CN104009188A - Method for improving hole injection ability of ITO transparent conductive film and application of ITO transparent conductive film - Google Patents
Method for improving hole injection ability of ITO transparent conductive film and application of ITO transparent conductive film Download PDFInfo
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- CN104009188A CN104009188A CN201410201085.XA CN201410201085A CN104009188A CN 104009188 A CN104009188 A CN 104009188A CN 201410201085 A CN201410201085 A CN 201410201085A CN 104009188 A CN104009188 A CN 104009188A
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Abstract
The invention relates to a method for improving the hole injection ability of an ITO transparent conductive film. The method comprises the steps: S1, adding one or two compounds of a structure shown in the structural formula (I) to a solvent ultra-dry benzene solution and fully mixing the compounds and the solvent ultra-dry benzene solution, wherein the volume ratio of the compounds to the solvent ultra-dry benzene solution is 0.1%-5%; S2, after UV light treatment is carried out on the surface of the ITO transparent conductive film, soaking the surface of the ITO transparent conductive film into the mixed solution prepared in the S1; S3, taking out the ITO transparent conductive film soaked in the S2, and purifying and drying the ITO transparent conductive film in an alcoholic solution to obtain the ITO transparent conductive film with the high hole injection ability.
Description
Technical field
The invention belongs to conductive film technical field of surface, be specifically related to the method for a kind of ITO of raising transparent conductive film hole injectability and the application in organic electroluminescence device thereof.
Background technology
Tin indium oxide (English full name is Indium tin oxide, referred to as ITO) transparent conductive film not only possesses excellent electric conductivity, and light transmittance reaches 90%, has transparent characteristic; (English full name is Organic Light-Emitting Diode to be widely used as organic electroluminescence device, referred to as OLED), (English full name is Liquid crystal displays to liquid crystal display device, referred to as LCD), (English full name is Organic Photovoltaic to organic photovoltaic battery, referred to as OPVs) etc. the electrode in device, can also doublely do optical transmission window.
Except occupying an leading position in flat panel display field, due to the impact of the surperficial electrical properties of ITO, the application in organic assembly field is perfect not enough.ITO transparent conductive film surface work function prepared by conventional method only has 4.5eV-4.8eV, and the highest electrons occupy track of the organic function layer of OLED (English full name is Highest Occupied Molecular Orbital, referred to as HOMO) energy level is about 5.7eV-6.3eV, hole to overcome be greater than 1eV barrier height inject OLED inside more difficult, need to apply very high voltage to OLED, and hole injection efficiency is not high, thereby cause OLED luminous intensity and light efficiency low, device stability is poor.In prior art, generally can on ITO, introduce hole injection layer, as poly-ethylenedioxy thiophene/poly styrene sulfonate (PEDOT:PSS) layer or molybdenum oxide layer, in order to mate the work function of HOMO energy level and ITO, thereby realize effective injection in hole.If can pass through ITO finishing, reduce the potential barrier of hole from electrode injection to OLED organic function layer HOMO, just can increase substantially OLED luminous intensity and light efficiency, extend device lifetime.
There is good electric property and optical property just because of ito thin film, therefore the research of studying its preparation method is a lot, and the method for existing raising ITO surface voids injectability comprises that acid is cleaned, ultraviolet light ozone treatment is clean, oxygen plasma treatment, magnetron sputtering method, vapour deposition process etc.Sour cleaning can change ITO surface polarity to a certain extent in theory, improve surface work function, but experiment effect is not remarkable to the raising of ITO surface voids injectability.The clean effect of in fact only playing clean ITO surface organic impurities of ultraviolet light ozone treatment, can not essence improve ITO surface voids injectability, and effect is very limited.Oxygen plasma treatment comprises that oxygen plasma is bathed and injection, when oxygen plasma treatment can clean ITO surface organic impurities, ITO surface termination oxygen composition is increased, and Surface Polarization strengthens, thereby improves ITO surface voids injectability.Japan Patent JP2006345377 discloses a kind of method that improves ITO surface work function of bathing by oxygen plasma, but, bathe the restriction that improves ITO surface termination oxygen composition and be subject to surface chemistry balance by oxygen plasma, it is very limited improving space, and uncontrollable, after processing finishes, ITO surface treatment effect can be degenerated at short notice; And, the more important thing is that ITO surface can not infiltrated in organic material by the firm oxygen atom of bonding, destroy the photoelectric characteristic of organic material.Chinese patent CN102610765A discloses a kind of method that improves ITO surface voids injectability of injecting by oxygen plasma, specifically adopt the mode that radio frequency or microwave discharge excite in vacuum chamber, to produce large volume plasma, connect high voltage negative pulse square wave power, energetic oxygen ions is injected into ITO surface and stays in ITO top layer; Although can improve ITO surface voids injectability, equipment investment is large, complex process, and the injection phase of oxonium ion in ITO is difficult to control, and therefore, requires further study it is constantly improved before realizing industrialization.
