CN102372844B - Thiophene organic semiconductor material and preparation method and application thereof - Google Patents
Thiophene organic semiconductor material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of photoelectronic materials, and discloses a thiophene organic semiconductor material and a preparation method and application thereof. The copolymer has a general formula (P), wherein in the formula, x+y is equal to 2; x is more than or equal to 1, and y is more than 0 and is less than 1; n is more than 1 and is less than or equal to 100; R1 and R4 are alkyl having 1 to 20 carbon atoms; and R2 and R3 are hydrogen and alkyl having 1 to 20 carbon atoms or phenyl substituted by alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms or are the phenyl. Compared with the prior art, the invention has the advantages that: the organic semiconductor material is prepared by polymerizing a cyclopentadiene [2,1-b:3,4-b'] bithiophene unit, a thiophene unit and a quinoxaline unit, so the carrier mobility of the organic semiconductor material is increased, spectral response is broadened, and the organic semiconductor material has high carrier transmission property and electrochemical property; and the alkyl and the like can be introduced by a simple and convenient method to improve solubility. The preparation process of the semiconductor material is simple and easy to operate and control, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of organic semiconductor material, relate to a class thiophene organic semiconductor material more specifically.The invention still further relates to preparation method and the application thereof of a class thiophene organic semiconductor material.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is research focus and the difficult point in photovoltaic field always.Be used for the silicon solar cell on ground at present owing to complex manufacturing, cost height, its application is restricted.In order to reduce cost, expand range of application, people are seeking novel solar cell material always for a long time.Polymer solar battery receives much concern because of advantage such as mode large-area preparation such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing, if its energy conversion efficiency can be brought up to the level near the commodity silicon solar cell, its market outlook will be very huge.Go up report conjugated polymers and C from N.S.Sariciftci in 1992 etc. at SCIENCE (N.SSariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474)
60Between photoinduction transfer transport phenomenon after, people have dropped into big quantity research aspect polymer solar battery, and have obtained development at full speed.At present, the research of polymer solar battery mainly concentrates on to body, acceptor co-mixing system, adopts PTB7 and PC
71The energy conversion efficiency of BM co-mixing system has reached about 7%, but still much lower than the efficiency of conversion of inorganic solar cell.The main restricting factor that limiting performance improves has: the carrier mobility that organic semiconductor device is relatively low, the spectral response of device and solar radiation spectrum do not match, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Because thiophene is five-membered ring structure, meet shock youngster rule, have moderate band gap, wideer spectral response, thermostability and environmental stability preferably, so the thiophene-based organic semiconductor material is the up-and-coming material of a class, its application in the photovoltaic field has obtained broad research.
Summary of the invention
The object of the present invention is to provide a class thiophene organic semiconductor material, in order to address the above problem.
The present invention also aims to provide the preparation method of a class thiophene organic semiconductor material.
The present invention also aims to provide a class thiophene organic semiconductor material at polymer solar battery, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus.
A class thiophene organic semiconductor material of the present invention has following general formula (P):
In the formula: x+y=2; 1≤x＜2,0＜y≤1; 1＜n≤100; R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl; The span of preferred n is: 6≤n≤61.
