CN103928628A - Modification indium tin oxide anode and preparation method thereof, and organic electroluminescent device - Google Patents

Modification indium tin oxide anode and preparation method thereof, and organic electroluminescent device Download PDF

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Publication number
CN103928628A
CN103928628A CN201310010848.8A CN201310010848A CN103928628A CN 103928628 A CN103928628 A CN 103928628A CN 201310010848 A CN201310010848 A CN 201310010848A CN 103928628 A CN103928628 A CN 103928628A
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tin oxide
indium
anode
fluorine
oxide anode
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CN103928628B (en
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周明杰
王平
冯小明
张娟娟
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Jiashan Weitang Asset Management Co.,Ltd.
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201610096055.6A priority Critical patent/CN105576141B/en
Priority to CN201610095917.3A priority patent/CN105895824B/en
Priority to CN201310010848.8A priority patent/CN103928628B/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H10K50/816—Multilayers, e.g. transparent multilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The embodiments of the invention disclose a modification indium tin oxide anode. The modification indium tin oxide anode comprises an indium tin oxide anode and a modification layer. The indium tin oxide anode comprises a glass substrate and an indium tin oxide film arranged on the surface of the glass substrate. The modification layer is arranged on the surface of the indium tin oxide film. The modification layer is a fluorine containing dipole layer existing in an In-F form, which is formed through bonding of the indium on the surface of the indium tin oxide film and fluorine. The mass percentage of the fluorine element of the fluorine containing dipole layer is 11%-20%. The ratio of the mass percentage of a tin element to the mass percentage of an indium element is 0.004-0.017. The existence of the fluorine containing dipole layer enables the work content of the surface of the anode to be improved. Besides, the embodiments of the invention further disclose a preparation method of the modification indium tin oxide anode, and an organic electroluminescent device using the modification indium tin oxide anode.

Description

A kind of indium-tin oxide anode and preparation method thereof and organic electroluminescence device modified
Technical field
The present invention relates to electronic device association area, relate in particular to a kind of indium-tin oxide anode and preparation method thereof and organic electroluminescence device modified.
Background technology
At present, in organic semiconductor industry, organic electroluminescence device (OLED) has that brightness is high, material range of choice is wide, driving voltage is low, entirely solidifies the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
In the structure of organic electroluminescence device, anode, as a pith of device architecture, is being born the effect that carrier injection is connected with circuit, and injection and the electrode of charge carrier are relevant with the interface potential barrier between organic material simultaneously.Anode is all generally to bear the effect that hole is injected, conventionally the conductive oxide film adopting is as tin indium oxide (ITO) etc., its work content only has 4.7eV, and the organic hole transferring material adopting, its HOMO energy level is conventionally in 5.1V left and right, cause like this hole to be injected and need to overcome larger potential barrier, thereby cause hole injection efficiency not high.The work content that improves ITO, will be conducive to improve the injection efficiency in hole greatly.Generally realize by the Sn/In ratio of reduction ITO surface-element or the content of raising Surface Oxygen atom the object that improves work content at present, in addition, form dipole layer at anode surface and also can reach this effect.
Summary of the invention
For solving the problems of the technologies described above, the present invention aims to provide a kind of indium-tin oxide anode and preparation method thereof of modifying, the method is by modifying processing by indium-tin oxide anode surface, make indium tin oxide films surface form fluorine-containing dipole layer, improve anode surface work content, thereby make this anode can greatly improve the injection efficiency in hole in application, improve device luminous efficiency.The present invention also provides the organic electroluminescence device that comprises above-mentioned modification indium-tin oxide anode.
First aspect, the invention provides a kind of indium-tin oxide anode of modifying, comprise indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, described decorative layer is the indium on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with fluorine, the quality percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, and tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element.
Preferably, the thickness of described indium tin oxide films is 70 ~ 200nm.
