CN102691038B - Anticorrosion ZnO film and preparation method thereof - Google Patents
Anticorrosion ZnO film and preparation method thereof Download PDFInfo
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- CN102691038B CN102691038B CN201210160698.4A CN201210160698A CN102691038B CN 102691038 B CN102691038 B CN 102691038B CN 201210160698 A CN201210160698 A CN 201210160698A CN 102691038 B CN102691038 B CN 102691038B
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Abstract
The invention discloses an anticorrosion ZnO film and a preparation method thereof and belongs to the technical field of semiconductor materials and devices. The anticorrosion ZnO film is prepared by a radio-frequency magnetron co-sputtering method, targets include an Sn target, an intrinsic ZnO target and an AZO target (Al-doped ZnO target), and the Sn-doped ZnO film and the Al-Sn co-doped ZnO film are prepared. After the intrinsic ZnO film is doped with Sn, anticorrosion of the intrinsic ZnO film is improved; and after the Al-doped ZnO film is doped with Sn (the Al-Sn co-doped ZnO film), anticorrosion of the Al-Sn co-doped ZnO film is also improved, and the Al-Sn co-doped ZnO film is better in anticorrosion than the Sn-doped ZnO film. The method is simple in preparation process and low in deposition temperature, used materials and the process are free of pollution to the environment, and the prepared ZnO film has the anticorrosion and transparent electric conduction functions, so that working stability of the ZnO film materials and devices in severe environments can be improved.
Description
Technical field
What the present invention relates to is a kind of electrically conducting transparent etching resistant film, relates in particular to ZnO film of the ZnO thin film doped and Al-Sn codoped of the corrosion resistant Sn of a kind of electrically conducting transparent and preparation method thereof.
Background technology
Transparent conductive film is the special photoelectric information functional material of a class, not only possesses good electrology characteristic, and has high light transmittance in visible light wave range scope, and infrared band scope has highly reflective, and ultraviolet band has good absorptivity.Exactly because transparent conductive film has excellent photoelectric characteristic, makes this class material have good application prospect in fields such as solar cell, liquid-crystal display, thin film transistor, ultraviolet detector, antistatic coating, cruise missile window and modern opportunities of combat.In transparent conductive film, ZnO film is cheap for manufacturing cost owing to having, nontoxic, be easy to the advantages such as doping and photoelectric properties excellence, being used widely of the various components and parts of this thin-film material and preparation, and according to the surrounding medium difference of real work, such as Different climate environment (industry, industrial, ocean, coastal waters), hygrothermal environment and some other rugged environment etc., therefore need to improve erosion resistance and the long term reliability of this class thin-film material in corrosive environment medium.
Summary of the invention
technical problem:the present invention is directed to the deficiencies in the prior art and limitation, provide a kind of magnetron sputtering technique that utilizes to prepare the ZnO electrically conducting transparent etching resistant film that can work in the environment that contains NaCl.
technical scheme:for achieving the above object, the present invention is achieved through the following technical solutions:
A kind of corrosion-resistant ZnO film, comprises ZnO, also contains Sn, the resistivity 6.99 × 10 that described Sn is ZnO thin film doped in prepared film
-2Ω cm ~ 1.06 × 10
-1Ω cm, the average transmittances of 400 ~ 900nm wave band is 69% ~ 82%, polarization resistance 6.20 × 10
4Ω ~ 1.20 × 10
6Ω.
In prepared film, also contain Al, the resistivity 1.49 × 10 of described Al, Sn codope ZnO film
-3Ω cm ~ 5.10 × 10
-3Ω cm, the average transmittances of 400 ~ 900nm wave band is 82% ~ 89%, polarization resistance 3.96 × 10
5Ω ~ 1.40 × 10
6Ω.
