CN115074666B - Preparation method of multilayer composite ITO film - Google Patents

Preparation method of multilayer composite ITO film Download PDF

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CN115074666B
CN115074666B CN202210659052.4A CN202210659052A CN115074666B CN 115074666 B CN115074666 B CN 115074666B CN 202210659052 A CN202210659052 A CN 202210659052A CN 115074666 B CN115074666 B CN 115074666B
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layer
ito
sputtering
multilayer composite
ito film
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CN115074666A (en
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朱归胜
焦培文
徐华蕊
赵昀云
蒋坤朋
汪坤喆
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate

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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The preparation method of the multilayer composite ITO film comprises the steps of taking argon as working gas, and sputtering an ITO layer on a substrate in a cavity pressure environment of 1 Pa-2 Pa in a magnetron sputtering mode; and a layer of M layer is sputtered on the ITO layer In the cavity pressure environment In a magnetron sputtering mode, wherein the M layer is a layer with In content not less than In 2 O 3 An In-containing layer having an In content; and another ITO layer sputtered on the M layer in the cavity pressure environment in a magnetron sputtering mode, wherein the sputtering of the two ITO layers and the M layer meets the requirement that the M layer has a thickness of 8-16 nm and has a total thickness of 200-600 nm with the two ITO layers, so that the light transmittance of the multilayer composite ITO film is ensured and the sheet resistance of the multilayer composite ITO film is reduced.

Description

Preparation method of multilayer composite ITO film
Technical Field
The invention relates to the technical field of ITO films, in particular to a preparation method of a multilayer composite ITO film.
Background
Tin doped indium oxide (ITO) is an n-type semiconductor material that is considered to be one of the most commonly used Transparent Conductive Oxide (TCO) materials due to its excellent optical and electrical properties. At present, the method has been widely applied to the fields of light emitting diodes, liquid crystal displays, gas sensors, solar cells and the like, such as space antistatic, glass defrosting, transparent electrode manufacturing of liquid crystal displays and the like for satellites. Transparency and conductivity are key indicators for evaluating TCO properties, but are contradictory. Typically, TCO materials with high transparency have lower conductivity and vice versa. In order to obtain a TCO with high transparency, it is desirable to have as small as possible TCO grains, but small grains, which have more grain boundaries, are greatly affected by scattering at the grain boundaries during the electron transfer process, and have low conductivity. With the development of large-size touch panels, the current transparent conductive film of the ITO film has a high resistivity, which makes it difficult to meet the application requirements of large-size touch panels.
Currently, the technology for improving the electrical properties of ITO thin films mainly comprises doping Au, ag, cu, al and its alloys with low-resistivity metal substances into ITO, and structurally forming a composite ITO thin film mainly by laminating thin film forms of such metal substances on the ITO thin film, so as to improve the electrical properties of the composite ITO thin film based on the electrical properties of such metal substances with low resistivity. However, since the film morphology of such metal substances and ITO is weak due to the difference in crystal characteristics, the film morphology of such metal substances and the binding force between the ITO film are weak, and accordingly the electrical properties and structure of the composite ITO film are not stable, and especially the low thickness requirement of the film morphology of such metal substances formed by the high visible light transmittance of the composite ITO film may further exacerbate the instability of the composite ITO film in terms of structure and electrical properties, corresponding to the technical defects of low yield and high cost of the composite ITO film caused in actual production activities, and further aggravated due to the high cost characteristics of such metal substances themselves. How to further improve the electrical property of the ITO film on the premise of keeping high visible light transmittance is a technical problem which needs to be solved currently.
Disclosure of Invention
The invention aims to overcome the instability of a composite ITO film in structure and electrical performance, ensure the light transmittance of the multilayer composite ITO film, reduce the sheet resistance of the multilayer composite ITO film, improve the yield of the composite ITO film, reduce the preparation cost of the composite ITO film and provide a preparation method of the multilayer composite ITO film.
