CN104956508A - Organic semiconductor material for solution process and organic semiconductor device - Google Patents

Organic semiconductor material for solution process and organic semiconductor device Download PDF

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Publication number
CN104956508A
CN104956508A CN201480005535.6A CN201480005535A CN104956508A CN 104956508 A CN104956508 A CN 104956508A CN 201480005535 A CN201480005535 A CN 201480005535A CN 104956508 A CN104956508 A CN 104956508A
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dntt
compound
solution process
organic semiconductor
branched alkyl
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CN104956508B (en
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泷宫和男
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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 a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions

Abstract

In the present invention, an organic semiconductor material for a solution process is represented by formula (1). In formula (1), each of (Y1) and (Y2) individually represents a chalcogen atom, one of R1 and R2 represents a branched alkyl, and the other represents hydrogen.

Description

Solution process organic semiconducting materials and organic semiconductor equipment
Technical field
The present invention relates to solution process organic semiconducting materials and organic semiconductor equipment.
Background technology
Make use of the organic semi-conductor membrane equipments such as organic FET equipment, organic el device in recent years attract attention and be practical.As organic semiconducting materials, study, develop various compound, such as dinaphtho thienothiophene (being DNTT below) presents excellent charge mobility and attracts attention (patent documentation 1,2) as the material demonstrating organic semiconducting materials characteristic.
Prior art document
Technical literature
Patent documentation 1: No. 2008/050726th, International Publication
Patent documentation 2: No. 2010/098372nd, International Publication
Summary of the invention
Invent problem to be solved
DNTT derivative disclosed in patent documentation 1 and 2 lacks dissolubility in organic solvent.Therefore, there is the problem that can not manufacture organic semiconductor layer based on solution process such as rubbing methods.
The present invention completes in view of above-mentioned item, object is, provides the excellence of solubility in organic solvent, can manufacture the solution process organic semiconducting materials and organic semiconductor equipment that utilize in organic semiconductor layer based on solution process such as rubbing methods.
The means of technical solution problem
The feature of the solution process organic semiconducting materials involved by the first viewpoint of the present invention is, contained 1 compound represented.
[chemical formula 1]
(in formula 1, Y 1and Y 2be separately chalcogen, R 1and R 2one is branched alkyl, another is hydrogen.)
In addition, the main chain of preferred described branched alkyl is more than C3.
In addition, the main chain of preferred described branched alkyl is more than C6.
In addition, the side chain of preferred described branched alkyl is more than C2.
In addition, the side chain of preferred described branched alkyl is bonded to the carbon of main chain more than 2.
In addition, the side chain of preferred described branched alkyl is bonded to the carbon of main chain more than 3.
In addition, preferred described Y 1and Y 2for sulphur atom or selenium atom.
The feature of the organic semiconductor equipment involved by the second viewpoint of the present invention is, comprises the solution process organic semiconducting materials involved by the first viewpoint of the present invention.
Invention effect
Solution process organic semiconducting materials involved in the present invention solubility is in organic solvent excellent.Therefore, organic semiconductor layer can be manufactured based on solution process such as rubbing methods.
Accompanying drawing explanation
[Fig. 1] is the chart representing XRD (Fig. 1 (C)) outside the absorption spectrum (Fig. 1 (A)) of 2,9-EH-DNTT film, photoelectron spectroscopy (Fig. 1 (B)), face.
[Fig. 2] is the chart representing XRD (Fig. 2 (C)) outside the absorption spectrum (Fig. 2 (A)) of 2-2-EH-DNTT film, photoelectron spectroscopy (Fig. 2 (B)), face.
[Fig. 3] represents the transmission characteristic (Fig. 3 (A)) of 2-2-EH-DNTT transistor unit, the chart of output characteristic (Fig. 3 (B)).
[Fig. 4] represents the transmission characteristic (Fig. 4 (A)) of ODTS treatment element, the chart of output characteristic (Fig. 4 (B)).
Embodiment
(solution process organic semiconducting materials)
The compound that solution process involved by present embodiment represents with organic semiconducting materials contained 1.
[chemical formula 2]
In formula 1, Y 1and Y 2be separately chalcogen (oxygen, sulphur, selenium, tellurium).Y 1and Y 2be preferably sulphur atom, selenium atom.In addition, Y 1and Y 2preferably identical.
In addition, in formula 1, R 1and R 2one be branched alkyl, another is hydrogen.The main chain of branched alkyl is preferably more than C3, is more preferably more than C6.In addition, the side chain of branched alkyl is more than C1, is more preferably more than C2.In addition, side chain is preferably bonded to the carbon of main chain more than 2, is more preferably bonded to the carbon of main chain more than 3.Side chain is away from condensed ring, and intermolecular interaction increases thus, and carrier mobility improves.In addition, branched alkyl is preferably saturated branched alkyl.