Summary of the invention
For this reason, to be solved by this invention be in prior art for improving the limited problem of ITO surface voids injectability effect, provide a kind of for improving the method for ITO transparent conductive film hole injectability.
Further, the present invention also provides a kind of organic electroluminescence device of the ITO transparent conductive film that contains described high hole injectability.
For achieving the above object, the present invention adopts following technical scheme:
A method that improves ITO transparent conductive film hole injectability, comprises the steps:
S1, in the super dry benzole soln of solvent, add the compound of structure shown in one or both structural formulas (I), the volume ratio of described compound and the super dry benzole soln of solvent is 0.1%-5%, fully mixes;
Wherein,
Y be selected from F, Cl, Br, I or-NH
2one wherein;
R
1be selected from P or Si; R
2be selected from-CH
3or-H; R
3be selected from-CH
3o or O;
N is selected from the integer between 1-10;
S2, by behind UV photo-irradiation treatment ITO transparent conductive film surface, ITO transparent conductive film surface is immersed in mixed solution made in step (1);
ITO transparent conductive film in S3, taking-up step (2) after immersion treatment, ultrasonic removal of impurities in alcoholic solution, is dried, and obtains the ITO transparent conductive film of high hole injectability.
Preferably, the compound of described step S1 has structure shown in structural formula (II) or structural formula (III):
Y be selected from F, Cl, Br, I or-NH
2one wherein;
N is selected from the integer between 1-10.
Further preferably, described n is selected from the integer between 2-6.
Further preferably, described structural formula (II) compound is:
C
6H
15ClO
3Si、C
6H
15BrO
3Si、C
7H
17ClO
3Si、C
6H
15IO
3Si、C
6H
17NO
3Si、C
7H
17BrO
3SiC
7H
17IO
3Si、C
5H
13BrO
3Si、C
5H
13IO
3Si、C
5H
15NO
3Si、C
7H
19NO
3Si、C
8H
19ClO
3Si、C
8H
19BrO
3Si、C
8H
19IO
3Si、C
8H
21NO
3Si、C
9H
21ClO
3Si、C
8H
21BrO
3Si、C
9H
21IO
3Si、C
9H
23NO
3Si；、C
13H
29ClO
3Si、C
13H
29BrO
3Si、C
13H
29IO
3Si、C
13H
31NO
3Si；、C
4H
11ClO
3Si、C
4H
11BrO
3Si、C
4H
11IO
3Si、C
4H
13NO
3Si；
Described structural formula (III) compound is:
C
2H
6ClO
3P、C
2H
6BrO
3P、C
2H
6IO
3P、C
2H
8NO
3P、C
3H
8ClO
3P、C
3H
8BrO
3P、C
3H
8IO
3P、C
3H
10NO
3P、C
4H
10ClO
3P、C
4H
10BrO
3P、C
4H
10IO
3P、C
4H
12NO
3P、C
5H
12ClO
3P、C
5H
12BrO
3P、C
5H
12IO
3P、C
5H
14NO
3P、C
6H
14ClO
3P、C
6H
14BrO
3P、C
6H
14IO
3P、C
6H
16NO
3P。
Super dry benzole soln described in described step S1 is toluene solution or chlorobenzene solution.