The invention still further relates to a kind of preparation scheme for preparing an above-mentioned class thiophene organic semiconductor material, it comprises the steps:
In the oxygen-free environment, with structural formula be
4,4-dialkyl group-2, two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene of 6-, structural formula are
4,4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene, and structural formula is
5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines are added in first organic solvent that contains first catalyzer for m: j: k in molar ratio, carry out Stille reaction 24～72 hours under 60-132 ℃ of condition, obtain structural formula and are
Described thiophene organic semiconductor material; Wherein, x+y=2; 1≤x＜2,0＜y≤1; 1＜n≤100; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl; M=j+k; The span of preferred n is: 6≤n≤61; Reaction formula is as follows
Among the preparation method of above-mentioned thiophene organic semiconductor material, also comprise described 5,8-two-(5-bromo-2-thienyl)-2, the preparation process of 3-two replacement-quinoxalines, preparation process is as follows:
With 3,6-, two bromo-O-Phenylene Diamines and alkyl second diketone hybrid reaction, make 5,8-, two bromo-2,3-two replacement-quinoxalines; Reaction formula is as follows:
In the oxygen-free environment, with described 5,8-two bromo-2,3-two replacement-quinoxalines, 3-alkyl-2-boric acid thiophene and anhydrous sodium carbonate join in second organic solvent that contains second catalyzer, reaction makes 5,8-two-(4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines; Wherein, described second catalyzer mixture that is organic palladium or organic palladium and organophosphor ligand; Described second organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Reaction formula is as follows:
In the oxygen-free environment, with N-bromo-succinimide (NBS, down together), described 5,8-two-(4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines join in the mixed solvent of sulfuric acid and trifluoroacetic acid in 10 ℃～30 ℃ reactions 12～48 hours down, obtain 5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines; Reaction formula is as follows:
Among the preparation method of above-mentioned thiophene organic semiconductor material, also comprise described 4,4-dialkyl group-2, the preparation process of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene of 6-, preparation process is as follows:
Under-78 ℃～-25 ℃, with 4,4-dialkyl group-cyclopentadiene [2,1-b:3,4-b '] two thiophene, butyllithium are added drop-wise in the 3rd organic solvent and mix, in mixed solution, add trimethyltin chloride then, make described 4,4-dialkyl group-2, the two tin trimethyl-cyclopentadiene [2 of 6-, 1-b:3,4-b '] two thiophene; Wherein, the 3rd organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Reaction formula is as follows:
Among the preparation method of above-mentioned thiophene organic semiconductor material, also comprise described 4,4-dialkyl group-2, the preparation process of 6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene, preparation process is as follows:
In the oxygen-free environment, with N-bromo-succinimide, 4,4-dialkyl group-cyclopentadiene [2,1-b:3,4-b '] two thiophene join in the mixed solvent of sulfuric acid and trifluoroacetic acid in 10 ℃～30 ℃ reactions 12～48 hours down, obtain described 4,4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene; Reaction formula is as follows:
Among the preparation method of above-mentioned thiophene organic semiconductor material,
Described first organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or the toluene;
Described first catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; Described first catalyst consumption is described 4,4-dialkyl group-2,0.05%～50% of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] the two thiophene mole dosage of 6-;
Described organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2
Described organophosphor ligand is P (o-Tol)
3
Compared with prior art, major advantage of the present invention is:
1. the cyclopentadiene [2 that contains in the organic semiconductor material molecule among the present invention, 1-b:3,4-b '] two thiophene units have particular structure, two thiphene ring in its structural unit are on same plane, thereby effectively prolonged the conjugation performance of this organic semiconductor material, reduce its energy gap, make current carrier between two main chains, shift to become and be more prone to, increased carrier mobility;
2. the thiophene unit that also contains simultaneously, this unit is five-membered ring structure, meets shock youngster rule, has moderate band gap, wideer spectral response, thermostability and environmental stability preferably; Quinoxaline unit has high electric transmission character as a kind of good body unit that is subjected to strong electron-withdrawing power, high second-order transition temperature, excellent electrochemical reduction character etc.And quinoxaline unit has stronger modifiability, can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance.
3. organic semiconductor material of the present invention is owing to comprise cyclopentadiene [2 simultaneously, 1-b:3,4-b '] two thiophene structural units, thiophene unit and quinoxaline unit, taken into account their performance advantage, and expanded the absorption region of this organic semiconductor material to sunlight, increased the matching degree with solar radiation spectrum, thus effectively expanded this organic semiconductor material at polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus;
The preparation of described organic semiconductor material by with the measured response thing in suitable reaction environment, thereby just can react and make target product by the control temperature, therefore, preparation technology is simple, is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is to be the structural representation of the organic solar batteries device of active coating with organic semiconductor material of the present invention;
Fig. 2 is to be the structural representation of the organic electroluminescence device of luminescent layer with organic semiconductor material of the present invention;
Fig. 3 is to be the structural representation of the organic field effect tube device of organic semiconductor layer with organic semiconductor material of the present invention.
Embodiment
An a kind of class thiophene organic semiconductor material provided by the invention has following general formula (P):
In the formula: x+y=2; 1≤x＜2,0＜y≤1; 1＜n≤100; R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl, the span of preferred n is: 6≤n≤61.
