CN101635332A - P-type doped organic film prepared by wet method and electroluminescent device provided with same - Google Patents
P-type doped organic film prepared by wet method and electroluminescent device provided with same Download PDFInfo
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Abstract
The invention discloses a P-type doped organic film prepared by a wet method. A co-doping system comprising a polymer material, an organic molecule hole injection or transport material and a P-type doping agent is formed in a mode of using solutions, and the organic film with the thickness of 20 nanometers to 1 micron is prepared by a wet method film-forming process. The invention also discloses an electroluminescent device provided with the P-type doped organic film prepared by the wet method, which comprises a substrate, a transparent anode, the P-type doped organic film, a hole transport layer, an organic luminescent layer, an electron transport layer, an electron injection layer and a cathode which are superposed in turn, wherein the P-type doped organic film is prepared on the transparent anode by the wet method. The P-type doped organic film makes the doping proportion controlled precisely, can achieve large-area preparation, has the advantages of simple process, simple and quick film forming, low requirements on equipment and environment, high yield and low cost, and is suitable for industrial production.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, more particularly, relate to and realize a kind of P-type doping organic film of wet method preparation and electroluminescent device of adopting with this P-type doping organic film, use and improve organic electroluminescence device efficient, life-span and reduce the requirement of organic electroluminescence device, thereby reduce the device preparation cost ito substrate.
Background technology
Organic electroluminescence device is at first by the people such as C.W.Tang of the Kodak company bi-layer devices structure (Appl.Phys.Lett., 51,913, (1987)) at report in 1987.Because organic electroluminescence device has active illuminating, the DC driven of low-voltage, full curing, wide visual angle, low-power, response speed is fast, advantages such as low cost, thereby have broad application prospects.Development through nearly more than two decades is obtaining rapid development aspect the improvement of material development and device architecture, organic electroluminescence device has been applied to small display curtain products such as MP3 and mobile phone.In order further to widen the purposes of organic electroluminescence device, currently the exploitation of luminous efficiency, glow color, durability functional material and the exploitation of full-color demonstration have actively been carried out being used to improve.In order further to improve the organic light-emitting device performance, be necessary to set up the device architecture that is suitable for material behavior and the manufacture method of device.
Although organic electroluminescence device has many advantages, to compare with inorganic electroluminescence device, the organic electroluminescence device driving voltage is higher, and the carrier mobility of organic layer is lower, and the thickness of organic layer is very big to the device drive voltage influence.Therefore, reduce driving voltage, improving charge carrier injection efficiency and carrier mobility is very important to the power-conversion efficiencies and the life-span of improving organic electroluminescence device.In order to address these problems, organic electroluminescence device has adopted P-type doping hole transmission layer and N-type doping electron transfer layer, promptly so-called P-I-N structure [(Appl.Phys.Lett.80:139 (2002); Appl.Phys.Lett., 83:3858 (2003); Appl.Phys.Lett., 85:3911 (2004); Appl.Phys.Lett.89:061111 (2006); Appl.Phys.Lett.91:233507 (2007)].
In the P-I-N structure devices, mostly P-type doping hole transmission layer is the organic molecule doping system, wherein P-type dopant organic molecule F4-TCNQ and TCNQ, inorganic oxidizer such as iodine I
2, iron oxide FeCl
3, ferric flouride FeF
3, antimony chloride SbCl
5, and metal oxide such as tungsten oxide WO
3, molybdenum oxide MoO
x, vanadium oxide V
2O
5, rheium oxide ReO
3Deng, material of main part mostly is the micromolecule hole mobile material.With m-MTDATA is the P-type doping hole transmission layer of material of main part, and its dopant has F4-TCNQ, TCNQ, MoO
x[Appl.Phys.Lett., 78:410 (2001); Appl.Phys.Lett., 80:139 (2001); Appl.Phys.Lett.92:093305 (2008))], and hole mobile material (4 commonly used, 4`-two [N-(1-naphthalene-N-phenyl-amido) biphenyl]) α-NPD, NPB, a-6T, (4,4`, 4``-three [N, N`-diphenyl amido] triphenylamine) TDATA, (4, two (N, N`-two-(4-the methoxyphenyl)) biphenyl of 4`-) MeO-TPD and (4,4`, 4``-three [N-(2-naphthyl)-N`-phenyl amido] triphenylamine) 2-TNATA, its corresponding dopant has F4-TCNQ, MoO
xWith tungsten oxide WO
3Deng [Appl.Phys.Lett.89:253506 (2006); Appl.Phys.Lett.92:093305 (2008); Appl.Phys.Lett.89:061111 (2006); Appl.Phys.Lett.89:253504 (2006)], such P-type mix and the report of P-I-N structure devices a lot, the low bright voltage, high efficiency, high brightness light-emitting devices of opening constantly occurs.
