HK1198183B - Method for producing metal oxide film and metal oxide film - Google Patents
Method for producing metal oxide film and metal oxide film Download PDFInfo
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- HK1198183B HK1198183B HK14111745.9A HK14111745A HK1198183B HK 1198183 B HK1198183 B HK 1198183B HK 14111745 A HK14111745 A HK 14111745A HK 1198183 B HK1198183 B HK 1198183B
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Description
Technical Field
The present invention relates to a method for producing a metal oxide film and an invention of a metal oxide film, and is applicable to a method for producing a metal oxide film used in, for example, a solar cell, an electronic device, or the like.
Background
As a method for forming a metal oxide film used in a solar cell, an electronic device, or the like, for example, a MOCVD (metal organic chemical vapor deposition) method using vacuum, a sputtering method, or the like is used. The metal oxide film produced by these methods for producing a metal oxide film is excellent in film properties.
For example, when a transparent conductive film is produced by the above-described method for producing a metal oxide film, the resistance of the transparent conductive film is low, and the resistance of the transparent conductive film does not increase even if the produced transparent conductive film is subjected to heat treatment.
Further, as a conventional document relating to formation of a zinc oxide film by MOCVD, for example, patent document 1 is known. Further, as a conventional document relating to the formation of a zinc oxide film by a sputtering method, for example, patent document 2 is known.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-124330
Patent document 2: japanese laid-open patent publication No. 9-45140
Disclosure of Invention
Problems to be solved by the invention
However, the MOCVD method is inferior in convenience because it requires high cost and requires the use of a material unstable in air in order to realize the method.
In the case of forming a thin film intended to be doped with impurities in a film by a sputtering method, a material containing a dopant material at a predetermined concentration in a main raw material is generally used as a target. Therefore, the dopant concentration in a thin film obtained by film formation using the same target is limited by the dopant concentration in the target. Therefore, for example, when thin films having different dopant concentrations are formed, it is necessary to derive the film forming conditions from the target material having each concentration. Further, when a stacked structure in which the doping concentration is changed is manufactured by a sputtering method, a plurality of apparatuses are required, and the apparatus cost increases, which is a problem.
Accordingly, an object of the present invention is to provide a method for producing a metal oxide film, which can produce a metal oxide film having good film characteristics (low resistance) at low cost. Further, an object of the present invention is to provide a method for producing a metal oxide film, which can more effectively realize low resistance of the metal oxide film. Further, another object is to provide a metal oxide film formed by the method for producing a metal oxide film.
Means for solving the problems
In order to achieve the above object, a method for producing a metal oxide film according to the present invention includes: (A) a step of forming a metal oxide film on a substrate by atomizing a zinc-containing solution and spraying the atomized solution onto the substrate in a non-vacuum state; and (B) a step of irradiating the metal oxide film with ultraviolet rays to reduce the resistance of the metal oxide film; the step (B) comprises: (B-1) a step of determining the wavelength of the ultraviolet light to be irradiated based on the film thickness of the metal oxide film, and (B-2) a step of irradiating the metal oxide film with the ultraviolet light having the wavelength determined in the step (B-1).
Effects of the invention
The method for producing a metal oxide film of the present invention according to claim 1 of the present invention includes: (A) a step of forming a metal oxide film on a substrate by atomizing a zinc-containing solution and spraying the atomized solution onto the substrate in a non-vacuum state; and (B) a step of irradiating the metal oxide film with ultraviolet rays to reduce the resistance of the metal oxide film; the step (B) comprises: (B-1) a step of determining the wavelength of the ultraviolet light to be irradiated based on the film thickness of the metal oxide film, and (B-2) a step of irradiating the metal oxide film with the ultraviolet light having the wavelength determined in the step (B-1).
Therefore, although the metal oxide film is formed on the substrate in a non-vacuum state and the resistance of the metal oxide film after the film formation is increased, the resistance of the metal oxide film can be decreased by the subsequent irradiation with ultraviolet rays (the resistance of the metal oxide film formed in a non-vacuum state can be decreased to the same level as the resistance of the metal oxide film formed in a vacuum state). In the present invention, since it is not necessary to use a device for forming a vacuum state and maintaining the vacuum state as a film forming device, cost reduction and convenience improvement can be achieved.