A preparation method who prepares described ZnO film, comprises the steps:
(1) using Sn and ZnO material as target, target is arranged in the chamber of magnetron sputtering equipment;
(2) clean substrate to be coated, the contamination of removing substrate surface, then dries up;
(3) substrate after drying up is put into rf magnetron sputtering chamber, the vacuum tightness being evacuated in chamber is less than 0.1Pa, and heated substrate to 100 DEG C ~ 200 DEG C;
(4) in chamber, pass into rare gas element, and substrate rotation is set;
(5), by magnetron sputtering mode, on Sn and two targets of ZnO, add radio-frequency voltage: Sn target radio-frequency voltage 0～16V, ZnO target radio-frequency voltage 0～32V, then deposits by the mode of two target co-sputterings the ZnO film that Sn adulterates.
A preparation method who prepares described ZnO film, comprises the steps:
(1) using Sn and AZO material as target, target is arranged in the chamber of magnetron sputtering equipment;
(2) clean substrate to be coated, the contamination of removing substrate surface, then dries up;
(3) substrate after drying up is put into rf magnetron sputtering chamber, the vacuum tightness being evacuated in chamber is less than 0.1Pa, and heated substrate to 100 DEG C ~ 200 DEG C;
(4) in chamber, pass into rare gas element, and substrate rotation is set;
(5) by magnetron sputtering mode, to adding radio-frequency voltage on Sn and two targets of AZO: Sn target radio-frequency voltage 0～6V, AZO target radio-frequency voltage 0～32V, the then ZnO film of the mode depositing Al-Sn codoped by two target co-sputterings.
principle:below the principle of the invention is further described:
Step 1, using ZnO, AZO and Sn material respectively as target, ZnO target, AZO target and Sn target are placed in the chamber of magnetron sputtering deposition equipment, radio-frequency voltage is directly added on target;
Step 2, clean substrate to be coated, remove the contamination of substrate surface, then dry up and put into chamber, and heated substrate temperature to 160 DEG C;
Step 3, treat that the vacuum tightness in chamber is extracted into 6 × 10
-499.999%) and Sn target (purity: 99.99%) corresponding radio frequency power source preheating 5 ~ 15 minutes when Pa, open ZnO target (purity:; Start to control substrate frame rotation (10r/min ~ 30r/min), pass into Ar gas 20sccm ~ 40sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power that ZnO target is set is 100W ~ 200W, regulates Sn target sputtering power to be respectively 0 ~ 30W; Pre-sputtering 5 ~ 10 minutes, removes target material surface oxidation and stains; Then rapidly two baffle plates are opened and timing; After growth finishes, by flapper closure, close vaccum-pumping equipment and take out sample afterwards;
Step 4, treat that the vacuum tightness in chamber is extracted into 5 × 10
-499.999%) and Sn target (purity: 99.99%) corresponding radio frequency power source preheating 5 ~ 15 minutes when Pa, open AZO target (purity:; Start to control substrate frame rotation (10r/min ~ 30r/min), pass into Ar gas 20sccm ~ 40sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power that AZO target is set is 100W ~ 200W, regulates Sn target sputtering power to be respectively 0 ~ 10W; Pre-sputtering 10 minutes, removes target material surface oxidation and stains; Then rapidly two baffle plates are opened and timing; After growth finishes, by flapper closure, close vaccum-pumping equipment and take out sample afterwards;
Step 5, in the face center preparation of film sample with the copper cash of silver slurry as test electrode, then put into 150 ~ 250 DEG C of tube furnaces, at N
2under atmosphere, carry out binder removal 15 minutes, on the surface of starching at silver after binder removal finishes and copper cash, apply one deck AB glue, adopt the NaCl solution that mass percent concentration is 3.5%;
Step 6, utilize CHI660D type electrochemical workstation to carry out the test of electrokinetic potential polarization curve to film, adopt three-electrode system: test electrode is working electrode, and platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode.Mass percent concentration is 3.5%NaCl solution, polarized potential sweep limit-1V ~ 2V, and scanning step is 2mV/s, the distance between working electrode and platinum electrode keeps about 10mm.First sample is submerged in solution and soak for some time, after open circuit potential is stable, start to test electrokinetic potential polarization curve.
