CN101403099A - Method of manufacturing metal doping ZnO film - Google Patents
Method of manufacturing metal doping ZnO film Download PDFInfo
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- CN101403099A CN101403099A CNA2008102008017A CN200810200801A CN101403099A CN 101403099 A CN101403099 A CN 101403099A CN A2008102008017 A CNA2008102008017 A CN A2008102008017A CN 200810200801 A CN200810200801 A CN 200810200801A CN 101403099 A CN101403099 A CN 101403099A
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Abstract
The invention relates to the field of semiconductor materials, in particular to a method for preparing a metal film doped with ZnO. The method is characterized by comprising the following steps: a substrate is arranged in a magnetron sputtering room after being cleaned and a reaction room thereof is pumped to vacuum with high cleanliness; high-purity metal strips are taken as adulterants and high-purity Zn are taken as materials, and metal strips are fixed on a Zn target according to a plurality of proportions; pure Ar gas and pure oxygen are taken as sputtering gas and reaction gas to be input into the vacuum reaction sputtering room by the control of a flowmeter for sputtering growth; and annealing treatment is carried out in vacuum environment after growth. The invention has the following beneficial effects: the control of metal doping content is realized, and the effect of oxidation on the metal target during the reaction sputtering is effectively reduced by the pattern of radio frequency sputtering during the reaction, thus leading the sputtering to keep continuous and stable; and finally, by being combined with the corresponding vacuum annealing technology, the optical and electrical properties of the MZO film are optimized. The preparation method simplifies technical processes, reduces the whole development procedure, shortens the period and saves the cost.
Description
[technical field]
The present invention relates to technical field of semiconductor, specifically a kind of preparation method of metal doping ZnO film.
[background technology]
All need to use transparent conductive electrode in optics such as solar cell and flat-panel monitor, this is the main application fields of transparent conductive film.Transparent conductive film need have following performance: 1. the transmissivity height of pair visible light (its wavelength contains 380 to 780nm), and average transmittance is greater than 80%; 2. good conductivity, resistivity is 10
-2Below the Ω cm.Wherein in the transparent band gap width big (Eg is greater than 3eV) that just means material of visible light wave range, this has just determined that the current carrier in its conduction band or the valence band is few.And on the other hand, often current carrier is many for the high metallic substance of specific conductivity, but because of its conduction band and valence band overlapping, so no energy gap, so extremely low in the transparency of visible light section metal.Have only and to satisfy simultaneously that visible luminous energy sees through and the material of these two kinds of conditions of high conductivity could use as transparency electrode.
In present transparency electrode, using the widest is the tin-doped indium oxide ito thin film.But it can have influence on the performance of device because of existing the indium diffusion, especially can cause the decay of thin-film solar cells performance.People reduce this diffusion by increasing the blocking layer, improve device performance, and this makes technology more complicated.In addition, because indium belongs to rare metal, so use this transparency electrode cost higher.
If the transparency electrode (M:ZnO is called for short MZO) that adopts Zn that the common earth's crust is rich in and M (metal) metallic element to make, this has the advantage on the price.Usually the resistance of ZnO is higher, be applied on transparent conductive film, and other metallic elements (as aluminium, gallium, indium, silver, lithium etc.) that then must mix improve its conductive characteristic, also can increase its high-temperature stability simultaneously.Therefore the metal of suitable doping is provided, can makes the electroconductibility of zinc oxide become good.Adjust through this class technology, just can make MZO reach the performance that high printing opacity that ITO has and high electricity are led.The optimizing process of its transmitance and resistance value can be by regulating the ratio control of Zn and metallic element.Research and development for MZO thin-film material and its process technique, this has caused that everybody payes attention to widely, though at present on the characteristic of MZO film still with some gap of ito thin film, but if can seek out the applicable product of MZO film, not only can reduce manufacturing cost on the one hand, more can reduce dependence ito thin film.Also have the preparation technology of present MZO film also very complicated, be not easy control and adjusting, whole research and development operation is many, and the cycle is long, and cost is also than higher.
