CN104060223A - Conductive thin film, preparation method and application thereof - Google Patents

Conductive thin film, preparation method and application thereof Download PDF

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Publication number
CN104060223A
CN104060223A CN201310092616.1A CN201310092616A CN104060223A CN 104060223 A CN104060223 A CN 104060223A CN 201310092616 A CN201310092616 A CN 201310092616A CN 104060223 A CN104060223 A CN 104060223A
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layer
tio
target
substrate
conductive film
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周明杰
王平
陈吉星
张振华
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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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Publication of CN104060223A publication Critical patent/CN104060223A/en
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Abstract

The invention relates to a conductive thin film, which comprises a stacked TiO2-xFx layer and a MO3 layer, wherein, x is 0.1-0.6, MO3 is at least one of tungsten oxide, molybdena and rhenium oxide. According to the invention, the above conductive thin film is characterized in that high work function MO3 is deposited on the surface of the TiO2-xFx layer to prepare the double layer conductive thin film, the conductive thin film can maintain good conductive performance of the TiO2-xFx layer, and the work function of the conductive thin film can be greatly increased. The invention also provides a preparation method and an application of the conductive thin film.

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 TiO 2-xf xlayer and MO 3layer, wherein, x is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
Described TiO 2-xf xthe thickness of layer is 50nm～300nm, described MO 3the thickness of layer is 0.5nm～5nm.
A preparation method for conductive film, comprises the following steps:
By TiO 2-xf xtarget, MO 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 -5pa～1.0 * 10 -3pa, described TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide;
At described substrate surface sputter TiO 2-xf xlayer, TiO described in sputter 2-xf xthe 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 ℃;
At described TiO 2-xf xthe surperficial sputter MO of layer 3layer, MO 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 TiO 2-xf xtarget is obtained by following steps: by TiO 2and TiF 4powder mixes, TiF 4molecular fraction be 2.6%～17.6%, the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
A substrate for organic electroluminescence device, comprises the substrate, the TiO that stack gradually 2-xf xlayer and MO 3layer, wherein, x is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
Described TiO 2-xf xthe thickness of layer is 50nm～300nm, described MO 3the thickness of layer is 0.5nm～5nm.
A preparation method for the substrate of organic electroluminescence device, comprises the following steps:
By TiO 2-xf xtarget, MO 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 -5pa～1.0 * 10 -3pa, described TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide;
At described substrate surface sputter TiO 2-xf xlayer, TiO described in sputter 2-xf xthe 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 ℃;
At described TiO 2-xf xthe surperficial sputter MO of layer 3layer, MO 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 TiO 2-xf xtarget is obtained by following steps: by TiO 2and TiF 4powder mixes, TiF 4molecular fraction be 2.6%～17.6%, the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
An organic electroluminescence device, comprises the anode, luminescent layer and the negative electrode that stack gradually, and described anode comprises stacked TiO 2-xf xlayer and MO 3layer, wherein, x is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
Described TiO 2-xf xthe thickness of layer is 50nm～300nm, described MO 3the thickness of layer is 0.5nm～5nm.
Above-mentioned conductive film passes through at TiO 2-xf xthe MO of the high work content of surface deposition of layer 3the double-deck conductive film of layer preparation, can keep TiO 2-xf xthe good conductivity of layer, makes again the work function of conductive film obtain significant raising, and conductive film is at 300～900nm wavelength region visible light transmissivity 85%～90%, square resistance scope 15～150 Ω/, surface work function 5.6～6.1eV; The preparation method of above-mentioned conductive film, only uses magnetic-controlled sputtering coating equipment to get final product continuous production TiO 2-xf xlayer and be deposited on TiO 2-xf xthe MO on layer surface 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 TiO 2-xf xlayer 10 and MO 3layer 30, wherein, TiO 2-xf xin x be 0.1～0.6, MO 3for Tungsten oxide 99.999 (WO 3), molybdenum oxide (MoO 3) and rhenium oxide (ReO 3) at least one.
