CN102206225B - Polymer semiconducting material and organic thin film transistor - Google Patents
Polymer semiconducting material and organic thin film transistor Download PDFInfo
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- CN102206225B CN102206225B CN 201110088350 CN201110088350A CN102206225B CN 102206225 B CN102206225 B CN 102206225B CN 201110088350 CN201110088350 CN 201110088350 CN 201110088350 A CN201110088350 A CN 201110088350A CN 102206225 B CN102206225 B CN 102206225B
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Abstract
The invention provides a compound with a structure shown in a formula (I) in the specification, a polymer and a polymer semiconducting material. An N atom is introduced into the compound and an alkyl chain is introduced into the N atom, so that the polymer based on the compound containing N and S hetero atoms has excellent solubility in an organic solvent. Furthermore, the compound provided by the invention contains thiofuran rings at two ends, and can effectively reduce the steric hindrance between adjacent units in the polymer based on the compound containing N and S hetero atoms, and improve the conjugation degree of the polymer, thus guaranteeing that an organic thin film transistor using the polymer semiconducting material has high mobility. The invention also provides the organic thin film transistor using the polymer semiconducting material. Experiment results show that the organic thin film transistor provided by the invention has a mobility of 0.073 cm<2>/V.s.
Description
Technical field
The present invention relates to technical field of semiconductor, more particularly, relate to a kind of polymer semiconductor material and OTFT.
Background technology
Polymer semiconductor's material is a kind of novel semiconductor material of being convenient to synthetic two aspect advantages that has optics, electric property and the polymkeric substance of inorganic semiconductor simultaneously, is widely used in the OTFT field.Because polymer semiconductor's material can adopt processing means such as solution spin coating, printing, printing to prepare electron devices such as lower-cost OTFT, thereby receives much concern in recent years.Regio-regular poly-(3-hexyl thiophene) is first polymer semiconductor's material with excellent hole transport performance (rr-P3HT), and its mobility can reach 0.1cm
2/ Vs (Nature, 1999,401,685-688.).But, oxidized easily or mix because poly-(3-hexyl thiophene) HOMO energy level (rr-P3HT) is too high, thus make the OTFT device instability of preparation, limited its application.
In order to solve the too high problem of HOMO energy level of polymer semiconductor's material, the various countries research worker has done big quantity research, found that: will contain heteroatomic condensed ring aromatic compound and introduce in the conjugated polymers, the HOMO energy level of polymkeric substance can be effectively reduced, polymer semiconductor's material of high mobility and high stability can be obtained to have concurrently.For example, American Chemical Society's magazine (J.Am.Chem.Soc., 2008,130 in 2008,13202-13203.) and the patent No. be the american documentation literature of US2007161776A1 reported a kind of with and four thiophene be the conjugated polymers of construction unit, mobility reaches 0.3cm
2/ Vs; JACS in 2010 (J.Am.Chem.Soc., 2010,132,5000-5001.) reported that a kind of is the conjugated polymers of construction unit with two thieno-naphthalenes.
But the polymer semiconductor's solvability of material in organic solvents such as chlorobenzene or toluene of above-mentioned report is relatively poor, thereby has limited the application of polymer semiconductor's material aspect OTFT.The inventor considers that a kind of compound, polymkeric substance and polymer semiconductor's material are provided, and this polymer semiconductor's material has good solubility, thereby satisfies the application in OTFT.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of compound, polymkeric substance and polymer semiconductor's material, and this polymkeric substance has good solubility in organic solvent; The present invention also provides a kind of OTFT of using this polymer semiconductor's material.
The invention provides the compound shown in a kind of formula (I):
Wherein, R
1Be alkyl; R
2Be H or alkyl; R
3Be H, halogen or trialkyltin.
Preferably, described R
1Be C
4～C
22Straight chained alkyl or C
4～C
22The branched chain alkyl.
Preferably, described R
2Be C
4～C
22Straight chained alkyl.
Preferably, described halogen is Br or I; Described trialkyltin is tributyl tin or tin trimethyl.
The present invention also provides the polymkeric substance shown in a kind of formula (II),
Wherein, R
11Be alkyl, R
21Be H or alkyl, Ar is the conjugate unit that contains thiophene unit, and n is the polymerization degree.
Preferably, described R
11Be C
4～C
22Straight chained alkyl or C
4～C
22The branched chain alkyl.
Preferably, described R
21Be C
4～C
22Straight chained alkyl.
Preferably, described Ar is a kind of in the structure shown in formula (III), formula (IV), formula V, the formula (VI),
Wherein, R
41, R
42, R
5, R
6And R
12Independent separately is alkyl; R
22Be H or alkyl.
Preferably, described R
41, R
42, R
5And R
6Independent separately is C
10～C
22Straight chained alkyl;
Described R
12Be C
4～C
22Straight chained alkyl or C
4～C
22The branched chain alkyl;
Described R
22Be C
4～C
22Straight chained alkyl.
The present invention also provides a kind of technique scheme polymer semiconductor's material that described polymkeric substance constitutes.
The present invention also provides a kind of OTFT, and charge transport layer is the described polymer semiconductor of a technique scheme material.
The invention provides a kind of compound, polymkeric substance and polymer semiconductor's material with formula (I) structure, the present invention introduces two kinds of heteroatomss of N, S in this compound, wherein, the N atom is positioned at the compound center, the present invention is by introducing the N atom, and on the N atom, introduce alkyl chain, provided by the inventionly in organic solvent, have good solubility thereby make based on the polymkeric substance that contains N, two kinds of heteroatomic compounds of S.In addition, compound provided by the invention has the thiphene ring that is positioned at the compound two ends, can effectively reduce based on steric hindrance between adjacent cells in the polymkeric substance that contains N, two kinds of heteroatomic compounds of S, improve the polymkeric substance conjugated degree, thereby guaranteed to use the OTFT of this polymer semiconductor's material to have higher mobility.The present invention also provides a kind of OTFT of using this polymer semiconductor's material, and experimental result shows that OTFT mobility provided by the invention is 0.073cm
2/ Vs.
Description of drawings
Fig. 1 is the structural representation of OTFT provided by the invention;
Fig. 2 is the output characteristic curve figure of the P-bTC16 of the embodiment of the invention 19 preparations as the OTFT of charge transport layer preparation;
Fig. 3 is the transfer characteristic curve figure of the P-bTC16 of the embodiment of the invention 19 preparations as the OTFT of charge transport layer preparation;
Fig. 4 is the output characteristic curve figure of the P-bTC16 of the embodiment of the invention 19 preparations as the OTFT of charge transport layer preparation;
Fig. 5 is the transfer characteristic curve figure of the P-bTC16 of the embodiment of the invention 19 preparations as the OTFT of charge transport layer preparation;
Fig. 6 is the atomic power shape appearance figure of the P-bTC10 initial film of the embodiment of the invention 17 preparations;
Fig. 7 is the atomic power shape appearance figure of the P-bTC10 of the embodiment of the invention 17 preparations at 20 minutes film of 180 ℃ of annealing;
Fig. 8 is the atomic power shape appearance figure of the P-bTC12 initial film of the embodiment of the invention 18 preparations;
Fig. 9 is the atomic power shape appearance figure of the P-bTC12 of the embodiment of the invention 18 preparations at 20 minutes film of 180 ℃ of annealing;
Figure 10 is the atomic power shape appearance figure of the P-bTC16 initial film of the embodiment of the invention 19 preparations;
Figure 11 is the atomic power shape appearance figure of the P-bTC16 of the embodiment of the invention 19 preparations at 40 minutes film of 150 ℃ of annealing.
Embodiment
Below the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
The invention discloses the compound shown in a kind of formula (I):
Wherein, R
1Be alkyl; R
2Be H or alkyl; R
3Be H, halogen or trialkyltin.Wherein, described R
1Be preferably straight chained alkyl or branched chain alkyl, more preferably C
4～C
22Straight chained alkyl or C
4～C
22The branched chain alkyl.Described R
2Be preferably straight chained alkyl, more preferably C
4～C
22Straight chained alkyl.Described halogen is preferably Br or I, and described trialkyltin is preferably tributyl tin or tin trimethyl.
Below the preparation method with compound of formula (I) structure provided by the invention is described in detail.
With R
2Be H, R
3For H is an example, preparation process is as follows:
Step (1): N-alkyl-2, the preparation of 7-dibromo carbazole:
According to following reaction equation, according to document (Synthesis, 2003,2470-2472.) preparation of the method that provides, with the concentration of 1 times of molar weight is 2 of 0.15～0.25 mol, dimethyl formamide (DMF) drips of solution of 7-dibromo carbazole is added in the DMF turbid solution of NaH that the concentration that contains 1.3 times of molar weights is 0.4 mol, stirring at room 30 minutes, the bromo alkane of 1.2 times of molar weights of adding is in stirring at room was fallen back in 12 hours, use dichloromethane extraction, anhydrous magnesium sulfate drying is used silica gel chromatography behind the removal solvent, obtains N-alkyl-2,7-dibromo carbazole, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl.
