CN105646528B - A kind of solubility thiophthene derivative and its preparation and application - Google Patents
A kind of solubility thiophthene derivative and its preparation and application Download PDFInfo
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- 0 *c1cc([s]c2c3[s]c(Br)c2)c3[s]1 Chemical compound *c1cc([s]c2c3[s]c(Br)c2)c3[s]1 0.000 description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N Cc(cc1)ccc1C#C Chemical compound Cc(cc1)ccc1C#C KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 2
- UTKPZZGBROTDKR-UHFFFAOYSA-N Brc1cc([s]c2c3[s]c(Br)c2)c3[s]1 Chemical compound Brc1cc([s]c2c3[s]c(Br)c2)c3[s]1 UTKPZZGBROTDKR-UHFFFAOYSA-N 0.000 description 1
- ITDBDPIGJKNUDU-UHFFFAOYSA-N C#Cc1cc([s]c2c3[s]c(C#C)c2)c3[s]1 Chemical compound C#Cc1cc([s]c2c3[s]c(C#C)c2)c3[s]1 ITDBDPIGJKNUDU-UHFFFAOYSA-N 0.000 description 1
- BBNFADGDQFVDDW-UHFFFAOYSA-N CC(C)[Si](C(C)C)(C(C)C)C#Cc1cc([s]c2c3[s]c(C#[Si+](C(C)C)(C(C)C)C(C)C)c2)c3[s]1 Chemical compound CC(C)[Si](C(C)C)(C(C)C)C#Cc1cc([s]c2c3[s]c(C#[Si+](C(C)C)(C(C)C)C(C)C)c2)c3[s]1 BBNFADGDQFVDDW-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides a kind of soluble thiophthene derivatives, have formula (1) structure.The present invention is preferable using flatness and conjugacy and three thiophene is cores, and a variety of substituent groups with alkynyl are introduced at its 2,6, is improving conjugacy that is deliquescent while can not destroying simultaneously three thiophene cores as much as possible, is realizing higher field-effect mobility.The present invention provides a kind of soluble thiophthene derivative and its Organic Thin Film Transistors used, and carrier mobility is up to 0.46cm2V‑1s‑1, switching current ratio is up to 106。
Description
Technical field
The present invention relates to organic semiconducting materials technical field, more particularly to a kind of soluble thiophthene derivative and its system
Standby and application.
Background technology
In recent years, as Organic Thin Film Transistors (Organic thin-film transistor, OTFT) is in integrated electricity
The development of road and sensor etc. application, it is very active to the research and development of high mobility organic semi-conducting material.It is solvable
The processing of liquid method is one of unique advantage of OTFT, and device cost can be greatly reduced by preparing device using solwution method, to advantageous
In the extensive use of device, this by solwution method but also prepare the research hotspot as OTFT.
Thiophenes are a kind of very promising small molecule materials, bithiophene as one such,
It is by thiphene ring and to get up to form the compound of similar acene structure, keeps thiphene ring coplanar to increase its conjugacy.With bithiophene
Derivative species seemingly, bithiophene also have two simultaneously, three simultaneously, four and and five and compound (see below).1998, Cambridge University Li
It is studied as the active layer of field-effect transistor Deng the dimer of use and three thiophene first, it is found that its mobility is
0.05cm2V-1s-1Left and right, but its switching current ratio is very high, up to 108[Li X C,Sirringhaus H,Garnier F,et
Al.J.Am.Chem.Soc., 1998,120:2206-2207].2005, Liu Yun pray etc. using and five thiophene as transistor
Active layer, and the optimization of appropriateness is carried out to device, field effect behavior is greatly improved, and mobility reaches
0.045cm2V-1s-1[Xiao K,Liu Y Q,Qi T,et al.J.Am.Chem.Soc.,2005,127:13281-13286]。
But the dissolubility of bithiophene analog derivative is poor, cannot be satisfied the requirement of solwution method processing OTFT, is still using vapor deposition mostly
Method carries out the preparation of device.
Currently, prior art has disclosed a variety of soluble benzothiophene derivatives, but for soluble and three thiophenes
The report of pheno derivative is also less.Takimiya etc. is prepared for the benzothiophene derivative Cn-BTBTs (n=5 of high-dissolvability
~14) (see below) is based on C13The hole mobility of the OTFTs of-BTBT is up to 17.2cm2V-1s-1[T Izawa,E
Miyazaki,K Takimiya.Adv.Mater.,2008,20(18):3388~3392], single crystal film skill is prepared in conjunction with printing
Art, C8The mobility of the OTFTs of-BTBT single crystal films reaches as high as 31.3cm2V-1s-1[H Minemawari,T Yamada,H
Matsui et al.Nature,2011,475(7356):364~367].Nakayama etc. is prepared for being based on using spin-coating method
C10The thin-film device of-DNTT, mobility average value reach 7.0cm2V-1s-1, prepared on plastic flexible substrate device migration
Rate is more up to 9.0cm2V-1s-1[K Nakayama,Y Hirose,J Soeda et al.Adv.Mater.,2011,23(14):
1626~1629].
