CN116189964A - ITO film and transparent conductive film - Google Patents
ITO film and transparent conductive film Download PDFInfo
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- CN116189964A CN116189964A CN202211677083.9A CN202211677083A CN116189964A CN 116189964 A CN116189964 A CN 116189964A CN 202211677083 A CN202211677083 A CN 202211677083A CN 116189964 A CN116189964 A CN 116189964A
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Abstract
An ITO film and a transparent conductive film are provided, wherein the ITO film improves the stability of an amorphous ITO film without annealing treatment, has no change in resistance value with time, improves moisture resistance and gas barrier properties, and overcomes cracks caused by bending; the transparent conductive film has excellent conductivity, transparency and durability. The ITO film of the present invention is characterized in that an amorphous ITO film having no annealing treatment is formed on the surface of a flexible substrate, and the film thickness of the amorphous ITO film is in the range of 30-320 nm, and the surface resistance of the amorphous ITO film is in the range of 9-105 (Ω/≡).
Description
The present invention is a divisional application based on the application of ITO film and transparent conductive film, which is the subject of the lok technical research industry, and the chinese invention application has application number 201811344911.0 and application date 2018, 11, 13.
Technical Field
The present invention relates to an ITO film and a transparent conductive film which are suitable for illumination using a solar cell, an organic EL display, and an organic EL.
Background
Transparent conductive films are used for touch panels, solar cells, electromagnetic wave/electrostatic shielding, and ultraviolet/infrared shielding, and particularly in illumination using solar cells, organic EL displays, and organic ELs, performance having a total light transmittance of 90% and a surface resistance of 5 to 10 (Ω/≡) is demanded.
However, patent document 1 discloses that an amorphous ITO film is used without annealing (example 5 and comparative example 4).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6106756
Disclosure of Invention
Technical problem to be solved by the invention
Therefore, in example 5, when silica was formed on the ITO film, it had high transparency, but in comparative example 4, silica was not formed on the ITO film, transparency was low, and scratch resistance was also problematic.
In patent document 1, in order TO reduce the resistance of the ito film, the thickness of the ito film is increased TO 90nm, and SnO is used TO improve the stability of the ito film 2 The content was 10wt%.
The object of the present invention is TO provide an ito film which improves the stability of an amorphous TO film without performing an annealing treatment, has no change in resistance value with time, improves moisture resistance and gas barrier properties, and overcomes cracks caused by bending; also provided is a transparent conductive film having excellent conductivity, transparency and durability.
Solution to the above technical problems
The ito film of the present invention according TO claim 1, wherein an amorphous ito film in an unannealed state is formed on the surface of a flexible substrate, wherein the amorphous ito film has a film thickness in the range of 30nm TO 320nm, and the amorphous ito film has a surface resistance in the range of 9 TO 105 (Ω/≡).
The invention according TO claim 2 is characterized in that, in the ito film according TO claim 1, polyethylene terephthalate is used as the base material.
The invention according TO claim 3 is characterized in that, in the ito film according TO claim 1 or 2, the film density of the amorphous ito film is 65% or more.
The invention according TO claim 4 is characterized in that, in the ito film according TO any one of claims 1 TO 3, the surface average roughness of the amorphous ito film is 9nm or less.
The invention according TO claim 5 is characterized in that, in the TO film according TO any one of claims 1 TO 4, snO contained in the amorphous TO film 2 In the range of 2wt% to 7 wt%.
The transparent conductive film according TO claim 6, wherein a first ito film is formed on the surface of the flexible substrate, a thin film metal layer is formed on the surface of the first ito film, and a second ito film is further formed on the surface of the thin film metal layer, wherein the first ito film is an amorphous ito film in an unannealed state; the second Io film is an amorphous Io film in a state where the annealing treatment is not performed, the film thickness is in a range of 30nm TO 320nm, and the surface resistance of the amorphous Io film is in a range of 9 TO 105 (Ω/≡).
The invention according to claim 7 is the transparent conductive film according to claim 6, wherein the thin film metal layer is an Ag layer having a thickness of 10nm to 20nm.
The invention according to claim 8 is characterized in that, in the transparent conductive film according to claim 6 or 7, polyethylene terephthalate is used as the base material.
The invention according TO claim 9 is characterized in that, in the transparent conductive film according TO any one of claims 6 TO 8, the film density of the second ito film is 65% or more.
