Embodiment
The present invention is elaborated.The present invention relates to through making specific organic heterocyclic molecule and the field-effect transistor and the manufacturing approach thereof that receive the dissolving of electronics property compound and/or be dispersed in the organic semiconducting materials that forms at least a organic solvent and use this organic semiconducting materials with cyanic acid.
At first, the compound to above-mentioned formula (1) expression describes.In the above-mentioned formula (1), R
1And R
2Expression does not independently of one another replace or the substituted C1-C36 aliphatic alkyl of halogen.Aliphatic alkyl is saturated or undersaturated straight chain, side chain or annular aliphatic alkyl, is preferably the straight or branched aliphatic alkyl, further is preferably the straight chain aliphatic alkyl.Carbon number is generally C1-C36, is preferably C2-C24, and more preferably C4-C20 further is preferably C6-C12.
As the concrete example of straight or branched representative examples of saturated aliphatic alkyl, can enumerate: methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, sec-amyl, n-hexyl, isohesyl, n-heptyl, Zhong Gengji, n-octyl, n-nonyl, Zhong Renji, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, n-eicosane base, docosyl, pentacosane base, positive octacosyl, positive melissyl, 5-(n-pentyl) decyl, heneicosyl, tricosyl, tetracosyl, cerul, heptacosane base, nonacosyl, positive melissyl, square acyl group, dotriacontyl, hexatriacontane base etc.In addition, as the concrete example of ring-type representative examples of saturated aliphatic alkyl, can enumerate: cyclohexyl, cyclopenta, adamantyl, norborny etc.Concrete example as straight or branched unsaturated fatty hydrocarbons base; Can enumerate: vinyl, aryl, 20 carbon dialkylenes, 11,14-20 carbon dialkylenes, geranyl (anti--3,7-dimethyl-2; 6-octadiene-1-yl), farnesyl-is (anti-; Instead-3,7,11-trimethyl-2; 6,10-12 carbon triolefin-1-yl), 4-pentenyl, 1-propinyl, 1-hexyn, 1-octyne base, 1-decynyl, 1-hendecyne base, 1-dodecyne base, 1-14 carbyne bases, 1-hexadecine base, 1-19 carbyne bases etc.
In straight chain, side chain and the annular aliphatic alkyl, preferred straight or branched aliphatic alkyl, preferred especially straight chain aliphatic alkyl.
Saturated or unsaturated fatty hydrocarbons base can enumerate saturated alkyl, comprise the thiazolinyl of carbon-to-carbon double bond and comprise the alkynyl of carbon-to-carbon triple bond, and more preferably alkyl or alkynyl further are preferably alkyl.As aliphatic hydrocarbon residue, also comprise above-mentioned saturated or aliphatic hydrocarbon residue that the unsaturated fatty hydrocarbons base combines, promptly the position in aliphatic alkyl comprises the situation of carbon-to-carbon double bond, carbon-to-carbon triple bond simultaneously.
The substituted aliphatic alkyl of halogen is meant that the halogen atom of any kind replaces with any amount in the optional position of above-mentioned aliphatic alkyl and the aliphatic alkyl that obtains.As halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms, iodine atom, preferably enumerate: fluorine atom, chlorine atom, bromine atoms, more preferably enumerate fluorine atom and bromine atoms.As the concrete example of the substituted aliphatic alkyl of halogen, can enumerate: chloromethyl, bromomethyl, trifluoromethyl, pentafluoroethyl group, positive perfluoro propyl, positive perfluoro butyl, positive perfluor amyl group, positive perfluoro capryl, positive perfluor decyl, (ten difluoros)-6-iodine hexyl, 2,2 just; 3; 3,3-five fluoropropyls, 2,2; 3,3-tetrafluoro propyl group etc.
The compound of above-mentioned formula (1) expression can synthesize through the known method of record in patent documentation 1 for example and the non-patent literature 1.
The purification process of the compound of above-mentioned formula (1) expression is not special to be limited, and can adopt known method such as recrystallization, column chromatography and vacuum sublimation purifying.In addition, can as required the said method combination be used.
The concrete example of the compound of above-mentioned formula shown in the following table 1 (1) expression.