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of soluble thiophthene derivative and its preparations
And application.
The technical solution adopted by the present invention is to achieve the above object：
It is a kind of solubility thiophthene derivative, derivative as shown in formula (1) structure,
In formula (1), R is hydrogen atom, C1~18Alkyl, C1~18Alkoxy, C1~18Halogenated alkoxy, C1~18Alkylthio group, C1~18
Halogenated alkylthio, C1~18Alkyl sulphonyl, C1~18It is halogenated alkyl sulfonyl, unsubstituted or be independently selected from following group and replace
Phenyl, xenyl, pyridyl group, thienyl：C1-C10Alkyl, C1-C10Alkoxy or C1-C10Halogenated alkoxy.
Preferably, R is hydrogen atom, C in the general formula (1)4-12Alkyl, C4-12Alkoxy, C4-12Halogenated alkoxy, C4-12
Alkylthio group, C4-12Halogenated alkylthio, C4-12Alkyl sulphonyl, C4-12Halogenated alkyl sulfonyl, it is unsubstituted or be independently selected from
Phenyl, xenyl, pyridyl group, the thienyl of lower group substitution：C1-C10Alkyl, C1-C10Alkoxy or C1-C10Halogenated alkoxy.
Further to be preferably, R is hydrogen atom, C in the general formula (1)6-10Alkyl, C6-10Alkoxy, C6-10Haloalkoxy
Base, C6-10Alkylthio group, C6-10Halogenated alkylthio, C6-10Alkyl sulphonyl, C6-10It is halogenated alkyl sulfonyl, unsubstituted or only
Vertical phenyl, xenyl, pyridyl group, thienyl selected from the substitution of following group：C1-C10Alkyl, alkoxy or halogenated alkoxy.
It is further that preferably particular compound is shown in formula (1),
3 bromo thiophene is generated simultaneously three thiophene by a kind of preparation method of solubility thiophthene derivative through lithiation；So
Afterwards by gained and three thiophene products progress bromination reaction；After reaction Sonogashira is carried out with the terminal alkyne compound with substituent group
Coupling reaction obtains the soluble thiophthene derivative with formula (1) structure.
The lithiation is that 3 bromo thiophene is generated the vulcanization of 3,3 '-Dithiophenes with n-BuLi in the presence of the solvent
Object, then the 3 of generation, 3 '-Dithiophene sulfide and n-BuLi are subjected to lithiation and obtain simultaneously three thiophene, entire lithiation
It is carried out 6~24 hours in -78 DEG C~35 DEG C；
The product of the lithiation is with bromo fourth lactim with 1:1~1:3 molar ratio in the presence of the solvent in-
10 DEG C~25 DEG C carry out bromination reaction 6~24 hours；
The product of the bromination reaction is with Terminal Acetylenes (R ≡) compound with substituent group with 1:2~1:6 molar ratio is organic
In the presence of palladium catalyst, cuprous iodide and solvent, Sonogashira reactions 12~36 hours are carried out in 20 DEG C~40 DEG C, i.e.,
Obtain soluble acene compound shown in the formula (1) containing 2 alkynyls in structure.
Organic palladium catalyst loading is the 1%~20% of the amount (mol) of the terminal alkyne compound substance with substituent group, iodate
Cuprous additive amount is the 1%~20% of the amount (mol) of the terminal alkyne compound substance with substituent group.
Solvent in above-mentioned each reaction is one or more of in toluene, tetrahydrofuran, dichloromethane；
Organic palladium catalyst is tetra-triphenylphosphine palladium, palladium, tris(dibenzylideneacetone) dipalladium, bi triphenyl phosphine
It is one or more of in palladium chloride；
The terminal alkyne compound with substituent group is 4- hexyls phenylacetylene, 4- heptyl phenylacetylene, 4- octyls phenylacetylene, 4- nonyls
Base phenylacetylene, 4- decyls phenylacetylene, trimethylsilyl acetylene, triisopropyl silico acetylene, 2- acetylene -5- hexyl thiophenes, 2- acetylene -5-
Heptyl thiophene, 2- acetylene -5- octyl thiophenes, 2- acetylene -5- nonyls thiophene, 2- acetylene -5- decylthiophenes.
Be added in Sonogashira reactions simultaneously diisopropylamine can fast reaction rate, and diisopropylamine additive amount
It is the 5%~30% of amount of solvent.
