Hydrogen-doped zinc oxide visible-near infrared transparent conductive film and preparation method thereof

Abstract

This invention belongs to the field of transparent conductive film technology, and discloses a hydrogen-doped zinc oxide visible-near-infrared transparent conductive film and its preparation method. The transparent conductive film exhibits a transmittance of not less than 60% in the 0.38μm–0.78μm wavelength range and not less than 70% in the 0.78μm–2.50μm wavelength range, while maintaining a conductivity higher than 0.8 × 10⁻⁶ at room temperature. 3 S·cm ‑1 The preparation method is as follows: using magnetron sputtering with zinc oxide as the target material and an inert gas mixed with hydrogen and / or water vapor as the sputtering gas, by controlling the total volume ratio of hydrogen and water vapor in the sputtering gas to 2-10%, and controlling the sputtering gas pressure and sputtering power density, a hydrogen-doped zinc oxide transparent conductive film can be deposited on the substrate. This invention effectively solves the technical problem of traditional transparent conductive films being unable to achieve both high near-infrared transmittance and high conductivity by controlling the composition and crystallinity of the film, thereby controlling the carrier concentration and improving mobility.

Description

Technical Field

[0001] This invention belongs to the field of transparent conductive film technology, and more specifically, relates to a hydrogen-doped zinc oxide visible-near-infrared transparent conductive film and its preparation method. Background Technology

[0002] Transparent conductive films are widely used in optoelectronic devices due to their combination of high optical transmittance and excellent conductivity. Currently, transparent conductive films suitable for the visible light band (0.38–0.78 μm) are relatively mature, with indium tin oxide (In₂O₃:Sn, ITO) being a representative example of commercially available transparent conductive oxide films and holding a considerable market share. With further innovation in military fields such as optoelectronic detection and camouflage, as well as civilian fields such as solar cells and smart windows, transparent conductive films must not only meet the requirement of high visible light transparency but also maintain good transmittance in the near-infrared region (0.78–2.50 μm) (transmittance is often required to be no less than 60%). While commercially available ITO materials can achieve transmittance exceeding 70% in the visible light band, their transmittance in the near-infrared band is typically below 50%, a limitation that restricts their application in scenarios requiring high near-infrared transparency.

[0003] According to the Drude model, the transparency window of conductive metal oxide materials is mainly determined by the semiconductor band-edge absorption and the plasmon resonance effect, with the plasmon resonance wavelength determining the upper wavelength limit of the material's transparency window. The high carrier concentration of ITO itself causes its plasmon resonance wavelength to be close to the visible light region, resulting in low near-infrared transmittance. Appropriately reducing the carrier concentration can induce a redshift in the plasmon resonance wavelength, thereby improving near-infrared transmittance. However, a decrease in carrier concentration will adversely affect the material's conductivity. Conversely, when the carrier concentration remains constant, higher carrier mobility results in stronger conductivity. To simultaneously optimize the near-infrared transmittance and conductivity of metal oxides, improving carrier mobility under appropriate carrier concentration control is crucial. In existing technologies, researchers have developed molybdenum-doped indium oxide (MoO) by replacing tin with molybdenum. This material exhibits a mobility approximately twice that of ITO with the same carrier concentration and a conductivity reaching 1.25 × 10⁻⁶. 4 S·cm -1 The transmittance at a wavelength of 1500 nm exceeds 60% (JEN Swallow, BAD Williamson and et al., Materials Horizons, 2020, 7, 236-243). Chinese patent specification CN116072326A also discloses a method for preparing transparent conductive thin films using multi-component oxides such as titanium oxide and hafnium oxide doped indium oxide targets, resulting in thin film materials with a mobility of 80.5–82.5 cm⁻¹. 2 ·V-1 ·s -1 It achieves a transmittance of 90.0% to 90.5% in the range of 0.40 to 1.20 μm, while simultaneously meeting the requirements of high visible-near infrared transmittance and high mobility.