But these P-type doping hole transmission layers with excellent properties P-I-N structure devices all are to realize more complicated on the technology with the method that high vacuum is steamed altogether.General P-type doping hole transmission layer needs two evaporation sources to work simultaneously at least, each evaporation source need accurately be controlled its evaporating temperature, could realize a certain doping that requires ratio, in the production operation of reality, if having to fluctuate slightly, the evaporating temperature of two kinds of materials or multiple material will influence their evaporation rate, cause the doping ratio imbalance, thereby influence the performance of prepared device.It is that high vacuum vapor deposition prepares important shortcoming and defect of P-type doping hole transmission layer that doping ratio is difficult to accurately control, and higher to equipment and environment requirement, and during consumption energy consumption, rate of finished products is lower, and the corresponding devices cost is also higher.In addition, high vacuum vapor deposition prepares P-type doping hole transmission layer, is difficult to realize the large tracts of land uniform deposition, and this does not conform to the large scale display device for organic electroluminescence device.So need seek simpler more excellent doping preparation technology, reduce the device production cost.
Summary of the invention
The object of the present invention is to provide the P-type doping organic film of a kind of wet method preparation and have the electroluminescent device of this film, doping ratio can accurately be controlled, and can realize large-area preparation, technology is simple, the film forming simple and fast, lower to equipment and environment requirement, rate of finished products is higher, with low cost, be applicable to industrialization production.
To achieve these goals, technical scheme of the present invention is:
A kind of P-type doping organic film of wet method preparation, be to use the mode of solution to form the codope system of polymeric material, the injection of organic molecule hole or transferring material and P-type dopant, prepare the organic film that thickness is 20nm (nanometer)-1 μ m (micron) by the wet method film-forming process.
Described polymeric material comprises polymethyl methacrylate (PMMA) at least, polystyrene (PS), Merlon (PC), polyimides (PI), polyurethane (PU), epoxy compound composition copolymer (APC), polyacrylic acid (PAA), polyvinylcarbazole inertia dielectric polymers such as (PVK) and have a kind of in the polymer of hole transport function.
Described organic molecule hole is injected or transferring material comprises N at least, N`-two (naphthalene-1-yl)-N, N`-diphenyl-benzidine (NPB) and N, N`-diphenyl-N, two (the 3-aminomethyl phenyls)-1 of N`-, 1-diphenyl-4,4`-diamines (TPD) and derivative, 4 thereof, 4`, 4``-three [N-(3-methyl)-N-anilino-] triphenylamine (MTDATA), 4,4`, 4``-three idol (3-aminomethyl phenyl aniline) triphenylamines (m-MTDATA), α six thiophene (a kind of among the α-6T).Preferentially select NPB and m-MTDATA for use.
Described P-type dopant comprises organic substance as 2,3,5,6-tetrafluoro-7,7,8, other derivatives of 8-four cyano quino bismethane (F4-TCNQ) and four cyano 1,4-benzoquinone bismethane (TCNQ), inorganic oxidizer such as iodine I
2, iron oxide FeCl
3, ferric flouride FeF
3, antimony chloride SbCl
5, and metal oxide such as tungsten oxide WO
3, molybdenum oxide MoO
x, vanadium oxide V
2O
5, rheium oxide ReO
3A kind of with in other metal halide.Preferentially select F4-TCNQ for use.
Electroluminescent device with P-type doping organic film of wet method preparation, the substrate, transparent anode, P-type doping organic film, hole transmission layer, organic luminous layer, electron transfer layer, electron injecting layer and the negative electrode that comprise stack successively, wherein, P-type doping organic film be polymer body material, the injection of organic molecule hole or transferring material and P-type dopant the codope system by wet method preparation on transparent anode and thickness be the organic film of 20nm-1 μ m.
Described substrate can be glass or flexible substrate, and wherein flexible substrate can be polyester or poly-phthalimide compounds.