The preparation method of soluble acene compound shown in other formulas (1), by the formula (1) of the siliceous acetenyl of above-mentioned gained
Shown in soluble acene compound be hydrolyzed to obtain 2,6- diacetylenes-and three thiophene, after reaction with the end with substituent group
Alkine compounds carry out Sonogashira coupling reactions, obtain soluble acene compound shown in other formulas (1)
The hydrolysis is that by 2,6- bis- (triisopropyl silico acetylene)-and three thiophene and tetrabutyl ammonium fluoride are with 1:1~
1:In the presence of the solvent, in 80 DEG C~110 DEG C reaction is hydrolyzed 2~8 hours in 4 molar ratio；
The product of the hydrolysis is with the terminal alkyne compound with substituent group with 1:2~1:6 molar ratio organic palladium catalyst,
In the presence of cuprous iodide and solvent, Sonogashira are carried out in 20 DEG C~40 DEG C and react 12~36 hours to get in structure
Soluble acene compound shown in formula (1) containing 4 alkynyls.
A kind of Organic Thin Film Transistors material, the Organic Thin Film Transistors are compound shown in general formula (1) with material.
Compound is as spin coating material shown in the general formula (1).
A kind of Organic Thin Film Transistors, Organic Thin Film Transistors are substrate, the dielectric layer for being provided with grid and both ends difference
It is provided with drain electrode and the semiconductor layer of source electrode, the semiconductor layer is soluble acene compound shown in general formula (1)；
Wherein, the semiconductor layer is compound on the dielectric layer, and the dielectric layer is compound on the substrate：Or institute
It gives an account of electric layer to be compound on the semiconductor layer, the semiconductor layer is compound on the substrate.
The semiconductor layer be soluble acene compound shown in general formula (1) is dissolved by organic solvent, and after through moving back
Fire, depositing electrode are to get to semiconductor layer.
The organic solvent is chloroform, trichloroethanes, chlorobenzene, dichloro-benzenes, trichloro-benzenes, chlorotoluene, toluene, diformazan
Benzene, methyl phenyl ethers anisole, naphthane or trimethylbenzene.
As abovementioned alkyl, can enumerate methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary butyl,
N-pentyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane
Base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base etc..
As above-mentioned halogenated alkyl, such as chloromethyl, 1- chloroethyls, 2- chloroethyls, 2- chlorine isobutyl group, 1,2- bis- can be enumerated
Chloroethyl, bis- chloro isopropyls of 1,3-, bis- chloro- tertiary butyls of 2,3-, tri- chloropropyls of 1,2,3-, tri- bromopropyls of 1,2,3-, iodomethyl, 1-
Iodine ethyl, 2- iodine ethyl, 2- iodine isobutyl group, 1,2- diiodo-s ethyl, 1,3- diiodo-s isopropyl, bis- iodo- tertiary butyls of 2,3-, 1,2,3-
Triiodo propyl, toluene fluoride, 1- methyl fluorides, 2- methyl fluorides, 2- fluorine isobutylbenzene, 1,2- bis-fluoro ethyls, difluoromethyl, trifluoromethyl,
Pentafluoroethyl group, perfluoroisopropyl, perfluoro butyl, perfluorocyclohexyl etc..
Above-mentioned alkoxy is OY1Represented group, Y1Example identical with the group illustrated in abovementioned alkyl can be enumerated,
Above-mentioned halogenated alkoxy is-OY2Represented group, Y2Example identical with the group illustrated in above-mentioned halogenated alkyl can be enumerated.
Above-mentioned alkylthio group is-SY1Represented group, Y1Example identical with the group illustrated in abovementioned alkyl can be enumerated,
Above-mentioned halogenated alkylthio is-SY2Represented group, Y2Example identical with the group illustrated in above-mentioned halogenated alkyl can be enumerated.
Abovementioned alkyl sulfonyl is-SO2Y1Represented group, Y1It can enumerate same as the group illustrated in abovementioned alkyl
Example, above-mentioned halogenated alkyl sulfonyl is-SO2Y2Represented group, Y2It can enumerate and illustrate in above-mentioned halogenated alkyl
The identical example of group.
Hereinafter, enumerating the concrete example of the Organic Thin Film Transistors compound of the present invention, the present invention is not limited to followingization
Close object.
It should be noted that in the electronic device of transistor etc, electricity can be obtained by using the material of high-purity
Field-effect mobility or the high device of on/off ratio.Therefore as needed, preferably pass through column chromatography, recrystallization, distillation, distillation etc.
Method is refined.It is preferred that can be combined by these process for purification Reusabilities, or by a method excessively, thus purity is improved.
