CN100455563C - Organic semiconductor compound and its preparation method and uses - Google Patents
Organic semiconductor compound and its preparation method and uses Download PDFInfo
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- CN100455563C CN100455563C CNB2005101157256A CN200510115725A CN100455563C CN 100455563 C CN100455563 C CN 100455563C CN B2005101157256 A CNB2005101157256 A CN B2005101157256A CN 200510115725 A CN200510115725 A CN 200510115725A CN 100455563 C CN100455563 C CN 100455563C
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Abstract
The invention discloses an organic semi-conductor compound and preparing method and application, which possesses structural formula as formula I, wherein R1, R2 and R3 is ethyl cyanoacetate subunit or O atom as formula II, which is not O atom at the same time; the R in the formula II is C1-8 alkyl. The invention possesses superior electronic transmission property, which is convenient to do mass synthesis.
Description
Technical field
The present invention relates to organic semiconductor compound and preparation method thereof and application.
Background technology
The semiconducter device of based semiconductor material manufacturing is the basis of hyundai electronics industry.In the semiconductor material research field, though the inorganic semiconductor material that with silicon is representative is widely used, in occupation of dominant position, organic semiconductor material also has been subjected to paying close attention to widely because of having the not available characteristics of many inorganic semiconductor materials in recent years in many electronic products.Characteristics such as for example, organic semiconductor has the easy modulation of structure-performance, is suitable for making flexible device, tooling cost is low.Be the organic photoconductor of representative with the phthalocyanine-like compound and be that the organic hole transport material of representative has obtained practical application (K.Y.Law widely with many arylamine, hydrazone compounds in xeroprinting technology (duplicating machine and laser printer), Chem.Rev.1993,93,449).In addition, organic semiconductor material also has wide application prospect (Chem.Mater.2004, Vol.16, No.23, Special Issue on Organic Electronics) in fields such as field-effect transistor, photodiode, solar cell.
The organic charge transport material is the big class important compound of one in the organic semiconductor, and they have not only constituted the main body of organic field effect tube, and the performance that improves above-mentioned other device has been played important role.According to the kind of institute's transmission charge, the organic charge transport material can be divided into hole mobile material and electron transport material two big classes; Perhaps continue to use the naming method in the inorganic semiconductor, be referred to as p type organic semiconductor and n type organic semiconductor respectively.Also have the small part material hole and electronics all to be had better transmission performance, promptly so-called ambipolar organic semiconductor in addition.The development of organic electronic transport material at present lags significantly behind the organic hole transport material, and wherein one of the main reasons is that oxygen has the stronger ability of accepting electronics, is easy to become the trap of electronics in electronic transmission process, thereby influences the performance of device greatly.In view of the organic electronic transport material all will play crucial effects in many organic functions devices, people have carried out than systematic research this field in recent years, the organic electronic transport material of some excellent propertys is developed, contains bigger organic conjugate system and stronger electron-withdrawing group in its molecular structure usually.For example, the perfluoro phthalocyanine that European patent EP 0921579-A2 reported (Z.N.Bao, A.J.Lovinger, J.Brown, J.Am.Chem.Soc.1998,120,207), benzene-naphthalene diimide (the H.E.Katz that the fluoroalkyl that U.S. Pat 6252245-B1 reported replaces, J.Johnson, A.J.Lovinger, W.Li, J.Am.Chem.Soc.2000,122,7787), the pentafluorophenyl group that U.S. Pat 6585914-B2 reported (A.Facchetti, M.-H.Yoon, C.L.Stem, H.E.Katz, T.J.Marks, Angew.Chem.Int.Ed.2003,42,3900) or fluoroalkyl (A.Facchetti, M.Mushrush, H.E.Katz, T.J.Marks, Adv.Mater.2003,15,33) oligothiophene of modifying etc.Though the research and development of organic electronic transport material make remarkable progress in recent years, yet, how to design synthetic both had good electronic transmission performance and the stability under the atmosphere, have the organic electronic transport material of good solubility and lower production cost again, be still a difficult problem in this field.
Organic light receptor is the core component of laser printer and xerographic printer, since more ripe to the research of organic hole transport material, the mode of operation that the multilayer Photoreceptors in the practicality at present adopts the surface to fill negative electricity.When filling negative electricity, charger unit produces O
3Working environment is worsened, and device is easy to oxidation.From reducing production costs, improve Working environment, improve aspects such as Photoreceptors life-span and constant product quality and set out, bilayer that is just charging in the surface and single layer structure organic light receptor are important development directions from now on.Making this type of Photoreceptors needs the organic electronic transport material of excellent property.
Summary of the invention
The purpose of this invention is to provide a kind of organic semiconductor compound and preparation method thereof.
Organic semiconductor compound provided by the present invention, its structural formula be suc as formula I, wherein, and R
1, R
2, R
3Be the cyan-acetic ester subunit or the O atom of formula II structure, and R
1, R
2, R
3Be not the O atom simultaneously; R is that carbonatoms is the alkyl of 1-8 among the formula II.
