CN1827666B - Conjugated polymer containing sulfonic group substituted triarylamine and use thereof - Google Patents
Conjugated polymer containing sulfonic group substituted triarylamine and use thereof Download PDFInfo
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- CN1827666B CN1827666B CN2006100335142A CN200610033514A CN1827666B CN 1827666 B CN1827666 B CN 1827666B CN 2006100335142 A CN2006100335142 A CN 2006100335142A CN 200610033514 A CN200610033514 A CN 200610033514A CN 1827666 B CN1827666 B CN 1827666B
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Abstract
The invention discloses a conjugated polymer substituted by sulfonic group with triarylamines compound composition, which includes nonpolar substituent groups of monomer A and C and triarylamine monomer B substituted by sulfonic group; the said conjugated polymer can improve radioluminescence efficiency of devices such as luminescent device, photovoltaic device and so on as hole transport layer.
Description
Technical field
The present invention relates to a kind of organic compound, particularly a kind of conjugated polymers that contains sulfonic group substituted triarylamine.
The invention still further relates to the application of described polymkeric substance.
Background technology
(Organic Light-emitting diodes OLEDs) can be by small molecules [US4,539,507], and conjugated highpolymer [WO 90/13148] and dendrimer [WO 99/21935] are prepared from for organic electroluminescence device.The simplest OLED structure is an individual layer sandwich structure, is made up of anode, negative electrode and organic luminous layer, and luminescent layer is clipped between two electrodes of negative and positive.After applying suitable forward bias between anode and the negative electrode, hole and electronics are injected in the device by anode and negative electrode respectively, and be compound and produce exciton in luminescent layer, gives off energy in the mode of optical radiation.For reaching better device effect, the structures that adopt multilayer film to pile up add one deck hole transmission layer more between anode and luminescent layer, add the last layer electron transfer layer between negative electrode and luminescent layer, thereby make the injection of hole and electronics more smooth, recombination probability is increased.
In order to make above-mentioned device energy works better, electronics must inject and the minimum energy that is transferred to luminescent material occupied orbital (LUMO) not from negative electrode, and the hole must and be transferred to the highest energy occupied orbital (HOMO) of luminescent material by the anode injection.Respectively corresponding its oxidation of the HOMO of luminescent material and lumo energy and reduction potential can be regulated by introducing different substituting groups.
For making electronic energy be injected into the LUMO track of luminescent material better from negative electrode, the energy difference between the work function of cathode material and the lumo energy of luminescent material should be as much as possible little.Same, better being injected into the HOMO track of luminescent material for making cavity energy, the work function of anode material should be tried one's best and the HOMO energy level of luminescent material mates.The anode material of now general electroluminescent device is the tin indium oxide (ITO) of layer of transparent, and its work function is about 4.8 electron-volts.Yet, the HOMO energy level of many luminescent materials the 5.2-5.8 electron-volt or more than, clearly, the HOMO energy level of the work function of ITO and luminescent material does not match.
A kind of terms of settlement is to add one deck hole transmission layer between luminescent layer and ITO, and its work function is between the HOMO of ITO and luminescent material energy level.A hole transmission layer like this can help the hole to be injected into the HOMO of luminescent material from ITO, and in addition, it can also stop from the negative electrode injected electrons, and hole and electronics are limited in the luminescent layer, reaches the compound of maximum likelihood.The research that has the hole mobile material of good mechanical property, thermostability and chemical property simultaneously becomes a focus.
Also can form stable positively charged ion and have higher hole mobility owing to be easy to oxidation, the tri-arylamine group compound is applied among the OLEDs as hole mobile material widely.A series of small molecules that contain triarylamine group and polymkeric substance be being synthesized by success.Low-molecular-weight tri-arylamine group compound is because the physical properties of himself is separated out as easy crystallization, and second-order transition temperature is low etc., is restricted in the application of OLEDs.Usually to use the technology of vacuum evaporation with this compounds during as hole transmission layer, this technology relative complex, device and equipment cost height is unfavorable for realizing the preparation of large screen display device.By triarylamine group is incorporated in the polymkeric substance, the defective of low-molecular-weight tri-arylamine group compound can be overcome, and relative simple technology can be used, as spin coating, spray ink Printing waits and carries out the device preparation.There have been many polymkeric substance that contain triarylamine group to be in the news in recent years as hole mobile material.
WO 98/06773 has reported a series of C1 of having～24 alkyl, substituted radicals such as alkoxyl group be the polymkeric substance of main chain with three arylamine, being used for poly-fluorenes as hole transmission layer it is the blue-light device of luminescent material, and they have the hole transport effect device performance explanation preferably.
WO 03000773 has reported by the Suzuki coupled reaction and has synthesized a series of alkyl that contain with hole transport performance, alkoxyl group, carboxylic acid ester groups, substituted radicals such as cyano group be the polymkeric substance of main chain with three arylamine.
What WO 99/32537 had reported that the alkyl chain of a series of C1 of having～40 replaces is the polymkeric substance of main chain with three arylamine, come the regulatory molecule amount by end-blocking, they can be dissolved in the solvent of preparation multilayer OLED commonly used, in toluene, dimethylbenzene, can be used as hole mobile material and be applied among the OLED.
US 5,681, and 664 have reported that series contains the polymkeric substance hole mobile material of the ester ring family component of three arylamine and C4～7.
WO 01/66618 has reported that a series of main chains contain the multipolymer of fluorenes and triarylamine group, by on three arylamine, introducing the redox potential that different substituting groups is regulated them, and propose to adopt a series of oxidizing potentials hole transmission layer from low to high successively to pile up progressively the hole injection barrier between ITO and the luminescent layer of overcoming.
WO 02/28938 has reported that a series of fluorenes and the multipolymer that has the substituting group triphenylamine are doped in the luminescent material as hole mobile material, substituting group on the triphenylamine can be a carboxyl, the alkyl of C1～20, the alkoxyl group of C1～20, carboxylic acid ester groups, trifluoromethyl etc.
US 2001/017155 has reported that a series of ethene replace the monomeric preparation of three arylamine and obtain the non-conjugated polyethylene based polymers that a series of side chains contain triarylamine group by negatively charged ion or radical polymerization, regulate its redox potential by introduce different substituting groups on three arylamine.
US 2005/008893 has reported that a series of side chains contain the non-conjugated polyethylene based polymers of triarylamine group, and this base polymer can well form level and smooth film attached to the ITO surface.
