to give a white powder. The product was dissolved in a small amount of chloroform and recrystallized from a large portion of methanol to yield white crystals (yield: 1.
  • Mass spectrometry molecular ion peak m/z 328.2;
  • acetylacetone rare earth salt M (AcAc) 3 (0.45 mmol) into 8 ml of n-butanol
  • the reaction was heated to reflux for 24 h under nitrogen. After cooling to room temperature, the solvent was drained, dissolved in chloroform, and trichloromethane and n-hexane were used as eluent to give 5 mg of the desired product.
  • the acetylacetone rare earth salt M(AcAc) 3 may also be referred to as an acetylacetone rare earth complex.
  • the embodiment provides an organic field effect transistor, as shown in FIG. 1 , including a substrate 10 , a gate layer 1 , a gate insulating layer 2 , a semiconductor material layer 3 , and a source drain 4 formed on the substrate 10 .
  • the semiconductor material layer is composed of the above-described double-layer sandwich structure compound.
  • the electron mobility of the above semiconductor material layer 3 is obtained to be 1.0-1.5 cm 2 /(V ⁇ s).
  • This embodiment provides a method for preparing a compound having a double-layer sandwich structure, which is similar to that of Example 3, and differs from Example 3 in that the molar ratio of o-xylene, iodine, reducing agent, and liquid bromine is 0.3 mol. : 11 mmol: 11 mmol: 0.5 mol;
  • the molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.030 mol:0.15 mol;
  • the molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.015 mol: 0.015 mol: 0.025 mol;
  • the molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is 0.015 mol:0.025 mol;
  • the molar ratio of the 4,5-dicarbonylbutoxy-o-dicyanobenzene to the diisoindole and acetylacetone rare earth complex is 1.5 mmol: 1.135 mmol: 0.50 mmol.
  • the reaction temperature of the step (2) is 120 ° C; the reaction temperature of the step (3) is 110 ° C; the reaction temperature of the step (4) is 120 ° C; the reaction temperature of the step (5) is 110 ° C
  • This embodiment provides a method for preparing a compound having a double-layer sandwich structure, which is similar to that of Example 3, and differs from Example 3 in that the molar ratio of o-xylene, iodine, reducing agent, and liquid bromine is 0.25 mol. : 10.3 mmol: 10.6 mmol: 0.45 mol;
  • the molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.027 mol:0.12 mol;
  • the molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.011 mol: 0.014 mol: 0.023 mol;
  • the molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is 0.011 mol: 0.024 mol;
  • the molar ratio of the 4,5-dicarbonylbutyoxy-o-dicyanobenzene to the diisoindole and acetylacetone rare earth complex is 1.2 mmol: 1.130 mmol: 0.47 mmol.
  • the specific embodiments of the above embodiments can also be subjected to many changes; for example, the synthesis conditions of the compound of the double-layer sandwich structure such as the reaction temperature, the reaction time, the reaction solvent, etc. can be adjusted according to actual conditions, and the specificity of the organic field effect transistor The structure can be changed as needed.
  • This embodiment provides a method for fabricating an organic field effect transistor, including the following steps:
  • a source drain is simultaneously fabricated on the layer of semiconductor material.
  • the semiconductor material layer is formed by a phase transfer method:
  • the diatom solution (1 mM) in which the compound of the double-layer sandwich structure of the above example was dissolved was rapidly injected into a larger amount of methanol (25 mL) with a micro syringe, and gently agitated with a syringe, and then the precipitated nanostructure was taken out from the solution. A layer of semiconductor material is obtained.
  • the temperature, concentration and injection speed of the whole experiment can be different, and the results obtained show good repeatability.
  • the precipitated nanostructured UV can be tested by dispersing in methanol.
  • the TEM and SEM photographs can be taken by dropping the sample on a pure carbon film. Among them, when performing SEM, the surface of the sample needs to be sprayed with gold of 1-2 nm thick.
  • the prepared nanostructure sample was dropped onto a silica substrate, and after the solvent was evaporated to dryness, a gold wire was used as a template, and the gold electrode was thermally evaporated onto the nanomaterial.
  • the distance between the two electrodes is 55 microns, and the current-voltage properties can be tested at room temperature using a Keithley 4200 semiconductor tester.
  • the display device may be any product or component having a display function, such as a liquid crystal display panel, an electronic paper, an OLED panel, a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator, and the like.
  • a display function such as a liquid crystal display panel, an electronic paper, an OLED panel, a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator, and the like.
  • the embodiments of the present disclosure can at least partially solve the problem that the synthesis and separation of the existing polyphthalocyanine compounds are difficult and difficult to apply to the OFET.
  • the compound of the present disclosure is a planar-based dinuclear phthalocyanine double-layer sandwich compound, and the compound of the present disclosure is simple in preparation method and is suitable for use as a semiconductor material for organic field effect transistors. After being used in an OFET, the electron mobility of the semiconductor material layer reached 1.0-1.5cm 2 / (V ⁇ s) .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Thin Film Transistor (AREA)

Abstract

The present invention provides a polyphthalocyanine compound, a compound of a double-layer sandwiched structure and a preparation method therefor, an organic field-effect transistor and a preparation method therefor, and s display device. The molecular structural formula of the polyphthalocyanine compound is formula (I), the double-layer sandwiched structure has the following structure: formula (II), wherein M is a rare earth element, and formula (III) represents the polyphthalocyanine compound.