Described transparent anode can adopt inorganic material or organic conductive polymer, this inorganic material can or be a kind of metal in gold, copper, silver or the zinc for a kind of metal oxide in tin indium oxide, zinc oxide or the tin oxide, and the organic conductive polymer is polythiophene, the basic benzene sulfonic acid sodium salt of polyethylene or polyaniline.
Described negative electrode can be metal, alloy or metal fluoride and metal composite electrode, described metal can be selected from lithium, magnesium, aluminium, calcium, strontium, indium, described alloy be selected from lithium, magnesium, aluminium, calcium, strontium, indium respectively with the alloy of copper, gold, silver, described metal fluoride and the preferred LiF/Al of metal composite electrode.
The material of described hole transmission layer is diamine compounds and triphenylamine compounds, preferentially selects NPB, TPD for use.
The material of described organic luminous layer is a kind of material in metal organic complex, aromatic condensed ring compounds, o-phenanthroline compounds or the carbazoles derivative, and various fluorescent dye and phosphorescence doping luminescent layer.
The material of described electron transfer layer is a kind of material in metal organic complex, aromatic condensed ring compounds, the o-phenanthroline compounds.
After adopting such scheme, the present invention mainly is the codope system of polymer body material, the injection of organic molecule hole or transferring material and P-type dopant, be prepared from P-type doping organic film by wet methods such as even glue or silk screen printings, and utilize this P-type relevant organic electroluminescence device of organic film preparation that mixes.P-type doping organic film phase prior art of the present invention is compared, for with the film of follow-up organic function layer independence moulding, its doping ratio can accurately be controlled, film thickness can realize that 20nm-1 μ m adjusts continuously flexibly, can realize large-area preparation, simplified device preparing process, the film forming simple and fast, lower to equipment and environment requirement, improved the stability and the efficient of device, reduced the requirement of device preparation, increased the contact of P-type doping organic film and transparent anode and follow-up organic function layer transparent anode surface smoothnesss such as ito substrates, reduce device cost, be applicable to industrialization production.
Description of drawings
Fig. 1 is an organic electroluminescence device structural representation of the present invention;
Fig. 2 is that the organic electroluminescence device of the embodiment of the invention 1 is doped with the curve chart that organic electroluminescence devices is compared under the same conditions useful life with traditional P-type;
Fig. 3 is that the organic electroluminescence device of the embodiment of the invention 2 is doped with the curve chart that organic electroluminescence devices is compared under the same conditions useful life with the P-type of evaporation;
Fig. 4 is the ITO AFM surface topography map (RootMean Square:1.34888nm) of the embodiment of the invention 1 and embodiment 2;
Fig. 5 is the P-type of evaporation in the embodiment of the invention 1 organic film surface appearance AFM figure (Root Mean Square:1.06994nm) that mixes;
Fig. 6 is the P-type of spin coating in the embodiment of the invention 1 organic film surface appearance AFM figure (Root Mean Square:0.585716nm) that mixes;
Fig. 7 is the P-type of evaporation in the embodiment of the invention 2 organic film surface appearance AFM figure (Root Mean Square:0.959576nm) that mixes;
Fig. 8 is the P-type of spin coating in the embodiment of the invention 2 organic film surface appearance AFM figure (Root Mean Square:0.559877nm) that mixes.
The figure number explanation
1 transparent conduction base sheet, 2 first electrode layers (anode layer)
3 P-type doping organic films, 4 hole transmission layers
5 luminescent layers, 6 electron transfer layers
7 the second electrode lays (cathode layer), 8 DC power supply
Be illustrated by specific embodiment below in conjunction with accompanying drawing, it is clearer that the present invention can become.
Embodiment
With reference now to Fig. 1,, the preferred structure of electroluminescent device of the present invention is as follows:
Glass (plastics) substrate 1/ITO (anode layer 2)/compound P-type doping organic film 3/ hole transmission layer 4/ luminescent layer 5/ electron transfer layer 6/ cathode layer 7, anode layer 2 is connected DC power supply 8 with cathode layer 7.According to the said structure formula, be described below in conjunction with the detailed execution mode of preparation process of device:
The washing agent of (1) utilization heat is ultrasonic to be cleaned the transparent conduction base sheet ito glass with the ultrasonic method of deionized water, place it in oven dry under the infrared lamp after the cleaning, wherein the ITO film above the transparent conduction base sheet 1 is as the anode layer 2 of device, the square resistance of ITO film is 5 Ω～100 Ω, and thickness is 80～280nm.Substrate can also be flexible substrate except that selecting glass for use, and wherein flexible substrate can be polyester or poly-phthalimide compounds.Transparent anode can adopt inorganic material or organic conductive polymer, this inorganic material can also or be a kind of metal in gold, copper, silver or the zinc with a kind of metal oxide in zinc oxide or the tin oxide except that selecting tin indium oxide (ITO) for use, the organic conductive polymer is polythiophene, the basic benzene sulfonic acid sodium salt of polyethylene or polyaniline.