The invention is realized in the following way:
a method of preparing a multilayer composite ITO film, the method of preparing a multilayer composite ITO film comprising the steps of:
s1, sputtering an ITO layer on a substrate in a cavity pressure environment of 1 Pa-2 Pa in a magnetron sputtering mode by taking argon as working gas;
s2, using argon as working gas, and sputtering a layer of M layer on the ITO layer In a magnetron sputtering mode In the cavity pressure environment, wherein the M layer is that the In content is more than or equal to In 2 O 3 An In-containing layer having an In content; and
and S3, sputtering another ITO layer on the M layer in the cavity pressure environment by using argon as working gas in a magnetron sputtering mode, wherein the sputtering of the two ITO layers and the M layer meets the condition that the M layer has a thickness of 8-16 nm and has a total thickness of 200-600 nm with the two ITO layers.
In one embodiment, in the step (S2), the target used for sputtering the M layer is a metal In target with a purity of 99% or more.
In an embodiment, in the step (S2), the M layer is sputtered at a sputtering power of 60W to 150W and a sputtering time of 5S to 20S so that the thickness of the M layer can be controlled in a thickness range of 8nm to 16 nm.
In one embodiment, in the step (S1) and the step (S3), the target material used for sputtering the ITO layer is indium-tin ratio of 1: 9.
In one embodiment, in the step (S1) and the step (S3), a sputtering power for sputtering the ITO layer is controlled to be in a range of 100W to 200W.
In one embodiment, before the step (S2), the method further comprises the steps of: and (2) sputtering a metal Ti layer on the ITO layer in a cavity pressure environment of 1 Pa-2 Pa by using argon as a working gas in a magnetron sputtering mode, wherein in the step (S2), the M layer is continuously sputtered on the ITO layer sputtered with the metal Ti layer.
In one embodiment, after the step (S2), the method further comprises the steps of: and (3) sputtering a metal Ti layer on the M layer in a cavity pressure environment of 1 Pa-2 Pa by taking argon as working gas in a magnetron sputtering mode, wherein in the step (S3), the ITO layer is continuously sputtered on the M layer sputtered with the metal Ti layer.
In an embodiment, the total sputtering time of the two ITO layers and the M layer in the step (S1), the step (S2) and the step (S3) is controlled to be equal to or longer than 10mins and equal to or shorter than 11mins, so that the total thickness of the M layer and the two ITO layers can be controlled to be in a thickness range of 200nm to 600 nm.
In one embodiment, before the step (S1), the method further includes the steps of: and (3) obtaining a cavity pressure environment with argon as working gas and cavity pressure of 1 Pa-2 Pa in a mode of introducing argon into the cavity at the cavity pressure of less than or equal to 5 x 10 (-4) Pa.
In an embodiment, the steps (S1), (S2) and (S3) further include the steps of:
the substrate is heated at a heating temperature of 300 ℃ to 400 ℃.
According to another aspect of the present invention, there is also provided a multilayer composite ITO film including:
an ITO layer is sputtered on a substrate in a magnetron sputtering mode in a cavity pressure environment of 1 Pa-2 Pa by taking argon as working gas; and an M layer sputtered on the ITO layer In a magnetron sputtering mode In the cavity pressure environment by taking argon as working gas, wherein the M layer is an In-containing layer with In content more than or equal to In2O 3; and another ITO layer sputtered on the M layer in a magnetron sputtering mode in the cavity pressure environment by taking argon as working gas, wherein the sputtering of the two ITO layers and the M layer meets the condition that the M layer has a thickness of 8 nm-16 nm and has a total thickness of 200 nm-600 nm with the two ITO layers.
In one embodiment, the target used for sputtering the M layer by using a magnetron sputtering mode is a metal In target with the purity of more than or equal to 99%.
In one embodiment, the sputtering power of the M layer is 60W-150W by magnetron sputtering, and the corresponding sputtering time is 5 s-20 s, so that the thickness of the M layer can be controlled in the thickness range of 8 nm-16 nm.
In one embodiment, the targets used for sputtering the two ITO layers by magnetron sputtering are indium-tin ratio of 1: 9.
In one embodiment, the sputtering power of the ITO layer is 100W-200W by adopting a magnetron sputtering mode.
In an embodiment, the multilayer composite ITO film further includes a metal Ti layer sputtered between the M layer and one of the ITO layers by magnetron sputtering in a chamber pressure environment of 1Pa to 2Pa using argon as a working gas.
In an embodiment, the total sputtering time of the M layer and the two ITO layers is more than or equal to 10mins and less than or equal to 11mins in a magnetron sputtering mode, so that the total thickness of the M layer and the two ITO layers can be controlled within a thickness range of 200 nm-600 nm.