The invention according TO claim 10 is the transparent conductive film according TO any one of claims 6 TO 9, wherein the second ito film has a surface average roughness of 9nm or less.
The invention according TO claim 11 is the transparent conductive film according TO any one of claims 6 TO 10, wherein the second ito film contains SnO 2 In the range of 2wt% to 7 wt%.
Effects of the invention
According TO the present invention, it is possible TO provide an ito film which has no change in resistance value with time, has improved moisture resistance and gas barrier properties, and is free from cracks due TO bending.
Further, according to the present invention, a transparent conductive film having excellent conductivity, transparency, and durability can be provided.
Drawings
Fig. 1 is a table showing measurement results of the hall numbers using example 1 and comparative example 1.
FIG. 2 is a graph showing the results of a bending test using example 2 and comparative example 1, in which the diameter is 1.0 mm.
Fig. 3 is a graph showing the results of the no-load bending test using example 2 and comparative example 1.
FIG. 4 is a graph showing the results of the 80℃storage characteristics of example 2.
FIG. 5 is a graph showing the results of the storage characteristics at 60℃and 90% RH using example 2.
FIG. 6 is a graph showing the results of thermal cycling tests at-30℃and 80℃using example 2.
Fig. 7 is a table showing the heat resistance results of examples 3, comparative examples 2 and comparative example 3.
FIG. 8 is a table showing the results of hot water depth test at 50℃in example 3, comparative example 2 and comparative example 3.
FIG. 9 is a table showing the results of hot water depth test at 60℃to 80℃in example 3, comparative example 2 and comparative example 3.
FIG. 10 is a table showing the results of the atmospheric temperature standing test in the atmosphere using example 3, comparative example 2 and comparative example 3.
Fig. 11 is a graph showing the results of the no-load bending test using example 3 and comparative example 3.
FIG. 12 is a photomicrograph of the surfaces of the TO films of example 1 and comparative example 1.
Fig. 13 is a graph showing the measurement result of the surface roughness of the test piece shown in fig. 12.
Detailed Description
According TO the ITO film of embodiment 1 of the present invention, the film thickness of the amorphous ITO film is in the range of 30nm TO 320nm, and the surface resistance of the amorphous ITO film is in the range of 9 TO 105 (. OMEGA/. About.o.s.o). According TO the present embodiment, by providing an amorphous ito film with a high density, stability can be improved, and it is possible TO provide an ito film which has no change in resistance with time, has improved moisture resistance and gas barrier properties, and overcomes cracks caused by bending.
In the transparent conductive film according TO embodiment 6 of the present invention, the first ito film is an amorphous ito film in a state where annealing is not performed, the second ito film is an amorphous ito film in a state where annealing is not performed, the film thickness is in the range of 30nm TO 320nm, and the surface resistance of the amorphous ito film is in the range of 9 TO 105 (Ω/≡). According to the present embodiment, a transparent conductive film excellent in conductivity, transparency, and durability can be provided.
Embodiment 7 of the present invention is the transparent conductive film according to embodiment 6, wherein the thin film metal layer is an Ag layer having a thickness of 10nm to 20nm. According TO the present embodiment, ag having poor durability can be protected by the second TO film TO improve durability, and the total light transmittance of about 50% of Ag can be improved TO about 90% by the second TO film.
In embodiment 9 of the present invention, in the transparent conductive thin films according TO embodiments 6 TO 8, the film density of the second ito film is 65% or more. According TO the present embodiment, the stability can be improved by setting the film density of the amorphous ito film TO 65% or more.
In embodiment 10 of the present invention, in the transparent conductive film according TO embodiments 6 TO 9, the surface average roughness of the second ito film is 9nm or less. According TO the present embodiment, by setting the surface average roughness of the amorphous ito film TO 9nm or less, the film density of the amorphous ito film can be 65% or more, thereby improving the stability.
Embodiment 11 of the present invention is the followingIn the transparent conductive films according TO embodiments 6 TO 10, snO contained in the second ITO film is formed 2 In the range of 2wt% to 7 wt%. According to the present embodiment, snO is formed by 2 In the range of 2wt% to 7wt%, transparency can be improved.