(2) compound P-type doping organic film 3: use the mode of solution to form polymeric material by designing requirement, the codope system of injection of organic molecule hole or transferring material and P-type dopant, wherein, polymeric material comprises PMMA at least, PS, PC, PI, PU, APC, PAA, inertia dielectric polymer such as PVK and have a kind of in the polymer of hole transport function, the organic molecule hole is injected or transferring material comprises NPB and TPD and derivative thereof at least, MTDATA, m-MTDATA, a kind of among α-6T preferentially selects NPB and m-MTDATA for use, P-type dopant comprises that organic substance is as 2,3,5,6-tetrafluoro-7,7,8, other derivatives of 8-four cyano quino bismethane (F4-TCNQ) and TCNQ, inorganic oxidizer such as I
2, FeCl
3, FeF
3, SbCl
5, and metal oxide WO
3, MoO
x, V
2O
5, ReO
3A kind of with in some other metal halide etc. preferentially selects F4-TCNQ for use.The ito glass of above-mentioned cleaning, drying is placed on the KW-4A sol evenning machine, with the P-type doped solution of the different doping ratios that configure method spin-coating film with static batching, the thickness that the rotating speed of concentration, sol evenning machine by control solution and even glue time are controlled spin-coated thin film, do dried under proper condition, thickness is 20-200nm.
(3) preparation of each organic function layer: substrate spin coating and that do after the dried is put in the vacuum chamber, carry out evaporation one deck hole mobile material successively and form hole transmission layer 4, hole mobile material is diamine compounds and triphenylamine compounds, preferentially select NPB, TPD for use, the evaporation speed of material film is 0.01～0.5nm/s, and thickness is 10～80nm; Evaporation one deck luminous organic material forms organic luminous layer 5 on hole mobile material, luminous organic material is a kind of material in metal organic complex, aromatic condensed ring compounds, o-phenanthroline compounds or the carbazoles derivative, and various fluorescent dyes and phosphorescence doping luminescent layer, the evaporation speed of material film is 0.01～0.5nm/s, and thickness is 20～80nm; Evaporation one deck electron transport material forms electron transfer layer 6 on luminous organic material, electron transport material is a kind of material in metal organic complex, aromatic condensed ring compounds, the o-phenanthroline compounds, the evaporation speed of material film is 0.01～0.5nm/s, and thickness is 20～80nm;
(4) preparation of negative electrode 7: keep above-mentioned vacuum chamber internal pressure constant, evaporation metal, alloy-layer or metal fluoride and metal composite layer are as the cathode layer of device successively on above-mentioned electron transfer layer 6, and thickness is 20～200nm.Wherein alloy-layer adopts the method for double source evaporation to mix.Metal specifically can be selected from lithium, magnesium, aluminium, calcium, strontium, indium, described alloy be selected from lithium, magnesium, aluminium, calcium, strontium, indium respectively with the alloy of copper, gold, silver, metal fluoride and the preferred LiF/Al of metal composite electrode.
(5) ready-made device is taken out vacuum chamber, the current-voltage-light characteristic of test component and electroluminescent spectrum under atmospheric environment, the while is the life-span of test component under atmospheric environment also.