In one embodiment, when the M layer and the two ITO layers are sputtered by magnetron sputtering, the substrate on which the ITO layers are sputtered is heated at a heating temperature of 300-400 ℃.
These and other objects, features and advantages of the present invention will become more fully apparent from the following description and appended drawings.
The invention has the technical advantages and beneficial effects that:
1. the invention relates to a preparation method of a multilayer composite ITO film, which comprises at least one ITO layer and a metal In layer combined with the ITO layer, so as to be based on the main component In the ITO layer 2 O 3 The method is characterized In that the method is used for oxidizing In and the In is homologous, so that the combination stability between the In metal layer and the ITO layer is ensured, and the stability of the structure and the electrical performance of the composite ITO film is ensured.
2. According to the preparation method of the multilayer composite ITO film, the characteristics that the thermal expansion coefficients of the metal In layer and the ITO layer are close are guaranteed, the stability of the combination between the metal In layer and the ITO layer at high temperature is guaranteed, and the stability of the structure and the electrical property of the composite ITO film at high temperature is guaranteed.
3. According to the preparation method of the multilayer composite ITO film, the multilayer composite ITO film comprises at least two ITO layers, and the metal In layer is arranged between the two ITO layers and is respectively combined with the two ITO layers, so that the metal In layer is protected from being damaged easily under the low thickness requirement of the metal In layer formed by the high visible light transmittance of the multilayer composite ITO film, and the stability of the structure and the electrical property of the composite ITO film is ensured.
4. The preparation method of the multilayer composite ITO film is based on In which the metal In layer is possibly oxidized and formed In the using process of the multilayer composite ITO film 2 O 3 The composite ITO film has the advantages of being homologous to the ITO layer and still having conductive characteristics, and ensures the stability and service life of the electrical performance of the composite ITO film in the use process.
5. The preparation method of the multilayer composite ITO film of the invention is based on In which a metal In layer is possibly oxidized and formed In the preparation process of the multilayer composite ITO film 2 O 3 The preparation method has the advantages of being homologous to the ITO layer and still having conductive characteristics, and reduces the requirements on the preparation environment and the consistency precision of the technological parameters of the multilayer composite ITO film, thereby being beneficial to simplifying the preparation process of the multilayer composite ITO film and reducing the preparation cost of the multilayer composite ITO film.
6. The preparation method of the multilayer composite ITO film of the invention is based on In which a metal In layer is possibly oxidized and formed In the preparation and use processes of the multilayer composite ITO film 2 O 3 The corresponding metallic In layer is understood to mean that the In content is ≡in 2 O 3 The In-containing layer of the In content can reduce the purity requirement of the raw material for preparing the In-containing layer and the atmosphere requirement for preparing the In-containing layer In the preparation process of the multilayer composite ITO film, thereby being beneficial to simplifying the preparation process of the multilayer composite ITO film and reducing the preparation cost of the multilayer composite ITO film.
7. The preparation method of the multilayer composite ITO film is based on a metal In layer and In which is possibly oxidized and formed In the preparation process of the multilayer composite ITO film 2 O 3 All have the same source advantage with the ITO layer, and the ITO layer and the In-containing layer of the multilayer composite ITO film can be prepared by the same methodIs prepared separately in the same preparation environment, thereby being beneficial to simplifying the preparation process of the multilayer composite ITO film and reducing the preparation cost of the multilayer composite ITO film.
8. The preparation method of the multilayer composite ITO film is based on a metal In layer and In which is possibly oxidized and formed In the preparation process of the multilayer composite ITO film 2 O 3 The advantage of homology with the ITO layer is that homologous pollution generated when the ITO layer is prepared by the same preparation method In the same preparation environment is difficult to destroy the stability of the structure and the electrical property of the In-containing layer and the ITO layer which are prepared later, so that the cleaning frequency of the preparation environment is reduced, the preparation efficiency of the multilayer composite ITO film can be improved, and the preparation cost of the multilayer composite ITO film is reduced.
9. According to the preparation method of the multilayer composite ITO film, the In-containing layer between two ITO layers has the thickness of 8-16 nm, and the total thickness of the In-containing layer and the two ITO layers is 200-600 nm, so that the high visible light transmittance and the electrical property of the multilayer composite ITO film are ensured.