Description

多聚酞菁化合物、双层三明治结构的化合物及其制备方法、有机场效应晶体管及其制备方法、和显示装置Polyphthalocyanine compound, double-layer sandwich structure compound, preparation method thereof, organic field effect transistor, preparation method thereof, and display device
对相关申请的交叉引用Cross-reference to related applications
本公开要求2017年5月19日提交的中国专利申请号201710356744.0的优先权，其全部内容通过引用结合在此。The present disclosure claims priority to Chinese Patent Application No. 201710356744.0, filed on May 19, 2009, the entire content of
技术领域Technical field
本公开属于有机化合物合成技术领域，具体涉及一种多聚酞菁化合物、双层三明治结构的化合物及其制备方法、有机场效应晶体管及其制备方法、和显示装置。The present disclosure belongs to the technical field of organic compound synthesis, and in particular relates to a polyphthalocyanine compound, a double-layer sandwich structure compound, a preparation method thereof, an organic field effect transistor, a preparation method thereof, and a display device.
背景技术Background technique
酞菁由于其化合物种类的多样性，高的化学稳定性(在空气中加热400-500℃不发生明显分解)，独一无二的光学、电学、磁性以及其它的与其分子大环之间π-π相互作用有关的物理性质，受到了人们的广泛重视，并将其作为半导体材料应用于OFET的研究中。Due to the diversity of its compounds, phthalocyanine has high chemical stability (no obvious decomposition when heated at 400-500 ° C in air), and unique optical, electrical, magnetic and other π-π interactions with its molecular macrocycles. The physical properties related to the role have received widespread attention and have been applied as semiconductor materials to the study of OFETs.
发明人发现现有技术中至少存在如下问题：相对于单体酞菁而言，由于共轭体系的扩大，多聚酞菁类化合物的合成、分离比较困难，由于合成技术的限制，多聚酞菁类化合物很难应用于OFET中。The inventors have found that at least the following problems exist in the prior art: compared with the monomeric phthalocyanine, the synthesis and separation of the polyphthalocyanine compound are difficult due to the expansion of the conjugated system, and the polypyrene is limited due to the limitation of the synthesis technique. Cyanine compounds are difficult to apply to OFETs.
发明内容Summary of the invention
本公开提供一种多聚酞菁化合物，其分子结构式如下： The present disclosure provides a polyphthalocyanine compound having a molecular structural formula as follows:
Figure PCTCN2017115273-appb-000001
Figure PCTCN2017115273-appb-000001
本公开提供还提供一种双层三明治结构的化合物，其具有以下结构：The present disclosure provides a compound that also provides a two-layer sandwich structure having the following structure:
Figure PCTCN2017115273-appb-000002
Figure PCTCN2017115273-appb-000002
其中，M是稀土元素，并且Where M is a rare earth element, and
Figure PCTCN2017115273-appb-000003
表示
Figure PCTCN2017115273-appb-000003
Express
Figure PCTCN2017115273-appb-000004
Figure PCTCN2017115273-appb-000004
本公开还提供一种上述双层三明治结构的化合物的制备方法，包括：The present disclosure also provides a method for preparing a compound of the above double-layer sandwich structure, comprising:
采用4，5-二羰基丁烷氧基-邻二氰基苯、二异吲哚、乙酰丙酮稀土配合物M(AcAc)3在正丁醇存在的条件下反应合成得到所Using 4,5-dicarbonylbutoxy-o-dicyanobenzene, diisonon, acetylacetone rare earth complex M (AcAc) 3 in the presence of n-butanol to synthesize
述双层三明治结构的化合物。优选地，所述反应温度为100-120℃。A compound of a double layer sandwich structure. Preferably, the reaction temperature is from 100 to 120 °C.
优选地，所述4，5-二羰基丁烷氧基-邻二氰基苯与二异吲哚、乙酰丙酮稀土配合物M(AcAc)3的摩尔比为1-1.5mmol∶0.125-1.135mmol∶0.45-0.50mmol。Preferably, the molar ratio of the 4,5-dicarbonylbutyoxy-o-dicyanobenzene to diisoindole and acetylacetone rare earth complex M(AcAc) 3 is 1-1.5 mmol: 0.125-1.135 mmol. 0.45-0.50 mmol.
优选地，所述制备方法还包括以下步骤： Preferably, the preparation method further comprises the following steps:
(1)将邻二甲苯、碘、还原剂和液溴在第一溶剂的存在下反应合成4，5-二溴邻二甲苯；(1) reacting o-xylene, iodine, a reducing agent and liquid bromine in the presence of a first solvent to synthesize 4,5-dibromo-o-xylene;
(2)采用所述4，5-二溴邻二甲苯和水在高锰酸钾存在的条件下反应合成4，5-二溴邻苯二甲酸；(2) using the 4,5-dibromo-o-xylene and water in the presence of potassium permanganate to synthesize 4,5-dibromophthalic acid;
(3)采用4，5-二溴邻苯二甲酸和1-溴丁烷在相转移催化剂、氢氧化钾、和水存在的条件下反应合成4，5-二溴邻苯二甲酸丁酯；以及(3) using 4,5-dibromophthalic acid and 1-bromobutane to synthesize butyl 4,5-dibromophthalate in the presence of a phase transfer catalyst, potassium hydroxide, and water; as well as
(4)采用所述4，5-二溴邻苯二甲酸丁酯和氰化亚铜在二甲基甲酰胺存在的条件下反应合成所述4，5-二羰基丁烷氧基-邻二氰基苯。(4) using the 4,5-dibromophthalic acid butyl ester and cuprous cyanide in the presence of dimethylformamide to synthesize the 4,5-dicarbonylbutanoxy-o-two Cyanobenzene.
优选地，所述第一溶剂包括二氯甲烷，所述还原剂包括铁粉。Preferably, the first solvent comprises dichloromethane and the reducing agent comprises iron powder.
优选地，所述催化剂包括四辛基溴化铵。Preferably, the catalyst comprises tetraoctyl ammonium bromide.
优选地，所述步骤(2)反应温度为100-120℃；步骤(3)反应温度为100-120℃；所述步骤(4)反应温度为100℃。Preferably, the reaction temperature of the step (2) is 100-120 ° C; the reaction temperature of the step (3) is 100-120 ° C; and the reaction temperature of the step (4) is 100 ° C.
优选地，所述邻二甲苯、碘、还原剂、液溴的摩尔比为0.2-0.3mol∶10-11mmol∶10-11mmol∶0.4-0.5mol；Preferably, the molar ratio of the o-xylene, iodine, reducing agent, liquid bromine is 0.2-0.3 mol: 10-11 mmol: 10-11 mmol: 0.4-0.5 mol;
所述4，5-二溴邻二甲苯、高锰酸钾的摩尔比为0.025-0.030mol∶0.1-0.15mol；The molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.025-0.030 mol: 0.1-0.15 mol;
所述4，5-二溴邻苯二甲酸与1-溴丁烷、氢氧化钾的摩尔比为0.01-0.015mol∶0.01-0.015mol∶0.02-0.025mol；The molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.01-0.015 mol: 0.01-0.015 mol: 0.02-0.025 mol;
所述4，5-二溴邻苯二甲酸丁酯与氰化亚铜的摩尔比为0.01-0.015mol∶0.02-0.025mol。The molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is from 0.01 to 0.015 mol: 0.02 to 0.025 mol.
本公开还提供一种有机场效应晶体管，包括半导体材料层，所述半导体材料层由上述双层三明治结构的化合物构成。The present disclosure also provides an organic field effect transistor comprising a layer of semiconductor material comprised of a compound of the double layer sandwich structure described above.
优选地，所述半导体材料层的电子迁移率为1.0-1.5cm2/(V·s)。Preferably, the layer of semiconductor material has an electron mobility of 1.0-1.5 cm 2 /(V·s).