Embodiment 1:
With reference now to Fig. 1,, the electroluminescent device of foundation first embodiment of the present invention is following structure:
Glass (plastics) substrate/ITO (100nm)/PMMA:m-MTDATA:F4-TCNQ (90nm)/NPB (10nm)/Alq
3(60nm)/LiF (0.5nm)/Al (80nm)
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in oven dry under the infrared lamp after the cleaning, wherein the ITO film above the conductive substrate is as the anode layer of device, the square resistance of ITO film is 5 Ω～100 Ω, thickness is 80～280nm, is ITO AFM surface topography map as Fig. 4;
(2) compound P-type doping hole injection layer: the ito glass of above-mentioned cleaning, drying is placed on the KW-4A sol evenning machine, with the P-type doped solution of the different doping ratios that configure method spin-coating film with static batching, the thickness that the rotating speed of concentration, sol evenning machine by control solution and even glue time are controlled spin-coated thin film, do dried under proper condition, thickness is 90nm, is the P-type of spin coating organic film surface appearance AFM figure that mixes as Fig. 6; Fig. 5 adopts the P-type of evaporation organic film surface appearance AFM figure that mixes for another example;
(3) preparation of each organic function layer: substrate spin coating and that do after the dried is put in the vacuum chamber, carried out evaporation one deck hole mobile material NPB successively, the evaporation speed of material film is 0.01～0.5nm/s, and thickness is 10nm; Evaporation one deck luminous organic material Alq on hole mobile material
3, the evaporation speed of material film is 0.01～0.5nm/s, thickness is 60nm, simultaneously luminescent material Alq
3The double electron transfer layer of doing;
(4) preparation of negative electrode: keep above-mentioned vacuum chamber internal pressure constant, the Al composite cathode layer of the LiF of evaporation 0.5nm and 80nm successively on above-mentioned electron transfer layer.
(5) ready-made device is taken out vacuum chamber, the current-voltage-light characteristic of test component and electroluminescent spectrum under atmospheric environment, the while is the life-span of test component under atmospheric environment also.
Referring to Fig. 2, be doped with organic electroluminescence devices with traditional P-type and compare (glass substrate/ITO (100nm)/m-MTDATA:F4-TCNQ (90nm)/NPB (10nm)/Alq under the same conditions useful life
3(60nm)/and LiF (0.5nm)/Al (80nm), the line that is positioned at the lower left among the figure is depicted as the life curve of evaporation P-type doping hole injection layer organic electroluminescence device, and (initial intensity is 100cd/m
2, the life-span of device is that luminous intensity decays to half time of initial intensity), be positioned at the life curve that top-right line is represented compound P-type doping hole injection layer organic electroluminescence device, wherein the relative m-MTDATA doping ratio of F4-TCNQ is 2mol%.
As can be seen from the figure, the life-span of evaporation P-type doping hole injection layer organic electroluminescence device is 21.8 hours, and the life-span of the compound P-type of spin coating doping hole injection layer organic electroluminescence device was about 31.5 hours.
Embodiment 2:
With reference now to Fig. 1,, the electroluminescent device of foundation second embodiment of the present invention is following structure:
Glass (plastics) substrate/ITO (100nm)/PMMA:NPB:m-MTDATA:F4-TCNQ (90nm)/NPB (10nm)/Alq
3(60nm)/LiF (0.5nm)/Al (80nm)
(1) is carved with the cleaning of the glass substrate of ITO in advance: the respective process of reference example 1;
(2) compound P-type doping hole injection layer: the respective process of reference example 1; Fig. 8 is the P-type of the spin coating organic film surface appearance AFM figure that mixes, and Fig. 7 is the P-type of evaporation organic film surface appearance AFM figure that mixes;
(3) preparation of each organic function layer: the respective process of reference example 1;
(4) preparation of negative electrode: the respective process of reference example 1;
(5) respective process of reference example 1;
Referring to Fig. 3, be doped with organic electroluminescence devices with the P-type of evaporation and compare (glass substrate/ITO (100nm)/m-MTDATA:NPB:F4-TCNQ (90nm)/NPB (10nm)/Alq under the same conditions useful life
3(60nm)/and LiF (0.5nm)/Al (80nm), the line of lower left is depicted as the life curve of evaporation P-type doping hole injection layer organic electroluminescence device (initial intensity is 100cd/m among the figure
2, the life-span of device is that luminous intensity decays to half time of initial intensity), top-right line is represented the life curve of compound P-type doping hole injection layer organic electroluminescence device, and wherein the relative m-MTDATA doping ratio of F4-TCNQ is 2mol%.
As can be seen from the figure, the life-span of evaporation P-type doping hole injection layer organic electroluminescence device is 19.6 hours, and the life-span of the compound P-type of spin coating doping hole injection layer organic electroluminescence device was greater than 30 hours.