10. The invention provides a multilayer composite ITO film, which is prepared by sputtering air pressure of 1.0Pa and argon air flow of 80sccm at the substrate temperature of 400 ℃, has a transmittance of 97.9 percent at lambda=550 nm, has a sheet resistance of 8.10 (omega/sq.) and has higher transmittance and lower sheet resistance compared with a single-layer ITO film prepared by Jaeyeon Kim (Characteristics of ITO/Ag/ITO Hybrid Layers Prepared by Magnetron Sputtering for Transparent Film Heaters, journal of the Op11111cal Society of Korea, vol.20, no.6, december 2016, pp.807-812) and the like, and has the same excellent photoelectric performance and lower cost compared with the ITO/Ag/ITO multilayer composite film prepared by the multilayer composite ITO film, and specific data are shown in Table 1.
Table 1:
table 1 shows the photoelectric properties of a single-layer ITO film, an ITO/Ag/ITO multilayer composite film, and an ITO/In/ITO multilayer composite film.
Drawings
FIG. 1 is a schematic structural diagram of a multilayer composite ITO film of examples 1-5.
FIG. 2 is a schematic structural diagram of a multilayer composite ITO film of example 6.
FIG. 3 is a cross-sectional SEM images of multi-layered composite ITO thin films of examples 1-6.
FIG. 4 is a graph showing the visible light transmittance of the multi-layered composite ITO thin film according to various embodiments.
Fig. 5 shows the sheet resistance and transmittance at visible wavelength λ=550 nm of the multilayer composite ITO film of the different embodiments.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art. The basic principles of the invention defined in the following description may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
The invention provides a multilayer composite ITO film and a preparation method thereof, wherein the multilayer composite ITO film comprises at least one ITO layer and a metal In layer combined with the ITO layer so as to be based on the main component In the ITO layer 2 O 3 The method is characterized In that the method is used for oxidizing In and the In is homologous, so that the combination stability between the In metal layer and the ITO layer is ensured, and the stability of the structure and the electrical performance of the composite ITO film is ensured.
Specifically, the multi-layer composite ITO film includes at least two ITO layers, wherein the metal In layer is respectively combined with two ITO layers between the two ITO layers, so as to protect the metal In layer from being damaged and ensure the stability of the structure and electrical properties of the composite ITO film under the low thickness requirement of the metal In layer formed by the high visible light transmittance of the multi-layer composite ITO film.
It is worth mentioning that, based on the characteristic that the thermal expansion coefficients of the metal In layer and the ITO layer are close, the stability of the combination between the metal In layer and the ITO layer at high temperature can be ensured, so that the stability of the structure and the electrical property of the composite ITO film at high temperature can be ensured.
Further, in formed by oxidation of the metal In layer during the preparation and use of the multi-layer composite ITO film 2 O 3 The definition of the metallic In layer is understood to mean that the In content is greater than or equal to In, which is homologous to the ITO layer and still has conductive properties 2 O 3 In-containing layers of In content, the consistent precision requirements of the preparation environment and the technological parameters of the multilayer composite ITO film and the purity requirements and the atmosphere requirements of the raw materials for preparing the In-containing layers can be reduced In the preparation process of the multilayer composite ITO film, so that the preparation process of the multilayer composite ITO film is simplified, the preparation cost of the multilayer composite ITO film is reduced, and the stability of the electrical performance and the service life of the composite ITO film are ensured In the use process of the multilayer composite ITO film.
It is worth mentioning that In may be oxidized during the preparation of the multi-layered composite ITO thin film due to the metal In layer 2 O 3 All are homologous to the ITO layer, the ITO layer and the In-containing layer of the multilayer composite ITO film can be prepared respectively In the same preparation environment by the same preparation method, and homologous pollution generated by preparing the ITO layer In the same preparation environment by the same preparation method is difficult to destroy the stability of the structure and the electrical property of the In-containing layer and the ITO layer which are prepared subsequently, which is correspondingly beneficial to reducing the cleaning frequency of the preparation environment and simplifying the multilayer composite ITO filmThe preparation process of the film improves the preparation efficiency of the multilayer composite ITO film and reduces the preparation cost of the multilayer composite ITO film.
