CN108193179B - Multilayer infrared transparent conductive film and preparation method thereof - Google Patents

Multilayer infrared transparent conductive film and preparation method thereof Download PDF

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CN108193179B
CN108193179B CN201711456751.4A CN201711456751A CN108193179B CN 108193179 B CN108193179 B CN 108193179B CN 201711456751 A CN201711456751 A CN 201711456751A CN 108193179 B CN108193179 B CN 108193179B
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王鑫
郑传涛
王一丁
郑伟涛
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Jilin University
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Abstract

The invention belongs to the technical field of infrared optical materials and electronic film materials, and particularly relates to a multilayer infrared transparent conductive film and a preparation method thereof, wherein the multilayer infrared transparent conductive film comprises a five-layer structure, and the five-layer structure sequentially comprises the following components in sequence from bottom to top: substrate, IHfO transparent conductive layer, metal layer, IHfO transparent conductive layer and Al2O3The multilayer film has high transmittance and conductivity in the middle infrared band and good stability, and the invention also provides a preparation method of the multilayer infrared transparent conductive film, wherein the film is prepared by adopting a magnetron sputtering method and an ion beam auxiliary evaporation method, the preparation process is simple, and mass preparation can be realized.

Description

Multilayer infrared transparent conductive film and preparation method thereof
Technical Field
The invention belongs to the technical field of infrared optical materials and electronic thin film materials, and particularly relates to a multilayer infrared transparent conductive thin film and a preparation method thereof.
Background
The infrared transparent conductive film can well solve the problems of dust prevention and dehumidification of a detector window, and can release static electricity accumulated on the surface of the infrared transparent conductive film in time, so that the surface is antistatic and non-sticky, and water vapor on the surface can be removed by electrifying and heating. Therefore, the infrared transparent conductive film with high transmittance and low resistivity has important effects on dust prevention and dehumidification of an infrared system, and has wide application prospects in the fields of electromagnetic wave shielding technology, infrared imaging, spacecraft windows and the like.
In the infrared band, the absorption of the infrared light by free carriers is strong, and the infrared transparent conductive oxide film with high transmittance and low resistivity needs to have higher carrier mobility and lower carrier concentration, so for a single-layer oxide film, it is difficult to have both high transmittance and high conductivity in the infrared band, especially in the mid-infrared and far-infrared bands, and for a general transparent conductive oxide film, when it is exposed in the air for a long time, it will adsorb water vapor, oxygen, etc. in the air, thereby reducing the photoelectric properties of the film, so that there is an urgent need to develop a conductive oxide film with high transmittance and low resistivity in the infrared band.
Disclosure of Invention
In order to overcome the problems, the invention provides a multilayer infrared transparent conductive film and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the utility model provides an infrared transparent conductive film of multilayer, includes five layer structure, follows supreme down and is in proper order: substrate 1, first IHfO transparent conductive layer 2, metal layer 3, second IHfO transparent conductive layer 4 and Al2O3A protective layer 5, wherein the first IHfO transparent conductive layer 2 is deposited on the substrate 1 by adopting a radio frequency magnetron sputtering method, the metal layer 3 is deposited on the first IHfO transparent conductive layer 2 by adopting a direct current magnetron sputtering method, the second IHfO transparent conductive layer 4 is deposited on the metal layer 3 by adopting a radio frequency magnetron sputtering method, and Al2O3The protective layer 5 is evaporated on the second IHfO transparent conductive layer 4 using ion beam assisted thermal evaporation.
The substrate 1 is made of an infrared transparent material, specifically sapphire or quartz.
The first IHfO transparent conducting layer 2 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 20-100 nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The metal layer 3 is prepared by a direct-current magnetron sputtering method, the material is one of Cu, Mo or Ag, the deposition temperature is 25-400 ℃, the thickness is 1-20 nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, the working gas pressure is 0.1-2 Pa, and the layer is used for increasing the conductivity of the multilayer film.
The second IHfO transparent conducting layer 4 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 20-100 nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The Al is2O3The protective layer 5 is prepared by an ion beam assisted thermal evaporation method, the deposition temperature is 25-300 ℃, and the thickness is 1-10 nm.
