CN104210167A - Conductive film, preparation method and applications thereof - Google Patents

Conductive film, preparation method and applications thereof Download PDF

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Publication number
CN104210167A
CN104210167A CN201310206446.5A CN201310206446A CN104210167A CN 104210167 A CN104210167 A CN 104210167A CN 201310206446 A CN201310206446 A CN 201310206446A CN 104210167 A CN104210167 A CN 104210167A
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layer
rzo
cro
target
zinc oxide
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周明杰
陈吉星
王平
冯小明
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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 comprises a RZO layer and a CrO3 layer, wherein the RZO layer and the CrO3 layer are laminated together, and the RZO layer is made of aluminum doped zinc oxide, gallium doped zinc oxide, or indium doped zinc oxide. The dual-layer conductive film is prepared by depositing a CrO3 layer with a high work function on the surface of the RZO layer, thus the good conductive performance of the RZO layer is maintained, and the work function of the conductive film is prominently improved. The invention further provides a preparation method and applications of the conductive film.

Description

Conductive film, its preparation method and application thereof
Technical field
The present invention relates to photoelectric semiconductor material, particularly relate to conductive film, its preparation method, the substrate using the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device.
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 that transparent conductive film anode has higher surface work function.And the work function of the zinc oxide of aluminium, gallium and indium doping generally only has 4.3eV, also 4.5 ~ 5.1eV can only be reached after the process such as UV light radiation or ozone, larger energy level difference distance is also had 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, be necessary, for the lower problem of conductive film work function, to provide the higher conductive film of a kind of work function, its preparation method, the substrate using the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device.
A kind of conductive film, comprises stacked RZO layer and CrO 3layer, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
The thickness of described RZO layer is 50nm ~ 300nm, described CrO 3the thickness of layer is 0.5nm ~ 5nm.
A preparation method for conductive film, comprises the following steps:
By RZO target and CrO 3target and substrate load the vacuum cavity of magnetic-controlled sputtering coating equipment, and wherein, the vacuum of vacuum cavity is 1.0 × 10 -3pa ~ 1.0 × 10 -5pa, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide;
At described substrate surface sputter RZO layer, described in sputter, the technological parameter of RZO 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 DEG C ~ 750 DEG C;
At described RZO layer surface sputter CrO 3layer, CrO described in sputter 3the technological 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, and underlayer temperature is 250 DEG C ~ 750 DEG C; And
Peel off described substrate, obtain described conductive film.
Described RZO target is obtained by following steps: by ZnO and R 2o 3powder mixes and obtains mixture, wherein, and R 2o 3the mass percent that powder accounts for mixture is 0.5% ~ 10%, R 2o 3for at least one in alchlor, three gallium oxides and three indium oxides, the powder mixed is sintered at 900 DEG C ~ 1300 DEG C and makes target.
Described CrO 3target is obtained by following steps: by CrO 3powder sinters and makes target at 800 DEG C ~ 1200 DEG C.
A substrate for organic electroluminescence device, comprises the substrate stacked gradually, stacked RZO layer and CrO 3layer, wherein, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
The thickness of described RZO layer is 50nm ~ 300nm, described CrO 3the thickness of layer is 0.5nm ~ 5nm.
A preparation method for the substrate of organic electroluminescence device, comprises the following steps:
By RZO target and CrO 3target and substrate load the vacuum cavity of magnetic-controlled sputtering coating equipment, and wherein, the vacuum of vacuum cavity is 1.0 × 10 -3pa ~ 1.0 × 10 -5pa;
At described substrate surface sputter RZO layer, described in sputter, the technological parameter of RZO 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 DEG C ~ 750 DEG C;
At described RZO layer surface sputter CrO 3layer, CrO described in sputter 3the technological 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, and underlayer temperature is 250 DEG C ~ 750 DEG C.
