CN102807555B - Naphthyl anthracene-substituted dibenzothiophene sulphone organic semiconductor material and preparation method and application thereof - Google Patents
Naphthyl anthracene-substituted dibenzothiophene sulphone organic semiconductor material and preparation method and application thereof Download PDFInfo
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- 0 *c1ccc2c(-c3cc(cccc4)c4cc3)c(cccc3)c3c(-c3ccc(-c(ccc(-c4c(cccc5)c5c(-c5cc6ccccc6cc5)c5c4cc(*)cc5)c4)c4S4(=O)=O)c4c3)c2c1 Chemical compound *c1ccc2c(-c3cc(cccc4)c4cc3)c(cccc3)c3c(-c3ccc(-c(ccc(-c4c(cccc5)c5c(-c5cc6ccccc6cc5)c5c4cc(*)cc5)c4)c4S4(=O)=O)c4c3)c2c1 0.000 description 1
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Abstract
The invention discloses a naphthyl anthracene-substituted dibenzothiophene sulphone organic semiconductor material and a preparation method and application thereof. A general formula (I) of a molecular structure is shown in the specification, wherein in the general formula (I), R is alkyl having 1 to 6 carbon atoms. The naphthyl anthracene-substituted dibenzothiophene sulphone organic semiconductor material has high heat stability and cavity transmission performance under the mutual action and influence of a naphthyl anthracene unit and a dibenzothiophene sulphone unit. According to the preparation method, the naphthyl anthracene-substituted dibenzothiophene sulphone organic semiconductor material can be obtained only by controlling reaction condition and controlling the quantity of reactants, so that a process is simple and easy to operate and control and is suitable for industrial production, the production cost is reduced, and the yield of the product is high.
Description
Technical field
The invention belongs to photoelectric material technical field, relate to specifically dibenzothiophene sulfone organic semiconductor material of a kind of naphthyl anthracene replacement and its preparation method and application.
Background technology
Along with the development of information age, there is the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating and be more and more subject to people's concern.OLED technology is paid close attention to by global scientist, and relevant enterprise and laboratory are all in the research and development of carrying out this technology.As a kind of novel LED technology, there is active illuminating, light, thin, good contrast, energy consumption organic electroluminescence device low, that can be made into the features such as flexible device material has been proposed to higher requirement.
1987, the Tang of Eastman Kodak company of the U.S. and VanSlyke reported the breakthrough in organic electroluminescent research.And to realize the application purposes such as panchromatic demonstration and illumination, in three primary colours, blue light is absolutely necessary.Excellent material also relatively lacks at present, especially blue light material, and excellent blue light material not only can be realized efficient, stable blue emission, but also can, using it as material of main part, be shifted and be obtained green glow and ruddiness by energy.Therefore the luminescent properties that improves blue light is significant to realizing the panchromatic demonstration of organic electroluminescent and solid luminescence lighting tool.But the carrier transmission performance of existing blue light emitting material is poor, cause the luminosity factor of existing blue light emitting material low, a little less than luminous intensity.
Anthracene single crystal is the blue organic electroluminescent material using the earliest, but because its easy crystallization makes device unstable.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, the dibenzothiophene sulfone organic semiconductor material of the naphthyl anthracene replacement that a kind of thermostability and hole transport performance excellence, luminous intensity and luminosity factor are high is provided.
Another object of the present invention is to provide the dibenzothiophene sulfone organic semiconductor material preparation method of the naphthyl anthracene replacement that a kind of technique is simple, productive rate is high, be easy to operate and control.
Further aim of the present invention be to provide dibenzothiophene sulfone organic semiconductor material that above-mentioned naphthyl anthracene replaces at organic electroluminescent device, organic solar batteries, organic field effect tube, organic optical memory, organic non-linear optical properties or/and the application in organic laser.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
The dibenzothiophene sulfone organic semiconductor material that naphthyl anthracene replaces, its general formula of molecular structure is following (I):
(I), in formula, R is C
1～C
6alkyl.