JP 2003/137936 has reported that a series of side chains contain the non-conjugated polyethylene based polymers of triarylamine group, and this base polymer well forms level and smooth hole transmission layer attached to the ITO surface, is difficult for after the film forming being destroyed by solvent.
Foregoing invention does not relate to the preparation and the relevant information of the tri-arylamine group monomer and the polymkeric substance of polar functionalities or ionic group, resulting polymkeric substance generally all is dissolved in non-polar organic solvent, and its weak point is that resulting polymers and luminescent material commonly used have close solvability.When these polymkeric substance were applied to the multilayer luminescent device as hole mobile material, resulting hole transmission layer was subjected to nip in the luminescent material solution easily and is destroyed, causes element leakage, thereby influences its work-ing life.In addition, the electroconductibility of these materials is relatively low, therefore needs higher working voltage, and energy consumption is bigger.
Because luminous high polymer device (PLEDs) has lower cost for material, is easy to the big area moulding, driving voltage is low, and energy consumption is little, and emission wavelength can pass through the outstanding advantage of the tuning grade of material structure, has started a revolution of information display technology.That PLEDs adopts is the preparation technology of spin coating and spray ink Printing etc. so-called " wet method ", and this technology is differing materials to be dissolved in the solvent come spin coating or spray ink Printing film forming with solution again behind the formation homogeneous phase solution.The simple relatively and control easily of such technology, but its weak point is to occur easily in the preparation of devices process mixing problem between the adjacent interfaces.
According to the preparation process of multilayer PLEDs, hole mobile material will be dissolved in certain solvent and to form the homogeneous solution system and use this solution spin-coating film on ITO again.Spin coating luminescent layer thereon afterwards, in this process, because the present hole mobile material of reporting and luminescent material mostly have identical solubleness in non-polar organic solvent, formed hole transmission layer has when the spin coating luminescent layer by the dissolution with solvents in the luminescent material solution and destructive danger.A method that addresses this problem is behind the spin coating hole transmission layer it to be carried out aftertreatment to make its solvability reduction or become insoluble.Hole mobile material PEDOT[EP 0686662 commonly used], will be heating and curing at about 200 ℃ again after its spin-coating film, thereby solvability is reduced.WO 2005/059951 has reported that the polymkeric substance of three arylamine that a series of C1 of containing～20 alkyl or alkoxyl group replace is used as hole transmission layer, with its solution spin-coating film that is dissolved in dimethylbenzene, after this is heated and makes its solvability reduction.WO2005/036666 has reported a series of polymkeric substance that contain three arylamine that have easy cracked carboxylic acid esters group replacement, this base polymer is dissolvable in water spin-coating film in the organic solvent commonly used, after this by can making the carboxylic acid esters group cracking on three arylamine to its heating, thereby make it become insoluble.
In addition, some by light or heat cross-linking to change also being synthesized of its deliquescent hole mobile material that contains three arylamine by success.
WO 97/33193 has reported a series of crosslinkable active groups that contain, as hydroxyl, and acrylic, methacrylic acid group, vinyl, maleimide base, alkyl replaces siloxanes, and the derivative of tri-arylamine group that cyclic ethers base etc. replace makes it crosslinked and solvability reduces by heating or illumination.
WO 2005/060624 has reported that side chain terminal has the triarylamine derivative of organosilicon functional group, with itself and the polymer-doped back of the tri-arylamine group with hole transport performance spin-coating film, to its heating thereby its crosslinked solvability that makes is reduced, and cavity transmission ability is not subjected to obvious influence.
WO 2005/083034 has reported the polymkeric substance of a series of crosslinkable three arylamine at side chain, can regulate its redox potential by introducing different substituents, reduces by crosslinked their solvability that makes.
Above-mentioned contain three arylamine and the crosslinked back of hole mobile material that can be crosslinked and crosslinked before by comparison performance generally can decrease, this may since the hair line that side reaction that takes place in the cross-linking process and crosslinked volumetric shrinkage are afterwards produced cause.But its weak point is generally to need to add a spot of initiator in crosslinking reaction, and these initiators are difficult to remove fully as impurity, become the trap that causes the hole quencher easily.In addition, crosslinked degree of carrying out is difficult to control, reaction repeated relatively poor.Formed hair line causes device leakage easily in the cross-linking process, reduces the work-ing life of device.These defectives make the application of above-mentioned cross-linking type hole mobile material be restricted.
Another kind method is the solvability that the group of introducing other on three arylamine changes hole mobile material, and the organic solvent of being used always when making it be insoluble to the spin coating luminescent material is as toluene, dimethylbenzene, chlorobenzene, chloroform etc.WO 99/54385 has reported that a series of fluorenes and carboxylic acid group replace the multipolymer of three arylamine, and this base polymer is owing to carboxylic acid group's modification is insoluble to toluene, in the dimethylbenzene equal solvent.Be dissolved in polar solvent N with this analog copolymer, solution in the dinethylformamide (DMF) comes spin coating to prepare hole transmission layer, when the spin coating luminescent layer, can avoid the mixing between the interface, the carboxylic acid group is a kind of weak acid simultaneously, and the strong acid type substituting group has the raising effect to work function, specific conductivity and the solubleness in polar solvent of gained hole mobile material.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of conjugated polymers that contains sulfonic group substituted triarylamine is provided, it has special solvability, avoids the interface mixing under the prerequisite that does not influence its hole transport performance.
The invention still further relates to described polymkeric substance uses in luminous, the photovoltaic devices such as (opto-electronic conversion, photaesthesia) of preparation as hole transmission layer.