Described RZO target is obtained by following steps: by ZnO and R 2o 3powder mixes and obtains mixture, wherein, and R 2o 3the mass percent that powder accounts for mixture is 0.5% ~ 10%, R 2o 3for at least one in alchlor, three gallium oxides and three indium oxides, the powder mixed is sintered at 900 DEG C ~ 1300 DEG C and makes target;
Described CrO 3target is obtained by following steps: by CrO 3powder sinters and makes target at 800 DEG C ~ 1200 DEG C.
A kind of organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, described anode comprises stacked RZO layer and CrO 3layer, wherein RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
Above-mentioned conductive film is by the CrO in the surface deposition high work content of RZO layer 3layer prepares bilayer conductive film, the good electric conductivity of RZO layer can be kept, the work function of conductive film is made again to obtain significant raising, conductive film is at 300 ~ 900nm wave-length coverage visible light transmissivity 85% ~ 90%, square resistance scope 10 ~ 95 Ω/, surface work function 5.3 ~ 6.2eV; The preparation method of above-mentioned conductive film, only uses magnetic-controlled sputtering coating equipment to get final product continuous production RZO layer and CrO 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, reduces the injection barrier of carrier, can improve luminous efficiency significantly.
Accompanying drawing explanation
Fig. 1 is the structural representation of the conductive film of an embodiment;
Fig. 2 is the structural representation of the 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 conductive film prepared by embodiment 1;
Fig. 5 is the voltage of device embodiments and electric current and brightness relationship figure.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments to conductive film, its preparation method, use the substrate of the organic electroluminescence device of this conductive film, its preparation method and organic electroluminescence device to illustrate further.
Refer to Fig. 1, the conductive film 100 of an embodiment comprises stacked RZO layer 10 and CrO 3layer 20.
The thickness of described RZO layer 10 is 50nm ~ 300nm, is preferably 150nm,
Described CrO 3the thickness of layer 20 is 0.5nm ~ 5nm, is preferably 2nm.
Above-mentioned conductive film 100 is by the CrO in the surface deposition high work content of RZO layer 10 3layer 20 prepares multilayer conductive film, the good electric conductivity of RZO layer 10 can be kept, the work function of conductive film 100 is made again to obtain significant raising, conductive film 100 is at 300 ~ 900nm wave-length coverage visible light transmissivity 85% ~ 90%, square resistance scope 10 ~ 95 Ω/, surface work function 5.3 ~ 6.2eV.
The preparation method of above-mentioned conductive film 100, comprises the following steps:
S110, by RZO target and CrO 3target and substrate load the vacuum cavity of magnetic-controlled sputtering coating equipment, and wherein, the vacuum of vacuum cavity is 1.0 × 10 -3pa ~ 1.0 × 10 -5pa, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
The target of RZO described in present embodiment is obtained by following steps: by ZnO and R 2o 3powder mixes and obtains mixture, wherein, and R 2o 3the mass percent that powder accounts for mixture is 0.5% ~ 10%, R 2o 3for at least one in alchlor, three gallium oxides and three indium oxides, the powder mixed is sintered at 900 DEG C ~ 1300 DEG C and makes target.
Substrate is glass substrate.Preferably, substrate uses acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning before use.
In present embodiment, the vacuum of vacuum cavity is preferably 5 × 10 -4pa.
Step S120, at substrate surface sputter RZO layer 10, the technological parameter of sputter RZO 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 DEG C ~ 750 DEG C.
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 DEG C.
The thickness of the RZO layer 10 formed is 50nm ~ 300nm, is preferably 150nm.
Step S130, at the surperficial sputter CrO of RZO layer 10 3layer 20, sputter CrO 3the technological 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, and underlayer temperature is 250 DEG C ~ 750 DEG C.
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 DEG C.
The CrO formed 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 RZO layer 10 and CrO 3layer 20, technique is comparatively simple.
Refer to Fig. 2, the substrate 200 of the organic electroluminescence device of an embodiment, comprise stacked substrate 201, RZO layer 202 and CrO 3layer 203.
Substrate 201 is glass substrate.The thickness of substrate 201 is 0.1mm ~ 3.0mm, is preferably 1mm.