Step (2): N-alkyl-2,7-two bromo-3, the preparation of 6-diiodocarbazol:
According to following reaction equation, with the N-alkyl-2 of step (1) preparation, 7-dibromo carbazole is dissolved in 80 ℃ the Glacial acetic acid, and concentration is 0.05～0.2 mol, adds the KI of 2.6 times of molar weights and the KIO of 1.3 times of molar weights
3, reaction solution is used dichloromethane extraction in 80 ℃ of stirrings were fallen back in 4～8 hours, and anhydrous magnesium sulfate drying is used acetone recrystallization behind the removal solvent, obtains N-alkyl-2,7-two bromo-3, the 6-diiodocarbazol, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl.
Step (3): N-alkyl-2,7-two bromo-3, the preparation of 6-two (trimethylsilyl acetylene base) carbazole:
According to following reaction equation, under argon gas atmosphere and room temperature condition, 2～2.1 times of molar weight trimethylsilyl acetylenes slowly are added drop-wise to the N-alkyl-2 that step (2) prepares, 7-two bromo-3,6-diiodocarbazol (1 times of molar weight), two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2Cl
2) (0.5～5mol%), cuprous iodide (CuI) (1～10mol%), volume ratio is (1～5): in 1 the tetrahydrofuran (THF) and the mixture of triethylamine, concentration is 0.1～0.2 mol, stirring at room 48 hours, filter, the ethyl acetate washing precipitation, collect organic phase, wash organic phase respectively with saturated ammonium chloride solution and saturated aqueous common salt, anhydrous magnesium sulfate drying is removed solvent, carries out purifying with silica gel column chromatography, obtain N-alkyl-2,7-two bromo-3,6-two (trimethylsilyl acetylene base) carbazole, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl.
Step (4a) N-alkyl two thieno-s [2,3-b; 7,6-b] preparation of carbazole:
According to following reaction equation, under argon gas atmosphere, N-alkyl-2 with the preparation of the step (3) of 1 times of molar weight, 7-two bromo-3, nine hydrated sodium sulfides of 6-two (trimethylsilyl acetylene base) carbazole, 4 times of molar weights and the mixture of N-Methyl pyrrolidone (NMP), concentration is 0.02～0.1 mol, 190 ℃ of following heated and stirred 12 hours, mixture is poured in the saturated ammonium chloride solution into extracted with diethyl ether, saturated common salt water washing organic phase, anhydrous magnesium sulfate drying is removed solvent, uses silica gel chromatography, obtain N-alkyl two thieno-s [2,3-b; 7,6-b] carbazole, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl.
With R
3Be H, R
2For alkyl is an example, the preparation process with compound of formula (I) structure provided by the invention is preferably:
Step (4b) N-alkyl-2,7-diformazan sulfenyl-3, the preparation of 6-two (trimethylsilyl acetylene base) carbazole:
According to following reaction equation, under argon gas atmosphere and-78 ℃ of cooling conditionss, N-alkyl-2 to step (3) preparation, 7-two bromo-3, the hexane solution of the n-Butyl Lithium (n-BuLi) of the 2.5M of 2.2 times of molar weights of dropping in the tetrahydrofuran solution of 6-two (trimethylsilyl acetylene base) carbazole, after 1 hour, add 2.2 times of molar weight Methyl disulfide (CH-78 ℃ of stirrings
3SSCH
3), rise to room temperature reaction and spend the night, post reaction mixture is poured in the water, dichloromethane extraction, saturated common salt water washing organic layer, organic layer is removed solvent through anhydrous magnesium sulfate drying, uses silica gel chromatography, obtain N-alkyl-2,7-diformazan sulfenyl-3,6-two (trimethylsilyl acetylene base) carbazole, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl.
Step (5b) 4, and 7-two iodo-N-alkyl two thieno-s [2,3-b; 7,6-b] preparation of carbazole:
According to following reaction equation, under argon gas atmosphere and 45 ℃ of conditions, to the N-alkyl-2 of step (4b) preparation, 7-diformazan sulfenyl-3 adds iodine (I in the dichloromethane solution of 6-two (trimethylsilyl acetylene base) carbazole
2) (4 times of molar weights), stir reaction in 6～9 hours down at 45 ℃, post reaction mixture is poured in the Sulfothiorine saturated solution, dichloromethane extraction, saturated common salt water washing organic layer, organic layer is through anhydrous magnesium sulfate drying, remove solvent, use silica gel chromatography, obtain 4,7-two iodo-N-alkyl two thieno-s [2,3-b; 7,6-b] carbazole, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl.
Step (6b) 4, and 7-dioxane alkynyl-N-alkyl two thieno-s [2,3-b; 7,6-b] preparation of carbazole:
According to following reaction equation, under argon gas atmosphere and room temperature condition, alkyl alkynes (2-2.1 times of molar weight) slowly is added drop-wise to 4 of step (5b) preparation, 7-two iodo-N-alkyl two thieno-s [2,3-b; 7,6-b] carbazole (1 times of molar weight), two (triphenylphosphine) palladium chloride (Pd (PPh
3)
2Cl
2) (0.5～5mol%), cuprous iodide (CuI) (1～10mol%), volume ratio is (1～5): in 1 the tetrahydrofuran (THF) and the mixture of triethylamine, concentration is 0.1～0.2 mol, stirring at room 48 hours, and the ethyl acetate washing precipitation, collect organic phase, wash organic phase twice respectively with saturated ammonium chloride solution and saturated aqueous common salt, anhydrous magnesium sulfate drying is removed solvent, carry out purifying with silica gel column chromatography, obtain 4, and 7-dioxane alkynyl-N-alkyl two thieno-s [2,3-b; 7,6-b] carbazole, described N-alkyl (is R
1) be C
4～C
22Straight chain or branched chain alkyl; The alkane alkynyl (promptly
) be C
4～C
22Straight chain alkane alkynyl.
Step (7b) 4, and 7-dialkyl group-N-alkyl two thieno-s [2,3-b; 7,6-b] preparation of carbazole:
According to following reaction equation, at ambient temperature, to 4,7-dioxane alkynyl-N-alkyl two thieno-s [2,3-b; 7,6-b] carbazole, weight ratio is 10% Pd/C, feeds hydrogen in the mixture of tetrahydrofuran (THF), stirring at room 12 hours filters Pd/C, removes solvent, uses silica gel chromatography, obtains 4,7-dialkyl group-N-alkyl two thieno-s [2,3-b; 7,6-b] carbazole, described N-alkyl (is R
1) be C
4-C
22Straight chain or branched chain alkyl, the alkane alkynyl is (promptly
) be C
4-C
22Straight chain alkane alkynyl, alkyl (is R
2) be C
4-C
22Straight chained alkyl.
Step (4c) meets R in the formula (I)
3Preparation for the compound of Br:
According to following reaction equation, at ambient temperature, the bromo-succinimide (NBS) of 2.05 times of molar weights joined several times meet R in the formula (I)
3Be the N of the compound of H, in the mixture of dinethylformamide (DMF), stirring at room 12 hours is poured in the water, dichloromethane extraction, saturated common salt washing organic phase twice, anhydrous magnesium sulfate drying, remove solvent, use silica gel chromatography, promptly obtain meeting R in the formula (I)
3Compound for Br.
Step (4d) meets R in the formula (I)
3Preparation for the compound of I:
The method that provides among preparation method and (4c) is identical, uses
The iodo succimide(NIS) bromo-succinimide (NBS) that adopts in the alternative steps (4c) promptly obtains meeting R in the formula (I)
3Compound for I.
Step (4e) meets R in the formula (I)
3Preparation for the compound of tin alkyl:
According to following reaction equation, under argon gas atmosphere and-20 ℃ of cooling conditionss, R in meeting formula (I)
3For dripping the hexane solution of the n-Butyl Lithium (n-BuLi) (2.1 times of molar weights) of 2.5M in tetrahydrofuran (THF) (THF) solution of the compound of H.-20 ℃ stir half hour after, the trimethyltin chloride or the tributyltin chloride that add 2.1 times of molar weights, rise to room temperature and stir and spend the night, post reaction mixture is poured in the water, dichloromethane extraction, saturated common salt water washing organic layer, organic layer is through anhydrous magnesium sulfate drying, recrystallization behind the removal solvent promptly obtains meeting R in the formula (I)
3Compound for tin alkyl.