The invention also provides a preparation method of the multilayer infrared transparent conductive film, which comprises the following steps:
the method comprises the following steps: cleaning the substrate 1 in an ultrasonic cleaner for 15min by using an acetone solution (analytically pure) at normal temperature and normal pressure, cleaning in the ultrasonic cleaner for 15min by using an ethanol solution (analytically pure), and cleaning in the ultrasonic cleaner for 15min by using deionized water;
step two: drying the substrate 1 cleaned in the first step, putting the substrate into a sputtering chamber, starting to vacuumize when the vacuum degree is less than 1.0 multiplied by 10-3When Pa, introducing Ar gas, and carrying out pre-sputtering for 15 min;
step three: preparing a first IHfO transparent conducting layer 2 by a radio frequency magnetron sputtering method, and depositing the first IHfO transparent conducting layer 2 on the substrate 1 subjected to the pre-sputtering for 15min in the step two by adopting the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts HfO with the purity not lower than 99.99 percent2Doped In2O3The doping concentration of the target material is 1-6 wt%; the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-60W, the working pressure is 0.1-2 Pa, and the deposition temperature is 20-300 ℃; obtaining a single-layer film;
step four: preparing a metal layer 3 by adopting a direct current magnetron sputtering method, wherein the material is one of Cu, Mo or Ag, and depositing the metal layer 3 on the first IHfO transparent conducting layer 2 of the single-layer film in the third step by adopting the direct current magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a direct current power supply, the target material adopts a metal Cu, Mo or Ag target material with the purity not less than 99.99%, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, the working air pressure is 0.1-2 Pa, and the deposition temperature is 20-300 ℃; obtaining two layers of films;
step five: preparing a second IHfO transparent film by adopting a radio frequency magnetron sputtering methodA conducting layer 4, and depositing a second IHfO transparent conducting layer 4 on the metal layer 3 of the two layers of films in the step four by adopting a radio frequency magnetron sputtering method; the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts HfO with the purity not lower than 99.99 percent2Doped In2O3The target material has the doping concentration of 1-6 wt%, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-60W, the working pressure is 0.1-2 Pa, and the deposition temperature is 20-300 ℃ to obtain a three-layer film;
step six: taking the three-layer film sample in the fifth step out of the sputtering chamber, and annealing for 10-60 minutes at 100-400 ℃ in a nitrogen atmosphere;
step seven: preparation of Al by ion beam assisted thermal deposition2O3A protective layer 5, and depositing Al on the surface of the annealed three-layer film sample by adopting an ion beam assisted thermal deposition method2O3A protective layer 5 made of Al with a purity of not less than 99.99%2O3Particles with the particle size of 1-3 mm, the deposition temperature of 20-300 ℃, the thickness of 1-10 nm and the deposition rate of
Figure GDA0002668458550000021
The invention has the following beneficial effects:
1. the invention prepares Al on the uppermost layer of the film2O3The protective layer has good transmittance in an infrared band, can isolate air and increases the stability of the multilayer film.
2. The film has higher transmittance and conductivity in the middle infrared band, and the transmission spectrum and the resistivity of the multilayer film can be regulated and controlled by regulating and controlling the thickness of each film layer: if the conductivity needs to be improved, the thickness of the metal layer film can be increased, and the transmittance is correspondingly reduced; if the transmittance needs to be increased, the thickness of the metal layer film can be reduced, and the conductivity is correspondingly reduced.
3. The invention adopts magnetron sputtering method and ion beam auxiliary evaporation method to prepare the film, the preparation process is simple, and mass preparation can be realized.
Drawings
FIG. 1 is a schematic structural diagram of a multilayer infrared transparent conductive film of the present invention.
FIG. 2 is a flow chart of the preparation of the multilayer infrared transparent conductive film of the present invention.
FIG. 3 shows an infrared transmission spectrum in the embodiment 1 of the present invention.
FIG. 4 shows an infrared transmission spectrum in the embodiment 2 of the present invention.
FIG. 5 shows an infrared transmission spectrum in the embodiment 3 of the present invention.
Wherein: 1, a substrate; 2 a first IHfO transparent conductive layer; 3, a metal layer; 4 a second IHfO transparent conductive layer; 5Al2O3And a protective layer.
