WO2017212961A1 - Polymère contenant du bore et son utilisation - Google Patents

Polymère contenant du bore et son utilisation Download PDF

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Publication number
WO2017212961A1
WO2017212961A1 PCT/JP2017/019845 JP2017019845W WO2017212961A1 WO 2017212961 A1 WO2017212961 A1 WO 2017212961A1 JP 2017019845 W JP2017019845 W JP 2017019845W WO 2017212961 A1 WO2017212961 A1 WO 2017212961A1
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boron
containing polymer
polymer compound
nitrogen
ring
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PCT/JP2017/019845
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Japanese (ja)
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武士 大前
英樹 羽田
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綜研化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions

Definitions

  • the present invention relates to a boron-containing polymer compound and its use.
  • the polymer organic semiconductor has an advantage that an excellent film quality can be easily obtained upon application and the device characteristics are easily stabilized. It is known that in order to make the high molecular organic semiconductor more mobile, it is desirable that a unit structure having a large ⁇ -conjugated area is introduced and that the high molecular weight semiconductor be a higher molecular weight body.
  • Non-Patent Document 1 it is disclosed in Non-Patent Document 1 that the LUMO / HOMO level is deepened by introducing a boron-nitrogen coordination bond structure, and it is disclosed in Patent Document 1 that the organic semiconductor performance can be improved. ing.
  • a polymer organic semiconductor having a unit having a large ⁇ -conjugated area has a problem in handling in the coating process because its solubility is lowered when the molecular weight is increased and the stability in the solution is deteriorated accordingly.
  • the molecular arrangement has a great influence on the properties, so unless the chain-like substituents are placed at appropriate positions in the structure, the arrangement and arrangement of the molecules in the organic semiconductor film after drying is not appropriate. Disappear.
  • the molecular arrangement since the molecular arrangement also has a great influence on mobility, even if solubility is improved, it does not necessarily lead to further improvement in mobility. Therefore, it is difficult to achieve both solubility and mobility.
  • Patent Document 1 only provides a dimer structure.
  • Non-Patent Document 1 although polymerization was successful, the side chain was not appropriate and the ⁇ -conjugated area of the unit structure was small, so that sufficient semiconductor characteristics were not obtained.
  • the present invention has been made in view of such circumstances, and the LUMO / HOMO level is deep, and the unit structure has a wide ⁇ -conjugated plane, and can have a high molecular weight due to high solubility.
  • the present invention provides a boron-containing polymer compound for an organic semiconductor that can be suitably used for applications such as an organic thin film solar cell, organic EL, organic transistor, organic memory, electronic paper, thermoelectric conversion element, and optical sensor.
  • the structure W is represented by the following formula (1) including a structure W having at least two boron-nitrogen coordination bonds and a structure ⁇ that is a divalent substituent having a conjugated structure.
  • a high molecular compound containing a structural unit m represents 0 or 1;
  • the structure W is represented by the following formula (2) or (3): Rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure, Rings Y 1 and Y 2 are 5-membered rings having the boron-nitrogen coordination bond, any one of ⁇ 1 and ⁇ 3 is a nitrogen atom, one of ⁇ 2 and ⁇ 4 is a nitrogen atom, R 1 to R 4 may be the same or different, may be bonded to boron via another skeleton, and may have at least a linear or branched alkyl group having 10 to 40 carbon atoms that may be substituted.
  • the present inventor has studied a boron-containing polymer compound having excellent mobility. As a result, at least two boron-nitrogen coordination bonds are introduced into a unit structure having a wide conjugate plane, and an alkyl group is contained on the boron atom. It has been found that by introducing a substituent, a polymer compound having a deep LUMO / HOMO level and a high molecular weight contributing to improvement in mobility and having a wide conjugated plane in the unit structure can be provided.
  • the polymer compound can be used as an organic semiconductor.
  • the weight average amount is 2 ⁇ 10 4 to 1 ⁇ 10 6 .
  • W is bonded to adjacent W or ⁇ via a 5-membered ring in W.
  • the organic semiconductor containing said boron containing high molecular compound is provided.
  • the boron-containing polymer compound according to an embodiment of the present invention can be used as an organic semiconductor, and is a polymer compound represented by the following formula (1).