TiO 2-xf xthe thickness of layer 10 is 50nm～300nm, is preferably 150nm.
MO 3the thickness of layer 30 is 0.5nm～5nm, is preferably 2nm.
Above-mentioned conductive film 100 passes through at TiO 2-xf xthe MO of the high work content of surface deposition of layer 10 3the double-deck conductive film of layer preparation, can keep TiO 2-xf xthe good conductivity of 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 15～150 Ω/, surface work function 5.60～6.1eV.
The preparation method of above-mentioned conductive film 100, comprises the following steps:
S110, by TiO 2-xf xtarget, MO 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 -5pa～1.0 * 10 -3pa, TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
In present embodiment, described TiO 2-xf xtarget is obtained by following steps:: by TiO 2and TiF 4powder mixes, TiF 4molecular fraction be 2.6%～17.6%, the powder mixing sintering at 900 ℃～1300 ℃ is made to target.Preferably, TiF 4molecular fraction be 12.5%, the powder mixing sintering at 1250 ℃ is made TiO 2-xf xtarget.
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 TiO 2-xf xlayer 10, sputter TiO 2-xf xthe processing parameter of layer 10 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 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The TiO forming 2-xf xthe thickness of layer 10 is 50nm～300nm, is preferably 150nm.
Step S130, at TiO 2-xf xlayer 10 surperficial sputter MO 3layer 30, sputter MO 3the processing parameter of layer 30 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 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The MO forming 3the thickness of layer 30 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 TiO 2-xf xlayer 10 and be deposited on TiO 2-xf xthe MO on layer 10 surface 3layer 30, technique is comparatively simple.
Refer to Fig. 2, the substrate 200 of the organic electroluminescence device of an embodiment, comprises stacked substrate 201, TiO 2-xf xlayer 202 and MO 3layer 203, wherein, TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
Substrate 201 is glass substrate.The thickness of substrate 201 is 0.1mm～3.0mm, is preferably 1mm.
TiO 2-xf xthe thickness of layer 202 is 50nm～300nm, is preferably 150nm.
MO 3the thickness of layer 203 is 0.5nm～5nm, is preferably 2nm.
The substrate 200 of above-mentioned organic electroluminescence device is passed through at TiO 2-xf xthe surface deposition MO of layer 202 3the double-deck conductive film of layer preparation, can keep TiO 2-xf xthe good conductivity of 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 15～150 Ω/, surface work function 5.06～6.1eV.
The preparation method of the substrate 200 of above-mentioned organic electroluminescence device, comprises the following steps:
S210, by TiO 2-xf xtarget, MO 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 -5pa～1.0 * 10 -3pa, TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
In present embodiment, TiO 2-xf xtarget is obtained by following steps: by TiO 2and TiF 4powder mixes, TiF 4molecular fraction be 2.6%～17.6%, the powder mixing sintering at 900 ℃～1300 ℃ is made to target.Preferably, TiF 4molecular fraction be 12.5%, the powder mixing sintering at 1250 ℃ is made TiO 2-xf xtarget.
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 TiO 2-xf xlayer 202, sputter TiO 2-xf xthe processing parameter of layer 202 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 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The TiO forming 2-xf xthe thickness of layer 202 is 50nm～300nm, is preferably 150nm.
Step S203, at TiO 2-xf xlayer 202 surperficial sputter MO 3layer 30, sputter MO 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 ℃.
Preferably, base target spacing is 60mm, and sputtering power is 100W, magnetron sputtering operating pressure 2Pa, and working gas is argon gas, and the flow of working gas is 25sccm, and underlayer temperature is 500 ℃.
The MO 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 on substrate 201, to prepare TiO continuously 2-xf xlayer 202 and be deposited on TiO 2-xf xthe MO on layer 202 surface 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 TiO 2-xf xlayer 10 and MO 3layer 30, wherein, TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.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.