In turn.As refined final process, preferably sublimation purifying is at least repeated 2 times above.It is preferred that by obtained by the above method
The material that the purity that HPLC is measured is 90% or more further preferably uses 95% or more material, particularly preferably uses 99%
Above material can play material it is possible thereby to improve the field effect mobility or switching current ratio of Organic Thin Film Transistors
The original specific performance of material.
The organic semiconducting materials of the present invention can be used as spin coating with material to use.
The present invention also provides a kind of Organic Thin Film Transistors, including substrate, be provided with grid dielectric layer and both ends point
It is not provided with drain electrode and the semiconductor layer of source electrode, the semiconductor layer includes that soluble bithiophene described above derives
Object；Wherein, the semiconductor layer is compound on the dielectric layer, and the dielectric layer is compound on the substrate：Or it is given an account of
Electric layer is compound on the semiconductor layer, and the semiconductor layer is compound on the substrate.
In the present invention, the Organic Thin Film Transistors (OTFT) includes substrate.It is described essentially commonly used in the art basic,
Can be silicon chip, glass or plastic tab.For preparing flexible device, the Organic Thin Film Transistors frequently with plastic base,
Such as polyester (polyester), makrolon (polycarbonate) or polyimides (polyimide) material.The present invention couple
The thickness of the substrate is not particularly limited, and generally 10 microns~10 millimeters, for flexible plastic substrates, thickness is preferably
50 microns~5 millimeters, for the hard substrate of silicon chip, thickness is preferably 0.5 millimeter~10 millimeters.
The Organic Thin Film Transistors includes dielectric layer, is provided with grid.The grid is formed by conductive material, can be with
It is metallic film, conducting polymer thin film, the conductive film formed by conductive ink or conducting resinl or substrate itself such as heavy doping
Silicon chip.Wherein, the metallic film can be aluminium, gold, silver, chromium or tin indium oxide (ITO)；The conducting polymer thin film can
To be poly- (3,4- dichloroethanes the thiophene) (PEDOT of poly- (styrene sulfonate) doping：PSS)；The conductive ink can be
Carbon black (carbon black)；The conducting resinl can be elargol (silver colloid).The thickness of the grid can basis
Depending on material therefor, for the grid formed by metallic film, thickness is generally 10 nanometers~100 nanometers；For by conduction
The grid that polymer is formed, thickness are generally 0.5 micron~10 microns.
The dielectric layer is usually by the thin of inorganic material, organic polymer or organic polymer and inorganic material hybrid material
Film is formed.Wherein, the inorganic material is silica, silicon nitride, aluminium oxide, barium titanate, pick acid barium or tantalum pentoxide；Institute
It is polymethyl methacrylate (PMMA), polyvinylphenol (PVP), polyvinyl alcohol (PVA), polystyrene to state organic polymer
(PS), polyvinyl chloride (PVC) or polyimides.The thickness of the dielectric layer depends on the dielectric constant of material therefor, generally
10 nanometers~500 nanometers.
Dressing agent may be used in the present invention, and selectively the dielectric layer is modified, and to form decorative layer, is situated between to change
Interfacial property between electric layer and semiconductor layer is beneficial to improve the performance of organic thin film transistor device.The dressing agent includes
Silicon-containing compound, phosphorous acid compound and high dielectric constant polymer etc..Wherein, the silicon-containing compound can be obtained on dielectric layer
Free hydroxyl chemically reacts, and the self-assembled monolayer (slef-assemble monolayer) for being widely used in dielectric layer is repaiied
Decorations；Common silicon-containing compound includes octadecyl trichlorosilane alkane (ODTS), phenyl trichlorosilane and fluorine-containing alkyltrichlorosilanes
Deng, specific silicon-containing compound dressing agent and method of modifying can refer to Applied Physics impurity (J.Appl.Phys., 2004,96,
Associated description 6431-6438).The phosphorous acid compound can also be applied to the self-assembled monolayer modification of dielectric layer；Commonly
Phosphorous acid compound includes the phosphoric acid etc. of the phosphoric acid and phenyl substitution of carbon chain lengths 12~16, and specific phosphoric acid is compound-modified
The correlation that agent and method of modifying can refer to B volumes of physical chemistry magazine (J.Phys.Chem.B, 2003,107,5877-5881) is retouched
It states.The high dielectric constant polymer includes polymethyl methacrylate (PMMA), polyvinylphenol (PVP), polyvinyl alcohol
(PVA), polystyrene (PS), polyvinyl chloride (PVC) or polyimides etc., specific type can refer to advanced material magazine
The associated description of (Adv.Mater., 2005,17,1705-1725).
