CN110085741A - A kind of semiconductor material and preparation method and application - Google Patents
A kind of semiconductor material and preparation method and application Download PDFInfo
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- CN110085741A CN110085741A CN201810078425.2A CN201810078425A CN110085741A CN 110085741 A CN110085741 A CN 110085741A CN 201810078425 A CN201810078425 A CN 201810078425A CN 110085741 A CN110085741 A CN 110085741A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- WIFMYMXKTAVDSQ-UHFFFAOYSA-N 2-bromo-1-benzothiophene Chemical compound C1=CC=C2SC(Br)=CC2=C1 WIFMYMXKTAVDSQ-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- -1 4- n-octyl Chemical group 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VJYJBBMMLIDJEF-UHFFFAOYSA-N 1-benzothiophen-2-amine Chemical compound C1=CC=C2SC(N)=CC2=C1 VJYJBBMMLIDJEF-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical compound B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 0.000 description 2
- UVBFFPZGOOKWNR-UHFFFAOYSA-N 1-bromo-4-octoxybenzene Chemical compound CCCCCCCCOC1=CC=C(Br)C=C1 UVBFFPZGOOKWNR-UHFFFAOYSA-N 0.000 description 2
- OEEJLOZQSKNWQQ-UHFFFAOYSA-N 2-nitro-1-benzothiophene Chemical compound C1=CC=C2SC([N+](=O)[O-])=CC2=C1 OEEJLOZQSKNWQQ-UHFFFAOYSA-N 0.000 description 2
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- BDDIUTHMWNWMRJ-UHFFFAOYSA-N octane;hydrobromide Chemical compound Br.CCCCCCCC BDDIUTHMWNWMRJ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
Classifications
-
- 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
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to a kind of high-performance organic thin film transistor p-type semiconductor material, preparation method, element manufacturing and application, the material is a series of derivatives based on BTBT core.The material is to be obtained using coupling reaction, using it as organic semi-conductor OTFT device, have the characteristics that mobility is high, threshold voltage is lower, stability is preferable, it is high to can solve existing BTBT sill threshold voltage, it is difficult to further apply the problems in practical application.
Description
Technical field
The present invention relates to organic photoelectrical material devices field, in particular to a kind of high-performance organic thin film transistor semiconductor
Material and preparation method and application.
Background technique
Organic Thin Film Transistors (OTFT) is a kind of using organic material as the thin film field-effect pipe of carrier blocking layers.
It is one kind by voltage come control device, i.e., by changing electric field to control the active device of solid material conductive capability.
And organic semiconducting materials therein, it is simple, at low cost with more easily modification, manufacture craft compared with inorganic semiconductor material
It is honest and clean, and the advantages of small size, electronic component flexible can be prepared, thus there is boundless application prospect.
The device performance of OTFT depends on several factors, and wherein organic semi-conductor intrinsic properties has conclusive shadow to it
It rings.The Cloud Distribution of semiconductor molecule itself and its intermolecular electron cloud overlapping degree largely affect device
Performance.The organic semiconductor of BTBT core with pi-conjugated feature has very high electron cloud overlapping degree, receives extensive pass
Note.
However, since the organic semiconducting materials of BTBT core have relatively low HOMO energy level, in OTFT device with gold
The work content of electrode mismatches, thus its threshold voltage is relatively large, limits further answering for BTBT core organic semiconducting materials
With.
Summary of the invention
The present invention provides a kind of high-performance organic thin film transistor semiconductor material, molecular structural formula general formula such as Fig. 1.
Wherein, the R is-CnH2n+1, 1 < n≤50；The alkyl chain can be straight chain or fork chain；
Specifically, oxygen alkane chain is introduced the BTBT-Ph with strong pi-conjugated feature by the present invention, to partly be led by organic
The strong electron donation of body oxygen alkane chain promotes the HOMO energy level of material, to reduce the band of its in OTFT with gold electrode work content
Gap, and then the contact resistance between semiconductor material and electrode is reduced, reduce the threshold voltage of OTFT；
The present invention also provides the preparation method of the organic thin film transistor semiconductor material, unified representation is as shown in Figure 2.
