CN104178740A - Conductive film, preparing method thereof and applications of the conductive film - Google Patents

Conductive film, preparing method thereof and applications of the conductive film Download PDF

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CN104178740A
CN104178740A CN201310194876.XA CN201310194876A CN104178740A CN 104178740 A CN104178740 A CN 104178740A CN 201310194876 A CN201310194876 A CN 201310194876A CN 104178740 A CN104178740 A CN 104178740A
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layer
tito
target
meo
conductive film
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周明杰
王平
陈吉星
钟铁涛
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering 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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Abstract

A conductive film is provided. The conductive film comprises a TITO layer and an MeO3 layer which are laminated, wherein the TITO layer is indium oxide co-doped with titanium and stannum, the chemical formula of the indium oxide co-doped with titanium and stannum is In2O3:xSn<4+>,yTi<4+>, the x is 0.05-0.2, the y is 0.03-0.15, and the MeO3 layer is one of molybdenum oxide, tungsten oxide and rhenium oxide. The conductive film with double layers is prepared by depositing the MeO3 layer with high work function onto the surface of the TITO layer, thus maintaining the good electric conductive performance of the TITO layer and significantly improving the work function of the conductive film. A preparing method and applications of the conductive film are also provided.

Description

Conductive film, its preparation method and application
Technical field
The present invention relates to photoelectric semiconductor material, particularly relate to conductive film, its preparation method, use substrate, its preparation method and the organic electroluminescence device of the organic electroluminescence device of this conductive film.
Background technology
Conductive film electrode is the basic component of organic electroluminescence device (OLED), and the quality of its performance directly affects the luminous efficiency of whole device.Wherein, the doped semiconductor of Cadmium oxide is Recent study transparent conductive film material the most widely, has higher visible light transmittance rate and low resistivity.But improve the luminous efficiency of device, require transparent conductive film anode to there is higher surface work function.And the work function of the zinc oxide of aluminium, gallium and indium doping generally only has 4.3eV, through also reaching 4.5～5.1eV after the processing such as UV optical radiation or ozone, also has larger energy level difference distance with the HOMO energy level (being typically 5.7～6.3eV) of general organic luminous layer, cause the increase of carrier injection potential barrier, hinder the raising of luminous efficiency.
Summary of the invention
Based on this, being necessary, for the lower problem of conductive film work function, provides conductive film, its preparation method that a kind of work function is higher, the substrate of using the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device.
A conductive film, comprises stacked TITO layer and MeO 3layer, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
The thickness of described TITO layer is 50nm～300nm, described MeO 3the thickness of layer is 0.5nm～5nm.
A preparation method for conductive film, comprises the following steps:
By TITO target and MeO 3target and substrate pack the vacuum cavity of magnetic-controlled sputtering coating equipment into, and wherein, the vacuum tightness of vacuum cavity is 1.0 * 10 -3pa～1.0 * 10 -5pa, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide;
At described substrate surface sputter TITO layer, described in sputter, the processing parameter of TITO layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, and underlayer temperature is 250 ℃～750 ℃;
At described TITO layer surface sputter MeO 3layer, MeO described in sputter 3the processing parameter of layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃; And
Peel off described substrate, obtain described conductive film.
Described TITO target is obtained by following steps: by In 2o 3, SnO 2and TiO 2powder is that 0.65～0.92:0.05～0.2:0.03～0.15 mixes according to mol ratio, and the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
Described MeO 3target is obtained by following steps: by molybdenum oxide, powder in Tungsten oxide 99.999 and rhenium oxide a kind of at 800 ℃～1200 ℃ sintering make target.
A substrate for organic electroluminescence device, comprises the substrate stacking gradually, stacked TITO layer and MeO 3layer, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
The thickness of described TITO layer is 50nm～300nm, described MeO 3the thickness of layer is 0.5nm～5nm.