Utilize crystalline quality and the crystalline structure of Bruker D8 Advance type X-ray diffractometer to film sample to test sign, the results are shown in Figure 1(a) and Fig. 2 (a).The XRD of ZnO film under the different Sn sputtering powers that Fig. 1 (a) obtains for embodiment 1.Three samples all show c-axis preferred orientation as seen from the figure, and Sn sputtering power is the diffraction peak that the sample of 10W and 20W is not all observed Sn simple substance or Sn oxide compound, only occurs ZnO(002) diffraction peak, illustrate that its orientation is better.And be in 30W sample, to have occurred faint ZnSnO at Sn sputtering power
3diffraction peak.EDS records Sn content in three samples and is followed successively by 1.58 at%, 2.31 at% and 3.43 at%.Under the different Sn sputtering powers that Fig. 2 (a) obtains for embodiment 7, Al-Sn mixes the XRD of ZnO film altogether.Three samples all show obvious c-axis preferred orientation as seen from the figure, do not observe the diffraction peak about simple substance Al and Sn and oxide compound thereof.There is strong diffraction peak 34.6 ° of left and right in three samples, this peak is corresponding ZnO(002 just in time) diffraction peak of crystal face, it is all hexagonal wurtzite structure that the Al-Sn that shows preparation mixes ZnO film altogether.EDS records Sn content in the sample that Sn sputtering power is 5W and 10W and is respectively 1.14 at% and 1.47 at%.Along with the increase of Sn sputtering power, Al-Sn mixes ZnO film (002) diffraction peak intensity altogether first to be increased afterwards and reduces, halfwidth is followed successively by 0.307,0.304,0.369, this illustrates the crystalline quality that can improve film that adds of appropriate Sn, but in excessive Sn(sample, Sn content is greater than 3.5 at%) add and also can cause thin film crystallization degradation.
Utilize KDY-1 type four point probe sheet resistance tester and AMBIOS XP-1 type step instrument to carry out electrical performance testing to film, the results are shown in Figure 1(b) and Fig. 2 (b).The resistivity of ZnO film under the different Sn sputtering powers that Fig. 1 (b) obtains for embodiment 1.The resistivity of ZnO film presents and first reduces the trend raising afterwards with the increase of Sn sputtering power as we can see from the figure.In the time that the sputtering power of Sn is 20W, ZnO film has lowest resistivity 6.99 × 10
-2Ω cm.The resistivity that under the different Sn sputtering powers that Fig. 2 (b) obtains for embodiment 7, Al-Sn mixes ZnO film altogether.The resistivity that Al-Sn mixes ZnO film altogether as we can see from the figure presents and first reduces the trend raising afterwards with the increase of Sn sputtering power.In the time that the sputtering power of Sn is 5W, Al-Sn mixes altogether ZnO film and has lowest resistivity 1.49 × 10
-3Ω cm.
Utilize Shimadzu UV-2550 type ultraviolet-visible spectrophotometer to carry out transmission spectrum test to film, the results are shown in Figure 1(c) and Fig. 2 (c).The ZnO film of the different Sn sputtering powers that Fig. 1 (c) obtains for embodiment 1 ultraviolet-visible optical band transmitance at room temperature.As seen from the figure, there is precipitous ABSORPTION EDGE in 370nm left and right in all samples, and along with the increase of Sn sputtering power, the transmitance of ZnO film is on a declining curve.All samples are 68% ~ 82% at the average transmittances of 400nm ~ 900nm wave band.The Al-Sn of the different Sn sputtering powers that Fig. 2 (c) obtains for embodiment 7 mixes ZnO film ultraviolet-visible optical band transmitance at room temperature altogether.As seen from the figure, there is precipitous ABSORPTION EDGE in all samples in about 350nm, along with the increase of Sn sputtering power, it is on a declining curve that Al-Sn mixes the transmitance of ZnO film altogether.All samples are 81% ~ 89% at the average transmittances of 400nm ~ 900nm wave band.