Table 1
Compound N o. |
R1 |
R2 |
1 |
CH
3 |
CH
3 |
2 |
C
2H
5 |
C
2H
5 |
3 |
Positive C
3H
7 |
Positive C
3H
7 |
4 |
Uncle C
4H
9 |
Uncle C
4H
9 |
5 |
Positive C
5H
11 |
Positive C
5H
11 |
6 |
Secondary C
5H
11 |
Secondary C
5H
11 |
7 |
Positive C
6H
13 |
Positive C
6H
13 |
8 |
Different C
6H
13 |
Different C
6H
13 |
9 |
Positive C
7H
15 |
Positive C
7H
15 |
10 |
Secondary C
7H
15 |
Secondary C
7H
15 |
11 |
Positive C
8H
17 |
Positive C
8H
17 |
12 |
Positive C
9H
19 |
Positive C
9H
19 |
13 |
Positive C
10H
21 |
Positive C
10H
21 |
14 |
Positive C
11H
23 |
Positive C
11H
23 |
15 |
Positive C
12H
25 |
Positive C
12H
25 |
16 |
Positive C
13H
27 |
Positive C
13H
27 |
17 |
Positive C
14H
29 |
Positive C
14H
29 |
18 |
Positive C
15H
31 |
Positive C
15H
31 |
19 |
Positive C
16H
33 |
Positive C
16H
33 |
20 |
Positive C
17H
35 |
Positive C
17H
35 |
21 |
Positive C
18H
37 |
Positive C
18H
37 |
22 |
Positive C
20H
41 |
Positive C
20H
41 |
23 |
Positive C
22H
45 |
Positive C
22H
45 |
24 |
Positive C
24H
49 |
Positive C
24H
49 |
25 |
Positive C
30H
61 |
Positive C
30H
61 |
26 |
Positive C
36H
73 |
Positive C
36H
73 |
27 |
C
5H
9(C
5H
11)
2 |
C
5H
9(C
5H
11)
2 |
28 |
Positive C
9H
19 |
Secondary C
9H
19 |
29 |
Positive C
6H
13 |
Secondary C
9H
19 |
30 |
Positive C
8H
17 |
Positive C
10H
21 |
31 |
Positive C
8H
17 |
Positive C
12H
25 |
32 |
Positive C
8H
16Cl
|
Positive C
8H
16Cl
|
33 |
Positive C
8H
16Br
|
Positive C
8H
16Br
|
34 |
CH
2Cl
|
CH
2Cl
|
35 |
C
3F
7 |
C
3F
7 |
36 |
C
4F
9 |
C
4F
9 |
37 |
C
8F
17 |
C
8F
17 |
38 |
C
10F
21 |
C
10F
21 |
39 |
-CH
2C
2F
5 |
-CH
2C
2F
5 |
40 |
-CH
2CF
2CHF
2 |
-CH
2CF
2CHF
2 |
41 |
-CH=CH
2 |
-CH=CH
2 |
42 |
-CH
2CH=CH
2 |
-CH
2CH=CH
2 |
43 |
-C
4H
8CH=CH
2 |
-C
4H
8CH=CH
2 |
44 |
-C≡CC
6H
13 |
-C≡CC
6H
13 |
45 |
-C≡CC
8H
17 |
-C≡CC
8H
17 |
46 |
-C≡CC
10H
21 |
-C≡CC
10H
21 |
47 |
-C≡CC
12H
25 |
-C≡CC
12H
25 |
48 |
-C≡CC
6H
13 |
-C≡CC
6H
13 |
49 |
Ring C
5H
9 |
Ring C
5H
9 |
50 |
Ring C
6H
11 |
Ring C
6H
11 |
The electronics property compound that receives with cyanic acid is the additive that is doped in the organic semiconducting materials, and not special the qualification can be enumerated four cyano 1,4-benzoquinone bismethane (following brief note is TCNQ) or derivatives thereof; Particularly, preferably use TCNQ, 2,3; 5; 6-tetrafluoro four cyano-1,4-benzoquinones bismethane (following brief note is F4-TCNQ), trifluoromethyl four cyano 1,4-benzoquinone bismethane (CF3TCNQ), 2,5-difluoro four cyano 1,4-benzoquinone bismethane (F2TCNQ), fluorine four cyano 1,4-benzoquinone bismethane (FTCNQ), TCNE (TCNE), 11; 11; 12, the 1,4-benzoquinone diformazan alkanes with cyanic acid of record in the 12-four cyano naphthalene-2,6-quinone bismethane (TNAP) or Japanese publication communique " TOHKEMY 2008-530773 communique ".Wherein preferred especially TCNQ or F4-TCNQ.
The compound of organic semiconducting materials of the present invention through making above-mentioned formula (1) expression at least with have cyanic acid receive the dissolving of electronics property compound or be dispersed in the organic solvent form; The compound of above-mentioned formula (1) expression with have cyanic acid can respectively contain by electronics property compound a kind of, also can with the compound of above-mentioned formula (1) expression with have cyanic acid mixed by one in the electronics property compound or both multiple derivatives to use.The compound that contains above-mentioned formula (1) expression with have in the organic semiconducting materials that receives electronics property compound of cyanic acid; The electronics property compound that receives with cyanic acid is generally the scope of 0.1 ~ 40 quality % with respect to the content of the compound of above-mentioned formula (1) expression; Be preferably 0.1 ~ 20 quality %, more preferably 0.1 ~ 10 quality %.When content surpasses 40 quality %, characteristic value is reduced because of turn-off current increases.Under the situation of using TCNQ or F4-TCNQ, special preferred content is below the 10 quality %.