And the dibenzothiophene sulfone organic semiconductor material preparation method that above-mentioned naphthyl anthracene replaces, comprises the steps:
The compd A, the compd B that provide respectively following structural formula to represent, wherein, R is C
1～C
6alkyl,
Under the condition existing with organo-metallic catalyst, organic solvent in oxygen-free environment, compd A, compd B are carried out to Suzuiki coupling reaction, obtain the dibenzothiophene sulfone organic semiconductor material that following general structure replaces for the naphthyl anthracene of (I) expression
Further, the dibenzothiophene sulfone organic semiconductor material that above-mentioned naphthyl anthracene replaces is at organic electroluminescent device, organic solar batteries, and organic field effect tube, organic optical memory, organic non-linear optical properties is or/and the application in organic laser.
The dibenzothiophene sulfone organic semiconductor material that above-mentioned naphthyl anthracene replaces, by interaction and the impact of naphthyl anthracene unit and dibenzothiophene sulfone unit, makes it have excellent thermostability and hole transport performance, and its luminous intensity and luminous efficiency are high; Logical Analysis of overheat demonstration, the dibenzothiophene sulfone organic semiconductor material that this naphthyl anthracene replaces has excellent thermostability; Show by the spectroscopic analysis to its photoluminescence, its maximum emission wavelength is at blue light range.Wherein, dibenzothiophene sulfone unit is as electron deficiency group, the dibenzothiophene sulfone organic semiconductor material that naphthyl anthracene is replaced has higher electronic mobility, when by the luminescent layer that utilizes this organic semiconductor material to prepare during for organic luminescent device, be conducive to the charge balance of luminescent layer, thereby improve this organic luminescent device luminous intensity and luminous efficiency.Naphthyl anthracene unit has effectively improved the stability of the dibenzothiophene sulfone organic semiconductor material of this naphthyl anthracene replacement, makes this organic semiconductor material have suitable carrier transmission characteristics.R group has effectively improved solvability and the film forming properties of the dibenzothiophene sulfone organic semiconductor material of naphthyl anthracene replacement, has strengthened fluorescent emission, has expanded the range of application of this organic semiconductor material.
The dibenzothiophene sulfone organic semiconductor material preparation method that this naphthyl anthracene replaces only need can obtain by the consumption of controlling reaction conditions and reactant, technique is simple, is easy to operate and control, and has reduced production cost, the yield of product is high, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the dibenzothiophene sulfone organic semiconductor material preparation method's of embodiment of the present invention naphthyl anthracene replacement schema;
Fig. 2 utilizes dibenzothiophene sulfone organic semiconductor material that naphthyl anthracene that embodiment 1 obtains replaces to prepare the fluorescence radiation spectrogram of DNMAFSO film;
Fig. 3 is the dibenzothiophene sulfone organic semiconductor material that replaces of the naphthyl anthracene prepared using embodiment 1 as the structural representation of organic electroluminescence device that makees luminescent layer;
Fig. 4 is the structural representation of the dibenzothiophene sulfone organic semiconductor material that replaces of the naphthyl anthracene prepared using embodiment 1 as the solar cell device of active coating:
Fig. 5 is the structural representation of the dibenzothiophene sulfone organic semiconductor material that replaces of the naphthyl anthracene prepared using embodiment 1 as the organic field effect tube device of organic semiconductor layer.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with specific embodiments and the drawings, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Refer to Fig. 1, show the dibenzothiophene sulfone organic semiconductor material general formula of molecular structure of a kind of naphthyl anthracene replacement of the embodiment of the present invention, it is following (I):
(I), in formula, R is C
1～C
6alkyl.