Utilize CHI660D type electrochemical workstation to carry out the test of electrokinetic potential polarization curve to film, the results are shown in Figure 3, table 1, Fig. 4 and table 2.Fig. 3 is the polarization curve of ZnO film under the different Sn sputtering powers that obtain of embodiment 1.The data of ZnO film parameter fitting under the intrinsic ZnO film that table 1 obtains for embodiment 1 and different Sn sputtering power.As can be seen from Table 1, the corrosion potential of all samples changes less, and the ZnO thin film doped corrosion electric current density of Sn is all than an approximately little order of magnitude of intrinsic ZnO film, polarization resistance is more much bigger than intrinsic ZnO film, illustrates and can improve the erosion resistance of ZnO film in 3.5% NaCl solution adding of Sn.The ZnO thin film doped corrosion electric current density of Sn first reduces rear increase along with the increase of Sn sputtering power, and polarization resistance first increases and reduces afterwards, and in the time that the sputtering power of Sn is 20W, ZnO film has minimum corrosion electric current density 2.59 × 10
-8a/cm
2with maximum polarization resistance 1.20 × 10
6Ω.The data that under the ZnO thin film doped and different Sn sputtering powers of Al that table 2 obtains for embodiment 7, Al-Sn mixes ZnO film parameter fitting altogether.Can find out, the corrosion potential of all samples changes less, the corrosion electric current density that all Al-Sn mix ZnO film is altogether all than ZnO thin film doped little of Al, and polarization resistance, than ZnO thin film doped large of Al, illustrate and improved the ZnO thin film doped erosion resistance of Al adding of Sn; Al-Sn mixes the corrosion electric current density of ZnO film altogether along with the increase of Sn sputtering power reduces gradually, and polarization resistance increases gradually, and in the time that the sputtering power of Sn is 10W, Al-Sn mixes altogether ZnO film and has minimum corrosion electric current density 1.30 × 10
-8a/cm
2with maximum polarization resistance 1.40 × 10
6Ω.
beneficial effect:due to the application of technique scheme, can improve ZnO film and Al ZnO thin film doped in neutral NaCl environment job stability.The present invention has the following advantages: (1) is conducive to improve intrinsic ZnO film and the ZnO thin film doped electric property of Al.The electroconductibility of intrinsic ZnO film is poor, can reach 10 by its resistivity after it being carried out to Sn doping
-2Ω cm, and be about 77% at the average transmittance of 400nm ~ 900nm wavelength band.; After ZnO film is carried out to Al-Sn codoped, the electric property of film is further improved, and at the average transmittance of 400nm ~ 900nm wavelength band more than 80%.(2) increase the corrosion resistance of film, improved erosion resistance.With intrinsic ZnO film and Al ZnO thin film doped compared with, after film is carried out to Sn doping, their corrosion resistance has improved 3 ~ 19 times, so just can improve the stability that it works in severe environment.
Brief description of the drawings
Fig. 1 is crystalline quality and the photoelectric characteristic figure (ZnO sputtering power 150W) of the ZnO film of the different Sn sputtering powers that obtain of embodiment 1
Wherein: (a) be the XRD spectrum of the ZnO film of the Sn doping of different Sn sputtering powers.
(b) be the resistivity of the ZnO film of the Sn doping of different Sn sputtering powers.
(c) be the ultraviolet-visible optical band transmitance of the ZnO film of the Sn doping of different Sn sputtering powers.
Fig. 2 is crystalline quality and the photoelectric characteristic figure (AZO sputtering power 150W) of the ZnO film of the Al-Sn codoped of the different Sn sputtering powers that obtain of embodiment 7
Wherein: (a) be the XRD spectrum of the ZnO film of the Al-Sn codoped of different Sn sputtering powers.
(b) be the resistivity of the ZnO film of the Al-Sn codoped of different Sn sputtering powers.
(c) be the ultraviolet-visible optical band transmitance of the ZnO film of the Al-Sn codoped of different Sn sputtering powers.
Fig. 3 is the polarization curve (ZnO sputtering power 150W) of the ZnO film of the different Sn sputtering powers that obtain of embodiment 1.