  • the unit structure includes a structure ⁇ which is a divalent substituent having a conjugated structure in addition to W. That is, m is 0 or 1, preferably 1. This is because it is assumed that the structure containing ⁇ has both structures serving as a donor and an acceptor in the unit structure, the interaction between the molecular chains tends to be strong, and the mobility is improved. .
  • the unit structure represented by W in the above formula (1) is a structure represented by the following formula (2) or (3) having at least two boron-nitrogen coordination bonds.
  • the electronic bias between boron and nitrogen is thought to strengthen the interaction between the molecular chains.
  • the electronic bias becomes larger and the molecule It is considered that the mobility is improved by the stronger interaction between the chains.
  • W is composed of rings X 1 , X 2 , Y 1 , Y 2 , and Z, and rings X 1 , X 2 , and Z represent a single ring or a condensed ring having a conjugated structure.
  • ⁇ 1 and ⁇ 2 may be the same as or different from each other, and are preferably the same. Further, ⁇ 3 and ⁇ 4 may be the same or different from each other, preferably the same. When they are the same, there is an advantage that the synthesis is easier than when they are different, and since the target property is high, the arrangement and arrangement of the molecular chains are likely to be appropriate, and the mobility tends to be high.
  • One of ⁇ 1 and ⁇ 3 is a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in ring Y 1 , and the other is not particularly limited, but is, for example, a carbon atom.
  • One of ⁇ 2 and ⁇ 4 is a nitrogen atom that forms a boron-nitrogen coordination bond with a boron atom in the ring Y 2 , and the other is not particularly limited, but is, for example, a carbon atom.
  • Rings X 1 and X 2 are monocyclic or condensed rings having a conjugated structure and may contain a nitrogen atom that forms a boron-nitrogen coordination bond.
  • Rings X 1 and X 2 may not contain a hetero atom, but are preferably a hetero ring containing a hetero atom.
  • the heterocyclic ring is, for example, pyrrole, furan, thiophene, selenophene, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine and the like, and these are condensed structures, more preferably containing a sulfur atom.
  • thiophene thienothiophene
  • benzothiophene benzodithiophene
  • thiazole thiazolothiazole and the like, more preferably thiophene or thiazole.
  • rings X 1 and X 2 contain a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in the rings Y 1 and Y 2
  • examples thereof include imidazole, pyrazole, thiazole, and pyridine.
  • Preferred are thiazole and pyridine, and more preferred are rings X 1 and X 2 containing a sulfur atom, for example, thiazole.
  • the monocyclic ring or condensed ring of the rings X 1 and X 2 may be substituted as long as the semiconductor properties are not impaired, and the substituent is not limited, but specifically, a linear, branched, or cyclic alkyl Group, alkoxy group, alkylthio group, sulfo group, hydroxy group, carboxy group, amino group, amide group, ester group, phenyl group, etc., and substituted with sulfo group, hydroxy group, carboxy group, amino group, halogen group It may be a linear or branched alkyl group, an alkoxyalkyl group, an alkylene oxide group, a phenyl group or the like, and may have a plurality of substituents.
  • W is bonded to adjacent W or ⁇ via a 5-membered ring or 6-membered ring in W, preferably bonded via a 5-membered ring. This is because in the case of a five-membered ring, there is little steric repulsion with the adjacent W or ⁇ , it is easy to form a continuous planar structure, and the mobility is considered to be improved.
  • Ring Z is a monocyclic or condensed ring having a conjugated structure and may contain a nitrogen atom forming a boron-nitrogen coordination bond. Ring Z may or may not contain heteroatoms, such as benzene, naphthalene, anthracene, pyrazine, thienothiophene, benzodithiophene, thiazolothiazole, benzobisthiazole, and the like.
  • ring Z contains a nitrogen atom that forms a boron-nitrogen coordination bond with the boron atom in rings Y 1 and Y 2
  • ring Z is, for example, pyrazine, thiazolothiazole, naphthyridine, benzobisthiazole, pyrazino Bisthiazole and the like.
  • Preferred is thiazolothiazole or benzobisthiazole.