A preparation method for the substrate of organic electroluminescence device, comprises the following steps:
By TITO target and MeO 3target and substrate pack the vacuum cavity of magnetic-controlled sputtering coating equipment into, and wherein, the vacuum tightness of vacuum cavity is 1.0 * 10 -3pa～1.0 * 10 -5pa, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide;
At described substrate surface sputter TITO layer, described in sputter, the processing parameter of TITO layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, and underlayer temperature is 250 ℃～750 ℃;
At described TITO layer surface sputter MeO 3layer, MeO described in sputter 3the processing parameter of layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃.
Described TITO target is obtained by following steps: by In 2o 3, SnO 2and TiO 2powder is that 0.65～0.92:0.05～0.2:0.03～0.15 mixes according to mol ratio, and the powder mixing sintering at 900 ℃～1300 ℃ is made to target;
Described MeO 3target is obtained by following steps: by molybdenum oxide, powder in Tungsten oxide 99.999 and rhenium oxide a kind of at 800 ℃～1200 ℃ sintering make target.
An organic electroluminescence device, comprises the anode, luminescent layer and the negative electrode that stack gradually, and described anode comprises stacked TITO layer and MeO 3layer, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
Above-mentioned conductive film is by the MeO of the high work content of surface deposition at TITO layer 3the double-deck conductive film of layer preparation, the good conductivity that can keep TITO layer, make again the work function of conductive film obtain significant raising, conductive film is at 300～900nm wavelength region visible light transmissivity 85%～90%, square resistance scope 10～55 Ω/, surface work function 5.7～6.2eV; The preparation method of above-mentioned conductive film, only uses magnetic-controlled sputtering coating equipment to get final product continuous production TITO layer and MeO 3layer, technique is comparatively simple; Use this conductive film as the anode of organic electroluminescence device, between the surface work function of conductive film and the HOMO energy level of general organic luminous layer, gap is less, has reduced the injection barrier of current carrier, can improve significantly luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the conductive film of an embodiment;
Fig. 2 is the structural representation of substrate of the organic electroluminescence device of an embodiment;
Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 4 is the transmitted spectrum spectrogram of the conductive film of embodiment 1 preparation;
Fig. 5 is voltage and electric current and the brightness relationship figure of device embodiment.
Embodiment
Below in conjunction with the drawings and specific embodiments, conductive film, its preparation method, the substrate of using the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device are further illustrated.
Refer to Fig. 1, the conductive film 100 of an embodiment comprises stacked TITO layer 10 and MeO 3layer 20.
The thickness of described TITO layer 10 is 50nm～300nm, is preferably 150nm,
Described MeO 3the thickness of layer 20 is 0.5nm～5nm, is preferably 2nm.
Above-mentioned conductive film 100 is by the MeO of the high work content of surface deposition at TITO layer 10 3layer 20 is prepared multilayer conductive film, the good conductivity that can keep TITO layer 10, make again the work function of conductive film 100 obtain significant raising, conductive film 100 is at 300～900nm wavelength region visible light transmissivity 85%～90%, square resistance scope 10～55 Ω/, surface work function 5.7～6.2eV.
The preparation method of above-mentioned conductive film 100, comprises the following steps:
S110, by TITO target and MeO 3target and substrate pack the vacuum cavity of magnetic-controlled sputtering coating equipment into, and wherein, the vacuum tightness of vacuum cavity is 1.0 * 10 -3pa～1.0 * 10 -5pa, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
The target of TITO described in present embodiment is obtained by following steps: by In 2o 3, SnO 2and TiO 2powder is that 0.65～0.92:0.05～0.2:0.03～0.15 mixes according to mol ratio, and the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
MeO in present embodiment 3target is obtained by following steps: by molybdenum oxide, powder in Tungsten oxide 99.999 and rhenium oxide a kind of at 800 ℃～1200 ℃ sintering make target.
Substrate is glass substrate.Preferably, substrate is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning before use.
In present embodiment, the vacuum tightness of vacuum cavity is preferably 5 * 10 -4pa.