(formula I)
(formula II)
Segment it, The compounds of this invention can be expressed as the compound of formula III, formula IV and formula V respectively, and its title is respectively 2, and 2 ', 2 "-(5H-three benzos [a, f, k] three indenes-5,10,15-three subunits) three (2-cyan-acetic esters); 2,2 '-(15-carbonyl-5H-three benzos [a, f, k] three indenes-5,10 (15H)-two subunits) two (2-cyan-acetic esters) and (10,15-dicarbapentaborane-5H-three benzos [a, f, k] three indenes-5-subunit)-2-cyan-acetic ester.
(formula III) (formula IV)
(formula V)
Wherein, R is that carbonatoms is the alkyl of 1-8, can be alkyl straight chain or the band side chain.
The preparation method of organic semiconductor compound of the present invention is that structure is carried out the Knoevenagel reaction suc as formula the trimerization indone of VI and structure suc as formula the cyan-acetic ester of VII, obtains the organic semiconductor compound of formula I structure after reaction product is purified; The mol ratio of trimerization indone and cyan-acetic ester is 1: 1-100.
Wherein, R is that carbonatoms is the alkyl of 1-8 among the formula VII.
In above-mentioned reaction, when the molar ratio of this trimerization indone and cyan-acetic ester is big (1: 10-100) help forming the formula III compound, ratio hour (1: 1-5) help forming formula IV, V compound.In addition, the use of ultrasonic wave in reaction process also helps forming the formula III compound.
In above-mentioned Knoevenagel reaction, used catalyzer can be selected common Knoevenagel catalysts for use, and preferred catalyzer is selected from one or more in titanium tetrachloride, tellurium tetrachloride, aluminium sesquioxide, aluminum phosphate, Potassium monofluoride, pyridine, hexahydropyridine and the N-methylmorpholine.
The solvent of above-mentioned Knoevenagel reaction is chloroparaffin (as a methylene dichloride, chloroform, 1,2-ethylene dichloride etc.), aromatic hydrocarbon solvent (as toluene, chlorobenzene etc.), ether solvent (as ether etc.).
When carrying out this Knoevenagel reaction, can carry out stir process and supersound process; Preferred method is to adopt ultrasound treatment patterns to carry out.This is because react under ultrasound condition, can obtain higher productive rate and more single-minded product.Trace it to its cause, on the one hand be because supersound process makes that the extremely low trimerization indone of solubleness can disperse better in organic solvent commonly used in reaction solution, thereby increased the touch opportunity between two kinds of reactants; On the other hand, ultrasonic wave also helps reactant to overcome the bigger activation energy that is brought by sterically hindered as the energy source that adds, thereby increases substantially speed of reaction.
Reaction product is carried out recrystallization behind routine operations such as chromatographic column separation or solvent wash separation, obtain the organic semiconductor compound of described formula I structure.
Another object of the present invention provides the application of organic semiconductor compound of the present invention.
Organic semiconductor compound of the present invention can be used to make organic functional device, particularly makes bilayer and the single layer organic photoreceptor that is just charging in the surface.
The invention provides a kind of double-deck organic light receptor, it comprises that conductive basal layer, electron transfer layer and current carrier produce layer, conductive basal layer and electron transfer layer are connected to the both sides that described current carrier produces layer, wherein, electron transfer layer is made of fluoropolymer resin and organic semiconductor compound of the present invention, and current carrier produces layer and is made of phthalocyanines organic light-guide body particle and fluoropolymer resin.
Wherein, the mass ratio of fluoropolymer resin and organic semiconductor compound is 1: 0.33-3, the mass ratio of fluoropolymer resin and phthalocyanines organic light-guide body is 1: 1-2.Fluoropolymer resin commonly used is polycarbonate, polyvinyl acetal, polyolefine, polystyrene, polymeric amide or polyester.
The present invention also provides a kind of single layer organic photoreceptor, comprises conductive basal layer and organic light-guide electrolemma layer, and wherein, organic light-guide electrolemma layer is to be made of fluoropolymer resin and organic semiconductor compound of the present invention and phthalocyanines organic light-guide body.
Wherein, the mass ratio of phthalocyanines organic light-guide body and organic semiconductor compound is 1: 0.1-10, the mass ratio of phthalocyanines organic light-guide body and fluoropolymer resin are 1: 1-100.Fluoropolymer resin commonly used is polycarbonate, polyvinyl acetal, polyolefine, polystyrene, polymeric amide or polyester.
In the chemical structure of organic semiconductor compound of the present invention, trimerization indone parent provides a bigger conjugated system, and the introducing of cyan-acetic ester not only can make conjugated system be further expanded, and have the cyano group of electron-withdrawing power and the lowest unoccupied molecular orbital (LUMO) that ester group can also significantly reduce entire compound, thereby make it be easier to accept and transmission electronic.Simultaneously, the ester group in the molecule also makes whole molecule have good solubility in a lot of organic solvents, thereby can use lower-cost solution-treated method such as spin coating when making device.These double-deck organic light receptors and single layer organic photoreceptor can be used for making the Photoreceptors parts in laser printer, the xerographic printer.