Detailed Description
In the present invention, all the range values in the experimental conditions are theoretically achievable, but the operation is not necessarily performed by forcing to reach the end point value in the actual experimental process, so experimental data of all the end point values are not given in the following examples.
Example 1
As shown in fig. 1, the multilayer infrared transparent conductive film comprises a five-layer structure, which is sequentially from bottom to top: substrate 1, first IHfO transparent conductive layer 2, metal layer 3, second IHfO transparent conductive layer 4 and Al2O3A protective layer 5, wherein the first IHfO transparent conductive layer 2 is deposited on the substrate 1 by adopting a radio frequency magnetron sputtering method, the metal layer 3 is deposited on the first IHfO transparent conductive layer 2 by adopting a direct current magnetron sputtering method, the second IHfO transparent conductive layer 4 is deposited on the metal layer 3 by adopting a radio frequency magnetron sputtering method, and Al2O3The protective layer 5 is evaporated on the second IHfO transparent conductive layer 4 using ion beam assisted thermal evaporation.
The substrate 1 is made of infrared transparent material, specifically quartz.
The first IHfO transparent conducting layer 2 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 30nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The metal layer 3 is prepared by a direct-current magnetron sputtering method, the material is Mo, the deposition temperature is 25-400 ℃, the thickness is 5nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, the working gas pressure is 0.1-2 Pa, and the layer is used for increasing the conductivity of the multilayer film.
The second IHfO transparent conducting layer 4 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 30nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The Al is2O3The protective layer 5 is prepared by an ion beam assisted thermal evaporation method, the deposition temperature is 25-300 ℃, and the thickness is 3 nm.
As shown in fig. 2, the method for preparing the multilayer infrared transparent conductive film comprises the following steps:
the method comprises the following steps: cleaning the substrate 1 in an ultrasonic cleaner for 15min by using an acetone solution (analytically pure) at normal temperature and normal pressure, cleaning in the ultrasonic cleaner for 15min by using an ethanol solution (analytically pure), and cleaning in the ultrasonic cleaner for 15min by using deionized water;
step two: drying the substrate 1 cleaned in the first step, putting the substrate into a sputtering chamber, starting to vacuumize when the vacuum degree is less than 1.0 multiplied by 10-3When Pa, introducing Ar gas, and carrying out pre-sputtering for 15 min;
step three: preparing a first IHfO transparent conducting layer 2 by a radio frequency magnetron sputtering method, and depositing the first IHfO transparent conducting layer 2 with the thickness of 30nm on the substrate 1 subjected to pre-sputtering for 15min in the step two by adopting the radio frequency magnetron sputtering method, wherein the specific deposition experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts 2wt percent HfO with the purity of 99.99 percent2Doped In2O3A target (the diameter of the target is 46mm, the thickness of the target is 3mm, a copper back plate with the thickness of 3mm is bound behind the target), Ar is working gas, the flow rate of Ar is 20sccm, the sputtering power is 25W, the working pressure is 1.33Pa, the deposition temperature is room temperature, and the rotating speed of a substrate 1 is 20rpm, so that a single-layer film is obtained;
step four: preparing a metal layer 3 by adopting a direct current magnetron sputtering method, using a material Mo, and depositing the metal layer 3 on the first IHfO transparent conducting layer 2 of the single-layer film in the third step by adopting the direct current magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a direct current power supply, the target material adopts a Mo metal target with the purity of 99.99 percent (the diameter of the target material is 46mm, the thickness of the target material is 6mm), the working gas is Ar, the flow rate of Ar is 20sccm, the sputtering power is 30W, the deposition temperature is 100 ℃, the working pressure is 1.33Pa, and the rotating speed of the substrate 1 is 20 rpm; obtaining two layers of films;