The present invention also provides a kind of preparation method of a class thiophene organic semiconductor material, comprises the steps:
Step S1,5,8-two bromo-2, the preparation of 3-two replacement-quinoxalines
With 3,6-, two bromo-O-Phenylene Diamines and alkyl second diketone hybrid reaction, make 5,8-, two bromo-2,3-two replacement-quinoxalines; Reaction formula is as follows:
Step S2,5,8-two-(4-alkyl-2-thienyl)-2, the preparation of 3-two replacement-quinoxalines
In the oxygen-free environment, with described 5,8-two bromo-2,3-two replacement-quinoxalines, 3-alkyl-2-boric acid thiophene and anhydrous sodium carbonate join in second organic solvent that contains second catalyzer, reaction makes 5,8-two-(4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines; Wherein, described second catalyzer mixture that is organic palladium or organic palladium and organophosphor ligand; Described second organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Reaction formula is as follows:
Step S3,5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines
In the oxygen-free environment, with N-bromo-succinimide (NBS, down together), described 5,8-two-(4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines join in the mixed solvent of sulfuric acid and trifluoroacetic acid in 10 ℃～30 ℃ reactions 12～48 hours down, obtain 5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines; Reaction formula is as follows:
Step S4,4,4-dialkyl group-2, the preparation of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene of 6-
Under-78 ℃～-25 ℃, with 4,4-dialkyl group-cyclopentadiene [2,1-b:3,4-b '] two thiophene, butyllithium are added drop-wise in the 3rd organic solvent and mix, in mixed solution, add trimethyltin chloride then, make described 4,4-dialkyl group-2, the two tin trimethyl-cyclopentadiene [2 of 6-, 1-b:3,4-b '] two thiophene; Wherein, the 3rd organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; Reaction formula is as follows:
Step S5,4,4-dialkyl group-2, the preparation of 6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene
In the oxygen-free environment, with N-bromo-succinimide, 4,4-dialkyl group-cyclopentadiene [2,1-b:3,4-b '] two thiophene join in the mixed solvent of sulfuric acid and trifluoroacetic acid in 10 ℃～30 ℃ reactions 12～48 hours down, obtain described 4,4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene; Reaction formula is as follows:
The preparation of step S6, thiophene organic semiconductor material
In the oxygen-free environment, with 4,4-dialkyl group-2, two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene, 4 of 6-, 4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene, and 5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines are added in first organic solvent that contains first catalyzer for m: j: k in molar ratio, under 60-132 ℃ of condition, carried out Stille reaction 24～72 hours, and obtained structural formula and be
Described thiophene organic semiconductor material; Wherein, x+y=2; 1≤x＜2,0＜y≤1; 1＜n≤100; R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl; M=j+k; The span of preferred n is: 6≤n≤61; Reaction formula is as follows
In the above-mentioned preparation process, among the step S6, described first organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or the toluene; Described first catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; Described first catalyst consumption is described 4,4-dialkyl group-2,0.05%～50% of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] the two thiophene mole dosage of 6-; Described organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2Described organophosphor ligand is P (o-Tol)
3In the mixture of organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1: 1～20.
Oxygen-free environment of the present invention mainly is made of nitrogen and/or rare gas element.
Quinoxaline unit is as a kind of good body unit that is subjected to strong electron-withdrawing power, and the application in photoelectric material is very extensive; The compound that contains quinoxaline unit has high electric transmission character, high second-order transition temperature, excellent electrochemical reduction character etc.And quinoxaline unit has stronger modifiability, can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance.Therefore it has a wide range of applications in organic photoelectrical material.
Yet the material that contains above three unit does not simultaneously still have document and patent report at present, and this has just limited its range of application greatly.Therefore, the present invention has developed a class thiophene organic semiconductor material, enlarges them in the range of application in fields such as organic solar batteries.
In order to understand the content of patent of the present invention better, further specify technology case of the present invention below by concrete example and legend, specifically comprise the preparation of material preparation and device, but these embodiments do not limit the present invention.In the present invention, a class thiophene organic semiconductor material is mainly as organic semiconductor material.
One class thiophene organic semiconductor material of embodiment 1 present embodiment, structural formula is as follows:
In the formula, R
1, R
4, R
2, R
3Be C
1-C
20Alkyl; Its preparation process is as follows:
One, 5,8-two-(5-bromo-4-replacement-2-thienyl)-2,3-dialkyl group-quinoxaline, structural formula is as follows:
Now with 5,8-two-(5-bromo-2-(4-dodecyl) thienyl)-2,3-dioctyl-quinoxaline is that example is illustrated.