Novel organic semi-conductor compound provided by the present invention has good electronic transmission performance, is convenient in enormous quantities synthetic; This compound can be made as just charging bilayer and the individual layer Photoreceptors that is used for laser printer, xerographic printer and optoelectronic switch, such Photoreceptors with organic compound of the present invention as electron transport material, with the phthalocyanines organic light-guide body as carrier generation materials.Show good photoconductivity energy under the operating mode that bilayer provided by the present invention and single layer organic photoreceptor are just charging on the surface, its photoconduction performance has reached the level of the double-deck Photoreceptors of negative charging that is widely used at present.Positive battery charger operation mode makes the Photoreceptors that is provided have more advantage at aspects such as device stability and environmental protection than the Photoreceptors of negative charging, is with a wide range of applications.
Description of drawings
Fig. 1 is the uv-visible absorption spectra figure of compounds X of the present invention;
Fig. 2 is the present invention's double-deck Photoreceptors section structure synoptic diagram that just charging;
Fig. 3 is the present invention's individual layer Photoreceptors section structure synoptic diagram that just charging.
Embodiment
In order to be described more specifically the present invention, now provide some synthetic embodiment and Application Example.But content involved in the present invention is not limited only to these examples.
First part synthesizes embodiment
Used trimerization indone in reaction can synthesize (E.V.Dehmlow, T.Kelle, Synth.Commun.1997,27,2021) according to literature method, and other raw materials all can be commercially available.
Embodiment 1, do catalyzer Synthetic 2,2 ', 2 with titanium tetrachloride and N-methylmorpholine "-(5H-three benzos [a, f, k] three indenes-5,10,15-three subunits) three (2-methyl-cyanacetate) (compound VIII, C
39H
21N
3O
6)
Get trimerization indone 0.77g (2mmol) and methyl-cyanacetate 1.8ml (20mmol), add 50ml methylene dichloride as reaction solvent.Use ultrasonicly, under agitation be added dropwise to 1.3ml titanium tetrachloride (12mmol) and 4.0ml N-methylmorpholine (36mmol) then successively the pre-dispersed 30min of this mixture.With the reaction system sealing, place ultrasonic water bath, react 5h down at 25 ℃.In reaction system, add 120ml water, add the 150ml methylene dichloride again and extract.Get organic phase and will can get dark red solid behind the solvent evaporate to dryness.With ethyl acetate and methyl alcohol this solid is washed successively, recrystallization in the mixed solvent of ethanol and methylene dichloride obtains red tabular crystal 0.73g (productive rate is 58%) at last.
Mass spectrum (EI-MS) characterizes and records molecular ion peak M/Z=627;
Ultimate analysis value (quality percentage composition): C, 74.58% (74.64%); H, 3.39% (3.37%); N, 6.57% (6.70%); O, 15.46% (15.29%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the VIII.
Embodiment 2, make catalyzer synthetic compound 2,2 ', 2 with titanium tetrachloride and pyridine "-(5H-three benzos [a, f, k] three indenes-5,10,15-three subunits) three (2-ethyl cyanacetate) (Compound I X, C
42H
27N
3O
6)
Get trimerization indone 0.77g (2mmol) and methyl-cyanacetate 1.8ml (20mmol), add 50ml methylene dichloride as reaction solvent.Use ultrasonicly, under agitation be added dropwise to 1.3ml titanium tetrachloride (12mmol) and 2.9ml pyridine (36mmol) then successively the pre-dispersed 30min of this mixture.With the reaction system sealing, place ultrasonic water bath, react 5h down at 25 ℃.In reaction system, add 120ml water, add the 150ml methylene dichloride again and extract.Get organic phase and will can get dark red solid behind the solvent evaporate to dryness.With ethyl acetate and methyl alcohol this solid is washed successively, recrystallization in the mixed solvent of ethanol and methylene dichloride obtains red tabular crystal 0.65g (productive rate is 52%) at last.
Mass spectrum (EI-MS) characterizes and records molecular ion peak M/Z=627;
Ultimate analysis value (quality percentage composition): C, 74.55% (74.64%); H, 3.43% (3.37%); N, 6.62% (6.70%); O, 15.40% (15.29%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the IX.
Embodiment 3, make catalyzer synthetic compound IX with titanium tetrachloride and N-methylmorpholine
Get trimerization indone 0.77g (2mmol) and ethyl cyanacetate 2.1ml (20mmol), add the 50ml methylene dichloride and make reaction solvent.Use ultrasonicly, under agitation be added dropwise to 1.3ml titanium tetrachloride (12mmol) successively then and 4.4ml N-methylmorpholine (40mmol) is made catalyzer the pre-dispersed 30min of this mixture.With the reaction system sealing, and place ultrasonic water bath, react 5h down at 25 ℃.In reaction system, add 120ml water, add the 150ml methylene dichloride again and extract.Getting organic phase and it is concentrated, by 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses red component wherein.At last in the mixed solvent of ethanol and methylene dichloride, it is carried out recrystallization, obtain red tabular crystal 0.68g (productive rate is 51%).