The present invention also provides the polymkeric substance shown in a kind of formula (II),
Wherein, R
11Be alkyl, R
21Be H or alkyl, Ar is the conjugate unit that contains thiophene unit, and n is the polymerization degree.Wherein, described R
11Be preferably straight chained alkyl or branched chain alkyl, more preferably C
4～C
22Straight chained alkyl or C
4～C
22The branched chain alkyl.Described R
21Be preferably straight chained alkyl, more preferably C
4～C
22Straight chained alkyl.Described Ar is preferably shown in formula (III), formula (IV), formula V, the formula (VI) a kind of in the structure,
Wherein, R
41, R
42, R
5, R
6And R
12Independent separately is alkyl; R
22Be H or alkyl.Described R
41, R
42, R
5And R
6Independently be preferably C separately
10～C
22Straight chained alkyl; Described R
12Be preferably C
4～C
22Straight chained alkyl or C
4～C
22The branched chain alkyl; Described R
22Be preferably C
4～C
22Straight chained alkyl.
In addition, the present invention also provides a kind of polymer semiconductor's material that is made of the described polymkeric substance of technique scheme.
Polymkeric substance with formula (II) structure provided by the invention preferably is prepared as follows:
I. the preparation of polymerization single polymerization monomer
(1) 2,5-two bromo-3, the preparation of 4-dialkyl group thiophene:
According to document (Chem.Eur.J., 2004, the preparation of the method that 3331-3340) provides, reaction equation is as follows.
At first prepare 3,4-dialkyl group thiophene: with the magnesium chips of 3 times of molar weights, the 1-bromoalkane of 2.8 times of molar weights is a raw material, and ether is a solvent, and reaction system concentration is 2 mol, makes alkyl bromination magnesium solution; Be furnished with to another under the anhydrous and oxygen-free condition and add 3 of 1 times of molar weight that the merchant sells, 4-dibromo thiophene, the Ni of 3% molar weight (dppp) Cl in the reaction flask of constant pressure funnel
2And ether (reaction system concentration is 0.75 mol), the above-mentioned grignard reagent that has made is imported in the constant pressure funnel, dropwise post-heating to little reaction 12 hours of boiling, drip 1M dilute hydrochloric acid, extracted with diethyl ether is used the saturated aqueous common salt washed twice, anhydrous magnesium sulfate drying, desolventize the back underpressure distillation and obtain 3,4-dialkyl group thiophene;
Prepare 2 then, 5-two bromo-3,4-dialkyl group thiophene: the drips of solution of liquid bromine and chloroform is added to 3, in the solution of 4-dialkyl group thiophene and chloroform/acetic acid (volume ratio is 1: 2), reaction system concentration is 0.5 mol, and stirring at room is after 12 hours, pour in the water, chloroform extraction is used the saturated aqueous common salt washed twice, anhydrous magnesium sulfate drying after desolventizing, is used silica gel chromatography, obtain 2,5-two bromo-3,4-dialkyl group thiophene, described alkyl (is R
41) be C
10～C
22Straight chained alkyl.
(2) 5,5 '-two bromo-4,4 '-preparation of dialkyl group-2,2 '-two thiophene: according to document (J.Am.Chem.Soc.2009,5586-5608; Polymer, 1990,1379-1383; Macromolecules, 2007, the method preparation that 7425-7428.) provides, reaction equation is as follows.
At first prepare the 3-alkylthrophene: with the magnesium chips of 1.5 times of molar weights, the 1-bromoalkane of 1.3 times of molar weights is a raw material, and ether is a solvent, and concentration is 0.5 mol, makes alkyl bromination magnesium solution; In being furnished with the reaction flask of constant pressure funnel, another adds 3 bromo thiophene (1 times of molar weight), Ni (dppp) Cl under the anhydrous and oxygen-free condition
2(0.7mol%) and ether, reaction system concentration is 0.5 mol, the grignard reagent that has prepared is imported in the constant pressure funnel system, dropwise post-heating to little reaction 12 hours of boiling, drip 1M dilute hydrochloric acid, extracted with diethyl ether is used the saturated aqueous common salt washed twice, anhydrous magnesium sulfate drying desolventizes the back underpressure distillation and obtains product 3-alkylthrophene;
Prepare 4 then, 4 '-dialkyl group-2,2 '-two thiophene: under the anhydrous and oxygen-free condition, under-78 ℃ of conditions, in the diethyl ether solution of the Tetramethyl Ethylene Diamine (TMEDA) of the 3-of 1 times of molar weight alkylthrophene and 1.1 times of molar weights, drip the hexane solution of the n-Butyl Lithium (n-BuLi) (1.1 times of molar weights) of 2.5M, reflux 1 hour, be cooled to-78 ℃, the anhydrous cupric chloride that adds 1.2 times of molar weights, during stirring at room was fallen back in 12 hours, extracted with diethyl ether is used the saturated aqueous common salt washed twice, anhydrous magnesium sulfate drying.After desolventizing, silica gel chromatography, obtain 4,4 '-dialkyl group-2,2 '-two thiophene;
Prepare at last 5,5 '-two bromo-4,4 '-dialkyl group-2,2 '-two thiophene: under the room temperature condition, the bromo-succinimide (NBS) of 2.05 times of molar weights is joined 4,4 several times '-volume ratio of dialkyl group-2,2 '-two thiophene is in 1: 1 the mixture of acetic acid/chloroform, concentration is 0.1 mol, stirring at room 12 hours is poured in the water chloroform extraction into, twice of saturated common salt washing organic phase, anhydrous magnesium sulfate drying is removed solvent, uses silica gel chromatography, ethyl alcohol recrystallization, obtain 5,5 '-two bromo-4,4 '-dialkyl group-2,2 '-two thiophene, described alkyl (is R
42) be C
10～C
22Straight chained alkyl.
(3) 2,5-two bromo-3, the preparation of 6-dialkyl group thieno-[3,2-b] thiophene: according to document (Adv.Mater., 2006, the preparation of the method that 3029-3032) provides, reaction equation is as follows.
At first with commercially available 3,4-dibromo thiophene and alkyl acyl chloride are raw material, obtain 2-alkyl-carbonyl-3 by friedel-crafts acylation, the 4-dibromo thiophene, 2-alkyl-carbonyl-3,4-dibromo thiophene and ethyl thioglycolate by the auxiliary ring closure reaction that carries out of salt of wormwood, obtain also [3,2-b] thiophene of 2-ethyl acetate base-3-alkyl-6-bromothiophene in dimethyl formamide (DMF);
Be alkali with sodium hydroxide again, hydrolysis in ethanol obtains 2-carboxyl-3-alkyl-6-bromothiophene also [3,2-b] thiophene, under copper powder and quinoline system, take off carboxylic acid, obtain 3-alkyl-6-bromothiophene also [3,2-b] thiophene, with 1-alkyl alkynes and 3-alkyl-6-bromothiophene also [3,2-b] thiophene be raw material, utilize Sonogashira reaction to obtain 3-alkyl alkynyl-6-bromothiophene also [3,2-b] thiophene, be that catalyzer carries out hydrogen reducing with palladium carbon again, obtain 3,6-dialkyl group thieno-[3,2-b] thiophene;
In the acetic acid chloroform system, carry out bromo at last, finally obtain 2 with NBS, 5-two bromo-3,6-dialkyl group thieno-[3,2-b] thiophene, described alkyl (is R
5And R
6) be C
10～C
22Straight chained alkyl, and R
5And R
6Be identical or different straight chained alkyl.
II. the preparation of polymkeric substance
Under argon atmospher, will meet the R of structural formula (I)
3For the compound of trialkyltin and the two bromo compounds that meet formula (III)-(VI) were dissolved in toluene in 1.02: 1 in molar ratio, concentration is 0.01～0.1mol/L, with the Pd of 0.02 times of molar weight
2(dba)
3For three (o-methyl-phenyl-) phosphine of catalyzer, 0.16 times of molar weight is an assistant ligand, with mixture under the lucifuge condition 120 ℃ the reaction 48 hours, add 4-toluene bromide (20mmol%), continue reaction 12 hours, cool to room temperature precipitates in methyl alcohol, then successively with acetone, hexane, chloroform extracting respectively, precipitate in methyl alcohol more at last, vacuum-drying obtains polymkeric substance.
Compared with prior art, the invention provides the compound of a kind of formula (I) structure, polymkeric substance and polymer semiconductor's material of formula (II) structure, the present invention introduces two kinds of heteroatomss of N, S at described compound, and wherein, the N atom is positioned at the compound center.The present invention is by introducing the N atom, and introduces alkyl chain on the N atom, makes provided by the inventionly to have good solubility based on the polymkeric substance that contains N, two kinds of heteroatomic compounds of S in organic solvent.In addition, compound provided by the invention has the thiphene ring that is positioned at the compound two ends, can effectively reduce based on steric hindrance between adjacent cells in the polymkeric substance that contains N, two kinds of heteroatomic compounds of S, improve the polymkeric substance conjugated degree, thereby guaranteed to use the OTFT of this polymer semiconductor's material to have higher mobility.。
The present invention also provides a kind of OTFT, and charge transport layer is the described polymer semiconductor of a technique scheme material.Wherein, described charge transfer layer thickness is preferably 30～100nm, more preferably 30～60nm.Described charge transport layer is preferably prepared by the method for solution deposition; Described charge transport layer is preferably through thermal anneal process, annealing or under differing temps, carry out gradient annealing under the more preferably single temperature, and the thermal annealing temperature of described charge transport layer is preferably 20～200 ℃, more preferably 30～180 ℃.