  • Rings Y 1 and Y 2 are 5-membered rings having a boron-nitrogen coordination bond.
  • the boron atoms forming the boron-nitrogen coordination bond in the rings Y 1 and Y 2 have alkyl group-containing substituents R 1 to R 4 which may be the same or different.
  • the two boron atoms may be located on different sides as in the above formula (2), or may be located on the same side as in the above formula (3). You may do it.
  • the appropriate position differs depending on the substituents introduced into each ring, so that the position is not limited to any one. In any case, it has two boron-nitrogen coordination bonds, and the same effect is considered to be achieved. . However, from the viewpoint of ease of synthesis, it is considered that it is often advantageous to be located on different sides as in the above formula (2).
  • R 1 to R 4 may be the same or different, and are monovalent substituents having at least one linear or branched alkyl group having 10 to 40 carbon atoms which may be substituted.
  • the alkyl group may be directly bonded to the boron atom or may be bonded via another skeleton.
  • the number of carbon atoms of the alkyl group is preferably 12 or more, more preferably 14 or more.
  • the number of carbon atoms of the alkyl group is preferably 30 or less, more preferably 25 or less.
  • the said carbon number is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 32, 33, 34, 35, 36, 37, 38, 39, 40, and may be within a range between any two of the numerical values exemplified here.
  • the solubility in a solvent mainly means the solubility in a halogen solvent, an aromatic solvent, etc., specifically, chloroform, chlorobenzene, dichlorobenzene, toluene, mesitylene, anisole, tetralin, cyclohexyl. It means solubility in benzene.
  • Examples of the substituent that may substitute the alkyl group in R 1 to R 4 include a sulfo group, a hydroxy group, an alkoxy group, an alkylthio group, a carboxy group, an ester group, an amino group, an amide group, a halogen group, A phenyl group and the like;
  • examples of the other skeleton include heteroatoms such as oxygen, nitrogen, and sulfur, a benzene ring, a naphthalene ring, an azulene ring, and an anthracene ring.
  • Aromatic ring such as phenanthrene ring, pyrene ring, chrysene ring, tetracene ring, triphenylene ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyranthrene ring, pyridine , Imidazole, thiophene and the like, and a plurality of them may be combined. Further, an alkyl chain having 1 to 6 carbon atoms may be interposed between another skeleton and boron.
  • R 1 to R 4 are preferably such that a linear or branched alkyl group is directly bonded to boron, or bonded to boron through oxygen or sulfur and / or a phenyl group, benzyl group, phenethyl group, Preferably, a linear or branched alkyl group is directly bonded to boron, and more preferably, a linear alkyl group is directly bonded to boron.
  • Synthesis of boron-containing compounds can be synthesized by various methods.
  • W represented by the above formula (2) can be synthesized by the following reaction formula (5) or It can be synthesized by the route of reaction formula (6).
  • R 1 to R 4 in Formula (5) are the same as in Chemical Formula (2), and R 5 represents halogen.
  • R 1 to R 4 in formula (6) are the same as in chemical formula (2), and R 5 represents halogen.
  • the reaction vessel is not particularly limited, and glass, Teflon (registered trademark), or the like can be used.
  • the reaction solvent is not particularly limited, and may be any solvent in which the reaction proceeds, and examples thereof include tetrahydrofuran, tert-butyl methyl ether, acetonitrile, phenol, benzene, toluene and the like.
  • the inert gas includes nitrogen, argon, helium and the like.
  • the stirring method is not particularly limited, but a stirrer or a shaker may be used.
  • the purification step may be any step that can isolate the target product, and known methods can be used. Specific examples include separation extraction, isolation by column chromatography, and recrystallization. Isolation and purification may be performed in combination.
  • the base is not particularly limited, and may be any base that allows BN crosslinking reaction to proceed.
  • Examples of the base include alkyl lithium, and specific examples include methyl lithium, n-butyl lithium, sec-butyl lithium. Tert-butyllithium and the like.
  • the cooling temperature when adding the base is ⁇ 100 ° C. to ⁇ 50 ° C., preferably ⁇ 90 ° C. to ⁇ 70 ° C. Specifically, this temperature is, for example, ⁇ 100, ⁇ 90, ⁇ 80, ⁇ 70, ⁇ 60, or 50 ° C., and may be within a range between any two of the numerical values exemplified here.