Example 1
Hard coating treatment of both surfaces of PET (polyethylene terephthalate) having a thickness of 125 μm was performed to form a substrate using a coating containing 5wt% SnO 2 In an argon atmosphere containing about 1% oxygen gas, and forming an ito film (thickness of about d=35 nm) having a surface resistance r=75 TO 83 (Ω/≡) on one surface of the substrate by sputter plating under a vacuum of 0.1 TO 0.9Pa (about 0.6 Pa).
The total light transmittance of the ito (indium oxide containing tin oxide) film of example 1 was 84%. In addition, HGM-2DP from Wash tester was used to measure total light transmittance.
Example 2
An TO film (thickness of about d=30 nm) having a surface resistance r=100 TO 105 (Ω/≡) was formed in the same manner as in example 1.
In this way, examples 1 and 2 are ito films in which an amorphous ito film was formed on the surface of a flexible substrate without annealing treatment.
Various plastic films (sheets) having transparency can be used for the substrate having flexibility. As the plastic film, for example, a plastic film containing polyester, polycarbonate, polyamide, polyimide, polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl alcohol, polyacrylate, polyarylate, or polyphenylene sulfide can be used as the resin component. Among these, polyester is particularly preferable, and among the polyesters, polyethylene terephthalate is particularly preferable. Polyethylene terephthalate has excellent flexibility and transparency, and is suitable for forming amorphous ito films. The total light transmittance of the PET film substrate subjected to the double-sided hard coating treatment was about 91%. The film base material temperature during sputtering plating was normal temperature. In addition, the sputtering method here uses a usual magnetron electrode method.
Comparative example 1
Hard coating treatment of both surfaces of PET (polyethylene terephthalate) having a thickness of 125 μm was performed to form a substrate using a coating containing 5wt% SnO 2 An ITO film (thickness of about d=25 nm) having a surface resistance r=170 (Ω/≡) was formed on one surface of the substrate by sputter plating under a vacuum of 0.1 to 0.9Pa (about 0.6 Pa) in an argon atmosphere containing about 1% oxygen gas. Then, in the atmosphere, heating was performed under a heating atmosphere of about 150 ℃ for about 50 minutes to form a thin film-crystallized ITO thin film having a surface resistance r=142 (Ω/≡). In addition, in order to prevent an increase in haze to the PET film substrate at the time of annealing, a double-sided hard-coated PET film substrate was used.
(evaluation method 1)
Fig. 1 is a table showing measurement results of the hall numbers using example 1 and comparative example 1.
ResiTest 8330, manufactured by Toyo Tekka Co., ltd, was used for the measurement.
As can be seen from the results shown in fig. 1, example 1 is a high-density film because of having higher mobility than comparative example 1.
(evaluation method 2)
FIG. 2 is a graph showing the results of a bending test using example 2 and comparative example 1, in which the diameter is 1.0 mm.
Fig. 2a is a conceptual diagram of the test, fig. 2b is a photograph showing the film surface after the test, and fig. 2c is a table showing the measurement results.
As shown in fig. 2b and 2c, no crack occurred in example 2, as compared to the crack occurred in comparative example 1.
(evaluation method 3)
FIG. 3 is a graph showing the results of the load-free bending test using example 2 and comparative example 1
Fig. 3a is a conceptual diagram of the test, and fig. 3b is a table showing the measurement results.
As can be seen from the results of the no-load bending test, example 2 also withstands repeated bending, as compared with comparative example 1.
The transparent conductive film of the present invention is an amorphous ITO film in which the first ITO film is not annealed, the second ITO film is an amorphous ITO film in which the second ITO film is not annealed, the film thickness is in the range of 30nm to 320nm, and the surface resistance of the amorphous ITO film is in the range of 9 to 105 (Ω/≡).
(evaluation method 4)
FIG. 4 is a graph showing the results of the 80℃storage characteristics of example 2.
As shown in fig. 4, the resistance value does not change with time even after 1000 hours have elapsed.
(evaluation method 5)
FIG. 5 is a graph showing the results of the storage characteristics at 60℃and 90% RH using example 2.
As shown in fig. 5, the resistance value does not change with time even after 1000 hours have elapsed.
(evaluation method 6)
FIG. 6 is a graph showing the results of thermal cycling tests at-30℃and 80℃using example 2.
As shown in fig. 6, the resistance value does not change with time even after 1000 hours have elapsed.