step five: preparing a second IHfO transparent conducting layer 4 by adopting a radio frequency magnetron sputtering method, and depositing the second IHfO transparent conducting layer 4 on the metal layer 3 of the two layers of films in the fourth step by adopting the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts 2wt percent HfO with the purity of 99.99 percent2Doped In2O3The method comprises the following steps of (1) obtaining a target (the diameter of the target is 46mm, the thickness of the target is 3mm, a copper back plate with the thickness of 3mm is bound behind the target), wherein the working gas is Ar, the Ar flow is 20sccm, the sputtering power is 25W, the working pressure is 1.33Pa, the deposition temperature is room temperature, and the rotating speed of a substrate is 20rpm, so that three layers of films are obtained;
step six: taking the three-layer film sample in the fifth step out of the sputtering chamber, and annealing for 30 minutes at 300 ℃ in a nitrogen atmosphere;
step seven: preparation of Al by ion beam assisted thermal deposition2O3A protective layer 5, and depositing Al on the surface of the annealed three-layer film sample by adopting an ion beam assisted thermal deposition method2O3A protective layer 5 made of Al with a purity of not less than 99.99%2O3Particles with a particle size of 1-3 mm, a deposition temperature of room temperature, a thickness of 3nm, a deposition rate of
Figure GDA0002668458550000041
Referring to FIG. 3, the infrared transmission spectrum of the film obtained in example 1 is shown, the transmittance in the middle infrared band is more than 75%, and the film resistivity is 1.10-2Ω·cm。
Example 2
As shown in fig. 1, the multilayer infrared transparent conductive film comprises a five-layer structure, which is sequentially from bottom to top: substrate 1, first IHfO transparent conductive layer 2, metal layer 3, second IHfO transparent conductive layer 4 and Al2O3A protective layer 5, wherein the first IHfO transparent conductive layer 2 is deposited on the first IHfO transparent conductive layer 2 by adopting a radio frequency magnetron sputtering method, the metal layer 3 is deposited on the first IHfO transparent conductive layer 2 by adopting a direct current magnetron sputtering method, the second IHfO transparent conductive layer 4 is deposited on the metal layer 3 by adopting a radio frequency magnetron sputtering method, and Al2O3The protective layer 5 is evaporated on the second IHfO transparent conductive layer 4 using ion beam assisted thermal evaporation.
The substrate 1 is made of an infrared transparent material, specifically sapphire.
The first IHfO transparent conducting layer 2 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 30nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The metal layer 3 is prepared by a direct-current magnetron sputtering method, the material is Cu, the deposition temperature is 25-400 ℃, the thickness is 6nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, the working gas pressure is 0.1-2 Pa, and the layer is used for increasing the conductivity of the multilayer film.
The second IHfO transparent conducting layer 4 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 30nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The Al is2O3The protective layer 5 is prepared by an ion beam assisted thermal evaporation method, the deposition temperature is 25-300 ℃, and the thickness is 3 nm.
The invention also provides a preparation method of the multilayer infrared transparent conductive film, which comprises the following steps as shown in figure 2:
the method comprises the following steps: cleaning the substrate 1 in an ultrasonic cleaner for 15min by using an acetone solution (analytically pure) at normal temperature and normal pressure, cleaning in the ultrasonic cleaner for 15min by using an ethanol solution (analytically pure), and cleaning in the ultrasonic cleaner for 15min by using deionized water;
step two: drying the substrate 1 cleaned in the first step, putting the substrate into a sputtering chamber, starting to vacuumize when the vacuum degree is less than 1.0 multiplied by 10-3When Pa, introducing Ar gas, and carrying out pre-sputtering for 15 min;
step three: preparing a first IHfO transparent conducting layer 2 by a radio frequency magnetron sputtering method, and depositing the first IHfO transparent conducting layer 2 on the substrate 1 subjected to the pre-sputtering for 15min in the step two by adopting the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts In doped with 2 wt% HfO2 with the purity of 99.99 percent2O3The method comprises the following steps of (1) obtaining a single-layer film by using a target (the diameter of the target is 46mm, the thickness of the target is 3mm, a copper back plate with the thickness of 3mm is bound behind the target), using Ar as a working gas, enabling the Ar flow to be 20sccm, the sputtering power to be 30W, the working pressure to be 1.33Pa, the rotating speed of a substrate 1 to be 20rpm, and the deposition temperature to be room temperature;