1), 5,8-dibromo 2,3-dioctyl-quinoxaline, structural formula is as follows:
With 5,8-, two bromo-2,3-dioctyl quinoxaline be prepared as example illustrated, preparation process is as described below:
Under 120 ℃, (0.5g, (0.28g is in acetic acid 1mmol) (30mL) solution 1.85mmol) to join compound dioctyl second diketone with 3,6-, two bromo-O-Phenylene Diamines.Backflow is spent the night, and reaction solution is poured in the water, and sodium bicarbonate is neutralized to neutrality.Chloroform extraction, saturated common salt water washing, anhydrous sodium sulfate drying.The rotary evaporation desolventizing, thick product column chromatography gets white solid, and chloroform/normal hexane recrystallization obtains product then, productive rate 80%.MS(EI)m/z：512(M
+)
2) 5,8-two-(4-dodecyl 2-thienyl)-2,3-dioctyl-quinoxaline
Under nitrogen atmosphere, will contain 5,8-, two bromo-2,3-dioctyl quinoxaline (0.85g, 1.67mmol), 3-dodecyl-2-boric acid thiophene (1.5g, 4.0mmol), anhydrous sodium carbonate (5.3g, 50mmol), Pd (PPh
3)
4(0.1g, (the THF 80mL of tetrahydrofuran aqueous solution 0.08mmol); H
2O, mixed solution 20mL) is heated to backflow, stirs then and spends the night. reaction solution poured in the water, and suction filtration, washing gets product with gained crude product column chromatography, productive rate 65%.MS(MALDI)m/z：855(
+)
3) 5,8-two-(5-bromo-4-dodecyl-2-thienyl)-2,3-dioctyl-quinoxaline
Under nitrogen atmosphere, with NBS (0.54,3.0mmol) join and contain 5,8-two (2-thienyl)-2,3-dioctyl-quinoxaline (1.2g, in tetrahydrofuran (THF) 1.4mmol) (THF 50mL) solution, stirred overnight at room temperature.The crude product column chromatography that reaction solution is spin-dried for gets product, productive rate 77%.MS(MALDI)m/z：1013(M
+)
Two, 4,4-dialkyl group-2, two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene of 6-and 4,4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene, structural formula is as follows:
According to Macromolecules 2007,40,1981 disclosed methods have prepared corresponding product.Now with 4,4-dioctyl-2, two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene of 6-are that example is illustrated.
Under-78 ℃, ((2.5mmol is in tetrahydrofuran solution 1.0g) (100mL) 7.5mmol) to be added drop-wise to 4,4-dioctyl-cyclopentadiene [2,1-b:3,4-b '], two thiophene for 5.3mL, 1.4mol/L with t-BuLi.Mixed solution is slowly returned to room temperature, stirring 0.5h.Be cooled to-78 ℃ then, (7.5mmol 7.5mL) is added drop-wise in the above-mentioned solution with trimethyltin chloride.Slowly recover room temperature, stirring is spent the night.With the cancellation of above-mentioned reaction solution water, rotary evaporation is removed tetrahydrofuran (THF), the chloroform/water extraction, and water washing, anhydrous sodium sulfate drying is removed organic phase and is obtained solid.Productive rate 69%.MS(MALDI)m/z：728.3(M
+)
Below be in the present embodiment one, thiophene-based organic semiconductor material (P
1, P
2, P
3, P
4, P
5, P
6) in R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be C
1-C
20The preparation process of alkyl
Three, thiophene-based organic semiconductor material P
1
Under nitrogen protection, will contain compound 5,8-two-(5-bromo-4-dodecyl-2-thienyl)-2; 3-dioctyl-quinoxaline (0.51g; 0.5mmol), 4,4-dimethyl-2; two tin trimethyl-the cyclopentadiene [2 of 6-; 1-b:3,4-b '] two thiophene (0.27g, chlorobenzene 0.5mmol) (25mL) solution; feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 132 ℃ of reactions 48 hours then, obtains thiophene-based organic semiconductor material P
1Mixed solution
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains thiophene-based organic semiconductor material P
1Solid product.Productive rate 59%.Molecular?weight(GPC，THF，R.I)：M
n＝32500，(M
w/M
n＝2.1)。
Four, thiophene-based organic semiconductor material P
2
Under nitrogen protection, will contain compound 5,8-two-(5-bromo-2-thienyl)-2; 3-dioctyl-quinoxaline (0.34g; 0.5mmol), 4,4-dioctyl-2; two tin trimethyl-the cyclopentadiene [2 of 6-; 1-b:3,4-b '] two thiophene (0.36g, chlorobenzene 0.5mmol) (25mL) solution; feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 110 ℃ of reactions 24 hours then, obtains thiophene-based organic semiconductor material P
2Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains thiophene-based organic semiconductor material P
2Solid product.Productive rate 74%.Molecular?weight(GPC，THF，R.I)：M