[0004] The aforementioned near-infrared transparent conductive films all use indium oxide (IO) as the matrix for doping, and most commonly used transparent conductive films are also based on IO materials. However, indium, the main raw material for IO, is a scarce resource. With the rapid increase in demand for indium from industries such as new energy, consumer electronics, and optical communication, as well as environmental policies restricting the mining of indium ore, price fluctuations and supply stability issues will severely restrict the large-scale production of IO-based transparent conductive materials. Therefore, designing and fabricating indium-free visible-near-infrared transparent conductive materials with high mobility and low cost is of great significance to the development of the optoelectronic technology field. Summary of the Invention

[0005] To address the aforementioned deficiencies or improvement needs of existing technologies, the present invention aims to provide a hydrogen-doped zinc oxide visible-near-infrared transparent conductive film and its preparation method. By controlling the composition and crystallinity of the film, thereby controlling the carrier concentration and improving mobility, the technical problem of traditional transparent conductive films being unable to achieve both high near-infrared transmittance and high conductivity can be effectively solved. The transparent conductive film obtained by the present invention has a transmittance of not less than 60% in the visible light band (0.38–0.78 μm) and a transmittance of not less than 70% in the near-infrared band (0.78–2.50 μm), with good conductivity. Furthermore, since the present invention obtains hydrogen-doped zinc oxide, the use of indium is avoided, overcoming the high cost disadvantage of indium-containing transparent conductive films. Simultaneously, the simple magnetron sputtering process (especially room-temperature magnetron sputtering) allows this visible-near-infrared transparent conductive film to be suitable for a wider range of applications.

[0006] To achieve the above objectives, according to one aspect of the present invention, a hydrogen-doped zinc oxide visible-near-infrared transparent conductive thin film is provided, characterized in that its preparation method is as follows: using magnetron sputtering with zinc oxide as the target material and an inert gas mixed with hydrogen and / or water vapor as the sputtering gas, by controlling the total volume percentage of hydrogen and water vapor in the sputtering gas to 2-10%, controlling the sputtering gas pressure to 0.2-1.2 Pa, and the sputtering power density to 3.0-5.0 W·cm⁻¹. -2 This allows for the deposition of hydrogen-doped zinc oxide visible-near-infrared transparent conductive films on the substrate;

[0007] This hydrogen-doped zinc oxide visible-near-infrared transparent conductive film exhibits a transmittance of no less than 60% in the 0.38 μm–0.78 μm wavelength range and no less than 70% in the 0.78 μm–2.50 μm wavelength range, with a conductivity higher than 0.8 × 10⁻⁶ at room temperature.3 S·cm -1 .

[0008] As a further preferred embodiment of the present invention, the carrier mobility of the transparent conductive film is higher than 35 cm⁻¹ at room temperature. 2 ·V -1 ·s -1 Sheet resistance less than 30Ω·sq -1 .

[0009] As a further preferred embodiment of the present invention, the thickness of the transparent conductive film is 100–800 nm.

[0010] According to another aspect of the present invention, the present invention provides a method for preparing the above-mentioned hydrogen-doped zinc oxide visible-near-infrared transparent conductive thin film, characterized by comprising the following steps:

[0011] S1. Prepare the zinc oxide target and a clean substrate;

[0012] S2. Mount the substrate and zinc oxide target onto the substrate base and target base of the magnetron sputtering equipment, respectively;

[0013] S3. Evacuate the magnetron sputtering equipment until the vacuum level in the equipment chamber drops to 1×10⁻⁶. -5 ~1×10 -3 At a pressure of Pa, an inert gas mixture of hydrogen and / or water vapor is introduced into the chamber, with the total volume percentage of hydrogen and water vapor in the mixture controlled at 2–10%. Simultaneously, the sputtering pressure is controlled at 0.2–1.2 Pa, and the sputtering power density at 3.0–5.0 W·cm⁻¹. -2 By performing magnetron sputtering in this way, hydrogen-doped zinc oxide visible-near-infrared transparent conductive films can be deposited on the substrate.