Wherein, the R is-CnH2n+1, 1 < n≤50；The alkyl chain can be straight chain or fork chain.The semiconductor material by
Two kinds of intermediate products pass through Suzuki coupling under the effect of the catalyst and obtain；
It includes but is not limited to have that the present invention, which also resides in the protection organic thin film transistor semiconductor material being used to prepare,
Application in the various devices such as machine thin film transistor (TFT)；
Further, the present invention also resides in the device that protection contains the semiconductor material；
Device is preferably organic thin film transistor device, and vapor deposition or solution rotation can be used in the device organic semiconductor thin-film
Apply etc. modes obtain, preferred film of the present invention the preparation method is as follows:
By organic semiconducting materials heating sublimation under vacuum conditions, thus on the Si/SiO2 pretreated by OTS
Cooling deposition, to form Organic Thin Film Transistors film.Wherein, source electrode, drain metal such as Au etc. is in same vacuum condition
Lower vapor deposition obtains, and then obtains organic thin film transistor device.
Heretofore described semiconductor material is a series of derivatives based on BTBT core.The material is using coupling
It reacts and obtains, using it as organic semi-conductor OTFT device, there is mobility is high, threshold voltage is lower, stability is preferable etc.
Feature it is high to can solve existing BTBT sill threshold voltage, it is difficult to further apply the problems in practical application.
Detailed description of the invention
Fig. 1 is organic thin film transistor semiconductor material molecular structural formula of the present invention；
Fig. 2 is organic thin film transistor semiconductor material preparation method schematic diagram of the present invention；
Fig. 3 is 2- (4- n-octyl oxygroup benzene) [1] benzothiophene [3,2-b] [1] benzo thiophene described in the embodiment of the present invention 1
Pheno molecular structural formula；
Fig. 4 is that semiconductor material described in the embodiment of the present invention 1 is calculated with the HOMO of similar alkyl chain material, lumo energy
Comparative result figure；
Fig. 5 is the cyclic voltammetry curve of semiconductor material and similar alkyl chain material described in the embodiment of the present invention 1；
Fig. 6 is the transfer characteristic song that semiconductor material described in the embodiment of the present invention 1 prepares organic thin film transistor device
Line；
Fig. 7 is the output characteristics song that semiconductor material described in the embodiment of the present invention 1 prepares organic thin film transistor device
Line；
Fig. 8 is 2- (4- iso-octyl oxygroup benzene) [1] benzothiophene [3,2-b] [1] benzo thiophene described in the embodiment of the present invention 2
Pheno molecular structural formula.
Specific embodiment
The content of present invention is illustrated below in conjunction with embodiment.
Embodiment 1
R is-C8H17(normal octane base), the organic thin film transistor semiconductor material molecular structural formula be Fig. 3 shown in,
The preparation method is as follows:
A. by [1] benzothiophene [3,2-b] [1] benzothiophene (10g, 41.6mmol) with fuming nitric aicd (11.4g,
It 180.9mmol) is nitrified, reaction dissolvent is methylene chloride (1000mL), and 30min, fully reacting are reacted under the conditions of -50 DEG C
Solid is washed with methylene chloride afterwards, and is recrystallized in toluene, dry 2- nitro-[1] benzothiophene [3,2-b] [1]
Benzothiophene；By obtained yellow solid (1.0g, 3.5mmol) and iron powder (3.4g, 60.9mmol) and 5% aqueous ammonium chloride solution
Reduction reaction 12h is carried out under the conditions of (3mL) is 80 DEG C in toluene (140mL), and solid, the anhydrous sulphur of filtrate are filtered off after fully reacting
Sour sodium is dry, removes solvent and obtains 2- amino-[1] benzothiophene [3,2-b] [1] benzothiophene.By copper bromide (2.8g,
10min is stirred under the conditions of 0.012mol) with nitrous acid special butyl ester (1.7g, 0.016mol) 65 DEG C in acetonitrile (50mL), slowly
2- amino-[1] benzothiophene [3,2-b] [1] benzothiophene (2.6g, 0.01mol) is added and reacts 2h, is cooled to after fully reacting
Room temperature pours into the hydrochloric acid (50mL) of 6M, filters out the solid of precipitation, obtains 2- with water and ethanol washing, then by column chromatographic purifying
Bromo- [1] benzothiophene [3,2-b] [1] benzothiophene.
B. by p bromophenol (20.7g, 0.12mol) and n-octane bromide (19.3g, 0.1mol) and potassium carbonate
(16.6g, 0.12mol) is added in acetone (200mL), and return stirring 48h is cooled to room temperature after complete reaction at 60 DEG C,
The solvent in filtrate is removed after filter mixed liquor, 4- n-octyloxy bromobenzene is chromatographed to obtain by column；By 4- n-octyloxy bromobenzene
(14.2g, 0.05mol) is dissolved in anhydrous tetrahydro furan (200mL), and n-BuLi (30mL) reaction is added under the conditions of -78 DEG C
20min, adds isopropanol pinacol borate (15mL, 0.075mol) reaction 30min, and temperature is warmed to room temperature reaction 48h,
Solution is added in ice water after complete reaction and is extracted with ethyl acetate three times, and is mutually washed oily three times with saturated common salt, is used
Solvent is removed after anhydrous sodium sulfate is dry.It chromatographs to obtain penta ring of 1,3,2- dioxy boron, 4,4,5,5- tetramethyl -2- finally by column
(4- n-octyl oxygroup benzene).