Like this, the dibenzothiophene sulfone organic semiconductor material that above-mentioned naphthyl anthracene replaces, by interaction and the impact of naphthyl anthracene unit and dibenzothiophene sulfone unit, makes it have excellent thermostability and hole transport performance, and its luminous intensity and luminous efficiency are high; Logical Analysis of overheat demonstration, the dibenzothiophene sulfone organic semiconductor material that this naphthyl anthracene replaces has excellent thermostability; Show by the spectroscopic analysis to its photoluminescence, its maximum emission wavelength is at blue light range.Wherein, dibenzothiophene sulfone unit is as electron deficiency group, the dibenzothiophene sulfone organic semiconductor material that naphthyl anthracene is replaced has higher electronic mobility, when by the luminescent layer that utilizes this organic semiconductor material to prepare during for organic luminescent device, be conducive to the charge balance of luminescent layer, thereby improve this organic luminescent device luminous intensity and luminous efficiency.Naphthyl anthracene unit has effectively improved the stability of the dibenzothiophene sulfone organic semiconductor material of this naphthyl anthracene replacement, makes this organic semiconductor material have suitable carrier transmission characteristics.R group has effectively improved solvability and the film forming properties of the dibenzothiophene sulfone organic semiconductor material of naphthyl anthracene replacement, has strengthened fluorescent emission, has expanded the range of application of this organic semiconductor material.
Preferably, in above-mentioned (I) formula, R is preferably C
1～C
3alkyl.Therefore, this preferred R group has further improved solvability and film forming properties and the thermal stability of the dibenzothiophene sulfone organic semiconductor material of naphthyl anthracene replacement.
The embodiment of the present invention also provides the preparation method of the dibenzothiophene sulfone organic semiconductor material of above-mentioned naphthyl anthracene replacement, and the technical process of the method refers to Fig. 1.The dibenzothiophene sulfone organic semiconductor material preparation method that this naphthyl anthracene replaces comprises the steps:
S1: the compd A, the compd B that provide respectively following structural formula to represent, wherein, R is C
1～C
6alkyl,
S2: under the condition existing with organo-metallic catalyst, organic solvent in oxygen-free environment, compd A, compd B are carried out to Suzuiki coupling reaction, obtain the dibenzothiophene sulfone organic semiconductor material that following general structure replaces for the naphthyl anthracene of (I) expression; The Suzuiki coupling reaction formula of this step S2 can be expressed as follows:
Particularly, in the dibenzothiophene sulfone organic semiconductor material preparation method's that above-mentioned naphthyl anthracene replaces step S1, compd A, compd B can directly be buied from the market or prepare by existing synthetic method, and compd A can prepare according to the preparation method in step S11 in following embodiment 1 certainly.R group in compd B is preferably C
1～C
3straight chain or branched alkyl.
In the dibenzothiophene sulfone organic semiconductor material preparation method's that above-mentioned naphthyl anthracene replaces step S2, the temperature of Suzuiki coupling reaction is preferably 60 ℃～130 ℃, and the time is preferably 20 hours～and 40 hours.The temperature and time of this preferred coupled reaction, can further promote this Suzuiki coupling reaction forward to carry out, and further improves the speed of Suzuiki coupling reaction and the yield of the dibenzothiophene sulfone organic semiconductor material that product naphthyl anthracene replaces.Meanwhile, shorten the reaction times, reduced energy consumption.
In above-mentioned steps S2, compd A and compd B mol ratio be preferably 1: 2～and 3.Add reactant according to this ratio, can guarantee that compd A, B fully react, thereby further improve the productive rate of conduction hole type electroluminescent material, reduce production costs.
In above-mentioned steps S2, Suzuiki coupling reaction needs organo-metallic catalyst, and this organo-metallic catalyst is preferably organic palladium catalyzer, or the mixture of organic palladium catalyzer and organophosphorus ligand.Wherein, organic palladium catalyzer preferably but be not only Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2cl
2deng, organophosphorus ligand preferably but be not only P (o-Tol)
3deng.This organo-metallic catalyst addition is preferably 0.001～0.1 times of compd A mole.In the time that organo-metallic catalyst is the mixture of organic palladium catalyzer and organophosphorus ligand, the mol ratio of organic palladium catalyzer and organophosphorus ligand is preferably 1: 4.The preferred kind of this organo-metallic catalyst and addition, can effectively further improve the yield of Suzuiki coupling reaction speed and product.