In the present invention, the wavelength of the ultraviolet light to be irradiated is determined according to the film thickness of the metal oxide film. Therefore, the metal oxide film can be irradiated with ultraviolet rays having a wavelength capable of improving the efficiency of lowering the resistance (further reducing the resistivity in a short time) depending on the film thickness of the metal oxide film.
The objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description and the accompanying drawings.
Drawings
FIG. 1 is a view showing the configuration of a film forming apparatus for explaining a method of forming a metal oxide film according to the present invention.
Fig. 2 is a diagram for explaining a method for producing a metal oxide film (particularly, a method for reducing resistance) according to the present invention.
Fig. 3 is a graph of experimental data for explaining the effect of the method for producing a metal oxide film of the present invention.
Fig. 4 is a graph of experimental data for explaining the effect of the method for producing a metal oxide film of the present invention.
Fig. 5 is an experimental data table for explaining the effect of the method for producing a metal oxide film of the present invention.
Fig. 6 is a graph of experimental data for explaining the effect of the method for producing a metal oxide film of the present invention.
Fig. 7 is a graph of experimental data for explaining the effect of the method for producing a metal oxide film of the present invention.
Detailed Description
The present invention will be specifically described below with reference to the drawings showing embodiments of the present invention.
< embodiment >
In the method for producing a metal oxide film of the present invention, a film formation process is performed under a non-vacuum (atmospheric pressure). Specifically, the method for producing a metal oxide film according to the present invention will be described with reference to a production apparatus (film formation apparatus) shown in fig. 1.
First, a solution 5 containing at least zinc is prepared. Here, an organic solvent such as ether or alcohol is used as the solvent of the solution 5. The prepared solution 5 is filled in a container 3A.
On the other hand, water (H) is used2O) as an oxidation source 6, and the vessel 3B is filled with the oxidation source 6. As the oxidizing source 6, oxygen, ozone, hydrogen peroxide, N, or the like may be used in addition to water2O、NO2For example, water is preferable from the viewpoint of low cost and easy handling (hereinafter, the oxidation source 6 is water). In the case of forming a metal oxide film containing a dopant, the dopant is added to water as the oxidation source 6 or to the zinc-containing solution 5 depending on the solubility and reactivity of the dopant. In addition, it is also possible to provide another container (not shown in fig. 1) and supply the dopant to the substrate 1 by another system.
Next, the solution 5 and the oxidizing source 6 are separately atomized. An atomizer 4A is disposed at the bottom of the container 3A, and an atomizer 4B is disposed at the bottom of the container 3B. The solution 5 in the container 3A is atomized by the atomizer 4A, and the oxidizing source 6 in the container 3B is atomized by the atomizer 4B.
The atomized solution 5 is supplied to the nozzle 8 through a path L1, and the atomized oxidation source 6 is supplied to the nozzle 8 through a path L2. Here, as shown in fig. 1, the path L1 and the path L2 are different paths.
On the other hand, as shown in fig. 1, a substrate 1 is placed on a heater 2. Here, the substrate 1 is placed under a non-vacuum (atmospheric pressure). The atomized solution 5 and the atomized oxidation source 6 are sprayed onto the substrate 1 placed under the non-vacuum (atmospheric pressure) condition through the nozzle 8. Here, the substrate 1 is heated by the heater 2 to, for example, about 200 ℃.
Through the above steps, a metal oxide film (zinc oxide film as a transparent conductive film) having a predetermined film thickness is formed on the substrate 1 placed under a non-vacuum (atmospheric pressure) atmosphere. The film thickness of the metal oxide film can be adjusted to a desired thickness by adjusting the supply amount of the solution 5 and the like.
Further, the metal oxide film formed under a non-vacuum (atmospheric pressure) condition has a higher resistance than a metal oxide film formed under a vacuum condition such as a sputtering method. Therefore, the following processes are performed in the method for producing a metal oxide film of the present invention.