The Organic Thin Film Transistors includes semiconductor layer, and both ends are respectively arranged with drain electrode and source electrode.The source
Material identical with the grid may be used in electrode and the drain electrode, but to ensure electrode material and semiconductor layer material
Between have small contact resistance.The present invention is not particularly limited the thickness etc. of the drain electrode and the source electrode, and thickness is excellent
40 nanometers~100 nanometers are selected as, the breadth length ratio of the conducting channel of formation is preferably 30.
The semiconductor layer includes the soluble thiophthene derivative with formula (I) structure described above, described solvable
Property thiophthene derivative in organic solvent have preferable dissolubility, using solwution method be easy to processing film forming, so as to letter
Change the preparation method of Organic Thin Film Transistors.For example, relative to simultaneously three thiophene, the present invention has the solubility of formula (I) structure simultaneously
The raising of the dissolubility of thiophene derivant at least 100%.In the present invention, the organic solvent can be chloroform, three
Chloroethanes, chlorobenzene, dichloro-benzenes, trichloro-benzenes, chlorotoluene, toluene, dimethylbenzene, methyl phenyl ethers anisole, naphthane or trimethylbenzene.Wherein, three
Chloromethanes, trichloroethanes, chlorobenzene, dichloro-benzenes, trichloro-benzenes or chlorotoluene etc. belong to chlorinated solvent, and the solubility bithiophene spreads out
Solubility of the biology in toluene solvant is generally 0.05wt%~5wt%.
Meanwhile the soluble thiophthene derivative can improve the carrier mobility of Organic Thin Film Transistors, conducive to answering
With.The semiconductor layer preferably also includes polymer, i.e., the described soluble thiophthene derivative, which is blended to be formed with polymer, partly leads
Body layer.The polymer includes polymer containing triaryl amine (poly (triarylamine)), polycarbazole, polyfluorene, polythiophene, poly- second
Alkene, polystyrene, polymethyl methacrylate, polyvinylphenol and makrolon etc..
In the present invention, the preparation method of semiconductor layer is preferably specially：The soluble thiophthene derivative is made into
Film is prepared after solution, annealed, depositing electrode obtains semiconductor layer.
In the present invention, it includes spin coating to prepare the processing technology of film after the soluble thiophthene derivative wiring solution-forming
(spin-coating), dip-coating (dip-coating), blade coating (blade-coating), silk-screen printing (screening-
Printing), the common solwution method film technique at this stage such as inkjet printing (inkjet-printing).The thickness of the film
Degree is preferably controlled to 10 nanometers~100 nanometers, and more preferably control is 30 nanometers~60 nanometers.The temperature of the annealing is preferably 50
DEG C~150 DEG C, more preferably 80 DEG C~120 DEG C；The time of the annealing is preferably 10 minutes~50 minutes, more preferably 20 points
Clock~40 minute.
In the present invention, the semiconductor layer is compound on the dielectric layer, the dielectric layer be compound in it is described substantially；
Or the dielectric layer is compound on the semiconductor layer, the semiconductor layer is compound on the substrate.In addition, the dielectric
Include layer-selective decorative layer.
Advantage for present invention：
Compared with prior art, soluble thiophthene derivative provided by the invention has formula (1) structure, is 2,6- bis-
Replace simultaneously terthiophene.The inhomogeneities such as alkyl, alkoxy, the alkylthio group that the present invention introduces different carbon chain lengths to 2 and 6
The substituent group of type, the selectivity using this pair and three thiophene replace, and can improve deliquescent while not break as much as possible
Bad and three thiophene conjugacy, can reduce the harmful effect of substituent group pair and the arrangement mode of three thiophene cores in the film, into
And realize higher field-effect mobility.Therefore, can be had using soluble thiophthene derivative provided by the invention
The Organic Thin Film Transistors of high mobility.The experimental results showed that being existed using soluble thiophthene derivative provided by the invention
The solubility of conventional organic solvent reaches 50mg/ml, meets the requirement that solwution method prepares thin film transistor (TFT), and prepared is organic thin
Film transistor, carrier mobility can reach 0.46cm2V-1s-1, on-off ratio is up to 106。
In addition, the present invention enriches the type of soluble thiophthene derivative, and the present invention is using soluble bithiophene
Derivative prepares Organic Thin Film Transistors in the method for liquid deposition, and method is easy, cost is relatively low.
Description of the drawings
Fig. 1 is the first structural schematic diagram of Organic Thin Film Transistors provided in an embodiment of the present invention；Wherein, 1 is base
Plate, 2 be grid, and 3 be dielectric layer, and 4 be decorative layer, and 5 be semiconductor layer, and 6 be source electrode, and 7 be drain electrode；Semiconductor layer 5 is compound
In on decorative layer 4, decorative layer 4 is compound on dielectric layer 3, and dielectric layer 3 is compound on substrate 1；Grid 2 is set on dielectric layer 3,
Source electrode 6 and drain electrode 7 are set to the upper surface at 5 both ends of semiconductor layer.