Wherein: (a) for Sn sputtering power be the polarization curve of 0 o'clock ZnO film.
(b) polarization curve of ZnO film while being 10W for Sn sputtering power.
(c) polarization curve of ZnO film while being 18W for Sn sputtering power.
(d) polarization curve of ZnO film while being 20W for Sn sputtering power.
(e) polarization curve of ZnO film while being 24W for Sn sputtering power.
(f) polarization curve of ZnO film while being 30W for Sn sputtering power.
Fig. 4 is the polarization curve (AZO sputtering power 150W) of the ZnO film of the Al-Sn codoped of the different Sn sputtering powers that obtain of embodiment 7.
Wherein: (a) for Sn sputtering power be the polarization curve of 0 o'clock ZnO film.
(b) polarization curve of ZnO film while being 5W for Sn sputtering power.
(c) polarization curve of ZnO film while being 7W for Sn sputtering power.
(d) polarization curve of ZnO film while being 10W for Sn sputtering power.
Fig. 5 is the polarization curve of intrinsic ZnO film, Sn doping ZnO (Sn sputtering power 20W) film and Al-Sn codope ZnO (Sn sputtering power 10W) film.
Embodiment
Below in conjunction with example, the invention will be further described, but should not limit the scope of the invention with this.In the present embodiment, with reference to " electric and electronic product Essential Environment testing regulation " (GB2423.17-81), adopt ocean and industrial environment in the NaCl solutions simulate practical service environment that mass percent concentration is 3.5%.
embodiment 1: a kind of corrosion-resistant ZnO film and preparation method thereof, comprises the steps:
(1) using ZnO and Sn material respectively as target, ZnO target and Sn target are placed in the chamber of magnetron sputtering deposition equipment, radio-frequency power supply is directly added on target;
(2) clean ultra-clear glasses substrate to be coated, the contamination of removing substrate surface, then dries up and puts into chamber, and heated substrate temperature to 160 DEG C;
(3) treat that the vacuum tightness in sputtering chamber is evacuated to 6 × 10
-4pa, opens Sn target and ZnO target (purity: radio frequency power source 99.999%) preheating 10 minutes; Start to control substrate frame rotation (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power that ZnO target is set is 150W, and it is 0 that Sn target sputtering power is set, and pre-sputtering 10 minutes is removed surface oxidation and contamination; Then open baffle plate and start deposit film, growth time is 30 minutes; After growth finishes, baffle plate is closed rapidly, close vaccum-pumping equipment and take out sample afterwards.
(4) will on the intrinsic ZnO film sample of above-mentioned preparation, prepare face electrode, tackiness agent adopts silver slurry, uses copper cash as electrode cable;
(5) utilize CHI660D type electrochemical workstation to carry out the test of electrokinetic potential polarization curve to film, adopt three-electrode system: test electrode is working electrode, and platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode.Mass percent concentration is 3.5%NaCl solution, polarized potential sweep limit-1V ~ 2V, and scanning step is 2mV/s, the distance between working electrode and platinum electrode keeps about 10mm.First sample is submerged in solution and soak for some time, after open circuit potential is stable, start to test electrokinetic potential polarization curve.
(6) result of implementation: the polarization curve of intrinsic ZnO film and the data of matching thereof are as shown in table 1.The polarization resistance 6.18 × 10 of intrinsic ZnO film
4Ω.
Table 1 is the data that embodiment 1 obtains intrinsic ZnO film and different Sn sputtering power ZnO film parameter fittings.
Table 1
| Sn sputtering power/W | E corr/V | J corr/A?cm -2 | R p/Ω |
| 0 | -0.598 | 2.19×10 -7 | 61757.2 |
| 10 | -0.625 | 4.92×10 -8 | 346975.3 |
| 18 | -0.627 | 4.41×10 -8 | 398939.1 |
| 20 | -0.642 | 2.59×10 -8 | 1188024.0 |
| 24 | -0.615 | 2.87×10 -8 | 1048760.1 |
| 30 | -0.599 | 3.12×10 -8 | 512259.6 |
embodiment 2:press the method described in embodiment 1, it is 10W that Sn target sputtering power is set, make it with ZnO target simultaneously cosputtering prepare the ZnO film of Sn doping.And then the technique of repetition embodiment 1.