Second aspect, the invention provides a kind of preparation method who modifies indium-tin oxide anode, comprises the following steps:
Described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface;
Described indium-tin oxide anode is immersed in the fluorine-containing aqueous solutions of organic acids that concentration is 0.2 ~ 2mol/L, at 5 ~ 20 DEG C, soak after 0.5 ~ 2 minute, take out, dry;
Dried described indium-tin oxide anode is placed in to plasma apparatus, pass into fluoro-gas, making the gas pressure in plasma apparatus is 10Pa ~ 60Pa, adjustment radio-frequency power is 40w ~ 100w, carry out plasma treatment 5 ~ 10 minutes, obtain modifying indium-tin oxide anode, the surface of described modification indium-tin oxide anode has decorative layer, and described decorative layer is the indium on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with fluorine.
The percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, and tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element.
Described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface.Preparation in the following way: clean glass substrate is provided, adopts magnetron sputtering method sputter on described glass substrate to prepare indium tin oxide films.
Described glass substrate is commercially available simple glass.
Preferably, the cleaning operation of described glass substrate is specially: adopt successively liquid detergent, deionized water, isopropyl alcohol and acetone to carry out respectively ultrasonic cleaning 20 minutes, then nitrogen dries up.
Preferably, the thickness of described indium tin oxide films is 70 ~ 200nm.
Described indium-tin oxide anode is immersed in the fluorine-containing aqueous solutions of organic acids that concentration is 0.2 ~ 2mol/L, at 5 ~ 20 DEG C, soak after 0.5 ~ 2 minute, take out, dry.
Preferably, described fluorine-containing organic acid is difluoroacetic acid, trifluoroacetic acid or 2,2-difluoro propionic acid.
Preferably, the concentration of described fluorine-containing aqueous solutions of organic acids is 0.5 ~ 1mol/L.
Described dry concrete mode is not done particular restriction.Preferably, described drying process was: 50 ~ 80 DEG C of vacuumizes 12 ~ 24 hours.
Described indium-tin oxide anode by fluorine-containing organic acid preliminary treatment after, its adsorption has a large amount of functional fluoropolymer groups, because fluorine has strong electron-withdrawing power, therefore these functional fluoropolymer groups will be at tin indium oxide (ITO) surface and indium In forming section In-F key, thereby the part Sn on tin indium oxide (ITO) surface is replaced by F, but the In-F key now forming is not very stable, need do further processing.
Dried described indium-tin oxide anode is placed in to plasma apparatus, passes into fluoro-gas and carry out plasma treatment, obtain modifying indium-tin oxide anode.The surface of this modification indium-tin oxide anode has decorative layer, and described decorative layer is the In on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with F.
Preferably, described fluoro-gas is carbon tetrafluoride or three fluorocarbonss.
In plasma treatment procedure, the gas pressure in plasma apparatus is 10 ~ 60Pa, and radio-frequency power is 40 ~ 100w, and the time of plasma treatment is 5 ~ 10 minutes.
Indium-tin oxide anode, after fluoro-gas plasma treatment, will make unsettled In-F key become more stable; Meanwhile, the fluorine in fluoro-gas also can form In-F key with the indium on ITO surface (In), and the tin (Sn) on ITO surface is further replaced by fluorine (F); In addition, the functional fluoropolymer group that does not become key with ITO that is adsorbed on surface after fluorine-containing organic acid preliminary treatment also will form In-F key with In, thereby further improve the In-F key ratio on ITO surface, improve the percentage composition of anode surface element F, reduced the Sn/In constituent content ratio of anode surface.So, the fluorine-containing dipole layer that one deck exists with In-F form will be formed on anode ITO surface, the percentage composition of the fluorine element of this fluorine-containing dipole layer is 11 ~ 20%, tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element, therefore,, with respect to the ito anode of common unmodified, this fluorine-containing dipole layer exists and can improve ito anode surface work content as decorative layer, inject the potential barrier that need to overcome thereby reduce hole, improve hole injection efficiency.This is because the existence of dipole layer will improve the vacuum level E on ITO surface vac, improve a numerical value δ, make like this Fermi level E of anode fwith vacuum level E vacdifference DELTA E compared original difference many δ.According to the definition of work content, work content is the difference of material Fermi level and vacuum level, so just means that work content has improved δ numerical value.The existence that is fluorine-containing dipole layer has improved anode surface work content.