Under the situation of not damaging effect of the present invention, for the characteristic of improving field-effect transistor or give other characteristics, can in organic semiconducting materials of the present invention, mix other organic semiconducting materials or various additive as required.As above-mentioned additive, can enumerate: viscosity modifier, surface tension modifier, levelling agent, bleeding agent, rheology control agent, alignment agent, dispersant etc.
Above-mentioned content of additive is 0 ~ 30 quality % with respect to the total amount of organic semiconducting materials of the present invention, is preferably 0 ~ 20 quality %, more preferably 0 ~ 10 quality %.
Organic semiconducting materials of the present invention through with the compound of formula (1) expression with receive the dissolving of electronics property compound or be dispersed in the coating and printing Technological adaptability that improves organic semiconducting materials in the solvent.As spendable solvent, as long as can make then not special qualification of compound film forming on substrate, preferred organic solvent can use single organic solvent, also can multiple organic solvent be mixed and use.Particularly, can use: halogenated hydrocarbon solvents such as chloroform, carrene, dichloroethanes; Alcohols solvents such as methyl alcohol, ethanol, isopropyl alcohol, butanols; Fluorinated alohol kind solvents such as octafluoropentanol, five fluorine propyl alcohol; Esters solvents such as ethyl acetate, butyl acetate, ethyl benzoate, diethyl carbonate; Aromatic hydrocarbon solvents such as toluene, xylenes, benzene, chlorobenzene, mesitylene, ethylbenzene, diethylbenzene, triethylbenzene (TEB), dichloro-benzenes, chloronaphthalene, tetrahydronaphthalene, decahydronaphthalenes, cyclohexyl benzene; Ketones solvents such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone; Amide solvents such as dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone; Ether solvent such as oxolane, isobutyl ether; Varsols such as hexane, cyclohexane, octane, decane, tetralin; Nitrile solvents such as acetonitrile, propionitrile, butyronitrile, benzonitrile etc., above-mentioned solvent can use separately, also can mix use.The compound of formula (1) expression with receive electronics property compound concentrations according to the thickness of the semiconductor layer of solvent types, making and different, count 0.001 ~ 50 quality % with respect to the solvent in the mixed liquor with total amount, be preferably 0.01 ~ 20 quality %.In addition, semi-conducting material of the present invention needs only dissolving or is dispersed in the above-mentioned organic solvent, and from forming the aspect of film more uniformly, preferred dissolution becomes uniform solution.
Field-effect transistor of the present invention (Field effect transistor; Below brief note is FET sometimes) have two electrodes of source electrode and drain electrode that contact with semiconductor layer, come control flows to cross this two interelectrode electric currents through the voltage that is applied to across gate insulator layer on another electrode that is called grid.Field-effect transistor comprises above-mentioned organic film.
Several modes of field-effect transistor of the present invention shown in Fig. 1, the configuration of each layer and electrode can suitably be selected according to the purposes of element.Need to prove, to Fig. 1 in the identical label of identical title mark.
Then each inscape to field-effect transistor of the present invention shown in Figure 1 describes, but the invention is not restricted to this.
Substrate 1 needs and can under the situation that each layer formed thereon do not peeled off, keep.For example can use: insulating properties materials such as resin plate, resin film, paper, glass, quartz, pottery; On conductivity substrate such as metal or alloy, be coated with the formation thing that insulating layer coating forms; By various materials that constitute of resin and inorganic material etc. etc.Wherein, as normally used resin film, for example can enumerate: PETG, PEN, polyether sulfone, polyamide, polyimides, Merlon, cellulose triacetate, PEI etc.When using resin film or paper, it is flexible that semiconductor element is had, the flexibility that becomes and light weight, thus practicality is improved.The thickness of substrate is generally 1 μ m ~ 10mm, is preferably 5 μ m ~ 3mm.