n＝47500，M
w/M
n＝1.9)。
Five, thiophene-based organic semiconductor material P
3
Under nitrogen protection; to contain compound 5, and 8-two-(5-bromo-4-NSC 62789 base-2-thienyl)-2-methyl-3-NSC 62789 base-quinoxaline (0.65g, 0.5mmol); 4; 4-dioctyl-2, two tin trimethyl-cyclopentadiene [2, the 1-b:3 of 6-; 4-b '] two thiophene (0.36g; 0.5mmol) chlorobenzene (25mL) solution, feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 85 ℃ of reactions 56 hours then, obtains thiophene-based organic semiconductor material P
3Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then.Then mixed solution being heated to 80 ℃ of stirrings spends the night; Organic phase is by the column chromatography of aluminum oxide, chloroform drip washing; Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains thiophene-based organic semiconductor material P
3Solid product.Productive rate 59%.Molecular?weight(GPC，THF，R.I)：M
n＝95300，M
w/M
n＝2.1)。
Six, thiophene-based organic semiconductor material P
4
Under nitrogen protection; to contain compound 5; 8-two-(5-bromo-4-methyl-2-thienyl)-2, and 3-dioctyl-quinoxaline (0.35g, 0.5mmol); 4; 4-two (NSC 62789 base)-2, two tin trimethyl-cyclopentadiene [2, the 1-b:3 of 6-; 4-b '] two thiophene (0.53g, chlorobenzene 0.5mmol) (25mL) solution.Feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 60 ℃ of reactions 72 hours then, obtains thiophene-based organic semiconductor material P
4Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains thiophene-based organic semiconductor material P
4Solid product.Productive rate 45%.Molecular?weight(GPC，THF，R.I)：M
n＝7500，M
w/M
n＝2.1)。
Seven, thiophene-based organic semiconductor material P
5
Under nitrogen protection, will contain compound 5,8-two-(5-bromo--2-thienyl)-2,3-dioctyl-quinoxaline (0.17g; 0.25mmol), 2,6-, two bromo-4; 4-dioctyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene (0.14g; 0.25mmol), 4,4-dioctyl-2; two tin trimethyl-cyclopentadiene [2,1-b:3, the 4-b '] two thiophene (0.36g of 6-; 0.5mmol) chlorobenzene (25mL) solution, feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 132 ℃ of reactions 68 hours then, obtains thiophene-based organic semiconductor material P
5Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night.With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, taking out under the suction filtration, vacuum pump spends the night obtains thiophene-based organic semiconductor material P
5Solid product.Productive rate 65%.Molecular?weight(GPC，THF，R.I)：M
n＝73500，M
w/M
n＝1.9)。
Eight, thiophene-based organic semiconductor material P
6
Under nitrogen protection, will contain compound 5,8-two-(5-bromo--2-thienyl)-2,3-dioctyl-quinoxaline (0.033g; 0.05mmol), 2,6-, two bromo-4; 4-dioctyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene (0.25g; 0.45mmol), 4,4-dioctyl-2; two tin trimethyl-cyclopentadiene [2,1-b:3, the 4-b '] two thiophene (0.36g of 6-; 0.5mmol) chlorobenzene (25mL) solution, feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 120 ℃ of reactions 36 hours then, obtains thiophene-based organic semiconductor material P
6Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, taking out under the suction filtration, vacuum pump spends the night obtains thiophene-based organic semiconductor material P
6Solid product.Productive rate 68%.Molecular?weight(GPC，THF，R.I)：M
n＝82500，M
w/M
n＝1.7)。
One class thiophene organic semiconductor material of embodiment 2 present embodiments, structural formula is as follows:
In the formula, R
1, R
4Be alkyl, R
2, R
3Be C
1-C
20The phenyl that replaces of alkyl; Its preparation process is as follows:
One, 5,8-two-(5-bromo--2-thienyl)-2,3-phenylbenzene-quinoxaline
Now with 5,8-two-(5-bromo-4-NSC 62789 base-2-thienyl)-2,3-phenylbenzene-quinoxaline be prepared as example illustrated.Preparation process is as described below:
Under nitrogen atmosphere, with NBS (0.6g 3.3mmol) joins and contains 5,8-two (4-dodecyl-2-thienyl)-2,3-dioctyl-quinoxaline (1.2g, in tetrahydrofuran (THF) 1.53mmol) (THF 50mL) solution, stirred overnight at room temperature.The crude product column chromatography that reaction solution is spin-dried for gets product, productive rate 73%.MS(MALDI)m/z：941(M
+)
Wherein, 4,4-dialkyl group-2, the preparation of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b '] two thiophene of 6-, 4,4-dialkyl group-2, the preparation of 6-two bromo-cyclopentadiene [2,1-b:3,4-b '] two thiophene is with reference to embodiment one.