In above-mentioned steps S2, Suzuiki coupling reaction also need to carry out in oxygen-free environment, and this is in order to prevent organo-metallic catalyst and the oxygen reaction in Suzuiki coupling reaction, guarantees the activity of catalyzer.This oxygen-free environment can adopt vacuum or be full of rare gas element and realize, and is preferably full of rare gas element and realizes oxygen-free environment, and this rare gas element is the conventional rare gas element of the art, as nitrogen, argon gas etc.
In above-mentioned steps S2, the organic solvent in Suzuiki coupling reaction is preferably at least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or toluene, and its consumption at least should guarantee carrying out smoothly of Suzuiki coupling reaction.
In above-mentioned steps S2, be Suzuiki coupling reaction due to what carry out, therefore, can in Suzuiki coupling reaction system, add appropriate alkali, addition is according to existing conventional interpolation.This alkali can but be not only Cs
2cO
3, K
2cO
3, Na
2cO
3or Li
2cO
3.
In the dibenzothiophene sulfone organic semiconductor material preparation method who replaces at above-mentioned naphthyl anthracene, only need can obtain by the consumption of controlling reaction conditions and reactant, technique is simple, be easy to operate and control, reduced production cost, the yield of product is high, is suitable for suitability for industrialized production.
The dibenzothiophene sulfone organic semiconductor material that above-mentioned naphthyl anthracene replaces, due to the molecular structure of self, makes it have good thermostability, hole transport performance and solubility property.The dibenzothiophene sulfone organic semiconductor material replacing just because of embodiment of the present invention naphthyl anthracene has above-mentioned good performance, makes it can be at organic electroluminescent device, organic solar batteries, organic field effect tube, organic optical memory, organic non-linear optical properties or/and the application in organic laser.
Now in conjunction with specific embodiments, the present invention is further elaborated.
Embodiment 1
The dibenzothiophene sulfone organic semiconductor material that the present embodiment naphthyl anthracene replaces is the dibenzothiophene sulfone organic compound 2 that naphthyl anthracene replaces, 7-bis-(1-methyl isophthalic acid 0-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNMAFSO) and preparation method thereof, the following I of its structural formula
1shown in:
The preparation process of above-mentioned polymkeric substance is as follows:
S11: the compd A, the B that provide respectively following structural formula to represent,
Wherein, compd A is that the concrete preparation process of 2,7-dibromo dibenzothiophene sulfone is: the dense H that 4mmol dibenzothiophene sulfone is dissolved in to 30ml
2sO
4in, at room temperature adding 8.2mmol NBS, stirring reaction, after question response 24h, then is poured into water reaction solution, suction filtration, water and methanol wash, collect solid, then by solid recrystallization in chlorobenzene, obtains colourless needle-like solid 2,7-dibromo dibenzothiophene sulfone.This 2,7-dibromo dibenzothiophene sulfone productive rate: 49%, its mass spectroscopy is MS:m/z 374 (M
+), hydrogen nuclear magnetic resonance spectroscopy analysis is
1h NMR (500MHz, CDCl
3, ppm): δ=7.94～8.23 (d, 2H), δ=7.78 (t, 2H), δ=7.64 (d, 2H).Its chemical equation is as follows:
S12:2, the preparation of 7-bis-(1-methyl isophthalic acid 0-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNMAFSO), its chemical equation is as follows:
Concrete preparation process is: by above-claimed cpd A (2,7-dibromo dibenzothiophene sulfone) 3mmol, compd B (1-methyl isophthalic acid 0-(naphthalene-2-yl) anthracene-9-boric acid) 6.4mmol, catalyzer tetra-triphenylphosphine palladium (Pd (PPh
3)
4) 0.01mmol joins in reaction flask, vacuumizes, after logical nitrogen circulation 3 times, makes reaction system in anaerobic state, under nitrogen protection, adds the Na of anhydrous tetrahydro furan solvent 50mL, 2mol/L
2cO
3aqueous solution 34ml, is heated to 77 ± 3 ℃ of back flow reaction 24h by mixed solution.After question response finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, rear drying treatment is washed in three times, organic phase sodium chloride aqueous solution to adopt successively dichloromethane extraction, revolves to steam except after desolventizing to obtain crude product.By crude product process silica gel column chromatography separating-purifying, this silica gel column layer eluent used is V (sherwood oil): V (methylene dichloride)=3.5: 1, finally obtain yellow solid 2,7-bis-(1-methyl isophthalic acid 0-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone.Productive rate: 91%.This 2, the mass spectroscopy of 7-bis-(1-methyl isophthalic acid 0-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone is MS:m/z 849 (M
+), hydrogen nuclear magnetic resonance spectroscopy analysis is
1h NMR (500MHz, CDCl
3, ppm): δ=8.38～8.23 (m, 16H), δ=7.88～7.76 (m, 14H), δ=7.72～7.65 (t, 4H), δ=2.62～2.61 (t, 6H).