优选地，还包括：衬底、栅极层、栅极绝缘层、源漏极；其中，所述栅极层位于所述衬底之上；所述栅极绝缘层位于所述栅极层之上；所述半导体材料层位于所述栅极绝缘层之上；所述源漏极位于所述半导体材料层之上。Preferably, the method further includes: a substrate, a gate layer, a gate insulating layer, a source and a drain; wherein the gate layer is over the substrate; and the gate insulating layer is located at the gate layer The semiconductor material layer is over the gate insulating layer; the source drain is above the semiconductor material layer.
本公开还提供一种上述的有机场效应晶体管的制备方法，包括以下步骤： The present disclosure also provides a method for fabricating the above-described organic field effect transistor, comprising the following steps:
在衬底上制备栅极层；Preparing a gate layer on the substrate;
在栅极层上制备栅极绝缘层；Preparing a gate insulating layer on the gate layer;
在栅极绝缘层上制备半导体材料层；Preparing a layer of semiconductor material on the gate insulating layer;
在半导体材料层上同时制备源漏极。A source drain is simultaneously fabricated on the layer of semiconductor material.
优选地，通过相转移方法形成所述半导体材料层。Preferably, the layer of semiconductor material is formed by a phase transfer method.
本公开还提供一种包括上述的有机场效应晶体管的显示装置。The present disclosure also provides a display device including the above-described organic field effect transistor.
附图说明DRAWINGS
图1为本公开的实施例4的有机场效应晶体管的结构示意图。1 is a schematic structural view of an organic field effect transistor according to Embodiment 4 of the present disclosure.
具体实施方式detailed description
为使本领域技术人员更好地理解本公开的技术方案，下面结合附图和具体实施方式对本公开作进一步详细描述。其中，附图标记为：1、栅极层；2、栅极绝缘层；3、半导体材料层；4、源漏极；10、衬底。The present disclosure will be further described in detail below in conjunction with the drawings and specific embodiments. Wherein, the reference numerals are: 1, the gate layer; 2, the gate insulating layer; 3, the semiconductor material layer; 4, the source and drain; 10, the substrate.
本公开针对现有的多聚酞菁类化合物的合成、分离比较困难，很难应用于OFET中的问题，提供一种多聚酞菁化合物、双层三明治结构的化合物及其制备方法、有机场效应晶体管及其制备方法、和显示装置。The present disclosure is difficult to synthesize and separate existing polyphthalocyanine compounds, and is difficult to apply to problems in OFETs, and provides a polyphthalocyanine compound, a double-layer sandwich structure compound, a preparation method thereof, and an airport. Effect transistor, its preparation method, and display device.
本公开提出了一种基于平面的双核酞菁双层三明治结构的化合物及其制备方法。本公开的双层三明治结构的化合物制备方法简单，适合作为有机场效应晶体管的半导体材料应用，将其用于OFET中后，半导体材料层的电子迁移率达到1.0-1.5cm2/(V·s)。The present disclosure proposes a planar-based dinuclear phthalocyanine double-layer sandwich structure compound and a preparation method thereof. The compound of the double-layer sandwich structure of the present disclosure is simple in preparation method and is suitable for use as a semiconductor material having an organic field effect transistor. After being used in an OFET, the electron mobility of the semiconductor material layer reaches 1.0-1.5 cm 2 /(V·s ).
在本公开的一个实施方案中，制备双层三明治结构的化合物的方法可以包括以下步骤：In one embodiment of the present disclosure, a method of preparing a compound of a two-layer sandwich structure may include the following steps:
(1)将邻二甲苯溶于第一溶剂中，并向其中加入碘、还原剂后冷却，将溶于第一溶剂的液溴滴入其中，反应合成4，5-二溴邻二甲苯；(1) dissolving o-xylene in a first solvent, adding iodine and a reducing agent thereto, cooling, and dissolving liquid bromine dissolved in the first solvent, and reacting to synthesize 4,5-dibromo-o-xylene;
(2)采用上述4，5-二溴邻二甲苯和水在高锰酸钾存在的条 件下加热，反应合成4，5-二溴邻苯二甲酸；(2) using the above 4,5-dibromo-o-xylene and water in the presence of potassium permanganate Heating under the conditions, the reaction synthesizes 4,5-dibromophthalic acid;
(3)采用上述4，5-二溴邻苯二甲酸和1-溴丁烷在相转移催化剂、氢氧化钾、和水存在的条件下加热，反应合成4，5-二溴邻苯二甲酸丁酯；(3) using the above 4,5-dibromophthalic acid and 1-bromobutane in the presence of a phase transfer catalyst, potassium hydroxide, and water to synthesize 4,5-dibromophthalic acid Butyl ester
(4)采用上述4，5-二溴邻苯二甲酸丁酯和氰化亚铜在二甲基甲酰胺存在的条件下加热，反应合成4，5-二羰基丁烷氧基-邻二氰基苯；(4) using the above 4,5-dibromophthalic acid butyl ester and cuprous cyanide in the presence of dimethylformamide to synthesize 4,5-dicarbonylbutyoxy-o-dicyanide Base benzene
(5)采用上述4，5-二羰基丁烷氧基-邻二氰基苯、二异吲哚、乙酰丙酮稀土配合物M(AcAc)3在正丁醇存在的条件下反应合成得到双层三明治结构的化合物。(5) using the above 4,5-dicarbonylbutoxy-o-dicyanobenzene, diisoindole, acetylacetone rare earth complex M (AcAc) 3 in the presence of n-butanol to synthesize a double layer A compound of sandwich structure.
实施例1：Example 1:
本实施例提供一种多聚酞菁化合物，其分子结构式如下：This embodiment provides a polyphthalocyanine compound having a molecular structural formula as follows:
Figure PCTCN2017115273-appb-000005
Figure PCTCN2017115273-appb-000005
实施例2：Example 2:
本实施例提供一种双层三明治结构的化合物，其具有以下结构：This embodiment provides a double-layer sandwich structure compound having the following structure:
Figure PCTCN2017115273-appb-000006
Figure PCTCN2017115273-appb-000006
其中，M是稀土元素，并且Where M is a rare earth element, and
Figure PCTCN2017115273-appb-000007
表示权利要求1所述的多聚酞菁化合物。
Figure PCTCN2017115273-appb-000007
The polyphthalocyanine compound of claim 1.
在该式中，出于简化的目的，用两个并排的四边形表示双核 化合物A。化合物A的主体结构是两个十六元环，具有四次旋转轴。这样，在每个四边形中，每条边可以代表化合物A中的一个异吲哚结构，每边中点代表与金属M配位的氮元素N，四个顶点代表不与M配位的氮元素N。应当注意，这样的画法是为了简明表现配位关系的目的。该式表示以实施例1的酞菁化合物为基底的双层三明治结构。In this formula, for the sake of simplicity, two side-by-side quadrilaterals are used to represent dual cores. Compound A. The main structure of Compound A is two sixteen-membered rings with four rotation axes. Thus, in each quadrilateral, each side can represent an isoindole structure in compound A, the midpoint on each side represents the nitrogen element N coordinated to metal M, and the four vertices represent nitrogen elements that do not coordinate with M. N. It should be noted that such a drawing is for the purpose of concise representation of the coordination relationship. This formula represents a two-layer sandwich structure based on the phthalocyanine compound of Example 1.
本实施例的双层三明治结构的化合物为基于平面的双核酞菁双层三明治化合物，该双层三明治结构的化合物制备方法简单，适合作为有机场效应晶体管的半导体材料应用，将其用于OFET中后，半导体材料层的电子迁移率达到1.0-1.5cm2/(V·s)。The double-layered sandwich structure compound of the present embodiment is a planar-based dinuclear phthalocyanine double-layer sandwich compound, and the double-layer sandwich structure compound is simple to prepare, and is suitable for use as a semiconductor material for organic field effect transistors, and is used in an OFET. Thereafter, the electron mobility of the semiconductor material layer reaches 1.0-1.5 cm 2 /(V·s).