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=669;
Ultimate analysis value (quality percentage composition) is: C, 75.25% (75.33%); H, 4.13% (4.06%); N, 6.11% (6.27%); O, 14.51% (14.34%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the IX.
Embodiment 4, make catalyzer synthetic compound IX with titanium tetrachloride and hexahydropyridine
Get trimerization indone 0.77g (2mmol) and ethyl cyanacetate 2.1ml (20mmol), add the 50ml methylene dichloride and make reaction solvent.Use ultrasonicly, under agitation be added dropwise to 1.3ml titanium tetrachloride (12mmol) successively then and 4.0ml hexahydropyridine (40mmol) is made catalyzer the pre-dispersed 30min of this mixture.With the reaction system sealing, and place ultrasonic water bath, react 5h down at 30 ℃.In reaction system, add 120ml water, add the 150ml methylene dichloride again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses red component wherein.At last in the mixed solvent of ethanol and methylene dichloride, it is carried out recrystallization, obtain red tabular crystal 0.66g (productive rate is 49%).
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=669;
Ultimate analysis value (quality percentage composition) is: C, 75.23% (75.33%); H, 4.12% (4.06%); N, 6.16% (6.27%); O, 14.49% (14.34%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the IX.
Embodiment 5, do catalyzer Synthetic 2,2 ', 2 with titanium tetrachloride and N-methylmorpholine "-(5H-three benzos [a, f, k] three indenes-5,10,15-three subunits) three (2-cyanoacetic acid butyl ester) (compounds X, C
48H
39N
3O
6)
Get trimerization indone 0.77g (2mmol) and the positive butyl ester 4.2ml of cyanoacetic acid (30mmol), add the 50ml methylene dichloride and make reaction solvent.Use ultrasonicly, under agitation be added dropwise to 1.3ml titanium tetrachloride (12mmol) successively then and 4.9ml N-methylmorpholine (44mmol) is made catalyzer the pre-dispersed 30min of this mixture.With the reaction system sealing, and place ultrasonic water bath, react 6h down at 30 ℃.In reaction system, add 120ml water, add the 150ml trichloromethane again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses red component wherein.At last in the mixed solvent of ethanol and methylene dichloride, it is carried out recrystallization, obtain orange red tabular crystal 0.63g (productive rate is 42%).
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=753;
Ultimate analysis value (quality percentage composition) is: C, 76.40% (76.48%); H, 5.26% (5.21%); N, 5.41% (5.57%); O, 12.93% (12.74%), in the bracket theoretical value.
Its uv-visible absorption spectra as shown in Figure 1.
Illustrate that the gained compound structure is suc as formula shown in the X.
Embodiment 6, usefulness Potassium monofluoride and aluminium sesquioxide (KF-Al
2O
3) make catalyzer synthetic compound X
Get the dihydrate of potassium fluoride (KF2H of 0.56g (6mmol)
2O) and (8mmol) neutral aluminium sesquioxide of 0.85g be dissolved in the 5ml water, solution removes water under reduced pressure after down stirring 1h in 70 ℃, the gained pressed powder is in 120 ℃ of dry 4h down.Get trimerization indone 0.77g (2mmol) and mix with above-mentioned catalyst fines, add the 50ml methylene dichloride and make reaction solvent with the positive butyl ester 4.2ml of cyanoacetic acid (30mmol).With the reaction system sealing, and place ultrasonic water bath, react 6h down at 25 ℃.In reaction system, add 120ml water, add the 150ml trichloromethane again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses red component wherein.At last in the mixed solvent of ethanol and methylene dichloride, it is carried out recrystallization, obtain orange red tabular crystal 0.69g (productive rate is 46%).
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=753;
Ultimate analysis value (quality percentage composition) is: C, 76.29% (76.48%); H, 5.28% (5.21%); N, 5.47% (5.57%); O, 12.96% (12.74%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the X.
Embodiment 7, do catalyzer Synthetic 2,2 ', 2 with titanium tetrachloride and N-methylmorpholine "-(5H-three benzos [a, f, k] three indenes-5,10,15-three subunits) three [2-cyanoacetic acid (2-ethyl oneself) ester] (compounds X I, C
60H
63N
3O
6)
Get trimerization indone 0.77g (2mmol) and cyanoacetic acid (the 2-ethyl is own) ester 6.3ml (30mmol), add the 50ml trichloromethane and make reaction solvent.Use ultrasonicly, under agitation be added dropwise to 1.3ml titanium tetrachloride (12mmol) successively then and 5.3mlN-methylmorpholine (48mmol) is made catalyzer the pre-dispersed 30min of this mixture.With the reaction system sealing, and place ultrasonic water bath, react 6h down at 60 ℃.In reaction system, add 120ml water, add the 150ml trichloromethane again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses red component wherein.In ethanol, it is carried out recrystallization at last, obtain red tabular crystal 0.72g (productive rate is 39%).