[0014] As a further preferred embodiment of the present invention, the sputtering time is 30 to 120 minutes, and the thickness of the resulting transparent conductive film is 100 to 800 nm.

[0015] As a further preferred embodiment of the present invention, the inert gas is at least one of argon and helium.

[0016] As a further preferred embodiment of the present invention, the substrate temperature is 20–60°C during the magnetron sputtering process.

[0017] According to another aspect of the present invention, the present invention provides the application of the above-mentioned hydrogen-doped zinc oxide visible-near-infrared transparent conductive film as a transparent conductive film in the 0.78μm to 2.50μm band, characterized in that the transmittance of the hydrogen-doped zinc oxide visible-near-infrared transparent conductive film in the 0.78μm to 2.50μm band is not less than 70%.

[0018] According to another aspect of the present invention, the present invention provides the application of the above-mentioned hydrogen-doped zinc oxide visible-near infrared transparent conductive film as a transparent conductive film in the 0.38μm to 0.78μm band, characterized in that the transmittance of the hydrogen-doped zinc oxide visible-near infrared transparent conductive film in the 0.38μm to 0.78μm band is not less than 60%.

[0019] Compared with the prior art, the present invention, through the above-described technical solution, designs a hydrogen-doped zinc oxide thin film and controls its composition and crystallinity, thereby controlling the carrier concentration and improving the mobility of the film. The resulting transparent conductive film exhibits a transmittance of no less than 60% in the visible light band (0.38–0.78 μm), a transmittance of no less than 70% in the near-infrared band (0.78–2.50 μm), and a conductivity higher than 0.8 × 10⁻⁶ at room temperature. 3 S·cm -1 Sheet resistance less than 30Ω·sq -1 The hydrogen-doped zinc oxide visible-near-infrared transparent conductive film of this invention is prepared by magnetron sputtering. Zinc oxide is used as the target material, and a mixed gas containing hydrogen and / or water vapor is used as the sputtering gas. Simultaneously, the hydrogen doping concentration is strictly controlled (by strictly controlling the total volume percentage of hydrogen and water vapor in the sputtering gas to 2-10%), the sputtering pressure to 0.2-1.2 Pa, and the sputtering power density to 3.0-5.0 W·cm⁻¹. -2 This method can effectively control the hydrogen doping amount and crystallinity of the prepared hydrogen-doped zinc oxide film. The resulting hydrogen-doped zinc oxide has a hexagonal wurtzite structure and good crystallinity, ensuring transmittance and conductivity in the near-infrared band.

[0020] Specifically, the present invention can achieve the following beneficial effects:

[0021] 1. The hydrogen-doped zinc oxide visible-near-infrared transparent conductive film obtained by this invention has a mobility exceeding 35 cm⁻¹. 2 ·V -1 ·s -1 It is significantly superior to other doped zinc oxide materials (the mobility is generally 1-30 cm⁻¹). 2 ·V -1 ·s -1 Therefore, it possesses excellent near-infrared transmittance and conductivity, specifically exhibiting a transmittance of no less than 70% and a conductivity higher than 0.8 × 10⁻⁶ in the near-infrared band (0.78–2.50 μm). 3 S·cm -1 Sheet resistance less than 30Ω·sq -1 .

[0022] Meanwhile, the transparent conductive film obtained by this invention has a transmittance of not less than 60% in the visible light band (0.38-0.78μm), and can be used in both the visible light band and the near-infrared band.

[0023] 2. The hydrogen-doped zinc oxide visible-near-infrared transparent conductive film of the present invention does not contain indium. Its main component is Zn, which is inexpensive and abundant, and can effectively reduce the raw material cost of transparent conductive films.