step four: preparing a metal layer 3 by adopting a direct current magnetron sputtering method, wherein the material is Cu, and depositing the metal layer 3 on the first IHfO transparent conducting layer 2 of the single-layer film in the third step by adopting the direct current magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a direct current power supply, the target material adopts a Cu metal target with the purity of 99.99 percent (the diameter of the target material is 46mm, the thickness of the target material is 6mm), the working gas is Ar, the flow rate of Ar is 20sccm, the sputtering power is 30W, the working pressure is 1.33Pa, the rotating speed of the substrate 1 is 20rpm, and the deposition temperature is 100 ℃, so that two layers of films are obtained;
step five: preparing a second IHfO transparent conducting layer 4 by adopting a radio frequency magnetron sputtering method, and depositing the second IHfO transparent conducting layer 4 on the metal layer 3 of the two layers of films in the fourth step by adopting the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts 2wt percent HfO with the purity of 99.99 percent2Doped In2O3A target (the diameter of the target is 46mm, the thickness of the target is 3mm, a copper back plate with the thickness of 3mm is bound behind the target), Ar is working gas, the Ar flow is 20sccm, the sputtering power is 30W, and the working gas pressure is 1.33Pa, the rotating speed of the substrate 1 is 20rpm, and the deposition temperature is room temperature; obtaining three layers of films;
step six: taking the three-layer film sample in the fifth step out of the sputtering chamber, and annealing for 30 minutes at 300 ℃ in a nitrogen atmosphere;
step seven: preparation of Al by ion beam assisted thermal deposition2O3A protective layer 5, and depositing Al on the surface of the annealed three-layer film sample by adopting an ion beam assisted thermal deposition method2O3A protective layer 5 made of Al with a purity of not less than 99.99%2O3Particles with a particle size of 1-3 mm, a deposition temperature of room temperature, a thickness of 3nm, a deposition rate of
Figure GDA0002668458550000061
Referring to FIG. 4, the infrared transmission spectrum of the film obtained in example 2 is shown, the transmittance in the mid-infrared band is greater than 60%, and the film resistivity is 4.10-3Ω·cm。
Example 3
As shown in fig. 1, the multilayer infrared transparent conductive film comprises a five-layer structure, which is sequentially from bottom to top: substrate 1, first IHfO transparent conductive layer 2, metal layer 3, second IHfO transparent conductive layer 4 and Al2O3A protective layer 5, wherein the first IHfO transparent conductive layer 2 is deposited on the first IHfO transparent conductive layer 2 by adopting a radio frequency magnetron sputtering method, the metal layer 3 is deposited on the first IHfO transparent conductive layer 2 by adopting a direct current magnetron sputtering method, the second IHfO transparent conductive layer 4 is deposited on the metal layer 3 by adopting a radio frequency magnetron sputtering method, and Al2O3The protective layer 5 is evaporated on the second IHfO transparent conductive layer 4 using ion beam assisted thermal evaporation.
The substrate 1 is made of an infrared transparent material, specifically sapphire.
The first IHfO transparent conducting layer 2 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 100nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The metal layer 3 is prepared by a direct-current magnetron sputtering method, the material is Cu, the deposition temperature is 25-400 ℃, the thickness is 8nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, the working gas pressure is 0.1-2 Pa, and the layer is used for increasing the conductivity of the multilayer film.
The second IHfO transparent conducting layer 4 is a hafnium-doped indium oxide thin film and is prepared by a radio frequency magnetron sputtering method, the deposition temperature is 25-400 ℃, the thickness is 100nm, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, and the working air pressure is 0.1-2 Pa.
The Al is2O3The protective layer 5 is prepared by an ion beam assisted thermal evaporation method, the deposition temperature is 25-300 ℃, and the thickness is 3 nm.