The structural representation of the OTFT that the present invention relates to as shown in Figure 1.Among Fig. 1: 1 is substrate; 2 is grid; 3 is dielectric layer; 4 is decorative layer; 5 is charge transport layer, and charge transport layer 5 is polymer semiconductor's material of the present invention's preparation; 6 represent the source metal electrode; Metal electrode is leaked in 7 representatives.
According to the present invention, be substrate 1 and grid 2 with heavily doped n type silicon chip, on it with the thick silicon-dioxide of 300nm as dielectric layer 3, electric capacity is 10nF/cm
2, silicon dioxide dielectric layers 3 can optionally be carried out chemically modified to form a decorative layer 4, with the interfacial property of change dielectric layer 3 with the charge transfer interlayer, thus the performance of raising OTFT.
Used modification reagent is preferably siliceous compounds, phosphoric acid compound or high-k polymer materials among the present invention; Wherein silane compound can with the free hydroxyl generation chemical reaction on the dielectric layer 3, thereby the self-assembled monolayer (self-assemble monolayer) that is applied to dielectric layer 3 is modified; Described siliceous compounds preferably includes octadecyl trichlorosilane (OTS-C18), octyl group trichlorosilane (OTS-C8), hexamethyldisilazane (HMDS), benzyl trichlorosilane (BTS), phenyl-trichloro-silicane or contains the fluoroalkyl trichlorosilane, concrete reagent and modifying method can be with reference to applicating physical magazine (J.Appl.Phys., 2004,96,6431-6438); The phosphoric acid compound also is applied to the self-assembled monolayer of dielectric layer 3 and modifies, and preferably includes carbon chain lengths and be the phosphoric acid that 12～16 phosphoric acid or phenyl replace, and concrete reagent and modifying method can be collected (J.Phys with reference to physical chemistry magazine B; Chem.B, 2003,107,5877-5881); Described high-k polymkeric substance preferably includes polymethylmethacrylate (PMMA), polyvinylphenol (PVP), polyvinyl alcohol (PVA), polystyrene (PS), polyvinyl chloride (PVA) or polyimide, concrete kind is preferably advanced material (Adv.Mater., 2005,17,1705-1725).
Polymer semiconductor's material of the present invention's preparation preferably deposits on the substrate that contains above-mentioned layer 1～4 as charge transport layer 5 by solution method, the thickness of charge transport layer 5 is preferably measured with the step instrument, the thick gold of 40nm is as source metal electrode 6 and leak metal electrode 7, source metal electrode 6 and leak metal electrode 7 preferably through the mask plate hydatogenesis to polymer semiconductor's layer, the conducting channel breadth-length ratio of the device of preparation is preferably 30.
Because polymer semiconductor provided by the invention material has good solubility, therefore, polymer semiconductor's material of the present invention's preparation is preferably by solution method processing film forming, as charge transport layer 5, the preparation method comprises: spin-coating film: with polymer semiconductor's material dissolves of the present invention preparation at chloroform, tetrahydrofuran (THF), in toluene or the chlorobenzene, be preferably chlorobenzene and toluene, concentration is preferably 3～10 mg/ml, be preferably 7 mg/ml, through the tetrafluoroethylene membrane filtration, drip on the decorative layer 4 that is coated on the aforesaid substrate that has prepared that places on the instrument of filming, spin speed is preferably 700～1500rpm, 1000rpm more preferably, the spin coating time is preferably 30～60 seconds, more preferably 60 seconds.The film preparation process is carried out under air atmosphere, and the thickness of charge transport layer 5 is preferably 30～100 nanometers, more preferably 30～60 nanometers.
After polymer semiconductor's material of the present invention's preparation is processed into charge transport layer 5 by solution method, in order to improve the degree of order of charge transport layer 5, above-mentioned this layer is carried out thermal anneal process, can or carry out gradient annealing under differing temps in annealing under the single temperature, the thermal annealing temperature range is at 50～200 ℃.The film that utilizes above-mentioned post-treating method to obtain can utilize atomic force microscope (AFM) and x-ray diffractometer to carry out the sign of film morphology.
In order to further specify technical scheme of the present invention, the preferred embodiment of the invention is described below in conjunction with embodiment.
Embodiment 1:N-dodecyl-2,7-two bromo-3,6-diiodocarbazol synthetic
With 10mmol N-dodecyl-2, the mixed solution of 7-dibromo carbazole (4.93g) and 100ml Glacial acetic acid is heated to 80 ℃, solid dissolving, disposable adding 26.7mmol KI (4.43g) and 13.3mmolKIO
3(2.85g),, be poured in the water after 6 hours 80 ℃ of stirrings, dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, remove solvent, use acetone recrystallization, obtain white solid 5.20g, be i.e. N-dodecyl-2,7-two bromo-3, the 6-diiodocarbazol, productive rate: 70.1%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3): δ (ppm) 8.46 (s, 2H), 7.68 (s, 2H), 4.14 (t, 2H, J=7.2Hz), 1.79-1.83 (m, 2H), 1.24-1.32 (m, 18H), 0.88 (t, 3H, J=6.3Hz). ultimate analysis (C
24H
29Br
2I
2N (%)): calculated value: C, 38.69; H, 3.92; N, 1.88. observed value: C, 38.50; H, 3.80; N, 1.82.
Embodiment 2:N-dodecyl-2,7-two bromo-3,6-two (trimethylsilyl acetylene) carbazole synthetic
Under the argon gas atmosphere, to compound 16.0mmol N-dodecyl-2,7-two bromo-3,6-diiodocarbazol (11.9g), 224mg two (triphenyl phosphorus) palladium chloride (Pd (PPh
3)
2Cl
2), 60.9mg cuprous iodide (CuI), slowly drip 32.7mmol trimethylsilyl acetylene (3.20g) in the mixture of 80ml tetrahydrofuran (THF) and 80ml triethylamine, stirring at room 48 hours, organic phase is collected in the ethyl acetate washing precipitation, washs organic phase respectively twice with saturated ammonium chloride solution and saturated aqueous common salt, anhydrous magnesium sulfate drying, remove solvent, carry out purifying with silica gel column chromatography, eluent is that volume ratio is 1/4 methylene dichloride/sherwood oil, obtain solid 6.18g, be N-dodecyl-2,7-two bromo-3,6-two (trimethylsilyl acetylene) carbazole, productive rate: 56.4%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3): δ (ppm) 8.15 (s, 2H), 7.57 (s, 2H), 4.15 (t, 2H, J=7.2Hz), 1.79-1.83 (m, 2H), 1.24-1.32 (m, 18H), 0.87 (t, 3H, J=6.3Hz), 0.31 (s, 18H).
13C NMR (75MHz, CDCl
3) δ (ppm) 140.9,125.5,123.5,121.1,116.3,112.8,103.9,97.35,43.49,31.89,29.57,29.50,29.44,29.31,29.23,28.68,27.06,22.68,14.13.
Embodiment 3:N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the argon gas atmosphere, with 8.75mmol N-dodecyl-2,7-two bromo-3, the mixture of 6-two (trimethylsilyl acetylene) carbazole (6.00g), 35.0mmol nine hydrated sodium sulfides (8.41g) and 175ml N-Methyl pyrrolidone was 190 ℃ of following heated and stirred 12 hours, be poured in the saturated ammonium chloride solution, extracted with diethyl ether, saturated common salt washing organic phase, anhydrous magnesium sulfate drying is removed solvent, uses silica gel chromatography, eluent is a sherwood oil, obtain faint yellow solid 2.66g, promptly N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 67.9%.The structural characterization data are as follows:
1H NMR (300MHz, CDCl
3): δ (ppm) 8.55 (s, 2H), 7.91 (s, 2H), 7.47 (d, 2H, J=5.7Hz), 7.25 (d, 2H, J=5.7Hz), 4.32 (t, 2H, J=7.5Hz) 1.90-1.95 (m, 2H), 1.24-1.47 (m, 18H), 0.86 (t, 3H, J=6.9Hz) 0.31 (s, 18H).
13C NMR (150MHz, CDCl
3) 140.8,139.0,132.8,123.8,122.9,122.5,114.5,100.7,43.4,31.9,29.6,29.5,29.45,29.38,29.31,28.33,27.36,22.67,14.11, ultimate analysis (C
28H
33NS
2(%)): calculated value: C, 75.12; H, 7.43; N, 3.13. observed value: C, 74.95; H, 7.67; N, 2.95.MAIDI-TOF (C
28H
33NS
2): calculated value: 447.21; Observed value: 447.2.