Detect by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and when sweep velocity is 10 ℃/min, in the present embodiment 1, the heat decomposition temperature of the DNMAFSO organic semiconductor material of preparation is 415 ℃.
The fluorescence radiation spectrogram test of DNMAFSO film prepared by the present embodiment 1, test result as shown in Figure 2.As shown in Figure 2, this DNMAFSO film of the present embodiment is between 400 to 500nm, to have very strong luminous intensity at wavelength.
Embodiment 2
The dibenzothiophene sulfone organic semiconductor material that the present embodiment naphthyl anthracene replaces is the dibenzothiophene sulfone organic compound 2 that naphthyl anthracene replaces, 7-bis-(1-ethyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNEtAFSO) and preparation method thereof, the following I of its structural formula
2shown in:
The preparation process of above-mentioned polymkeric substance is as follows:
S21: the compd A, the B that provide respectively following structural formula to represent,
Wherein, 2,7-dibromo dibenzothiophene sulfone acquisition methods is identical with the step S11 of embodiment 1 for compd A.
S22:2, the preparation of 7-bis-(1-ethyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNEtAFSO), its chemical equation is as follows:
Concrete preparation process is: the organophosphorus ligand that is 1: 1 by above-claimed cpd A (2,7-dibromo dibenzothiophene sulfone) 3mmol, compd B (1-ethyl-10-(naphthalene-2-yl) anthracene-9-boric acid ester) 6.6mmol, mass ratio is P (o-Tol) and Pd
2(dba)
3mixture 0.01mmol joins in reaction flask, vacuumizes, after logical nitrogen circulation 3 times, makes reaction system in anaerobic state, under nitrogen protection, adds the Na of anhydrous glycol dinitrate ether solvents 50mL, 2mol/L
2cO
3aqueous solution 34ml, is heated to 70 ± 3 ℃ of back flow reaction 40h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, rear drying treatment is washed in three times, organic phase sodium chloride aqueous solution to adopt successively dichloromethane extraction, revolves to steam except after desolventizing to obtain crude product.By crude product process silica gel column chromatography separating-purifying, this silica gel column layer eluent used is V (sherwood oil): V (methylene dichloride)=4: 1, finally obtain yellow solid 2,7-bis-(1-ethyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone.This 2, the productive rate of 7-bis-(1-ethyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone is 93%, its mass spectroscopy is MS:m/z 877 (M
+).
Detect by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and when sweep velocity is 10 ℃/min, in the present embodiment 2, the heat decomposition temperature of the DNEtAFSO organic semiconductor material of preparation is 416 ℃.
Embodiment 3
The dibenzothiophene sulfone organic semiconductor material that the present embodiment naphthyl anthracene replaces is the dibenzothiophene sulfone organic compound 2 that naphthyl anthracene replaces, 7-bis-(the 1-tertiary butyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNBuAFSO) and preparation method thereof, the following I of its structural formula
3shown in:
I
3(DNBuAFSO)
The preparation process of above-mentioned polymkeric substance is as follows:
S31: the compd A, the compd B that provide respectively following structural formula to represent,
Wherein, 2,7-dibromo dibenzothiophene sulfone acquisition methods is identical with the step S11 of embodiment 1 for compd A.