Below be in the present embodiment two, thiophene-based organic semiconductor material (P
7, P
8, P
9) in R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be C
1～C
20The phenyl that alkyl replaces, or R
2, R
3Preparation process for phenyl
Two, thiophene-based organic semiconductor material P
7
Under argon shield, will contain compound 5,8-two-(5-bromo-4-dodecyl-2-thienyl)-2; 3-phenylbenzene-quinoxaline (0.47g; 0.5mmol), 4,4-dioctyl-2; two tin trimethyl-the cyclopentadiene [2 of 6-; 1-b:3,4-b '] two thiophene (0.36g, toluene 0.5mmol) (25mL) solution; feed argon gas, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed argon gas, bubbling 1h removes residual oxygen, is heated to 110 ℃ of reactions 56 hours then, obtains thiophene-based organic semiconductor material P
7Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, taking out under the suction filtration, vacuum pump spends the night obtains thiophene-based organic semiconductor material P
7Solid product.Productive rate 56%.Molecular?weight(GPC，THF，R.I)：M
n＝73500，M
w/M
n＝2.1)。
Three, thiophene-based organic semiconductor material P
8
Under nitrogen and the protection of argon gas gas mixture; to contain compound 5, and 8-two-(5-bromo-4-dodecyl-2-thienyl)-2-(4-aminomethyl phenyl)-3-(4-NSC 62789 base phenyl)-quinoxaline (0.62g, 0.5mmol); 4; 4-dioctyl-2, two tin trimethyl-cyclopentadiene [2, the 1-b:3 of 6-; 4-b '] two thiophene (0.36g; 0.5mmol) toluene (25mL) solution, feed nitrogen and argon gas gas mixture, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen and argon gas gas mixture, bubbling 1h removes residual oxygen, is heated to 110 ℃ of reactions 72 hours then, obtains thiophene-based organic semiconductor material P
8Mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, taking out under the suction filtration, vacuum pump spends the night obtains thiophene-based organic semiconductor material P
8Solid product.Productive rate 50%.Molecular?weight(GPC，THF，R.I)：M
n＝67500，M
w/M
n＝2.1)。
Four, thiophene-based organic semiconductor material P
9
Under nitrogen protection, will contain compound 5,8-two-(5-bromo-4-dodecyl-2-thienyl)-2; 3-two (4-octyl phenyl)-quinoxaline (0.58g; .0.5mmol), 4,4-dioctyl-2; two tin trimethyl-the cyclopentadiene [2 of 6-; 1-b:3,4-b '] two thiophene (0.36g, toluene 0.5mmol) (25mL) solution; feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 110 ℃ of reactions 58 hours then, obtains thiophene-based organic semiconductor material P
9The reactant mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, taking out under the suction filtration, vacuum pump spends the night obtains thiophene-based organic semiconductor material P
9Solid product.Productive rate 37%.Molecular?weight(GPC，THF，R.I)：M
n＝27500M
w/M
n＝1.9)。
One class thiophene organic semiconductor material P of embodiment 3 present embodiments
10, structural formula is as follows:
In the formula, R
2, R
3Be hydrogen, R
1, R
4Be C
1-C
20Alkyl;
Its preparation process is as follows:
Under nitrogen protection; to contain compound 5, and 8-two-(5-bromo-4-NSC 62789 base-2-thienyl)-quinoxaline (0.39g, 0.5mmol); 4; 4-dioctyl-2, two tin trimethyl-cyclopentadiene (2, the 1-b:3 of 6-; 4-b ') two thiophene (0.36g; 0.5mmol) chlorobenzene (25mL) solution, feed nitrogen, bubbling 0.5h removes residual oxygen.Add Pd then
2(dba)
30.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol).Continue to feed nitrogen, bubbling 1h removes residual oxygen, is heated to 110 ℃ of reactions 72 hours then, obtains thiophene-based organic semiconductor material P
10The reactant mixed solution.