Although think that the carbon number of branched alkyl is more, dissolubility in organic solvent more increases, but in embodiment described later, the carbon number of main chain is that C6 demonstrates very good dissolubility, in addition, if branched alkyl is long, then piling up property when likely manufacturing organic semiconductor layer is deteriorated, thus cause characteristic of semiconductor to reduce, think that the carbon number of main chain is preferably below C10 thus.
Should illustrate, in formula 1, R 1and R 2in any one be straight chained alkyl, another is when being the compound of hydrogen, this compound lacks dissolubility in organic solvent.Therefore, the solution process such as rubbing method are unsuitable for utilizing to manufacture organic semiconductor layer.
In addition, in formula 1, R 1and R 2when the two is the compound of branched alkyl, favorable solubility in organic solvent, on the other hand, the organic semiconductor layer using this compound to be manufactured by rubbing method etc. does not show transistor characteristic, thus can not be used as the organic semiconducting materials of solution process.
The compound that above-mentioned formula 1 represents can synthesize with reference to known method disclosed in patent documentation 1, patent documentation 2 etc.Such as can synthesize in the following manner, but be not limited to this.
As represented in following reaction scheme 1, first, 6-alkyl-2-methoxynaphthalene or 7-alkyl-2-methoxynaphthalene (compound (B)) is synthesized by 6-halo-2-methoxynaphthalene or 7-halo-2-methoxynaphthalene (compound (A)).Can carry out reacting synthesizing with the Grignard reagent of the alkyl bromination magnesium etc. with branched alkyl by making compound (A).
Then, compound (C) is synthesized.The synthesis of compound (C) can be carried out reacting synthesizing with dimethyl sulphide etc. by making compound (B).
Then, compound (D) is synthesized.Can carry out reacting synthesizing with Boron tribromide etc. by making compound (C).
Then, compound (E) is synthesized.Can be undertaken reacting synthesizing by making compound (D) and trifluoromethanesulfonic acid.
Should illustrate and should illustrate, in compound (A), one of X1 and X2 is halogen atom, and another is hydrogen.In addition, in compound (B) ~ (E), R 1and R 2one be branched alkyl, another is hydrogen.
[chemical formula 3]
Reaction scheme 1
In addition, as represented in following reaction scheme 2, by 2-methoxynaphthalene (compound (F)), synthesize compound (I) via compound (G), compound (H).The synthesis of compound (G), compound (H) and compound (I) can be synthesized respectively in the same manner as the synthesis of above-claimed cpd (C), compound (D), compound (E).
[chemical formula 4]
Reaction scheme 2
Then, as represented in following reaction scheme 3, by compound (J) is synthesized in above-mentioned two compounds (compound (E), (I)) condensation.Further by the compound (K) compound (J) closed loop synthesized as target compound.Can by carrying out ring-closure reaction to synthesize with iodine in chloroform.Should illustrate and should illustrate, in compound (E), (J), (K), R 1and R 2one be branched alkyl, another is hydrogen.
[chemical formula 5]
Reaction scheme 3
In above-mentioned synthetic method, as an example, to Y in formula 1 1and Y 2for the synthesis example of the compound of sulphur atom is illustrated, can by replacing above-mentioned dimethyl sulphide to carry out Y in synthesis type 1 with dimethyl selenide, dimethyl ether 1and Y 2for the compound of selenium atom, oxygen atom.
The compound that solution process represents with organic semiconducting materials contained 1, the compound dissolubility in organic solvent that formula 1 represents is high.So, the solution process organic semiconducting materials of contained 1 compound represented can be used, utilize the solution process such as the rubbing methods such as spin-coating method, ink-jet method, screen painting method, lithography, micro-contact-printing to manufacture organic semiconductor layer.In solution process, vacuum, the condition of high temperature can be formed as vapour deposition method, realize large-area organic semiconductor layer with low cost.
As the organic solvent that solution process organic semiconducting materials is solvable, such as chloroform can be enumerated, carrene, the halogenated hydrocarbons series solvents such as dichloroethanes, methyl alcohol, ethanol, propyl alcohol, the alcohol series solvents such as butanols, octafluoropentanol, the fluorinated alcohols series solvents such as five fluorine propyl alcohol, ethyl acetate, butyl acetate, ethyl benzoate, the ester series solvents such as diethyl carbonate, toluene, hexyl benzene, dimethylbenzene, mesitylene, chlorobenzene, dichloro-benzenes, methoxybenzene, chloronaphthalene, methyl naphthalene, the aromatic hydrocarbon series solvents such as naphthane, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, the ketone series solvents such as cyclohexane, dimethyl formamide, dimethylacetylamide, the acid amides series solvents such as 1-METHYLPYRROLIDONE, oxolane, diisobutyl ether, the ether series solvents such as diphenyl ether, octane, decane, the hydrocarbon system solvents etc. such as cyclohexane.