Described modification indium-tin oxide anode should properly be preserved, and preserving environment is vacuum environment <10 -3pa or be kept at N 2in glove box.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, described anode is for modifying indium-tin oxide anode, described modification indium-tin oxide anode comprises indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, described decorative layer is the indium on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with fluorine, the quality percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element.
Preferably, the thickness of described indium tin oxide films is 70 ~ 200nm.
Wherein, described functional layer comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
In the time that described functional layer is multilayer, described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are successively set on the ito thin film surface of modifying indium-tin oxide anode in order.
The material of described hole injection layer can be Phthalocyanine Zinc (ZnPc), CuPc (CuPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc), phthalocyanine platinum (PtPc) or 4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamines (m-MTDATA).The thickness of hole injection layer is 10 ~ 40nm.
The hole mobile material of described hole transmission layer can be N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD); N, N, N', N '-tetramethoxy phenyl)-benzidine (MeO-TPD); Two (N, N-bis-(4-methoxyphenyl) amino)-9 of 2,7-, 9-spiral shell two fluorenes (MeO-Sprio-TPD), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) or 2,2', 7,7 '-tetra-(N, N-hexichol amido)-9,9 '-spiral shell two fluorenes (S-TAD), the thickness of hole transmission layer is 20 ~ 50nm.
The material of described luminescent layer is the composite material that luminescent material doping hole mobile material or electron transport material form.
Described luminescent material can be 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 2, 3, 6, 7-tetrahydrochysene-1, 1, 7, 7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9, 9A, 1GH] cumarin (C545T), two (2-methyl-oxines)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-isopropyl-6-(1, 1, 7, 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq3), 5, 6, 11, 12-tetraphenyl naphthonaphthalene (Rubrene), 4, 4'-bis-(2, 2-diphenylethyllene)-1, 1'-biphenyl (DPVBi), two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (4, the fluoro-5-cyano-phenyl of 6-bis-pyridine-N, C2) pyridine carboxylic acid closes iridium (FCNIrpic), two (2 ', 4 '-difluorophenyl) pyridine] (tetrazolium pyridine) close iridium (FIrN4), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium (Ir (MDQ) 2 (acac)), two (1-phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium (Ir (piq) 2 (acac)), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) or three (2-phenylpyridines) close one or more in iridium (Ir (ppy) 3).The thickness of luminescent layer is 10 ~ 20nm.
The electron transport material of described electron transfer layer can be 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), (oxine)-aluminium (Alq3), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (as TAZ) or two (2-methyl-oxine-N 1, O 8)-(1,1'-biphenyl-4-hydroxyl) aluminium (BAlq).The thickness of electron transfer layer is 30 ~ 60nm.
The material of described electron injecting layer can be LiF, CsF or NaF, and thickness is 1nm;
Described negative electrode can adopt Ag, Al, and Sm, Yb, Mg-Ag alloy or Mg-Al alloy, thickness is 70 ~ 200nm.
Above-mentioned hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode all can adopt the mode of vacuum evaporation to prepare successively and modify in indium-tin oxide anode.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) preparation method of modification indium-tin oxide anode provided by the invention, by indium-tin oxide anode being carried out to fluorine-containing organic acid preliminary treatment and fluoro-gas plasma treatment, reduce the Sn/In constituent content ratio of anode surface, make indium-tin oxide anode surface form decorative layer simultaneously, the fluorine-containing dipole layer existing with the form of In-F, thus anode surface work content improved;
(2) preparation method of modification indium-tin oxide anode provided by the invention, technique is simple, and cost is low;
(3) modification indium-tin oxide anode provided by the invention, can be widely used in organic electroluminescence device and organic solar batteries, improves the efficiency of device.