Step S120, at substrate surface sputter TITO layer 10, the processing parameter of sputter TITO layer 10 is: base target spacing is 45mm～95mm, sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, and underlayer temperature is 250 ℃～750 ℃.
Preferably, base target spacing is 60mm, and sputtering power is 100W, magnetron sputtering operating pressure 2.0Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The thickness of the TITO layer 10 forming is 50nm～300nm, is preferably 150nm.
Step S130, at the surperficial sputter MeO of TITO layer 10 3layer 20, sputter MeO 3the processing parameter of layer 20 is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃.
Preferably, base target spacing is 60mm, and sputtering power is 100W, magnetron sputtering operating pressure 2.0Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The MeO forming 3the thickness of layer 20 is 0.5nm～5nm, is preferably 2nm.
At the bottom of step S140, peeling liner, obtain conductive film 100.
The preparation method of above-mentioned conductive film, only uses magnetic-controlled sputtering coating equipment to get final product continuous production TITO layer 10 and MeO 3layer 20, technique is comparatively simple.
Refer to Fig. 2, the substrate 200 of the organic electroluminescence device of an embodiment, comprises stacked substrate 201, TITO layer 202 and MeO 3layer 203.
Substrate 201 is glass substrate.The thickness of substrate 201 is 0.1mm～3.0mm, is preferably 1mm.
The thickness of described TITO layer 202 is 50nm～300nm, is preferably 150nm.
Described MeO 3the thickness of layer 203 is 0.5nm～5nm, is preferably 2nm.
The substrate 200 of above-mentioned organic electroluminescence device is by the surface deposition MeO at TITO layer 202 3the double-deck conductive film of layer 203 preparation, the good conductivity that can keep TITO layer 202, make again the work function of the substrate 200 of organic electroluminescence device obtain significant raising, the substrate 200 of organic electroluminescence device is at 300～900nm wavelength region visible light transmissivity 85%～90%, square resistance scope 10～55 Ω/, surface work function 5.7～6.2eV.
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, comprises the following steps:
S210, by TITO target and MeO 3target and substrate 201 pack the vacuum cavity of magnetic-controlled sputtering coating equipment into, and wherein, the vacuum tightness of vacuum cavity is 1.0 * 10 -3pa～1.0 * 10 -5pa, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
In present embodiment, described TITO target is obtained by following steps: by In 2o 3, SnO 2and TiO 2powder is that 0.65～0.92:0.05～0.2:0.03～0.15 mixes according to mol ratio, and the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
Substrate is glass substrate.Preferably, substrate is used acetone, dehydrated alcohol and deionized water ultrasonic cleaning before use.
In present embodiment, the vacuum tightness of vacuum cavity is preferably 5 * 10 -4pa.
Step S220, at substrate surface sputter TITO layer 202, the processing parameter of sputter TITO layer 202 is: base target spacing is 45mm～95mm, sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, and underlayer temperature is 250 ℃～750 ℃.
Preferably, base target spacing is 60mm, and sputtering power is 100W, magnetron sputtering operating pressure 2.0Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The thickness of the TITO layer 202 forming is 50nm～300nm, is preferably 150nm.
Step S203, at the surperficial sputter MeO of TITO layer 202 3layer 203, sputter MeO 3the processing parameter of layer 203 is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃.
The MeO forming 3the thickness of layer 203 is 0.5nm～5nm, is preferably 2nm;
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, only uses magnetic-controlled sputtering coating equipment can on substrate 201, prepare continuously TITO layer 202 and MeO 3layer 203, technique is comparatively simple.