In addition, for solution process organic semiconducting materials, except the compound that formula 1 represents, in order to improve the masking, doping etc. of organic semiconductor layer, can additive package, other semi-conducting material.
(organic semiconductor equipment)
Organic semiconductor equipment involved by present embodiment is the equipment applying above-mentioned solution process organic semiconducting materials.As organic semiconductor equipment, such as, can enumerate the field-effect transistor with organic semiconductor layer, the luminaire etc. with organic carrier transport layer and/or luminescent layer.Organic semiconductor equipment can utilize known various manufacture method to manufacture, and is not particularly limited.
Embodiment
As following described, periodically synthesize 2-(2-ethylhexyl) dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being 2-2-EH-DNTT below).
(synthesis of 6-(2-ethylhexyl)-2-methoxynaphthalene (being compound 1 below))
[chemical formula 6]
Add in oxolane (being THF below) (30mL) and have the bromo-2-methoxynaphthalene (7.14g, 30mmol) of 6-and Ni (dppp) Cl 2in the solution of (813mg, 1.5mmol), at room temperature add the THF solution of 2-ethylhexyl magnesium bromide, reflux 24 hours.Should illustrate, for the THF solution of 2-ethylhexyl magnesium bromide, bromo-for 1-2-ethylhexyl bromine (9.0mL, 45mmol) and magnesium (1.17g, 48mmol) be added in THF (7.5mL) and prepares.
After cooling, with water (30mL) dilution mixture thing, the solid filtering of unreacted magnesium and generation is removed.
With ether (15mL × 3) extraction filtered fluid.The compound obtained with salt solution (30mL × 3) washing extraction, uses dried over mgso.By its drying under reduced pressure, obtain flaxen oily compound 1 (5.4g, yield 50%).
Below the determination data of the compound 1 obtained is shown in.
1H NMR(500MHz,CDCl 3)δ0.87(t,J＝7.1Hz,3H),0.92(t,J＝7.5Hz,3H)1.221.37(m,8H),1.67(sept,J＝6.2Hz,2H),2.68(t,J＝6.6Hz,2H),3.93(s,3H),7.13(s,1H),7.16(dd,J＝8.8,2.6Hz,1H),7.31(dd,J＝8.6,1.3Hz,1H),7.53(s,1H),7.67(d,J＝8.6Hz,1H),7.69(d,J＝8.6Hz,1H),
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,23.4,23.6,25.8,29.2,32.7,40.5,41.4,55.6,106.0,118.9,126.8,127.5,128.9,129.3,129.4,133.2,137.5,157.4；
EIMS(70eV)m/z＝270(M +).HRMS(APCI)Calcd for C 19H 26O:270.19782；Found:270.19791.
(synthesis of 6-(2-ethylhexyl)-3-methylsulfany-2-methoxynaphthalene (being compound 2 below))
[chemical formula 7]
Add in THF (2.7mL) in the solution having compound 1 (730mg, 2.7mmol), at-78 DEG C, add the 1.59M hexane solution of n-BuLi (2.0mL, 3.2mmol).
After this mixture is at room temperature stirred 1 hour, at-78 DEG C, add dimethyl disulfide (0.36mL, 4.1mmol).Then, the mixture of generation is at room temperature stirred 18 hours.
Mixture is injected into saturated aqueous ammonium chloride (5mL), extracts with ether (5mL × 3).
Compound salt solution (5mL × 3) washing extraction obtained, uses dried over mgso.It is under reduced pressure concentrated, obtains the oily compound 2 (853mg, quant.) of almost gilvous.
Should illustrate, sample for analysis is by silica gel column chromatography (developing solvent: dichloromethane/hexane (v/v=1:1, R f=0.35)) separation and purification uses.
Below the determination data of the compound 2 obtained is shown in.
1H NMR(500MHz,CDCl 3)δ0.87(t,J＝7.0Hz,3H),0.89(t,J＝7.2Hz,3H)1.25-1.36(m,8H),1.64(sept,J＝6.6Hz,2H),2.55(s,1H),2.66(t,J＝6.5Hz,2H),3.99(s,3H),7.07(s,1H),7.22(d,J＝8.3Hz,1H),7.42(s,1H)7.47(s,1H),7.62(d,J＝8.3Hz,1H),
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,14.9,23.4,25.8,29.3,32.8,40.5,41.5,56.2,105.0,123.2,126.3,126.5,127.9,129.6,129.7,130.7,128.0,154.3；
EIMS(70eV)m/z＝316(M +).HRMS(APCI)Calcd for C 20H 28OS:316.18554；Found:316.18576.