S32:2, the preparation of 7-bis-(the 1-tertiary butyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNBuAFSO), its chemical equation is as follows:
Concrete preparation process is: by above-claimed cpd A (2,7-dibromo dibenzothiophene sulfone) 3mmol, compd B (the 1-tertiary butyl-10-(naphthalene-2-yl) anthracene-9-boric acid) 6.8mmol, Pd (PPh
3)
2cl
20.01mmol joins in reaction flask, vacuumizes, leads to argon gas and circulate after 3 times, makes reaction system in anaerobic state, under argon shield, adds the Na of anhydrous glycol dinitrate ether solvents 50mL, 2mol/L
2cO
3aqueous solution 34ml, is heated to 77 ± 3 ℃ of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, rear drying treatment is washed in three times, organic phase sodium chloride aqueous solution to adopt successively dichloromethane extraction, revolves to steam except after desolventizing to obtain crude product.By crude product process silica gel column chromatography separating-purifying, this silica gel column layer eluent used is V (sherwood oil): V (methylene dichloride)=4.5: 1, finally obtain yellow solid 2,7-bis-(the 1-tertiary butyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone.This 2,7-bis-(the 1-tertiary butyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone productive rate is 93%, its mass spectroscopy is MS:m/z 933 (M
+).
Detect by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and when sweep velocity is 10 ℃/min, in the present embodiment 3, the heat decomposition temperature of the DNBuAFSO organic semiconductor material of preparation is 423 ℃.
Embodiment 4
The dibenzothiophene sulfone organic semiconductor material that the present embodiment naphthyl anthracene replaces is the dibenzothiophene sulfone organic compound 2 that naphthyl anthracene replaces, 7-bis-(1-n-hexyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNHAFSO) and preparation method thereof, the following I of its structural formula
4shown in:
The preparation process of above-mentioned polymkeric substance is as follows:
S31: the compd A, the B that provide respectively following structural formula to represent,
Wherein, 2,7-dibromo dibenzothiophene sulfone acquisition methods is identical with the step S11 of embodiment 1 for compd A.
S32:2, the preparation of 7-bis-(1-n-hexyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone (DNHAFSO), its chemical equation is as follows:
Concrete preparation process is: by above-claimed cpd A (2,7-dibromo dibenzothiophene sulfone) 3mmol, compd B (1-n-hexyl-10-(naphthalene-2-yl) anthracene-9-boric acid) 6.8mmol, Pd (PPh
3)
2cl
20.01mmol joins in reaction flask, vacuumizes, leads to argon gas and circulate after 3 times, makes reaction system in anaerobic state, under argon shield, adds the Na of anhydrous tetrahydro furan solvent 50mL, 2mol/L
2cO
3aqueous solution 34ml, is heated to 77 ± 3 ℃ of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, rear drying treatment is washed in three times, organic phase sodium chloride aqueous solution to adopt successively dichloromethane extraction, revolves to steam except after desolventizing to obtain crude product.By crude product process silica gel column chromatography separating-purifying, this silica gel column layer eluent used is V (sherwood oil): V (methylene dichloride)=6: 1, finally obtain yellow solid 2,7-bis-(1-n-hexyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone.This 2,7-bis-(1-n-hexyl-10-(naphthalene-2-yl) anthracene-9-yl) dibenzothiophene sulfone productive rate is 95%, its mass spectroscopy is MS:m/z 989 (M
+).
Detect by thermogravimetric analyzer (TGA), analysis condition is nitrogen atmosphere, and when sweep velocity is 10 ℃/min, in the present embodiment 4, the heat decomposition temperature of the DNHAFSO organic semiconductor material of preparation is 420 ℃.