In described step S2, the time that conductive glass surface is immersed in mixed solution made in step S1 is 2-6 hour.
In described step S2, the UV photo-irradiation treatment conductive glass surface time is 5-10 minute.
In described step S3, described alcoholic solution is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol.
In described step S3, described electro-conductive glass is ultrasonic 5-20 minute in described alcoholic solution.
A kind of organic electroluminescence device, comprises substrate, anode, at least one luminescent layer, functional layer and cathode layer successively,
Described anode is the ITO transparent conductive film that said method makes;
Described functional layer is hole transmission layer;
Described hole transmission layer is arranged on ITO transparent conductive film, and described luminescent layer is arranged between described hole transmission layer and described negative electrode.
Described functional layer also comprises electron transfer layer and/or electron injecting layer.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) provided by the inventionly contain chlorine (bromine, iodine or amido) siloxy alkane for improving the compound of ITO transparent conductive film hole injectability, ITO transparent conductive film forms great amount of hydroxy group after UV photo-irradiation treatment, described hydroxyl with contain chlorine (bromine, iodine or amido) siloxy alkane, in super dry toluene solvant or chlorobenzene solvent, hydrolysis occur, and then on ITO surface by the mode of molecular self-assembling, form the monolayer of chloride, bromine, iodine, amido, and then improve the hole injectability of ITO.The modification of the molecular self-assembling material that the present invention claims to ITO surface, is to introduce monolayer on ITO surface, has formed interface dipole, and then improve the surface work function of ITO, improve hole injectability, and improved its surface topography, device performance is improved.
(2) when Compound I TO transparent conductive film surface treatment of the present invention, only need carry out at normal temperatures and pressures, technique is simple, cost is low, mild condition, without vacuum equipment, without high temperature, be applicable to the formation of large-area substrates ITO conductive film, and to substrate not damaged, the industrialization of ito thin film is had to very important effect.Being easy to realize industrialization produces.
(3) adopt the organic electroluminescence device of ITO transparent conductive film of the present invention, ITO conductive film good film-forming property, surface ionization can be high, hole injection efficiency is high, also can be by changing number and the end group of carbochain, reach the object of Effective Regulation ITO surface ionization energy, therefore described ITO transparent conductive film surface ionization can be high, can effectively realize hole injects, without introducing hole injection layer, not only simplify device architecture, reduce cost, device can be realized well luminous, has also improved the performance of device.
(4) in addition, inventor also to the compound in step S1 be used for select, the volume ratio of itself and the super dry toluene of solvent is limited between 0.1%-5%, when volume ratio is too low while being less than 0.1%, contain the compounds such as chlorine (bromine, iodine or amido) siloxy alkane because the too low monolayer that cannot form of concentration; When volume ratio is too high while being greater than 5%, what contain that the compounds such as chlorine (bromine, iodine or amido) siloxy alkane form because of excessive concentration is polymolecular layer; Capital reduces the hole injectability of ITO.
Brief description of the drawings
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the surface topography map of the ITO of method after modifying described in embodiment 1;
Fig. 2 is the surface topography map of the ITO of method after modifying described in embodiment 3;
Fig. 3 is the surface topography map of the ITO of method after modifying described in embodiment 6;
Fig. 4 is the surface topography map of the ITO of method after modifying described in embodiment 7;
Fig. 5 is the ITO surface ion energy phenogram of the ITO of method after modifying described in embodiment 1;
Fig. 6 is the surface ion energy phenogram of the ITO of method after modifying described in embodiment 3;
Fig. 7 is the surface ion energy phenogram of the ITO of method after modifying described in embodiment 6;
Fig. 8 is the surface ion energy phenogram of the ITO of method after modifying described in embodiment 7;
Fig. 9 is the structural representation of organic electroluminescence device of the present invention;
Figure 10 is voltage-brightness curve of device 1-3;
Figure 11 is current density-luminous efficiency curve of device 1-3;
Figure 12 is the voltage-brightness curve of device 1,3,6;
Figure 13 is the current density-luminous efficiency curve of device 1,3,6;
Wherein, Reference numeral is:
1-substrate, 2-anode layer, 3-conductive membrane layer, 4-luminescent layer, 5-cathode layer.