Example 3
An Ag layer having a film thickness of about 10nm TO 20nm was formed on the surface of the ITO thin film of example 1 by sputtering plating under a vacuum of 0.1 TO 0.9Pa (about 0.6 Pa) using an Ag target. Furthermore, a composition containing 5wt% SnO was used 2 In an argon atmosphere containing about 1% oxygen gas, and forming an ito film (thickness of about 50 nm) having a surface resistance r=55 TO 75 (Ω/≡) on the surface of the Ag layer by sputter plating under a vacuum of 0.1 TO 0.9Pa (about 0.6 Pa).
In this way, example 3 was a transparent conductive film, a first ito film was formed on the surface of a flexible substrate, a thin film metal layer was formed on the surface of the first ito film, and a second ito film was formed on the surface of the thin film metal layer.
The surface resistance r=5.0 (Ω/≡) of the transparent conductive film of example 3, and the total light transmittance was 89%. The total transmittance of the Ag layers having a film thickness of about 10nm to 20nm was 50%.
Comparative example 2
Hard coating treatment of both surfaces of PET (polyethylene terephthalate) having a thickness of 125 μm was performed to form a substrate using a coating containing 5wt% SnO 2 In an argon atmosphere containing about 1% oxygen gas, and forming an ito film (thickness of about 25 nm) having a surface resistance r=170 (Ω/≡) on one surface of the substrate by sputter plating under a vacuum of 0.1 TO 0.9Pa (about 0.6 Pa). Then, an Ag layer having a thickness of about 10nm TO 20nm was formed on the surface of the ITO film by sputtering plating using an Ag target at a vacuum of 0.1 TO 0.9Pa (about 0.6 Pa). Further, an ito film having a thickness of about 50nm was formed on the surface of the Ag layer by sputter plating under a vacuum of 0.1 TO 0.9Pa (about 0.6 Pa) in an argon atmosphere containing about 1% oxygen gas using the ito target. Immediately after plating, the surface resistance was r=5.5 (Ω/≡), and the total light transmittance was 85%. Then, in the atmosphere, the 2 ito films (thickness of about 25nm and about 50nm, respectively) were crystallized by heating for about 50 minutes under a heating atmosphere of about 150 ℃. After crystallization, the surface resistance was r=5.0 (Ω/≡), and the total light transmittance was 89%.
Comparative example 3
Two surfaces of PET (polyethylene terephthalate) having a thickness of 125 μm were subjected to hard coating treatment to form a substrate, and an Ag layer having a film thickness of about 10nm to 20nm was formed on one surface of the substrate by sputtering plating under a vacuum of 0.1 to 0.9Pa (about 0.6 Pa) using an Ag target. After the Ag layer was formed, the surface resistance was r=5.0 (Ω/≡), and the total light transmittance was 50%.
(evaluation method 7)
Fig. 7 is a table showing the heat resistance results of examples 3, comparative examples 2 and comparative example 3.
The heat resistance test was carried out under an atmosphere of 150 ℃.
As shown in fig. 7, example 3 gave good results even when 22 hours had elapsed, but comparative example 2 had a change in heat resistance with time after 22 hours had elapsed. Comparative example 3 has lost the heat-resistant function at the time point when 2 hours passed.
(evaluation method 8)
FIG. 8 is a table showing the results of the 50℃temperature and depth test using example 3, comparative example 2 and comparative example 3.
As shown in fig. 8, example 3 gave good results even after 60 minutes had elapsed, but comparative example 2 began to be affected after 20 minutes had elapsed. Comparative example 3 Ag layer was deteriorated to be discolored and peeled off at the time point of 5 minutes elapsed.
(evaluation method 9)
FIG. 9 is a table showing the results of hot water depth tests at 60℃to 80℃using example 3, comparative example 2 and comparative example 3.
As shown in fig. 9, example 3 gave good results even after 60 minutes had elapsed, but comparative example 2 began to be affected after 40 minutes had elapsed. Comparative example 3 the Ag layer was deteriorated to be discolored and peeled off before 5 minutes passed.
(evaluation method 10)
FIG. 10 is a table showing the results of the room temperature standing test in the atmosphere using example 3, comparative example 2 and comparative example 3.
As shown in fig. 10, example 3 gave good results even after 9 months, but comparative example 2 started to be affected after 3 months, and a part of the Ag layer was discolored after 9 months. Comparative example 3 before 2 months elapsed, the Ag layer deteriorated to be discolored and peeled off.