A kind of conjugated polymers that contains sulfonic group substituted triarylamine of the present invention, its structure is:
Wherein, n
1+ n
3=0.5, n
1+ n
2+ n
3=1;
A has the component of following formula structure for containing nonpolar substituted radical:
In the formula: R1, R2, R3 are alkyl, the alkoxyl group of one or more H, C1～C20, m=1 or 2, n=1,2,3 ...,
And/or
In the formula: R3, R4 are the alkyl of H, C1～C20, n=1,2,3 ...,
And/or
In the formula: R3, R4 are alkyl, the alkoxyl group of H, C1～C20, n=1,2,3 ...,
And/or
In the formula: R3, R4 are the alkyl of H, C1～C20, n=1,2,3 ...,
And/or
Wherein: R3, R4 are alkyl, the alkoxyl group of H, C1～C20, n=1,2,3 ...,
And/or
In the formula: R3 is the alkyl of H, C1-C20, n=1,2,3
B has three arylamine components of following formula structure for containing sulfonic acid group:
In the formula: R1, R2 is alkyl, the alkoxyl group of one or more H, C1～C20, perhaps, haloalkyl, nitro, cyano group, amide group, ketone group, phosphinyl, phosphate-based, sulfonate group for one or more halogen atoms, C1～C20, R3 is alkyl, alkoxyl group, the haloalkyl of C0～C20, X is hydrogen, lithium, sodium, potassium, ammonium, m=1 or 2; N=1,2,3 N1=1 or 2;
C has the component of following formula structure for containing nonpolar substituted radical:
In the formula: R1 is the perfluor substituted alkyl of one or more C1～C20 or is one or more nitros, cyano group, carboxylic acid ester groups, amide group, phosphate-based, sulfonate group, m=1 or 2, n=1,2,3 ...
Preferred version: molar content 〉=30% of described B component in polymkeric substance.
A kind of method for preparing above-mentioned polymkeric substance; be that monomer A, B, C and palladium are dissolved in pH value is 10 N; in dinethylformamide (DMF) buffered soln (when containing hypoboric acid ester substituent among monomer A, B, the C; adding tetrahydrofuran (THF) (THF) in described buffered soln separates with hydrotropy); obtain reaction solution; charge into Ar gas, under its protection, coupled reaction takes place, reaction solution was refluxed 3 days.Cool to room temperature then precipitates reaction solution and to obtain crude product in acetone, crude product is dissolved in minimum dimethyl sulfoxide (DMSO) (DMSO) after, with by molecular weight being 3500 film dialysis three days.And then precipitation vacuum-drying and making in acetone.
Above-mentioned polymkeric substance is as the application of hole transmission layer, be to take multilayered structure, between luminescent conjugated polymers and ITO, insert the polyelectrolytes film that skim contains described polymkeric substance, reduce the injection barrier in hole, strengthen the injection efficiency in hole, the balanced bipolar current carrier makes hole-electron recombination to reach the efficient of improving radioluminescence.
The present invention compared with prior art has following advantage:
(1) no matter polymkeric substance of the present invention can be realized excellent hole transport to the red, green, blue three-colour light-emitting material of which kind of band gap width.
(2) polymkeric substance of the present invention is dissolvable in water methyl alcohol, N, in one or more solvents that mix of dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), water isopolarity solvent, and be not dissolved in the used organic solvent of preparation luminescent material solution commonly used, as toluene, dimethylbenzene, chlorobenzene, therefore the interface mixing phenomena can not take place between hole transmission layer and the luminescent layer in chloroform etc. when constructing multilayer device.
(3) polymers soln of the present invention can be by rotation, and modes such as printing apply skim on ITO, need not long-time heating or ultraviolet lighting to change its solvability, and device preparation technology is simple.
(4) polymer materials of the present invention has good thermostability and electrochemical stability, and the stability of device itself also improves greatly, in organic and macromolecular LED display screen technology the potential using value is arranged.
Description of drawings
Fig. 1 is based on blue light material PFO, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTFTS-Na layer, among the figure: ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTFTS-Na/PFO/Ba/Al, symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTFTS-Na/PFO/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO/Ba/Al, symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO/Ba/Al.
Fig. 2 is based on blue light material PFO, has or not the device luminosity and the luminous external quantum efficiency comparison diagram of PTFTS-Li layer, and among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTFTS-Li/PFO/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTFTS-Li/PFO/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO/Ba/Al.
Fig. 3 is based on blue light material PFO, has or not PTP-OBSO
3The device luminosity of Na layer and luminous external quantum efficiency comparison diagram, among the figure: symbol ■ and represent that respectively structure is ITO/PTP-OBSO
3The luminosity of the device of Na/PFO/Ba/Al and external quantum efficiency; Symbol ◆ and ◇ represents that respectively structure is ITO/PEDOT:PSS/PTP-OBSO
3The luminosity of the device of Na/PFO/Ba/Al and external quantum efficiency; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO/Ba/Al.
Fig. 4 is based on the PFO-DBT15 that glows, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTFTS-Na layer, among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTFTS-Na/PFO-DBT15/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTFTS-Na/PFO-DBT15/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-DBT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-DBT15/Ba/Al.
Fig. 5 is based on the PFO-DBT15 that glows, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTFTS-Li layer, among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTFTS-Li/PFO-DBT15/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTFTS-Li/PFO-DBT15/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-DBT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-DBT15/Ba/Al.
Fig. 6 is based on the PFO-DBT15 that glows, and has or not PTP-OBSO
3The device luminosity of Na layer and luminous external quantum efficiency comparison diagram, among the figure: symbol ■ and represent that respectively structure is ITO/PTP-OBSO
3The luminosity of the device of Na/PFO-DBT15/Ba/Al and external quantum efficiency; Symbol ◆ and ◇ represents that respectively structure is ITO/PEDOT:PSS/PTP-OBSO
3The luminosity of the device of Na/PFO-DBT15/Ba/Al and external quantum efficiency; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-DBT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-DBT15/Ba/Al.
Fig. 7 is based on the PFO-DBT15 that glows, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTP11-Na layer, among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTP11-Na/PFO-DBT15/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTP11-Na/PFO-DBT15/Ba/Al: symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-DBT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-DBT15/Ba/Al.
Fig. 8 is based on the PFO-DBT15 that glows, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTP31-Na layer, among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTP31-Na/PFO-DBT15/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTP31-Na/PFO-DBT15/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-DBT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-DBT15/Ba/Al.
Fig. 9 is based on the PFO-BT15 of green light, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTFTS-Na layer, among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTFTS-Na/PFO-BT15/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTFTS-Na/PFO-BT15/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-BT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-BT15/Ba/Al.
Figure 10 is based on the PFO-BT15 of green light, the device luminosity and the luminous external quantum efficiency comparison diagram that have or not the PTFTS-Li layer, among the figure: symbol ■ and represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PTFTS-Li/PFO-BT15/Ba/Al; Symbol ◆ and ◇ represents that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PTFTS-Li/PFO-BT15/Ba/Al; Symbol
With
Represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PEDOT:PSS/PFO-BT15/Ba/Al; Symbol ● and zero represent that respectively structure is the luminosity and the external quantum efficiency of the device of ITO/PFO-BT15/Ba/Al.