Refer to Fig. 3, the organic electroluminescence device 300 of an embodiment comprises substrate 301, anode 302, luminescent layer 303 and the negative electrode 304 stacking gradually.Anode 302 is made by conductive film 100, comprises stacked TITO layer 10 and MeO 3layer 20.Substrate 301 is glass substrate, is appreciated that, according to the difference of organic electroluminescence device 300 concrete structures, substrate 301 can omit.The material of luminescent layer 303 is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl-Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylidene anthracene (AND), two (2-methyl-oxine)-(4-xenol) aluminium (BALQ), 4-(dintrile methene)-2-sec.-propyl-6-(1,1,7,7-tetramethyl-Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTI), dimethylquinacridone (DMQA), oxine aluminium (Alq3), two (4,6-difluorophenyl pyridine-N, C 2) pyridine formyl closes iridium (FIrpic), two (2-methyl-phenylbenzene [f, h] quinoxaline) (methyl ethyl diketone) and close iridium (Ir (MDQ) 2(acac)) or three (2-phenylpyridines) close iridium (Ir (ppy) 3).The material of negative electrode 304 is silver (Ag), gold (Au), aluminium (Al), platinum (Pt) or magnesium silver alloys.
The thickness of described TITO layer 10 is 50nm～300nm, is preferably 150nm.
Described MeO 3the thickness of layer 20 is 0.5nm～5nm, is preferably 2nm.
Be appreciated that above-mentioned organic electroluminescence device 300 also can arrange other functional layers according to user demand.
Above-mentioned organic electroluminescence device 300, use conductive film 100 as the anode of organic electroluminescence device, surface work function 5.7～the 6.2eV of conductive film, and between the HOMO energy level (being typically 5.7～6.3eV) of general organic luminous layer, gap is less, reduce the injection barrier of current carrier, can improve luminous efficiency.
Be specific embodiment below.
Embodiment 1
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.82:0.1:0.08 mixes through even according to mole number, and at 1250 ℃, sintering diameter into is 50mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.1Sn 4+, 0.08Ti 4+, then by 150g MoO 3at 1100 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and MoO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 * 10 -4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃, and sputtering power is 100W.Priority sputter TITO target and MoO 3target, deposits respectively the film of 150nm and 2nm film, obtains In 2o 3: 0.1Sn 4+, 0.08Ti 4+-MoO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 12 Ω/, surface work function tester records surface work function 6.1eV.
Refer to Fig. 4, Figure 4 shows that the transmitted spectrum of the transparent conductive film obtaining, use ultraviolet-visible pectrophotometer test, test wavelength is 300～900nm.Film has reached 91% at visible ray 470～790nm wavelength region average transmittances as seen from Figure 4.
Select In 2o 3: 0.1Sn 4+, 0.08Ti 4+-MeO 3double-deck transparent conductive film is as the anode of organic semiconductor device, in the above evaporation luminescent layer Alq 3, and negative electrode employing Ag, prepare organic electroluminescence device.
Refer to Fig. 5, Fig. 5 is voltage and electric current and the brightness relationship figure of the organic electroluminescence device prepared of above-mentioned device embodiment, in accompanying drawing 5, curve 1 is voltage and current density relation curve, can find out that device starts from 5.5V luminous, curve 2 is voltage and brightness relationship curve, and high-high brightness is 93cd/m 2, show that device has the good characteristics of luminescence.