实施例3：Example 3:
本实施例提供一种双层三明治结构的化合物的制备方法，包括以下制备步骤：This embodiment provides a method for preparing a compound having a double-layer sandwich structure, comprising the following preparation steps:
(1)合成4，5-二溴邻二甲苯：(1) Synthesis of 4,5-dibromo-o-xylene:
Figure PCTCN2017115273-appb-000008
Figure PCTCN2017115273-appb-000008
将邻二甲苯24ml(0.2mol)溶于30ml干燥的二氯甲烷中，一边搅拌一边向上述溶液中加入碘2.5g(10mmol)以及还原铁粉0.6g(10mmol)。混合物用冰浴冷却至零度。另将液溴20.5ml(0.4mol)溶于10ml干燥的二氯甲烷中，将上述溶液用滴液漏斗在六小时内均匀缓慢滴入反应混合物，以倒扣在10％氢氧化钠溶液中的漏斗吸收放出的溴化氢气体。反应在零度下连续搅拌38小时，之后在室温下继续搅拌6小时。反应混合物先用5％氢氧化钠溶液洗涤至无色，分离有机层；之后再用5％亚硫酸氢钠溶液洗涤至中性，分离有机层，加入无水硫酸钠干燥。放置一夜后抽滤，滤液在旋转蒸发仪上减压蒸馏得到浅棕色油状液体。向液体中加入8-10倍体积的甲醇，搅拌加热至沸，然后停止搅拌，降温至零度重结晶。获得透明针状晶体32.7g，产率62％。 24 ml (0.2 mol) of o-xylene was dissolved in 30 ml of dry dichloromethane, and while stirring, 2.5 g (10 mmol) of iodine and 0.6 g (10 mmol) of reduced iron powder were added to the above solution. The mixture was cooled to zero with an ice bath. In addition, 20.5 ml (0.4 mol) of liquid bromine was dissolved in 10 ml of dry dichloromethane, and the solution was uniformly and slowly dropped into the reaction mixture in a dropping funnel over six hours to be inverted in a 10% sodium hydroxide solution. The funnel absorbs the evolved hydrogen bromide gas. The reaction was continuously stirred at zero for 38 hours, after which stirring was continued for 6 hours at room temperature. The reaction mixture was washed with 5% sodium hydroxide solution until colorless. The organic layer was separated, and then washed with 5% sodium hydrogensulfite solution until neutral. The organic layer was separated and dried over anhydrous sodium sulfate. After standing overnight, it was suction filtered, and the filtrate was evaporated under reduced pressure on a rotary evaporator to give a pale brown oily liquid. 8-10 volumes of methanol were added to the liquid, stirred and heated to boiling, then the stirring was stopped, and the temperature was reduced to zero to recrystallize. A transparent needle crystal was obtained in an amount of 32.7 g, and the yield was 62%.
将所得的产物4，5-二溴邻二甲苯进行测试分析如下：The obtained product 4,5-dibromo-o-xylene was tested and analyzed as follows:
所得4，5-二溴邻二甲苯的熔点为88℃；The obtained 4,5-dibromo-o-xylene has a melting point of 88 ° C;
核磁共振氢谱(300MHz，CDCl3)中，7.37(单峰，2H，苯环)，2.18(单峰，6H，甲基)；Nuclear magnetic resonance spectroscopy (300MHz, CDCl3), 7.37 (monomodal, 2H, benzene ring), 2.18 (monomodal, 6H, methyl);
MALDI.TOF质谱：分子离子峰264.0；MALDI.TOF mass spectrometry: molecular ion peak 264.0;
元素分析：C8H8Br2：C，36.36；H，2.92。Elemental analysis: C 8 H 8 Br 2 : C, 36.36; H, 2.92.
(2)合成4，5-二溴邻苯二甲酸：(2) Synthesis of 4,5-dibromophthalic acid:
Figure PCTCN2017115273-appb-000009
Figure PCTCN2017115273-appb-000009
将上述的4，5一二嗅邻二甲苯6.5g(0.025mol)研细，加入200ml水中，搅拌形成悬浊液，加热至沸。将高锰酸钾粉末15.8g(0.1mol)均分为三等分，每隔二小时一次加入反应混合物中，共反应6小时。反应混合物冷却至室温，缓慢加入亚硫酸氢钠还原剩余的高锰酸钾，直到紫红色完全消失为止。向反应混和物中加入氢氧化钾调pH值至12以上。反应混合物用布氏漏斗抽滤，获得无色澄清滤液，此滤液为4，5一二溴邻苯二甲酸钾溶液。滤渣用1％KOH溶液洗涤两次，洗涤液合并入滤液。向滤液中缓慢滴加浓盐酸(18M)酸化至pH约等于2，析出大量白色絮状4，5-二溴邻苯二甲酸沉淀。用布氏漏斗抽滤，滤饼以少量1％盐酸溶液洗涤，之后置于放有变色硅胶的干燥器内干燥。获得白色有光泽固体7.3g，产率90％。6.5 g (0.025 mol) of the above-mentioned 4,5-dioxin o-xylene was finely ground, added to 200 ml of water, stirred to form a suspension, and heated to boiling. 15.8 g (0.1 mol) of potassium permanganate powder was equally divided into three equal portions, and the reaction mixture was added to the reaction mixture once every two hours for a total of 6 hours. The reaction mixture was cooled to room temperature, and the remaining potassium permanganate was slowly added by adding sodium hydrogensulfite until the magenta completely disappeared. Potassium hydroxide was added to the reaction mixture to adjust the pH to 12 or higher. The reaction mixture was suction filtered with a Buchner funnel to give a colorless, crude filtrate, which was a solution of potassium 4,5-dibromophthalate. The filter residue was washed twice with a 1% KOH solution, and the washing liquid was combined into a filtrate. Concentrated hydrochloric acid (18 M) was slowly added dropwise to the filtrate to acidify to a pH of about 2, and a large amount of white flocculent 4,5-dibromophthalic acid precipitated. It was suction filtered with a Buchner funnel, and the filter cake was washed with a small amount of 1% hydrochloric acid solution, and then dried in a desiccator in which discoloration silica gel was placed. A white glossy solid 7.3 g was obtained with a yield of 90%.
将所得的产物4，5-二溴邻苯二甲酸进行测试分析如下：The test product 4,5-dibromophthalic acid was tested and analyzed as follows:
产物4，5-二溴邻苯二甲酸熔点300℃以上；The product 4,5-dibromophthalic acid has a melting point of 300 ° C or more;
因产物难溶于普通有机溶剂故未能得到满意的核磁结果，且元素分析结果也因提纯困难导致误差稍大；MALDI.TOF质谱：分子离子峰m/z 323.2；Because the product is difficult to dissolve in common organic solvents, satisfactory nuclear magnetic results are not obtained, and the elemental analysis results are slightly more error due to purification difficulties; MALDI.TOF mass spectrometry: molecular ion peak m/z 323.2;
元素分析：C8H4O4Br2：C，27.73；H，1.20。Elemental analysis: C 8 H 4 O 4 Br 2 : C, 27.73; H, 1.20.
(3)合成4，5-二溴邻苯二甲酸丁酯： (3) Synthesis of butyl 4,5-dibromophthalate:
Figure PCTCN2017115273-appb-000010
Figure PCTCN2017115273-appb-000010