The thickness of described RZO layer 202 is 50nm ~ 300nm, is preferably 150nm,
Described CrO 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 CrO at RZO layer 202 3layer 203 prepares bilayer conductive film, the good electric conductivity of RZO layer 202 can be kept, the work function of the substrate 200 of organic electroluminescence device is made again to obtain significant raising, the substrate 200 of organic electroluminescence device is at 300 ~ 900nm wave-length coverage visible light transmissivity 85% ~ 90%, square resistance scope 10 ~ 95 Ω/, surface work function 5.3 ~ 6.2eV.
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, comprises the following steps:
S210, by RZO target and CrO 3target and substrate 201 load the vacuum cavity of magnetic-controlled sputtering coating equipment, and wherein, the vacuum of vacuum cavity is 1.0 × 10 -3pa ~ 1.0 × 10 -5pa, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
In present embodiment, described RZO target is obtained by following steps: by ZnO and R 2o 3powder mixes and obtains mixture, wherein, and R 2o 3the mass percent that powder accounts for mixture is 0.5% ~ 10%, R 2o 3for at least one in alchlor, three gallium oxides and three indium oxides, the powder mixed is sintered at 900 DEG C ~ 1300 DEG C and makes target.
Substrate is glass substrate.Preferably, substrate uses acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning before use.
In present embodiment, the vacuum of vacuum cavity is preferably 5 × 10 -4pa.
Step S220, at substrate surface sputter RZO layer 202, the technological parameter of sputter RZO 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 DEG C ~ 750 DEG C.
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 DEG C.
The thickness of the RZO layer 202 formed is 50nm ~ 300nm, is preferably 150nm.
Step S203, at the surperficial sputter CrO of RZO layer 202 3layer 203, sputter CrO 3the technological 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, and underlayer temperature is 250 DEG C ~ 750 DEG C.
The CrO formed 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 prepare RZO layer 202 and CrO on the substrate 201 continuously 3layer 203, technique is comparatively simple.
Refer to Fig. 3, the organic electroluminescence device 300 of an embodiment comprises the substrate 301, anode 302, luminescent layer 303 and the negative electrode 304 that stack gradually.Anode 302 is made up of conductive film 100, comprises stacked RZO layer 10 and CrO 3layer 20.Substrate 301 is glass substrate, is appreciated that the difference according to organic electroluminescence device 300 concrete structure, and substrate 301 can omit.The material of luminescent layer 303 is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (AND), two (2-methyl-oxine)-(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), two (4,6-difluorophenyl pyridinato-N, C 2) pyridinecarboxylic closes iridium (FIrpic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) 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 alloy.
The thickness of described RZO layer 10 is 50nm ~ 300nm, is preferably 150nm.
Described CrO 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 5.3 ~ the 6.2eV of conductive film, and gap is less between the HOMO energy level (being typically 5.7 ~ 6.3eV) of general organic luminous layer, reduce the injection barrier of carrier, can luminous efficiency be improved.
Be specific embodiment below.
Embodiment 1
Select purity be 99.9% powder, by 194g ZnO powder and 6g Al 2o 3powder is through Homogeneous phase mixing, and at 1250 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (AZO) ceramic target of the aluminium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by AZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 100W.Successively sputtering AZO target and CrO 3target, deposits the film of 150nm and 2nm film respectively, obtains AZO-CrO 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.
Refer to Fig. 4, Figure 4 shows that the transmitted spectrum of the transparent conductive film obtained, use ultraviolet-uisible spectrophotometer test, test wavelength is 300 ~ 900nm.Film reaches 90% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity as seen from Figure 4.
Select AZO-CrO 3double-deck transparent conductive film as the anode of organic semiconductor device, at evaporation luminescent layer Alq above 3, and negative electrode adopts Ag, prepares organic electroluminescence device.
Refer to Fig. 5, Fig. 5 is the voltage of organic electroluminescence device prepared by above-mentioned device embodiments and electric current and brightness relationship figure, curve 1 is voltage and current density relation curve in figure 5, device luminescence from 5.5V can be found out, curve 2 is voltage and brightness relationship curve, and high-high brightness is 124cd/m 2, show that device has the good characteristics of luminescence.