Source electrode 2, drain electrode 3, grid 6 use the material with conductivity.For example can use: metal such as platinum, gold, silver, aluminium, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, barium, lithium, potassium, sodium and contain the alloy of above-mentioned metal; InO
2, ZnO
2, SnO
2, electroconductive oxide such as ITO; Electroconductive polymer compounds such as polyaniline, polypyrrole, polythiophene (PEDOT-PSS etc.), polyacetylene, poly (phenylenevinylene), polydiacetylene; Organic charges such as BED-TTF migration complex compound; Semiconductors such as silicon, germanium, GaAs; Material with carbon elements such as carbon black, fullerene, CNT, graphite; Deng.In addition, can mix, as dopant, for example can use: acid such as hydrochloric acid, sulfuric acid, sulfonic acid electroconductive polymer compound or semiconductor; PF
5, AsF
5, FeCl
3Deng lewis acid; Halogen atoms such as iodine; Metallic atoms such as lithium, sodium, potassium; Deng.In order to reduce the contact resistance of electrode, can adopt the method for doping molybdenum oxide or metal carried out the processing of mercaptan etc.In addition, also can use the conductive composite material that in above-mentioned material, is dispersed with metallics such as carbon black or gold, platinum, silver, copper.Be connected with wiring on each electrode 2,3,6, wiring is also used with the essentially identical material of electrode and is made.The thickness of source electrode 2, drain electrode 3, grid 6 is different because of material, is generally 0.1nm ~ 100 μ m, is preferably 0.5nm ~ 10 μ m, more preferably 1nm ~ 5 μ m.
Gate insulator layer 5 material for having insulating properties for example can use: the copolymer that polymer such as poly-p-xylylene, polyacrylate, polymethyl methacrylate, polystyrene, polyvinylphenol, polyamide, polyimides, Merlon, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfones, epoxy resin, phenolic resins and they combine; Oxides such as silicon dioxide, aluminium oxide, titanium oxide, tantalum oxide; SrTiO
3, BaTiO
3Etc. strong dielectricity oxide; Dielectrics such as silicon nitride, aluminum nitride and other nitride, sulfide, fluoride or be dispersed with the polymer etc. of the particle of above-mentioned dielectric.The thickness of gate insulator layer 5 is different because of material, is generally 0.1nm ~ 100 μ m, is preferably 0.5nm ~ 50 μ m, more preferably 5nm ~ 10 μ m.
What the organic semiconducting materials that contains in the semiconductor layer 4 comprised above-mentioned formula (1) at least and had cyanic acid receives electronics property compound; Can the multiple mixing of derivative separately be used; This semi-conducting material need contain more than the 50 quality % with respect to total amount; Preferably contain more than the 80 quality %, more preferably contain more than the 95 quality %.At this moment, improve or give other characteristics, can mix other organic semiconducting materials or various additive as required for the characteristic of improving field-effect transistor.In addition, semiconductor layer 4 can be made up of multilayer.The thickness of semiconductor layer 4 is got over Bao Yuehao in the scope of not losing necessary function.For field-effect transistor, if having predetermined above thickness then property of semiconductor element do not rely on thickness, but thickness is when blocked up, the situation that leakage current increases is many.On the contrary, thickness is crossed when approaching, and can't form the passage (raceway groove) of electric charge, therefore needs suitable thickness.The thickness that is used to make semiconductor show the semiconductor layer of necessary function is generally 0.1nm ~ 10 μ m, is preferably 0.5nm ~ 5 μ m, more preferably 1nm ~ 3 μ m.
Material as protective layer 7; Not special the qualification; Preferred for example use the: film that forms by various resins such as acrylic resins such as epoxy resin, polymethyl methacrylate, polyurethane, polyimides, polyvinyl alcohol, fluororesin, polyolefin or the film that forms by dielectrics such as inorganic oxide film such as silica, aluminium oxide, silicon nitride or nitride films, especially preferably oxygen transmission rate, resin (polymer) that water absorption rate is low.In addition, also can be used for the protective material that is used for OLED display and develops.The thickness of protective layer can adopt thickness arbitrarily according to its purpose, is generally 100nm ~ 1mm.When forming protective layer, can reduce the influence of outside atmosphere such as humidity, in addition, also have the on/off that can improve device and make the stable advantage of electrical characteristics than waiting.
Field-effect transistor of the present invention can demonstrate good printing adaptability through carrying out following processing: as the acid treatment that utilizes hydrochloric acid, sulfuric acid, acetate etc. of substrate surface carrying out washing treatment; Utilize the alkali treatment of NaOH, potassium hydroxide, calcium hydroxide, ammonia etc.; Ozone treatment; Fluorination treatment; The Cement Composite Treated by Plasma of oxygen or argon gas etc.; The formation of Langmuir-Blodget (Langmuir-Blodgett) film is handled; The formation of other insulators or semi-conductive film is handled; Mechanical treatment; Electric treatment such as corona discharge etc., in addition, can be as required between above-mentioned each layer or the outer surface of semiconductor element other layers are set.In addition; Through carrying out surface treatment and control the position of catching on molecularly oriented and crystallinity, minimizing electrode interface or the insulator layer of substrate, electrode etc. and the interface portion of the semiconductor layer that forms afterwards in that the substrate of stacked semiconductor layer or insulator layer are first-class in advance; Thus; Improvement characteristic such as carrier mobility or regulate the balance of the hydrophilic/hydrophobic of substrate surface; Thus, can further improve the uniformity of device through improveing the membranous of formation film above that and the coating on substrate.As above-mentioned substrate processing, for example can enumerate: utilize phenethyl trichlorosilane etc. silane coupled processing, thiol treatment, utilize milled processed of fiber etc. etc.