Embodiment
Below in conjunction with embodiment each constituent monomers proposed by the invention is described, the present invention is not limited to this.
Embodiment 1: preparation 4,4 '-dibromo triphenylamine
According to " synthetic metal " (Syn.Met) 122 (2001) 363 disclosed methods prepare 4,4 '-dibromo triphenylamine.Take by weighing triphenylamine (4.9 grams, 20 mmoles) and measure N, dinethylformamide (DMF) joins in 250 milliliters of there-necked flasks for 100 milliliters, start and stir the i.e. all dissolvings in back, at room temperature in this solution, add N-bromo-succinimide (NBS) (7.12 grams, 40 mmoles), reaction is at room temperature removing solvent under reduced pressure below 70 ℃ two days later, carry out post behind water and the dichloromethane extraction and separate, steam and obtain product 7.9 grams, productive rate 98% after desolventizing.1HNMR, 13CNMR and GC-MASS test shows are target product 4,4 '-dibromo triphenylamine.Its chemical equation is as follows:
Embodiment 2: preparation has substituent triarylamine compounds
Preparation has substituent triarylamine compounds with preparation N, and N-phenylbenzene-(4-trifluoromethyl) aniline is example, prepares N according to world patent WO 0166618 disclosed method in 2000, N-phenylbenzene-(4-trifluoromethyl) aniline.In 500 milliliters there-necked flask, be weighed into pentanoic (15.57 grams, 92 mmoles), (4-trifluoromethyl) iodobenzene (31.43 grams, 115 mmoles), palladium (404 milligrams, 1.8 mmoles), tri-o-tolyl phosphorus (1.19 grams, 3.9 mmole), sodium tert-butoxide (12.50 grams, 130 mmoles) and dry purified toluene (200 milliliters).This suspension refluxes under inert atmosphere and stirred 12 hours.After this with its filtration, steaming desolventizes the back and carries out the post separation with toluene as eluent.After desolventizing, steaming obtains product 23.16 grams, productive rate 80%.1HNMR, 13CNMR and GC-MASS test shows are target product N, N-phenylbenzene-(4-trifluoromethyl) aniline.Its chemical equation is as follows:
In the formula: R is a trifluoromethyl, m=1 or 2, n 〉=1.
Embodiment 3: the preparation dibromo replaces triarylamine compounds
The preparation dibromo replaced triarylamine compounds with N, and two pairs of bromophenyls of N--(4-trifluoromethyl) aniline is example, according to world patent WO 0166618 disclosed method preparation in 2000.Under nitrogen protection, take by weighing N; N-phenylbenzene-(4-trifluoromethyl) aniline (23.16 grams; 74 mmoles) be dissolved among 200 milliliters of anhydrous DMF, in this solution, dropwise add NBS (27.6 grams, 155 mmoles) and be dissolved in the solution of 200 milliliters of DMF and keep the reaction internal temperature to be lower than 20 ℃.1 hour afterreaction finishes, with it to going in 3 premium on currency.Crude product is precipitated out, and filters and with sherwood oil-ether (volume ratio 80/100) recrystallization several times, obtains product 15.2 and restrain.1HNMR, 13CNMR and GC-MASS test shows are target product N, two pairs of bromophenyls of N--(4-trifluoromethyl) aniline.Its chemical equation is as follows:
In the formula: R is a trifluoromethyl, m=1 or 2, n 〉=1.
Embodiment 4: preparation hypoboric acid ester replaces triarylamine compounds
Preparation hypoboric acid ester replaces triarylamine compounds with N-(4-trifluoromethylbenzene)-4, and 4 '-hypoboric acid ester substituted diphenylamine is an example.Take by weighing according to the prepared exsiccant N of example 3; two pairs of bromophenyls of N--(4-trifluoromethyl) aniline (9 grams; 19.05 mmole) be dissolved in refining dried 130 milliliters of tetrahydrofuran (THF)s (THF); the dry argon gas protection drips 25 milliliters of n-Butyl Lithium (1.6 mol down in the time of-78 ℃; normal hexane is a solvent; 40 mmoles), drip and finish, reaction mixture stirred 1.5 hours down at-78 ℃ at least; add 2-isopropoxy-4 subsequently fast; 4,5,5-tetramethyl--1; 3; 2-ethylenedioxy boric acid ester (25 milliliters, 123.24 mmoles) continues down to stir 2 hours at-78 ℃.Allow reaction mixture rise to room temperature gradually then, stirring reaction at least 36 hours.Subsequently reaction mixture is poured in the water, used extracted with diethyl ether, merge the ether phase, also use anhydrous magnesium sulfate drying with the salt water washing, boil off solvent, the resistates sherwood oil: ethyl acetate=recrystallization got white solid in 19: 1.1HNMR, 13C NMR, GC-MASS and ultimate analysis show that gained is target product N-(4-trifluoromethylbenzene)-4,4 '-hypoboric acid ester pentanoic.Its chemical equation is as follows:
In the formula: R is a trifluoromethyl, m=1 or 2, n 〉=1.
Embodiment 5: the preparation sulfonic group replaces triarylamine compounds
It is example with preparation 1-(N, two pairs of bromophenyls of N-) amido-4-benzene sulfonic acid sodium salt that the preparation sulfonic group replaces triarylamine compounds.Take by weighing embodiment 1 prepared 4,4 '-dibromo triphenylamine (4.2 grams, 10.4 mmole) be dissolved in 70 milliliters of methylene dichloride, in this solution, dropwise add (0.93 milliliter of chlorsulfonic acid under the room temperature, 13.54 mmole) and at room temperature stirring reaction is one hour, afterwards this solution is restrained in the trash ices to going into 200, the aqueous sodium hydroxide solution of adding 50% approximates 9 up to pH value.With using the distilled water recrystallization behind the precipitation usefulness B suction filtration that produces, obtain white solid.(2.8 grams, 53%).1HNMR, 13C NMR and ultimate analysis show that gained is target product 1-(N, two pairs of bromophenyls of a N-) amido-4-benzene sulfonic acid sodium salt.Its chemical equation is as follows:
Embodiment 6: the terminal side substitution triarylamine compounds that has sulfonic acid group of preparation
Preparation is terminal to have the side substitution triarylamine compounds of sulfonic acid group to contain the example that is prepared as of sodium sulfonate group functional group side substitution triphenylamine.