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=921;
Ultimate analysis value (quality percentage composition) is: C, 78.08% (78.15%); H, 6.94% (6.89%); N, 4.41% (4.56%); O, 10.57% (10.40%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the XI.
Embodiment 8, make catalyzer synthetic compound XI with aluminum phosphate and aluminium sesquioxide
Get the aluminum phosphate of 0.73g (6mmol) and (8mmol) neutral aluminium sesquioxide of 0.85g and be dissolved in the 5ml water, solution removes water under reduced pressure behind the stirring 1h down in 70 ℃, and the gained pressed powder is dry 5h under 120 ℃.Get trimerization indone 0.77g (2mmol) and mix with above-mentioned catalyst fines, add the 50ml trichloromethane and make reaction solvent with cyanoacetic acid (the 2-ethyl is own) ester 6.3ml (30mmol).With the reaction system sealing, and place ultrasonic water bath, react 6h down at 60 ℃.In reaction system, add 120ml water, add the 150ml trichloromethane again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses red component wherein.In ethanol, it is carried out recrystallization at last, obtain red tabular crystal 0.68g (productive rate is 37%).
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=921;
Ultimate analysis value (quality percentage composition) is: C, 78.02% (78.15%); H, 6.97% (6.89%); N, 4.45% (4.56%); O, 10.56% (10.40%), in the bracket theoretical value.
Illustrate that the gained compound structure is suc as formula shown in the XI.
Embodiment 9, (10,15-dicarbapentaborane-5H-three benzos [a, f, k] three indenes-5-subunit)-2-cyanoacetic acid butyl ester (compounds X II, C
34H
21NO
4) synthetic
Get trimerization indone 0.77g (2mmol) and the positive butyl ester 0.4ml of cyanoacetic acid (3mmol), add the 50ml chlorobenzene and make reaction solvent.Use ultrasonicly, under agitation be added dropwise to 0.3ml titanium tetrachloride (3mmol) successively then and 1.3ml N-methylmorpholine (12mmol) is made catalyzer the pre-dispersed 30min of this mixture.With the reaction system sealing, at 25 ℃ of following induction stirring reaction 6h.In reaction system, add 120ml water, add the 150ml trichloromethane again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses first orange component wherein.At last in the mixed solvent of ethanol and methylene dichloride, it is carried out recrystallization, obtain orange tabular crystal.
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=507.
Illustrate that the gained compound structure is suc as formula shown in the XII.
Embodiment 10,2,2 '-(15-carbonyl-5H-three benzos [a, f, k] three indenes-5,10 (15H)-two subunits) two (2-cyanoacetic acid butyl ester) (compounds X III, C
41H
30N
2O
5) synthetic
Get trimerization indone 0.77g (2mmol) and the positive butyl ester 0.7ml of cyanoacetic acid (5mmol), add the 50ml chlorobenzene and make reaction solvent.Use ultrasonicly, under agitation be added dropwise to 0.7ml titanium tetrachloride (6mmol) successively then and 2.7ml N-methylmorpholine (24mmol) is made catalyzer the pre-dispersed 30min of this mixture.With the reaction system sealing, at 25 ℃ of following induction stirring reaction 6h.In reaction system, add 120ml water, add the 150ml trichloromethane again and extract.Get organic phase and it is concentrated.By 200-300 purpose silicagel column, is eluent with the methylene dichloride with concentrated solution, accesses wherein second orange red component.At last in the mixed solvent of ethanol and methylene dichloride, it is carried out recrystallization, obtain orange red tabular crystal.
Mass spectrum (EI-MS) characterize molecular ion peak M/Z=630.
Illustrate that the gained compound structure is suc as formula shown in the XIII.
The second section Application Example
Organic semiconductor compound of the present invention has bigger electron affinity and electron transport ability preferably, can be used as the carrier transmission material of double-deck organic light receptor and single layer organic photoreceptor.
As Fig. 2, organic semiconductor compound of the present invention and fluoropolymer resin are mixed and made into electron transfer layer 11 according to a certain percentage, and produce layer 12 with the current carrier made by phthalocyanines organic light-guide body and fluoropolymer resin and combine, constitute double-deck organic light receptor with conductive basal layer 13, have good photoconduction performance under the operating mode that this bilayer organic light receptor is just charging on the surface, its light decay sensitivity has reached the level of the negative charging multilayer Photoreceptors of practicability.