Specific embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
Compound used in the present invention is as C
6h
15clO
3si, C
7h
17clO
3si, C
6h
15brO
3si, C
6h
15iO
3si, C
6h
17nO
3si, super dry toluene, super dry chlorobenzene, ethanol, isopropyl alcohol etc., has bought in each large industrial chemicals market at home.
Embodiment 1
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 5 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 0.1% C
6h
15clO
3in the super dry toluene mixture of Si and solvent, soak, the time is 4 hours;
Then the ITO transparent conductive film soaking is put in the solution of ethanol, carried out ultrasonicly, the time is 10 minutes, removes other residual solvents; Dry up, obtain the ITO transparent conductive film of high hole injectability.
Embodiment 2
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 8 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 4% C
6h
15clO
3si and C
6h
15brO
3in Si mixture (volume ratio 1:1) and the super dry toluene mixture of solvent, soak, the time is 2 hours;
Then the ITO transparent conductive film soaking is put in the solution of ethanol, carried out ultrasonicly, the time is 8 minutes, removes other residual solvents; Dry up, obtain the ITO transparent conductive film of high hole injectability.
Embodiment 3
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 5 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 2% C
7h
17clO
3in the super dry toluene mixture of Si and solvent, soak, the time is 5 hours;
Then the ITO transparent conductive film soaking is put in the solution of ethanol, carried out ultrasonicly, the time is 6 minutes, removes other residual solvents; Dry up, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
Embodiment 4
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 5 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 0.1% C
6h
15brO
3in the super dry toluene mixture of Si and solvent, soak, the time is 6 hours;
Then the ITO transparent conductive film soaking is put in the solution of ethanol, carried out ultrasonicly, the time is 5 minutes, removes other residual solvents;
Dry up, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
Embodiment 5
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 10 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 5% C
6h
15clO
3in the super dry toluene mixture of Si and solvent, soak, the time is 2 hours;
Then the ITO transparent conductive film soaking is put in the solution of isopropyl alcohol, carried out ultrasonicly, the time is 20 minutes, removes other residual solvents;
Be to be dried 6 hours under 80 ° of conditions in temperature, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
Embodiment 6
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 6 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 2% C
6h
15brO
3in the super dry toluene mixture of Si and solvent, soak, the time is 4 hours;
Then the ITO transparent conductive film soaking is put in the solution of isopropyl alcohol, carried out ultrasonicly, the time is 10 minutes, removes other residual solvents;
Be to be dried 4 hours under 80 ° of conditions in temperature, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
Embodiment 7
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 10 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 0.2% C
6h
15iO
3in the super dry toluene mixture of Si and solvent, soak, the time is 6 hours;
Then the ITO transparent conductive film soaking is put in the solution of isopropyl alcohol, carried out ultrasonicly, the time is 5 minutes, removes other residual solvents;
Dry up, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
Embodiment 8
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 5 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 2% C
6h
17nO
3in the super dry toluene mixture of Si and solvent, soak, the time is 5 hours;
Then the ITO transparent conductive film soaking is put in the solution of ethanol, carried out ultrasonicly, the time is 6 minutes, removes other residual solvents;
Dry up, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
Embodiment 9
First ITO transparent conductive film (the good electrode pattern of etching) is placed under uviol lamp, carries out UV illumination, the time is 6 minutes;
Then,, by ITO transparent conductive film after treatment, put into volume ratio and be 2% C
6h
15clO
3si and C
6h
15brO
3in Si mixture (volume ratio 3:1) and the super dry chlorobenzene mixture of solvent, soak, the time is 3 hours;
Then the ITO transparent conductive film soaking is put in the solution of ethanol, carried out ultrasonicly, the time is 20 minutes, removes other residual solvents;
Dry up, ITO surface treatment finishes, and obtains the ITO transparent conductive film of high hole injectability.