Fig. 2 is second of structural schematic diagram of Organic Thin Film Transistors provided in an embodiment of the present invention；Wherein, Fig. 2 and Fig. 1
Differ only in, source electrode 6 and drain electrode 7 are respectively arranged at the lower surface at 5 both ends of semiconductor layer.
Fig. 3 is the third structural schematic diagram of Organic Thin Film Transistors provided in an embodiment of the present invention, wherein dielectric layer 3
It is compound on semiconductor layer 5, semiconductor layer 5 is compound on decorative layer 4, and decorative layer 4 is compound on substrate 1；Grid 2 is set to Jie
In electric layer 3, source electrode 6 and drain electrode 7 are respectively arranged at the lower surface at 5 both ends of semiconductor layer.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only for the feature that further illustrates the present invention and a little, rather than to the limit of invention claim
System.
The preparation of 1 compound of embodiment (A-1)
3 bromo thiophene (8ml, 0.08mol), ether (32ml) are added in reactor that is dry and being continually fed into nitrogen,
- 78 DEG C are cooled to, n-BuLi (32ml, 0.08mol) is slowly added to, is stirred 40 minutes.Then reaction solution is warming up to 0
DEG C, remove butyl bromide under vacuum, rejoin ether (32ml), then solution is cooled to -78 DEG C, be added sulphur (2.56g,
0.08mol), it stirs 30 minutes.Be warming up to 0 DEG C stir 30 minutes, into solution be added paratoluensulfonyl chloride (15.22g,
0.08mol), kept for 0 DEG C react 30 minutes.40 DEG C are warming up to, keeps the temperature 4 hours.Second part of 3- lithium-is prepared according to above-mentioned step
Thiophene (1.2eq.), n-BuLi (38.4ml, 0.096mol) and 3 bromo thiophene (8.93ml, 0.072mol).Reaction solution liter
Temperature removes butyl bromide, and rejoin ether to 0 DEG C under vacuum.It is at -78 DEG C, the ether of second part of 3- lithiums-thiophene is molten
Liquid is added in first part of reaction solution, keeps the temperature 1 hour, then heats to room temperature, reaction is overnight.Second day by reaction solution
It is cooled to 0 DEG C, is slowly added to n-BuLi (70.4ml, 0.176mol) thereto, stirs 30 minutes, is then refluxed for 1 hour.Drop
Dichloride copper (24.42g, 0.184mol) is added to 0 DEG C in temperature, stirs 1 hour, then be warming up to room temperature, and reaction is overnight.Filtering life
At solid, collect organic phase, column chromatography purify (n-hexane).It is recrystallized with n-hexane, obtains flaxen powder
(4.74g, yield 30.3%).
Compound 1 (2.94g, 15.0mmol), dry DMF (60ml) are added into flask, is cooled to 0 DEG C, delays thereto
It is slow that bromo fourth lactim (5.87g, 33.0mmol) is added.After charging, it is warming up to room temperature, and be stirred overnight.It will reaction
Solution is poured into water generation precipitation, and filtering is used in combination methanol to wash.Product is recrystallized with chloroform/methanol mixed solvent, vacuum
It is dried to obtain pale solid (5.14g, yield 97%).
Compound 2 (0.750g, 2.1mmol), [Pd are added in reactor that is dry and being continually fed into nitrogen
(PPh3)4] the dry tetrahydrofuran (15ml) of (122mg, 5%mol), cuprous iodide (15mg, 3%mol).Nitrogen is bubbled 15 points
Then the diisopropylamine of 3ml is added in clock into solution, continue to be bubbled 5 minutes.4- hexyl phenylacetylenes are added dropwise into solution
(0.98g, 5.3mmol), reaction solution is stirred at room temperature, and reacts 12 hours.Vacuum distillation removes solvent, and crude product utilizes column
Chromatography is purified (dichloromethane/petroleum ether=1:4) pale yellow solid (1.05g, yield 88%), is obtained.
The preparation of 2 compound of embodiment (A-2)
Difference from Example 1 is, 4- hexyls phenylacetylene 4- heptyl phenylacetylenes is replaced, then according to embodiment
The step of prepare compound (A-2), be shown below.
The preparation of 3 compound of embodiment (A-3)
Difference from Example 1 is, 4- hexyls phenylacetylene 4- octyl phenylacetylenes is replaced, then according to embodiment
The step of prepare compound (A-3), be shown below.
The preparation of 4 compound of embodiment (A-8)
Difference from Example 1 is, 4- hexyl phenylacetylenes is replaced with trimethylsilyl acetylene, then according to embodiment
The step of prepare compound (A-8), be shown below.