In particular, the In-containing layer of the multi-layer composite ITO film has a thickness of 8nm to 16nm and has a total thickness of 200nm to 600nm with two ITO layers, so as to ensure high visible light transmittance and electrical properties of the multi-layer composite ITO film.
That is, the multi-layer composite ITO film of the present invention comprises two ITO layers and an M layer, wherein the M layer is positioned between the two ITO layers, wherein the M layer is an In-containing layer with In content not less than In2O3 to ensure the stability of the mutual combination between the M layer and the two ITO layers and the structural stability of the multi-layer composite ITO film, wherein the M layer has a thickness of 8nm to 16nm, and has a total thickness of 200nm to 600nm with the two ITO layers, so as to reduce the sheet resistance of the multi-layer composite ITO film while ensuring the light transmittance of the multi-layer composite ITO film.
In order to prepare the multilayer composite ITO film, the invention provides a preparation method of the multilayer composite ITO film by taking a physical vapor deposition method as an example, and the preparation method comprises the following steps:
s1, sputtering an ITO layer on a substrate in a cavity pressure environment of 1 Pa-2 Pa by using argon as working gas in a magnetron sputtering mode;
s2, using argon as working gas, and sputtering a layer of M layer on the ITO layer In a magnetron sputtering mode In the cavity pressure environment, wherein the M layer is that the In content is more than or equal to In 2 O 3 An In-containing layer having an In content;
s3, using argon as working gas, sputtering another ITO layer on the M layer in the cavity pressure environment in a magnetron sputtering mode, wherein the sputtering of the two ITO layers and the M layer meets the requirement that the M layer has a thickness of 8-16 nm, and the total thickness of the two ITO layers and the M layer is 200-600 nm.
It is understood that, for the measurement of the thickness of the M layer having a thickness at the nano-level and being thinner relative to the thickness of the multilayer composite ITO film, since both the process of manufacturing the measurement sample from the multilayer composite ITO film and the measurement process of the sample affect the actual measurement result, the range definition of the thickness of the M layer having a thickness of 8nm to 16nm is a reasonable estimation range including an error range based on the measurement result in combination with the correspondence between the ratio of the sputtering time of the M layer and the total sputtering time of the multilayer composite ITO film and the total thickness of the multilayer composite ITO film.
According to the method for preparing a multi-layered composite ITO film of the present invention, in a state where the substrate is a soda lime glass substrate, a visible light transmittance spectrum of the corresponding multi-layered composite ITO film prepared by the method for preparing a different embodiment is illustrated in fig. 4, and fig. 5 shows a sheet resistance and transmittance at visible light wavelength λ=550 nm of the corresponding multi-layered composite ITO film.
Example 1:
and 1) arranging an ITO target, a metal In target and a substrate to be coated In a vacuum chamber. Wherein, after the substrate to be coated is cleaned by detergent, the substrate is sequentially ultrasonically treated for 20min in deionized water and absolute ethyl alcohol, and then is dried by nitrogen.
Step 2) the vacuum degree of the vacuum chamber is pumped to below 5 x 10 (-4) Pa.
And 3) introducing working gas argon into the vacuum chamber.
And 4) switching on the direct current power supply of the ITO target and the metal In target In the step 1).
Step 5) sputtering ITO, in, ITO on the substrate to be coated in sequence, and preparing an ITO layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 100W, the sputtering time is 5mins, the distance between the target and the substrate is 8cm, the sputtering air pressure is 1Pa, and the substrate heating temperature is 350 ℃; the process for preparing the In layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 60W, the sputtering time is 5s, the distance between the target and the substrate is 8cm, the sputtering air pressure is 1Pa, the substrate heating temperature is 300 ℃, the total sputtering time is 10 minutes and 5 seconds, and the total thickness is 420nm, and the implementation effects are shown in figures 1, 4 and 5.
Example 2:
and 1) arranging an ITO target, a metal In target and a substrate to be coated In a vacuum chamber. Wherein, after the substrate to be coated is cleaned by detergent, the substrate is sequentially ultrasonically treated for 20min in deionized water and absolute ethyl alcohol, and then is dried by nitrogen.
Step 2) the vacuum degree of the vacuum chamber is pumped to below 5 x 10 (-4) Pa.
And 3) introducing working gas argon into the vacuum chamber.
And 4) switching on the direct current power supply of the ITO target and the metal In target In the step 1).