Embodiment 4:N-dodecyl-3, and 8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under argon gas atmosphere and-20 ℃ of cooling conditionss, to 1.00mmol N-dodecyl two thieno-s [2,3-b; 7,6-b] drip n-Butyl Lithium (n-BuLi) hexane solution (0.84ml) of 2.10mmol 2.5M in tetrahydrofuran (THF) (10ml) solution of carbazole (447mg),-20 ℃ stir half hour after, add 2.05mmol trimethyltin chloride (409mg), rise to room temperature and stir and spend the night; Post reaction mixture is poured in the water, dichloromethane extraction, saturated common salt water washing organic layer, organic layer obtains light yellow solid 657mg with the normal hexane recrystallization behind the removal solvent, i.e. N-dodecyl-3 through anhydrous magnesium sulfate drying, 8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 85.0%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3): δ (ppm) 8.52 (s, 2H), 7.78 (s, 2H), 7.53 (s, 2H), 4.31 (t, 2H, J=7.20Hz), 1.89-1.94 (m, 2H), 1.23-1.42 (m, 18H), 0.87 (t, 3H, J=6.90Hz), 0.45 (s, 18H).
13C NMR (150MHz, CDCl
3) 143.37,140.71,136.29,134.48,131.98,122.58,113.53,100.06,43.39,31.89,29.57,29.50,29.45,29.31,28.28,27.33,22.67,14.11. ultimate analysis (C
34H
49NS
2Sn
2(%)): calculated value: C, 52.81; H, 6.39; N, 1.81. observed value: C, 52.61; H, 6.42; N, 1.30.
Embodiment 5:N-(2-amyl group hexyl)-2,7-two bromo-3,6-diiodocarbazol synthetic
With 8.76mmol N-(2-amyl group hexyl)-2, the mixed solution of 7-dibromo carbazole (4.20g) and 110ml Glacial acetic acid is heated to 80 ℃, disposable adding 23.4mmol KI (3.88g) and 11.7mmol KIO
3(2.50g), stirred 6 hours at 80 ℃, be poured in the water dichloromethane extraction, the saturated common salt water washing, anhydrous magnesium sulfate drying is removed solvent, is that the mixed solvent recrystallization of 3: 1 ethanol and chloroform obtains khaki color solid 5.44g with volume ratio, be N-(2-amyl group hexyl)-2,7-two bromo-3,6-diiodocarbazol, productive rate: 85%.The structural characterization data are as follows:
1H NMR (CDCl
3, 300MHz) δ (ppm) 8.47 (s, 2H), 7.85 (s, 1H), 7.70 (s, 1H), 4.34 (tt, J=10.1,5.0Hz, 1H), 2.29-2.06 (m, 2H), 1.94-1.82 (m, 2H), 1.33-1.06 (m, 5H), 0.82-0.70 (m, 3H).
Embodiment 6:N-(2-amyl group hexyl)-2,7-two bromo-3,6-two (trimethylsilyl acetylene base) carbazole synthetic
Under the argon gas atmosphere, at 6.86mmol N-(2-amyl group hexyl)-2,7-two bromo-3,6-diiodocarbazol (5.00g), 0.15mmol two (triphenyl phosphorus) palladium chloride (Pd (PPh
3)
2Cl
2) (94mg), slowly drip 14.5mmol trimethylsilyl acetylene (1.55ml) in the mixture of 0.15mmol cuprous iodide (26mg), 20ml tetrahydrofuran (THF) and 10ml triethylamine, stirring at room 20 hours; Reaction solution is poured in the water, used dichloromethane extraction three times, wash organic layer with saturated sodium-chloride water solution again, anhydrous magnesium sulfate drying.Crude product concentrates after silica gel chromatography, and eluent is that volume ratio is 8/1 sherwood oil/CH
2Cl
2, obtain faint yellow viscous liquid 3.91g, i.e. N-(2-amyl group hexyl)-2,7-two bromo-3,6-two (trimethylsilyl acetylene base) carbazole, productive rate: 85%.The structural characterization data are as follows:
1H NMR (CDCl
3, 300MHz) δ (ppm) 8.17 (s, 2H), 7.74 (s, 1H), 7.58 (s, 1H), 4.36 (tt, J=10.3,5.2Hz, 1H), 2.24-2.05 (m, 2H), 2.02-1.73 (m, 2H), 1.35-0.85 (m, 12H), 0.76 (t, J=6.8Hz, 6H), 0.30 (s, 18H).
Embodiment 7:N-(2-amyl group hexyl) two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the argon gas atmosphere, with 4.47mmol N-(2-amyl group hexyl)-2,7-two bromo-3, the mixture of 6-two (trimethylsilyl acetylene base) carbazole (3.00g), 17.88mmol nine hydrated sodium sulfides (4.29g) and 90ml N-Methyl pyrrolidone was 190 ℃ of following heated and stirred 12 hours, be poured in the saturated ammonium chloride solution, extracted with diethyl ether, saturated common salt water washing organic phase, anhydrous magnesium sulfate drying is removed solvent, uses silica gel chromatography, eluent is a sherwood oil, obtain white solid 1.56g, promptly N-(2-amyl group hexyl) two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 81%.The structural characterization data are as follows:
1H NMR (CDCl
3, 300MHz) δ (ppm) 8.56 (d, J=9.9Hz, 2H), 7.96 (s, 1H), 7.81 (s, 1H), 7.46 (d, J=5.5Hz, 2H), 7.32 (d, J=5.0Hz, 2H), 4.59 (tt, J=10.2,5.1Hz, 1H), 2.52-2.18 (m, 2H), and 2.15-1.83 (m, 2H), 1.37-0.99 (m, 12H), 0.74 (t, J=7.0Hz, 6H).
Embodiment 8:N-(2-octyl group nonyl)-2,7-two bromo-3,6-diiodocarbazol synthetic
With 8.87mmol N-(2-octyl group nonyl)-2, the mixture heating up to 80 of 7-dibromo carbazole (5.00g) and 120ml Glacial acetic acid ℃ adds 28.4mmol KI (4.72g) and 13.8mmol KIO
3(3.00g), stir 6h, reaction solution is poured in the water at 80 ℃, dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, remove solvent, separate with silica gel column chromatography, sherwood oil is an eluent, get colourless viscous liquid 6.00g, be N-(2-octyl group nonyl)-2,7-two bromo-3,6-diiodocarbazol, productive rate: 83.0%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3, ppm): 8.49 (s, 1H), 8.46 (s, 1H), 7.85 (s, 1H), 7.69 (s, 1H), 4.34 (m, 1H), 2.16 (m, 2H), 1.88 (m, 2H), 1.19 (m, 22H), 0.90 (m, 2H), 0.83 (t, J=6.9Hz, 6H).
Embodiment 9:N-(2-octyl group nonyl)-2,7-two bromo-3,6-two (trimethylsilyl acetylene base) carbazole synthetic
At 4.91mmol N-(2-octyl group nonyl)-2,7-two bromo-3,6-diiodocarbazol (4.00g), 0.13mmol Pd (PPh
3)
2Cl
2(92.9mg); 0.13mmol CuI (25.2mg); slowly drip 14.3mmol trimethylsilyl acetylene (1.38g) in the mixed solution of 33ml triethylamine and the dry 33ml tetrahydrofuran (THF) of crossing; after reaction is spent the night under argon shield; reaction solution is poured in the 200ml distilled water; dichloromethane extraction; saturated aqueous common salt and distilled water wash respectively, and anhydrous magnesium sulfate drying is removed solvent; separate with silica gel column chromatography; sherwood oil is an eluent, gets yellow solid 3.2g, i.e. N-(2-octyl group nonyl)-2; 7-two bromo-3; 6-two (trimethylsilyl acetylene base) carbazole, productive rate: 86.3%, the structural characterization data are as follows:
1HNMR (300MHz, CDCl
3, ppm): 8.16 (s, 2H), 7.66 (, 2H), 4.36 (m, 1H), 2.15 (m, 2H), 1.88 (m, 2H), 1.19 (m, 22H), 0.91 (m, 2H), 0.83 (t, J=6.9Hz, 6H), 0.24 (m, 18H).
Embodiment 10:N-(2-octyl group nonyl) two thieno-s [2,3-b; 7,6-b] carbazole synthetic
With 0.40mmol N-(2-octyl group nonyl)-2,7-two bromo-3, the mixed solution of 6-two (trimethylsilyl acetylene) carbazole (0.3g), 1.6mmol nine hydrated sodium sulfides (0.38g) and 14ml NMP are heated to 190 ℃ of reactions 12 hours, be poured in the saturated ammonium chloride solution, extracted with diethyl ether, saturated common salt water washing organic phase, anhydrous magnesium sulfate drying, remove solvent, use silica gel chromatography, eluent is a sherwood oil, obtains white solid 0.18g, be N-(2-octyl group nonyl) two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 85.7%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3, ppm): 8.57 (s, 1H), 8.54 (s, 1H), 7.96 (s, 1H), 7.80 (s, 1H), 7.45 (d, J=5.7Hz, 2H), 7.32 (d, J=4.2Hz, 2H), 4.58 (m, 1H), 2.35 (m, 2H), 1.95 (m, 2H), 1.19 (m, 22H), 0.87 (m, 2H), 0.79 (t, J=6.6Hz, 6H).