将上述4，5-二溴邻苯二甲酸3.24g(0.01mol)与氢氧化钾1.12g(0.02mol)加入100ml蒸馏水中，搅拌至完全溶解。为使溶解过程加速在搅拌过程中可适当加热。向溶液中加入1-溴丁烷3.86g(0.01mol)和相转移催化剂四辛基溴化铵(TOAB)2g，反应混合物加热到100度，在氮气保护下搅拌回流4小时，然后冷却到室温。反应液以甲苯萃取(3次，每次3Oml)，合并有机相并加入无水硫酸镁干燥。静置一夜后用布氏漏斗抽滤，滤液在旋转蒸发仪上减压蒸馏得到淡黄色油状液体。产品通过硅胶色谱柱纯化，以氯仿作为洗提液，在254nm波长紫外灯下收集紫外显色带。经两次提纯后最终得到纯净的4，5-二溴邻苯二甲酸丁酯4.22g，产率77％。3.24 g (0.01 mol) of the above 4,5-dibromophthalic acid and 1.12 g (0.02 mol) of potassium hydroxide were added to 100 ml of distilled water, and stirred until completely dissolved. In order to accelerate the dissolution process, it can be appropriately heated during the stirring process. To the solution was added 3.86 g (0.01 mol) of 1-bromobutane and 2 g of a phase transfer catalyst tetraoctyl ammonium bromide (TOAB). The reaction mixture was heated to 100 ° C, and stirred under nitrogen for 4 hours, then cooled to room temperature. . The reaction mixture was extracted with toluene (3×3 mL). After standing overnight, it was suction filtered with a Buchner funnel, and the filtrate was evaporated under reduced pressure on a rotary evaporator to give a pale yellow oily liquid. The product was purified by silica gel column chromatography using chloroform as an eluent, and the UV color band was collected under a UV light of 254 nm wavelength. After two purifications, 4.22 g of pure 4,5-dibromophthalic acid butyl ester was obtained in a yield of 77%.
将所得的产物4，5-二溴邻苯二甲酸丁酯进行测试分析如下：The obtained product 4,5-dibromophthalic acid butyl ester was tested and analyzed as follows:
质谱：分子离子峰m/z 433.87；Mass spectrometry: molecular ion peak m/z 433.87;
元素分析：C18H20O4Br2：C，44.22；H，4.55；O，14.45。Elemental analysis: C 18 H 20 O 4 Br 2 : C, 44.22; H, 4.55; O, 14.45.
(4)合成4，5-二羰基丁烷氧基-邻二氰基苯：(4) Synthesis of 4,5-dicarbonylbutoxy-o-dicyanobenzene:
Figure PCTCN2017115273-appb-000011
Figure PCTCN2017115273-appb-000011
将上述的4，5-二溴邻苯二甲酸的丁酯5.48g，0.01mol与氰化亚铜1.79g，0.02mol加入DMF100ml中，反应混合物在氮气保护下搅拌加热回流2小时。冷至室温后，将反应混合物倒入200ml蒸馏水中，以甲苯萃取(3次，每次35ml)。合并有机相，用蒸馏水多次洗涤(五到十次)以除去残留的细小颗粒溴化亚铜。向洗涤后的甲苯溶液中加入无水硫酸镁干燥。静置一夜后用布氏漏斗抽滤，减压蒸馏除去溶剂得到棕色油状液体。产品通过硅胶色谱柱纯化，以1∶1体积比的氯仿/正己烷混合溶液作为洗提液，首 先在254lun波长紫外灯下收集第一个紫外显色带，是反应不完全的4-溴-5-氰基邻苯二甲酸丁酯；然后收集第二个紫外显色带，是目标产物4，5二羰基丁烷氧基-邻二氰基苯。经两次提纯后蒸干溶液获得白色粉末。产物溶于少量氯仿，在大量甲醇中重结晶，获得白色晶体1.19g，产率27％。5.48 g of the above-mentioned butyl 4-, 5-dibromophthalic acid, 0.01 mol and 1.79 g of cuprous cyanide, 0.02 mol were added to 100 ml of DMF, and the reaction mixture was heated under reflux with nitrogen for 2 hours. After cooling to room temperature, the reaction mixture was poured into 200 ml of distilled water and extracted with toluene (3 times, 35 ml each time). The organic phases were combined and washed several times with distilled water (five to ten times) to remove residual fine particles of cuprous bromide. Drying with anhydrous magnesium sulfate was added to the washed toluene solution. After standing overnight, it was suction filtered with a Buchner funnel, and the solvent was evaporated under reduced pressure to give a brown oily liquid. The product was purified by silica gel column chromatography with a 1:1 ratio of chloroform/n-hexane mixed solution as the eluent. First, the first ultraviolet color band is collected under the ultraviolet light of 254 lun, which is the incomplete reaction of 4-bromo-5-cyanophthalic acid butyl ester; then the second ultraviolet color band is collected, which is the target product 4 , 5 dicarbonylbutanoxy-o-dicyanobenzene. After two purifications, the solution was evaporated to give a white powder. The product was dissolved in a small amount of chloroform and recrystallized from a large portion of methanol to yield white crystals (yield: 1.
将所得的产物4，5-二羰基丁烷氧基-邻二氰基苯进行测试分析如下：The obtained product 4,5-dicarbonylbutyoxy-o-dicyanobenzene was tested and analyzed as follows:
质谱：分子离子峰m/z 328.2；Mass spectrometry: molecular ion peak m/z 328.2;
元素分析：C18H20O4N2：C，65.74；H，6.44；N，8.43。Elemental analysis: C 18 H 20 O 4 N 2 : C, 65.74; H, 6.44; N, 8.43.
(5)合成多聚酞菁化合物：(5) Synthesis of polyphthalocyanine compounds:
Figure PCTCN2017115273-appb-000012
Figure PCTCN2017115273-appb-000012
Figure PCTCN2017115273-appb-000013
Figure PCTCN2017115273-appb-000013
其中among them
Figure PCTCN2017115273-appb-000014
Figure PCTCN2017115273-appb-000014
将4，5-二羰基丁烷氧基-邻二氰基苯328mg(1mmol)与二异吲哚26mg(0.125mmol)，乙酰丙酮稀土盐M(AcAc)3(0.45mmol)入8ml正丁醇，反应物在氮气氛围中加热回流24h。冷至室温后，将溶剂抽干，加入三氯甲烷溶解，以三氯甲烷和正己烷为淋洗液，得到目标产物5mg，产率1.1％。乙酰丙酮稀土盐M(AcAc)3也 可以称为乙酰丙酮稀土配合物。328 mg (1 mmol) of 4,5-dicarbonylbutoxy-o-dicyanobenzene and 26 mg (0.125 mmol) of diisoindole, acetylacetone rare earth salt M (AcAc) 3 (0.45 mmol) into 8 ml of n-butanol The reaction was heated to reflux for 24 h under nitrogen. After cooling to room temperature, the solvent was drained, dissolved in chloroform, and trichloromethane and n-hexane were used as eluent to give 5 mg of the desired product. The acetylacetone rare earth salt M(AcAc) 3 may also be referred to as an acetylacetone rare earth complex.
实施例4：Example 4:
本实施例提供一种有机场效应晶体管，如图1所示，包括衬底10，形成于衬底10上的栅极层1、栅极绝缘层2、半导体材料层3、源漏极4，其中，半导体材料层由上述的双层三明治结构的化合物构成。The embodiment provides an organic field effect transistor, as shown in FIG. 1 , including a substrate 10 , a gate layer 1 , a gate insulating layer 2 , a semiconductor material layer 3 , and a source drain 4 formed on the substrate 10 . Among them, the semiconductor material layer is composed of the above-described double-layer sandwich structure compound.
通过变换不同电压，选取不同位点进行测试，获得上述半导体材料层3的电子迁移率为1.0-1.5cm2/(V·s)。By changing different voltages and selecting different sites for testing, the electron mobility of the above semiconductor material layer 3 is obtained to be 1.0-1.5 cm 2 /(V·s).
实施例5Example 5
本实施例提供一种双层三明治结构的化合物的制备方法，其与实施例3的类似，其与实施例3的区别在于，邻二甲苯、碘、还原剂、液溴的摩尔比为0.3mol∶11mmol∶11mmol∶0.5mol；This embodiment provides a method for preparing a compound having a double-layer sandwich structure, which is similar to that of Example 3, and differs from Example 3 in that the molar ratio of o-xylene, iodine, reducing agent, and liquid bromine is 0.3 mol. : 11 mmol: 11 mmol: 0.5 mol;
所述4，5-二溴邻二甲苯、高锰酸钾的摩尔比为0.030mol∶0.15mol；The molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.030 mol:0.15 mol;
所述4，5-二溴邻苯二甲酸与1-溴丁烷、氢氧化钾的摩尔比为0.015mol∶0.015mol∶0.025mol；The molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.015 mol: 0.015 mol: 0.025 mol;
所述4，5-二溴邻苯二甲酸丁酯与氰化亚铜的摩尔比为0.015mol∶0.025mol；The molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is 0.015 mol:0.025 mol;