Application Example 1
The dibenzothiophene sulfone organic semiconductor material that the naphthyl anthracene prepared using embodiment 1 replaces is DNMAFSO as the preparation of organic electroluminescence device (OLED) of making luminescent layer:
Refer to Fig. 3, DNMAFSO prepared by demonstration employing above-described embodiment 1 is as the organic electroluminescence device that makees luminescent layer, and it comprises the glass-base 11, anode 12, hole transmission layer 13, luminescent layer 14, hole blocking layer 15, electron transfer layer 16, buffer layer 17 and the negative electrode 18 that are cascading.Wherein, anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Hole transmission layer 13 can be N, N '-bis-(Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines (NPB); Luminescent layer 14 comprises DNMAFSO prepared by above-described embodiment 1; Hole blocking layer 15 is 2,9-dimethyl-4,7-phenylbenzene-9,10-phenanthroline (BCP); Electron transfer layer 16 is oxine aluminium (Alq
3); Buffer layer 17 can adopt LiF; Negative electrode 16 is metal Al layer.Thereby the present embodiment organic electroluminescence device representation is: glass/ITO/NPB/DNMAFSO/BCP/Alq
3/ LiF/Al.
The manufacturing processed of this organic electroluminescence device is as follows:
1) ito glass is carried out to ultrasonic cleaning, and after processing with oxygen-Plasma, form the substrate of glass-base 11 and anode 12 combinations;
2) at the surperficial spin coating one deck of ito anode 12 NPB as hole transmission layer 13, the conjugated polymers DNMAFSO that then prepares in embodiment 1 at the surperficial spin coating one deck of hole transmission layer 13 forms luminescent layer 14;
3) spin coating one deck BCP and one deck Alq successively on luminescent layer 14
3, form respectively hole blocking layer 15, electron transfer layer 16;
4) on electron transfer layer 16 outside surfaces, adopt vacuum evaporation technology to apply one deck LiF and form buffer layer 17;
5) at buffer layer 17 surface vacuum evaporation metal aluminium, form the metal aluminium lamination 18 as negative electrode, obtain organic electroluminescence device; Wherein, the thickness of metal aluminium lamination 16 is 170nm.
Certainly, the thickness of metal aluminium lamination 16 can also be 30nm, 130nm, 60nm.
Application Example 2
The dibenzothiophene sulfone organic semiconductor material that the naphthyl anthracene prepared using the embodiment of the present invention 1 replaces is as the preparation of the solar cell device of active coating:
Refer to Fig. 4, this solar cell device comprises the glass-base 21, transparent anode 22, middle supplementary layer 23, active coating 24, the negative electrode 25 that stack gradually.Transparent anode 22 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Middle supplementary layer 23 adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS).Active coating 24 comprises electron donor material and electron acceptor material, the DNMAFSO that electron donor material adopts embodiment 1 to prepare, and electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (referred to as PCBM).Negative electrode 25 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 30nm, 130nm or 60nm.Glass-base 21 can be used as bottom, when making, choose ito glass, and after ultrasonic cleaning, with oxygen-Plasma processing, supplementary layer 23 in the middle of applying on ito glass, in the middle of the DNMAFSO again being prepared by embodiment 1 and electron acceptor material are coated on after by blend on supplementary layer 23, form active coating 24, and then by vacuum evaporation technology deposition cathode 25 on active coating 24, obtain above-mentioned solar cell device.This solar cell device also needs through heating 4 hours under 110 degrees Celsius of air tight conditions, drop to again room temperature, after device is annealed, can effectively increase order and the regularity between the interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 25Al layer is respectively 170nm.
As shown in Figure 4, under illumination, light transmission glass-base 21 and ITO electrode 22, the conduction hole type electroluminescent material in active coating 24 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission collected by negative electrode, hole is along electron donor material to ito anode transmission collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, when external load 26, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, be convenient to large batch of preparation.
Application Example 3
The preparation of the dibenzothiophene sulfone organic semiconductor material organic field effect tube that the naphthyl anthracene of preparing containing the embodiment of the present invention 1 replaces:
Refer to Fig. 5, this organic field effect tube comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 being cascading and is located at source electrode 35 and the drain electrode 36 on organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si), and insulation layer 32 can be but be not limited to micro-nano (as 450nm) thick SiO
2.The DNMAFSO that organic semiconductor layer 34 adopts above-described embodiment 1 to prepare.Source electrode 35 and drain electrode 36 all can adopt but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane alkane (OTS).