As the method that each layer is set among the present invention, can for example suitably use: vacuum vapour deposition, sputtering method, rubbing method, print process, sol-gal process etc., if consider productivity ratio, print processes such as then preferred rubbing method, ink jet printing.
Then, based on the mode example of Fig. 1 the manufacturing approach of field-effect transistor of the present invention is explained as follows.
(substrate and substrate processing)
Field-effect transistor of the present invention is made (with reference to figure 1) through required electrode and various layer are set on above-mentioned substrate 1.Also can on this substrate, carry out above-mentioned surface treatment etc.The thickness of substrate 1 is got over Bao Yuehao in the scope that does not hinder necessary function.The thickness of substrate 1 is different because of material, is generally 1 μ m ~ 10mm, is preferably 5 μ m ~ 3mm.
(formation of source electrode and drain electrode)
Use formation source electrode 2 and drain electrodes 3 on substrate 1 such as above-mentioned electrode material.The material of source electrode 2 and drain electrode 3 can be identical, also can be different.As the method that forms electrode, for example can enumerate: vacuum vapour deposition, sputtering method, rubbing method, thermal transfer, print process, sol-gal process etc.Preferably carry out patterning when film forming or after the film forming as required to form desired shape.Also can make as the method for patterning in all sorts of ways, can enumerate for example with the patterning of photoresist and the photoetching process of etching combination etc.In addition, also can utilize soft lithographies such as print processes such as ink jet printing, silk screen printing, hectographic printing, letterpress, micro-contact-printing and the multiple method that combines of said method carried out patterning.Source electrode 2 is different because of material with the thickness of drain electrode 3, is generally 0.1nm ~ 100 μ m, is preferably 0.5nm ~ 10 μ m, more preferably 1nm ~ 5 μ m.The thickness of source electrode 2 and drain electrode 3 can be identical, also can be different.
(formation of semiconductor layer)
The organic film that semiconductor layer is to use the above-mentioned organic semiconducting materials of having explained to form through coating and printing technology.Also can organic film be renamed as organic semiconductor thin-film.Coating and printing technology is meant following semiconductor layer manufacture method: the compound that makes the above-mentioned formula for example of the present invention of the organic semiconducting materials with solvent soluble (1) expression in advance with have receiving the dissolving of electronics property compound or being dispersed in the organic solvent of cyanic acid; The lysate of the organic semiconducting materials that obtains is coated with or prints; And carry out drying, thereby can easily form semiconductor layer with good characteristic of semiconductor.The manufacturing approach of utilizing coating or printing is that coating and printing technology can be made large-area field-effect transistor and need not to make the environment when making device to reach the vacuum or the condition of high temperature with low cost; Therefore also favourable in industry, preferred especially in the manufacture method of various semiconductor layers.
Particularly, the compound through making above-mentioned formula (1) expression with have cyanic acid receive the dissolving of electronics property compound or be dispersed in prepare organic semiconducting materials of the present invention in the solvent.Can with the compound of formula (1) expression with have cyanic acid receive electronics property compound to dissolve simultaneously or disperses to prepare, also can with the compound of formula (1) expression with have cyanic acid dissolved respectively by electronics property compound or be dispersed in to mix afterwards in the solvent prepare.The compound of the formula in the organic semiconducting materials of the present invention (1) expression with have cyanic acid receive electronics property compound concentrations (using under the situation of multiple above-claimed cpd total concentration respectively) different according to the thickness of the semiconductor layer of solvent types, making for multiple compound; Be generally 0.001 ~ 50 quality % with respect to the solution total amount, be preferably 0.01 ~ 20 quality %.For the film forming that improves semiconductor layer, improve the field-effect transistor characteristic or give other characteristics, also can additive package or the semi-conducting material of other kinds.
Preparation is during organic semiconducting materials, the compound that need make above-mentioned formula (1) expression with have receiving the dissolving of electronics property compound or being dispersed in the solvent of cyanic acid, can according to circumstances carry out heating for dissolving and handle.Also can further use filter that the organic semiconducting materials that obtains is filtered and remove impurity etc.When being applied to the organic semiconducting materials after filtering on the substrate, the film forming that can observe semiconductor layer improves, and therefore can preferably use.