The preparation of 5 compound of embodiment (A-9)
Difference from Example 1 is, 4- hexyls phenylacetylene triisopropyl silico acetylene is replaced, then according to implementation
The step of example, prepares compound (A-9), is shown below.
The preparation of 6 compound of embodiment (A-10)
Synthesis obtains compound (A-9) as described in Example 5, adds in reactor that is dry and being continually fed into nitrogen
Enter compound (A-9) (1.00g, 1.80mmol) and tetrabutyl ammonium fluoride (0.94g, 3.60mmol), syringe be used in combination that nothing is added
Water-toluene (20ml).Solution leads to nitrogen gas stirring 5 hours at reflux.TLC is used for detecting reaction end.After reaction,
50ml deionized waters are added and are washed three times.Organic layer is obtained by extraction and removes solvent, obtains crude product, column chromatography purification
(petroleum ether) obtains compound 3 (0.40g, yield 90%).
Compound 3 (0.40g, 1.64mmol), Pd (PPh are added in dry reactor3)2Cl2(58mg, 5%mol),
The dry tetrahydrofuran (20ml) of cuprous iodide (10mg, 3%mol), be added dropwise into solution 4- hexyls phenylacetylene (0.73g,
3.94mmol), reaction solution is stirred at room temperature, and reacts 12 hours.Vacuum distillation remove solvent, crude product using column chromatography into
Row purification (dichloromethane/petroleum ether=1:4) pale yellow solid chemical compound (A-10) (0.87g, yield 87%), is obtained.
The preparation of 7 compound of embodiment (A-11)
Difference from Example 6 is, 4- hexyls phenylacetylene 4- heptyl phenylacetylenes is replaced, then according to embodiment
The step of prepare compound (A-11), be shown below.
The preparation of 8 compound of embodiment (B-1)
Difference from Example 1 is, 4- hexyls phenylacetylene 2- acetylene -5- hexyl thiophenes are replaced, then according to
The step of embodiment, prepares compound (B-1), is shown below.
The preparation of 9 compound of embodiment (B-2)
Difference from Example 1 is, 4- hexyls phenylacetylene 2- acetylene -5- heptyl thiophene is replaced, then according to
The step of embodiment, prepares compound (B-2), is shown below.
The preparation of 10 compound of embodiment (B-3)
Difference from Example 1 is, 4- hexyls phenylacetylene 2- acetylene -5- octyl thiophenes are replaced, then according to
The step of embodiment, prepares compound (B-3), is shown below.
The preparation of 11 compound of embodiment (B-4)
Difference from Example 1 is, 4- hexyls phenylacetylene 2- acetylene -5- nonyl thiophene is replaced, then according to
The step of embodiment, prepares compound (B-4), is shown below.
The preparation of 12 compound of embodiment (B-5)
Difference from Example 1 is, 4- hexyls phenylacetylene 2- acetylene -5- decylthiophenes are replaced, then according to
The step of embodiment, prepares compound (B-4), is shown below.
The compound that above-described embodiment obtains is shown in Table 1 in the solubility of Conventional solvents.
Solubility of 1 organic semiconductor compound of table in conventional organic solvent
| Compound | Solubilitya(mg/ml) |
| Toluene | Chloroform | Dichloromethane | Acetone | |
| A-1 | 25 | 25 | 25 | 10 |
| A-8 | 50 | 50 | 50 | 25 |
| A-9 | 50 | 50 | 50 | 25 |
| A-10 | 25 | 25 | 25 | 10 |
| B-1 | 30 | 30 | 30 | 15 |
| B-3 | 30 | 30 | 30 | 10 |
aSolubility is the quality for the compound that can be dissolved in 1 milliliter of solvent.
The preparation of 13~embodiment of embodiment, 17 silicon wafer substrate Organic Thin Film Transistors
Using the n-type silicon chip of heavy doping as substrate；
It is covered with thickness on the substrate to be 300nm, be provided with the silicon dioxide dielectric layers of grid, the grid is heavily doped
Miscellaneous n-type silicon chip；
The silicon dioxide dielectric layers are modified using octyl tri-chlorination silane, form decorative layer；
Thickness is covered on the decorative layer in 30 nanometers~60 nanometers of semiconductor layer, the preparation of the semiconductor layer
Journey difference is as follows：The soluble bithiophene that embodiment 1, embodiment 4, embodiment 5, embodiment 8, embodiment 10 obtain is selected to derive
Object is made into the toluene solution of a concentration of 0.5wt% respectively as semi-conducting material, rotating speed be 1000rpm, rotational time 60
Film is formed under conditions of second, is then annealed, for the temperature and time of the annealing referring to table 2, table 2 is the embodiment of the present invention
The main technologic parameters and performance of the Organic Thin Film Transistors of offer.After annealing, the gold that redeposited thickness is 50 nanometers is as source
The breadth length ratio of electrode and drain electrode, the conducting channel of formation is 30 (W/L=3000 microns/100 microns=30), obtains semiconductor
Layer, eventually forms Organic Thin Film Transistors.After obtaining Organic Thin Film Transistors, then use above-mentioned acquisition compound according to routine
Mode measures its transfer curve respectively, and each carrier mobility, the result of switching current ratio are referring to table 2.
