CN112713133A - Transparent conductive substrate containing metal layer and preparation method thereof - Google Patents
Transparent conductive substrate containing metal layer and preparation method thereof Download PDFInfo
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- CN112713133A CN112713133A CN202011560375.5A CN202011560375A CN112713133A CN 112713133 A CN112713133 A CN 112713133A CN 202011560375 A CN202011560375 A CN 202011560375A CN 112713133 A CN112713133 A CN 112713133A
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- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49838—Geometry or layout
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Abstract
The invention provides a transparent conductive substrate containing a metal layer and a preparation method thereof, wherein the preparation method comprises the following steps: transparent supporting substrate and polycrystalline SnO stacked in sequence2Barrier layer, Ag-Au metal layer, NiCr alloy layer and F-doped SnO2And a protective layer. Forming a transparent conductive substrate having Ag-Au metal layer as main conductive layer, polycrystalline SnO2The barrier layer can effectively prevent elements in the transparent support substrate from diffusing into the metal layer, ensure the purity of the metal layer and improve the conductivity of the transparent conductive substrate; the NiCr alloy layer can effectively prevent the oxidation and diffusion of the metal layer; f-doped SnO2The protective layer effectively prolongs the service life of the transparent conductive substrate; in addition, the preparation method has low process difficulty and environmentIs friendly and easy to be applied in large scale.
Description
Technical Field
The invention relates to the field of transparent conductive substrates, in particular to a transparent conductive substrate containing a metal layer and a preparation method thereof.
Background
China is in a period of rapid development of industrialization and urbanization, and has wide territory and large population, and the energy consumption intensity is high. However, energy sources, especially non-renewable energy sources, in China are relatively in short supply. With the further expansion of economic scale, great pressure is placed on energy supply, and contradiction between supply and demand will exist for a long time. In addition, the large-scale use of fossil energy places an extremely severe burden on our ecological environment. During the 75 th united nations' congress, China proposed that the independent contribution of the country will be improved, and the carbon dioxide emission strives to reach the peak value 2030 years ago, and strives to achieve carbon neutralization 2060 years ago. The new industries for accelerating the growth of new energy resources and the like are clearly put forward in the fourteen-five planning of China. Solar energy is one of the first choice in the future new energy field, and the global solar energy installation reaches 8519GW in 2050. Under the background, the second generation and the third generation solar cells are bound to meet the gold period of innovation development. As a light-transmitting surface and an electrode of the thin film solar cell, tco (transparent Conductive oxide) glass is an essential raw material in the production process of the thin film solar cell. Furthermore, TCO has a very wide application as a transparent conductive electrode in liquid crystal displays, photodetectors, and flat panel displays.
As the research on the transparent conductive substrate becomes deeper and deeper, a SnO using a metal layer with a thickness of nanometer size as an interlayer2/Ag/SnO2The transparent conductive substrate enters the field of vision of people. This structure makes full use of SnO2The material has the advantages of hard texture, strong corrosion resistance and good conductive performance of the metal material, therefore,high light transmittance and good conductivity can be obtained. However, the transparent conductive substrate with such a structure cannot withstand high temperature treatment, and the light transmittance and the conductivity are significantly reduced after the high temperature treatment. However, the transparent conductive substrate applied in the solar cell manufacturing process inevitably needs to be subjected to high temperature treatment. For example, in a CdTe solar cell fabrication process, the transparent conductive substrate needs to be subjected to a high temperature treatment of 550 ℃, and the like.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a transparent conductive substrate containing a metal layer and a method for manufacturing the same, which are used to solve the problems of low light transmittance and conductivity of the substrate due to the difficulty in withstanding high temperature of the transparent conductive substrate containing a metal layer in the prior art.
To achieve the above and other related objects, the present invention provides a transparent conductive substrate including a metal layer, the transparent conductive substrate including:
transparent supporting substrate and polycrystalline SnO stacked in sequence2Barrier layer, Ag-Au metal layer, NiCr alloy layer and F-doped SnO2And a protective layer.
Optionally, the transparent support substrate comprises a single layer or a laminate formed from one or more of the group consisting of a glass substrate, a ceramic substrate and a plastic substrate.
Optionally, the transparent support substrate is ultra-white float glass.