[0024] 3. The preparation method provided by this invention is based on magnetron sputtering technology, which is simple and suitable for large-scale production applications. During magnetron sputtering, the substrate temperature can be 20-60°C, especially at room temperature (the substrate does not require additional heating), and it is suitable for a variety of substrates, including flexible materials with low high-temperature tolerance. Attached Figure Description

[0025] Figure 1 These are scanning electron microscope (SEM) images of the surface and cross-section of the hydrogen-doped zinc oxide transparent conductive film prepared in Example 1 of this invention. Figure 1 (a) in the image corresponds to the surface SEM image. Figure 1 (b) corresponds to the cross-sectional SEM image.

[0026] Figure 2 This is an X-ray diffraction (XRD) pattern of the hydrogen-doped zinc oxide transparent conductive film prepared in Example 1 of the present invention.

[0027] Figure 3 This is the transmission spectrum of the hydrogen-doped zinc oxide transparent conductive film prepared in Example 1 of this invention. The data for the "ZnO:H / soda-lime glass" curve were measured with air as the baseline, while the data for the "ZnO:H" curve were measured with blank soda-lime glass as the baseline.

[0028] Figure 4 This is a scanning electron microscope (SEM) image of the surface of the hydrogen-doped zinc oxide transparent conductive film in Embodiment 2 of the present invention.

[0029] Figure 5 This is the transmission spectrum of the hydrogen-doped zinc oxide transparent conductive film in Embodiment 2 of the present invention.

[0030] The data for the "ZnO:H / soda-lime glass" curve were measured with air as the baseline, while the data for the "ZnO:H" curve were measured with blank soda-lime glass as the baseline.

[0031] Figure 6 This is a scanning electron microscope (SEM) image of the surface of the hydrogen-doped zinc oxide transparent conductive film in Embodiment 3 of the present invention.

[0032] Figure 7 This is the transmission spectrum of the hydrogen-doped zinc oxide transparent conductive film in Embodiment 3 of the present invention.

[0033] The data for the "ZnO:H / PET" curve were measured with air as the baseline, while the data for the "ZnO:H" curve were measured with blank PET as the baseline. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0035] The soda-lime glass used in the following examples was purchased from Zhuhai Kaiwei Optoelectronics Technology Co., Ltd., specifically model KV-SLG-001-100100, with a thickness of 1.1 mm; the PET film used was purchased from Shenzhen Hongsheng Plastics Co., Ltd., specifically model HS-PET02, with a thickness of 50 μm.

[0036] This invention utilizes magnetron sputtering to prepare hydrogen-doped zinc oxide visible-near-infrared transparent conductive thin films, which can be operated according to the following steps:

[0037] S1. Clean the substrate with ultrasonic cleaning and dry it with nitrogen gas.

[0038] S2, the substrate and zinc oxide target are respectively mounted on the substrate base and target base of the magnetron sputtering equipment;

[0039] S3, turn on the vacuum system of the magnetron sputtering equipment, and wait for the vacuum level in the equipment chamber to drop to 1×10⁻⁶. -5 ~1×10 -3 At Pa, a mixed gas containing hydrogen and / or water vapor is introduced into the chamber, and the chamber pressure is controlled by adjusting the flow rate of the mixed gas.

[0040] S4, set the sputtering power density, ignite the sputtering gas, adjust the sputtering time, and deposit the hydrogen-doped zinc oxide visible-near-infrared transparent conductive film on the substrate surface.