(evaluation method 11)
Fig. 11 is a graph showing the results of the no-load bending test using example 3 and comparative example 3. The test method was the same as the evaluation method 3.
In example 3 and comparative example 3, good results were obtained for both the resistivity change rate and the total light transmittance after 5000 bending tests.
FIG. 12 is a photomicrograph of the ITO thin film surface of example 1 and comparative example 1.
FIG. 12a is the ITO film of example 1, FIG. 12b is the ITO film of comparative example 1, and the test pieces are each 10 μm by 2.5. Mu.m.
Fig. 13 is a graph showing the measurement result of the surface roughness of the test piece shown in fig. 12.
FIG. 13a is the ITO film of example 1, and FIG. 13b is the ITO film of comparative example 1. For the surface roughness measurement, an ET200 type microform measuring machine manufactured by sakaguchi of the company, ltd was used. Further, a scanning probe microscope (Dimension Icon SPM) manufactured by bruk corporation was used for a photomicrograph and measurement of surface pits.
The surface average roughness Ra (nm) =4.1 of the ITO film of example 1, and the surface average roughness Ra (nm) =9.5 of the ITO film of comparative example 1. Further, the surface average roughness Ra (nm) =5 of the double-sided hard coat film base material used in example 1.
In the case where an ITO film is used and a lower surface resistance value is required, there is generally a method of increasing the thickness of the ITO film layer.
Example 4
The film thickness of the amorphous ITO film was formed to about 320nm by the same method as in example 1.
The total light transmittance of the ITO film at this time was about 82%, and the surface resistance R was about 9 (Ω/≡).
Further, it was confirmed that the average hole diameter and the hole ratio of the ITO film were amorphous high-density films similar to those in example 1, and that the resistance value did not change with time.
Comparative example 4
Comparative example 4 an ITO film (thickness about 300 nm) having a surface resistance r=15 (Ω/≡) was formed by sputtering plating in the same manner as in comparative example 1.
TO prevent the change of the resistance value with time, the thin film crystallized ito film was formed by heating in the atmosphere at about 150 ℃ for about 50 minutes in a heating atmosphere.
As a result, curling occurs on the transparent conductive film with the ito film surface as the upper surface, and cracks (cracks) occur in a part of the ito film, and the surface resistance value becomes r=10 TO infinity (crack portion) (Ω/≡), and a stable resistance value cannot be obtained.
Hereinafter, the film density will be described.
The film density results from the hole rate per unit area. The void fraction is defined as the ratio of the total length of the measured void diameter of the recess to the measured length. Then, a recess having a depth of 22nm or more was regarded as a void, and a diameter at a position of 1/2 of the depth of the recess was regarded as a size of the void (void diameter).
As a result of the measurement, the average hole diameter was 0.32 μm and the hole ratio was 9.5% in the TO film of example 1, and the average hole diameter was 0.46 μm and the hole ratio was 36.5% in the TO film of comparative example 1.
The film density was 90.5% in the ito film of example 1, and was 36.5% in the ito film of comparative example 1, and was 63.5%.
As described above, in the ito film of the present invention, the amorphous ito film has a surface resistance in the range of 9 TO 105 (Ω/≡) by making the film thickness of the amorphous ito film in the range of 30nm TO 320nm, so that the amorphous ito film has a high density film, and thus stability can be improved, and it is possible TO provide an ito film having a resistance value which does not change with time, improved moisture resistance and gas barrier properties, and which overcomes cracks caused by bending.
The surface average roughness of the amorphous ito film is preferably 9nm or less, more preferably 4.1nm or less, and by setting the surface average roughness of the amorphous ito film TO 9nm or less, the film density of the amorphous ito film can be set TO 65% or more, thereby improving the stability.
The amorphous ito film preferably has a film density of 65% or more, more preferably 90% or more, and stability can be improved by setting the film density of the amorphous ito film TO 65% or more.
SnO contained in amorphous ITO film 2 Preferably in the range of 2wt% to 7wt%, and more preferably 5wt% as shown in example 1 and example 2. By mixing SnO 2 The transparency can be enhanced by setting the content to be in the range of 2wt% to 7 wt%.