[summary of the invention]
Purpose of the present invention is exactly will solve above-mentioned deficiency and the preparation method of a kind of metal doping ZnO film of providing, is applicable to the technical study of the transparent conductive film of solar cell and flat-panel monitor, is presented as simple to operate, practical and effectively.
Design a kind of preparation method of metal doping ZnO film for achieving the above object, it is characterized in that step is as follows:
(1) substrate is put into the magnetic control sputtering device chamber after cleaning, and its reaction chamber extracts into the high-cleanness, high vacuum;
(2) adopting the high purity metal bar is that hotchpotch and high purity Zn are raw material, and metal strip is fixed on the Zn target; The area ratio that used metal strip accounts for the Zn target can draw through measurements and calculations, in conjunction with sputter productive rates different under both the same terms, can determine metal doping amount in the ZnO film thus;
(3) be sputter gas and reactant gases with pure Ar gas and purity oxygen, through under meter control input vacuum reaction sputtering chamber;
(4) under 0.1-3 pascal pressure, room temperature condition, it is ZnO thin film doped to carry out the sputter growing metal;
(5) metal doping ZnO film after the growth, anneal under vacuum environment can obtain the sample that optical property and electric property are optimized afterwards.
Described metal strip be in Al, In, Ga, Ag or the Li metal one or several.
The purity of metal is more than 99.99%, and the purity of Zn is more than 99.95%, and oxygen argon control ratio is 1: 1, and the oxygen argon flow amount is 10-40sccm.
Fixed form between metal strip and the circular Zn target adopts the radial mode in the symmetric center of circle to fix.
The vacuum tightness of described anneal is that 0.01-20Pa, temperature are 200～600 degrees centigrade, annealing time 30～120min.
Used substrate is silicon or quartz or glass or organic transparent substrates.
Reaction chamber vacuum tightness extracts to being higher than 2 * 10
-4Pa.
The metal-doped amount of obtained metal doping ZnO film is 0.01-30%.
Beneficial effect of the present invention: adopt the method for reaction rf magnetron sputtering to prepare the MZO film, and by the fixing method of number of metal bar on the Zn target, realized control to metal-doped amount, adopt the pattern of radio-frequency sputtering can effectively reduce metallic target oxidated influence in reactive sputtering in the reaction, make sputter keep continual and steady, engage corresponding vacuum annealing process at last, optimized the optics and the electric property of MZO film.This method has been simplified the complex process that common adjusting doping metals content prepares the ZnO powder target, reduced whole research and development operation, shortened the cycle, saved cost, the control and the adjusting of metal-doped amount have been realized, the optics and the electric property of film are optimized, thereby have very strong practical value.
[description of drawings]
Fig. 1 (a) is a synoptic diagram of fixing 2 Al bars on the Zn target of the present invention;
Fig. 1 (b) is a synoptic diagram of fixing 4 Al bars on the Zn target of the present invention;
Fig. 1 (c) is a synoptic diagram of fixing 2 Ag bars on the Zn target of the present invention;
Fig. 1 (d) is a synoptic diagram of fixing 2 Al and 2 Ag on the Zn target of the present invention;
Fig. 2 is the typical shape appearance figure of the ZnO film of the Al of mixing metal of the present invention;
Fig. 3 is the EDX power spectrum of the ZnO film of the Al of mixing metal of the present invention;
Fig. 4 is the optical transmission collection of illustrative plates of the Al of mixing metal ZnO film of the present invention.
Among Fig. 1,1 is the Zn target, and 2 is the Al bar, and 3 is the Ag bar.
[embodiment]
Embodiment one: preparation Al metal doping ZnO film the steps include:
(1) substrate cleans: get glass substrate, put on the specimen holder of rf magnetron sputtering chamber after it is cleaned, substrate is desired the deposit placed face down, effectively avoids impurity staining substrate.
(2) extract high vacuum: sputtering chamber vacuum tightness is evacuated to 2 * 10
-4Pa is to obtain the high-cleanness, high vacuum.