As Fig. 3, organic semiconductor compound of the present invention is mixed according to a certain percentage with phthalocyanines organic light-guide body and fluoropolymer resin, and on conductive basal layer 22, be coated with into organic film 21, obtain single layer organic photoreceptor, show good performance under the operating mode that this single layer organic photoreceptor is just charging on the surface.Compare with the individual layer Photoreceptors of only being made up of phthalocyanines optical conductor and resin, this individual layer Photoreceptors has better light decay sensitivity, and performance perameter such as rest potential has also obtained tangible improvement.
Embodiment 11, Compound I X is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=2: 1.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In 1 of polycarbonate (PC), in the 2-dichloroethane solution (100g/l), with Compound I X dissolving, wherein the mass ratio of IX and resin is IX: PC=11: 10.This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the electron transfer layer that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, electron transfer layer and aluminium base the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Embodiment 12, Compound I X is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=3: 2.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In 1 of polycarbonate (PC), in the 2-dichloroethane solution (100g/l), with Compound I X dissolving, wherein the mass ratio of IX and resin is IX: PC=11: 10.This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the electron transfer layer that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, electron transfer layer and aluminium base the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Embodiment 13, compounds X is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=2: 1.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In polycarbonate (PC)/1, with the compounds X dissolving, wherein the mass ratio of X and resin is X: PC=6: 5 among the 2-dichloroethane solution (100g/l).This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the carrier blocking layers that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, carrier blocking layers and aluminium base the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Embodiment 14, compounds X is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=1: 1.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In polycarbonate (PC)/1, with the compounds X dissolving, wherein the mass ratio of X and resin is X: PC=6: 5 among the 2-dichloroethane solution (100g/l).This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the carrier blocking layers that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, carrier blocking layers and aluminium base the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Embodiment 15, compounds X I is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=2: 1.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In polycarbonate (PC)/1, with compounds X I dissolving, wherein the mass ratio of XI and resin is XI: PC=7: 5 among the 2-dichloroethane solution (100g/l).This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the carrier blocking layers that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, carrier blocking layers and aluminium base common the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Embodiment 16, compounds X II is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=2: 1.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In polycarbonate (PC)/1, with compounds X II dissolving, wherein the mass ratio of XII and resin is XII: PC=6: 5 among the 2-dichloroethane solution (100g/l).This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the carrier blocking layers that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, carrier blocking layers and aluminium base common the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Embodiment 17, compounds X III is used for the preparation double-deck organic light receptor that just charging
Y type TiOPc (Y-TiOPc) powder is carried out supersound process in the pimelinketone solution of polyvinyl butyral acetal (PVB), make the colloid coating fluid, the mass ratio of its Y-TiOPc and resin is Y-TiOPc: PVB=2: 1.This coating fluid on aluminium base after the spin-coating film, made the current carrier that thickness is about 1 micron in 70 ℃ of dry 3h and produces layer.In polycarbonate (PC)/1, with compounds X III dissolving, wherein the mass ratio of XIII and resin is XIII: PC=6: 5 among the 2-dichloroethane solution (100g/l).This coating fluid after sprawling film forming on the above-mentioned current carrier generation layer, is made the carrier blocking layers that thickness is about 10 microns in 60 ℃ of dry 3h.Described double-deck organic light receptor promptly produces layer, carrier blocking layers and aluminium base common the composition by current carrier.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 1.
Just the charging correlated performance parameter of double-deck organic light receptor of table 1. part
| Embodiment number | V 0(V) | R d(V/s) | E 1/2(μJ/cm 2) | V R(V) |
| 11 | 572 | 34 | 0.32 | 57 |
| 12 | 544 | 30 | 0.48 | 84 |
| 13 | 565 | 37 | 0.30 | 53 |
| 14 | 570 | 24 | 0.85 | 103 |
| 15 | 578 | 37 | 0.28 | 45 |
| 16 | 609 | 28 | 0.40 | 78 |
| 17 | 587 | 30 | 0.37 | 66 |
1, test condition: corona voltage, 5.5kV; Wavelength, 780nm; Light intensity, 1 μ W.
2, the meaning of each physical parameter representative: V
0, the initial surface charging potential; R
d, the rate of decay of surface potential during unglazed the photograph; E
1/2, surface potential decays to the required luminous energy of initial potential one half; V
R, the surperficial rest potential behind the illumination 10s.
The result of embodiment 11-17 shows, novel organic semi-conductor compound provided by the present invention has good electron transport ability in the double-deck organic light receptor that just charges, the over-all properties of such double-deck organic light receptor, especially light decay sensitivity has reached the level of the double-deck organic light receptor of negative charging of practicability.
