CN103243297A - Halogen-doped AZO conductive film and preparation method thereof - Google Patents
Halogen-doped AZO conductive film and preparation method thereof Download PDFInfo
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- CN103243297A CN103243297A CN2012100301847A CN201210030184A CN103243297A CN 103243297 A CN103243297 A CN 103243297A CN 2012100301847 A CN2012100301847 A CN 2012100301847A CN 201210030184 A CN201210030184 A CN 201210030184A CN 103243297 A CN103243297 A CN 103243297A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 59
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 55
- 150000002367 halogens Chemical class 0.000 claims description 55
- 239000000919 ceramic Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 38
- 239000011787 zinc oxide Substances 0.000 description 38
- 239000011521 glass Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229960000935 dehydrated alcohol Drugs 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000009832 plasma treatment Methods 0.000 description 9
- 238000004506 ultrasonic cleaning Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Abstract
The invention belongs to the field of conductive films and discloses a halogen-doped AZO conductive film and a preparation method thereof. The general chemical formula of the conductive film is ZnO1-xRx:yAl<3+>; wherein R is a doping element, R is one selected from the group consisting of F, Cl or Br, x is in the range of 0.05-0.2, and y is in the range of 0.01-0.1. The present invention uses a magnetron sputtering apparatus to prepare the halogen-doped AZO conductive film. The halogen-doped AZO conductive film has a visible light transmittance of 85-90% in the wavelength range of 450-790 nm, a square resistance range of 20-100 omega/square, and a surface work function of 5.3-5.9 eV.
Description
Technical field
The present invention relates to the conductive film field, relate in particular to a kind of halogen doping AZO conducting film and preparation method thereof.
Background technology
The transparent conductive film electrode is the basic component of organic electroluminescence device (OLED), and the quality of its performance directly affects the luminous efficiency of entire device.Wherein, tin indium oxide (ITO) is the most frequently used transparent conductive film material, has higher visible light transmittance rate and low resistivity.And aluminum zinc oxide (AZO) material is to study the most popular ITO equivalent material, the raw material cheapness, and asepsis environment-protecting has excellent photoelectric performance.At present, the electroconductibility of AZO and light transmission progress into the commercial stage near ITO.But in the OLED device, use as anode, also require the transparent conductive film anode to have higher surface work function.And the work function of AZO generally has only 4.2～4.5eV, through also reaching 4.7～5.1eV after the processing such as UV optical radiation or ozone, (be typically 5.7～6.3eV) and also have bigger energy level difference distance with the HOMO energy level of general organic luminous layer, cause the increase of current carrier injection barrier, hindering the raising of luminous efficiency.。
Summary of the invention
One of problem to be solved by this invention is to provide a kind of preparation method that can improve the halogen doping AZO conducting film of luminous efficiency.
A kind of preparation method of halogen doping AZO conducting film, its preparation technology is as follows:
S1, take by weighing Al
2O
3, ZnO and ZnR
2Powder after evenly mixing, 900～1300 ℃ of following sintering processes, makes ceramic target; Wherein, R is selected from F, Cl or Br; Al
2O
3, ZnO and ZnR
2The mole number of powder is respectively 0.005～0.05mol, 0.8～0.95mol and 0.05～0.2mol;
S2 the ceramic target that obtains among the step S1 and substrate are packed in the vacuum cavity of magnetron sputtering film device, and vacuum cavity is set to vacuum state;
S3, adjustment magnetron sputtering plating processing parameter is: basic target spacing is 45～95mm, and magnetron sputtering operating pressure 0.2～4Pa, the flow of argon gas working gas are 10～35sccm, and underlayer temperature is 250 ℃～750 ℃, and sputtering power is 30～150W; Then film processed obtains described halogen doping AZO conducting film; The chemical general formula of this halogen doping AZO conducting film is ZnO
1-xR
x: yAl
3+Wherein, R is doped element, and the span of x is that the span of 0.05～0.2, y is 0.01～0.1.