Claims (12)
1, a kind of P-type doping organic film of wet method preparation, it is characterized in that: be to use the mode of solution to form the codope system of polymeric material, the injection of organic molecule hole or transferring material and P-type dopant, by the organic film of wet method film-forming process preparation.
2, the P-type doping organic film of a kind of wet method preparation as claimed in claim 1, it is characterized in that: the thickness of this organic film is 20nm-1 μ m.
3, the P-type doping organic film of a kind of wet method preparation as claimed in claim 1, it is characterized in that: described polymeric material comprises polymetylmethacrylate at least, polystyrene PS, polycarbonate, polyimides PI, polyurethane PU, epoxy compounds copolymer A PC, polyacrylic acid PAA, inertia dielectric polymer such as polyvinylcarbazole PVK and have a kind of in the polymer of hole transport function.
4, the P-type doping organic film of a kind of wet method preparation as claimed in claim 1, it is characterized in that: described organic molecule hole is injected or transferring material comprises N at least, N`-two (naphthalene-1-yl)-N, N`-diphenyl-benzidine NPB and N, N`-diphenyl-N, two (the 3-aminomethyl phenyls)-1 of N`-, 1-diphenyl-4,4`-diamines TPD and derivative thereof, 4,4`, 4``-three [N-(3-methyl)-N-anilino-] triphenylamine MTDATA, 4,4`, a kind of among 4``-three idol (3-aminomethyl phenyl aniline) triphenylamine m-MTDATA, the α six thiophene α-6T.
5, the P-type doping organic film of a kind of wet method preparation as claimed in claim 1, it is characterized in that: described P-type dopant comprises that organic substance is as 2,3,5,6-tetrafluoro-7,7,8, other derivatives of 8-four cyano quino bismethane F4-TCNQ and four cyano 1,4-benzoquinone bismethane TCNQ, inorganic oxidizer such as iodine I
2, iron oxide FeCl
3, ferric flouride FeF
3, antimony chloride SbCl
5, and metal oxide such as tungsten oxide WO
3, molybdenum oxide MoO
x, vanadium oxide V
2O
5, rheium oxide ReO
3A kind of with in other metal halide.
6, the electroluminescent device that has the P-type doping organic film of wet method preparation, it is characterized in that: the substrate, transparent anode, P-type doping organic film, hole transmission layer, organic luminous layer, electron transfer layer, electron injecting layer and the negative electrode that comprise stack successively, wherein, P-type doping organic film be polymer body material, the injection of organic molecule hole or transferring material and P-type dopant the codope system by wet method preparation on transparent anode and thickness be the organic film of 20nm-1 μ m.
7, as the electroluminescent device of the P-type doping organic film that has the wet method preparation as described in the claim 6, it is characterized in that: described substrate is glass or flexible substrate, and wherein flexible substrate is polyester or poly-phthalimide compounds.
8, as the electroluminescent device of the P-type doping organic film that has the wet method preparation as described in the claim 6, it is characterized in that: described transparent anode adopts inorganic material or organic conductive polymer, this inorganic material is a kind of metal oxide in tin indium oxide, zinc oxide or the tin oxide or is a kind of metal in gold, copper, silver or the zinc that the organic conductive polymer is polythiophene, the basic benzene sulfonic acid sodium salt of polyethylene or polyaniline.
9, as the electroluminescent device of the P-type doping organic film that has the wet method preparation as described in the claim 6, it is characterized in that: described negative electrode is metal, alloy or metal fluoride and metal composite electrode, described metal is selected from lithium, magnesium, aluminium, calcium, strontium, indium, described alloy be selected from lithium, magnesium, aluminium, calcium, strontium, indium respectively with the alloy of copper, gold, silver.
10, as the electroluminescent device of the P-type doping organic film that has the wet method preparation as described in the claim 6, it is characterized in that: the material of described hole transmission layer is diamine compounds and triphenylamine compounds.
11, as the electroluminescent device of the P-type doping organic film that has the wet method preparation as described in the claim 6, it is characterized in that: the material of described organic luminous layer is a kind of material in metal organic complex, aromatic condensed ring compounds, o-phenanthroline compounds or the carbazoles derivative, and fluorescent dye and phosphorescence doping luminescent layer.
12, as the electroluminescent device of the P-type doping organic film that has the wet method preparation as described in the claim 6, it is characterized in that: the material of described electron transfer layer is a kind of material in metal organic complex, aromatic condensed ring compounds, the o-phenanthroline compounds.
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