[0041] The following are specific examples:

[0042] Example 1

[0043] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target bases of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 8 × 10⁻⁶. -5 Pa. A mixture of hydrogen and argon gas, with hydrogen comprising 10% by volume, is introduced into the chamber. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 0.5 Pa. The sputtering power density is set to 4.0 W·cm⁻¹. -2 Sputtering for 60 minutes at a substrate temperature of 30°C yielded a hydrogen-doped zinc oxide transparent conductive film with a thickness of 518.8 nm. Figure 1 ). Figure 2 The image shows the XRD pattern of a hydrogen-doped zinc oxide transparent conductive film, which exhibits a well-crystalline hexagonal wurtzite structure. Figure 3 As shown, the transmittance of the hydrogen-doped zinc oxide transparent conductive film is between 64% and 99% in the visible light band and between 70% and 99% in the near-infrared band. Hall effect measurements show that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film are 47.4 cm⁻¹. 2 ·V -1 ·s -1 1.07×10 3 S·cm -1 16Ω·sq -1 .

[0044] Example 2

[0045] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target base of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 5 × 10⁻⁶. -4 Pa. A mixture of water vapor and argon gas, with water vapor comprising 10% by volume, is introduced into the chamber. The flow rate of the water vapor and argon gas mixture is adjusted to maintain a chamber pressure of 0.2 Pa. The sputtering power density is set to 5.0 W·cm³. -2 Sputtering for 30 minutes at a substrate temperature of 35°C resulted in the following morphology of a hydrogen-doped zinc oxide transparent conductive film: Figure 4 .like Figure 5 As shown, the transmittance of the hydrogen-doped zinc oxide transparent conductive film is between 68% and 99% in the visible light band and between 82% and 99% in the near-infrared band. Hall effect measurements show that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film are 42.7 cm⁻¹. 2 ·V -1 ·s -1 1.01×103 S·cm -1 28Ω·sq -1 .

[0046] Example 3

[0047] The polyethylene terephthalate (PET) film was ultrasonically cleaned sequentially in ethanol and deionized water for 10 minutes each, and then dried with nitrogen. The PET film and intrinsic zinc oxide ceramic target were mounted on the substrate and target bases of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 8 × 10⁻⁶. -4 Pa. A mixture of hydrogen and argon gas is introduced into the chamber, with hydrogen comprising 5% by volume. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 0.8 Pa. The sputtering power density is set to 3.5 W·cm³. -2 Sputtering for 75 minutes at a substrate temperature of 25°C resulted in the following morphology of a hydrogen-doped zinc oxide transparent conductive film: Figure 6 .like Figure 7 As shown, the transmittance of the hydrogen-doped zinc oxide transparent conductive film is between 60% and 99% in the visible light band and between 82% and 99% in the near-infrared band. Hall effect measurements show that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film are 41.6 cm⁻¹. 2 ·V -1 ·s -1 1.04×10 3 S·cm -1 18Ω·sq -1 .

[0048] Example 4

[0049] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the aluminum-doped zinc oxide ceramic target (2% aluminum doping by mass) were mounted on the substrate and target base of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 5 × 10⁻⁶. -4 Pa. A mixture of hydrogen and argon gas is introduced into the chamber, with hydrogen comprising 2% by volume. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 0.75 Pa. The sputtering power density is set to 4 W·cm⁻¹. -2 Sputtering for 70 minutes at a substrate temperature of 35°C resulted in a hydrogen-doped zinc oxide transparent conductive film with transmittance of 70–99% in the visible light band and 70–99.9% in the near-infrared band. Hall effect measurements showed that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film were 35.1 cm⁻¹. 2 ·V -1 ·s -11.04×10 3 S·cm -1 24Ω·sq -1 .

[0050] Example 5

[0051] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target bases of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 6 × 10⁻⁶. -4 Pa. A mixture of hydrogen and argon gas is introduced into the chamber, with hydrogen comprising 8% by volume. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 1.2 Pa. The sputtering power density is set to 4.5 W·cm³. -2 Sputtering for 90 minutes at a substrate temperature of 40°C resulted in a hydrogen-doped zinc oxide transparent conductive film with a transmittance of 70–99% in the visible light band and 70–99.5% in the near-infrared band. Hall effect measurements showed that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film were 36.5 cm⁻¹. 2 ·V -1 ·s -1 1.06×10 3 S·cm -1 28Ω·sq -1 .