(synthesis of 6-(2-ethylhexyl)-3-methylsulfany-2 hydroxy naphthalene (being compound 3 below))
[chemical formula 8]
Add in carrene (5mL) in the solution having compound 2 (681mg, 2.2mmol), at-78 DEG C, drip the dichloromethane solution (about 2M, 1.1mL, 4.3mmol) of Boron tribromide.
After mixture is at room temperature stirred 5 hours, join (about 2g) in ice.
Mixture carrene (5mL × 3) extraction that purifying is obtained.
By salt solution (5mL × 3) washing organic phase, by dried over mgso, under reduced pressure concentrate.
By residue silica gel column chromatography (developing solvent: dichloromethane/hexane (v/v=1/1, R f=0.28)) carry out separation and purification, obtain yellow oily compound 3 (650mg, quant.).
Below the determination data of the compound 3 obtained is shown in.
1H NMR(500MHz,CDCl 3)δ0.88(t,J＝6.9Hz,3H),0.91(t,J＝7.3Hz,3H)1.25-1.36(m,8H),1.66(sept,J＝6.0Hz,2H),2.43(s,1H),2.65(t,J＝6.4Hz,2H),6.60(s,1H),7.26(d,J＝8.4Hz,1H),7.47(s,1H)7.60(d,J＝8.4Hz,1H),7.95(s,1H),
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,20.2,23.4,02325.8,29.2,32.7,40.5,41.3,109.4,124.4,126.5,127.0,129.4129.6,133.8(×2),137.8,152.4；IR(KBr)ν3411cm -1(OH)；
EIMS(70eV)m/z＝302(M +).HRMS(APCI)Calcd for C 19H 26O:302.16989；Found:302.17023.
(synthesis of 6-(2-ethylhexyl)-3-methylsulfany-2-(trifyl oxygen base) naphthalene (being compound 4 below))
[chemical formula 9]
Add in carrene (7mL) and have compound 3 (640mg, 2.1mmol) with pyridine (0.89mL, 6.4mmol) and carried out, in degassed solution, at 0 DEG C, adding trifluoromethanesulfanhydride anhydride (0.7mL, 4.2mmol).
At room temperature stir after 25 minutes, after water (5mL) and hydrochloric acid (4M, 2mL) dilution mixture thing, extract with carrene (5mL × 3).
By salt solution (5mL × 3) washing organic phase, by dried over mgso, under reduced pressure concentrate, obtain the almost pure compound of yellow oily 4 (800mg, 87%).
Below the determination data of the compound 4 obtained is shown in.
1H NMR(500MHz,CDCl 3)δ0.87(t,J＝7.2Hz,3H),0.89(t,J＝7.5Hz,3H)1.24-1.36(m,8H),1.67(sept,J＝6.4Hz,2H),2.59(s,3H),2.67(d,J＝7.0Hz,1H),2.69(d,d,J＝7.2Hz,1H),7.32(dd,J＝1.5,8.4Hz,1H),7.54(s,1H),7.63(s,1H)7.68(s,1H),7.71(d,J＝8.4Hz,1H),
13C NMR(126MHz,CDCl 3)；δ11.1,14.5,16.2,23.4,25.8,29.2,32.7,40.7,41.4,120.0,120.3(q,J＝315Hz)126.5,126.7,127.8,129.2,129.8,130.0,131.0,133.2,142.1,145.2；
IR(KBr)ν1425,1210cm -1(-O-SO 2-)；
EIMS(70eV),HRMS(APCI)Calcd for C 20H 25F 3O 3S 2:434.11917；Found:434.11905.
(synthesis of anti-form-1-(3-methylsulfany naphthalene-2-base)-2-(6-(2-ethylhexyl)-3-methylsulfany naphthalene-2-base) ethene (being compound 5 below))
[chemical formula 10]
At DMF (N; dinethylformamide) add in (48mL) and have compound 4 (2.58g; 5.94mmol), 3-methylsulfany-2-(trifyl oxygen base) naphthalene (1.91g; 5.94mmol) and anti-form-1; two (tributylstamlyl) ethene (3.6g of 2-; 5.94mmol) and carried out, in degassed solution, adding Pd (PPh 3) 4(343mg, 0.3mmol, 5mol%).
This mixture is heated 24 hours with 90 DEG C in darkroom.Thereafter, dilute with water, uses chloroform extraction.
With salt water washing extract, by dried over mgso, under reduced pressure concentrate.
By residue by silicagel pad (developing solvent: carrene), obtain yellow solid compound 5 (910mg, 32%).
Below the determination data of the compound 5 obtained is shown in.