  • the stirring for several hours after the addition of the base is not particularly limited, but is, for example, 1 to 6 hours, and preferably 1 to 4 hours. Specifically, this time is, for example, 1, 2, 3, 4, 5 or 6 hours, and may be within a range between any two of the numerical values exemplified here.
  • the substituted borane is not particularly limited as long as it is a borane having substituents R 1 to R 4 that can be used in the present invention and in which a BN crosslinking reaction proceeds.
  • the stirring time after adding the borane is not particularly limited, but is, for example, 1 to 24 hours, preferably 8 to 24 hours. Specifically, this time is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15, 18, 21 or 24 hours. It may be within the range between any two.
  • the stirring temperature after adding the borane is ⁇ 78 ° C. to 25 ° C., preferably 0 ° C. to 25 ° C. Specifically, this temperature is, for example, 0, 5, 10, 15, 20, or 25 ° C., and may be within a range between any two of the numerical values exemplified here.
  • boron tribromide is used as borane
  • BBr 2 is converted into a crosslinked product
  • a Grignard reaction is performed using a Grignard reagent such as alkylmagnesium bromide to introduce substituents R 1 to R 4 . May be.
  • ⁇ in the above formula (1) represents a divalent substituent having a conjugated structure, and is preferably represented by the following formula (7).
  • the group is unsubstituted or substituted with one or more groups R 6 and a and b may be the same or different and represent an integer of 0-2.
  • R 6 represents H, a halogen, a cyano group, or a linear or branched alkyl group having 1 to 40 carbon atoms, an alkoxy group, or an alkylthio group.
  • the site bonded to W is —CH ⁇ CH—, —C ⁇ C—, or a 5-membered ring. This is because in these cases, there is little steric repulsion with the bonded W, it is easy to form a continuous planar structure, and the mobility is considered to be improved.
  • the structure shown in the following formula (8) is exemplified, but not limited thereto.
  • the boron-containing polymer compound of the present invention may contain a copolymer containing the structure represented by the chemical formula (1) in the polymer compound, but in order to further strengthen the interaction between the molecular chains.
  • the weight average molecular weight (Mw) of the boron-containing polymer compound of the present invention is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as “GPC”), and is usually 2 ⁇ 10 4 to 2 ⁇ . 10 8 .
  • the weight average molecular weight of the polymer compound is preferably 2 ⁇ 10 4 to 1 ⁇ 10 6 , more preferably 3 ⁇ 10 4 to 5 ⁇ 10. 5 .
  • the method for polymerizing the boron-containing polymer compound including the above formula (1) is not particularly limited, but Suzuki coupling, Still coupling Ullmann reaction, Gracer reaction, Heck reaction, Negishi coupling, Sonogashira coupling, Kumada Coupling and the like can be used, and Suzuki coupling and Stille coupling are preferable in terms of ease of synthesis and few restrictions on the monomers that can be used.
  • W and / or ⁇ bonded with boronic acid or a boronic acid ester and halogenated W and / or ⁇ are used as raw materials in the presence of a palladium catalyst and a base. It is preferable to carry out the reaction in a reaction system in which the catalyst is not deactivated in an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently substituted with argon gas, nitrogen gas or the like.
  • W and / or ⁇ bonded with organotin is reacted with halogenated W and / or ⁇ in the presence of a palladium catalyst. It is preferable to carry out the reaction in a reaction system in which the catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas. For example, it is preferable to carry out in a system sufficiently substituted with argon gas, nitrogen gas or the like.
  • boron-containing polymer compound of the present invention is not limited, but it can be used as a p-type organic semiconductor, an n-type organic semiconductor, an ambipolar semiconductor, an organic thin film solar cell, organic EL, organic transistor, organic memory, electronic It can be suitably used for applications such as paper, thermoelectric conversion elements, and optical sensors.
  • the weight average molecular weight of the polymer compound (polymer) was determined by using a high-speed GPC device (manufactured by Tosoh Corporation, model HLC-8320GPC ECcoSEC), an ultraviolet absorption detector (manufactured by Tosoh Corporation, model UV-8320).