That is, in the method for producing a metal oxide film of the present invention, as shown in fig. 2, ultraviolet rays 13 are irradiated to the entire main surface of the metal oxide film 10 formed on the substrate 1 by using an ultraviolet lamp 12 or the like. The irradiation with the ultraviolet ray 13 can reduce the resistance (resistivity) of the metal oxide film 10.
In the method for producing a metal oxide film of the present invention, the wavelength of the ultraviolet light 13 to be irradiated is determined in accordance with the film thickness of the metal oxide film 10 in the ultraviolet light irradiation treatment. Then, the entire main surface of the metal oxide film 10 is irradiated with ultraviolet light 13 having the predetermined wavelength.
The method for determining the wavelength of the ultraviolet light 13 to be irradiated will be described in detail using the following specific experimental examples.
Fig. 3 and 4 are experimental data showing the relationship between the resistivity of the metal oxide film (zinc oxide film) and the ultraviolet irradiation at each of a plurality of film thicknesses of the metal oxide film. Here, fig. 4 is a graph of data on film thickness of a metal oxide film selected to have an arbitrary film thickness from the experimental data shown in fig. 3.
As shown on the horizontal axis of fig. 3 and 4, the metal oxide film formed under a non-vacuum condition was subjected to 1 st heat treatment for 20 minutes, the metal oxide film after the 1 st heat treatment was irradiated with ultraviolet rays having a central wavelength of 254nm for 60 minutes, then the metal oxide film was irradiated with ultraviolet rays having a central wavelength of 365nm for 60 minutes, then the metal oxide film was subjected to 2 nd heat treatment for 20 minutes, the metal oxide film after the 2 nd heat treatment was irradiated with ultraviolet rays having a central wavelength of 365nm for 60 minutes, and then the metal oxide film was irradiated with ultraviolet rays having a central wavelength of 254nm for 60 minutes.
As shown in fig. 3 and 4, the vertical axis represents the resistivity (Ω · cm) of the metal oxide film. Fig. 3 is a graph showing data on a metal oxide film having a film thickness (259nm, 303nm, 334nm, 374nm, 570nm, 650nm, 1344nm, 1462nm, 1863nm, 2647nm, 3033nm, 3041nm, 3805nm, 3991nm, 8109nm), and fig. 4 is a graph showing data on a metal oxide film having a film thickness (334nm, 570nm, 650nm, 1344nm, 3033 nm).
The 1 st and 2 nd heating processes are heating at a temperature (for example, 300 ℃ or lower) at which the crystallinity of the metal oxide film does not change (oxygen vacancies filling ZnO or the like), and in the 1 st and 2 nd heating processes shown in fig. 3 and 4, the metal oxide film is heated at 200 ℃.
The metal oxide film (ZnO: zinc oxide film) used in the experiment after deposition was an oxide film produced (deposited) by the above-described steps using the apparatus shown in fig. 1. The heating temperature of the substrate 1 during film formation is 200 ℃, the supply amount of the zinc (Zn) -containing solution 5 is 0.7 to 0.8 mmol/min, and the supply amount of water as the oxidation source 6 is 44 to 89 mmol/min. In addition, the zinc concentration in the zinc-containing solution 5 was 0.35 mol/liter.
The metal oxide film formed under non-vacuum conditions has a higher resistivity than the metal oxide film formed under vacuum conditions. As shown in the experimental data shown in fig. 3 and 4, it is known that the resistivity of the metal oxide film formed in a non-vacuum state is lowered by applying ultraviolet irradiation to the metal oxide film.
As is clear from fig. 3 and 4, the resistivity of the metal oxide film after the resistivity is lowered increases when the heat treatment is performed. As is clear from fig. 3 and 4, the resistivity increased by the heat treatment can be decreased again by the irradiation with ultraviolet rays.
Therefore, when the metal oxide film having a high resistance after being formed in a non-vacuum state is irradiated with ultraviolet rays and the metal oxide film has a high resistance due to the heating step, it is effective to irradiate the metal oxide film after the heating step with ultraviolet rays from the viewpoint of lowering the resistance of the metal oxide film. Here, even if the heating step (heating treatment) of the metal oxide film and the ultraviolet irradiation treatment are repeatedly performed, the resistance increased by the heating treatment can be reduced after the ultraviolet irradiation treatment.