Among the above-mentioned halogen doping AZO conducting film preparation method:
Among the step S1, preferred, Al
2O
3, ZnO and ZnR
2The mole number of powder is respectively 0.3mol, 0.9mol and 0.1mol, and correspondingly, among the step S3, the span of x is that the span of 0.1, y is 0.06; The sintering temperature of described target preparation is 1250 ℃.
Among the step S3, preferred, described basic target spacing is 60mm; Described magnetron sputtering operating pressure is 2.0Pa; The flow of described argon gas working gas is 25sccm; Described underlayer temperature is 500 ℃; Described sputtering power is 100W.
Two of problem to be solved by this invention is to provide a kind of halogen doping AZO conducting film that adopts above-mentioned preparation method to make, and it is ZnO that this halogen doping AZO conducting film comprises the film general formula
1-xR
x: yAl
3+Wherein, R is doped element, and R is selected from F, Cl or Br, and the span of x is that the span of 0.05～0.2, y is 0.01～0.1; Preferably, the span of x is that the span of 0.1, y is 0.06;
Above-mentioned halogen doping AZO conducting film, its square resistance scope are that 20～100 Ω/ and surface work function are 5.3～5.9eV.
Halogen doping AZO conducting film of the present invention, at 450～790nm wavelength region visible light transmissivity 85%～90%, square resistance scope 20～100 Ω/, surface work function 5.3～5.9Ev, use this film as the anode of OLED, its luminous efficiency is significantly improved.
The present invention adopts magnetron sputtering equipment to prepare halogen doping AZO conducting film, and its preparation technology is simple, be easy to control.
Description of drawings
Fig. 1 is preparation technology's schema of halogen doping AZO conducting film among the embodiment;
The transmitted spectrum of the halogen doping AZO conducting film sample that Fig. 2 makes for embodiment 1.
Embodiment
A kind of halogen doping AZO conducting film that provides in the present embodiment, the chemical general formula of this halogen doping AZO conducting film is ZnO
1-xR
x: yAl
3+Wherein, R is doped element, and R is selected from F, Cl or Br, and the span of x is that the span of 0.05～0.2, y is 0.01～0.1; Preferably, the span of x is that the span of 0.1, y is 0.06; Square resistance scope 20～100 Ω/ and the surface work function of described halogen doping AZO conducting film are 5.3～5.9eV; This AZO conducting film is that to add AZO with ZnO:Al3 be the electrically conducting transparent base material, halogen (as, F, Cl or Br) be doped to the work function modifying element.
The above-mentioned halogen doping AZO conducting film preparation method who provides in the present embodiment, as shown in Figure 1, its preparation technology is as follows:
The preparation of S1, ceramic target: take by weighing Al
2O
3, ZnO and ZnR
2Powder, after evenly mixing, sintering under 900～1300 ℃ (preferred 1250 ℃), naturally cooling obtains the ceramic target sample, and it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter; Wherein, R is selected from F, Cl or Br; Al
2O
3, ZnO and ZnR
2The mole number of powder is respectively 0.005～0.05mol, 0.8～0.95mol and 0.05～0.2mol;
S2, with the vacuum cavity of the ceramic target among the step S1 and substrate (as, glass) the magnetron sputtering film device of packing into, vacuum cavity is arranged to vacuum state, the vacuum tightness of vacuum state is to adopt mechanical pump and molecular pump that cavity is evacuated to 1.0 * 10
-3Pa～1.0 * 10
-5Pa, preferred vacuum tightness is 5.0 * 10
-4Pa;
S3, adjustment magnetron sputtering plating processing parameter are: basic target spacing is 45～95mm, preferred 60mm; Underlayer temperature is 250 ℃～750 ℃, preferred 500 ℃; Gas flow 10～the 35sccm of argon gas working gas, preferred 25sccm; Magnetron sputtering operating pressure 0.2～4Pa, preferred 2.0Pa; Sputtering power is 30～150W, excellent 100W; After the processing parameter adjustment finished, then film processed made described halogen doping AZO conducting film; The chemical general formula of this halogen doping AZO conducting film is ZnO
1-xR
x: yAl
3+Wherein, R is doped element, and the span of x is that the span of 0.05～0.2, y is 0.01～0.1.