The organic semiconducting materials of as above preparation is applied on the substrate (exposed division of source electrode and drain electrode).As coating process, can adopt: rubbing methods such as The tape casting, spin-coating method, dip coating, scraper rubbing method, steel wire bar rubbing method, spraying process; Print processes such as ink jet printing, silk screen printing, hectographic printing, letterpress, intaglio printing; Soft lithographies such as micro-contact-printing etc.; And with the multiple method that combines of said method.In addition; As with the similar method of rubbing method, can also adopt: thus will be through transferring on the substrate to the monomolecular film that drips the semiconductor layer that above-mentioned organic semiconducting materials makes on the water surface and carrying out range upon range of Langmuir-Blodget method, utilize capillarity to import to method between the substrate etc. with two substrate clampings the material of liquid crystal or liquation state.Utilize the thickness of the semiconductor layer of said method making in the scope of not damaging function, to get over Bao Yuehao.When thickness was blocked up, leakage current increased sometimes.The thickness of semiconductor layer is identical with above-mentioned semiconductor layer 4.
The semiconductor layer of making like this can be improved characteristic of semiconductor through reprocessing.For example; After forming semiconductor layer, substrate is heat-treated, thus, the strain that in film, produces based on can relax film forming the time and can controlling diaphragm in reasons such as sequence, orientation; The raising and the stabilisation of characteristic of semiconductor can be realized, pin hole etc. can also be reduced.As long as be formed with semiconductor layer, then can heat-treat in any stage.The not special restriction of heat treated temperature is generally room temperature ~ 150 ℃, is preferably 40 ~ 120 ℃, further is preferably 45 ~ 100 ℃.The not special restriction of heat treatment period is generally 1 second ~ 24 hours, is preferably 1 minute ~ 1 hour.Atmosphere during heat treatment can be in atmosphere, also can be under inert atmospheres such as nitrogen or argon gas.
(formation of gate insulator layer)
Use above-mentioned insulating material etc. on semiconductor layer 4, to form gate insulator layer 5 (with reference to figure 1).As the formation method of gate insulator layer 5, for example can enumerate: rubbing methods such as spin-coating method, spraying process, dip coating, The tape casting, scraper rubbing method, scraper rubbing method; Print processes such as silk screen printing, hectographic printing, ink-jet; Dry method such as vacuum vapour deposition, molecular beam epitaxial growth method, ionization group bunch bundle method, ion plating method, sputtering method, atmospheric pressure plasma method, CVD method; Deng.In addition, also can use sol-gal process, as the pellumina on the aluminium, on the metal surface, form the method for oxidation film.
The thickness of gate insulator layer 5 is got over Bao Yuehao in the scope of not damaging its function, be generally 0.1nm ~ 100 μ m, is preferably 0.5nm ~ 50 μ m, more preferably 5nm ~ 10 μ m.
(formation of grid)
Grid 6 can form through the method identical with the manufacture method of drain electrode 3 with source electrode 2.Thickness is different because of material, is generally 1nm ~ 100 μ m, is preferably 0.5nm ~ 10 μ m, more preferably 1nm ~ 5 μ m.
(protective layer)
When using above-mentioned protective layer material to form protective layer 7, have that the influence that can make outside atmosphere drops to bottom line and the stable advantage (with reference to figure 1) of electrical characteristics that makes field-effect transistor.The thickness of protective layer 7 can adopt thickness arbitrarily according to its purpose, is generally 100nm ~ 1mm.When forming protective layer, can adopt the whole bag of tricks; Under the situation that protective layer is formed by resin; For example can enumerate: coating contains makes behind the solution of resin it dry and form the method for carrying out polymerization behind method, coating or the vapor deposition resin monomer of resin molding etc., can after film forming, carry out crosslinking Treatment.Under the situation that protective layer is formed by inorganic matter, for example can use: the formation method in the coating and printing technologies such as formation method in sputtering method, the vapour deposition method equal vacuum technology or sol-gal process.Field-effect transistor of the present invention can also be provided with protective layer as required except being provided with the protective layer in semiconductor layer surface between each layer.Set protective layer plays a role to the stabilisation of the electrical characteristics of field-effect transistor sometimes.
The operating characteristic of field-effect transistor generally constitutes decisions such as (thickness of source electrode-drain electrode spacing and width, insulating barrier etc.) by the static capacity of the carrier mobility of semiconductor layer, conductivity, insulating barrier, element.The organic material that uses in the semiconductor layer of field-effect transistor requires to have high carrier mobility, can demonstrate high carrier mobility as organic semiconducting materials with the compound that the of the present invention above-mentioned formula (1) that low cost is made is represented.In addition, field-effect transistor of the present invention can be made through the lower technology of temperature, thereby flexible materials such as the plastic plate that under hot conditions, can't use, plastic film also can be used as the substrate use.As a result, can make light weight, flexibility is good and survivable element, can be as the switch element of the active matrix of display etc.As display, for example can enumerate: LCD, polymer dispersion type liquid crystal display, electrophoretype display, EL display, electrochromism escope, particle rotation escope etc.In addition; The film forming of field-effect transistor of the present invention is good, therefore, can utilize coating to wait coating and printing technology to make; To compare cost very low with existing vacuum evaporation process, can also be applicable to the manufacturing of the field-effect transistor of large area display purposes.