Note that, in fig. 3 and 4, the gradient showing the decrease in the resistivity of the metal oxide film after the irradiation of ultraviolet light having a central wavelength of 254nm (referred to as first ultraviolet light) after the 1 st heat treatment and the gradient showing the decrease in the resistivity of the metal oxide film after the irradiation of ultraviolet light having a central wavelength of 365nm (referred to as second ultraviolet light) after the 2 nd heat treatment are focused.
It can be said that, in the case of a metal oxide film having a relatively thin film thickness, the first ultraviolet irradiation can significantly reduce the resistivity of the metal oxide film in a shorter time than the second ultraviolet irradiation. On the other hand, in the case of a metal oxide film having a relatively large film thickness, the second ultraviolet irradiation can significantly reduce the resistivity of the metal oxide film in a shorter time than the case of the first ultraviolet irradiation.
That is, from the viewpoint of effectively reducing the resistance, it is effective to select and determine the most appropriate wavelength of the ultraviolet rays to be irradiated, depending on the film thickness of the metal oxide film.
Specifically, from the viewpoint of effectively reducing the resistance, it is desirable to select a large value as the wavelength of ultraviolet light as the thickness of the metal oxide film becomes larger. This is because the depth of penetration of the metal oxide film by ultraviolet rays is proportional to the wavelength of the ultraviolet rays.
That is, the light entrance depth d is represented by d 1/α. Here, α is an absorption coefficient, and α is 4 π k/λ (k: attenuation coefficient, λ: wavelength). That is, the depth of penetration of the ultraviolet light into the metal oxide film is proportional to the wavelength of the ultraviolet light (the ultraviolet light can penetrate deeper into the metal oxide film as the wavelength of the ultraviolet light is larger).
Therefore, if ultraviolet light of a larger wavelength is not applied to a metal oxide film having a large thickness, the metal oxide film having the large thickness is not irradiated with ultraviolet light in the entire thickness direction thereof, and as a result, the efficiency of lowering the resistance of the metal oxide film is lowered. Therefore, from the viewpoint of effectively reducing the resistance, it is desirable to increase the wavelength of the ultraviolet ray to be determined in proportion to the thickness of the metal oxide film.
When the wavelength of the ultraviolet ray is longer than 380nm, the metal oxide film (zinc oxide film) does not absorb the ultraviolet ray. Therefore, the wavelength of ultraviolet rays to be irradiated to the zinc oxide film needs to be 380nm or less.
Further, a light source for irradiating ultraviolet rays having a wavelength of 254nm and a light source for irradiating ultraviolet rays having a wavelength of 365nm are available at relatively low cost. Therefore, it was found that it is very advantageous to select either one of the wavelengths 254nm and 365nm depending on the film thickness of the metal oxide film in order to more effectively reduce the resistance.
FIG. 5 is a table showing which wavelength of 254nm or 365nm is useful for the ultraviolet ray irradiated depending on the film thickness of the metal oxide film. Here, fig. 5 is a diagram completed using the data shown in fig. 3.
In the uppermost column of FIG. 5, the film thicknesses of the metal oxide films (259nm, 303nm, 334nm, 374nm, 570nm, 650nm, 1344nm, 1462nm, 1863nm, 2647nm, 3033nm, 3041nm, 3805nm, 3991nm, and 8109nm) are shown. In addition, the leftmost column of fig. 5 indicates the irradiation time of the ultraviolet rays (1 minute, 5 minutes, 10 minutes, 30 minutes, 60 minutes).
The numerical values in the columns of fig. 5 are (resistivity of metal oxide film after irradiation time when ultraviolet light having a center wavelength of 254nm is irradiated)/(resistivity of metal oxide film after irradiation time when ultraviolet light having a center wavelength of 365nm is irradiated).