As Figure 1-5, be respectively ITO transparent conductive film that embodiment 1,4,7,8 preparation methods make and the surface topography map of modified ITO not, as seen from the figure, the surface of the ITO transparent conductive film that embodiment 1,4,7,8 preparation methods make is rented rugosity and is respectively 1.571nm, 1.723nm, 1.736nm and 1.398nm, and the surface roughness of modified ITO is not 2.016nm.Therefore can learn to there is the ITO surface topography of self assembly molecule layer, all smooth than the ITO surface topography of unmodified, highly beneficial to forming smooth organic function layer, can obtain efficient organic electroluminescence device performance.
By changing end group Cl, Br, I, NH
2can effectively regulate ITO surface ion energy, can find out from Fig. 6-11, the surface ionization of the ITO transparent conductive film that not modified ITO and embodiment 1,4,7,8 preparation methods make can be respectively 5.76ev, 5.41ev, 5.14ev, 4.46ev can match with organic functional material, effectively reduce injection barrier, improve hole injection efficiency; Wherein end group is NH
2modification, may be used in the device architecture of emission structure at top.
Embodiment 10
A kind of organic electroluminescence device, as shown in Figure 9, organic electroluminescence device of the present invention comprises substrate 1, anode layer 2, conductive membrane layer 3, luminescent layer 4, cathode layer 5.
Described substrate 1 is transparency carrier, can be glass substrate or flexible base, board, and flexible base, board adopts a kind of material in polyesters, polyimides compounds, and substrate 1 is above with anode layer.What the present invention used is glass substrate.
Described anode layer 2 can adopt inorganic material or organic conductive polymer, inorganic material is generally the higher metals of work function such as the metal oxides such as tin indium oxide (ITO), zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, organic conductive polymer is preferably a kind of material in polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS), polyaniline (hereinafter to be referred as PANI).The preferred ITO of the present invention does anode.
Described cathode layer 5 is general adopts the alloy of metal that the work functions such as lithium, magnesium, calcium, strontium, aluminium, indium are lower or they and copper, gold, silver, or metal and the alternately electrode layer of formation of metal fluoride, as, Mg:Ag alloy-layer successively and Ag layer, lithium fluoride successively or lithium nitride layer and Ag layer, lithium fluoride or lithium nitride layer and Al layer successively, select Mg:Ag alloy-layer and Ag layer in the present invention.
The application's luminescent layer 4 comprises luminescent material, adopts Alq in the present invention
3as luminescent material, can be also that other material of main parts and dopant dye steam altogether as luminescent layer 4.
On anode layer 2 surfaces, be combined with the conductive membrane layer 3 that can improve anode layer surface voids injectability.
Especially, be combined with between the anode layer 2 of conductive membrane layer 3 and luminescent layer 4 and can also comprise hole transmission layer.
To provide some embodiment below, specific explanations technical scheme of the present invention.It should be noted that the following examples are only for helping understanding invention, instead of limitation of the present invention.
Embodiment 11
The present embodiment is OLED device Preparation Example, and in the present embodiment, organic electroluminescence device structure is:
Substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/negative electrode
Substrate and anode using ITO transparent conductive film prepared in embodiment 1 as device, first ultrasonic processing in commercial cleaning agent, in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent, under clean environment, be baked to and remove moisture content completely, by ultraviolet light and ozone clean, and with low energy cation bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10
-5～9 × 10
-3pa, on above-mentioned anode tunic, vacuum evaporation CBP is as hole transmission layer, and evaporation speed is
evaporation thickness is 50nm;
Vacuum evaporation material of main part AlQ on hole injection layer
3, evaporation speed is
evaporation total film thickness is 50nm;
Vacuum evaporation Mg:Ag (10:1) layer on luminescent layer, thickness is 150nm.On Mg:Ag (10:1) layer, evaporation Ag layer is as the negative electrode of device, and thickness is 50nm, and wherein Mg:Ag is than being mol ratio.
The concrete device architecture of device 1 is:
ITO/CBP(50nm)/Alq
3(50nm)/Mg:Ag(150nm)/Ag(50nm)
Embodiment 12
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 3 as device, prepare device 2.
Embodiment 13
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 4 as device, prepare device 3.
Embodiment 14
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 5 as device, prepare device 4.