Field-effect transistor of the present invention also can be used as digital elements such as memory circuit element, signal drive circuit element, signal processing circuit element or analog element uses, and through said elements is made up, can make IC-card or IC tag.In addition, field-effect transistor of the present invention can change its characteristic through outside stimuluss such as chemical substances, therefore can also expect to use as the FET transducer.
Need to prove, the present invention includes the mode of following (2) ~ (7).
(2) like (1) described organic semiconducting materials, wherein, the R in the formula (1)
1And R
2Be the straight chain aliphatic alkyl below the C12 independently of one another.
(3) like (1) or (2) described organic semiconducting materials, wherein, the electronics property compound that receives with cyanic acid is a four cyano 1,4-benzoquinone bismethane or derivatives thereof.
(4) like each described organic semiconducting materials in (1) ~ (3), wherein, the electronics property compound that receives with cyanic acid is below the 10 quality % with respect to the content of the compound of formula (1) expression.
(5) a kind of field-effect transistor is characterized in that, comprises the organic film that is obtained by each described organic semiconducting materials in (1) ~ (4).
(6) a kind of manufacturing approach of field-effect transistor, wherein, through each described organic semiconducting materials in coating or printing (1) ~ (4) and carry out drying and form organic film.
(7) a kind of manufacturing approach of field-effect transistor; Be used to make the field-effect transistor that possesses grid, gate insulator layer, semiconductor layer, source electrode and drain electrode; Wherein, carry out drying and form organic film through each described organic semiconducting materials in coating between source electrode on substrate or gate insulator layer and the drain electrode or printing (1) ~ (4) is parallel.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not limited to these embodiment.Among the embodiment, if not special the appointment, then part is represented mass parts, and % representes quality %.Need to prove, all atmosphere, carry out from the evaluation that is prepared into characteristic of semiconductor of semi-conducting material.
(preparation of stock solution)
The compound (11) of record in the table 1 is dissolved in chloroform, makes it reach 2%, the stock solution of preparation compound (11).On the other hand, TCNQ (Tokyo changes into manufacturing) and F4-TCNQ (Tokyo changes into manufacturing) are dissolved in acetonitrile, make it reach 0.2% respectively, prepare the stock solution of TCNQ and F4-TCNQ respectively.
[embodiment 1]
(preparation of semi-conducting material)
The stock solution of the stock solution of 100 parts of compounds (11), 20 parts of TCNQ, 80 parts of chloroforms are mixed, and preparation contains the mixed solution 1 of organic semiconducting materials of chloroform-acetonitrile (9:1) of 1% compound (11), 0.02% TCNQ.
(making of transistor unit)
The mixed solution 1 that contains compound (11) and TCNQ that utilizes spin-coating method to prepare in advance is applied to the band SiO through the 300nm of UV-ozone treatment
2On the n doping type silicon wafer of heat oxide film, then, this substrate was heated 10 minutes down at 80 ℃ on hot plate, then, drying is 1 minute under 120 ℃, forms organic film.Vacuum vapour deposition gold evaporation on this organic film through using metal mask is made bottom gate-top contact element as source electrode and drain electrode (channel length 50 μ m, channel width 2mm).
(evaluating characteristics)
For the organic field effect tube that obtains; Use analyzing parameters of semiconductor appearance (4155C that Agilent makes), make drain voltage be-60V, make gate voltage Vg+20~-4 characteristic of semiconductor on the substrate are estimated under the condition that changes between the 80V.The mean value of the mobility of 4 electrodes that calculate as a result, is 0.31cm
2/ Vs is 0.02cm as the standard deviation of the index of the fluctuation of expression in the substrate
2/ Vs.In addition, threshold voltage average out to-29V, standard deviation is 1.3V, making current is 2.3 * 10
-4A, standard deviation is 2.6 * 10
-5A demonstrates the uniformity in high characteristic of semiconductor and the substrate.In addition, turn-off current is 10
-11The A level is not even observe turn-off current when receiving electronics property material yet and raise being added with.And, even in being exposed to atmosphere one the week situation under, also can reach mobility is 0.32cm
2/ Vs, threshold voltage are-31V that making current is 2.2 * 10
-4A has kept good characteristic of semiconductor.