Optionally, the polycrystalline SnO2The thickness of the barrier layer is between 20nm and 200nm, the thickness of the Ag-Au metal layer is between 5nm and 15nm, the thickness of the NiCr alloy layer is between 0.5nm and 3nm, and the F-doped SnO2The thickness of the protective layer is between 5nm and 100 nm.
Optionally, the molar ratio of the Au element to the Ag element in the Ag-Au metal layer is between 0% and 10%, and the atomic ratio of the Ni element to the Cr element in the NiCr alloy layer is 4: 1, said F-doped SnO2The molar ratio of the F element to the Sn element in the protective layer is between 0 and 30 percent.
The invention also provides a preparation method of the transparent conductive substrate containing the metal layer, which comprises the following steps:
s1: providing a transparent support substrate;
s2: forming polycrystalline SnO on the transparent support substrate2A barrier layer;
s3: forming an Ag-Au metal layer on the surface of the structure obtained in the step S2;
s4: forming a NiCr alloy layer on the surface of the structure obtained in the step S3;
s5: forming F-doped SnO on the surface of the structure obtained in step S42And a protective layer.
Optionally, step S5 is followed by a step of vacuum annealing, by which the crystallinity of each layer is increased, and the annealing temperature of the vacuum annealing is between 200 ℃ and 700 ℃.
Optionally, in step S2, the polycrystalline SnO is formed by magnetron sputtering or chemical vapor deposition2And the coating temperature is between 200 and 800 ℃.
Optionally, in step S3, the Ag-Au metal layer is formed at room temperature by using a magnetron sputtering technique, wherein an Au element is doped in an Ag target to form an Au-doped Ag target, and a molar ratio of the Au element to the Ag element in the Ag target is between 0% and 10%.
Optionally, in step S4, the NiCr alloy layer is formed at room temperature by using a magnetron sputtering technique, wherein an atomic ratio of the Ni element to the Cr element in the NiCr alloy layer is 4: 1.
optionally, in step S5, forming the F-doped SnO by using a magnetron sputtering technique2A protective layer in which an F element is doped in SnO2In the target material, F-doped SnO is formed2Target material of said SnO2The molar ratio of the F element to the Sn element in the target material is between 0 and 30 percent, and the coating temperature is between 23 and 200 ℃.
Optionally, the structure obtained in step S4 is placed in a magnetron sputtering device to be heated to an annealing temperature, vacuum annealing is performed, and then the temperature is adjusted to a coating temperature to perform the F-doped SnO2And (5) coating the protective layer.
Optionally, the polycrystalline SnO2The thickness of the barrier layer is between 20nm and 200nm, the thickness of the Ag-Au metal layer is between 5nm and 15nm, the thickness of the NiCr alloy layer is between 0.5nm and 3nm, and the F-doped SnO2The thickness of the protective layer is between 5nm and 100 nm.
As described above, the transparent conductive substrate including a metal layer of the present invention and the method for preparing the same includes: transparent supporting substrate and polycrystalline SnO stacked in sequence2Barrier layer, Ag-Au metal layer, NiCr alloy layer and F-doped SnO2And a protective layer. The transparent conductive substrate is prepared by reacting SnO2Crystallization of the barrier layer to form polycrystalline SnO2Barrier layer, in contrast to amorphous SnO2Barrier layer, polycrystalline SnO2The transparent conductive substrate is more compact and has higher stability, and elements such as sodium, potassium and the like in the transparent supporting substrate are prevented from diffusing into the Ag-Au metal layer, so that the purity of the Ag-Au metal layer is ensured, and the conductivity of the transparent conductive substrate is improved; in addition, the Au element is doped in the Ag metal layer, and due to the specific chemical stability and thermal stability of the Au element, the Au element is added, so that the Ag metal layer has a certain pinning effect, and meanwhile, the oxidation resistance is also improved; moreover, the NiCr alloy layer is inserted, and the NiCr alloy layer can effectively increase the bonding force between the film layers, prevent the oxidation of the Ag-Au metal layer and reduce the oxidation of the Ag-Au metal layer and the F-doped SnO2Interdiffusion of elements between the protective layers. The preparation method adopts a vacuum annealing process to effectively increase the crystallinity of each film layer, thereby greatly improving the stability of the film layer and finally ensuring the light transmittance and the electric conductivity of the transparent conductive substrate after the high-temperature process; finally, the preparation method has low process difficulty, is environment-friendly and is easy for large-scale application.