[0052] Example 6

[0053] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target bases of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 1×10⁻⁶. -4 Pa. A mixture of hydrogen and argon gas, with hydrogen comprising 10% by volume, is introduced into the chamber. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 0.8 Pa. The sputtering power density is set to 3.0 W·cm³. -2 Sputtering for 120 minutes at a substrate temperature of 40°C resulted in a hydrogen-doped zinc oxide transparent conductive film with a transmittance of 77–90% in the visible light band and 75–90% in the near-infrared band. Hall effect measurements showed that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film were 44.4 cm⁻¹. 2 ·V -1 ·s -1 0.89×10 3 S·cm -1 29Ω·sq-1 .

[0054] Comparative Example 1

[0055] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target bases of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 8 × 10⁻⁶. -5 Argon gas is introduced into the chamber, and the argon gas flow rate is adjusted to achieve a chamber pressure of 0.8 Pa. The sputtering power density is set to 4.0 W·cm³. -2 Sputtering for 60 minutes at a substrate temperature of 30°C resulted in a transparent zinc oxide film with a transmittance of 60–99% in the visible light band and 85–99% in the near-infrared band. However, the sheet resistance of this transparent zinc oxide film was greater than 3 × 10⁻⁶. 5 Ω·sq -1 .

[0056] Comparative Example 2

[0057] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target base of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 5 × 10⁻⁶. -5 Pa. A mixture of hydrogen and argon gas, with hydrogen comprising 10% by volume, is introduced into the chamber. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 1.6 Pa. The sputtering power density is set to 5.0 W·cm³. -2 Sputtering for 30 minutes at a substrate temperature of 30°C resulted in a hydrogen-doped zinc oxide transparent conductive film with transmittance of 72-99% in the visible light band and 78-99% in the near-infrared band. However, Hall effect measurements showed that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film were 13.67 cm⁻¹. 2 ·V -1 ·s -1 335S·cm -1 138Ω·sq -1 .

[0058] Comparative Example 3

[0059] The soda-lime glass was ultrasonically cleaned sequentially in acetone, ethanol, and deionized water for 10 minutes each, and then dried with nitrogen. The soda-lime glass and the intrinsic zinc oxide ceramic target were mounted on the substrate and target base of the magnetron sputtering equipment. The vacuum system of the magnetron sputtering equipment was turned on, and evacuation began until the chamber vacuum reached 5 × 10⁻⁶. -5Pa. A mixture of hydrogen and argon gas, with hydrogen comprising 10% by volume, is introduced into the chamber. The flow rate of the hydrogen and argon mixture is adjusted to achieve a chamber pressure of 0.8 Pa. The sputtering power density is set to 2.5 W·cm³. -2 Sputtering for 30 minutes at a substrate temperature of 30°C resulted in a hydrogen-doped zinc oxide transparent conductive film with a transmittance of 60–99% in the visible light band and 90–95% in the near-infrared band. However, Hall effect measurements showed that the mobility, conductivity, and sheet resistance of this hydrogen-doped zinc oxide transparent conductive film were 0.18 cm⁻¹. 2 ·V -1 ·s -1 7.83 S·cm -1 1.12×10 4 Ω·sq -1 .

[0060] The above embodiments are merely examples. For instance, in addition to intrinsic zinc oxide, the target material can also be zinc oxide doped with other trace metal elements (such as aluminum, titanium, tungsten, molybdenum, etc., with a doping mass fraction not exceeding 2%). As another example, during magnetron sputtering, the substrate temperature can also be other temperatures within the range of 20 to 60°C.