TiO 2-xf xthe thickness of layer is 50nm～300nm, is preferably 150nm.MO 3the thickness of layer 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 5.6～the 6.1eV 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, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 12.5%, and at 1250 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.6f 0.4ceramic target, the MoO of 150g 3at 1100 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 60mm.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 sputtered with Ti O 1.6f 0.4and MoO 3target, deposit respectively 150 and the film of 2nm film, obtain TiO 1.6f 0.4-MoO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 30 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 90% at visible ray 470～790nm wavelength region average transmittances as seen from Figure 4.
Selecting purity is 99.9% powder TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 12.5%, and at 1250 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.6f 0.4ceramic target, the MoO of 150g 3at 1100 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 60mm.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 sputtered with Ti O 1.6f 0.4and MoO 3target, deposit respectively 150 and the film of 2nm film, obtain TiO 1.6f 0.4-MoO 3double-deck transparent conductive film, TiO 1.6f 0.4-MoO 3transparent 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 5.0V luminous, curve 2 is voltage and brightness relationship curve, and high-high brightness is 118cd/m 2, show that device has the good characteristics of luminescence.
Embodiment 2
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 2.6%, and at 900 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.9f 0.1ceramic target, the MoO of 150g 3at 800 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 sputtered with Ti O 1.9f 0.1and MoO 3target, deposit respectively 50 and the film of 5nm film, obtain TiO 1.9f 0.1-MoO 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 5.9eV.
Embodiment 3
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 17.6%, and at 1300 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.4f 0.6ceramic target, the MoO of 150g 3at 800 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 ℃.Sputtering power is 30W.Priority sputtered with Ti O 1.4f 0.6and MoO 3target, deposit respectively 300 and the film of 0.5nm film, obtain TiO 1.4f 0.6-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 5.7eV.
Embodiment 4
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 12.5%, and at 1250 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.6f 0.4ceramic target, the WO of 150g 3at 1100 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 60mm.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 sputtered with Ti O 1.6f 0.4and WO 3target, deposit respectively 150 and the film of 2nm film, obtain TiO 1.6f 0.4-WO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 30 Ω/, surface work function tester records surface work function 6.1eV.
Embodiment 5
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 2.6%, and at 900 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.9f 0.1ceramic target, the WO of 198g 3at 800 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 sputtered with Ti O 1.9f 0.1and WO 3target, deposit respectively 50 and the film of 5nm film, obtain TiO 1.9f 0.1-WO 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 5.9eV.
Embodiment 6
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 17.6%, and at 1300 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.4f 0.6ceramic target, the WO of 150g 3at 800 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 ℃., sputtering power is 30W.Priority sputtered with Ti O 1.4f 0.6and WO 3target, deposit respectively 300 and the film of 0.5nm film, obtain TiO 1.4f 0.6-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 5.7eV.
Embodiment 7
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 12.5%, and at 1250 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.6f 0.4ceramic target, the ReO of 150g 3at 1100 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 60mm.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 sputtered with Ti O 1.6f 0.4and ReO 3target, deposit respectively 150 and the film of 2nm film, obtain TiO 1.6f 0.4-ReO 3double-deck transparent conductive film.
Test result: adopt four point probe resistance meter to record square resistance 30 Ω/, surface work function tester records surface work function 6.1eV.
Embodiment 8
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 2.6%, and at 900 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.9f 0.1ceramic target, the ReO of 198g 3at 800 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 sputtered with Ti O 1.9f 0.1and ReO 3target, deposit respectively 50 and the film of 5nm film, obtain TiO 1.9f 0.1reO 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 5.9eV.