Embodiment 2
Select purity be 99.9% powder, by 180g ZnO powder and 20g Al 2o 3powder is through Homogeneous phase mixing, and at 900 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (AZO) ceramic target of the aluminium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by AZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 150W.Successively sputtering AZO target and CrO 3target, deposits the film of 50nm and 5nm film respectively, obtains AZO-CrO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 95 Ω/, surface work function tester records surface work function 5.7eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 90% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 3
Select purity be 99.9% powder, by 199g ZnO powder and 1g Al 2o 3powder is through Homogeneous phase mixing, and at 1300 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (AZO) ceramic target of the aluminium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by AZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 30W.Successively sputtering AZO target and CrO 3target, deposits the film of 300nm and 0.5nm film respectively, obtains AZO-CrO 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 5.3eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 88% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 4
Select purity be 99.9% powder, by 194g ZnO powder and 6g Ga 2o 3powder is through Homogeneous phase mixing, and at 1250 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (GZO) ceramic target of the gallium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by GZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 100W.Successively sputtering GZO target and CrO 3target, deposits the film of 150nm and 2nm film respectively, obtains GZO-CrO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 26 Ω/, surface work function tester records surface work function 6.2eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 91% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 5
Select purity be 99.9% powder, by 180g ZnO powder and 20g Ga 2o 3powder is through Homogeneous phase mixing, and at 900 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (GZO) ceramic target of the gallium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by GZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 150W.Successively sputtering GZO target and CrO 3target, deposits the film of 50nm and 5nm film respectively, obtains GZO-CrO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 70 Ω/, surface work function tester records surface work function 5.7eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 89% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 6
Select purity be 99.9% powder, by 199g ZnO powder and 1g Ga 2o 3powder is through Homogeneous phase mixing, and at 1300 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (GZO) ceramic target of the gallium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by GZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 30W.Successively sputtering GZO target and CrO 3target, deposits the film of 300nm and 0.5nm film respectively, obtains GZO-CrO 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.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 91% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 7
Select purity be 99.9% powder, by 194g ZnO powder and 6g In 2o 3powder is through Homogeneous phase mixing, and at 1250 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (IZO) ceramic target of the indium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by IZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 100W.Successively sputtering IZO target and CrO 3target, deposits the film of 150nm and 2nm film respectively, obtains IZO-CrO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 25 Ω/, surface work function tester records surface work function 6.0eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 89% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 8
Select purity be 99.9% powder, by 180g ZnO powder and 20g In 2o 3powder is through Homogeneous phase mixing, and at 900 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (IZO) ceramic target of the indium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by IZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 150W.Successively sputtering IZO target and CrO 3target, deposits the film of 50nm and 5nm film respectively, obtains IZO CrO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 90 Ω/, surface work function tester records surface work function 5.6eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 91% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
Embodiment 9
Select purity be 99.9% powder, by 199g ZnO powder and 1g In 2o 3powder is through Homogeneous phase mixing, and at 1300 DEG C, sinter diameter into is 50mm, and thickness is zinc oxide (IZO) ceramic target of the indium doping of 2mm, then by 200g CrO 3at 1100 DEG C, sinter diameter into is 50mm, and thickness is the target of 2mm, then by IZO target and CrO 3target loads in vacuum cavity.Then, successively use acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning glass substrate, put into vacuum cavity.The distance of target and substrate is set as 45mm.With mechanical pump and molecular pump, the vacuum 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 DEG C, and sputtering power is 30W.Successively sputtering IZO target and CrO 3target, deposits the film of 300nm and 0.5nm film respectively, obtains IZO-CrO 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 5.9eV.
Use ultraviolet-uisible spectrophotometer is tested, and test wavelength is 300 ~ 900nm.Film reaches 91% at visible ray 470 ~ 790nm wave-length coverage mean transmissivity.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 RZO layer and CrO 3layer, wherein, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
2. conductive film according to claim 1, is characterized in that, the thickness of described RZO layer is 50nm ~ 300nm, described CrO 3the thickness of layer is 0.5nm ~ 5nm.