(1) the preparation methoxyl group replaces dibromo three arylamine
Under the room temperature and under nitrogen protection with toluene (50 milliliters); 4-anisidine (6.16 grams; 50 mmoles); 1-bromo-4-iodobenzene (31.8 grams; 110 mmoles); phenanthroline (0.337 gram, 1.87 mmoles), cuprous chloride (0.196 gram; 1.87 mmole); hydroxide flake potassium (86%, 26.8 gram, 391 mmoles) joins in 250 milliliters of there-necked flasks that mechanical stirrer is housed; reacted 48 hours to backflow and under this temperature at 30 minutes internal heating; after this add 150 milliliters of toluene and the extraction of 100 ml distilled waters after it being cooled to 75 ℃, tell organic phase, add anhydrous magnesium sulfate drying.Finish after-filtration and steam of drying desolventizes, and post separates and purify (with sherwood oil: ethyl acetate=19: 1 is an eluent).Product is colourless mucus (8 grams, 37%).1HNMR, 13C NMR and GC-MS show that gained is target product N, two pairs of bromophenyls of N--4-anisidine.Its chemical equation is as follows:
(2) hydroxyl replaces the preparation of dibromo three arylamine
With N, two pairs of bromophenyls of N--4-hydroxyanilines be prepared as example illustrated.Under room temperature and nitrogen protection to N; two pairs of bromophenyls of N--4-anisidine (5.3 grams; 12.2 mmole) be dissolved in the solution of 90 milliliters of refining exsiccant methylene dichloride and splash into (1.75 milliliters of boron tribromides; 18.5 mmole) in the solution of 18.5 milliliters of dry methylene chloride, after dropwising at room temperature stirring reaction spend the night.Inferior end of day reaction is slowly poured it in 250 ml waters, and was stirred one hour.After this organic phase is separated, water to water white transparency, merges organic phase with dichloromethane extraction, drying, and post separates and purifies (sherwood oil: methylene dichloride=1: 3 is an eluent).Obtaining product is light green solid (4.5 grams, 88%).1HNMR and 13C NMR show that gained is target product N, two pairs of bromophenyls of N--4-hydroxyanilines.Its chemical equation is as follows:
(3) contain the preparation of side substitution dibromo three arylamine of sulfonic acid group
With N, the preparation of two pairs of bromophenyls of N--4-sodium sulfonate oxygen-butyl aniline is illustrated.In the solution of 45 milliliters of dehydrated alcohols, at room temperature add N to sodium methylate (0.38 gram, 7 mmoles) under the nitrogen protection, two pairs of bromophenyls of N--4-hydroxyanilines (2.0 grams, 4.8 mmoles).This mixture heating up to refluxing, is injected 1 with syringe after 1 hour, 4-butyl sulfonic acid lactone (1.03 grams, 7.5 mmole), refluxing and will react end after 24 hours, is that adularescent powder dress precipitation generates after cooling down, and places refrigerator overnight that it is settled out fully.Inferior daily B suction filtration, and with cold absolute ethanol washing filter cake.Obtaining product after 80 ℃ of vacuum-dryings is white powder (1.6 grams, 58%).1HNMR, 13C NMR and ultimate analysis show that gained is target product N, two pairs of bromophenyls of N--4-sodium sulfonate oxygen-butyl aniline.
N, substituting group comprises in two pairs of bromophenyls of N--4-sulfo aniline: the sodium sulfonate propyl group, the potassium sulfonate propyl group, sulfonic acid lithium propyl group, the sodium sulfonate butyl, the potassium sulfonate butyl, sulfonic acid lithium butyl etc., but be not limited thereto.Positively charged ion in the sulfonate is a sodium ion, but is not limited thereto, and also can be hydrogen ion, lithium ion, ammonium ion etc.
Embodiment 7: preparation poly-[N-(4-sodium sulfonate group benzene)-4,4 '-pentanoic-be total to-1,4-benzene] (PTP-Na)
Take by weighing 1,4-two phenylo boric acids (0.829 gram, 5 mmoles) are with the 1-(N of preparation among the embodiment 5; two pairs of bromophenyls of N-) amido-4-benzene sulfonic acid sodium salt (2.525 grams, 5 mmoles), 25 milligrams of palladium; be dissolved in the buffered soln of 50mlDMF/80mlPH=10, be reflected under the Ar gas shiled, refluxed 3 days.Cool to room temperature precipitates reaction solution in acetone then, after crude product is dissolved in minimum DMSO, dialysed three days with the film that by molecular weight is 3500, repeatedly change water during this time to remove oligopolymer and DMSO, reduce pressure afterwards the water steaming is removed, obtain solid product after 80 ℃ of vacuum-dryings.1HNMR, 13C NMR, and ultimate analysis shows that gained is a subject polymer.Its chemical equation is as follows:
Embodiment 8: preparation poly-[N-(4-sodium sulfonate oxygen-butyl benzene)-4,4 '-pentanoic-be total to-1,4-benzene] (PTP-OBSO3Na)
Embodiment 9: preparation poly-[N-(4-sodium sulfonate oxygen-butyl benzene)-4,4 '-pentanoic-al t-1,4-benzene-co-N-(4-sodium sulfonate group benzene)-4,4 '-pentanoic-alt-1,4-benzene] (PTP11-Na)
Embodiment 10: preparation PTP31-Na
Embodiment 11: preparation poly-{ N-phenyl-4,4 '-pentanoic-be total to-[N-(4-sodium sulfonate group benzene)]-4 4 '-pentanoic } (PTPA-Na)
Take by weighing prepared N-phenyl-4 according to embodiment 4; 4 '-hypoboric acid ester pentanoic (2.485 grams; 5 mmoles); 1-(N, two pairs of bromophenyls of the N-) amido-4-benzene sulfonic acid sodium salt of preparation among the embodiment 5 (2.525 grams, 5 mmoles); the 25mg palladium; be dissolved in the buffered soln of 15mlTHF/50mlDMF/80mlPH=10, be reflected under the Ar gas shiled, refluxed 3 days.Cool to room temperature precipitates reaction solution in acetone then, after crude product is dissolved in minimum DMSO, dialysed three days with the film that by molecular weight is 3500, repeatedly change water during this time to remove oligopolymer and DMSO, reduce pressure afterwards the water steaming is removed, obtain solid product after 80 ℃ of vacuum-dryings.1HNMR, 13C NMR, and ultimate analysis shows that gained is a subject polymer.Its chemical equation is as follows:
Embodiment 12: preparation poly-{ [N-(4-trifluoromethylbenzene)]-4,4 '-pentanoic-be total to-[N-(4-sodium sulfonate group benzene)]-4 4 '-pentanoic } (PTFTS-Na)
Embodiment 13: preparation poly-{ [N-(4-trifluoromethylbenzene)]-4,4 '-pentanoic-be total to-[N-(4-sulfonic benzo)]-4 4 '-pentanoic } (PTFTS-H)