Embodiment 9
Selecting purity is 99.9% powder, TiF 4and TiO 2after even mixing, TiF 4the molecular fraction that accounts for mixture is 17.6%, and at 1300 ℃, sintering diameter into is 50mm, the TiO that thickness is 2mm 1.4f 0.6ceramic target, the ReO of 150g 3at 800 ℃, sintering diameter into is 50mm, the ceramic target that thickness is 2mm, and two targets are packed 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 ℃., sputtering power is 30W.Priority sputtered with Ti O 1.4f 0.6and ReO 3target, deposit respectively 300 and the film of 0.5nm film, obtain TiO 1.4f 0.6-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 5.7eV.
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 TiO 2-xf xlayer and MO 3layer, wherein, x is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
2. conductive film according to claim 1, is characterized in that, described TiO 2-xf xthe thickness of layer is 50nm～300nm, described MO 3the thickness of layer is 0.5nm～5nm.
3. a preparation method for conductive film, is characterized in that, comprises the following steps:
By TiO 2-xf xtarget, MO 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 -5pa～1.0 * 10 -3pa, described TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide;
At described substrate surface sputter TiO 2-xf xlayer, TiO described in sputter 2-xf xthe 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 ℃;
At described TiO 2-xf xthe surperficial sputter MO of layer 3layer, MO 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 TiO 2-xf xtarget is obtained by following steps: by TiO 2and TiF 4powder mixes, TiF 4molecular fraction be 2.6%～17.6%, the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
5. a substrate for organic electroluminescence device, is characterized in that, comprises the substrate, the TiO that stack gradually 2-xf xlayer and MO 3layer, wherein, x is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
6. the substrate of organic electroluminescence device according to claim 5, is characterized in that, described TiO 2-xf xthe thickness of layer is 50nm～300nm, described MO 3the thickness of layer is 0.5nm～5nm.
7. a preparation method for the substrate of organic electroluminescence device, is characterized in that, comprises the following steps:
By TiO 2-xf xtarget, MO 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 -5pa～1.0 * 10 -3pa, described TiO 2-xf xx in target is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide;
At described substrate surface sputter TiO 2-xf xlayer, TiO described in sputter 2-xf xthe 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 ℃;
At described TiO 2-xf xthe surperficial sputter MO of layer 3layer, MO 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 ℃.
8. the preparation method of the substrate of organic electroluminescence device according to claim 7, is characterized in that, described TiO 2-xf xtarget is obtained by following steps: by TiO 2and TiF 4powder mixes, TiF 4molecular fraction be 2.6%～17.6%, the powder mixing sintering at 900 ℃～1300 ℃ is made to target.
9. 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 TiO 2-xf xlayer and MO 3layer, wherein, x is 0.1～0.6, MO 3for at least one in Tungsten oxide 99.999, molybdenum oxide and rhenium oxide.
10. organic electroluminescence device according to claim 9, is characterized in that, described TiO 2-xf xthe thickness of layer is 50nm～300nm, described MO 3the thickness of layer is 0.5nm～5nm.
CN201310092616.1A 2013-03-21 2013-03-21 Conductive thin film, preparation method and application thereof Pending CN104060223A (en)

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CN112359336A (en) * 2020-10-27 2021-02-12 金堆城钼业股份有限公司 Preparation method of high-purity and high-density molybdenum trioxide target
CN114737159A (en) * 2022-04-14 2022-07-12 金堆城钼业股份有限公司 Molybdenum trioxide sputtering target, preparation method and target mold

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104178727A (en) * 2013-05-22 2014-12-03 海洋王照明科技股份有限公司 Conductive film and preparation method and application thereof
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CN112359336B (en) * 2020-10-27 2023-05-26 金堆城钼业股份有限公司 Preparation method of high-purity and high-density molybdenum trioxide target material
CN114737159A (en) * 2022-04-14 2022-07-12 金堆城钼业股份有限公司 Molybdenum trioxide sputtering target, preparation method and target mold
CN114737159B (en) * 2022-04-14 2024-04-30 金堆城钼业股份有限公司 Molybdenum trioxide sputtering target material, preparation method and target material mold

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Application publication date: 20140924