The manufacturing processed of this organic field effect tube is as follows:
1) clean doped silicon substrate 31, deposition has the SiO of insulating effect
2layer 32;
2) at SiO
2on insulation layer 32, apply OTS, form OTS layer 33;
3) on OTS layer 33, apply the DNMAFSO that one deck is prepared at embodiment 1, form organic semiconductor layer 34;
4) source electrode 35 and the drain electrode 36 of metallic gold material are set on organic semiconductor layer 34, obtain organic field effect tube.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the dibenzothiophene sulfone organic semiconductor material that naphthyl anthracene replaces, its general formula of molecular structure is following (I):
(I), in formula, R is C
1～C
6alkyl.
2. the dibenzothiophene sulfone organic semiconductor material that naphthyl anthracene according to claim 1 replaces, is characterized in that: R is C
1～C
3straight chain or branched alkyl.
3. the dibenzothiophene sulfone organic semiconductor material preparation method that naphthyl anthracene replaces, comprises the steps:
The compd A, the compd B that provide respectively following structural formula to represent, wherein, R is C
1～C
6alkyl,
Under the condition existing with organo-metallic catalyst, organic solvent in oxygen-free environment, compd A, compd B are carried out to Suzuiki coupling reaction, obtain the dibenzothiophene sulfone organic semiconductor material that following general structure replaces for the naphthyl anthracene of (I) expression
4. the dibenzothiophene sulfone organic semiconductor material preparation method that naphthyl anthracene according to claim 3 replaces, is characterized in that: the temperature of described Suzuiki coupling reaction is 60～130 ℃, the time is 20～40 hours.
5. the dibenzothiophene sulfone organic semiconductor material preparation method that naphthyl anthracene according to claim 3 replaces, is characterized in that: described compd A and compd B mol ratio are 1: 2～3.
6. the dibenzothiophene sulfone organic semiconductor material preparation method that naphthyl anthracene according to claim 3 replaces, is characterized in that: described organo-metallic catalyst addition is compd A 0.001～0.1 times.
7. the dibenzothiophene sulfone organic semiconductor material preparation method who replaces according to the naphthyl anthracene described in claim 3 or 6, is characterized in that: described organo-metallic catalyst is organic palladium catalyzer, or the mixture of organic palladium catalyzer and organophosphorus ligand.
8. the dibenzothiophene sulfone organic semiconductor material preparation method that naphthyl anthracene according to claim 7 replaces, is characterized in that: described organic palladium catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2cl
2in at least one; Described organophosphorus ligand is P (o-Tol)
3.
9. the dibenzothiophene sulfone organic semiconductor material preparation method that naphthyl anthracene according to claim 3 replaces, is characterized in that: the organic solvent of described Suzuiki coupling reaction is at least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or toluene.
10. the dibenzothiophene sulfone organic semiconductor material replacing according to the arbitrary described naphthyl anthracene of claim 1 to 2 at organic electroluminescent device, organic solar batteries, organic field effect tube, organic optical memory, organic non-linear optical properties or/and the application in organic laser.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3905814A (en) * | 1972-09-15 | 1975-09-16 | Oce Van Der Grinten Nv | Dibenzothiophene oxide or dioxide sensitizers for organic photoconductors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3905814A (en) * | 1972-09-15 | 1975-09-16 | Oce Van Der Grinten Nv | Dibenzothiophene oxide or dioxide sensitizers for organic photoconductors |
Non-Patent Citations (2)
| Title |
|---|
| 二苯并噻吩砜类化合物的合成和光学性能;李业新等;《济南大学学报(自然科学版)》;20100131;第24卷(第1期);第64-67页 * |
| 李业新等.二苯并噻吩砜类化合物的合成和光学性能.《济南大学学报(自然科学版)》.2010,第24卷(第1期),第64-67页. |
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