Mp 78-79℃；
1H NMR(500MHz,CDCl 3)δ0.88(t,J＝7.1Hz,3H),0.92(t,J＝8.6Hz,3H),1.24-1.38(m,8H),1.67(sept,J＝7.4Hz,1H),2.60(s,1H),2.69(d,d,J＝6.7,6.8Hz,2H),7.27(s,1H),7.44(tt,J＝1.1,7.5Hz,2H),7.50(s,1H),7.60(s,1H),7.64(s,1H),7.65(s,1H),7.66(d,J＝7.5Hz,1H),7.74(d,J＝8.3Hz,1H),7.77(d,J＝8.3Hz,1H),7.85(d,J＝7.5Hz,1H),8.06(s,1H),8.09(s,1H)；
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,16.7,16.8,23.4,25.8,29.3,32.8,40.8,41.4,124.3,124.5,125.3,125.4,126.0,126.4,126.8,126.9,128.0,128.2,128.3,128.4,129.1,130.3,131.9,133.7,133.8,134.5,135.4,136.0,136.2,140.7；
EIMS(70eV)m/z＝484(M +).HRMS(APCI)Calcd for C 32H 36S 2:484.22529；Found:484.22568.
(synthesis of 2-2-EH-DNTT)
[chemical formula 11]
In chloroform (15mL), add compound 5 (720mg, 1.5mmol) and iodine (11g, 45mmol), stir 20 hours at 80 DEG C.
This mixture is joined in aqueous solution of sodium bisulfite (20mL).
Thereafter, with chloroform extraction, with salt water washing extract, by dried over mgso, under reduced pressure concentrate.
Use hexanes wash residue, obtain faint yellow solid 2-2-EH-DNTT (186mg, 28%).
Below the determination data of the 2-2-EH-DNTT obtained is shown in.
Mp>300℃；
1H NMR(500MHz,CDCl 3)δ0.88(t,J＝7.0Hz,3H),0.92(t,J＝7.4Hz,3H),1.26-1.38(m,8H),1.72(sept,J＝6.4Hz,1H),2.74(d,d,J＝7.2,7.1Hz,2H),7.36(d,J＝8.4Hz,1H)7.52-7.54(m,2H),7.67(s,1H),7.94(d,J＝8.4Hz,1H),7.94-7.96(m,1H),8.03-8.05(m,1H),8.33(s,1H),8.34(s,1H),8.36(s,1H),8.42(s,1H)；
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,23.3,25.9,29.2,32.8,40.8,41.2,120.2,120.3,122.1,122.7,126.0,126.2,126.8,127.7,128.3,128.4,128.6,130.2,130.7,131.6,131.7,132.0(×2),132.8,133.6,134.2,140.1,141.1；
EIMS(70eV)m/z＝452(M +).HRMS(APCI)Calcd for C 30H 28S 2:452.16269；Found:452.16248.
In addition, as comparative example, as following described, periodically synthesize 2,9-bis-(2-ethylhexyl) dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being 2,9-EH-DNTT below).
(anti-form-1, the synthesis of two (6-(2-ethylhexyl)-3-methylsulfany naphthalene-2-base) ethene of 2-(being compound 6 below))
[chemical formula 12]
Add in DMF (27mL) and have compound 4 (1.48g, 3.4mmol) and anti-form-1, two (tributylstamlyl) ethene of 2-has also carried out adding Pd (PPh in degassed solution 3) 4(158mg, 0.13mmol, 4mol%).
This mixture is heated 24 hours with 90 DEG C in darkroom.Thereafter, dilute with water, uses chloroform extraction.
With salt water washing extract, by dried over mgso, under reduced pressure concentrate.
By residue by silicagel pad (developing solvent: carrene), obtain yellow solid compound 11 (880mg, 87%).
Below the determination data of the compound 6 obtained is shown in.
Mp 64-65℃；
1H NMR(500MHz,CDCl 3)δ0.87(t,J＝7.2Hz,6H),0.90(t,J＝7.4Hz,6H)1.25-1.37(m,16H),1.69(sept,J＝6.1Hz,4H),2.59(s,2H),2.67(d,J＝6.9Hz,4H),2.69(d,J＝7.1Hz,2H),7.25(d,J＝8.4Hz,2H),7.49(s,2H),7.59(s,2H),7.64(s,2H)7.75(d,J＝8.4Hz,2H),8.01(s,2H),
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,17.8,23.4,25.8,29.3,32.8,40.8,41.4,124.3,125.2,126.4,127.9,128.2,128.6,130.4,133.8,134.6,136.0,140.6；
EIMS(70eV)m/z＝596(M +).HRMS(APCI)Calcd for C 40H 52S 2:596.35049；Found:596.35077.
(synthesis of 2,9-EH-DNTT)
[chemical formula 13]
In chloroform (37mL), add compound 6 (2.2g, 3.7mmol) and iodine (28g, 111mmol), stir 20 hours at 80 DEG C.