Step 5) sputtering ITO, in, ITO on the substrate to be coated in sequence, and preparing an ITO layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 120W, the sputtering time is 5mins, the distance between the target and the substrate is 8cm, the sputtering air pressure is 1.2Pa, and the substrate heating temperature is 400 ℃; the process for preparing the In layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 80W, the sputtering time is 10s, the distance between the target and the substrate is 8cm, the sputtering air pressure is 1.2Pa, the substrate heating temperature is 400 ℃, the total sputtering time is 10 minutes and 10 seconds, the total thickness is 485nm, and the implementation effects are shown in figures 1, 4 and 5.
Example 3:
and 1) arranging an ITO target, a metal In target and a substrate to be coated In a vacuum chamber. Wherein, after the substrate to be coated is cleaned by detergent, the substrate is sequentially ultrasonically treated for 20min in deionized water and absolute ethyl alcohol, and then is dried by nitrogen.
Step 2) the vacuum degree of the vacuum chamber is pumped to below 5 x 10 (-4) Pa.
And 3) introducing working gas argon into the vacuum chamber.
And 4) switching on the direct current power supply of the ITO target and the metal In target In the step 1).
Step 5) sputtering ITO, in, ITO on the substrate to be coated in sequence, and preparing an ITO layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 150W, the sputtering time is 5mins, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1.5Pa, and the substrate heating temperature is 350 ℃; the process for preparing the In layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 150W, the sputtering time is 15s, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1.5Pa, the substrate heating temperature is 350 ℃, the total sputtering time is 10 minutes and 15 seconds, and the total thickness is 526nm, and the implementation effects are shown in figures 1, 4 and 5.
Example 4:
and 1) arranging an ITO target, a metal In target and a substrate to be coated In a vacuum chamber. Wherein, after the substrate to be coated is cleaned by detergent, the substrate is sequentially ultrasonically treated for 20min in deionized water and absolute ethyl alcohol, and then is dried by nitrogen.
Step 2) the vacuum degree of the vacuum chamber is pumped to below 5 x 10 (-4) Pa.
And 3) introducing working gas argon into the vacuum chamber.
And 4) switching on the direct current power supply of the ITO target and the metal In target In the step 1).
Step 5) sputtering ITO, in, ITO on the substrate to be coated in sequence, and preparing an ITO layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 200W, the sputtering time is 5mins, the distance between the target and the substrate is 8cm, the sputtering air pressure is 2Pa, and the substrate heating temperature is 400 ℃; the process for preparing the In layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 100W, the sputtering time is 20s, the distance between the target and the substrate is 8cm, the sputtering air pressure is 2Pa, the substrate heating temperature is 350 ℃, the total sputtering time is 10 minutes and 20 seconds, the total thickness is 558nm, and the implementation effects are shown in figures 1, 4 and 5.
Example 5:
and 1) arranging an ITO target and a substrate to be coated of a metal In target In a vacuum chamber. Wherein, after the substrate to be coated is cleaned by detergent, the substrate is sequentially ultrasonically treated for 20min in deionized water and absolute ethyl alcohol, and then is dried by nitrogen.
Step 2) the vacuum degree of the vacuum chamber is pumped to below 5 x 10 (-4) Pa.
And 3) introducing working gas argon into the vacuum chamber.
And 4) switching on the direct current power supply of the ITO target and the metal In target In the step 1).
Step 5) sputtering ITO, in, ITO on the substrate to be coated in sequence, and preparing an ITO layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 120W, the sputtering time is 5mins, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1Pa, and the substrate heating temperature is 350 ℃; the process for preparing the In layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 60W, the sputtering time is 10s, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1Pa, the substrate heating temperature is 300 ℃, the total sputtering time is 10 minutes and 10 seconds, and the total thickness is 510nm, and the implementation effects are shown in figures 1, 4 and 5.
Example 6:
and 1) arranging an ITO target, a metal Ti target and a metal In target as substrates to be coated In the vacuum chamber. Wherein, after the substrate to be coated is cleaned by detergent, the substrate is sequentially ultrasonically treated for 20min in deionized water and absolute ethyl alcohol, and then is dried by nitrogen.
Step 2) the vacuum degree of the vacuum chamber is pumped to below 5 x 10 (-4) Pa.