[embodiment 2]
(preparation of semi-conducting material)
The stock solution of the stock solution of 100 parts of compounds (11), 10 parts of TCNQ, 80 parts of chloroforms, 10 parts of acetonitriles are mixed, and preparation contains the mixed solution 2 of organic semiconducting materials of chloroform-acetonitrile (9:1) of 1% compound (11), 0.01% TCNQ.
(making of transistor unit)
Except semi-conducting material is changed to the mixed solution 2 from mixed solution 1, likewise operate with embodiment 1, make bottom gate-top contact element.
(evaluating characteristics)
With the same condition of embodiment 1 under estimate characteristic of semiconductor.The mean value of the mobility of 4 electrodes is 0.58cm
2/ Vs is 0.038cm as the standard deviation of the index of the fluctuation of expression in the substrate
2/ Vs.In addition, threshold voltage average out to-26V, standard deviation is 0.9V, making current is 4.5 * 10
-4A, standard deviation is 3.7 * 10
-6A demonstrates the uniformity in high characteristic of semiconductor and the substrate.In addition, turn-off current is 10
-11The A level, even be added with when receiving electronics property material, turn-off current also raises.And, even in being exposed to atmosphere one the week situation under, also can reach mobility is 0.59cm
2/ Vs, threshold voltage are-30V that making current is 4.1 * 10
-4A has kept good characteristic of semiconductor.
[embodiment 3]
(preparation of semi-conducting material)
The stock solution of the stock solution of 100 parts of compounds (11), 20 parts of F4-TCNQ, 80 parts of chloroforms are mixed, and preparation contains the mixed solution 2 of organic semiconducting materials of chloroform-acetonitrile (9:1) of 1% compound (11), 0.02% F4-TCNQ.
(making of transistor unit)
Except semi-conducting material is changed to the mixed solution 3 from mixed solution 1, likewise operate with embodiment 1, make bottom gate-top contact element.
(evaluating characteristics)
With the same condition of embodiment 1 under estimate characteristic of semiconductor.The mean value of the mobility of 4 electrodes is 0.42cm
2/ Vs is 0.007cm as the standard deviation of the index of the fluctuation of expression in the substrate
2/ Vs.In addition, threshold voltage average out to-20V, standard deviation is 0.3V, making current is 4.0 * 10
-4A, standard deviation is 9.1 * 10
-6A demonstrates the uniformity in high characteristic of semiconductor and the substrate.In addition, turn-off current is 10
-11The A level, even be added with when receiving electronics property material, turn-off current also raises.And, even in being exposed to atmosphere one the week situation under, also can reach mobility is 0.42cm
2/ Vs, threshold voltage are-20V that making current is 3.9 * 10
-4A has kept good characteristic of semiconductor.
[comparative example 1]
(preparation of semi-conducting material)
The stock solution of 100 parts of above-claimed cpds (11), 80 parts of chloroforms, 20 parts of acetonitriles are mixed, and preparation does not contain the mixed solution 4 of organic semiconducting materials that receives electronics property compound, contains the chloroform-acetonitrile (9:1) of 1% compound (11).
(making of transistor unit)
Except semi-conducting material is changed to the mixed solution 4 from mixed solution 1, likewise operate with embodiment 1, make bottom gate-top contact element.
(evaluating characteristics)
With the same condition of embodiment 1 under estimate characteristic of semiconductor.The mean value of the mobility of 4 electrodes is 0.22cm
2/ Vs is 0.062cm as the standard deviation of the index of the fluctuation of expression in the substrate
2/ Vs.In addition, threshold voltage average out to-44V, standard deviation is 1.5V, making current is 8.3 * 10
-5A, standard deviation is 2.9 * 10
-5A compares with embodiment 1,2, and mobility and making current reduce, and threshold voltage increases.Demonstrate in addition, represent that the standard deviation of fluctuation of each characteristic is also big than embodiment.
Evaluation result by above characteristic of semiconductor distinguishes that the field-effect transistor that comprises organic semiconducting materials of the present invention is stably worked in atmosphere, have high characteristic of semiconductor and durability.Distinguish in addition, compared by the comparative example of electronics property material with not containing, not only can improve any one characteristic of semiconductor in mobility, threshold voltage, the making current, but also can improve the uniformity in the face.Confirmed in addition: not only when making semiconductor layer, needn't use the vacuum vapour deposition that needs special installation etc.; Even not needing numerous and diverse operation such as the patterning of substrate surface in handling or function such as catching with minimizing is that the layer of purpose forms step, also can simply and at an easy rate make semiconductor layer through rubbing method etc., and can improve characteristic of semiconductor.Therefore, we can say that using the field-effect transistor of organic semiconducting materials of the present invention is the exceedingly useful field-effect transistor with transistor having excellent performance.
Label declaration
1 substrate
2 source electrodes
3 drain electrodes
4 semiconductor layers
5 gate insulator layer
6 grids
7 protective layers