  • the measurement solvent was chloroform
  • the GPC column was TSKguardcolumn HHR-H ⁇ 1 + TSKgel GMHHR-H ⁇ 1 (both manufactured by Tosoh Corporation).
  • ⁇ Evaluation of solubility> The boron-containing polymer compound was mixed with chloroform at 0.5% by weight and stirred at 20 ° C. for 15 minutes. A sample that was completely dissolved was marked with ⁇ , and a sample that had undissolved was marked with ⁇ .
  • HOMO ionization potential
  • a solution prepared by dissolving a boron-containing polymer compound (P1) in chloroform at a concentration of 5 mg / g was dropped onto a conductive film of glass with a fluorine-doped tin oxide film, and dried at room temperature in the atmosphere as a measurement sample. The ionization potential was measured using an ionization potential measuring apparatus (PYS-201, manufactured by Sumitomo Heavy Industries, Ltd.).
  • the mobility was measured by evaluating a field effect transistor (TFT).
  • TFT field effect transistor
  • ZEOCOAT ES2110-10 manufactured by Nippon Zeon Co., Ltd.
  • spin coating 500 rpm / 3 sec. And 2000 rpm / 15 sec.
  • a glass substrate on which a Cr gate electrode having a thickness of 500 mm was formed was formed, and 90 ° C. for 2 min. After heating at 150 ° C. for 1 hr.
  • a gate insulating film was formed by heating at Next, a boron-containing polymer compound (P1) solution (0.5 wt%, chlorobenzene solvent) is applied onto the substrate by a spin coating method (1000 rpm, 60 sec.), And is heated at 80 ° C. for 30 minutes on a hot plate in nitrogen. .
  • An organic semiconductor thin film was formed by annealing.
  • gold was vacuum-deposited to a film thickness of 50 nm using a metal mask to form a source electrode and a drain electrode having a channel length of 50 ⁇ m, and a bottom gate / top contact type organic thin film transistor was manufactured.
  • the organic transistor fabricated as described above was measured for current-voltage (IV) characteristics in the atmosphere, and the charge mobility was determined from the saturation region.
  • reaction solution was returned to room temperature and stirred at room temperature for 1 hour. After concentration of the reaction solution, 0.39 g (0.24 mmol) of the boron-containing compound (A1-2) was obtained as a pale orange solid in a yield of 79% by column chromatography using a developing solvent chloroform.
  • Synthesis Example 2 Synthesis of boron-containing compounds A2 and A2-2 / Synthesis of boron-containing compound A2
  • dimesitylfluoroborane was used as a raw material instead of trihexadecylborane.
  • 0.463 g (0.543 mmol) was used as a yellow solid in 28% yield.
  • Example 1 Synthesis and Evaluation of Boron-Containing Polymer Compound (P1) 0.10 g (0.0624 mmol) of boron-containing compound (A1-2), 5,5′-dibromo-2, 2′-bithiophene (Tokyo Chemical Industry) 20.2 mg (0.0624 mmol), tris (dibenzylideneacetone) dipalladium 2.9 mg (5 mol%), tri (o-tolyl) phosphine 1.9 mg (10 mol%), Chlorobenzene (5 mL) was added, and the mixture was stirred for 8 hours under heating under reflux.
  • P1 Synthesis and Evaluation of Boron-Containing Polymer Compound (P1) 0.10 g (0.0624 mmol) of boron-containing compound (A1-2), 5,5′-dibromo-2, 2′-bithiophene (Tokyo Chemical Industry) 20.2 mg (0.0624 mmol), tris (dibenzylideneacetone
  • Example 2 Synthesis and evaluation of boron-containing polymer compound (P2)
  • P1 synthesis method of boron-containing polymer compound (P1)
  • 5,5'-dibromo-2,2'-bithiophene Tokyo Chemical Industry
  • 5,5 ′′ -dibromo-2,2 ′: 5 ′, 2 ′′ -terthiophene Tokyo Chemical Industry
  • 63 mg of a boron-containing polymer compound (P2) was obtained as a dark purple solid.
  • the evaluation results are shown in Table 1.