And 3) introducing working gas argon into the vacuum chamber.
And 4) switching on the direct current power supply of the ITO target and the metal In target In the step 1).
Step 5) sputtering ITO, ti, in, ti, ITO on the substrate to be coated in sequence, and preparing an ITO layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 120W, the sputtering time is 5mins, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1Pa, and the substrate heating temperature is 350 ℃; the process for preparing the Ti layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 80W, the sputtering time is 10s, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1Pa, and the heating temperature of the substrate is 300 ℃; the process for preparing the In layer of the ITO film by adopting direct current sputtering comprises the following steps: the coating power is 60W, the sputtering time is 10s, the distance between the target and the substrate is 10cm, the sputtering air pressure is 1Pa, the substrate heating temperature is 300 ℃, the total sputtering time is 10 minutes and 10 seconds, and the total thickness is 568nm, and the implementation effects are shown in figures 2, 4 and 5.
It will be appreciated by persons skilled in the art that the above embodiments are examples only, wherein the features of the different embodiments may be combined with each other to obtain an embodiment which is easily understood from the disclosure of the invention but which is not explicitly indicated in the drawings, to which the invention is not limited.
It will be appreciated by persons skilled in the art that the embodiments of the invention described above and shown in the drawings are by way of example only and are not limiting. The objects of the present invention have been fully and effectively achieved. The functional and structural principles of the present invention have been shown and described in the examples and embodiments of the invention may be modified or practiced without departing from the principles described.

Claims (10)

1. The preparation method of the multilayer composite ITO film is characterized by comprising the following steps of:
s1, sputtering an ITO layer on a substrate in a cavity pressure environment of 1 Pa-2 Pa by using argon as working gas in a magnetron sputtering mode;
s2, using argon as working gas, and sputtering a layer of M layer on the ITO layer In a magnetron sputtering mode In the cavity pressure environment, wherein the M layer is that the In content is more than or equal to In 2 O 3 An In-containing layer having an In content;
s3, using argon as working gas, sputtering another ITO layer on the M layer in the cavity pressure environment in a magnetron sputtering mode, wherein the sputtering of the two ITO layers and the M layer meets the requirement that the M layer has a thickness of 8-16 nm, and the total thickness of the two ITO layers and the total thickness of 200-600 nm.
2. The method of claim 1, wherein In the step (S2), the target used for sputtering the M layer is a metal In target having a purity of 99% or more.
3. The method of manufacturing a multilayer composite ITO thin film according to claim 2, characterized in that in the step (S2), the M layer is sputtered with a sputtering power of 60W to 150W and a sputtering time of 5S to 20S so that the thickness of the M layer can be controlled in a thickness range of 8nm to 16 nm.
4. The method of producing a multilayer composite ITO thin film according to claim 3, wherein in said step (S1) and said step (S3), the target used for sputtering said ITO layer is an ITO target.
5. The method of producing a multilayer composite ITO film according to claim 4, wherein in the step (S1) and the step (S3), the sputtering power for sputtering the ITO layer is controlled to be in the range of 100W to 200W.
6. The method for producing a multilayer composite ITO film according to any one of claims 1 to 5, characterized by further comprising, before the step (S2), the steps of: and (2) sputtering a metal Ti layer on the ITO layer in a cavity pressure environment of 1 Pa-2 Pa by using argon as a working gas in a magnetron sputtering mode, wherein in the step (S2), the M layer is continuously sputtered on the ITO layer sputtered with the metal Ti layer.
7. The method for producing a multilayer composite ITO film according to any one of claims 1 to 5, characterized by further comprising, after the step (S2), the steps of: and (3) sputtering a metal Ti layer on the M layer in a cavity pressure environment of 1 Pa-2 Pa by taking argon as working gas in a magnetron sputtering mode, wherein in the step (S3), the ITO layer is continuously sputtered on the M layer sputtered with the metal Ti layer.
8. The method according to claim 5, wherein the total sputtering time for the two ITO layers and the M layer in the step (S1), the step (S2) and the step (S3) is controlled to be 10mins to 11mins so that the total thickness of the M layer and the two ITO layers can be controlled to be in a thickness range of 200nm to 600 nm.