This mixture is joined in aqueous solution of sodium bisulfite (20mL).
Thereafter, with chloroform extraction, with salt water washing extract, by dried over mgso, under reduced pressure concentrate.
Use hexanes wash residue, obtain faint yellow solid 2,9-EH-DNTT (966mg, 46%).
Below the determination data of obtain 2,9-EH-DNTT is shown in.
Mp 218-219℃；
1H NMR(500MHz,CDCl 3)δ0.87(t,J＝7.1Hz,6H),0.92(t,J＝7.5Hz,6H)1.25-1.37(m,16H),1.72(sept,J＝6.0Hz,4H),2.73(d,J＝6.7Hz,2H),2.74(d,J＝7.1Hz,2H)7.34(d,J＝8.5Hz,2H),7.65(s,2H),7.92(d,J＝8.5Hz,2H),8.29(s,2H),8.32(s,2H)；
13C NMR(126MHz,CDCl 3)；δ11.2,14.5,23.4,25.9,29.2,32.8,40.8,41.3,120.1,122.1,126.8,128.3(×2),130.2,132.1,133.7,140.0,141.1；
EIMS(70eV)m/z＝564(M +).HRMS(APCI)Calcd for C 38H 44S 2:594.28789；Found:594.28815.
In addition, as comparative example, 2-ethylhexyl magnesium bromide is replaced with decyl magnesium bromide, in addition, carry out in the same manner as the synthesis of above-mentioned 2-2-EH-DNTT, synthesis 2-decyl-dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being 2-D-DNTT below).
[chemical formula 14]
(synthesis of 2,9-D-DNTT)
In addition, as comparative example, 2-ethylhexyl magnesium bromide is replaced with decyl magnesium bromide, in addition, with above-mentioned 2, the synthesis of 9-EH-DNTT is similarly carried out, synthesis 2,9-didecyl dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being 2,9-D-DNTT below).
[chemical formula 15]
(evaluation of solubility)
Make 2-2-EH-DNTT, 2,9-EH-DNTT, 2-D-DNTT, 2,9-D-DNTT is dissolved in the chloroform of room temperature respectively, measures solubility.The results are shown in table 1.
[table 1]
The compound (2-2-EH-DNTT, 2,9-EH-DNTT) with branched alkyl demonstrates good dissolubility.On the other hand, the compound (2-D-DNTT, 2,9-D-DNTT) with straight chained alkyl does not dissolve in a solvent, thus knownly can not be used as coating organic semiconducting materials.
(evaluation of film physical property)
With 2-2-EH-DNTT and 2, the 9-EH-DNTT making film of favorable solubility in a solvent, evaluate its physical property.
(2-2-EH-DNTT film, the making of 2,9-EH-DNTT films, evaluation)
2-2-EH-DNTT is dissolved in chloroform the solution preparing 0.3g/L, after film filter filters, is carrying out above-mentioned surface-treated n-type silicon substrate makes the thick 2-2-EH-DNTT film of about 100nm by spin-coating method.In addition, 2,9-EH-DNTT film is made as described above with 2,9-EH-DNTT.
The absorption spectrum of 2,9-EH-DNTT film is shown in Fig. 1 (A).In the absorption spectrum of 2,9-EH-DNTT film, as compared to the vapor-deposited film without substituent dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being DNTT below), can be observed obvious short wavelength's displacement.It can thus be appreciated that intermolecular interaction is weak under filminess.
In addition, the photoelectron spectroscopy of 2,9-EH-DNTT film is shown in Fig. 1 (B).Ionization potential according to 2,9-EH-DNTT films of photoelectron spectroscopy estimation is 5.7eV, then increase compared with the 5.4eV replacing DNTT with nothing.This can illustrate that intermolecular interaction weakens.
In addition, X-ray diffraction result outside the face of 2,9-EH-DNTT film is shown in Fig. 1 (C).In Fig. 1 (C), although visible crystals peak, the interfloor distance estimated is the short of 16 dusts, and molecular orientation can not say it is the form of wishing.
Then, the absorption spectrum of 2-2-EH-DNTT film is shown in Fig. 2 (A).The absorption spectrum of 2-2-EH-DNTT film demonstrates the absworption peak same with DNTT, compares with 2,9-EH-DNTT film, can observe clear and definite long wavelength shifted.This demonstrates intermolecular interaction under filminess and 2,9-EH-DNTT film and compares and recover.
In addition, the photoelectron spectroscopy of 2-2-EH-DNTT film is shown in Fig. 2 (B).Ionization potential according to the film of photoelectron spectroscopy estimation is 5.0eV, then reduction compared with the 5.4eV replacing DNTT with nothing, and is identical with asymmetric straight chained alkyl body, has also implied to there is intermolecular interaction thus.