Mixed solution is added drop-wise to carries out sedimentation, suction filtration, methanol wash, drying in the methyl alcohol; With the chlorobenzene dissolving, join in the aqueous solution of Thiocarb then; Then mixed solution being heated to 80 ℃ of stirrings spends the night; With the column chromatography of organic phase by aluminum oxide, chloroform drip washing; Organic solvent is removed in decompression, the methyl alcohol sedimentation, and suction filtration, the gained solid extracted three days with the acetone Soxhlet; The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains thiophene-based organic semiconductor material P
10Solid product.Productive rate 69%.Molecular?weight(GPC，THF，R.I)：M
n＝52500，M
w/M
n＝2.3)。
The present invention also provides a class thiophene organic semiconductor material at polymer solar battery, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus, this thiophene organic semiconductor material has following general formula (P):
In the formula: x+y=2; X 〉=1,0＜y＜1; 1＜n≤100; R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl.
The present invention also provides a class thiophene organic semiconductor material at polymer solar battery, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus.
Following examples be a class thiophene organic semiconductor material at polymer solar battery, organic field effect tube, Application for Field such as organic electroluminescence device.
The structure of this polymer solar cell device is: glass 11/ITO layer 12/PEDOT:PSS layer 13/ active coating 14/Al layer 15; Wherein, the material of active coating 14 is mixture, comprises electron donor material, and PCBM is electron acceptor material; Electron donor material is thiophene organic semiconductor material of the present invention, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM); ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid).
This organic solar batteries preparation of devices process is:
Tin indium oxide (ITO) layer 12 in that surface deposition one deck square resistance of glass substrate 11 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is 50-300nm;
Ito glass process ultrasonic cleaning, and with after oxygen-Plasma processing, be coated with the PEDOT:PSS layer 13 that last layer plays modification on the ITO surface, thickness is 50-300nm;
Adopt spin coating technique to apply one deck active coating 14 at described poly-(3,4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, thickness is 50-300nm; The material of this active coating is thiophene organic semiconductor material and [6,6] phenyl-C
61The mixture of-methyl-butyrate (being called for short PCBM);
At the surface vacuum evaporation metal aluminium of described active coating, form the metal aluminium lamination 15 as negative electrode, obtain described organic solar batteries device;
With the organic solar batteries device with epoxy encapsulation after, place under 120 ℃ of air tight conditions annealing 2 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Wherein, the thickness of ITO, PEDOT:PSS, active coating, Al layer is respectively and is 120nm, 60nm, 100nm, 110nm.
The structure of this organic electroluminescence device is: glass 21/ITO layer 22/ luminescent layer 23/LiF buffer layer 24/Al layer 25; Wherein: luminescent layer is material with thiophene organic semiconductor material of the present invention.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 in that surface deposition one deck square resistance of glass substrate 21 is 10-20 Ω/mouth forms the conductive layer as anode, and thickness is 50-300nm;
Be the luminescent layer 23 of material at ITO surface preparation one deck with a class thiophene organic semiconductor material of the present invention by spin coating technique, thickness is 50-300nm;
Vacuum evaporation LiF on luminescent layer, as buffer layer 24, thickness is 0.3-2nm;
Vacuum evaporation metallic aluminium on described luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains described organic electroluminescence device.
The structure of this organic field effect tube is: the SiO that Si 31/450nm is thick
2Insulation layer 32/ is used for modifying SiO
2Octadecyl trichlorosilane (OTS) layer 33/ organic semiconductor layer 34/ be source electrode (S) 35 and the drain electrode (D) 36 of material with the gold; Wherein, organic semiconductor layer is material with a class thiophene organic semiconductor material of the present invention; Source electrode (S) and drain electrode (D) also can adopt copper material.
The preparation process of this organic field effect tube is:
At first, apply one deck SiO on a surface cleaning doped silicon wafer 31 later
2Insulation layer 32; Secondly, at described SiO
2Apply the octadecyl trichlorosilane layer 33 that one deck plays modification on the insulation layer, thickness is 10-200nm; Then, the organic semiconductor layer 34 that spin coating one deck is material with thiophene organic semiconductor material of the present invention on described octadecyl trichlorosilane layer, thickness is 50-300nm; At last, being arranged at intervals with the gold at described organic semiconductor layer is source electrode (S) 35 and the drain electrode (D) 36 of material, obtains described organic field effect tube.
Should be understood that above-mentioned statement at preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a class thiophene organic semiconductor material of following general formula (P):
In the formula: x+y=2; 1≤x＜2,0＜y≤1; 1＜n≤100; R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl.