Drawings
Fig. 1 is a schematic structural diagram of a transparent conductive substrate containing a metal layer according to the present invention.
Fig. 2 is a process flow chart of the method for preparing the transparent conductive substrate containing a metal layer according to the present invention.
Description of the element reference numerals
1 transparent support substrate
2 polycrystalline SnO2Barrier layer
3 Ag-Au metal layer
4 NiCr alloy layer
5F doped SnO2Protective layer
S1-S5
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 and fig. 2. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
As described in the background, existing SnO2/Ag/SnO2The transparent conductive substrate is difficult to bear high temperature, and the light transmittance and the conductivity of the substrate are remarkably reduced after the high temperature. For this reason, the inventors have conducted extensive studies and analysis to find out various causes that may cause the problem, and it is considered that there are two causes that decrease of the light transmittance and the electric conductivity of the transparent conductive substrate after a high temperature, one is SnO2The layer being thin and containing oxygen in free form, SnO2/Ag/SnO2The Ag metal layer of the structure can be oxidized at high temperature, so that the light transmittance of the substrate is influenced; secondly, atom thermal vibration in each film layer is intensified at high temperature, so that interdiffusion occurs among different film layers, and the Ag metal layerThe conductive property of the substrate is reduced due to the gradual thinning under the diffusion effect.
Based on this recognition, the inventors propose a transparent conductive substrate including a metal layer, as shown in fig. 1, the transparent conductive substrate including:
transparent supporting substrate 1 and polycrystalline SnO which are sequentially superposed2A barrier layer 2, an Ag-Au metal layer 3, a NiCr alloy layer 4 and F-doped SnO2And a protective layer 5. The F-doped SnO2The protective layer 5 is SnO2: f, FTO for short.
First, by making SnO2Crystallization of the barrier layer to form polycrystalline SnO2Barrier layer 2, in contrast to amorphous SnO2Barrier layer, polycrystalline SnO2The Ag-Au conductive substrate is more compact and has higher stability, and elements such as sodium, potassium and the like in the transparent supporting substrate can be prevented from diffusing into the Ag-Au metal layer 3, so that the purity of the Ag-Au metal layer 3 is ensured, and the conductivity of the transparent conductive substrate is improved; in addition, the Au element is doped in the Ag metal layer, and due to the specific chemical stability and thermal stability of the Au element, the Au element is added to have a certain pinning effect on the Ag metal layer, and forms a pinning center, so that the diffusion of Ag is inhibited, and meanwhile, the oxidation resistance is also improved; moreover, the NiCr alloy layer 4 is inserted, and the NiCr alloy layer 4 can effectively increase the bonding force between film layers, prevent the oxidation of the Ag-Au metal layer 3 and reduce the oxidation of the Ag-Au metal layer 3 and the F-doped SnO2Interdiffusion of elements between the protective layers. Finally, the transparent conductive substrate is subjected to a high-temperature process to ensure the light transmittance and the conductivity of the transparent conductive substrate.
As an example, the transparent support substrate 1 includes a single layer or a laminate layer formed of one or more of the group consisting of a glass substrate, a ceramic substrate, and a plastic substrate. That is, the transparent support substrate 1 may have a single-layer structure or a multi-layer laminated structure, and is characterized by having a certain strength, a supporting function, and a good light transmission property.
As an example, the polycrystalline SnO2The thickness of the barrier layer 2 is between 20nm and 200nm, the thickness of the Ag-Au metal layer 3 is between 5nm and 15nm, andthe thickness of the NiCr alloy layer 4 is between 0.5nm and 3nm, and the F-doped SnO2The thickness of the protective layer 5 is between 5nm and 100 nm. The polycrystalline SnO2The thickness of the barrier layer 2 is preferably set between 20nm and 200nm, so that the surface smoothness of the substrate can be ensured; the thickness of the Ag-Au metal layer 3 is selected by considering both electrical property and light transmittance, the conductivity is reduced when the Ag-Au metal layer is too thin, and the light transmittance is reduced when the Ag-Au metal layer is too thick, so that the preferred thickness is set to be between 5nm and 15nm, and the conductivity and the light transmittance can be ensured; the thickness of the NiCr alloy layer 4 should be selected in consideration of both the refractive index and the bonding performance, the thicker the NiCr alloy layer, the better the bonding performance, but the larger the refractive index of the NiCr alloy layer, the too thick the NiCr alloy layer may cause the transmittance to decrease significantly, so the preferred thickness is set between 0.5nm and 3 nm.