Brief description of the drawings
Fig. 1 is the structure chart of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is organic electroluminescence device and the current density of existing organic electroluminescence device and the graph of a relation of voltage that the embodiment of the present invention 4 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method who modifies indium-tin oxide anode, comprises the following steps:
(1) get glass substrate, adopt successively liquid detergent, deionized water, isopropyl alcohol and acetone to carry out respectively ultrasonic cleaning 20 minutes, then nitrogen dries up; On glass substrate, adopt magnetron sputtering method to prepare the indium tin oxide films that thickness is 100nm, obtain indium-tin oxide anode;
(2) described indium-tin oxide anode is immersed in the difluoroacetic acid aqueous solution that concentration is 2mol/L, at 10 DEG C, soak after 0.5 minute, take out, 50 DEG C of vacuumize 12 hours;
(3) dried indium-tin oxide anode is placed in to plasma apparatus, pass into carbon tetrafluoride (CF4) gas and carry out plasma treatment, obtain modifying indium-tin oxide anode, the surface of modifying indium-tin oxide anode has decorative layer, and decorative layer is the In on indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with F.
In plasma treatment procedure, the gas pressure in plasma apparatus is 10Pa, and radio-frequency power is 50w, and the time of plasma treatment is 6 minutes.
The modification indium-tin oxide anode that the present embodiment makes, its finishing coat is the fluorine-containing dipole layer existing with the form of In-F, this dipole layer will improve the vacuum level E on ITO surface vac, improve a numerical value δ, make like this Fermi level E of anode fwith vacuum level E vacdifference DELTA E compared original difference many δ.According to the definition of work content, work content is the difference of material Fermi level and vacuum level, so just means that work content has improved δ numerical value.The surperficial work content of not modified indium-tin oxide anode is generally 4.7eV, and the surperficial work content of the modification indium-tin oxide anode that the present embodiment prepares is 5.7eV.
Embodiment 2
A preparation method who modifies indium-tin oxide anode, comprises the following steps:
(1) get glass substrate, adopt successively liquid detergent, deionized water, isopropyl alcohol and acetone to carry out respectively ultrasonic cleaning 20 minutes, then nitrogen dries up; On glass substrate, adopt magnetron sputtering method to prepare the indium tin oxide films that thickness is 70nm, obtain indium-tin oxide anode;
(2) indium-tin oxide anode is immersed in the trifluoroacetic acid aqueous solution that concentration is 0.2mol/L, at 20 DEG C, soak after 2 minutes, take out, 80 DEG C of vacuumize 12 hours;
(3) dried indium-tin oxide anode is placed in to plasma apparatus, pass into three fluorocarbonss (CHF3) gas and carry out plasma treatment, obtain modifying indium-tin oxide anode, the surface of modifying indium-tin oxide anode has decorative layer, and decorative layer is the In on indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with F.
In plasma treatment procedure, the gas pressure in plasma apparatus is 30Pa, and radio-frequency power is 40w, and the time of plasma treatment is 10 minutes.
The surperficial work content of the modification indium-tin oxide anode that the present embodiment prepares is 5.8eV.
Embodiment 3
A preparation method who modifies indium-tin oxide anode, comprises the following steps:
(1) get glass substrate, adopt successively liquid detergent, deionized water, isopropyl alcohol and acetone to carry out respectively ultrasonic cleaning 20 minutes, then nitrogen dries up; On glass substrate, adopt magnetron sputtering method to prepare the indium tin oxide films that thickness is 200nm, obtain indium-tin oxide anode;
(2) indium-tin oxide anode being immersed to concentration is 2 of 1mol/L, in the 2-difluoro propionic acid aqueous solution, soaks after 1 minute at 5 DEG C, takes out 60 DEG C of vacuumize 24 hours;
(3) dried indium-tin oxide anode is placed in to plasma apparatus, passes into carbon tetrafluoride (CF 4) gas carries out plasma treatment, obtains modifying indium-tin oxide anode, the surface of modifying indium-tin oxide anode has decorative layer, and decorative layer is the In on indium tin oxide films surface the becomes key formation fluorine-containing dipole layer existing with In-F form with F.