(3) regulate metal and doping thereof: get 2 blocks of Al metal strips and be fixed on the Zn target, the fixed form of metal strip is the radial mode in the symmetric center of circle.The area ratio that used metal strip accounts for the Zn target can draw through measurements and calculations, in conjunction with sputter productive rates different under both the same terms, can determine metal doping amount in the ZnO film thus, and the metal-doped amount of metal doping ZnO film is controlled at about 4-10%.
(4) regulate sputtering atmosphere: with the O of purity 99.99%
2With 99.99% Ar as reaction and sputter gas, through under meter control input vacuum reaction sputtering chamber; Its oxygen argon ratio control is 1: 1, and the oxygen argon flow amount is 25sccm.
(5) rf magnetron sputtering growth: use the radio-frequency sputtering power of 120W, under 0.4 pascal's pressure, room temperature condition, earlier to the pre-sputter 3min of target, reach the purpose of cleaning target, it is ZnO thin film doped to carry out sputter growth Al then.
(6) vacuum annealing is handled: after the thin film deposition, through excess temperature 400 degree vacuum annealings 30 minutes.
Embodiment two: (1), (2), (4) (5) (6) remain unchanged in the whole thin film preparation process of embodiment one, only change (3) and regulate Al metal strip number, get 4 blocks of Al metal strips and are fixed on the Zn target, and fixed form is the radial mode in the symmetric center of circle.Can obtain the film of different metal doping like this.
Embodiment three: (1), (2), (4) (5) (6) remain unchanged in the whole thin film preparation process of example one, only change (3) and change metal strip, get 2 blocks of Ag metal strips and are fixed on the Zn target, and fixed form is the radial mode in the symmetric center of circle.Can obtain the metal-doped ZnO film of Ag like this.
Embodiment four: (1), (2), (4) (5) (6) remain unchanged in the whole thin film preparation process of example one, only change (3) and change metal strip and quantity thereof, get 2 Al bars and 2 Ag bars are fixed on the Zn target, fixed form is the radial mode in the symmetric center of circle.Can obtain the ZnO film of different al, the metal-doped amount of Ag like this.
Fig. 2 is a shape appearance figure of mixing the ZnO film of Al metal, and its surfacing is fine and close, even.
Fig. 4 is the optical transmission collection of illustrative plates of mixing Al metal ZnO film (film up to more than 90%, presents ZnO intensive ultraviolet absorption edge at 390nm wavelength place in the transmissivity of visible region).(EDX detects Al content and accounts for 5% the film of curve 1 corresponding 2 Al bars preparation, and it is 2 * 10 that the Hall effect side gets film conductivity among the figure
-3Ω cm).
(EDX detects Al content and accounts for 10% the film of curve 2 corresponding 4 Al bars preparations, and it is 5 * 10 that the Hall effect side gets film conductivity
-3Ω cm).
Above-mentioned enforcement will help understands the present invention, but does not limit content of the present invention.
Claims (8)
1. the preparation method of a metal doping ZnO film is characterized in that step is as follows:
(1) substrate is put into the magnetic control sputtering device chamber after cleaning, and its reaction chamber extracts into the high-cleanness, high vacuum;
(2) adopting the high purity metal bar is that hotchpotch and high purity Zn are raw material, and metal strip is fixed on the Zn target; The metal doping amount can be determined by area ratio and both productive rates different under identical sputtering condition of the shared Zn target of metal strip in the ZnO film.
(3) be sputter gas and reactant gases with pure Ar gas and purity oxygen, through under meter control input vacuum reaction sputtering chamber;
(4) under 0.1-3 pascal pressure, room temperature condition, it is ZnO thin film doped to carry out the sputter growing metal;
(5) metal doping ZnO film after the growth, anneal under vacuum environment can obtain sample afterwards.
2. the preparation method of a kind of metal doping ZnO film as claimed in claim 1, it is characterized in that described metal strip be in Al, In, Ga, Ag or the Li metal one or several.
3. the preparation method of a kind of metal doping ZnO film as claimed in claim 1 or 2, the purity that it is characterized in that metal is more than 99.99%, and the purity of Zn is more than 99.95%, and oxygen argon control ratio is 1: 1, and the oxygen argon flow amount is 10-40sccm.