For example, the molar ratio of the Au element to the Ag element in the Ag — Au metal layer 3 is between 0% and 10%, and the atomic ratio of the Ni element to the Cr element in the NiCr alloy layer 4 is 4: 1. the molar ratio of the Au element to the Ag element in the Ag-Au metal layer 3 is between 0% and 10%, the production cost is reduced while the pinning effect of the Au element is ensured, and in addition, the atomic ratio of the Ni element to the Cr element in the NiCr alloy layer 4 is set as 4: 1, the high temperature stability and the mechanical property of the NiCr alloy layer are better.
Based on the transparent conductive substrate containing the metal layer, as shown in fig. 1 and fig. 2, the invention further provides a preparation method of the transparent conductive substrate containing the metal layer, wherein the preparation method comprises the following steps:
s1: providing a transparent support substrate 1;
s2: forming polycrystalline SnO on the transparent support substrate 12A barrier layer 2;
s3: forming an Ag-Au metal layer 3 on the surface of the structure obtained in the step S2;
s4: forming a NiCr alloy layer 4 on the surface of the structure obtained in the step S3;
s5: forming F-doped SnO on the surface of the structure obtained in step S42And a protective layer 5.
The preparation method has low difficulty of the preparation process, small environmental pollution and easy large-scale application, and the obtained transparent conductive substrate has good high-temperature resistance.
As an example, an annealing process may be added after step S5, in which the formed stacked structure is annealed in a vacuum environment, and the annealing temperature is between 200 ℃ and 700 ℃. Compared with annealing in the atmosphere, vacuum annealing can effectively prevent each film layer in the laminated structure from being oxidized in the annealing process. The crystallinity of each film layer in the laminated structure can be further improved through the step, so that the overall performance of the transparent conductive substrate is improved. As another example, the annealing process may be performed before step S5 by using a magnetron sputtering apparatus with high vacuum and heating characteristics to plate F-doped SnO2Before the protective layer, carrying out vacuum annealing treatment in a magnetron sputtering device to improve the SnO except the F doping2The crystallinity of the other film layers than the protective layer 5.
Illustratively, in step S2, the polycrystalline SnO is formed2The method of the barrier layer 2 can adopt magnetron sputtering technology or Chemical Vapor Deposition (CVD) technology, and the coating temperature is between 200 ℃ and 800 ℃. Illustratively, the polycrystalline SnO may be coated during the glass forming process in a tin bath or an annealing furnace by an in-line CVD technique2The film coating temperature of the barrier layer 2 is between 500 and 800 ℃; the polycrystalline SnO may also be formed by off-line CVD techniques2The coating temperature of the barrier layer 2 is between 400 and 650 ℃; the polycrystalline SnO may also be formed by magnetron sputtering techniques2The film coating temperature of the barrier layer 2 is between 200 and 650 ℃.
As an example, in step S3, the Ag — Au metal layer 3 is formed at room temperature by using a magnetron sputtering technique, wherein an Au element is doped in an Ag target to form an Au-doped Ag target, wherein the room temperature is generally between 23 ℃ and 27 ℃. Preferably, the molar ratio of the Au element to the Ag element in the Ag target is between 0% and 10%, and for example, may be 2%, 4%, 6%, or 8%.
As an example, in step S4, the NiCr alloy layer 4 is formed at room temperature by using a magnetron sputtering technique, wherein an atomic ratio of the Ni element to the Cr element in the NiCr alloy layer 4 is 4: 1, the room temperature here is generally between 23 ℃ and 27 ℃.