Embodiment 15
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 6 as device, prepare device 5.
Embodiment 16
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 7 as device, prepare device 6.
Embodiment 17
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 8 as device, prepare device 7.
Embodiment 18
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be substrate and anode using ITO transparent conductive film prepared in embodiment 9 as device, prepare device 8.
Comparative example 1
Preparation process, device architecture and material therefor and instrument be with embodiment 10, unique different be the ito glass substrate not modified using surface substrate and the anode as device, prepare comparative device 1.
The high-high brightness L to device 1-8 by screen intensity meter (ST-86LA) and current-voltage tester (KEITHLEY4200-SCS)
max(cd/m
2), maximum current efficiency eta L
maxand maximum power efficiency η p. (cd/A)
max(lm/W) test, performance data is as shown in the table:
Embodiment 18-59
The compound that embodiment 18-59 adopts is respectively C
7h
17brO
3si, C
7h
17iO
3si, C
5h
13brO
3si, C
5h
13iO
3si, C
5h
15nO
3si, C
7h
19nO
3si, C
8h
19clO
3si, C
8h
19brO
3si, C
8h
19iO
3si, C
8h
21nO
3si, C
9h
21clO
3si, C
8h
21brO
3si, C
9h
21iO
3si, C
9h
23nO
3si; , C
13h
29clO
3si, C
13h
29brO
3si, C
13h
29iO
3si, C
13h
31nO
3si; , C
4h
11clO
3si, C
4h
11brO
3si, C
4h
11iO
3si, C
4h
13nO
3si, C
2h
6clO
3p, C
2h
6brO
3p, C
2h
6iO
3p, C
2h
8nO
3p, C
3h
8clO
3p, C
3h
8brO
3p, C
3h
8iO
3p, C
3h
10nO
3p, C
4h
10clO
3p, C
4h
10brO
3p, C
4h
10iO
3p, C
4h
12nO
3p, C
5h
12clO
3p, C
5h
12brO
3p, C
5h
12iO
3p, C
5h
14nO
3p, C
6h
14clO
3p, C
6h
14brO
3p, C
6h
14iO
3p or C
6h
16nO
3p, wherein improve the method for ITO transparent conductive film hole injectability, embodiment 18-21 is with embodiment 1, and embodiment 22-25 is with embodiment 2, and embodiment 26-30 is with embodiment 3, embodiment 31-35 is with embodiment 4, embodiment 36-40 embodiment 5, embodiment 41-45 is with embodiment 6, and embodiment 46-50 is with embodiment 7, embodiment 51-55 is with embodiment 8, and embodiment 56-59 is with embodiment 9; The preparation method of device is respectively with embodiment 10.Embodiment 18-59 prepares respectively device 9-50.
The high-high brightness L to device 1-8 by screen intensity meter (ST-86LA) and current-voltage tester (KEITHLEY4200-SCS)
max(cd/m
2), maximum current efficiency eta L
maxand maximum power efficiency η p. (cd/A)
max(lm/W) test, performance data is as shown in the table:
Figure 12,13 is respectively voltage-brightness curve and the current density-luminous efficiency curve of device 1,3,6, in device, the device that contains the not modified ito glass substrate in surface, within the scope of driving voltage 3-21V, can not realize luminous, continue to add driving voltage, device is easily breakdown, and device described in embodiment 10-16 can both be realized well luminous, the ito glass substrate not modified with surface as the substrate of device compared with anode, device performance grows out of nothing, current efficiency can be brought up to 3.67cd/A, this result shows, in preparation technology, use the device of ITO transparent conductive film prepared in embodiment 1-9, can avoid introducing hole injection layer, thereby reduce preparation flow and reduced production cost.
Described in the present invention, containing the anode layer of conductive film, can effectively realize hole and inject, not only simplify device architecture, reduced cost, but also the performance of raising device.In actual applications; organic function layer can be according to the needs that use and the selection of luminescent material; change the structure of organic function layer; such as organic function layer can only include organic luminous layer; or go out outside luminescent layer; also comprise at least one deck in electron injecting layer, electron transfer layer, hole transmission layer, hole blocking layer, electronic barrier layer, can realize equally object of the present invention, belong to protection scope of the present invention.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all execution modes.And the apparent variation of being extended out thus or variation are still among protection scope of the present invention.