The data of transmitance, polarization curve and the matching thereof of the ZnO thin film doped X-ray diffractogram of result of implementation: Sn, resistivity, 200nm ~ 900nm wave band are respectively as shown in Fig. 1, Fig. 3 and table 1.
embodiment 3:press the method described in embodiment 1, it is 18W that Sn target sputtering power is set, make it with ZnO target simultaneously cosputtering prepare the ZnO film of Sn doping.And then the technique of repetition embodiment 1.
The data of transmitance, polarization curve and the matching thereof of the ZnO thin film doped resistivity of result of implementation: Sn, 200nm ~ 900nm wave band are respectively as shown in Fig. 1, Fig. 3 and table 1.
embodiment 4:press the method described in embodiment 1, it is 20W that Sn target sputtering power is set, make it with ZnO target simultaneously cosputtering prepare the ZnO film of Sn doping.And then the technique of repetition embodiment 1.
The data of transmitance, polarization curve and the matching thereof of the ZnO thin film doped X-ray diffractogram of result of implementation: Sn, resistivity, 200nm ~ 900nm wave band are respectively as shown in Fig. 1, Fig. 3 and table 1.The ZnO thin film doped resistivity of Sn is 6.99 × 10
-2Ω cm, the average transmittances of 400nm ~ 900nm wave band is 77%, polarization resistance is 1.20 × 10
6Ω.
embodiment 5:press the method described in embodiment 1, it is 24W that Sn target sputtering power is set, make it with ZnO target simultaneously cosputtering prepare the ZnO film of Sn doping.And then the technique of repetition embodiment 1.
The data of transmitance, polarization curve and the matching thereof of the ZnO thin film doped resistivity of result of implementation: Sn, 200nm ~ 900nm wave band are respectively as shown in Fig. 1, Fig. 3 and table 1.
embodiment 6:press the method described in embodiment 1, it is 30W that Sn target sputtering power is set, make it with ZnO target simultaneously cosputtering prepare the ZnO film of Sn doping.And then the technique of repetition embodiment 1.
The data of transmitance, polarization curve and the matching thereof of the ZnO thin film doped X-ray diffractogram of result of implementation: Sn, resistivity, 200nm ~ 900nm wave band are respectively as shown in Fig. 1, Fig. 3 and table 1.The ZnO thin film doped resistivity of Sn is 8 × 10
-2Ω cm, the average transmittances of 400nm ~ 900nm wave band is 69%, polarization resistance is 5.12 × 10
5Ω.
embodiment 7: a kind of corrosion-resistant ZnO film and preparation method thereof, comprises the steps:
(1) using AZO and Sn material respectively as target, AZO target (the ZnO target of Al doping, Al
2o
3: 2wt%) and Sn target be placed in the chamber of magnetron sputtering deposition equipment, radio-frequency power supply is directly added on target;
(2) clean simple glass substrate to be coated, the contamination of removing substrate surface, then dries up and puts into chamber, and heated substrate temperature to 160 DEG C;
(3) treat that the vacuum tightness in sputtering chamber is evacuated to 5 × 10
-4pa, opens Sn target and AZO target (purity: radio frequency power source 99.999%) preheating 10 minutes; Start to control substrate frame rotation (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power that AZO target is set is 150W, and it is 0 that Sn target sputtering power is set, and pre-sputtering 10 minutes is removed surface oxidation and contamination; Then open baffle plate and start deposit film; After growth finishes, baffle plate is closed rapidly, close vaccum-pumping equipment and take out sample afterwards.