As an example, in step S5, the F-doped SnO is formed by magnetron sputtering technique2A protective layer 5 in which an element F is doped SnO2In the target material, F-doped SnO is formed2The coating temperature of the target material is between 23 and 200 ℃, and preferably, the SnO2The molar ratio of the F element to the Sn element in the target material is between 0 and 30 percent. The temperature of the coating film is set to be between 23 ℃ and 200 ℃, so that the protective effect on the substrate is achieved, the Ag-Au metal layer can be effectively prevented from being oxidized and the Ag-Au metal layer can be effectively prevented from being diffused in the preparation process, and the service life of the transparent conductive substrate is effectively prolonged. Further, when step S5 is performed, the structure obtained in step S4 may be placed in a magnetron sputtering device to be heated to the annealing temperature, and then vacuum annealing is performed, and then the temperature is adjusted to the plating temperature to perform the F-doped SnO2And (5) coating the protective layer. .
As an example, the polycrystalline SnO2The thickness of the barrier layer 2 is between 20nm and 200nm, the thickness of the Ag-Au metal layer 3 is between 5nm and 15nm, the thickness of the NiCr alloy layer 4 is between 0.5nm and 3nm, and the F-doped SnO2The thickness of the protective layer 5 is between 5nm and 100 nm.
The transparent conductive substrate including a metal layer and the method for manufacturing the same according to the present invention will be further described with reference to specific examples.
Example one
As shown in FIG. 1, the transparent conductive substrate containing a metal layer according to the present embodiment includes a transparent support substrate 1 and a polycrystalline SnO layer stacked in this order2A barrier layer 2, an Ag-Au metal layer 3, a NiCr alloy layer 4 and F-doped SnO2And a protective layer 5.
The preparation process comprises the following steps:
a) providing ultra-white float glass with the thickness of 3.2mm as the transparent supporting substrate 1, ultrasonically cleaning the transparent supporting substrate in deionized water for 10min, then transferring the transparent supporting substrate into absolute ethyl alcohol for ultrasonic cleaning for 10min, drying, and depositing SnO with the thickness of about 50nm on the surface of the transparent supporting substrate by utilizing a radio frequency magnetron sputtering technology2A thin film to form the polycrystalline SnO2A barrier layer 2. Wherein, the radio frequency magnetron sputteringThe target material adopted in the sputtering technology is SnO2The sputtering gas is argon, and the coating temperature is 400 ℃.
b) And (c) taking out the sample in the step (a), and growing a layer of Ag-Au metal film with the thickness of 10nm on the surface of the sample by utilizing a direct current magnetron sputtering technology to form an Ag-Au metal layer 3. Wherein, the target material adopted in the DC magnetron sputtering technology is an Au-doped Ag target material, the molar ratio of Au doping is 7 percent, the sputtering gas is argon, and the coating temperature is room temperature, namely between 23 and 27 ℃.
c) And (c) after taking out the sample in the step (b), depositing a NiCr film with the thickness of about 1.5nm on the surface of the sample by utilizing a direct current magnetron sputtering technology to form the NiCr alloy layer 4. Wherein, the target material adopted in the DC magnetron sputtering technology is NiCr target material, the atomic ratio of Ni element and Cr element in the NiCr target material is 4: 1, the sputtering gas is argon, and the coating temperature is room temperature, namely between 23 and 27 ℃.
d) Taking out the sample in the step c, and depositing F-doped SnO with the thickness of about 50nm on the surface of the sample by utilizing a radio frequency magnetron sputtering technology2Thin film to form the F-doped SnO2And a protective layer 5. Wherein, the target material adopted in the radio frequency magnetron sputtering technology is F-doped SnO2The sputtering gas is argon, and the coating temperature is room temperature, namely 23-27 ℃.
e) And d, taking out the sample in the step d, putting the sample into a muffle furnace, and annealing for 30min at 500 ℃. And before annealing, vacuumizing the muffle furnace to obtain the required transparent conductive substrate containing the metal layer.
Example two
As shown in FIG. 1, the transparent conductive substrate containing a metal layer according to the present embodiment includes a transparent support substrate 1 and a polycrystalline SnO layer stacked in this order2A barrier layer 2, an Ag-Au metal layer 3, a NiCr alloy layer 4 and F-doped SnO2And a protective layer 5.