Take by weighing according to 600 milligrams of the prepared PTFTS-Na of embodiment 12, in this solution, add 30 ml deionized water after being dissolved among 15 milliliters of DMSO again, after the chromatographic column of this solution by 001X7 (732) strongly acidic styrene's Zeo-karb of activation treatment is housed crosses, collect effluent liquid, filter and with this solution with by molecular weight being 3500 film dialysis three days, repeatedly change water during this time to remove DMSO and impurity, water is steamed remove afterwards, obtain solid product after 80 ℃ of vacuum-dryings.1HNMR, 13C NMR, and ultimate analysis shows that gained is a subject polymer.Its chemical equation is as follows:
Embodiment 14: preparation poly-{ [N-(4-trifluoromethylbenzene)]-4,4 '-pentanoic-be total to-[N-(4-sulfonic acid lithium base benzene)]-4 4 '-pentanoic } (PTFTS-Li)
Take by weighing according to 600 milligrams of the prepared PTFTS-H of embodiment 13, in this solution, add 30 ml deionized water after being dissolved among 15 milliliters of DMSO again, the LiOH aqueous solution of Dropwise 5 0% is about 9 until pH value in this solution, this solution stirring is spent the night, filter and dialysed three days with the film that by molecular weight is 3500, repeatedly change water during this time to remove DMSO and excessive LiOH, water is steamed remove afterwards, obtain solid product after 80 ℃ of vacuum-dryings.1HNMR, 13C NMR, and ultimate analysis shows that gained is a subject polymer.Its chemical equation is as follows:
Embodiment 15: preparation poly-{ [N-(4-trifluoromethylbenzene)]-4,4 '-pentanoic-be total to-[N-(4-tetrabutyl sulfonic acid ammonium-benzene)]-4 4 '-pentanoic } (PTFTS-N)
Repeat embodiment 14, LiOH is changed to tetrabutylammonium hydroxide ammonia, other conditions are constant.1HNMR, 13C NMR, and ultimate analysis shows that gained is a subject polymer.
Wherein tetrabutylammonium hydroxide ammonia can wait and replace with ammoniacal liquor, tetramethyl-aqua ammonia, tetraethyl-aqua ammonia, tetrapropyl aqua ammonia.Its chemical equation is as follows:
Repeat the foregoing description 13,14 and 15, with PTFTS-Na be changed to PTP-Na, PTPA-Na, PTP-OBSO3Na prepare a series of contain different from cationic polymkeric substance.
The solvability of polymkeric substance in the different solvents system that the foregoing description is prepared, as shown in table 1.
Table 1
Wherein: " ++ " expression is easily molten, and "+" expression is partly dissolved, and "-" expression is insoluble.
Prepared optics and the electrochemical properties of polymkeric substance under solid film of the foregoing description is as shown in table 2.
Table 2
| Polymkeric substance | Maximum absorption (nanometer) | Optical bandwidth (eV) | Oxidizing potential (V) | HOMO (eV) | LUMO (eV) | Emission maximum (nanometer) |
| PTP-Na PTPA-Na PTP-OBSO 3Na PTP11-Na PTP31-Na PTFTS-Na | 367 361 376 363 361 357 | 2.96 2.94 2.87 2.89 2.94 2.99 | 0.86 0.85 0.68 0.64 0.72 0.84 | 5.26 5.25 5.08 5.04 5.12 5.24 | 2.30 2.31 2.21 2.15 2.18 2.25 | 440 431 450 449 445 425 |
The LUMO value is to calculate according to the difference that has absorbed the oxidizing potential that optical bandwidth that initial line calculates and electrochemistry records.
The polymer P TFTS-Na and the cationic exchange product P TFTS-Li thereof that contain perfluor band alkyl and sulfonic acid group below with main chain, and side chain has that polymer P TP-OBSO3Na, the PTP11-Na of sulphonate-base functional group and PTP31-Na are that example explanation polymkeric substance of the present invention is luminous in preparation as hole transmission layer, the application in the photovoltaic devices such as (opto-electronic conversion, photaesthesia).
Embodiment 16
With the ITO conductive glass, square resistance～20 Ω/, precut become 15 millimeters * 15 millimeters square sheets.Use acetone, micron order semi-conductor special purpose detergent, deionized water, Virahol ultrasonic cleaning successively, it is standby that nitrogen purging is placed on constant temperature oven.Before the use, the clean sheet of ITO in the oxygen plasma etch instrument with plasma bombardment 10 minutes.Select for use PVK available from Aldrich company, with the tetrachloroethane obtain solution.PEDOT:PSS aqueous dispersions (about 1%) is available from Bayer company, and buffer layer is with the spin coating of sol evenning machine (KW-4A) high speed, and thickness is by strength of solution and rotating speed decision, with surface profiler (Alpha-Tencor500 of Tritek company type) actual measurement monitoring.After the film forming, in the constant temperature vacuum drying oven, drive away solvent residues, post bake.
In white vase, after the weighing, change fluorescent conjugated polymer over to nitrogen protection film forming special gloves case (VAC company), in toluene, dissolve, with 0.45 micron membrane filtration.Polymer light-emitting layer optimum thickness is 70～90 nanometers.Thickness is measured with the TENCORALFA-STEP-500 surface profiler.PTFTS-Na is dissolved in methyl alcohol (adding a small amount of DMF), be mixed with the solution of 0.9% concentration, with 0.45 micron membrane filtration.With sol evenning machine respectively at the ITO substrate with get rid of and generate skim PTFTS-Na polymkeric substance, about 40 nanometers of its thickness on the ITO substrate of PEDOT:PSS layer.After in the vacuum transition storehouse, draining, swaying hair photosphere in the above again.Barium aluminium electrode evaporation vacuum tightness in vacuum plating unit reaches 3 * 10-4Pa and finishes when following.The thickness of plated film speed and each layer electrode is by quartz resonator film thickness monitor (STM-100 type, Sycon company) monitoring in real time.The light-emitting zone of device is defined as 0.15 square centimeter by mask and the mutual zone that covers of ITO.All preparation process are all carried out in the glove box of nitrogen inert atmosphere is provided.The I-E characteristic of device, luminous intensity and external quantum efficiency are recorded by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode.