Embodiment 11:N-(2-octyl group nonyl)-3, and 8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the anhydrous and oxygen-free condition, with 2.38mmol N-(2-octyl group nonyl) two thieno-s [2,3-b; 7,6-b] carbazole (1.3g) is dissolved in the 25ml tetrahydrofuran (THF), cryosel is bathed cooling 10 minutes, slowly splash into 5.0mmoln-BuLi (2.0ml), rose to stirring at room 1 hour after under cryosel is bathed, stirring 30 minutes, bathe cooling 10 minutes with cryosel once more, disposable adding 4.88mmol trimethyltin chloride (2.05g), in stirred overnight at room temperature, reaction solution is poured in the KF aqueous solution stirs CH
2Cl
2Extraction, the saturated common salt water washing, anhydrous magnesium sulfate drying gets faint yellow solid 1.42g with ethyl alcohol recrystallization after removing solvent, i.e. N-(2-octyl group nonyl)-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 68.6%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3, ppm): 8.55 (s, 1H), 8.52 (s, 1H), 7.96 (s, 1H), 7.80 (s, 1H), 7.53 (m, 2H), 4.58 (m, 1H), 2.37 (m, 2H), 1.93 (m, 2H), 1.15 (m, 22H), 0.87 (m, 2H), 0.79 (t, J=6.6Hz, 6H), 0.43 (m, 18H).
Embodiment 12:N-dodecyl-2,7-dimethyl thioether-3,6-two (trimethylsilyl acetylene base) carbazole synthetic
Under the anhydrous and oxygen-free condition, with 1.2mmol N-dodecyl-2,7-two bromo-3,6-two (trimethylsilyl acetylene base) carbazole (0.82g) is dissolved in the 20ml tetrahydrofuran (THF), dry ice acetone bath cooling 15 minutes, slowly splash into 2.6mmoln-BuLi (1.1ml), under the dry ice acetone bath temperature, stirred 1 hour, slowly drip 2.6mmol Methyl disulfide (CH
3SSCH
3) (0.23ml), under dry ice acetone bath, stir after 30 minutes and rise to stirred overnight at room temperature, reaction solution is poured in the water stirs, CH
2Cl
2Extraction, the saturated common salt water washing, anhydrous magnesium sulfate drying behind the removal solvent, is used silica gel chromatography, and eluent is that volume ratio is 5/1 sherwood oil/CH
2Cl
2, obtain faint yellow solid 0.55g, i.e. N-dodecyl-2,7-dimethyl thioether-3,6-two (trimethylsilyl acetylene base) carbazole, productive rate: 73.9%, the structural characterization data are as follows:
1H NMR (600MHz, CDCl
3, ppm): 8.07 (s, 2H), 7.07 (s, 2H), 4.22 (t, J=7.2Hz, 2H), 2.50 (s, 6H), 1.83-1.85 (m, 2H), 1.23-1.33 (m, 18H), 0.88 (t, J=7.2Hz, 3H), 0.31 (s, 18H).
Embodiment 13:4, and 7-two iodo-N-dodecyls two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the anhydrous and oxygen-free condition, with 0.5mmol N-dodecyl-2,7-diformazan sulfenyl-3,6-two (trimethylsilyl acetylene base) carbazole (0.310g) is dissolved in the 10ml dichloromethane solution, under refluxad disposable adding 2mmol iodine (I
2) (0.507g), reflux conditions stirred 6 hours down; Post reaction mixture is poured in the Sulfothiorine saturated solution, and dichloromethane extraction, saturated common salt water washing organic layer, organic layer are through anhydrous magnesium sulfate drying, and precipitation, eluent are that volume ratio is sherwood oil/CH of 5/1
2Cl
2, obtain faint yellow solid 0.25g, promptly 4,7-two iodo-N-dodecyls two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 71.4%, the structural characterization data are as follows:
1H NMR (600MHz, CDCl
3, ppm): 8.55 (s, 2H), 7.77 (s, 2H), 7.51 (s, 2H), 4.34 (t, J=7.2Hz, 2H), 1.90-1.95 (m, 2H), 1.39-1.44 (m, 2H), 1.33-1.37 (m, 2H), 1.23-1.29 (m, 14H) 0.87 (t, J=7.2Hz, 3H).
Embodiment 14:4, and 7-two (dodecyne base)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the argon gas atmosphere, at 0.37mmol 4,7-two iodo-N-dodecyls two thieno-s [2,3-b; 7,6-b] carbazole (0.26g), 10mg two (triphenyl phosphorus) palladium chloride (Pd (PPh
3)
2Cl
2), 1.4mg slowly drip the dodecyne (0.78g) of 0.93mmol in the mixture of cuprous iodide (CuI), 2ml tetrahydrofuran (THF) and 2ml triethylamine, stirring at room 48 hours, organic phase is collected in the ethyl acetate washing precipitation, uses twice of saturated ammonium chloride solution and saturated common salt water washing organic phase, anhydrous magnesium sulfate drying, remove solvent, use silica gel chromatography, eluent is that volume ratio is sherwood oil/CH of 5/1
2Cl
2, obtain faint yellow solid 0.216g, promptly 4,7-two (dodecyne base)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 75.0%, the structural characterization data are as follows:
1H NMR (400MHz, CDCl
3, ppm): 8.69 (s, 2H), 7.74 (s, 2H), 7.42 (s, 2H), 4.32 (t, J=8Hz, 2H), 2.61 (t, J=8Hz, 4H), 1.92 (m, 2H), 1.74-1.78 (m, 4H), 1.55-1.58 (m, 46H) 0.82-0.89 (m, 9H).
Embodiment 15:4, and 7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the room temperature, to 0.23mmol 4,7-two (dodecyne base)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole (0.18g), feed hydrogen in the mixture of 145mg Pd/C (weight ratio is 10%) and 3ml tetrahydrofuran (THF), stirring at room 24 hours filters out Pd/C, removes solvent, uses silica gel chromatography, and eluent is that volume ratio is sherwood oil/CH of 10/1
2Cl
2, obtain faint yellow solid 0.13g, promptly 4,7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 72.0%, the structural characterization data are as follows:
1H NMR (300MHz, CDCl
3, ppm): 8.49 (s, 2H), 7.77 (s, 2H), 6.97 (s, 2H), 4.32 (t, J=8Hz, 2H), 2.97 (t, J=8Hz, 4H), 1.92 (m, 6H), 1.23-1.55 (m, 54H), 0.85-0.89 (m, 9H).
Embodiment 16:3,8-two bromo-4,7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole synthetic
Under the room temperature, to 0.500mmol 4,7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] in the mixture of carbazole (0.392g) and 5ml DMF, add 0.500mmol NBS (0.0890g) in batches, stirring at room 24 hours, reaction solution is poured in the saturated aqueous common salt into dichloromethane extraction, the saturated common salt washing, washing, anhydrous magnesium sulfate drying, removing solvent, is that eluent carries out silica gel chromatography with the sherwood oil, obtains 0.405g, promptly 3,8-two bromo-4, and 7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole, productive rate: 86.0%,
1H NMR (300MHz, CDCl
3, ppm): 8.52 (s, 2H), 7.79 (s, 2H), 4.32 (t, J=8Hz, 2H), 2.99 (t, J=8Hz, 4H), 1.93 (m, 6H), 1.23-1.55 (m, 54H), 0.86-0.89 (m, 9H).
Embodiment 17: poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-didecyl-2,2 '-two thiophene)] (being called for short P-bTC10) synthetic
Under the anhydrous and oxygen-free condition, with 0.408mmol N-dodecyl-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole (315mg), 0.40mol 5,5 '-two bromo-4,4 '-didecyl-2,2 '-two thiophene (242mg), 0.008mmol three (diphenylmethylene acetone) two palladiums (7.32mg) and tri-o-tolyl phosphorus (19.5mg, 0.064mmol) add in the 100mL Schlenk pipe, add 40mL toluene again, reaction mixture is heated to 120 ℃, react after 48 hours, add 0.163mmol 4-toluene bromide (28.0mg), continue reaction 12 hours; With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used acetone, normal hexane, chloroform extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the chloroform extract concentrates, obtain reddish-brown solid 0.280 gram after the filtration, promptly poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-didecyl-2,2 '-two thiophene)], productive rate: 78.4%, the structural characterization data are as follows:
1H NMR (400MHz, C
2D
2Cl
4): δ (ppm) 8.46 (s, 2H), 7.71 (s, 2H), 7.46 (s, 2H), 7.08 (s, 2H), 4.30 (s, 2H), 2.87 (s, 4H), 1.95 (s, 2H), 1.75 (s, 4H), 1.28-1.45 (br, 46H), 0.88 (s, 9H) .GPC:M
n=19 500g mol
-1, PDI=2.37. ultimate analysis (C
56H
77NS
4(%)): calculated value: C, 75.36; H, 8.70; N, 1.57. observed value: C, 75.27; H, 8.79; N, the P-bTC10 structure of 1.60. present embodiment preparation is as follows.