The preparation process comprises the following steps:
a) providing ultra-white float glass with the thickness of 3.2mm as the transparent supporting substrate 1, ultrasonically cleaning the transparent supporting substrate in deionized water for 10min, then ultrasonically cleaning the transparent supporting substrate in absolute ethyl alcohol for 10min, drying the transparent supporting substrate, and depositing the transparent supporting substrate on the surface of the transparent supporting substrate by using a chemical vapor deposition technologySnO of about 70nm2A thin film to form the polycrystalline SnO2A barrier layer 2. Wherein the introduced gas is MBTC, TFA, N2The plating temperature of the mixed gas of (3) was 550 ℃.
b) And (c) taking out the sample in the step (a), and growing a layer of Ag-Au metal film with the thickness of 10nm on the surface of the sample by utilizing a direct current magnetron sputtering technology to form an Ag-Au metal layer 3. Wherein, the target material adopted in the DC magnetron sputtering technology is an Au-doped Ag target material, the mol ratio of Au doping is 5 percent, the sputtering gas is argon, and the coating temperature is room temperature, namely between 23 and 27 ℃.
c) And (c) after taking out the sample in the step (b), depositing a NiCr film with the thickness of about 1.0nm on the surface of the sample by utilizing a direct current magnetron sputtering technology to form the NiCr alloy layer 4. Wherein, the target material adopted in the DC magnetron sputtering technology is NiCr target material, the atomic ratio of Ni element and Cr element in the NiCr target material is 4: 1, the sputtering gas is argon, and the coating temperature is room temperature, namely between 23 and 27 ℃.
d) Taking out the sample in the step c, and depositing F-doped SnO with the thickness of about 70nm on the surface of the sample by utilizing a radio frequency magnetron sputtering technology2Thin film to form the F-doped SnO2And a protective layer 5. Wherein, the target material adopted in the radio frequency magnetron sputtering technology is F-doped SnO2The sputtering gas is argon, and the coating temperature is room temperature, namely 23-27 ℃.
e) And d, taking out the sample in the step d, putting the sample into a muffle furnace, and annealing for 30min at 400 ℃. And before annealing, vacuumizing the muffle furnace to obtain the required transparent conductive substrate containing the metal layer.
EXAMPLE III
As shown in FIG. 1, the transparent conductive substrate containing a metal layer according to the present embodiment includes a transparent support substrate 1 and a polycrystalline SnO layer stacked in this order2A barrier layer 2, an Ag-Au metal layer 3, a NiCr alloy layer 4 and F-doped SnO2And a protective layer 5.
The preparation process comprises the following steps:
a) providing ultra-white float glass with the thickness of 3.2mm as the transparent support substrate 1, ultrasonically cleaning the glass in deionized water for 10min, and transferring the glass into absolute ethyl alcoholUltrasonically cleaning for 10min, drying, and depositing SnO with the thickness of about 50nm on the surface of the substrate by using a radio frequency magnetron sputtering technology2A thin film to form the polycrystalline SnO2A barrier layer 2. Wherein, the target material adopted in the radio frequency magnetron sputtering technology is SnO2The sputtering gas is argon, and the coating temperature is 400 ℃.
b) And (c) taking out the sample in the step (a), and growing a layer of Ag-Au metal film with the thickness of 10nm on the surface of the sample by utilizing a direct current magnetron sputtering technology to form an Ag-Au metal layer 3. Wherein, the target material adopted in the DC magnetron sputtering technology is an Au-doped Ag target material, the molar ratio of Au doping is 7 percent, the sputtering gas is argon, and the coating temperature is room temperature, namely between 23 and 27 ℃.
c) And (c) after taking out the sample in the step (b), depositing a NiCr film with the thickness of about 1.5nm on the surface of the sample by utilizing a direct current magnetron sputtering technology to form the NiCr alloy layer 4. Wherein, the target material adopted in the DC magnetron sputtering technology is NiCr target material, the atomic ratio of Ni element and Cr element in the NiCr target material is 4: 1, the sputtering gas is argon, and the coating temperature is room temperature, namely between 23 and 27 ℃.
d) After the NiCr alloy layer 4 is coated, vacuumizing the magnetron sputtering equipment to 10 DEG-4Pa, then raising the temperature to 400 ℃ and keeping the temperature for 30 min.
e) After the temperature of the magnetron sputtering equipment is reduced to room temperature, F-doped SnO with the thickness of about 80nm is deposited on the surface of the magnetron sputtering equipment by utilizing a radio frequency magnetron sputtering technology2Thin film to form the F-doped SnO2And a protective layer 5. Wherein, the target material adopted in the radio frequency magnetron sputtering technology is F-doped SnO2The sputtering gas is argon, and the coating temperature is room temperature, namely 23-27 ℃. Thus obtaining the required transparent conductive substrate containing the metal layer.