C. by bromo- [1] benzothiophene [3,2-b] [1] benzothiophene (2.0g, 6.3mmol) of 2-, 1,3,2- dioxy boron penta
Ring, 4,4,5,5- tetramethyl -2- (4- n-octyl oxygroup benzene) (3.1g, 9.4mmol) and methyl tricapryl ammonium chloride (3.8g,
Stirring in toluene (80mL) 9.4mmol) is added, the solution of potassium carbonate (12.5mL) of 2M and logical nitrogen are added after solid dissolution
Four (triphenyl phosphorus) palladiums (0.3g, 0.3mol) are added after 20min, is heated to 110 DEG C and reacts 48 hours, be cooled to after fully reacting
Room temperature is added in methanol (300mL), and gained is precipitated and is filtered, dry, and purifying furnace purifying obtains final product 2- afterwards twice, and (4- is just
Octyl oxygroup benzene) [1] benzothiophene [3,2-b] [1] benzothiophene.
D. the above-mentioned system semiconductor material is subjected to energy level calculating, comparison with HOMO, LUMO of similar alkyl chain material
As a result as shown in Figure 4；It is as shown in Figure 5 with the comparison of the cyclic voltammetry curve of similar alkyl chain material；By above-mentioned semiconductor material
It is prepared into organic thin film transistor device, the preparation method is as follows:
By organic semiconducting materials heating sublimation under vacuum conditions, thus on the Si/SiO2 pretreated by OTS
Cooling deposition, to form Organic Thin Film Transistors film.Wherein, source electrode, drain metal such as Au etc. is in same vacuum condition
Lower vapor deposition obtains, and then obtains organic thin film transistor device.The organic thin film transistor device of preparation, transfer characteristic curve
As shown in fig. 6, output characteristic curve is as shown in Figure 7.
Embodiment 2
R is-C8H17(isooctane base), the organic thin film transistor semiconductor material molecular structural formula be Fig. 8 shown in,
The preparation method is as follows:
A. by [1] benzothiophene [3,2-b] [1] benzothiophene (10g, 41.6mmol) with fuming nitric aicd (11.4g,
It 180.9mmol) is nitrified, reaction dissolvent is methylene chloride (1000mL), and 30min, fully reacting are reacted under the conditions of -50 DEG C
Solid is washed with methylene chloride afterwards, and is recrystallized in toluene, dry 2- nitro-[1] benzothiophene [3,2-b] [1]
Benzothiophene；By obtained yellow solid (1.0g, 3.5mmol) and iron powder (3.4g, 60.9mmol) and 5% aqueous ammonium chloride solution
Reduction reaction 12h is carried out under the conditions of (3mL) is 80 DEG C in toluene (140mL), and solid, the anhydrous sulphur of filtrate are filtered off after fully reacting
Sour sodium is dry, removes solvent and obtains 2- amino-[1] benzothiophene [3,2-b] [1] benzothiophene.By copper bromide (2.8g,
10min is stirred under the conditions of 0.012mol) with nitrous acid special butyl ester (1.7g, 0.016mol) 65 DEG C in acetonitrile (50mL), slowly
2- amino-[1] benzothiophene [3,2-b] [1] benzothiophene (2.6g, 0.01mol) is added and reacts 2h, is cooled to after fully reacting
Room temperature pours into the hydrochloric acid (50mL) of 6M, filters out the solid of precipitation, obtains 2- with water and ethanol washing, then by column chromatographic purifying
Bromo- [1] benzothiophene [3,2-b] [1] benzothiophene.
B. by p bromophenol (20.7g, 0.12mol) and bromo-iso-octane (19.3g, 0.1mol) and potassium carbonate
(16.6g, 0.12mol) is added in acetone (200mL), and return stirring 48h is cooled to room temperature after complete reaction at 60 DEG C,
The solvent in filtrate is removed after filter mixed liquor, the different octyloxy bromobenzene of 4- is chromatographed to obtain by column；By the different octyloxy bromobenzene of 4-
(14.2g, 0.05mol) is dissolved in anhydrous tetrahydro furan (200mL), and n-BuLi (30mL) reaction is added under the conditions of -78 DEG C
20min, adds isopropanol pinacol borate (15mL, 0.075mol) reaction 30min, and temperature is warmed to room temperature reaction 48h,
Solution is added in ice water after complete reaction and is extracted with ethyl acetate three times, and is mutually washed oily three times with saturated common salt, is used
Solvent is removed after anhydrous sodium sulfate is dry.It chromatographs to obtain penta ring of 1,3,2- dioxy boron, 4,4,5,5- tetramethyl -2- finally by column
(4- iso-octyl oxygroup benzene).