Embodiment 18: poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-two (dodecyl)-2,2 '-two thiophene)] (P-bTC12) synthetic
Under the anhydrous and oxygen-free condition, with N-dodecyl-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole (315mg, 0.408mmol), 5,5 '-two bromo-4,4 '-two (dodecyl)-2,2 '-two thiophene (264mg, 0.40mol), three (diphenylmethylene acetone), two palladium (7.32mg, 0.008mmol) and tri-o-tolyl phosphorus (19.5mg 0.064mmol) adds in the 100mL Schlenk pipe, adds 40mL toluene again, reaction mixture is heated to 120 ℃, reacts after 48 hours, add 4-toluene bromide (28.0mg, 0.163mmol), continue reaction 12 hours.With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used acetone, normal hexane, chloroform extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the chloroform extract concentrates, obtain reddish-brown solid 0.319 gram after the filtration, productive rate: 84.4%, the structural characterization data are as follows:
1H NMR (400MHz, C
2D
2Cl
4): δ (ppm) 8.46 (s, 2H), 7.71 (s, 2H), 7.48 (s, 2H), 7.09 (s, 2H), 4.30 (s, 2H), 2.90 (s, 4H), 1.97 (s, 2H), 1.78 (s, 4H), 1.29-1.46 (br, 54H), 0.88 (s, 9H), GPC:M
n=18 600g mol
-1, PDI=2.14. ultimate analysis (C
60H
85NS
4(%)): calculated value: C, 75.97; H, 9.03; N, 1.48. observed value: C, 75.94; H, 8.90; N, 1.41.The P-bTC12 structure of present embodiment preparation is as follows.
Embodiment 19: poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-two (hexadecyl)-2,2 '-two thiophene)] (P-bTC16) synthetic
Under the anhydrous and oxygen-free condition, with N-dodecyl-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] and carbazole (315mg, 0.408mmol), 5,5 '-two bromo-4,4 '-two (hexadecyl)-2,2 '-two thiophene (309mg, 0.40mol), three (diphenylmethylene acetone), two palladium (7.32mg, 0.008mmol) and tri-o-tolyl phosphorus (19.5mg 0.064mmol) adds in the 100mL Schlenk pipe, adds 40mL toluene again.Reaction mixture is heated to 120 ℃, reacts after 48 hours, (28.0mg 0.163mmol), continues reaction 12 hours, obtains polymkeric substance to add the 4-toluene bromide; With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used acetone, normal hexane, chloroform extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the chloroform extract concentrates, obtain orange red solid 0.320 gram after the filtration, productive rate: 75.5%, the structural characterization data are as follows:
1H NMR (400MHz, C
2D
2Cl
4): δ (ppm) 8.47 (s, 2H), 7.72 (s, 2H), 7.49 (s, 2H), 7.09 (s, 2H), 4.31 (s, 2H), 2.90 (s, 4H), 1.97 (s, 2H), 1.77 (s, 4H), 1.27-1.44 (br, 70H), 0.87 (s, 9H), GPC:M
n=21 700gmol
-1, PDI=1.91. ultimate analysis (C
68H
101NS
4(%)): calculated value: C, 76.99; H, 9.60; N, 1.32. observed value: C, 76.38; H, 9.67; N, the P-bTC16 structure of 1.32. present embodiment preparation is as follows.
Embodiment 20: poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-two (docosyl)-2,2 '-two thiophene)] (P-bTC22) synthetic
Under the anhydrous and oxygen-free condition, with N-dodecyl-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] and carbazole (315mg, 0.408mmol), 5,5 '-two bromo-4,4 '-two (docosyl)-2,2 '-two thiophene (376mg, 0.40mol), three (diphenylmethylene acetone), two palladium (7.32mg, 0.008mmol) and tri-o-tolyl phosphorus (19.5mg 0.064mmol) adds in the 100mL Schlenk pipe, adds 40mL toluene again.Reaction mixture is heated to 120 ℃, reacts after 48 hours, (28.0mg 0.163mmol), continues reaction 12 hours, obtains polymkeric substance to add the 4-toluene bromide; With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used acetone, normal hexane, chloroform extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the chloroform extract concentrates, obtain orange red solid 0.150 gram after the filtration, productive rate: 53.0%, the structural characterization data are as follows:
1H NMR (400MHz, C
2D
2Cl
4): 8.48 (s, 2H), 7.73 (s, 2H), 7.50 (s, 2H), 7.09 (s, 2H), 4.31 (s, 2H), 2.90 (s, 4H), 1.96 (s, 2H), 1.77 (s, 4H), 1.17-1.48 (br, 94H), 0.88 (s, 9H), GPC:M
n=5 500g mol
-1, PDI=1.66.Anal.Calcd for C
80H
125NS
4(%): C, 78.17; H, 10.25; N, 1.17.Found:C, 74.42; H, 9.84; N, the P-bTC22 structure of 1.18. present embodiment preparation is as follows.
Embodiment 21: poly-[3, and 8-N-(2-octyl group nonyl) two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-two (hexadecyl)-2,2 '-two thiophene)] (P-bTC17) synthetic
Under the anhydrous and oxygen-free condition, with N-(2-octyl group nonyl)-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] and carbazole (344mg, 0.408mmol), 5,5 '-two bromo-4,4 '-two (hexadecyl)-2,2 '-two thiophene (309mg, 0.40mol), three (diphenylmethylene acetone), two palladium (7.32mg, 0.008mmol) and tri-o-tolyl phosphorus (19.5mg 0.064mmol) adds in the 100mL Schlenk pipe, adds 40mL toluene again.Reaction mixture is heated to 120 ℃, reacts after 48 hours, (28.0mg 0.163mmol), continues reaction 12 hours, obtains polymkeric substance to add the 4-toluene bromide; With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used acetone, normal hexane, chloroform extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the chloroform extract concentrates, obtain orange red solid 0.280 gram after the filtration, productive rate: 61.9%, the structural characterization data are as follows:
1H NMR (400MHz, C
2D
2Cl
4): 8.49 (s, 2H), 7.82 (s, 2H), 7.49 (s, 2H), 7.10 (s, 2H), 4.57 (s, 1H), 2.90 (s, 4H), 2.34 (s, 2H), 2.03 (s, 2H), 1.77 (s, 4H), 1.17-1.46 (br, 76H), 0.82-0.87 (m, 12H), GPC:M
n=22 100g mol
-1, PDI=2.35. ultimate analysis (C
73H
111NS
4(%)): calculated value: C, 77.53; H, 9.89; N, 1.24. observed value: C, 76.90; H, 10.29; N, the P-bTC17 structure of 1.20. present embodiment preparation is as follows.