4. the preparation method of a kind of metal doping ZnO film as claimed in claim 3 is characterized in that the fixed form between metal strip and the circular Zn target adopts the radial mode in the symmetric center of circle to fix.
5. the preparation method of a kind of metal doping ZnO film as claimed in claim 4, the vacuum tightness that it is characterized in that described anneal is that 0.01-20Pa, temperature are 200～600 degrees centigrade, annealing time 30～120min.
6. the preparation method of a kind of metal doping ZnO film as claimed in claim 1 is characterized in that used substrate is silicon or quartz or glass or organic transparent substrates.
7. the preparation method of a kind of metal doping ZnO film as claimed in claim 1 is characterized in that reaction chamber vacuum tightness extracts to being higher than 2 * 10
-4Pa.
8. the preparation method of a kind of metal doping ZnO film as claimed in claim 1, the metal-doped amount that it is characterized in that obtained metal doping ZnO film is 0.01-30%.
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| CNA2008102008017A CN101403099A (en) | 2008-10-06 | 2008-10-06 | Method of manufacturing metal doping ZnO film |
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| CNA2008102008017A CN101403099A (en) | 2008-10-06 | 2008-10-06 | Method of manufacturing metal doping ZnO film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392237A (en) * | 2011-10-26 | 2012-03-28 | 东北大学 | Preparation method for Ag-Li co-doped zinc oxide film |
| CN103022473A (en) * | 2013-01-10 | 2013-04-03 | 西南大学 | Method for preparing gamma-Fe2O3 positive-pole material for lithium-ion battery |
| CN104060232A (en) * | 2014-06-20 | 2014-09-24 | 江阴恩特莱特镀膜科技有限公司 | Method for preparing hafnium-doped zinc oxide transparent conductive thin film |
| CN104078531A (en) * | 2014-06-30 | 2014-10-01 | 景德镇陶瓷学院 | Method for manufacturing ZnO:Li transparent conducting thin film with wide spectral domain light transmission characteristic and directly-growing meteor crater fabric surface |
| CN105032434A (en) * | 2015-06-01 | 2015-11-11 | 东南大学 | Preparation method of ferromagnetic ZnO visible light catalyst |
| CN110699640A (en) * | 2019-09-25 | 2020-01-17 | 安徽省含山县锦华氧化锌厂 | Preparation method of nano zinc oxide film with enhanced conductivity |
| CN110735109A (en) * | 2019-09-25 | 2020-01-31 | 安徽省含山县锦华氧化锌厂 | nanometer zinc oxide with indium element adulterant |
-
2008
- 2008-10-06 CN CNA2008102008017A patent/CN101403099A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392237A (en) * | 2011-10-26 | 2012-03-28 | 东北大学 | Preparation method for Ag-Li co-doped zinc oxide film |
| CN103022473A (en) * | 2013-01-10 | 2013-04-03 | 西南大学 | Method for preparing gamma-Fe2O3 positive-pole material for lithium-ion battery |
| CN104060232A (en) * | 2014-06-20 | 2014-09-24 | 江阴恩特莱特镀膜科技有限公司 | Method for preparing hafnium-doped zinc oxide transparent conductive thin film |
| CN104078531A (en) * | 2014-06-30 | 2014-10-01 | 景德镇陶瓷学院 | Method for manufacturing ZnO:Li transparent conducting thin film with wide spectral domain light transmission characteristic and directly-growing meteor crater fabric surface |
| CN104078531B (en) * | 2014-06-30 | 2016-04-13 | 景德镇陶瓷学院 | A kind of preparation method with the ZnO:Li transparent conductive film of wide range territory light transmission characteristic and crater matte direct growth |
| CN105032434A (en) * | 2015-06-01 | 2015-11-11 | 东南大学 | Preparation method of ferromagnetic ZnO visible light catalyst |
| CN110699640A (en) * | 2019-09-25 | 2020-01-17 | 安徽省含山县锦华氧化锌厂 | Preparation method of nano zinc oxide film with enhanced conductivity |
| CN110735109A (en) * | 2019-09-25 | 2020-01-31 | 安徽省含山县锦华氧化锌厂 | nanometer zinc oxide with indium element adulterant |
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