所述4，5-二羰基丁烷氧基-邻二氰基苯与二异吲哚、乙酰丙酮稀土配合物的摩尔比为1.5mmol∶1.135mmol∶0.50mmol。The molar ratio of the 4,5-dicarbonylbutoxy-o-dicyanobenzene to the diisoindole and acetylacetone rare earth complex is 1.5 mmol: 1.135 mmol: 0.50 mmol.
所述步骤(2)反应温度为120℃；步骤(3)反应温度为110℃；所述步骤(4)反应温度为120℃；所述步骤(5)反应温度为110℃The reaction temperature of the step (2) is 120 ° C; the reaction temperature of the step (3) is 110 ° C; the reaction temperature of the step (4) is 120 ° C; the reaction temperature of the step (5) is 110 ° C
实施例6Example 6
本实施例提供一种双层三明治结构的化合物的制备方法，其与实施例3的类似，其与实施例3的区别在于，邻二甲苯、碘、还原剂、液溴的摩尔比为0.25mol∶10.3mmol∶10.6mmol∶0.45mol； This embodiment provides a method for preparing a compound having a double-layer sandwich structure, which is similar to that of Example 3, and differs from Example 3 in that the molar ratio of o-xylene, iodine, reducing agent, and liquid bromine is 0.25 mol. : 10.3 mmol: 10.6 mmol: 0.45 mol;
所述4，5-二溴邻二甲苯、高锰酸钾的摩尔比为0.027mol∶0.12mol；The molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.027 mol:0.12 mol;
所述4，5-二溴邻苯二甲酸与1-溴丁烷、氢氧化钾的摩尔比为0.011mol∶0.014mol∶0.023mol；The molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.011 mol: 0.014 mol: 0.023 mol;
所述4，5-二溴邻苯二甲酸丁酯与氰化亚铜的摩尔比为0.011mol∶0.024mol；The molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is 0.011 mol: 0.024 mol;
所述4，5-二羰基丁烷氧基-邻二氰基苯与二异吲哚、乙酰丙酮稀土配合物的摩尔比为1.2mmol∶1.130mmol∶0.47mmol。The molar ratio of the 4,5-dicarbonylbutyoxy-o-dicyanobenzene to the diisoindole and acetylacetone rare earth complex is 1.2 mmol: 1.130 mmol: 0.47 mmol.
显然，上述各实施例的具体实施方式还可进行许多变化；例如：双层三明治结构的化合物的合成条件如反应温度，反应时间，反应溶剂等可以根据实际条件进行调整，有机场效应晶体管的具体结构可以根据需要进行改变。Obviously, the specific embodiments of the above embodiments can also be subjected to many changes; for example, the synthesis conditions of the compound of the double-layer sandwich structure such as the reaction temperature, the reaction time, the reaction solvent, etc. can be adjusted according to actual conditions, and the specificity of the organic field effect transistor The structure can be changed as needed.
实施例7：Example 7
本实施例提供一种有机场效应晶体管的制备方法，包括以下步骤：This embodiment provides a method for fabricating an organic field effect transistor, including the following steps:
在衬底上制备栅极层；Preparing a gate layer on the substrate;
在栅极层上制备栅极绝缘层；Preparing a gate insulating layer on the gate layer;
在栅极绝缘层上制备半导体材料层；Preparing a layer of semiconductor material on the gate insulating layer;
在半导体材料层上同时制备源漏极。A source drain is simultaneously fabricated on the layer of semiconductor material.
具体的，半导体材料层通过相转移的方法形成：Specifically, the semiconductor material layer is formed by a phase transfer method:
将上述实施例的双层三明治结构的化合物溶于的氯仿溶液(1mM)分别用微量注射器迅速注入较大量的甲醇中(25mL)，并用注射器轻轻搅动，然后将析出的纳米结构从溶液中取出得到半导体材料层。The diatom solution (1 mM) in which the compound of the double-layer sandwich structure of the above example was dissolved was rapidly injected into a larger amount of methanol (25 mL) with a micro syringe, and gently agitated with a syringe, and then the precipitated nanostructure was taken out from the solution. A layer of semiconductor material is obtained.
整个实验过程中的温度、浓度及注入速度可以有不同，所得结果均表现出良好的可重复性。析出的纳米结构的紫外可以分散在甲醇中测试。其TEM和SEM照片可以将样品滴在纯碳膜上拍摄。其中，做SEM时，样品表面需喷1-2nm厚的金。 The temperature, concentration and injection speed of the whole experiment can be different, and the results obtained show good repeatability. The precipitated nanostructured UV can be tested by dispersing in methanol. The TEM and SEM photographs can be taken by dropping the sample on a pure carbon film. Among them, when performing SEM, the surface of the sample needs to be sprayed with gold of 1-2 nm thick.
半导体材料层的电流-电压性质测试：Current-voltage property testing of semiconductor material layers:
将上述制备好的纳米结构样品滴到二氧化硅基片上，等溶剂挥发干以后，用一根金线做模版，金电极被热蒸镀到纳米材料上。两个电极之间的距离是55微米，电流-电压性质采用Keithley4200半导体测试仪在室温下测试即可。The prepared nanostructure sample was dropped onto a silica substrate, and after the solvent was evaporated to dryness, a gold wire was used as a template, and the gold electrode was thermally evaporated onto the nanomaterial. The distance between the two electrodes is 55 microns, and the current-voltage properties can be tested at room temperature using a Keithley 4200 semiconductor tester.
实施例8：Example 8
本实施例提供了一种显示装置，其包括上述的有机场效应晶体管。所述显示装置可以为：液晶显示面板、电子纸、OLED面板、手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪等任何具有显示功能的产品或部件。This embodiment provides a display device including the above-described organic field effect transistor. The display device may be any product or component having a display function, such as a liquid crystal display panel, an electronic paper, an OLED panel, a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator, and the like.
综上所述，本公开的实施方案可以至少部分解决现有的多聚酞菁类化合物的合成、分离比较困难，很难应用于OFET中的问题。本公开的化合物为基于平面的双核酞菁双层三明治化合物，本公开的化合物制备方法简单，适合作为有机场效应晶体管的半导体材料应用，将其用于OFET中后，半导体材料层的电子迁移率达到1.0-1.5cm2/(V·s)。In summary, the embodiments of the present disclosure can at least partially solve the problem that the synthesis and separation of the existing polyphthalocyanine compounds are difficult and difficult to apply to the OFET. The compound of the present disclosure is a planar-based dinuclear phthalocyanine double-layer sandwich compound, and the compound of the present disclosure is simple in preparation method and is suitable for use as a semiconductor material for organic field effect transistors. After being used in an OFET, the electron mobility of the semiconductor material layer reached 1.0-1.5cm 2 / (V · s) .
可以理解的是，以上实施方式仅仅是为了说明本公开的原理而采用的示例性实施方式，然而本公开并不局限于此。对于本领域内的普通技术人员而言，在不脱离本公开的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本公开的保护范围。 It is to be understood that the above embodiments are merely exemplary embodiments employed to explain the principles of the present disclosure, but the present disclosure is not limited thereto. Various modifications and improvements can be made by those skilled in the art without departing from the spirit and scope of the disclosure, and such modifications and improvements are also considered to be within the scope of the disclosure.