The technological parameter and performance for the Organic Thin Film Transistors that 2 embodiment of the present invention 13~17 of table provides
As shown in Table 2, the soluble thiophthene derivative provided using the embodiment of the present invention 5 prepares organic thin-film transistor
Pipe, carrier mobility can reach 0.46cm2V-1s-1, switching current ratio is up to 106。
As seen from the above embodiment, it can be obtained with compared with Gao Qian using soluble thiophthene derivative provided by the invention
The Organic Thin Film Transistors of shifting rate.The present invention is not limited to the above embodiments.In general, polycrystalline organic thin film disclosed in this invention
Body pipe can process the element to be formed in two and three dimensions integrated device.These integrated devices can apply to flexible integration circuit, have
Source matrix is shown etc..It can be processed with cryogenic fluid using the organic thin-film transistor device based on the present invention.
The explanation of above example is only intended to help to understand method and core concept of the invention.It should be pointed out that for
For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention
Dry improvement and modification, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
Claims (7)
1. a kind of solubility thiophthene derivative, it is characterised in that：Derivative such as formula（1）Shown in structure,
Formula（1）
Formula（1）In, R is trimethyl silicon substrate, triisopropylsilyl.
2. a kind of preparation method of soluble thiophthene derivative described in claim 1, it is characterised in that：3 bromo thiophene is passed through
Two step lithiations generate and three thiophene；Then by gained and three thiophene products progress bromination reaction；After reaction with band substituent group
Terminal alkyne compound carry out Sonogashira coupling reactions, obtain with formula（1）The soluble thiophthene derivative of structure；
The lithiation is, 3 bromo thiophene is small in -78 DEG C~35 DEG C progress lithiations 6~24 in the presence of the solvent
When；
The product of the lithiation is with bromo fourth lactim with 1:1~1:3 molar ratio is in the presence of the solvent in -10 DEG C
~25 DEG C carry out bromination reaction 6~24 hours；
The product of the bromination reaction is with the terminal alkyne compound with substituent group with 1:2~1:6 molar ratio organic palladium catalyst,
In the presence of cuprous iodide and solvent, carries out Sonogashira in 20 DEG C~40 DEG C and react 12~36 hours；Organic palladium chtalyst
Agent additive amount is the 1%~20% of the amount of the terminal alkyne compound substance with substituent group, and cuprous iodide additive amount is the end with substituent group
The 1%~20% of the amount of alkine compounds substance；
The solvent respectively reacted is one or more of in toluene, tetrahydrofuran, dichloromethane；
Organic palladium catalyst is tetra-triphenylphosphine palladium, palladium, three（Dibenzalacetone）Two palladiums, bi triphenyl phosphine dichloride
Change one or more of in palladium.
3. a kind of Organic Thin Film Transistors material, it is characterised in that:The Organic Thin Film Transistors is claim 1 with material
The soluble thiophthene derivative.
4. Organic Thin Film Transistors material as described in claim 3, it is characterised in that:The solubility thiophthene derivative
As spin coating material.
5. a kind of Organic Thin Film Transistors, it is characterised in that：Organic Thin Film Transistors be substrate, be provided with grid dielectric layer and
Both ends are respectively arranged with drain electrode and the semiconductor layer of source electrode, the semiconductor layer be shown in claim 1 it is soluble simultaneously
Thiophene derivant；
Wherein, the semiconductor layer is compound on the dielectric layer, and the dielectric layer is compound on the substrate：Or it is given an account of
Electric layer is compound on the semiconductor layer, and the semiconductor layer is compound on the substrate.
6. Organic Thin Film Transistors as described in claim 5, it is characterised in that：The semiconductor layer is by claim 1 institute
The soluble thiophthene derivative shown is dissolved by organic solvent, and then annealed, depositing electrode is to get to semiconductor layer.
7. Organic Thin Film Transistors as described in claim 6, it is characterised in that：The organic solvent is chloroform, trichlorine
Ethane, chlorobenzene, dichloro-benzenes, trichloro-benzenes, chlorotoluene, toluene, dimethylbenzene, methyl phenyl ethers anisole, naphthane or trimethylbenzene.
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