For example, attention is paid to column 3 (column 303nm in thickness) in FIG. 5. The value of the 2 nd row (row irradiated with ultraviolet rays for 1 minute) in the 3 rd column indicates: "0.8" is a value obtained by dividing "the resistivity of the metal oxide film after irradiation with ultraviolet light having a central wavelength of 254nm for 1 minute and having a thickness of 303 nm" by "the resistivity of the metal oxide film after irradiation with ultraviolet light having a central wavelength of 365nm for 1 minute and having a thickness of 303 nm" for the metal oxide film.
Further, attention is paid to, for example, the 7 th column (column having a film thickness of 650nm) in FIG. 5. The value of the 5 th row (row irradiated with ultraviolet rays for 30 minutes) in the 7 th column indicates: "2.6" is a value obtained by dividing "the resistivity of the metal oxide film after irradiation with ultraviolet light having a central wavelength of 254nm for 30 minutes in the case of irradiating the metal oxide film having a thickness of 650nm with ultraviolet light having a central wavelength of 365nm for 30 minutes in the case of irradiating the metal oxide film having a thickness of 650nm with ultraviolet light".
In the following, the ratio of (the resistivity of the metal oxide film after the irradiation time when ultraviolet light having a center wavelength of 254nm is irradiated)/(the resistivity of the metal oxide film after the irradiation time when ultraviolet light having a center wavelength of 365nm is irradiated) is referred to as "resistivity comparison ratio".
Here, the resistivity ratio smaller than "1" means: when ultraviolet light having a central wavelength of 254nm is irradiated, the resistance of the metal oxide film can be lowered more efficiently than when ultraviolet light having a central wavelength of 365nm is irradiated. In other words, a resistivity comparison greater than "1" indicates that: when ultraviolet light having a central wavelength of 365nm is irradiated, the resistance of the metal oxide film can be lowered with high efficiency as compared with the case of irradiation of ultraviolet light having a central wavelength of 254 nm.
As is clear from the table of fig. 5, when the metal oxide film is at least as thick as 570nm or less, the resistance of the metal oxide film can be reduced more efficiently when ultraviolet light having a central wavelength of 254nm is irradiated than when ultraviolet light having a central wavelength of 365nm is irradiated.
More specifically, fig. 6 shows this case. FIG. 6 shows the following graphs (vertical axis: resistivity (Ω. cm), horizontal axis: ultraviolet irradiation time (minutes)): the metal oxide film having a film thickness of 570nm was irradiated with ultraviolet rays having a central wavelength of 254nm and changed in resistivity, and irradiated with ultraviolet rays having a central wavelength of 365nm and changed in resistivity. As shown in fig. 6, when the metal oxide film having a film thickness of 570nm is irradiated with ultraviolet rays having a central wavelength of 254nm, the resistance of the metal oxide film can be lowered more efficiently than when the metal oxide film is irradiated with ultraviolet rays having a central wavelength of 365 nm.
On the other hand, as is clear from the table of FIG. 5, when the metal oxide film having a film thickness of at least 650nm is irradiated with ultraviolet rays having a central wavelength of 365nm, the resistance of the metal oxide film can be lowered more efficiently than when the metal oxide film is irradiated with ultraviolet rays having a central wavelength of 254 nm.
More specifically, fig. 7 shows this case. FIG. 7 shows the following graphs (vertical axis: resistivity (Ω. cm), horizontal axis: ultraviolet irradiation time (minutes)): the metal oxide film having a film thickness of 650nm was irradiated with ultraviolet rays having a central wavelength of 254nm and changed in resistivity, and irradiated with ultraviolet rays having a central wavelength of 365nm and changed in resistivity. As shown in FIG. 7, when the metal oxide film having a film thickness of 650nm is irradiated with ultraviolet rays having a central wavelength of 365nm, the resistance of the metal oxide film can be lowered with high efficiency, as compared with the case of irradiating ultraviolet rays having a central wavelength of 254 nm.
The average value was calculated from the data in the 6 th column (film thickness: 570nm) of fig. 5 and the data in the 7 th column (film thickness: 650nm) of fig. 5, by comparing the linear increase in the film thickness between 570nm and 650nm with the resistivity. It was thus found that: when the film thickness of the metal oxide film is about 590nm, the resistivity ratio is "1".