Claims (16)

  1. 一种多聚酞菁化合物，其分子结构式如下：A polyphthalocyanine compound having a molecular structural formula as follows:
    Figure PCTCN2017115273-appb-100001
    Figure PCTCN2017115273-appb-100001
  2. 一种双层三明治结构的化合物，其具有以下结构：A two-layer sandwich structure compound having the following structure:
    Figure PCTCN2017115273-appb-100002
    Figure PCTCN2017115273-appb-100002
    其中，M是稀土元素，并且Where M is a rare earth element, and
    Figure PCTCN2017115273-appb-100003
    表示
    Figure PCTCN2017115273-appb-100003
    Express
    Figure PCTCN2017115273-appb-100004
    Figure PCTCN2017115273-appb-100004
  3. 权利要求2所述的双层三明治结构的化合物的制备方法，包括：A method of preparing a double-layer sandwich structure compound according to claim 2, comprising:
    采用4，5-二羰基丁烷氧基-邻二氰基苯、二异吲哚、乙酰丙酮稀土配合物M(AcAc)3在正丁醇存在的条件下反应合成得到所述双层三明治结构的化合物。The double-layered sandwich structure is synthesized by reacting 4,5-dicarbonylbutoxy-o-dicyanobenzene, diisonon, and acetylacetone rare earth complex M(AcAc) 3 in the presence of n-butanol. compound of.
  4. 根据权利要求3所述的制备方法，其中：The preparation method according to claim 3, wherein:
    所述反应温度为100-120℃。 The reaction temperature is 100-120 °C.
  5. 根据权利要求3所述的制备方法，其中：The preparation method according to claim 3, wherein:
    所述4，5-二羰基丁烷氧基-邻二氰基苯与二异吲哚、乙酰丙酮稀土配合物M(AcAc)3的摩尔比为1-1.5mmol∶0.125-1.135mmol∶0.45-0.50mmol。The molar ratio of the 4,5-dicarbonylbutyoxy-o-dicyanobenzene to the diisoindole and acetylacetone rare earth complex M(AcAc) 3 is 1-1.5 mmol: 0.125-1.135 mmol: 0.45- 0.50 mmol.
  6. 根据权利要求3所述的制备方法，还包括以下步骤：The preparation method according to claim 3, further comprising the steps of:
    (1)将邻二甲苯、碘、还原剂和液溴在第一溶剂的存在下反应合成4，5-二溴邻二甲苯；(1) reacting o-xylene, iodine, a reducing agent and liquid bromine in the presence of a first solvent to synthesize 4,5-dibromo-o-xylene;
    (2)采用所述4，5-二溴邻二甲苯和水在高锰酸钾存在的条件下反应合成4，5-二溴邻苯二甲酸；(2) using the 4,5-dibromo-o-xylene and water in the presence of potassium permanganate to synthesize 4,5-dibromophthalic acid;
    (3)采用4，5-二溴邻苯二甲酸和1-溴丁烷在相转移催化剂、氢氧化钾、和水存在的条件下反应合成4，5-二溴邻苯二甲酸丁酯；以及(3) using 4,5-dibromophthalic acid and 1-bromobutane to synthesize butyl 4,5-dibromophthalate in the presence of a phase transfer catalyst, potassium hydroxide, and water; as well as
    (4)采用所述4，5-二溴邻苯二甲酸丁酯和氰化亚铜在二甲基甲酰胺存在的条件下反应合成所述4，5-二羰基丁烷氧基-邻二氰基苯。(4) using the 4,5-dibromophthalic acid butyl ester and cuprous cyanide in the presence of dimethylformamide to synthesize the 4,5-dicarbonylbutanoxy-o-two Cyanobenzene.
  7. 根据权利要求6所述的双层三明治结构的化合物的制备方法，其中，所述第一溶剂包括二氯甲烷，所述还原剂包括铁粉。The method of producing a double-layered sandwich structure according to claim 6, wherein the first solvent comprises dichloromethane and the reducing agent comprises iron powder.
  8. 根据权利要求6所述的双层三明治结构的化合物的制备方法，其中，所述催化剂包括四辛基溴化铵。The method of producing a double-layered sandwich structure according to claim 6, wherein the catalyst comprises tetraoctyl ammonium bromide.
  9. 根据权利要求6所述的双层三明治结构的化合物的制备方法，其中，所述步骤(2)反应温度为100-120℃；步骤(3)反应温度为100-120℃；所述步骤(4)反应温度为100-120℃。The method for preparing a double-layer sandwich structure according to claim 6, wherein the reaction temperature in the step (2) is 100-120 ° C; the reaction temperature in the step (3) is 100-120 ° C; the step (4) The reaction temperature is 100-120 °C.
  10. 根据权利要求6所述的双层三明治结构的化合物的制备方法，其中，The method for producing a double-layered sandwich structure according to claim 6, wherein
    所述邻二甲苯、碘、还原剂、液溴的摩尔比为0.2-0.3mol∶10-11mmol∶10-11mmol∶0.4-0.5mol； The molar ratio of the o-xylene, iodine, reducing agent, liquid bromine is 0.2-0.3 mol: 10-11 mmol: 10-11 mmol: 0.4-0.5 mol;
    所述4，5-二溴邻二甲苯、高锰酸钾的摩尔比为0.025-0.030mol∶0.1-0.15mol；The molar ratio of 4,5-dibromo-o-xylene and potassium permanganate is 0.025-0.030 mol: 0.1-0.15 mol;
    所述4，5-二溴邻苯二甲酸与1-溴丁烷、氢氧化钾的摩尔比为0.01-0.015mol∶0.01-0.015mol∶0.02-0.025mol；The molar ratio of the 4,5-dibromophthalic acid to 1-bromobutane and potassium hydroxide is 0.01-0.015 mol: 0.01-0.015 mol: 0.02-0.025 mol;
    所述4，5-二溴邻苯二甲酸丁酯与氰化亚铜的摩尔比为0.01-0.015mol∶0.02-0.025mol。The molar ratio of butyl 4,5-dibromophthalate to cuprous cyanide is from 0.01 to 0.015 mol: 0.02 to 0.025 mol.
  11. 一种有机场效应晶体管，其中，包括半导体材料层，所述半导体材料层由权利要求2所述的双层三明治结构的化合物构成。An organic field effect transistor comprising a layer of a semiconductor material, the layer of semiconductor material being composed of a compound of the double layer sandwich structure of claim 2.
  12. 根据权利要求11所述的有机场效应晶体管，其中，所述半导体材料层的电子迁移率为1.0-1.5cm2/(V·s)。The organic field effect transistor according to claim 11, wherein the semiconductor material layer has an electron mobility of 1.0 to 1.5 cm 2 /(V·s).
  13. 根据权利要求11所述的有机场效应晶体管，还包括：衬底、栅极层、栅极绝缘层、源漏极；其中，所述栅极层位于所述衬底之上；所述栅极绝缘层位于所述栅极层之上；所述半导体材料层位于所述栅极绝缘层之上；所述源漏极位于所述半导体材料层之上。The organic field effect transistor according to claim 11, further comprising: a substrate, a gate layer, a gate insulating layer, a source and a drain; wherein the gate layer is over the substrate; the gate An insulating layer is over the gate layer; the semiconductor material layer is over the gate insulating layer; and the source drain is over the semiconductor material layer.
  14. 一种权利要求11-13任一项所述的有机场效应晶体管的制备方法，包括以下步骤：A method of fabricating an organic field effect transistor according to any of claims 11-13, comprising the steps of:
    在衬底上制备栅极层；Preparing a gate layer on the substrate;
    在栅极层上制备栅极绝缘层；Preparing a gate insulating layer on the gate layer;
    在栅极绝缘层上制备半导体材料层；Preparing a layer of semiconductor material on the gate insulating layer;
    在半导体材料层上同时制备源漏极。A source drain is simultaneously fabricated on the layer of semiconductor material.
  15. 根据权利要求14所述的制备方法，其中，通过相转移方法形成所述半导体材料层。The production method according to claim 14, wherein the semiconductor material layer is formed by a phase transfer method.
  16. 一种包括权利要求11-13任一项所述的有机场效应晶体管的显示装置。 A display device comprising the organic field effect transistor of any of claims 11-13.
PCT/CN2017/115273 2017-05-19 2017-12-08 Polyphthalocyanine compound, compound of double-layer sandwiched structure and preparation method therefor, organic field-effect transistor and preparation method therefor, and display device WO2018209927A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710356744.0 2017-05-19
CN201710356744.0A CN107033152A (en) 2017-05-19 2017-05-19 A kind of poly phthalocyanine compound, organic field effect tube and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2018209927A1 true WO2018209927A1 (en) 2018-11-22