In addition, X-ray diffraction result outside the face of 2-2-EH-DNTT film is shown in Fig. 2 (C).The peak observed by X-ray diffraction outside face has implied it is molecular long axis is stood in crystal structure directed on real estate, and the interfloor distance of estimation is also 26 dusts, corresponding with the length of the molecular long axis also comprising alkyl.
(making of transistor unit, evaluation)
With 2-2-EH-DNTT and 2, the 9-EH-DNTT making bottom filling transistor unit of above-mentioned favorable solubility, and evaluate characteristic.
Using as gate electrode, there is the thick silicon oxide layer of 200nm, after n-type silicon substrate with high-concentration dopant fully washs, silicon oxide layer surface perfluoro decyl triethoxysilane (FDTS) of n-type silicon substrate carried out silane treatment.
2-2-EH-DNTT is dissolved in chloroform the solution preparing 0.3g/L, after film filter filters, is carrying out above-mentioned surface-treated n-type silicon substrate makes the thick 2-2-EH-DNTT film of about 100nm by spin-coating method.
To this film under nitrogen atmosphere with 200 DEG C of heating 30 minutes.
On 2-2-EH-DNTT film, vacuum evaporation gold, forms source electrode and drain electrode.Be made into the bottom filling top contact transistor npn npn element that flute length is 50 μm, groove width is 1.5mm like this.Below this transistor unit is remembered into transistor unit 2-2-EH-DNTT.
In addition, carry out as described above with 2,9-EH-DNTT, make bottom filling top contact transistor npn npn element.Below, this transistor unit is remembered into transistor unit 2,9-EH-DNTT.
With 2-2-EH-DNTT, for the transistor unit 2-2-EH-DNTT be made, make gate voltage V gwith 20 ~-60V, source and drain voltage across poles V dwith 0 ~-60V change detection transistor characteristic.Transmission characteristic is shown in Fig. 3 (A), output characteristic is shown in Fig. 3 (B).Going out mobility by these property calculation is 0.3cm 2/ Vs.
On the other hand, for transistor unit 2,9-EH-DNTT, also attempt measuring transistor characteristic as described above, but for transistor unit 2,9-EH-DNTT, do not reply completely, knownly not work as transistor.Resolved by the physical property of above-mentioned 2,9-EH-DNTT films, two ethylhexyl steric bulk can be obtained large, therefore, hinder molecule filling closely, significantly reduce intermolecular interaction.Also demonstrate that transistor unit 2,9-EH-DNTT is not replied thus, that is, the charge carrier be injected in film can not move.
(synthesis of 2-(3-ethylheptyl) dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being 2-3-EH-DNTT below))
2-ethylhexyl magnesium bromide is replaced with 3-ethylheptyl magnesium bromide, in addition, carry out in the same manner as the synthesis of the synthesis of the synthesis of the synthesis of the synthesis of the synthesis of above-claimed cpd 1, compound 2, compound 3, compound 4, compound 5,2-2-EH-DNTT successively, synthesis 2-3-EH-DNTT.
[chemical formula 16]
By obtain below the determination data of 2-3-EH-DNTT is shown in.
mp>300℃；
1H-NMR(500MHz,CDCl 3)δ0.90(t,J＝7.2Hz,3H),0.92(t,J＝6.6Hz,3H),1.25-1.43(m,9H),1.67-1.73(m,2H),2.80(t,J＝8.4Hz,2H),7.40(dd,J＝8.8and 1.5Hz,1H),7.52(d,J＝6.7Hz,1H),7.53(d,J＝6.4Hz,1H),7.71(s,1H),7.94-7.97(m,1H),7.96(d,J＝8.8Hz,1H),8.03-8.05(m,1H),8.33(s,1H),8.35(s,1H),8.36(s,1H),8.43(s,1H)；
13C-NMR(126MHz,CDCl 3)11.0,14.2,23.3,26.2,29.2,33.1,33.8,35.2,39.0,120.1(x3),120.2,121.9,122.0,122.5,122.6,125.5,125.6,125.8(x2),126.0(x2),127.5,127.7,127.8,128.4,128.5,130.2,131.6,131.7,132.0,132.1,132.7,133.5,134.2,141.0,141.1,141.4(x2)；
EI-MS(70eV)m/z 466(M +)；HR-MS(APCI)m/z calcd for C 31H 31S 2[M+H] +467.18617,found 467.18637；Anal.Calcd for C 31H 30S 2C；79.78,H；6.48％.Found.C；79.97,H；6.46％.
(evaluation of solubility)
Make 2-3-EH-DNTT be dissolved in the chloroform of room temperature, measure solubility.The solubility of 2-3-EH-DNTT is 0.67g/L, better than 2-2-EH-DNTT (0.43g/L).