For example, when the film thickness is linearly increased between 570nm and 650nm by the resistivity ratio, the film thickness of the metal oxide film having the resistivity ratio "1" is "572 nm" when the ultraviolet irradiation is performed for 1 minute, the film thickness of the metal oxide film having the resistivity ratio "1" is "583 nm" when the ultraviolet irradiation is performed for 5 minutes, the film thickness of the metal oxide film having the resistivity ratio "1" is "596 nm" when the ultraviolet irradiation is performed for 10 minutes, the film thickness of the metal oxide film having the resistivity ratio "1" is "586 nm" when the ultraviolet irradiation is performed for 30 minutes, and the film thickness of the metal oxide film having the resistivity ratio "1" is "607 nm" when the ultraviolet irradiation is performed for 60 minutes. By averaging the film thicknesses, it was found that the resistivity ratio was "1" when the film thickness of the metal oxide film was about 590 nm.
Namely, the inventors found that: in the case of a metal oxide film having a film thickness of less than 590nm, the metal oxide film can be made to have a lower resistance with high efficiency when irradiated with ultraviolet light having a central wavelength of 254nm, as compared with when irradiated with ultraviolet light having a central wavelength of 365 nm.
Furthermore, the inventors found that: in the case of a metal oxide film having a film thickness of greater than 590nm, when ultraviolet light having a central wavelength of 365nm is irradiated, the resistance of the metal oxide film can be lowered with high efficiency, as compared with the case of irradiation of ultraviolet light having a central wavelength of 254 nm.
In the case of a metal oxide film having a film thickness of 590nm, it is considered that the metal oxide film can be reduced in resistance with the same degree of efficiency in both the case of irradiation with ultraviolet rays having a central wavelength of 254nm and the case of irradiation with ultraviolet rays having a central wavelength of 365 nm.
Therefore, from the viewpoint of cost reduction of ultraviolet irradiation and improvement of resistance reduction efficiency, it is preferable that, when ultraviolet light is irradiated to the metal oxide film, a wavelength at least including 254nm is selected when the film thickness of the metal oxide film is less than 590nm, and the wavelength at least including 365nm is selected when the film thickness of the metal oxide film is greater than 590 nm.
It should be noted that the above descriptions (the resistance of the metal oxide film can be reduced by irradiating the metal oxide film after film formation and the metal oxide film after heat treatment with ultraviolet rays; from the viewpoint of achieving high-efficiency and low-resistance, the wavelength of the ultraviolet rays to be irradiated is selected and determined according to the film thickness of the metal oxide film), were confirmed both in the case where the metal oxide film contains a dopant and in the case where the metal oxide film does not contain a dopant. It was confirmed that even when a dopant is contained in the metal oxide film, the above descriptions are satisfied regardless of the kind of the dopant such as boron or indium.
As described above, in the method for producing a metal oxide film according to the present embodiment, the zinc-containing solution 5 is atomized, and the atomized solution 5 is sprayed onto the substrate 1 in a non-vacuum state, whereby the metal oxide film 10 is formed on the substrate 1 (fig. 1). Then, ultraviolet rays 13 are irradiated to the metal oxide film 10 (fig. 2).
Therefore, although the metal oxide film is formed on the substrate 1 in a non-vacuum state and the resistance of the metal oxide film after the film formation is high, the resistance of the metal oxide film can be lowered by the subsequent irradiation with ultraviolet rays (the resistance of the metal oxide film formed in a non-vacuum state can be lowered to the same level as the resistance of the metal oxide film formed in a vacuum state).
In the method for producing a metal oxide film according to the present embodiment, since it is not necessary to use a vacuum-based apparatus or the like as a production (film formation) apparatus (that is, a film formation process in a non-vacuum state), cost reduction and convenience can be achieved.
In the method for manufacturing a metal oxide film according to the present embodiment, the wavelength of ultraviolet light to be irradiated is determined according to the film thickness of the metal oxide film. For example, as the thickness of the metal oxide film becomes thicker, a larger value is selected as the wavelength of ultraviolet light.
Therefore, the metal oxide film can be irradiated with ultraviolet rays having a wavelength capable of reducing the resistance and increasing the efficiency (further reducing the resistivity in a short time) depending on the film thickness of the metal oxide film.