C. by bromo- [1] benzothiophene [3,2-b] [1] benzothiophene (2.0g, 6.3mmol) of 2-, 1,3,2- dioxy boron penta
Ring, 4,4,5,5- tetramethyl -2- (4- iso-octyl oxygroup benzene) (3.1g, 9.4mmol) and methyl tricapryl ammonium chloride (3.8g,
Stirring in toluene (80mL) 9.4mmol) is added, the solution of potassium carbonate (12.5mL) of 2M and logical nitrogen are added after solid dissolution
Four (triphenyl phosphorus) palladiums (0.3g, 0.3mol) are added after 20min, is heated to 110 DEG C and reacts 48 hours, be cooled to after fully reacting
Room temperature is added in methanol (300mL), and gained is precipitated and is filtered, dry, and purifying furnace purifying obtains final product 2- afterwards twice, and (4- is different
Octyl oxygroup benzene) [1] benzothiophene [3,2-b] [1] benzothiophene.
It should be understood that the embodiment of the present invention and application are not limited to above-mentioned citing, to ordinary skill people
For member, it can be modified or changed according to the above description, and all these modifications and variations all should belong to the appended power of the present invention
The protection scope that benefit requires.
Claims (8)
1. a kind of semiconductor material, which is characterized in that its molecular structural formula is as follows:
Wherein, the R group is-CnH2n+1, 1 < n≤50.
2. a kind of semiconductor material, which is characterized in that the semiconductor material is organic thin film transistor semiconductor material.
3. a kind of semiconductor material, which is characterized in that the R group is straight chain or fork chain.
4. a kind of preparation method of semiconductor material, which is characterized in that it is characterized in that, by bromo- [1] benzothiophene [3,2- of 2-
B] [1] benzothiophene and 1,3,2- dioxy boron, penta ring, 4,4,5,5- tetramethyl -2- (4-R base oxygroup benzene), in the effect of catalyst
It is coupled down to obtain the semiconductor material by Suzuki, reaction equation is as follows:
Wherein, the R group is-CnH2n+1, 1 < n≤50.
5. the preparation method of semiconductor material according to claim 4, which is characterized in that the catalyst is that methyl three is pungent
Ammonium chloride.
6. semiconductor material described in any one of claim 1-5, in the application being used to prepare in Organic Thin Film Transistors.
7. the device containing semiconductor material described in any one of claim 1-5.
8. device according to claim 7, which is characterized in that the device is Organic Thin Film Transistors.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534830A (en) * | 2011-03-10 | 2014-01-22 | 国立大学法人东京工业大学 | Organic semiconductor material |
| JP2016050207A (en) * | 2014-08-29 | 2016-04-11 | 日本化薬株式会社 | Novel condensed polycyclic aromatic compound and use therefor |
| JP2017066089A (en) * | 2015-09-30 | 2017-04-06 | 国立大学法人東京工業大学 | Benzothienobenzothiophene derivative, organic semiconductor material, and organic transistor |
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2018
- 2018-01-26 CN CN201810078425.2A patent/CN110085741A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534830A (en) * | 2011-03-10 | 2014-01-22 | 国立大学法人东京工业大学 | Organic semiconductor material |
| JP2016050207A (en) * | 2014-08-29 | 2016-04-11 | 日本化薬株式会社 | Novel condensed polycyclic aromatic compound and use therefor |
| JP2017066089A (en) * | 2015-09-30 | 2017-04-06 | 国立大学法人東京工業大学 | Benzothienobenzothiophene derivative, organic semiconductor material, and organic transistor |
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| Title |
|---|
| CHAO YAO等: "Design and characterization of methoxy modified organic semiconductors based on phenyl[1] benzothieno[3,2-b][1]benzothiophene", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
| CHRISTIAN RUZIE´等: "Design, synthesis, chemical stability, packing,cyclic voltammetry, ionisation potential, and charge transport of [1]benzothieno[3,2-b]-[1]benzothiophene derivatives", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
| YAOWU HE等: "Molecular phase engineering of organic semiconductors based on a [1]benzothieno[3,2-b][1]benzothiophene core", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
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