9. The method for producing a multilayer composite ITO film according to claim 8, characterized by further comprising, before the step (S1), the steps of: and (3) obtaining a cavity pressure environment with argon as working gas and cavity pressure of 1 Pa-2 Pa in a mode of introducing argon into the cavity at the cavity pressure of less than or equal to 5 x 10 (-4) Pa.
10. The method of manufacturing a multilayer composite ITO film according to claim 9, wherein in the step (S1), the step (S2), and the step (S3), further comprising the steps of: the substrate is heated at a heating temperature of 300 ℃ to 400 ℃.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5605610A (en) * 1994-12-17 1997-02-25 Anelva Corporation Method of fabricating transparent conductive ito films
US6342131B1 (en) * 1998-04-17 2002-01-29 Kabushiki Kaisha Toshiba Method of depositing a multilayer thin film by means of magnetron sputtering which controls the magnetic field
JP2010153386A (en) * 2002-10-04 2010-07-08 Sumitomo Metal Mining Co Ltd Transparent oxide electrode film and manufacturing method thereof, transparent electroconductive base material, solar cell and photo detection element
CN102677012A (en) * 2012-05-18 2012-09-19 中国科学院上海光学精密机械研究所 Preparation method of multi-layer transparent conductive film
CN102881357A (en) * 2012-09-06 2013-01-16 广州新视界光电科技有限公司 Compound transparent electroconductive film
CN103031524A (en) * 2012-12-14 2013-04-10 中国船舶重工集团公司第七二五研究所 Method for realizing metallization of back of indium tin oxide (ITO) target material by ion deposition
CN104616719A (en) * 2014-12-17 2015-05-13 青岛墨烯产业科技有限公司 Low-indium transparent electrode and preparation method thereof
WO2015192628A1 (en) * 2014-06-18 2015-12-23 北京北方微电子基地设备工艺研究中心有限责任公司 Method for depositing ito thin film and gan-based led chip
CN109811308A (en) * 2019-01-29 2019-05-28 晟光科技股份有限公司 A kind of ITO process for making conducting membrane
CN109890608A (en) * 2016-10-24 2019-06-14 日东电工株式会社 Electromagnetic wave permeable metallic luster component, article and metallic film using the component
CN112410743A (en) * 2020-11-05 2021-02-26 中国航发北京航空材料研究院 Preparation method of porous transparent conductive film

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5605610A (en) * 1994-12-17 1997-02-25 Anelva Corporation Method of fabricating transparent conductive ito films
US6342131B1 (en) * 1998-04-17 2002-01-29 Kabushiki Kaisha Toshiba Method of depositing a multilayer thin film by means of magnetron sputtering which controls the magnetic field
JP2010153386A (en) * 2002-10-04 2010-07-08 Sumitomo Metal Mining Co Ltd Transparent oxide electrode film and manufacturing method thereof, transparent electroconductive base material, solar cell and photo detection element
CN102677012A (en) * 2012-05-18 2012-09-19 中国科学院上海光学精密机械研究所 Preparation method of multi-layer transparent conductive film
CN102881357A (en) * 2012-09-06 2013-01-16 广州新视界光电科技有限公司 Compound transparent electroconductive film
CN103031524A (en) * 2012-12-14 2013-04-10 中国船舶重工集团公司第七二五研究所 Method for realizing metallization of back of indium tin oxide (ITO) target material by ion deposition
WO2015192628A1 (en) * 2014-06-18 2015-12-23 北京北方微电子基地设备工艺研究中心有限责任公司 Method for depositing ito thin film and gan-based led chip
CN104616719A (en) * 2014-12-17 2015-05-13 青岛墨烯产业科技有限公司 Low-indium transparent electrode and preparation method thereof
CN109890608A (en) * 2016-10-24 2019-06-14 日东电工株式会社 Electromagnetic wave permeable metallic luster component, article and metallic film using the component
CN109811308A (en) * 2019-01-29 2019-05-28 晟光科技股份有限公司 A kind of ITO process for making conducting membrane
CN112410743A (en) * 2020-11-05 2021-02-26 中国航发北京航空材料研究院 Preparation method of porous transparent conductive film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ITO靶材的研究与发展;阮进;陈敬超;于杰;杜晔平;;电工材料(第02期);全文 *
金属氧化物薄膜的超声雾化喷涂;黄芳龙, 陈旦初;太阳能学报(第04期);全文 *

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