In the method for producing a metal oxide film according to the present embodiment, when the thickness of the metal oxide film is less than 590nm, a wavelength including at least 254nm is preferably selected and determined, and when the thickness of the metal oxide film is greater than 590nm, a wavelength including at least 365nm is preferably selected and determined.
An ultraviolet light source having a wavelength of 254nm and an ultraviolet light source having a wavelength of 365nm are inexpensive. In addition, the ultraviolet ray capable of reducing the resistance with high efficiency is selected according to the film thickness of the metal oxide film. Therefore, in the method for producing a metal oxide film of the present invention in which the selection and determination of the wavelength are performed, the metal oxide film can be made low in resistance and high in efficiency, and the production cost can be reduced.
In the method for producing a metal oxide film according to the present embodiment, the metal oxide film may be formed and then irradiated with ultraviolet light to reduce the resistance of the metal oxide film, or the metal oxide film may be formed and then subjected to heat treatment to reduce the resistance of the metal oxide film.
Here, when the metal oxide film needs to be subjected to the heat treatment a plurality of times, the ultraviolet irradiation treatment may be performed each time after each heat treatment, or the heat treatment may be performed a plurality of times and the ultraviolet irradiation treatment may be performed 1 time after the last heat treatment. In view of the high efficiency and low resistance, it is desirable to select and determine the wavelength when the ultraviolet light is irradiated.
In some cases, it is desirable to heat-treat the metal oxide film at least 1 time after the metal oxide film is formed in the production process. Even in this case, by performing ultraviolet irradiation after the heat treatment, the metal oxide film having a high resistance can be reduced in resistance. Further, the wavelength at the time of the ultraviolet irradiation is selected and determined to be a predetermined value, and the metal oxide film having a high resistance is irradiated with the ultraviolet ray having the selected and determined wavelength, whereby the metal oxide film has a low resistance efficiently.
The present invention has been described in detail, but the above description is only illustrative in all cases, and the present invention is not limited thereto. Countless variations not illustrated should be understood as conceivable without departing from the scope of the present invention.
Drawings
1 substrate
2 heating device
3A, 3B container
4A, 4B atomizer
5 solution
6 oxidizing source
8 spray nozzle
10 Metal oxide film (transparent conductive film, Zinc oxide film)
12 ultraviolet lamp
13 ultraviolet ray
L1, L2 Path
Claims (5)
1. A method for producing a metal oxide film, comprising:
a: a step of forming a metal oxide film on a substrate by atomizing a zinc-containing solution and spraying the atomized solution onto the substrate in a non-vacuum state; and
b: a step of irradiating the metal oxide film with ultraviolet rays to reduce the resistance of the metal oxide film;
the step B comprises:
b-1: a step of determining the wavelength of the ultraviolet light to be irradiated based on the film thickness of the metal oxide film, and
b-2: and irradiating the metal oxide film with the ultraviolet ray having the wavelength determined in the step B-1.
2. The method of manufacturing a metal oxide film according to claim 1,
in the above-mentioned step B-1,
as the thickness of the metal oxide film becomes thicker, a larger value is selected as the wavelength of the ultraviolet light.
3. The method of manufacturing a metal oxide film according to claim 1,
in the above-mentioned step B-1,
when the film thickness of the metal oxide film is less than 590nm, the wavelength is selected to include at least 254 nm.
4. The method of manufacturing a metal oxide film according to claim 1,
in the step B-1, when the thickness of the metal oxide film is greater than 590nm, the wavelength is selected to include at least 365 nm.
5. The method of manufacturing a metal oxide film according to claim 1,
further comprises C: a step of heating the metal oxide film,
the step B is performed after the step C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPPCT/JP2012/052835 | 2012-02-08 | ||
| JP2012052835 | 2012-02-08 | ||
| PCT/JP2012/077416 WO2013118353A1 (en) | 2012-02-08 | 2012-10-24 | Method for producing metal oxide film and metal oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1198183A1 HK1198183A1 (en) | 2015-03-13 |
| HK1198183B true HK1198183B (en) | 2017-04-28 |
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