Claims (11)
1. a method that improves ITO transparent conductive film hole injectability, is characterized in that, comprises the steps:
S1, in the super dry benzole soln of solvent, add the compound of structure shown in one or both structural formulas (I), the volume ratio of described compound and the super dry benzole soln of solvent is 0.1%-5%, fully mixes;
Wherein,
Y be selected from F, Cl, Br, I or-NH
2one wherein;
R
1be selected from P or Si; R
2be selected from-CH
3or-H; R
3be selected from-CH
3o or O;
N is selected from the integer between 1-10;
S2, by behind UV photo-irradiation treatment ITO transparent conductive film surface, ITO transparent conductive film surface is immersed in mixed solution made in step (1);
ITO transparent conductive film in S3, taking-up step (2) after immersion treatment, ultrasonic removal of impurities in alcoholic solution, is dried, and obtains the ITO transparent conductive film of high hole injectability.
2. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, the compound of described step S1 has structure shown in structural formula (II) or structural formula (III):
Y be selected from F, Cl, Br, I or-NH
2one wherein;
N is selected from the integer between 1-10.
3. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, described n is selected from the integer between 2-6.
4. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, described structural formula (II) compound is:
C
6H
15ClO
3Si、C
6H
15BrO
3Si、C
7H
17ClO
3Si、C
6H
15IO
3Si、C
6H
17NO
3Si、C
7H
17BrO
3Si、C
7H
17IO
3Si、C
5H
13BrO
3Si、C
5H
13IO
3Si、C
5H
15NO
3Si、C
7H
19NO
3Si、C
8H
19ClO
3Si、C
8H
19BrO
3Si、C
8H
19IO
3Si、C
8H
21NO
3Si、C
9H
21ClO
3Si、C
8H
21BrO
3Si、C
9H
21IO
3Si、C
9H
23NO
3Si；、C
13H
29ClO
3Si、C
13H
29BrO
3Si、C
13H
29IO
3Si、C
13H
31NO
3Si；、C
4H
11ClO
3Si、C
4H
11BrO
3Si、C
4H
11IO
3Si、C
4H
13NO
3Si；
Described structural formula (III) compound is:
C
2H
6ClO
3P、C
2H
6BrO
3P、C
2H
6IO
3P、C
2H
8NO
3P、C
3H
8ClO
3P、C
3H
8BrO
3P、C
3H
8IO
3P、C
3H
10NO
3P、C
4H
10ClO
3P、C
4H
10BrO
3P、C
4H
10IO
3P、C
4H
12NO
3P、C
5H
12ClO
3P、C
5H
12BrO
3P、C
5H
12IO
3P、C
5H
14NO
3P、C
6H
14ClO
3P、C
6H
14BrO
3P、C
6H
14IO
3P、C
6H
16NO
3P。
5. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, the super dry benzole soln described in step S1 is toluene solution or chlorobenzene solution.
6. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, in described step S2, the time that conductive glass surface is immersed in mixed solution made in step S1 is 2-6 hour.
7. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, in described step S2, the UV photo-irradiation treatment conductive glass surface time is 5-10 minute.
8. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, in described step S3, described alcoholic solution is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol.
9. the method for raising according to claim 1 ITO transparent conductive film hole injectability, is characterized in that, in described step S3, described electro-conductive glass is ultrasonic 5-20 minute in described alcoholic solution.
10. an organic electroluminescence device, comprises substrate, anode, at least one luminescent layer, functional layer and cathode layer successively, it is characterized in that:
Described anode is the ITO transparent conductive film that the arbitrary described method of claim 1-8 makes;
Described functional layer is hole transmission layer;
Described hole transmission layer is arranged on ITO transparent conductive film, and described luminescent layer is arranged between described hole transmission layer and described negative electrode.
11. organic electroluminescence devices according to claim 10, is characterized in that: described functional layer also comprises electron transfer layer and/or electron injecting layer.
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