Further, as shown in example 3, not only the second ito film but also the first ito film is preferably an amorphous ito film having a film thickness in the range of 30nm TO 320nm and a surface resistance in the range of 9 TO 105 (Ω/≡). By changing the first ito film or the second ito film TO such an ito film, a transparent conductive film excellent in conductivity, transparency, and durability can be provided.
Further, the second ito film was set as an amorphous ito film as follows: the amorphous ito film has a surface resistance in the range of 9 TO 105 (Ω/≡) and a thin-film metal layer of 10 TO 20nm thick, whereby Ag having poor durability can be protected by the second ito film TO improve durability, and the total light transmittance of about 50% Ag can be improved TO about 90% by the second ito film.
In example 3, ag was used as the thin film metal layer, but not particularly limited to Ag, cu, A l, au, N i, N i/Cr, T i, sn, etc. or an alloy composed of two or more of them may be used alone.
Claims (11)
1. An ITO thin film, wherein an amorphous ITO film is formed on the surface of a flexible substrate in a state that the amorphous ITO film has not been annealed, wherein the film thickness of the amorphous ITO film is in the range of 30nm to 320nm, and the surface resistance of the amorphous ITO film is in the range of 9 to 105 (Ω/≡).
2. The ITO film of claim 1, wherein polyethylene terephthalate is used as the substrate.
3. The ITO thin film according to claim 1 or 2, wherein the amorphous ITO film has a film density of 65% or more.
4. The ITO thin film according to any one of claims 1 to 3, wherein the amorphous ITO film has a surface average roughness of 9nm or less.
5. The ITO thin film according to any one of claims 1 to 4, wherein the amorphous ITO film contains SnO 2 In the range of 2wt% to 7 wt%.
6. A transparent conductive film comprising a flexible substrate, a first ITO film formed on the surface of the flexible substrate, a thin film metal layer formed on the surface of the first ITO film, and a second ITO film formed on the surface of the thin film metal layer,
the first ITO film is an amorphous ITO film in a state of not being subjected to the annealing treatment; the second ITO film is an amorphous ITO film in a state where the annealing treatment is not performed, the film thickness is in the range of 30nm to 320nm, and the surface resistance of the amorphous ITO film is in the range of 9 to 105 (Ω/≡).
7. The transparent conductive film according to claim 6, wherein the thin film metal layer is an Ag layer having a thickness of 10nm to 20nm.
8. The transparent conductive film according to claim 6 or 7, wherein polyethylene terephthalate is used as the base material.
9. The transparent conductive film according to any one of claims 6 to 8, wherein the second ITO film has a film density of 65% or more.
10. The transparent conductive film according to any one of claims 6 to 9, wherein the amorphous second ITO film has a surface average roughness of 9nm or less.
11. The transparent conductive film according to any one of claims 6 to 10, wherein the second ITO film contains SnO 2 In the range of 2wt% to 7 wt%.
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| JP2018121485A JP7116994B2 (en) | 2018-06-27 | 2018-06-27 | ITO film and transparent conductive film |
| JP2018-121485 | 2018-06-27 | ||
| CN201811344911.0A CN110648783A (en) | 2018-06-27 | 2018-11-13 | ITO thin film and transparent conductive thin film |
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| JPH03213825A (en) * | 1989-11-20 | 1991-09-19 | Ricoh Co Ltd | Cell for liquid crystal display |
| JPH06106756A (en) | 1992-09-25 | 1994-04-19 | Fuji Xerox Co Ltd | Thermal head and manufacture thereof |
| JPH09272172A (en) * | 1996-04-04 | 1997-10-21 | Mitsui Toatsu Chem Inc | Laminated body |
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2018
- 2018-06-27 JP JP2018121485A patent/JP7116994B2/en active Active
- 2018-10-09 TW TW107135559A patent/TWI683017B/en active
- 2018-11-13 CN CN201811344911.0A patent/CN110648783A/en active Pending
- 2018-11-13 CN CN202211677083.9A patent/CN116189964A/en active Pending
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| KR102336155B1 (en) | 2021-12-06 |
| TWI683017B (en) | 2020-01-21 |
| CN110648783A (en) | 2020-01-03 |
| KR20200001441A (en) | 2020-01-06 |
| JP7116994B2 (en) | 2022-08-12 |
| JP2020001232A (en) | 2020-01-09 |
| TW202000950A (en) | 2020-01-01 |
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