Embodiment 18, compound VIII is used for the preparation single layer organic photoreceptor that just charging
In 1 of polycarbonate (PC), in the 2-dichloroethane solution (200g/l) with compound VIII dissolving, simultaneously with ranadylic phthalocyanine (II-VOPc) powder of II type 1, in the 2-ethylene dichloride by the ultrasonic stable colloidal solutions that makes.Above-mentioned two parts of solution are mixed, obtain uniform and stable green coating fluid behind the stirring 3h, wherein the mass ratio of each component is II-VOPc: VIII: PC=9: 10: 30, VOPc accounted for 18% of solute total mass.This coating fluid behind the generate film of aluminium base upper berth, is promptly made the single layer organic photoreceptor that described thickness is about 10 microns in 60 ℃ of dry 3h.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
Embodiment 19, Compound I X is used for the preparation single layer organic photoreceptor that just charging
In 1 of polycarbonate (PC), among the 2-dichloroethane solution (200g/l) with Compound I X dissolving, simultaneously with ranadylic phthalocyanine (II-VOPc) powder of II type 1, in the 2-ethylene dichloride by the ultrasonic stable colloidal solutions that makes.Above-mentioned two parts of solution are mixed, obtain uniform and stable green coating fluid behind the stirring 3h, wherein the mass ratio of each component is II-VOPc: IX: PC=6: 7: 20, VOPc accounted for 18% of solute total mass.This coating fluid behind the generate film of aluminium base upper berth, is promptly made the single layer organic photoreceptor that described thickness is about 10 microns in 60 ℃ of dry 3h.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
Embodiment 20, compounds X is used for the preparation single layer organic photoreceptor that just charging
In 1 of polycarbonate (PC), among the 2-dichloroethane solution (200g/l) with compounds X dissolving, simultaneously with ranadylic phthalocyanine (II-VOPc) powder of II type 1, in the 2-ethylene dichloride by the ultrasonic stable colloidal solutions that makes.Above-mentioned two parts of solution are mixed, obtain uniform and stable green coating fluid behind the stirring 3h, wherein the mass ratio of each component is II-VOPc: X: PC=6: 7: 20, VOPc accounted for 18% of solute total mass.This coating fluid behind the generate film of aluminium base upper berth, is promptly made the single layer organic photoreceptor that described thickness is about 10 microns in 60 ℃ of dry 3h.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
In polycarbonate (PC)/1, among the 2-dichloroethane solution (200g/l) with compounds X I dissolving, simultaneously with ranadylic phthalocyanine (II-VOPc) powder of II type 1, in the 2-ethylene dichloride by the ultrasonic stable colloidal solutions that makes.Above-mentioned two parts of solution are mixed, obtain uniform and stable green coating fluid behind the stirring 3h, wherein the mass ratio of each component is II-VOPc: XI: PC=3: 4: 10, VOPc accounted for 18% of solute total mass.This coating fluid behind the generate film of aluminium base upper berth, is promptly made the single layer organic photoreceptor that described thickness is about 10 microns in 60 ℃ of dry 3h.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
In 1 of polycarbonate (PC), among the 2-dichloroethane solution (200g/l) with compounds X II dissolving, simultaneously with ranadylic phthalocyanine (II-VOPc) powder of II type 1, in the 2-ethylene dichloride by the ultrasonic stable colloidal solutions that makes.Above-mentioned two parts of solution are mixed, obtain uniform and stable green coating fluid behind the stirring 3h, wherein the mass ratio of each component is II-VOPc: XII: PC=9: 10: 30, VOPc accounted for 18% of solute total mass.This coating fluid behind the generate film of aluminium base upper berth, is promptly made the single layer organic photoreceptor that described thickness is about 10 microns in 60 ℃ of dry 3h.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
Embodiment 23, compounds X III is used for the preparation single layer organic photoreceptor that just charging
In 1 of polycarbonate (PC), among the 2-dichloroethane solution (200g/l) with compounds X III dissolving, simultaneously with ranadylic phthalocyanine (II-VOPc) powder of II type 1, in the 2-ethylene dichloride by the ultrasonic stable colloidal solutions that makes.Above-mentioned two parts of solution are mixed, obtain uniform and stable green coating fluid behind the stirring 3h, wherein the mass ratio of each component is II-VOPc: XIII: PC=9: 10: 30, VOPc accounted for 18% of solute total mass.This coating fluid behind the generate film of aluminium base upper berth, is promptly made the single layer organic photoreceptor that described thickness is about 20 microns in 60 ℃ of dry 3h.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
Comparative example 1, only use ranadylic phthalocyanine (II-VOPc) preparation of the II type single layer organic photoreceptor that just charging
Ranadylic phthalocyanine (II-VOPc) powder of II type 1, by the ultrasonic stable colloidal solutions that makes, is added 1 of polycarbonate (PC), 2-dichloroethane solution (200g/l) in the 2-ethylene dichloride again in this colloidal solution.Obtain uniform and stable blue coating fluid after stirring 3h, wherein the mass ratio of two kinds of solutes is II-VOPc: PC=11: 50, and VOPc accounts for 18% of solute total mass.This coating fluid is promptly made the single layer organic photoreceptor that described thickness is about 20 microns in 60 ℃ of dry 3h behind the generate film of aluminium base upper berth.Use the EPA-8200 electrostatic analyzer to characterize, make this Photoreceptors surface fill positive electricity, the various performance parameters that records is listed in table 2.