As shown in fig. 2, the present invention also provides a method for preparing a multilayer infrared transparent conductive film, comprising the following steps:
the method comprises the following steps: cleaning the substrate 1 in an ultrasonic cleaner for 15min by using an acetone solution (analytically pure) at normal temperature and normal pressure, cleaning in the ultrasonic cleaner for 15min by using an ethanol solution (analytically pure), and cleaning in the ultrasonic cleaner for 15min by using deionized water;
step two: drying the substrate 1 cleaned in the first step, putting the substrate into a sputtering chamber, starting to vacuumize when the vacuum degree is less than 1.0 multiplied by 10-3When Pa, introducing Ar gas, and carrying out pre-sputtering for 15 min;
step three: preparing a first IHfO transparent conducting layer 2 by a radio frequency magnetron sputtering method, and depositing the first IHfO transparent conducting layer 2 on the substrate 1 subjected to the pre-sputtering for 15min in the step two by adopting the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts 2wt percent HfO with the purity of 99.99 percent2Doped In2O3A target (the diameter of the target is 46mm, the thickness of the target is 3mm, and a copper back plate with the thickness of 3mm is bound behind the target); working gas is Ar, the flow rate of Ar is 20sccm, the sputtering power is 30W, the working pressure is 1.33Pa, the rotating speed of the substrate 1 is 20rpm, and the deposition temperature is room temperature, so that a single-layer film is obtained;
step four: preparing a metal layer 3 by adopting a direct current magnetron sputtering method, wherein the material is Cu, and depositing the metal layer 3 on the first IHfO transparent conducting layer 2 of the single-layer film in the third step by adopting the direct current magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a direct current power supply, the target material adopts a Cu metal target with the purity of 99.99 percent (the diameter of the target material is 46mm, the thickness of the target material is 6mm), the working gas is Ar, the flow rate of Ar is 20sccm, the sputtering power is 30W, the working pressure is 1.33Pa, the rotating speed of the substrate 1 is 20rpm, and the deposition temperature is 100 ℃, so that two layers of films are obtained;
step five: preparing a second IHfO transparent conducting layer 4 by adopting a radio frequency magnetron sputtering method, and depositing the second IHfO transparent conducting layer 4 on the metal layer 3 of the two layers of films in the fourth step by adopting the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts 2wt percent HfO with the purity of 99.99 percent2Doped In2O3The method comprises the following steps of (1) obtaining a target (the diameter of the target is 46mm, the thickness of the target is 3mm, a copper back plate with the thickness of 3mm is bound behind the target), wherein the working gas is Ar, the Ar flow is 20sccm, the sputtering power is 30W, the working pressure is 1.33Pa, the rotating speed of a substrate 1 is 20rpm, and the deposition temperature is room temperature to obtain three layers of films;
step six: taking the three-layer film sample in the fifth step out of the sputtering chamber, and annealing for 30 minutes at 300 ℃ in a nitrogen atmosphere;
step seven: preparation of Al by ion beam assisted thermal deposition2O3 protective layer 5, and depositing Al on the surface of the annealed three-layer film sample by ion beam assisted thermal deposition2O3A protective layer 5 made of Al with a purity of not less than 99.99%2O3Particles with a particle size of 1-3 mm, a deposition temperature of room temperature, a thickness of 3nm, a deposition rate of
Figure GDA0002668458550000071
Referring to FIG. 5, the infrared transmission spectrum of the film obtained in example 3 is shown, the transmittance in the mid-infrared band is greater than 45%, and the film resistivity is 8.10-3Ω·cm。

Claims (7)

1. A kind ofMultilayer infrared transparent conductive film, its characterized in that includes five layer structure, follows supreme being in proper order down: a substrate (1), a first IHfO transparent conductive layer (2), a metal layer (3), a second IHfO transparent conductive layer (4) and Al2O3A protective layer (5), wherein the first IHfO transparent conductive layer (2) is deposited on the substrate (1) by adopting a radio frequency magnetron sputtering method, the metal layer (3) is deposited on the first IHfO transparent conductive layer (2) by adopting a direct current magnetron sputtering method, the second IHfO transparent conductive layer (4) is deposited on the metal layer (3) by adopting a radio frequency magnetron sputtering method, and Al2O3And the protective layer (5) is evaporated on the second IHfO transparent conductive layer (4) by adopting an ion beam assisted thermal evaporation method.
2. The multilayer infrared transparent conductive film according to claim 1, characterized in that the substrate (1) is an infrared transparent material, in particular sapphire or quartz.
3. The multilayer infrared transparent conductive film as claimed in claim 1, wherein the first IHfO transparent conductive layer (2) is a hafnium-doped indium oxide film, and is prepared by a radio frequency magnetron sputtering method, wherein the deposition temperature is 25-400 ℃, the thickness is 20-100 nm, the working gas is Ar, the Ar flow rate is 10-100 sccm, the sputtering power is 25W-100W, and the working gas pressure is 0.1-2 Pa.