Among above-mentioned preparation method's the step S1, preferred, Al
2O
3, ZnO and ZnR
2The mole number of powder is respectively 0.3mol, 0.9mol and 0.1mol, and correspondingly, among the step S3, the span of x is that the span of 0.1, y is 0.06.
Halogen doping AZO conducting film, at 450～790nm wavelength region visible light transmissivity 85%～90%, square resistance scope 20～100 Ω/, surface work function 5.3～5.9eV, use this film as the anode of OLED, its luminous efficiency is significantly improved.
Adopt magnetron sputtering equipment to prepare halogen doping AZO conducting film, its preparation technology is simple, be easy to control.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Substrate among following each embodiment all adopts glass.
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnF
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.03mol, ZnO is 0.9mol, ZnF
2Mole number be 0.1mol), after evenly mixing, at 1250 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 60mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 5.0 * 10
-4Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 25sccm; The magnetron sputtering operating pressure is 2.0Pa; Underlayer temperature is 500 ℃, and sputtering power is 100W; Then film processed, obtaining structural formula is ZnO
0.9F
0.1: 0.06Al
3+Halogen doping AZO conducting film; Piece resistance range 25 Ω/, the surface work function of this halogen doping AZO conducting film are 5.8eV.
The transmitted spectrum of the halogen doping AZO conducting film sample that Fig. 2 makes for embodiment 1; The test of use ultraviolet-visible pectrophotometer, the test wavelength is 250～800nm; As can be known, film has good through performance at visible-range among Fig. 2, is outstanding transparent conductive film material.
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnF
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.005mol, ZnO is 0.8mol, ZnF
2Mole number be 0.2mol), after evenly mixing, at 900 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 45mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 1.0 * 10
-3Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 10sccm; The magnetron sputtering operating pressure is 0.2Pa; Underlayer temperature is 250 ℃, and sputtering power is 150W; Then film processed, obtaining structural formula is ZnO
0.8F
0.2: 0.01Al
3+Halogen doping AZO conducting film; Piece resistance range 95 Ω/, the surface work function of this halogen doping AZO conducting film are 5.9eV.
Embodiment 3
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnF
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.05mol, ZnO is 0.95mol, ZnF
2Mole number be 0.05mol), after evenly mixing, at 1300 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 95mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 1.0 * 10
-5Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 35sccm; The magnetron sputtering operating pressure is 4.0Pa; Underlayer temperature is 750 ℃, and sputtering power is 30W; Then film processed, obtaining structural formula is ZnO
0.95F
0.05: 0.1Al
3+Halogen doping AZO conducting film; Piece resistance range 22 Ω/, the surface work function of this halogen doping AZO conducting film are 5.5eV.
Embodiment 4
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnCl
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.03mol, ZnO is 0.9mol, ZnCl
2Mole number be 0.1mol), after evenly mixing, at 1250 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 60mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 5.0 * 10
-4Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 25sccm; The magnetron sputtering operating pressure is 2.0Pa; Underlayer temperature is 500 ℃, and sputtering power is 100W; Then film processed, obtaining structural formula is ZnO
0.9Cl
0.1: 0.06Al
3+Halogen doping AZO conducting film; Piece resistance range 50 Ω/, the surface work function of this halogen doping AZO conducting film are 5.9eV.
Embodiment 5
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnCl
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.05mol, ZnO is 0.8mol, ZnCl
2Mole number be 0.2mol), after evenly mixing, at 900 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 45mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 1.0 * 10
-3Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 10sccm; The magnetron sputtering operating pressure is 0.2Pa; Underlayer temperature is 250 ℃, and sputtering power is 150W; Then film processed, obtaining structural formula is ZnO
0.8Cl
0.2: 0.1Al
3+Halogen doping AZO conducting film; Piece resistance range 30 Ω/, the surface work function of this halogen doping AZO conducting film are 5.4eV.