Family

ID=59538922

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/115273 WO2018209927A1 (en) 2017-05-19 2017-12-08 Polyphthalocyanine compound, compound of double-layer sandwiched structure and preparation method therefor, organic field-effect transistor and preparation method therefor, and display device

Country Status (2)

Country Link
CN (1) CN107033152A (en)
WO (1) WO2018209927A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107033152A (en) * 2017-05-19 2017-08-11 京东方科技集团股份有限公司 A kind of poly phthalocyanine compound, organic field effect tube and preparation method thereof
CN112159519B (en) * 2020-09-24 2021-07-06 中国科学院长春光学精密机械与物理研究所 Porous poly-phthalocyanine laser protection material with carbon bridging and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6461289A (en) * 1987-09-02 1989-03-08 Toyo Ink Mfg Co Optical recording medium
CN107033152A (en) * 2017-05-19 2017-08-11 京东方科技集团股份有限公司 A kind of poly phthalocyanine compound, organic field effect tube and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5722579B2 (en) * 2010-09-14 2015-05-20 山本化成株式会社 Ditetraazaporphyrin-based compound and dye-sensitized solar cell using the compound
CN105732646A (en) * 2016-01-29 2016-07-06 济宁学院 Sandwiched phthalocyanine rare-earth complex with two-photo absorption property and preparation method thereof
CN105541850B (en) * 2016-03-02 2018-05-15 京东方科技集团股份有限公司 A kind of phthalocyanine-like compound and its synthetic method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6461289A (en) * 1987-09-02 1989-03-08 Toyo Ink Mfg Co Optical recording medium
CN107033152A (en) * 2017-05-19 2017-08-11 京东方科技集团股份有限公司 A kind of poly phthalocyanine compound, organic field effect tube and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LV , WEI.: "Optically Active Homoleptic Bis(phthalocyaninato) Rare Earth Double-Decker Complexes Bearing Peripheral Chiral Menthol Moieties: Effect of pi - pi Interaction on the Chiral Information Transfer at the Molecular Level", INORGANIC CHEMISTRY, vol. 49, no. 14, 14 June 2010 (2010-06-14), pages 6628 - 6635, XP055424908 *
MORITA, TAKAUMI.: "Controlling the Dipole-Dipole Interactions between Terbium(III) Phthalocyaninato Triple-Decker Moieties through Spatial Control Using a Fused Phthalocyaninato Ligand", INORGANIC CHEMISTRY, vol. 52, no. 23, 13 November 2013 (2013-11-13), pages 13555 - 61, XP055612302 *
PUSHKAREV, VICTOR E.: "Preparation of nanosized sandwich-type structures based on planar binuclear phthalocyanines", MENDELEEV COMMUNICATIONS, vol. 19, no. 1, 31 December 2009 (2009-12-31), pages 24 - 26, XP025947609 *
WEI, WEI ET AL.: "Synthesis of Copper Carbonic Acid Phthalocyanine and Investigation on Its Optical and Electrical Properties, Journal of Function material", JOURNAL OF FUNCTION MATERIAL, vol. 29, no. 5, 31 December 1998 (1998-12-31), pages 486 - 488 *

Also Published As

Publication number Publication date
CN107033152A (en) 2017-08-11

Similar Documents

Publication Publication Date Title
Zhu et al. Efficient solution-processed nondoped deep-blue organic light-emitting diodes based on fluorene-bridged anthracene derivatives appended with charge transport moieties
TWI632148B (en) Compound and electronic device made of same
US11807616B2 (en) Organic compound, and electronic element and electronic device using same
WO2018108034A1 (en) Organic light-emitting device having double main-body structure
CN101960637A (en) Organic electroluminescent device
CN101679438A (en) Compound for organic electroluminescent device and organic electroluminescent device
JP2007084828A (en) Organic light-emitting compound and organic light-emitting element comprising the same
CN102356054A (en) Novel chrysene compound and organic light-emitting device having the compound
CN109796435A (en) Organic photoelectrical material and organic electroluminescence device including the organic material
CN113402561B (en) High-color-purity platinum (II) complex luminescent material based on spirofluorene structure and application thereof
TW200938543A (en) Compound having substituted pyridyl group and pyridoindole ring structure linked through phenylene group, and organic electroluminescent device
WO2018209927A1 (en) Polyphthalocyanine compound, compound of double-layer sandwiched structure and preparation method therefor, organic field-effect transistor and preparation method therefor, and display device
CN116283909B (en) Organic electronic transmission material and preparation method and application thereof
CN107312013B (en) General formula compound and application of organic electroluminescence
Yu et al. Fluorenone-based thermally activated delayed fluorescence materials for orange-red emission
WO2012103776A1 (en) Naphthacene-5,6:11,12-tetracarboxylic acid diimide compound and preparation method therefor
US20170256725A1 (en) Phthalocyanine compound and synthesis method and use thereof
CN102639473B (en) Novel benzo [c] phenanthrene compound and the organic luminescent device containing this compound
JP2018039777A (en) Peri-xanthenoxanthene bisimide compound, method for producing the same, organic el element, and organic thin film solar cell
WO2023005191A1 (en) Nitrogen-containing compound, and organic electroluminescent device and electronic apparatus containing same
US11479716B2 (en) Light-modulating material, light-modulating film, and light-modulating laminate
TW201144308A (en) Organic semiconductor material containing perylenetetracarboxylic acid diimide compound, and organic semiconductor element
JP2022020601A (en) Novel organic electroluminescent material, and element of the same
CN116143789A (en) Blue fluorescent doped compound, preparation method and application thereof
TW202104183A (en) Photoelectric conversion device including organic thin film made of compound having indenocarbazole ring

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: 17910121

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17910121

Country of ref document: EP

Kind code of ref document: A1