(making of transistor unit, evaluation)
Make bottom filling top contact transistor npn npn element with 2-3-EH-DNTT, evaluate characteristic.
Using as gate electrode, there is the thick silicon oxide layer of 200nm, n-type silicon substrate with high-concentration dopant fully washs.
2-3-EH-DNTT is dissolved in chloroform the solution preparing 0.3g/L, after film filter filters, is carrying out above-mentioned surface-treated n-type silicon substrate makes the thick 2-3-EH-DNTT film of about 100nm by spin-coating method.
To this film under nitrogen atmosphere with 100 DEG C of heating 30 minutes.
On 2-3-EH-DNTT film, vacuum evaporation gold, forms source electrode and drain electrode.The bottom filling top contact transistor npn npn element (Untreated element) of such making flute length 40 μm, groove width 3mm.
In addition, after the washing of n-type silicon substrate, silane treatment is carried out by 1,1,1,3,3,3-hexamethyldisiloxane (HMDS) in silicon oxide layer surface, makes bottom filling top contact transistor npn npn element (HMDS treatment element) as described above.
In addition, after the washing of n-type silicon substrate, silane treatment is carried out with eight decyltrichlorosilanes (ODTS) in silicon oxide layer surface, makes bottom filling top contact transistor npn npn element (ODTS treatment element) as described above.
In addition, after the washing of n-type silicon substrate, silane treatment is carried out on silicon oxide layer surface octyltrichlorosilane (OTS), make bottom filling top contact type body tube elements (OTS treatment element) as described above.
For each transistor unit be made into, make gate voltage V gwith 20 ~-60V, source and drain voltage across poles V dwith 0 ~-60V change detection transistor characteristic.By the carrier mobility (μ [cm of respective transistor unit 2v -1s -1]), critical voltage (V th[V]), on-off ratio (I on/off) be shown in table 2.In addition, the transmission characteristic of substrate ODTS being carried out the transistor unit that silane treatment is made is shown in Fig. 4 (A), output characteristic is shown in Fig. 4 (B).Should illustrate, transistor unit makes more than 15 respectively, and the carrier mobility in table 2 represents its mean value and peak (in parantheses).
[table 2]
In the transistor unit be made into by 2-3-EH-DNTT, compared with transistor unit 2-2-EH-DNTT, carrier mobility improves.Particularly for ODTS element substrate being carried out to ODTS process and be made, carrier mobility is the highest, is 1.6cm 2/ Vs is (average: 1.02cm 2/ Vs), demonstrate good transistor characteristic.This is presumably because that the side chain ethyl of ethylheptyl is away from DNTT skeleton, thus bone lattice intermolecular interaction improves.
Thought by above result, the MOLECULE DESIGN only importing like that branched alkyl such as formula 1 compound represented on a naphthalene is to meet dissolubility in organic solvent and transistor characteristic and requisite.
Should illustrate, the present invention can not carry out various execution mode and distortion with departing from the scope of the present invention.In addition, above-mentioned execution mode for the present invention will be described, instead of limits scope of the present invention.
The application based on No. 2013-9153, the Japan's patent application applied on January 22nd, 2013, on August 27th, 2013 application No. 2013-175678, Japan's patent application.The specification of No. 2013-9153, Japan's patent application, No. 2013-175678, Japan's patent application, Patent right requirement, accompanying drawing are all quoted in this specification as reference.
Utilization in industry
As mentioned above, solution process organic semiconducting materials involved in the present invention dissolubility is in a solvent excellent, therefore, the solution process such as rubbing method can be utilized to form organic semiconductor layer, therefore, may be used for manufacturing the semiconductor devices such as field-effect transistor.

Claims (8)

1. a solution process organic semiconducting materials, is characterized in that, contained 1 compound represented,
In formula 1, Y 1and Y 2be separately chalcogen, R 1and R 2one is branched alkyl, another is hydrogen.
2. solution process organic semiconducting materials according to claim 1, wherein, the main chain of described branched alkyl is more than C3.
3. solution process organic semiconducting materials according to claim 2, wherein, the main chain of described branched alkyl is more than C6.
4. the solution process organic semiconducting materials according to any one of claims 1 to 3, wherein, the side chain of branched alkyl is more than C2.
5. the solution process organic semiconducting materials according to any one of Claims 1 to 4, wherein, the side chain of described branched alkyl is bonded to the carbon of main chain more than 2.
6. solution process organic semiconducting materials according to claim 5, wherein, the side chain of described branched alkyl is bonded to the carbon of main chain more than 3.
7. the solution process organic semiconducting materials according to any one of claim 1 ~ 6, wherein, described Y 1and Y 2for sulphur atom or selenium atom.
8. an organic semiconductor equipment, is characterized in that, comprises the solution process organic semiconducting materials according to any one of claim 1 ~ 7.
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