Embodiment 6
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnCl
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.005mol, ZnO is 0.95mol, ZnF
2Mole number be 0.05mol), after evenly mixing, at 1300 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 95mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 1.0 * 10
-5Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 35sccm; The magnetron sputtering operating pressure is 4.0Pa; Underlayer temperature is 750 ℃, and sputtering power is 30W; Then film processed, obtaining structural formula is ZnO
0.95Cl
0.05: 0.01Al
3+Halogen doping AZO conducting film; Piece resistance range 25 Ω/, the surface work function of this halogen doping AZO conducting film are 5.7eV.
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnBr
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.03mol, ZnO is 0.9mol, ZnBr
2Mole number be 0.1mol), after evenly mixing, at 1250 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 60mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 5.0 * 10
-4Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 25sccm; The magnetron sputtering operating pressure is 2.0Pa; Underlayer temperature is 500 ℃, and sputtering power is 100W; Then film processed, obtaining structural formula is ZnO
0.9Br
0.1: 0.06Al
3+Halogen doping AZO conducting film; Piece resistance range 40 Ω/, the surface work function of this halogen doping AZO conducting film are 5.6eV.
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnBr
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.005mol, ZnO is 0.8mol, ZnBr
2Mole number be 0.2mol), after evenly mixing, at 900 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 45mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 1.0 * 10
-3Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 10sccm; The magnetron sputtering operating pressure is 0.2Pa; Underlayer temperature is 250 ℃, and sputtering power is 150W; Then film processed, obtaining structural formula is ZnO
0.8Br
0.2: 0.01Al
3+Halogen doping AZO conducting film; Piece resistance range 100 Ω/, the surface work function of this halogen doping AZO conducting film are 5.3eV.
Embodiment 9
1, select for use purity to be respectively 99.99% Al
2O
3, ZnO and ZnBr
2Powder (wherein, Al
2O
3Mole number be that the mole number of 0.05mol, ZnO is 0.95mol, ZnBr
2Mole number be 0.05mol), after evenly mixing, at 1300 ℃ of following sintering, naturally cooling obtains the ceramic target sample, it is that 50mm, thickness are the ceramic target of 2mm that the ceramic target sample is cut into diameter;
2, ceramic target is packed in the vacuum cavity of magnetron sputtering film device;
3, carry out oxygen plasma treatment successively with acetone, dehydrated alcohol and deionized water ultrasonic cleaning glass substrate, and to it, put into the vacuum cavity of magnetron sputtering film device after finishing; Wherein, the basic target spacing of target and glass is set at 95mm;
4, with mechanical pump and molecular pump the vacuum tightness of the vacuum cavity of magnetron sputtering film device is extracted into 1.0 * 10
-5Pa;
5, adjust the magnetron sputtering plating processing parameter: argon gas working gas flow is 35sccm; The magnetron sputtering operating pressure is 4.0Pa; Underlayer temperature is 750 ℃, and sputtering power is 30W; Then film processed, obtaining structural formula is ZnO
0.95Br
0.05: 0.1Al
3+Halogen doping AZO conducting film; Piece resistance range 70 Ω/, the surface work function of this halogen doping AZO conducting film are 5.5eV.