Just the charging correlated performance parameter of single layer organic photoreceptor of table 2 part
| Embodiment number | V 0(V) | E 1/2(μJ/cm 2) | E 1/5(μJ/cm 2) | V R(V) |
| 18 | 570 | 0.61 | 0.69 | 1 |
| 19 | 576 | 0.70 | 0.78 | 1 |
| 20 | 588 | 0.82 | 0.91 | 2 |
| 21 | 592 | 0.88 | 1.00 | 2 |
| 22 | 582 | 0.76 | 0.86 | 1 |
| 23 | 579 | 0.73 | 0.82 | 1 |
| Comparative example 1 | 609 | 1.02 | 1.38 | 16 |
1, test condition: corona voltage, 5.5kV; Wavelength, 780nm; Light intensity, 1 μ W.
2, the meaning of each physical parameter representative: V
0, the initial surface charging potential; E
1/2, surface potential decays to the required luminous energy of initial potential one half; E
1/5, surface potential decays to the required luminous energy of initial potential five/a period of time; V
R, the surperficial rest potential behind the illumination 10s.
The result of embodiment 18-23 and comparative example 1 shows, novel organic semi-conductor compound provided by the present invention can improve the photoconduction performance of the single layer organic photoreceptor that just charges significantly, especially performance perameters such as light decay sensitivity when surface potential is very low and rest potential.
Claims (12)
1, structure is suc as formula the organic semiconductor compound of I, wherein, and R
1, R
2, R
3Be the cyan-acetic ester subunit of O atom or formula II structure, and R
1, R
2, R
3Be not the O atom simultaneously; R is that carbonatoms is the alkyl of 1-8 among the formula II;
2, the preparation method of the described organic semiconductor compound of claim 1, be that structure is carried out the Knoevenagel reaction suc as formula the trimerization indone of VI and structure suc as formula the cyan-acetic ester of VII, obtain the organic semiconductor compound of described formula I structure after reaction product is purified; Described Knoevenagel reaction adopts ultrasound treatment patterns to carry out; The mol ratio of described trimerization indone and described cyan-acetic ester is 1: 1-100;
(formula VI)
(formula VII)
Wherein, R is that carbonatoms is the alkyl of 1-8 among the formula VII.
3, preparation method according to claim 2 is characterized in that: described Knoevenagel catalyst for reaction is selected from one or more in titanium tetrachloride, tellurium tetrachloride, aluminium sesquioxide, aluminum phosphate, Potassium monofluoride, pyridine, hexahydropyridine and the N-methylmorpholine; The solvent of described Knoevenagel reaction is chloroparaffin, aromatic hydrocarbon solvent or ether solvent.
4, according to claim 2 or 3 described preparation methods, it is characterized in that: described purifying is to adopt chromatographic column to separate or the solvent wash reaction product isolated, carries out recrystallization then, obtains the organic semiconductor compound of described formula I structure.
5, a kind of double-deck organic light receptor, comprise that conductive basal layer, electron transfer layer and current carrier produce layer, described conductive basal layer and described electron transfer layer are connected to the both sides that described current carrier produces layer, it is characterized in that: described electron transfer layer is made of fluoropolymer resin and the described organic semiconductor compound of claim 1, and described current carrier produces layer and is made of phthalocyanines organic light-guide body and fluoropolymer resin.
6, double-deck organic light receptor according to claim 5 is characterized in that: the mass ratio of described fluoropolymer resin and described organic semiconductor compound is 1: 0.33-3; The mass ratio of described fluoropolymer resin and phthalocyanines organic light-guide body is 1: 1-2.
7, according to claim 5 or 6 described double-deck organic light receptors, it is characterized in that: described fluoropolymer resin is polyolefine, polyester, polyvinyl acetal or polymeric amide.
8, double-deck organic light receptor according to claim 7 is characterized in that: described polyolefine is a polystyrene; Described polyester is a polycarbonate.
9, a kind of single layer organic photoreceptor comprises conductive basal layer and organic film, it is characterized in that: described organic film is to be made of fluoropolymer resin, the described organic semiconductor compound of claim 1 and phthalocyanines organic light-guide body.
10, single layer organic photoreceptor according to claim 9, it is characterized in that: the mass ratio of described phthalocyanines organic light-guide body and described organic semiconductor compound is 1: 0.1-10, the mass ratio of described phthalocyanines organic light-guide body and described fluoropolymer resin are 1: 1-100.
11, according to claim 9 or 10 described single layer organic photoreceptors, it is characterized in that: described fluoropolymer resin is polyolefine, polyester, polyvinyl acetal or polymeric amide.
12, single layer organic photoreceptor according to claim 11 is characterized in that: described polyolefine is a polystyrene; Described polyester is a polycarbonate.
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| . 胡德荣等.首都师范大学学报（自然科学版），第26卷第1期. 2005 |
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