Embodiment 22: poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-2,5-(3-undecane-6-dodecyl) thieno-[3,2-b] thiophene)] (P-TT) synthetic
Under the anhydrous and oxygen-free condition, with N-dodecyl-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole (315mg, 0.408mmol), 2,5-two bromo-3-undecanes-6-dodecane thieno-[3,2-b] thiophene (248mg, 0.40mol), (7.32mg is 0.008mmol) with tri-o-tolyl phosphorus (19.5mg for three (diphenylmethylene acetone), two palladiums, 0.064mmol) add in the 100mL Schlenk pipe, add 40mL toluene again; Reaction mixture is heated to 120 ℃, reacts after 48 hours, (28.0mg 0.163mmol), continues reaction 12 hours, obtains polymkeric substance to add the 4-toluene bromide; With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used the orthodichlorobenzene extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the orthodichlorobenzene extract concentrates obtains reddish-brown solid 0.203 gram, productive rate: 55.9% after the filtration.The structural characterization data are as follows:
1H NMR (400MHz, 1,2-Dichlorobenzene-d4): 8.51 (s, 2H), 7.81 (s, 2H), 7.53 (s, 2H), 4.30 (s, 2H), 2.91 (s, 4H), 1.97 (s, 2H), 1.72 (s, 4H), 1.23-1.46 (br, 52H), 0.89 (s, 9H), GPC:M
n=17 100g mol
-1, PDI=2.42. ultimate analysis (C
57H
81NS
4(%)): calculated value: C, 77.35; H, 8.99; N, 1.54. observed value: C, 76.94; H, 9.29; N, the P-TT structure of 1.32. present embodiment preparation is as follows:
Embodiment 23: poly-[3, and 8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-3,8-(4, and 7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole)] (P-bTCz) synthetic
Under the anhydrous and oxygen-free condition, with N-dodecyl-3,8-two (tin trimethyl) two thieno-s [2,3-b; 7,6-b] carbazole (315mg, 0.408mmol), 3,8-two bromo-4,7-two (dodecyl)-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole (377mg, 0.40mol), three (diphenylmethylene acetone), two palladiums (7.32mg, 0.008mmol) (19.5mg 0.064mmol) adds in the 100mL Schlenk pipe, adds 40mL toluene again with tri-o-tolyl phosphorus; Reaction mixture is heated to 120 ℃, reacts after 48 hours, (28.0mg 0.163mmol), continues reaction 12 hours to add the 4-toluene bromide.With polymkeric substance sedimentation in methyl alcohol, filter, the polymkeric substance of collecting is used acetone, normal hexane, chlorobenzene extracting successively in apparatus,Soxhlet's, sedimentation in methyl alcohol once more after the chlorobenzene extract concentrates obtains red solid 0.295g, productive rate 60.0% after the filtration.The structural characterization data are as follows:
1H NMR (400MHz, C
2D
2Cl
4): 8.55 (s, 4H), 7.84 (s, 4H), 7.51 (s, 2H), 4.35 (s, 4H), 2.91 (s, 4H), 1.98 (s, 4H), 1.74 (s, 4H), 1.23-1.46 (br, 72H), 0.84-0.87 (m, 12H), GPC:M
n=23400g mol
-1, PDI=2.15. ultimate analysis (C
80H
112N
2S
4(%)): calculated value: C, 78.12; H, 9.18; N, 2.28. observed value: C, 77.91; H, 8.99; N, the P-bTCz structure of 2.43. present embodiment preparation is as follows:
Embodiment 24～30
With heavily doped n type silicon chip is substrate and grid, is coated with the thick silicon dioxide dielectric layers of 300nm on it, and electric capacity is 10nF/cm
2, silicon dioxide dielectric layers is modified with HMDS, and the conjugated polymers that adopts preparation among the embodiment 17～23 respectively is as semiconductor material, be made into chlorobenzene solution respectively, concentration is 7 mg/ml, and rotating speed is 1000rpm, rotational time is 60 seconds, and film thickness is all between the 30-60 nanometer; Carry out thermal anneal process then, annealing temperature and time are seen tabulation 1; The gold (Au) that last deposit thickness is 50 nanometers is to form the source/drain electrode of film transistor device, and the carrier mobility of annealing temperature, time and film transistor device is listed in the table 1:
The performance measurement result of the thin film transistor of table 1 embodiment 24～30 preparations
As Fig. 2, shown in Figure 3, for the conjugated polymers semiconductor material of the embodiment of the invention 19 preparation (poly-[and 3,8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-two (hexadecyl)-2,2 '-two thiophene)] (P-bTC16)) as the output characteristic curve and the transfer characteristic curve of the OTFT of charge transport layer preparation, the film annealing temperature is 150 ℃, solvent is a chlorobenzene, and mobility reaches 0.073cm
2/ Vs.
Embodiment 31～36
With heavily doped n type silicon chip is substrate and grid, is coated with the thick silicon dioxide dielectric layers of 300nm on it, and electric capacity is 10nF/cm
2, silicon dioxide dielectric layers is modified with HMDS, and the conjugated polymers that adopts preparation among the embodiment 17～23 respectively is as semiconductor material, be made into toluene solution respectively, concentration is 7 mg/ml, and rotating speed is 1000rpm, rotational time is 60 seconds, and film thickness is all between the 30-60 nanometer.Carry out thermal anneal process then, annealing temperature and time are seen tabulation 1; The gold (Au) that last deposit thickness is 40 nanometers is to form the source/drain electrode of film transistor device, and the carrier mobility character of annealing temperature, time and film transistor device is listed in the table 2:
The performance measurement result of the thin film transistor of table 2 embodiment 31～36 preparations
As Fig. 4, shown in Figure 5, for the conjugated polymers semiconductor material of the embodiment of the invention 19 preparation (poly-[and 3,8-N-dodecyl two thieno-s [2,3-b; 7,6-b] carbazole-5,5 '-(4,4 '-two (hexadecyl)-2,2 '-two thiophene)] (P-bTC16)) as the output characteristic curve and the transfer characteristic curve of the OTFT of charge transport layer preparation, the film annealing temperature is 150 ℃, solvent is a toluene, and mobility reaches 0.05cm
2/ Vs.
Embodiment 37～43
With heavily doped n type silicon chip is substrate, be coated with the thick silicon dioxide dielectric layers of 300nm on it, silicon dioxide dielectric layers is modified with HMDS, the conjugated polymers that adopts embodiment 17～19 preparations respectively is as semiconductor material, be made into chlorobenzene solution respectively, concentration is 7 mg/ml, and rotating speed is 1000rpm, rotational time is 60 seconds, and film thickness is all between 30～60 nanometers.
As shown in the figure, Fig. 6 and Fig. 7 are respectively the atomic power shape appearance figure of P-bTC10 initial film and the atomic power shape appearance figure of 20 minutes film of 180 ℃ of annealing.Fig. 8 and Fig. 9 are respectively the atomic power shape appearance figure of initial film of P-bTC12 and the atomic power shape appearance figure of 20 minutes films of 180 ℃ of annealing.Figure 10 and Figure 11 are respectively and are the atomic power shape appearance figure of P-bTC16 initial film and 150 ℃ of atomic power shape appearance figures that move back 40 minutes film.As can be seen from the figure, the film of P-bTC10 presents low orderly nanostructure, and P-bTC12 and P-bTC16 present on nanoscale and be similar to bar-shaped structure, and this structure of annealed processing is more obvious.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined herein General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (4)
1. the compound shown in the formula (I):
Wherein, R
1Be C
4~ C
22Straight chained alkyl or C
4~ C
22The branched chain alkyl; R
2Be H or C
4~ C
22Straight chained alkyl; R
3Be H, Br, I, tributyl tin or tin trimethyl.
2. the polymkeric substance shown in the formula (II),
Wherein, R
11Be C
4~ C
22Straight chained alkyl or C
4~ C
22The branched chain alkyl, R
21Be H or C
4~ C
22Straight chained alkyl, n is the polymerization degree, Ar is a kind of in the structure shown in formula III, formula IV, formula (V), the formula VI,
Wherein, R
41, R
42, R
5And R
6Independent separately is C
10~ C
22Straight chained alkyl; R
12Be C
4~ C
22Straight chained alkyl or C
4~ C
22The branched chain alkyl; R
22Be H or C
4~ C
22Straight chained alkyl.
3. polymer semiconductor's material of constituting of the described polymkeric substance of a claim 2.
4. an OTFT is characterized in that, charge transport layer is the described polymer semiconductor of claim 3 material.
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| JP5859911B2 (en) * | 2012-05-07 | 2016-02-16 | 富士フイルム株式会社 | Organic thin film solar cell, composition used therefor, and method for producing semiconductor film |
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| CN103044663B (en) * | 2012-10-22 | 2015-06-17 | 浙江大学 | Method for preparing conductive conjugated polymer by heterogeneous catalytic carbon-carbon bond coupled reaction |
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| JP6246150B2 (en) | 2014-03-26 | 2017-12-13 | 富士フイルム株式会社 | Providing coating liquid for non-light-emitting organic semiconductor device, organic transistor, compound, organic semiconductor material for non-light-emitting organic semiconductor device, material for organic transistor, method for producing organic transistor, and method for producing organic semiconductor film |
| JP6082927B2 (en) * | 2014-03-26 | 2017-02-22 | 富士フイルム株式会社 | Organic transistor, compound, organic semiconductor material for non-luminescent organic semiconductor device, organic transistor material, coating solution for non-luminescent organic semiconductor device, organic transistor manufacturing method, organic semiconductor film manufacturing method, non-luminescent organic semiconductor device Organic semiconductor film and organic semiconductor material synthesis method |
| WO2019037107A1 (en) * | 2017-08-25 | 2019-02-28 | South University Of Science And Technology Of China | A novel imide building block, a copolymer thereof and their preparation methods, as well their uses in organic semiconductor devices |
| CN108623613A (en) * | 2018-04-24 | 2018-10-09 | 哈尔滨工业大学（威海） | A kind of preparation method and application of nitrogenous, sulphur fused ring compound |
| CN108767103B (en) * | 2018-05-29 | 2022-04-15 | 桂林电子科技大学 | High-performance P-type alpha-MgAgSb-based thermoelectric material and preparation method thereof |
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| CN114141708A (en) * | 2021-11-19 | 2022-03-04 | 惠州华星光电显示有限公司 | Transistor and manufacturing method thereof |
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