Embodiment 2
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.77:0.2:0.03 mixes through even according to mole number, and at 1350 ℃, sintering diameter into is 35mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.2Sn 4+, 0.03Ti 4+, then by 150g MoO 3at 1100 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and MoO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10 -3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃, and sputtering power is 150W.Priority sputter TITO target and MoO 3target, deposits respectively the film of 50nm and 5nm film, obtains In 2o 3: 0.2Sn 4+, 0.03Ti 4+-MoO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 53 Ω/, surface work function tester records surface work function 5.9eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 90% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 3
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.8:0.05:0.15 mixes through even according to mole number, and at 1350 ℃, sintering diameter into is 35mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.05Sn 4+, 0.15Ti 4+, then by 150g MoO 3at 800 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and MoO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10 -5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, and sputtering power is 30W.Priority sputter TITO target and MoO 3target, deposits respectively the film of 300nm and 0.5nm film, obtains In 2o 3: 0.05Sn 4+, 0.15Ti 4+-MoO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 20 Ω/, surface work function tester records surface work function 5.8eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 90% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 4
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.81:0.08:0.11 mixes through even according to mole number, and at 1250 ℃, sintering diameter into is 50mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.08Sn 4+, 0.11Ti 4+, then by 150g WO 3at 1100 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and WO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 * 10 -4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃, and sputtering power is 100W.Priority sputter TITO target and WO 3target, deposits respectively the film of 150nm and 2nm film, obtains In 2o 3: 0.08Sn 4+, 0.11Ti 4+-WO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 12 Ω/, surface work function tester records surface work function 6.1eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 91% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 5
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.82:0.13:0.05 mixes through even according to mole number, and at 1350 ℃, sintering diameter into is 35mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.13Sn 4+, 0.05Ti 4+, then by 150gWO 3at 1100 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and WO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10 -3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃, and sputtering power is 150W.Priority sputter TITO target and WO 3target, deposits respectively the film of 50nm and 5nm film, obtains In 2o 3: 0.13Sn 4+, 0.05Ti 4+-WO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 53 Ω/, surface work function tester records surface work function 5.9eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 89% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 6
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.72:0.18:0.1 mixes through even according to mole number, and at 1350 ℃, sintering diameter into is 35mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.18Sn 4+, 0.1Ti 4+, then by 150g WO 3at 800 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and WO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10 -5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, and sputtering power is 30W.Priority sputter TITO target and WO 3target, deposits respectively the film of 300nm and 0.5nm film, obtains In 2o 3: 0.18Sn 4+, 0.1Ti 4+-WO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 20 Ω/, surface work function tester records surface work function 5.8eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 91% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 7
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.81:0.11:0.08 mixes through even according to mole number, and at 1250 ℃, sintering diameter into is 50mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.11Sn 4+, 0.08Ti 4+, then by 150g ReO 3at 1100 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and ReO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 5.0 * 10 -4pa, the working gas flow of argon gas is 25sccm, and pressure is adjusted to 2.0Pa, and underlayer temperature is 500 ℃, and sputtering power is 100W.Priority sputter TITO target and ReO 3target, deposits respectively the film of 150nm and 2nm film, obtains In 2o 3: 0.11Sn 4+, 0.08Ti 4+-ReO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 12 Ω/, surface work function tester records surface work function 6.1eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 92% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 8
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.89:0.08:0.03 mixes through even according to mole number, and at 1350 ℃, sintering diameter into is 35mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.08Sn 4+, 0.03Ti 4+, then by 150g ReO 3at 1100 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and ReO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 45mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10 -3pa, the working gas flow of argon gas is 10sccm, and pressure is adjusted to 0.2Pa, and underlayer temperature is 250 ℃, and sputtering power is 150W.Priority sputter TITO target and ReO 3target, deposits respectively the film of 50nm and 5nm film, obtains In 2o 3: 0.08Sn 4+, 0.03Ti 4+-ReO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 53 Ω/, surface work function tester records surface work function 5.9eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 90% at visible ray 470～790nm wavelength region average transmittances.
Embodiment 9
Selecting purity is 99.9% powder, by In 2o 3, SnO 2and TiO 2powder is that 0.8:0.06:0.14 mixes through even according to mole number, and at 1350 ℃, sintering diameter into is 35mm, the TITO ceramic target that thickness is 2mm, and the chemical formula of TITO ceramic target is: In 2o 3: 0.06Sn 4+, 0.14Ti 4+, then by 150g ReO 3at 800 ℃, sintering diameter into is 50mm, the target that thickness is 2mm, then by TITO target and ReO 3target packs in vacuum cavity.Then, successively use acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as to 95mm.With mechanical pump and molecular pump, the vacuum tightness of cavity is extracted into 1.0 * 10 -5pa, the working gas flow of argon gas is 35sccm, and pressure is adjusted to 4.0Pa, and underlayer temperature is 750 ℃, and sputtering power is 30W.Priority sputter TITO target and ReO 3target, deposits respectively the film of 300nm and 0.5nm film, obtains In 2o 3: 0.06Sn 4+, 0.14Ti 4+-ReO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 20 Ω/, surface work function tester records surface work function 5.8eV.