In summary, the present invention provides a transparent conductive substrate including a metal layer and a method for manufacturing the same, the transparent conductive substrate including: transparent supporting substrate and polycrystalline SnO stacked in sequence2Barrier layer, Ag-Au metal layer, NiCr alloy layer and F-doped SnO2And a protective layer. The transparent conductive substrate is prepared by reacting SnO2Crystallization of the barrier layer to form polycrystalline SnO2Barrier layerCompared with amorphous SnO2Barrier layer, polycrystalline SnO2The transparent conductive substrate is more compact and has higher stability, and elements such as sodium, potassium and the like in the transparent supporting substrate are prevented from diffusing into the Ag-Au metal layer, so that the purity of the Ag-Au metal layer is ensured, and the conductivity of the transparent conductive substrate is improved; in addition, the Au element is doped in the Ag metal layer, and due to the specific chemical stability and thermal stability of the Au element, the Au element is added, so that the Ag metal layer has a certain pinning effect, and meanwhile, the oxidation resistance is also improved; moreover, the NiCr alloy layer is inserted, and the NiCr alloy layer can effectively increase the bonding force between the film layers, prevent the oxidation of the Ag-Au metal layer and reduce the oxidation of the Ag-Au metal layer and the F-doped SnO2Interdiffusion of elements between the protective layers. The preparation method adopts a vacuum annealing process to effectively increase the crystallinity of each film layer, thereby greatly improving the stability of the film layer and finally ensuring the light transmittance and the electric conductivity of the transparent conductive substrate after the high-temperature process; finally, the preparation method has low process difficulty, is environment-friendly and is easy for large-scale application. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (13)
1. A transparent conductive substrate comprising a metal layer, the transparent conductive substrate comprising:
transparent supporting substrate and polycrystalline SnO stacked in sequence2Barrier layer, Ag-Au metal layer, NiCr alloy layer and F-doped SnO2And a protective layer.
2. The transparent conductive substrate comprising a metal layer according to claim 1, wherein: the transparent support substrate comprises a single layer or a laminate formed of one or more of the group consisting of a glass substrate, a ceramic substrate, and a plastic substrate.
3. The transparent conductive substrate comprising a metal layer according to claim 2, wherein: the transparent support substrate is ultra-white float glass.
4. The transparent conductive substrate comprising a metal layer according to claim 1, wherein: the polycrystalline SnO2The thickness of the barrier layer is between 20nm and 200nm, the thickness of the Ag-Au metal layer is between 5nm and 15nm, the thickness of the NiCr alloy layer is between 0.5nm and 3nm, and the F-doped SnO2The thickness of the protective layer is between 5nm and 100 nm.
5. The transparent conductive substrate comprising a metal layer according to claim 1, wherein: the molar ratio of Au element to Ag element in the Ag-Au metal layer is 0-10%, and the atomic ratio of Ni element to Cr element in the NiCr alloy layer is 4: 1, said F-doped SnO2The molar ratio of the F element to the Sn element in the protective layer is between 0 and 30 percent.
6. A method for preparing a transparent conductive substrate including a metal layer, the method comprising:
s1: providing a transparent support substrate;
s2: forming polycrystalline SnO on the transparent support substrate2A barrier layer;
s3: forming an Ag-Au metal layer on the surface of the structure obtained in the step S2;
s4: forming a NiCr alloy layer on the surface of the structure obtained in the step S3;
s5: forming F-doped SnO on the surface of the structure obtained in step S42And a protective layer.
7. The method for preparing a transparent conductive substrate containing a metal layer according to claim 6, wherein: step S5 is followed by a step of vacuum annealing by which the crystallinity of each layer is increased, the annealing temperature of the vacuum annealing being between 200 ℃ and 700 ℃.