In plasma treatment procedure, the gas pressure in plasma processing chamber is 60Pa, and radio-frequency power is 100w, and the time of plasma treatment is 5 minutes.
The surperficial work content of the modification indium-tin oxide anode that the present embodiment prepares is 5.9eV.
The above embodiment of the present invention 1 ~ 3 gained modification indium-tin oxide anode and not modified common indium-tin oxide anode are carried out to surface-element analysis, method of testing adopts XPS(X ray photoelectric spectrum), instrument model is ESCA2000(VG Microtech Inc. company), test condition is for being used Al target K alpha ray source, and ray energy is 1486.6eV.Calculate respectively the 1s track of ito thin film surface C element, the 3d of In element 5/2track, the 3d of Sn element 5/2the 1s track of track O element, the 1s track of F element, calculates each element percentage composition, and its testing result is as shown in table 1.
Table 1
As can be seen from Table 1, not modified common indium-tin oxide anode, its surface is by C, O, In, tetra-kinds of element compositions of Sn, modify modification indium-tin oxide anode after treatment through the inventive method, surface how F element, illustrate through modifying processing, F element becomes key to be formed on ito thin film surface with In, thereby has formed on ito thin film surface the fluorine-containing dipole layer existing with In-F form.Can find out from elementary analysis data result, modification indium-tin oxide anode prepared by the present invention, the percentage composition of the F element of its fluorine-contained surface dipole layer has reached more than 11%, has been up to 19.46%.Process by modification of the present invention, the Sn/In on ITO surface is than significantly reducing simultaneously, minimumly dropped to 0.004 from 0.188.Illustrate that F has replaced the key mapping of part Sn, becomes key with In.
Embodiment 4
A kind of organic electroluminescence device, comprises the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described anode is modification indium-tin oxide anode prepared by the embodiment of the present invention 1.
Particularly, in the present embodiment, the material of hole injection layer is Phthalocyanine Zinc (ZnPc), and thickness is 15nm; The material of hole transmission layer is N, N'-diphenyl-N, and N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), thickness is 50nm; The material of luminescent layer is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) 1,3 of 8% mass fraction that adulterates, the composite material that 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) forms, is expressed as Ir (ppy) 3: TPBi(8%), thickness is 15nm; The electron transport material of electron transfer layer is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), and thickness is 50nm; The material of electron injecting layer is LiF, and thickness is 1nm; Negative electrode is Ag, and thickness is 100nm.
The structure of the present embodiment organic electroluminescence device is: ito anode/decorative layer/ZnPc (15nm)/TPD (50nm)/Ir (ppy) 3: TPBi (8%, 15nm)/TPBi (50nm)/LiF (1nm)/Ag (100nm).
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises, modifies ito anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and negative electrode 70.Wherein, modifying ito anode 10 and comprise ito anode 101 and decorative layer 102, for there is fluorine-containing dipole layer with the form of In-F in described decorative layer 102.
Compared with existing organic electroluminescence device, embodiment of the present invention organic electroluminescence device is owing to having adopted modification indium-tin oxide anode, and anode surface work content has improved, and hole injection efficiency improves, thereby the starting resistor of device is obviously reduced.The structure of existing organic electroluminescence device is: common unmodified ito anode/ZnPc (15nm)/TPD (50nm)/Ir (ppy) 3: TPBi (8%, 15nm)/TPBi (50nm)/LiF (1nm)/Ag (100nm).The starting resistor of existing organic electroluminescence device is 3.0eV, and the starting resistor of the present embodiment organic electroluminescence device is 2.1eV.