  • Example 3 Synthesis and evaluation of boron-containing polymer compound (P3)
  • P3 In the synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry) Using 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole, 52 mg of a boron-containing polymer compound (P3) was obtained as a blue solid.
  • the evaluation results are shown in Table 1.
  • Example 4 Synthesis and evaluation of boron-containing polymer compound (P4 )
  • P4 boron-containing polymer compound
  • P1 synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry)
  • 2,6-dibromodithieno [3,2-b: 2 ′, 3′-d] thiophene 58 mg of boron-containing compound (P4) was obtained as a dark purple solid.
  • the evaluation results are shown in Table 1.
  • Example 5 Synthesis and evaluation of boron-containing polymer compound (P5 )
  • P5 boron-containing polymer compound
  • P1 synthesis method of boron-containing polymer compound (P1), instead of 5,5'-dibromo-2,2'-bithiophene (Tokyo Chemical Industry)
  • a boron-containing polymer compound (P5) was obtained as a green solid.
  • Table 1 The evaluation results are shown in Table 1.
  • Compound B1 was prepared according to J.I. Mater. Chem. C, 2014, 2, 3457 and J.H. Mater. Chem. C, 2014, 2, 6376 were referred to and synthesized.
  • Comparative Example 2 Instead of the boron-containing polymer compound (P1) in Example 1, P3HT (manufactured by Soken Chemical Co., Ltd., Verazol HT, weight average molecular weight 47,000) was used, and the annealing conditions for transistor fabrication were 150 ° C. for 30 min. The evaluation was performed in the same manner except that it was changed to. The results are shown in Table 1.
  • P3HT manufactured by Soken Chemical Co., Ltd., Verazol HT, weight average molecular weight 47,000
  • Examples 1 to 5 all showed higher solubility in chloroform than the comparative examples.
  • semiconductor characteristics p-type semiconductor characteristics were exhibited, and a mobility of 10 ⁇ 4 cm 2 / Vs or higher and an on / off value of 10 4 or higher were exhibited.
  • Comparative Example 1 could not be polymerized, and Comparative Example 2 was undissolved in chloroform, and high solubility was not obtained.
  • semiconductor characteristics since the ionization potential is shallow, the atmospheric stability is low and the on / off value is low.

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Abstract

L'invention concerne un polymère contenant du bore pour semi-conducteurs organiques qui présente des potentiels LUMO/HOMO profonds et qui contient une structure unitaire ayant un grand plan π-conjugué et, malgré cela, permet d'obtenir un poids moléculaire élevé en raison de la solubilité élevée. Selon certains modes de réalisation, la présente invention concerne un polymère contenant du bore contenant un motif structural représenté par la formule (1), qui comprend une structure W ayant au moins deux liaisons de coordination bore-azote et une structure π qui est un substituant divalent ayant une structure conjuguée. Dans la formule (1), m est 0 ou 1, et la structure W est représentée par la formule (2) ou (3). Dans les formules (2) et (3), les cycles X1, X2, et Z représentent chacun un monocycle ou un cycle condensé ayant une structure conjuguée, les cycles Y1 et Y2 représentent chacun un cycle à cinq chaînons ayant la liaison de coordination bore-azote, soit α1 soit α3 représente un atome d'azote, soit α2 soit α4 représente un atome d'azote, et R1 à R4 peuvent être identiques ou différents et représentent chacun un substituant monovalent qui comprend au moins un groupe alkyle linéaire ou ramifié en C10-40, éventuellement substitué, et qui peut être lié à l'atome de bore par l'intermédiaire d'un autre squelette.
PCT/JP2017/019845 2016-06-08 2017-05-29 Polymère contenant du bore et son utilisation WO2017212961A1 (fr)

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CN112707926A (zh) * 2020-12-29 2021-04-27 华南理工大学 一种红色电致发光化合物及其制备方法与应用
CN114685763A (zh) * 2022-05-06 2022-07-01 青岛大学 一种基于三芳基硼的共轭高分子及其制备方法和应用

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CN114685763B (zh) * 2022-05-06 2023-08-22 青岛大学 一种基于三芳基硼的共轭高分子及其制备方法和应用

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