(4) will on the ZnO film sample of above-mentioned preparation Al doping, prepare face electrode, tackiness agent adopts silver slurry, uses copper cash as electrode cable;
(5) utilize CHI660D type electrochemical workstation to carry out the test of electrokinetic potential polarization curve to film, adopt three-electrode system: test electrode is working electrode, and platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode.Mass percent concentration is 3.5%NaCl solution, polarized potential sweep limit-1V ~ 2V, and scanning step is 2mV/s, the distance between working electrode and platinum electrode keeps about 10mm.First sample is submerged in solution and soak for some time, after open circuit potential is stable, start to test electrokinetic potential polarization curve.
(6) data of the resistivity of the ZnO film of result of implementation: Al doping, transmitance, polarization curve and the matching thereof of 200nm ~ 900nm wave band are respectively as shown in Fig. 2, Fig. 4 and table 2.The resistivity of the ZnO film of Al doping is 1.91 × 10
-3Ω cm, the average transmittances of 400nm ~ 900nm wave band is 89%, polarization resistance is 3.96 × 10
5Ω.
The data of the ZnO film parameter fitting of the Al-Sn codoped of the ZnO thin film doped and different Sn sputtering powers of Al that table 2 obtains for embodiment 1.
Table 2
| Sn sputtering power/W | E corr/V | J corr/A?cm -2 | R p/Ω |
| 0 | -0.628 | 6.51×10 -8 | 395541.7 |
| 5 | -0.601 | 5.19×10 -8 | 424826.2 |
| 7 | -0.628 | 1.82×10 -8 | 1149549.8 |
| 10 | -0.617 | 1.30×10 -8 | 1392659.8 |
embodiment 8:press the method described in embodiment 7, it is 5W that Sn target sputtering power is set, make it with AZO target simultaneously cosputtering prepare the ZnO film of Al-Sn codoped.And then the technique of repetition embodiment 7.
Result of implementation: the data of transmitance, polarization curve and the matching thereof of the X-ray diffractogram of the ZnO film of Al-Sn codoped, resistivity, 200nm ~ 900nm wave band are respectively as shown in Fig. 2, Fig. 4 and table 2.The resistivity of Al-Sn codope ZnO film is 1.49 × 10
-3Ω cm, the average transmittances of 400nm ~ 900nm wave band is 89%, polarization resistance is 4.25 × 10
5Ω.
embodiment 9: a kind of corrosion-resistant ZnO film and preparation method thereof, comprises the steps:
(1) using AZO and Sn material respectively as target, AZO target (the ZnO target of Al doping, Al
2o
3: 2wt%) and Sn target be placed in the chamber of magnetron sputtering deposition equipment, radio-frequency power supply is directly added on target;
(2) clean simple glass substrate to be coated, the contamination of removing substrate surface, puts into chamber after then drying up, and heated substrate temperature to 160 DEG C;
(3) treat that the vacuum tightness in sputtering chamber is evacuated to 5 × 10
-4pa, opens Sn target and AZO target (purity: radio frequency power source 99.999%) preheating 10 minutes; Start to control substrate frame rotation (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power that AZO target is set is 150W, and Sn target sputtering power is 6W, and pre-sputtering 10 minutes is removed surface oxidation and contamination; Then open baffle plate and start deposit film; After growth finishes, baffle plate is closed rapidly, close vaccum-pumping equipment and take out sample afterwards.
(4) result of implementation: the resistivity of the ZnO film of Al-Sn codoped, the transmitance of 200nm ~ 900nm wave band are as shown in Figure 2.
embodiment 10:press the method described in embodiment 7, it is 7W that Sn target sputtering power is set here, make it with AZO target simultaneously cosputtering prepare Al-Sn and mix altogether ZnO film.And then the technique of repetition embodiment 7.
Result of implementation: the data of the resistivity of the ZnO film of Al-Sn codoped, transmitance, polarization curve and the matching thereof of 200nm ~ 900nm wave band are respectively as shown in Fig. 2, Fig. 4 and table 2.
embodiment 11:press the method described in embodiment 7, it is 10W that Sn target sputtering power is set here, make it with AZO target simultaneously cosputtering prepare the ZnO film of Al-Sn codoped.And then the technique of repetition embodiment 7.