PTFTS-Na solution with 0.9% concentration, respectively at ITO substrate and the thin layer that gets rid of spin coating PTFTS-Na on the ITO substrate of PEDOT:PSS layer as hole transmission layer, PFO blue light conjugated polymer thin films with about 80 nanometer thickness is a luminescent layer, the vacuum evaporation covering as negative electrode, is made the polymer LED of the color of light of turning blue with Ba (2.7 electron-volts)/Al of low work function on luminescent layer.For showing the effect of hole transmission layer of the present invention, employing is at the ITO substrate and get rid of on the ITO substrate of PEDOT:PSS directly spin coating luminescent layer PFO blue light conjugated polymers as reference, vacuum evaporation covers Ba/Al as negative electrode on luminescent layer, and the polymer LED of making the color of light of turning blue is as the reference device.Measuring result is as shown in table 3.Compare with PFO blue light conjugated polymer material, have or not the luminosity of device of PTFTS-Na layer and luminous external quantum efficiency as shown in Figure 1.Table 3 is based on PFO blue light material polymkeric substance, with the electroluminescent properties of PTFTS-Na as the device of hole transmission layer.
Table 3
Example as seen thus, for PFO blue light conjugated polymers conventional device, after getting rid of the PTFTS-Na layer on the ITO substrate after directly getting rid of the PTFTS-Na layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.Can be that the device of ITO/PEDOT:PSS/PFO/Ba/Al is compared with structure.
Embodiment 17
Repeat embodiment 16, as hole transmission layer, other condition is constant with PTFTS-Li.Measuring result is as shown in table 4.Table 4 is based on PFO blue light material polymkeric substance, with the electroluminescent properties of PTFTS-Li as the device of hole transmission layer.Compare with PFO blue light conjugated polymer material, have or not luminosity and luminous external quantum efficiency such as Fig. 2 of the device of PTFTS-Li layer.
Table 4
Example as seen thus, for PFO blue light conjugated polymers conventional device, after getting rid of the PTFTS-Li layer on the ITO substrate after directly getting rid of the PTFTS-Li layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.Can be that the device of ITO/PEDOT:PSS/PFO/Ba/Al is compared with structure.Compare with the same device that gets rid of the PTFTS-Na layer, device performance also slightly improves.
Embodiment 18
Repeat embodiment 16, hole transmission layer is replaced into the polymkeric substance that side chain has the sulphonate-base functional group, PTP-OBSO
3Na, other condition is constant.Measuring result is as shown in table 5.Compare with PFO blue light conjugated polymer material, have or not PTP-OBSO
3The luminosity of the device of Na layer and luminous external quantum efficiency are as shown in Figure 3.Table 5 is based on PFO blue light material polymkeric substance, uses PTP-OBSO
3Na is as the electroluminescent properties of the device of hole transmission layer.
Table 5
As seen example to PFO blue light conjugated polymers conventional device, directly gets rid of PTP-OBSO on the ITO substrate thus
3Get rid of PTP-OBSO on Na layer or the ITO substrate after getting rid of PEDOT:PSS
3Behind the Na layer, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.But be lower than the device that structure is ITO/PEDOT:PSS/PFO/Ba/Al.
Embodiment 19
Repeat embodiment 16 with the polymer light-emitting stratification be changed to glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the multipolymer (PFO-DBT15) of 3-diazosulfide (DBT), other condition is constant.Measuring result is as shown in table 6.With based on glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the copolymer material of 3-diazosulfide (DBT) is compared, and has or not the luminosity of device of PTFTS-Na layer and luminous external quantum efficiency as shown in Figure 4.
Table 6 be based on glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the multipolymer (PFO-DBT15) of 3-diazosulfide (DBT) is with the electroluminescent properties of PTFTS-Na as the device of hole transmission layer.
Table 6
Example as seen thus, to the PFO-DBT15 conventional device that glows, after getting rid of the PTFTS-Na layer on the ITO substrate after directly getting rid of the PTFTS-Na layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.And be higher than the device that structure is ITO/PEDOT:PSS/PFO-DBT15/Ba/Al, voltage does not have too big increase by comparison.With structure is that the device of ITO/PEDOT:PSS/PVK/PFO-DBT15/Ba/Al is compared, and efficient is suitable, and voltage is lower.
Embodiment 20
Repeat embodiment 19, hole transmission layer is replaced into PTFTS-Li, other condition is constant.Measuring result is as shown in table 7.With glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the multipolymer (PFO-DBT15) of 3-diazosulfide (DBT) relatively have or not the luminosity of device of PTFTS-Li layer and luminous efficiency as shown in Figure 5.Table 7 is based on the PFO-DBT15 of red light material, with the electroluminescent properties of PTFTS-Li as the device of hole transmission layer.
Table 7
This example as seen, to the PFO-DBT15 conventional device that glows, after getting rid of the PTFTS-Li layer on the ITO substrate after directly getting rid of the PTFTS-Li layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.And be higher than the device that structure is ITO/PEDOT:PSS/PFO-DBT15/Ba/Al, voltage does not have large increase by comparison.With structure is that the device of ITO/PEDOT:PSS/PVK/PFO-DBT15/Ba/Al is compared, and efficient is suitable, and voltage is lower.
Embodiment 21
Repeat embodiment 19, hole transmission layer is replaced into the polymkeric substance that side chain has the sulphonate-base functional group, PTP-OBSO
3Na, other condition is constant.Measuring result is as shown in table 8.With glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the multipolymer (PFO-DBT15) of 3-diazosulfide (DBT) relatively has or not PTP-OBSO
3The luminosity of the device of Na layer and luminous efficiency are as shown in Figure 6.
Table 8 is based on the PFO-DBT15 of red light material, has the polymkeric substance of sulphonate-base functional group, PTP-OBSO with side chain
3Na is as the electroluminescent properties of the device of hole transmission layer.