[0061] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A hydrogen-doped zinc oxide visible-near-infrared transparent conductive film with good crystallinity, characterized in that, The preparation method is as follows: Using magnetron sputtering, zinc oxide is used as the target material, and an inert gas mixed with hydrogen and / or water vapor is used as the sputtering gas. The total volume percentage of hydrogen and water vapor in the sputtering gas is controlled to be 2-10%, the sputtering pressure is controlled to be 0.2-1.2 Pa, and the sputtering power density is controlled to be 3.0-5.0 W·cm⁻¹. -2 With a substrate temperature of 20~60℃, a hydrogen-doped zinc oxide visible-near-infrared transparent conductive film with good crystallinity can be deposited on the substrate; the XRD pattern of the hydrogen-doped zinc oxide visible-near-infrared transparent conductive film only has diffraction peaks of the (002) crystal plane and the (004) crystal plane, and has obvious preferential orientation growth characteristics. This well-crystallized hydrogen-doped zinc oxide visible-near-infrared transparent conductive film exhibits a transmittance of no less than 60% in the 0.38 μm–0.78 μm wavelength range and no less than 70% in the 0.78 μm–2.50 μm wavelength range, with a conductivity higher than 0.8 × 10⁻⁶ at room temperature. 3 S·cm -1 .

2. The hydrogen-doped zinc oxide visible-near-infrared transparent conductive film with good crystallinity as described in claim 1, characterized in that, At room temperature, the carrier mobility of the transparent conductive film is greater than 35 cm⁻¹. 2 ·V -1 ·s -1 Shear resistance less than 30 Ω·sq -1 .

3. The hydrogen-doped zinc oxide visible-near-infrared transparent conductive film with good crystallinity as described in claim 1, characterized in that, The thickness of the transparent conductive film is 100~800 nm.

4. The method for preparing a well-crystallized hydrogen-doped zinc oxide visible-near-infrared transparent conductive thin film as described in any one of claims 1-3, characterized in that, Includes the following steps: S1. Prepare the zinc oxide target and a clean substrate; S2. Mount the substrate and zinc oxide target onto the substrate base and target base of the magnetron sputtering equipment, respectively; S3. Evacuate the magnetron sputtering equipment until the vacuum level in the equipment chamber drops to 1×10⁻⁶. -5 ~1×10 - 3 At a pressure of Pa, an inert gas mixture containing hydrogen and / or water vapor is introduced into the chamber, with the total volume percentage of hydrogen and water vapor in the mixture controlled at 2-10%. Simultaneously, the sputtering pressure is controlled at 0.2-1.2 Pa, and the sputtering power density at 3.0-5.0 W·cm⁻¹. -2 In this way, magnetron sputtering is performed. During the magnetron sputtering process, the substrate temperature is 20~60℃, and a hydrogen-doped zinc oxide visible-near-infrared transparent conductive film with good crystallinity can be deposited on the substrate. The XRD pattern of this hydrogen-doped zinc oxide visible-near-infrared transparent conductive film only has diffraction peaks of the (002) crystal plane and the (004) crystal plane, which has obvious preferential orientation growth characteristics.

5. The preparation method according to claim 4, characterized in that, The sputtering time is 30 to 120 minutes, and the thickness of the resulting transparent conductive film is 100 to 800 nm.

6. The preparation method according to claim 4, characterized in that, The inert gas is at least one of argon and helium.

7. The application of the well-crystallized hydrogen-doped zinc oxide visible-near-infrared transparent conductive film as described in any one of claims 1-3 as a transparent conductive film in the 0.78 μm~2.50 μm wavelength band, characterized in that... The highly crystalline hydrogen-doped zinc oxide visible-near-infrared transparent conductive film has a transmittance of no less than 70% in the 0.78 μm to 2.50 μm wavelength range.

8. The application of the well-crystallized hydrogen-doped zinc oxide visible-near-infrared transparent conductive film as described in any one of claims 1-3 as a transparent conductive film in the 0.38 μm~0.78 μm wavelength band, characterized in that... The highly crystalline hydrogen-doped zinc oxide visible-near-infrared transparent conductive film has a transmittance of no less than 60% in the 0.38 μm to 0.78 μm wavelength range.

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