2. a class thiophene organic semiconductor material according to claim 1 is characterized in that the span of described n is: 6≤n≤61.
3. the preparation method of a class thiophene organic semiconductor material is characterized in that, this preparation method comprises the steps:
In the oxygen-free environment, with structural formula be
4,4-dialkyl group-2, two tin trimethyl-cyclopentadiene [2,1-b:3,4-b'] two thiophene of 6-, structural formula are
4,4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b'] two thiophene, and structural formula is
5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines are added in first organic solvent that contains first catalyzer for m:j:k in molar ratio, carry out Stille reaction 24～72 hours under 60-132 ℃ of condition, obtain structural formula and are
Described thiophene organic semiconductor material; Wherein, x+y=2; 1≤x＜2,0＜y≤1; 1＜n≤100; R
1, R
4Be C
1-C
20Alkyl; R
2, R
3Be hydrogen, C
1～C
20Alkyl; Or R
2, R
3Be C
1～C
20Alkyl or C
1～C
20The phenyl that replaces of alkoxyl group; Or R
2, R
3Be phenyl; M=j+k.
4. the preparation method of a class thiophene organic semiconductor material according to claim 3 is characterized in that, also comprise described 5,8-two-(5-bromo-4-alkyl-2-thienyl)-2, the preparation process of 3-two replacement-quinoxalines, preparation process is as follows:
With 3,6-, two bromo-O-Phenylene Diamines and alkyl second diketone hybrid reaction, make 5,8-, two bromo-2,3-two replacement-quinoxalines;
In the oxygen-free environment, with described 5,8-two bromo-2,3-two replacement-quinoxalines, 3-alkyl-2-boric acid thiophene and anhydrous sodium carbonate join in second organic solvent that contains second catalyzer, reaction makes 5,8-two-(4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines; Wherein, described second catalyzer mixture that is organic palladium or organic palladium and organophosphor ligand; Described second organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate;
In the oxygen-free environment, with N-bromo-succinimide, described 5,8-two-(4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines join in the mixed solvent of sulfuric acid and trifluoroacetic acid 10 ℃～30 ℃ reactions 12～48 hours down, obtain 5,8-two-(5-bromo-4-alkyl-2-thienyl)-2,3-two replacement-quinoxalines.
5. the preparation method of a class thiophene organic semiconductor material according to claim 3 is characterized in that, also comprise described 4,4-dialkyl group-2, the preparation process of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b'] two thiophene of 6-, preparation process is as follows:
Under-78 ℃～-25 ℃, with 4,4-dialkyl group-cyclopentadiene [2,1-b:3,4-b '] two thiophene, butyllithium are added drop-wise in the 3rd organic solvent and mix, in mixed solution, add trimethyltin chloride then, make described 4,4-dialkyl group-2, the two tin trimethyl-cyclopentadiene [2 of 6-, 1-b:3,4-b'] two thiophene; Wherein, the 3rd organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate.
6. the preparation method of a class thiophene organic semiconductor material according to claim 3 is characterized in that, also comprise described 4,4-dialkyl group-2, the preparation process of 6-two bromo-cyclopentadiene [2,1-b:3,4-b'] two thiophene, preparation process is as follows:
In the oxygen-free environment, with N-bromo-succinimide, 4,4-dialkyl group-cyclopentadiene [2,1-b:3,4-b '] two thiophene join in the mixed solvent of sulfuric acid and trifluoroacetic acid in 10 ℃～30 ℃ reactions 12～48 hours down, obtain described 4,4-dialkyl group-2,6-two bromo-cyclopentadiene [2,1-b:3,4-b'] two thiophene.
7. the preparation method of a class thiophene organic semiconductor material according to claim 3 is characterized in that, described first organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or the toluene.
8. the preparation method of thiophene organic semiconductor material according to claim 3 is characterized in that, described first catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; Described first catalyst consumption is described 4,4-dialkyl group-2,0.05%～50% of two tin trimethyl-cyclopentadiene [2,1-b:3,4-b'] the two thiophene mole dosage of 6-;
Described organic palladium is Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2
Described organophosphor ligand is P (o-Tol)
3
9. the preparation method of a class thiophene organic semiconductor material according to claim 3 is characterized in that, the span of described n is: 6≤n≤61.
10. a class thiophene organic semiconductor material as claimed in claim 1 is at organic solar batteries, organic field effect tube, organic electroluminescence device, organic optical storage, organic non-linear optical properties or organic laser apparatus Application for Field.
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