The test of use ultraviolet-visible pectrophotometer, test wavelength is 300～900nm.Film has reached 91% at visible ray 470～790nm wavelength region average transmittances.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a conductive film, is characterized in that, comprises stacked TITO layer and MeO 3layer, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
2. conductive film according to claim 1, is characterized in that, the thickness of described TITO layer is 50nm～300nm, described MeO 3the thickness of layer is 0.5nm～5nm.
3. a preparation method for conductive film, is characterized in that, comprises the following steps:
By TITO target and MeO 3target and substrate pack the vacuum cavity of magnetic-controlled sputtering coating equipment into, and wherein, the vacuum tightness of vacuum cavity is 1.0 * 10 -3pa～1.0 * 10 -5pa, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide;
At described substrate surface sputter TITO layer, described in sputter, the processing parameter of TITO layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, and underlayer temperature is 250 ℃～750 ℃;
At described TITO layer surface sputter MeO 3layer, MeO described in sputter 3the processing parameter of layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃; And
Peel off described substrate, obtain described conductive film.
4. the preparation method of conductive film according to claim 3, is characterized in that, described TITO target is obtained by following steps: by In 2o 3, SnO 2and TiO 2powder is that 0.65～0.92:0.05～0.2:0.03～0.15 mixes according to mol ratio, and the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
5. the preparation method of conductive film according to claim 3, is characterized in that, described MeO 3target is obtained by following steps: by molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide powder sintering at 800 ℃～1200 ℃ is made target.
6. a substrate for organic electroluminescence device, is characterized in that, comprises the substrate stacking gradually, stacked TITO layer and MeO 3layer, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
7. the substrate of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described TITO layer is 50nm～300nm, described MeO 3the thickness of layer is 0.5nm～5nm.
8. a preparation method for the substrate of organic electroluminescence device, is characterized in that, comprises the following steps:
By TITO target and MeO 3target and substrate pack the vacuum cavity of magnetic-controlled sputtering coating equipment into, and wherein, the vacuum tightness of vacuum cavity is 1.0 * 10 -3pa～1.0 * 10 -5pa, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide;
At described substrate surface sputter TITO layer, described in sputter, the processing parameter of TITO layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, the flow of working gas is 10sccm～35sccm, and underlayer temperature is 250 ℃～750 ℃;
At described TITO layer surface sputter MeO 3layer, MeO described in sputter 3the processing parameter of layer is: base target spacing is 45mm～95mm, and sputtering power is 30W～150W, magnetron sputtering operating pressure 0.2Pa～4Pa, and the flow of working gas is 10sccm～35sccm, underlayer temperature is 250 ℃～750 ℃.
9. the preparation method of the substrate of organic electroluminescence device according to claim 8, is characterized in that, described TITO target is obtained by following steps: by In 2o 3, SnO 2and TiO 2powder is that 0.65～0.92:0.05～0.2:0.03～0.15 mixes according to mol ratio, and the powder mixing sintering at 900 ℃～1300 ℃ is made to target;
Described MeO 3target is obtained by following steps: by molybdenum oxide, powder in Tungsten oxide 99.999 and rhenium oxide a kind of at 800 ℃～1200 ℃ sintering make target.
10. an organic electroluminescence device, comprises the anode, luminescent layer and the negative electrode that stack gradually, it is characterized in that, described anode comprises stacked TITO layer and MeO 3layer, wherein TITO layer is titanium tin codoped Indium sesquioxide, chemical formula is In 2o 3: xSn 4+, yTi 4+, x is that 0.05～0.2, y is 0.03～0.15, MeO 3layer is molybdenum oxide, a kind of in Tungsten oxide 99.999 and rhenium oxide.
CN201310194876.XA 2013-05-22 2013-05-22 Conductive film, preparing method thereof and applications of the conductive film Pending CN104178740A (en)

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Application publication date: 20141203