Fig. 2 is the graph of a relation of the organic electroluminescence device of the present embodiment and the current density of existing luminescent device and voltage.Wherein, curve 1 is the current density of the present embodiment organic electroluminescence device and the graph of a relation of voltage; The current density that curve 2 is existing organic electroluminescence device and the graph of a relation of voltage.As can be seen from the figure, under identical starting resistor, the present embodiment organic electroluminescence device can obtain higher Injection Current, thereby makes device have higher luminous efficiency.The luminous efficiency of existing organic electroluminescence device is 13.1lm/W, and the luminous efficiency of the present embodiment organic electroluminescence device is 26.4lm/W.This is because the present embodiment organic electroluminescence device has adopted modification indium-tin oxide anode, has improved the injection efficiency in hole, therefore can obtain higher Carrier Injection Efficiency, improves device organic electroluminescent efficiency.
Embodiment 5
A kind of organic electroluminescence device, comprises the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described anode is modification indium-tin oxide anode prepared by the embodiment of the present invention 2.The material of described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode and embodiment 4 are same.
The starting resistor of the present embodiment organic electroluminescence device is 2.1eV, and luminous efficiency is 31.1lm/w.
Embodiment 6
A kind of organic electroluminescence device, comprises the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, and described anode is modification indium-tin oxide anode prepared by the embodiment of the present invention 3.The material of described hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode and embodiment 4 are same.
The starting resistor of the present embodiment organic electroluminescence device is 2.0eV, and luminous efficiency is 35.2lm/w.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (9)

1. modify indium-tin oxide anode for one kind, comprise indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, it is characterized in that, described decorative layer is the indium on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with fluorine, the quality percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, and tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element.
2. modification indium-tin oxide anode as claimed in claim 1, is characterized in that, the thickness of described indium tin oxide films is 70 ~ 200nm.
3. a preparation method who modifies indium-tin oxide anode, is characterized in that, comprises the following steps:
Clean indium-tin oxide anode is provided; Described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface;
Described indium-tin oxide anode is immersed in the fluorine-containing aqueous solutions of organic acids that concentration is 0.2 ~ 2mol/L, at 5 ~ 20 DEG C, soak after 0.5 ~ 2 minute, take out, dry;
Dried described indium-tin oxide anode is placed in to plasma apparatus, pass into fluoro-gas, making the gas pressure in plasma apparatus is 10Pa ~ 60Pa, adjustment radio-frequency power is 40w ~ 100w, carry out plasma treatment 5 ~ 10 minutes, obtain modifying indium-tin oxide anode, the surface of described modification indium-tin oxide anode has decorative layer, and described decorative layer is the indium on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with fluorine.
4. the preparation method of modification indium-tin oxide anode as claimed in claim 3, is characterized in that, the percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, and tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element.
5. the preparation method of modification indium-tin oxide anode as claimed in claim 3, is characterized in that, described fluorine-containing organic acid is difluoroacetic acid, trifluoroacetic acid or 2,2-difluoro propionic acid.
6. the preparation method of modification indium-tin oxide anode as claimed in claim 3, is characterized in that, described fluoro-gas is carbon tetrafluoride or three fluorocarbonss.
7. the preparation method of modification indium-tin oxide anode as claimed in claim 3, is characterized in that, the thickness of described indium tin oxide films is 70 ~ 200nm.
8. an organic electroluminescence device, comprise anode, functional layer, luminescent layer and negative electrode, it is characterized in that, described anode is for modifying indium-tin oxide anode, described modification indium-tin oxide anode comprises indium-tin oxide anode and decorative layer, described indium-tin oxide anode comprises glass substrate and is arranged on the indium tin oxide films of described glass baseplate surface, described decorative layer is arranged on described indium tin oxide films surface, described decorative layer is the indium on described indium tin oxide films surface becomes key the to form fluorine-containing dipole layer existing with In-F form with fluorine, the quality percentage composition of the fluorine element of described fluorine-containing dipole layer is 11 ~ 20%, tin element is 0.004 ~ 0.017 with the quality percentage composition ratio of phosphide element.
9. organic electroluminescence device as claimed in claim 8, is characterized in that, the thickness of described indium tin oxide films is 70 ~ 200nm.
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