Table 8
As seen example to the PFO-DBT15 conventional device that glows, directly gets rid of PTP-OBSO on the ITO substrate thus
3Get rid of PTP-OBSO on Na layer or the ITO substrate after getting rid of PEDOT:PSS
3Behind the Na layer, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.And be higher than the device that structure is ITO/PEDOT:PSS/PFO-DBT15/Ba/A1, voltage slightly increases by comparison.Can be that the device of ITO/PEDOT:PSS/PVK/PFO-DBT15/Ba/Al is compared with structure, and voltage be lower.
Embodiment 22
Repeat embodiment 19, hole transmission layer is replaced into PTP11-Na, other condition is constant.Measuring result is as shown in table 9.With glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the multipolymer (PFO-DBT15) of 3-diazosulfide (DBT) relatively, has or not the luminosity of device of PTP11-Na layer and luminous efficiency as shown in Figure 7.
Table 9 is based on the PFO-DBT15 of red light material, with the device electroluminescent properties of PTP11-Na as hole transmission layer.
Table 9
Example as seen thus, to the PFO-DBT15 conventional device that glows, after getting rid of the PTP11-Na layer on the ITO substrate after directly getting rid of the PTP11-Na layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.And be higher than the device that structure is ITO/PEDOT:PSS/PFO-DBT15/Ba/Al, voltage slightly increases by comparison.Can be that the device of ITO/PEDOT:PSS/PVK/PFO-DBT15/Ba/A1 is compared with structure, and voltage be lower.
Embodiment 23
Repeat embodiment 19, hole transmission layer is replaced into PTP31-Na, other condition is constant.Measuring result is as shown in table 10.With glow 9,9-dioctyl fluorene (DOF) and 4,7-two thiophene-2,1, the multipolymer (PFO-DBT15) of 3-diazosulfide (DBT) relatively have or not the luminosity of device of PTP31-Na layer and luminous efficiency as shown in Figure 8.
Table 10 is based on the PFO-DBT15 of red light material, with the electroluminescent properties of PTP31-Na as the device of hole transmission layer.
Table 10
Example as seen thus, to the PFO-DBT15 conventional device that glows, after getting rid of the PTP31-Na layer on the ITO substrate after directly getting rid of the PTP31-Na layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.And be higher than the device that structure is ITO/PEDOT:PSS/PFO-DBT15/Ba/Al, voltage slightly increases by comparison.Efficient can be that the device of ITO/PEDOT:PSS/PVK/PFO-DBT15/Ba/Al is compared with structure, and voltage is lower.
Embodiment 24
Repeat embodiment 16, the polymer light-emitting stratification is changed to 9 of green light, 9-dioctyl fluorene (DOF) and 2,1, the multipolymer (PFO-BT15) of 3-diazosulfide (BT), other condition is constant.Measuring result is as shown in table 11.With the copolymer p FO-BT15 of green light relatively, have or not the luminosity of device of PTFTS-Na layer and luminous efficiency as shown in Figure 9.
Table 11 is based on the copolymer p FO-BT15 of green light material, with the electroluminescent properties of PTFTS-Na as the device of hole transmission layer.
Table 11
Example as seen thus, PFO-BT15 conventional device to green light, after getting rid of the PTFTS-Na layer on the ITO substrate after directly getting rid of the PTFTS-Na layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away, and be higher than the device that structure is ITO/PEDOT:PSS/PFO-BT15/Ba/Al, voltage slightly increases by comparison.Can be that the device of ITO/PEDOT:PSS/PVK/PFO-BT15/Ba/Al is compared with structure, and voltage be lower.
Embodiment 25
Repeat embodiment 24, as hole transmission layer, other condition is constant with PTFTS-Li.Measuring result is as shown in table 12, with the copolymer p FO-BT15 of green light, has or not the luminosity of device of PTFTS-Li layer and luminous efficiency as shown in figure 10.
Table 12 is based on the copolymer p FO-BT15 of green light material, with the electroluminescent properties of PTFTS-Li as the device of hole transmission layer.
Table 12
The result of example can prove absolutely the PFO-BT15 conventional device to green light thus, after getting rid of the PTFTS-Li layer on the ITO substrate after directly getting rid of the PTFTS-Li layer on the ITO substrate or getting rid of PEDOT:PSS, the performance of device all is higher than the performance of the device of direct swaying hair photosphere on the ITO substrate far away.And be higher than the device that structure is ITO/PEDOT:PSS/PFO-BT15/Ba/Al, voltage slightly increases by comparison.Can be that the device of ITO/PEDOT:PSS/PVK/PFO-BT15/Ba/Al is compared with structure, and voltage be lower.
Claims (3)
1. conjugated polymers that contains sulfonic group substituted triarylamine is characterized in that its structure is:
Wherein, n
1+ n
3=0.5, n
1+ n
2+ n
3=1;
A has the component of following formula structure for containing nonpolar substituted radical:
In the formula: R1, R2, R3 are alkyl, the alkoxyl group of H, a C1～C20, m=1 or 2, n=1,2,3 ...,
Or
In the formula: R3, R4 are alkyl, the alkoxyl group of H, C1～C20, n=1,2,3
B has three arylamine components of following formula structure for containing sulfonic acid group:
In the formula: R1, R2 is alkyl, the alkoxyl group of H, a C1～C20, perhaps, be haloalkyl, nitro, cyano group, amide group, ketone group, phosphinyl, phosphate-based, the sulfonate group of a halogen atom, C1～C20, R3 is alkyl, alkoxyl group, the haloalkyl of C0～C20, X is hydrogen, lithium, sodium, potassium, ammonium, m=1 or 2; N=1,2,3 N1=1 or 2;
C has the component of following formula structure for containing nonpolar substituted radical:
In the formula: R1 is the perfluor substituted alkyl of a C1～C20 or is a nitro, cyano group, carboxylic acid ester groups, amide group, phosphate-based, sulfonate group, m=1 or 2, n=1,2,3 ...
2. polymkeric substance according to claim 1 is characterized in that molar content 〉=30% of described B component in polymkeric substance.
3. the described polymkeric substance of one of claim 1-2 is characterized in that taking multilayered structure as the application of hole transmission layer, inserts the polyelectrolytes film that skim contains described polymkeric substance between luminescent conjugated polymers and tin indium oxide.
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