Should be understood that above-mentioned statement at preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. the preparation method of a halogen doping AZO conducting film is characterized in that, this preparation method's step is as follows:
S1, take by weighing Al
2O
3, ZnO and Znr
2Powder after evenly mixing, 900～1300 ℃ of following sintering processes, makes ceramic target; Wherein, R is selected from F, Cl or Br; Al
2O
3, ZnO and ZnR
2The mole number of powder is respectively 0.005～0.05mol, 0.8～0.95mol and 0.05～0.2mol;
S2, with among the step S1 ceramic target and substrate are packed in the vacuum cavity of magnetron sputtering film device, and vacuum cavity is arranged to vacuum state;
S3, adjustment magnetron sputtering plating processing parameter is: basic target spacing is 45～95mm, and magnetron sputtering operating pressure 0.2～4Pa, the flow of argon gas working gas are 10～35sccm, and underlayer temperature is 250 ℃～750 ℃, and sputtering power is 30～150W; Then film processed obtains described halogen doping AZO conducting film; The chemical general formula of this halogen doping AZO conducting film is ZnO
1-xR
x: yAl
3+Wherein, R is doped element, and the span of x is that the span of 0.05～0.2, y is 0.01～0.1.
2. the preparation method of halogen doping AZO conducting film according to claim 1 is characterized in that, among the described step S1, and Al
2O
3, ZnO and ZnR
2The mole number of powder is respectively 0.3mol, 0.9mol and 0.1mol, and correspondingly, among the step S3, the span of x is that the span of 0.1, y is 0.06.
3. the preparation method of halogen doping AZO conducting film according to claim 1 and 2 is characterized in that, among the described step S1, the sintering temperature of described target preparation is 1250 ℃.
4. the preparation method of halogen doping AZO conducting film according to claim 1 is characterized in that, among the described step S2, the vacuum tightness of described vacuum state is 1.0 * 10
-3Pa～1.0 * 10
-5Pa.
5. the preparation method of halogen doping AZO conducting film according to claim 4 is characterized in that, the vacuum tightness of described vacuum state is 5.0 * 10
-4Pa.
6. the preparation method of halogen doping AZO conducting film according to claim 1 is characterized in that, among the described step S3, described basic target spacing is 60mm; Described magnetron sputtering operating pressure is 2.0Pa; The flow of described argon gas working gas is 25sccm; Described underlayer temperature is 500 ℃; Described sputtering power is 100W.
7. a halogen doping AZO conducting film that adopts the described preparation method of claim 1 to make is characterized in that, it is ZnO that this halogen doping AZO conducting film comprises the film general formula
1-xR
x: yAl
3+Wherein, R is doped element, and R is selected from F, Cl or Br, and the span of x is that the span of 0.05～0.2, y is 0.01～0.1.
8. halogen doping AZO conducting film according to claim 7 is characterized in that, the span of x is that the span of 0.1, y is 0.06.
9. halogen doping AZO conducting film according to claim 7 is characterized in that, the square resistance scope of described halogen doping AZO conducting film is that 20～100 Ω/ and surface work function are 5.3～5.9eV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100301847A CN103243297A (en) | 2012-02-10 | 2012-02-10 | Halogen-doped AZO conductive film and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2192644A (en) * | 1986-06-04 | 1988-01-20 | Ricoh Kk | Transparent conductive film and the production thereof |
| CN101575697A (en) * | 2009-06-09 | 2009-11-11 | 北京科技大学 | ZnO-based transparent conductive film co-doped with Al-F and preparation method thereof |
| US20100193351A1 (en) * | 2009-02-05 | 2010-08-05 | THE INDUSTRY & ACADEMIC COOPERATION IN CHUNGNAM NATIONAL UNIVERSITY (IAC) of Republic of Korea | Method for preparing transparent conducting film coated with azo/ag/azo multilayer thin film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2192644A (en) * | 1986-06-04 | 1988-01-20 | Ricoh Kk | Transparent conductive film and the production thereof |
| US20100193351A1 (en) * | 2009-02-05 | 2010-08-05 | THE INDUSTRY & ACADEMIC COOPERATION IN CHUNGNAM NATIONAL UNIVERSITY (IAC) of Republic of Korea | Method for preparing transparent conducting film coated with azo/ag/azo multilayer thin film |
| CN101575697A (en) * | 2009-06-09 | 2009-11-11 | 北京科技大学 | ZnO-based transparent conductive film co-doped with Al-F and preparation method thereof |
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