4. The multilayer infrared transparent conductive film according to claim 1, wherein the metal layer (3) is prepared by a direct current magnetron sputtering method, the material is one of Cu, Mo or Ag, the deposition temperature is 25-400 ℃, the thickness is 1-20 nm, the working gas is Ar, the Ar flow rate is 10-100 sccm, the sputtering power is 25-100W, and the working gas pressure is 0.1-2 Pa.
5. The multilayer infrared transparent conductive film as claimed in claim 1, wherein the second IHfO transparent conductive layer (4) is a hafnium-doped indium oxide film, and is prepared by a radio frequency magnetron sputtering method, wherein the deposition temperature is 25-400 ℃, the thickness is 20-100 nm, the working gas is Ar, the Ar flow rate is 10-100 sccm, the sputtering power is 25W-100W, and the working gas pressure is 0.1-2 Pa.
6. The multilayer infrared transparent conductive film according to claim 1, wherein said Al is2O3The protective layer (5) is prepared by an ion beam assisted thermal evaporation method, the deposition temperature is 25-300 ℃, and the thickness is 1-10 nm.
7. The method for preparing a multilayer infrared transparent conductive film according to any one of claims 1 to 6, comprising the steps of:
the method comprises the following steps: cleaning the substrate (1) in an ultrasonic cleaner for 15min by using acetone solution for analytical purification at normal temperature and normal pressure, cleaning in the ultrasonic cleaner for 15min by using ethanol solution for analytical purification, and cleaning in the ultrasonic cleaner for 15min by using deionized water;
step two: drying the substrate (1) cleaned in the first step, putting the substrate into a sputtering chamber, starting to vacuumize when the vacuum degree is less than 1.0 multiplied by 10-3When Pa, introducing Ar gas, and carrying out pre-sputtering for 15 min;
step three: preparing a first IHfO transparent conducting layer (2) by a radio frequency magnetron sputtering method, and depositing the first IHfO transparent conducting layer (2) on the substrate (1) which is subjected to the pre-sputtering for 15min in the step two by the radio frequency magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts HfO with the purity not lower than 99.99 percent2Doped In2O3The doping concentration of the target material is 1-6 wt%; the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-60W, the working pressure is 0.1-2 Pa, and the deposition temperature is 20-300 ℃; obtaining a single-layer film;
step four: preparing a metal layer (3) by adopting a direct current magnetron sputtering method, wherein the material is one of Cu, Mo or Ag, and depositing the metal layer (3) on the first IHfO transparent conducting layer (2) of the single-layer film in the third step by adopting the direct current magnetron sputtering method, wherein the specific experimental conditions are as follows: the working power supply adopts a direct current power supply, the target material adopts a metal Cu, Mo or Ag target material with the purity not less than 99.99%, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-100W, the working air pressure is 0.1-2 Pa, and the deposition temperature is 20-300 ℃; obtaining two layers of films;
step five: preparing a second IHfO transparent conducting layer (4) by adopting a radio frequency magnetron sputtering method, and depositing the second IHfO transparent conducting layer (4) on the metal layer (3) of the two layers of films in the fourth step by adopting the radio frequency magnetron sputtering method; the specific experimental conditions are as follows: the working power supply adopts a radio frequency power supply with the frequency of 13.56MHz, and the target material adopts HfO with the purity not lower than 99.99 percent2Doped In2O3The target material has the doping concentration of 1-6 wt%, the working gas is Ar, the Ar flow is 10-100 sccm, the sputtering power is 25-60W, the working pressure is 0.1-2 Pa, and the deposition temperature is 20-300 ℃; obtaining three layers of films;
step six: taking the three-layer film sample in the fifth step out of the sputtering chamber, and annealing for 10-60 minutes at 100-400 ℃ in a nitrogen atmosphere;
step seven: preparation of Al by ion beam assisted thermal deposition2O3A protective layer (5) and depositing Al on the surface of the annealed three-layer film sample by adopting an ion beam assisted thermal deposition method2O3A protective layer 5 made of Al with a purity of not less than 99.99%2O3Particles with the particle size of 1-3 mm, the deposition temperature of 20-300 ℃, the thickness of 1-10 nm and the deposition rate of
Figure FDA0002668458540000021
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