8. The method for preparing a transparent conductive substrate containing a metal layer according to claim 6, wherein: in step S2, the polycrystalline SnO is formed by magnetron sputtering or chemical vapor deposition2And the coating temperature is between 200 and 800 ℃.
9. The method for preparing a transparent conductive substrate containing a metal layer according to claim 6, wherein: in step S3, the Ag-Au metal layer is formed at room temperature by using a magnetron sputtering technique, wherein an Au element is doped in an Ag target material to form an Au-doped Ag target material, and the molar ratio of the Au element to the Ag element in the Ag target material is between 0% and 10%.
10. The method for preparing a transparent conductive substrate containing a metal layer according to claim 6, wherein: in step S4, the NiCr alloy layer is formed at room temperature by a magnetron sputtering technique, wherein an atomic ratio of Ni element to Cr element in the NiCr alloy layer is 4: 1.
11. the method for preparing a transparent conductive substrate containing a metal layer according to claim 6, wherein: in step S5, the F-doped SnO is formed by magnetron sputtering technology2A protective layer in which an F element is doped in SnO2In the target material, F-doped SnO is formed2Target material of said SnO2The molar ratio of the F element to the Sn element in the target material is between 0 and 30 percent, and the coating temperature is between 23 and 200 ℃.
12. The method for preparing a transparent conductive substrate containing a metal layer according to claim 11, wherein: firstly, the structure obtained in the step S4 is placed in a magnetron sputtering device to be heated to the annealing temperature,carrying out vacuum annealing treatment, and then adjusting the temperature to the coating temperature to carry out the F-doped SnO2And (5) coating the protective layer.
13. The method for preparing a transparent conductive substrate containing a metal layer according to claim 6, wherein: the polycrystalline SnO2The thickness of the barrier layer is between 20nm and 200nm, the thickness of the Ag-Au metal layer is between 5nm and 15nm, the thickness of the NiCr alloy layer is between 0.5nm and 3nm, and the F-doped SnO2The thickness of the protective layer is between 5nm and 100 nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849732A (en) * | 2022-12-20 | 2023-03-28 | 中国建材国际工程集团有限公司 | Preparation method of flexible transparent electrode and flexible transparent electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030005956A1 (en) * | 2000-03-02 | 2003-01-09 | Masahiro Hirata | Photoelectric device |
| US20080107893A1 (en) * | 2004-04-23 | 2008-05-08 | Korotkov Roman Y | Electroconductive Tin Oxide Having High Mobility And Low Electron Concentration |
| CN102260846A (en) * | 2011-07-22 | 2011-11-30 | 复旦大学 | Polycrystalline tin dioxide resistance changing film and preparation method and application thereof |
| CN102603206A (en) * | 2012-03-21 | 2012-07-25 | 浙江大学 | Multilayer tin oxide fluorine-doped coated glass and preparation method thereof |
| CN205069151U (en) * | 2015-07-17 | 2016-03-02 | 张家港康得新光电材料有限公司 | Transparent conductive thin film and touch -sensitive screen |
-
2020
- 2020-12-25 CN CN202011560375.5A patent/CN112713133A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030005956A1 (en) * | 2000-03-02 | 2003-01-09 | Masahiro Hirata | Photoelectric device |
| US20080107893A1 (en) * | 2004-04-23 | 2008-05-08 | Korotkov Roman Y | Electroconductive Tin Oxide Having High Mobility And Low Electron Concentration |
| CN102260846A (en) * | 2011-07-22 | 2011-11-30 | 复旦大学 | Polycrystalline tin dioxide resistance changing film and preparation method and application thereof |
| CN102603206A (en) * | 2012-03-21 | 2012-07-25 | 浙江大学 | Multilayer tin oxide fluorine-doped coated glass and preparation method thereof |
| CN205069151U (en) * | 2015-07-17 | 2016-03-02 | 张家港康得新光电材料有限公司 | Transparent conductive thin film and touch -sensitive screen |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849732A (en) * | 2022-12-20 | 2023-03-28 | 中国建材国际工程集团有限公司 | Preparation method of flexible transparent electrode and flexible transparent electrode |
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