3. a preparation method for conductive film, is characterized in that, comprises the following steps:
By RZO target and CrO 3target and substrate load the vacuum cavity of magnetic-controlled sputtering coating equipment, and wherein, the vacuum of vacuum cavity is 1.0 × 10 -3pa ~ 1.0 × 10 -5pa, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide;
At described substrate surface sputter RZO layer, described in sputter, the technological parameter of RZO 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 DEG C ~ 750 DEG C;
At described RZO layer surface sputter CrO 3layer, CrO described in sputter 3the technological 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, and underlayer temperature is 250 DEG C ~ 750 DEG C; 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 RZO target is obtained by following steps: by ZnO and R 2o 3powder mixes and obtains mixture, wherein, and R 2o 3the mass percent that powder accounts for mixture is 0.5% ~ 10%, R 2o 3for at least one in alchlor, three gallium oxides and three indium oxides, the powder mixed is sintered at 900 DEG C ~ 1300 DEG C and makes target.
5. the preparation method of conductive film according to claim 3, is characterized in that, described CrO 3target is obtained by following steps: by CrO 3powder sinters and makes target at 800 DEG C ~ 1200 DEG C.
6. a substrate for organic electroluminescence device, is characterized in that, comprises the substrate stacked gradually, stacked RZO layer and CrO 3layer, wherein RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
7. the substrate of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described RZO layer is 50nm ~ 300nm, described CrO 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 RZO target and CrO 3target and substrate load the vacuum cavity of magnetic-controlled sputtering coating equipment, and wherein, the vacuum of vacuum cavity is 1.0 × 10 -3pa ~ 1.0 × 10 -5pa, described RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide;
At described substrate surface sputter RZO layer, described in sputter, the technological parameter of RZO 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 DEG C ~ 750 DEG C;
At described RZO layer surface sputter CrO 3layer, CrO described in sputter 3the technological 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, and underlayer temperature is 250 DEG C ~ 750 DEG C.
9. the preparation method of the substrate of organic electroluminescence device according to claim 8, is characterized in that, described RZO target is obtained by following steps: by ZnO and R 2o 3powder mixes and obtains mixture, wherein, and R 2o 3the mass percent that powder accounts for mixture is 0.5% ~ 10%, R 2o 3for at least one in alchlor, three gallium oxides and three indium oxides, the powder mixed is sintered at 900 DEG C ~ 1300 DEG C and makes target;
Described CrO 3target is obtained by following steps: by CrO 3powder sinters and makes target at 800 DEG C ~ 1200 DEG C.
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 RZO layer and CrO 3layer, wherein RZO layer is the zinc oxide of aluminium doping, the one in Ga-doped zinc oxide and indium doping zinc oxide.
CN201310206446.5A 2013-05-29 2013-05-29 Conductive film, preparation method and applications thereof Pending CN104210167A (en)

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CN109830545A (en) * 2019-02-14 2019-05-31 中国科学院半导体研究所 A kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery
WO2023106314A1 (en) * 2021-12-10 2023-06-15 Ｊｘ金属株式会社 Multilayer body having function of transparent conductive film

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CN102881357A (en) * 2012-09-06 2013-01-16 广州新视界光电科技有限公司 Compound transparent electroconductive film

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CN101262019A (en) * 2008-03-26 2008-09-10 北京师范大学 Photoelectrical chemical solar battery for silicon nano line
US20120122657A1 (en) * 2010-11-12 2012-05-17 Ramot At Tel-Aviv University Ltd. Rhenium nanostructures
CN102881357A (en) * 2012-09-06 2013-01-16 广州新视界光电科技有限公司 Compound transparent electroconductive film

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CN109830545A (en) * 2019-02-14 2019-05-31 中国科学院半导体研究所 A kind of aluminum-doped zinc oxide films surface modifying material, preparation method and battery
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Application publication date: 20141217