Result of implementation: the data of transmitance, polarization curve and the matching thereof of the X-ray diffractogram of the ZnO film of Al-Sn codoped, resistivity, 200nm ~ 900nm wave band are respectively as shown in Fig. 2, Fig. 4 and table 2.The resistivity of Al-Sn codope ZnO film is 5.10 × 10
-3Ω cm, the average transmittances of 400nm ~ 900nm wave band is 82%, polarization resistance is 1.40 × 10
6Ω.
Claims (8)
1. a corrosion-resistant ZnO film, comprises ZnO, it is characterized in that: in prepared film, also contain Sn, the ZnO thin film doped resistivity of described Sn is 6.99 × 10
-2Ω cm ~ 1.06 × 10
-1Ω cm, the average transmittances of 400 ~ 900nm wave band is 69% ~ 82%, polarization resistance is 6.20 × 10
4Ω ~ 1.20 × 10
6Ω.
2. a corrosion-resistant ZnO film, is characterized in that: in prepared film, also contain Sn and Al, the resistivity of described Al and Sn codope ZnO film is 1.49 × 10
-3Ω cm ~ 5.10 × 10
-3Ω cm, the average transmittances of 400 ~ 900nm wave band is 82% ~ 89%, polarization resistance is 3.96 × 10
5Ω ~ 1.40 × 10
6Ω.
3. a preparation method for ZnO film claimed in claim 1, is characterized in that comprising the steps:
(1) using Sn and ZnO material as target, target is arranged in the chamber of rf magnetron sputtering equipment;
(2) clean substrate to be coated, the contamination of removing substrate surface, then dries up;
(3) substrate after drying up is put into rf magnetron sputtering chamber, be evacuated to the base vacuum degree of chamber, and heated substrate to 100 DEG C ~ 200 DEG C;
(4) in chamber, pass into rare gas element, and substrate rotation is set;
(5) by rf magnetron sputtering mode, on Sn and two targets of ZnO, add radio-frequency voltage and radio frequency power: the radio-frequency voltage of Sn target is 0～16V, and sputtering power is 10W ~ 30W; The radio-frequency voltage of ZnO target is 0～32V, and sputtering power is 100W ~ 200W, deposits the ZnO film of Sn doping by the mode of two target co-sputterings.
4. a preparation method for ZnO film claimed in claim 2, is characterized in that comprising the steps:
(1) using Sn and AZO material as target, target is arranged in the chamber of rf magnetron sputtering equipment;
(2) clean substrate to be coated, the contamination of removing substrate surface, then dries up;
(3) substrate after drying up is put into rf magnetron sputtering chamber, be evacuated to the base vacuum degree of chamber, and heated substrate to 100 DEG C ~ 200 DEG C;
(4) in chamber, pass into rare gas element, and substrate rotation is set;
(5) by rf magnetron sputtering mode, on Sn and two targets of AZO, add radio-frequency voltage and radio frequency power: the radio-frequency voltage of Sn target is 0～6V, and sputtering power is 5 ~ 10W; The radio-frequency voltage of AZO target is 0～32V, and sputtering power is 100W ~ 200W, by the mode depositing Al of two target co-sputterings and the ZnO film of Sn codoped.
5. the preparation method of a kind of corrosion-resistant ZnO film according to claim 4, is characterized in that, the Al that contains 1wt% ~ 3wt% in the described AZO target of step (1)
2o
3.
6. according to the preparation method of a kind of corrosion-resistant ZnO film described in claim 3 or 4, it is characterized in that, the described substrate of step (2) is ultra-clear glasses or simple glass.
7. according to the preparation method of a kind of corrosion-resistant ZnO film described in claim 3 or 4, it is characterized in that, the described base vacuum degree of step (3) is less than or equal to 8 × 10
-4pa.
8. according to the preparation method of a kind of corrosion-resistant ZnO film described in claim 3 or 4, it is characterized in that, the described rare gas element of step (4) is Ar gas, and flow is 20sccm ~ 40sccm; Described substrate rotation rotating speed is 10r/min ~ 30r/min.
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