JP2021052125A - Method for manufacturing substrate with film - Google Patents

Abstract

To provide a method for manufacturing a substrate with a film, capable of effectively reducing the amount of side etching.SOLUTION: A method for manufacturing a substrate 10 with a film includes: a laminated film forming step of forming a laminated film 6 on a substrate 1, the laminated film including an inorganic film 2 including at least precious metal and a first plated metal film 3 formed on the inorganic film 2; a first etching step of patterning the first plated metal film 3 by using a first etchant; and a second etching step of patterning the inorganic film 2 by using a second etchant. The second etchant does not substantially include a component oxidizing the first plated metal film 3.SELECTED DRAWING: Figure 3

Description

The present invention relates to a method for manufacturing a substrate with a film in which a laminated film including a plated metal film or the like is patterned.

In display devices used in televisions, personal computers, smartphones, and the like, a substrate with a film provided with an electrode film in which a metal film is patterned is used. In such a substrate with a film, for example, after forming a metal film on the substrate, a resist film is formed on the metal film as an etching mask, and the metal film is etched with an etching solution and patterned. Manufactured.

For example, Patent Document 1 below contains a noble metal using an etching solution containing 2 to 5% by mass of hydrogen peroxide and 1% by mass or less of oxalic acid dihydrate and oxalate in total. A method for manufacturing a glass substrate with a film for patterning a laminated film in which a plated metal film is formed on an inorganic film is disclosed.

International Publication No. 2018/070184

It is known that during etching, a phenomenon in which a metal film below the resist film is etched at the edge of the resist film, that is, so-called side etching occurs. In recent years, the line width of an electrode film has become narrower for the purpose of increasing the definition of a display and reducing the visibility of a metal mesh pattern used as an electrode. Therefore, when the amount of side etching becomes large, there arises a problem that the variation in the line width of the electrode film becomes large.

In the method for manufacturing a glass substrate with a film of Patent Document 1, it is said that the amount of side etching can be reduced by using the above-mentioned etching solution. However, even with the method for manufacturing a glass substrate with a film of Patent Document 1, the amount of side etching may not be sufficiently reduced, and the variation in the line width of the electrode film cannot be sufficiently reduced. There's a problem.

An object of the present invention is to provide a method for manufacturing a substrate with a film, which can effectively reduce the amount of side etching.

The method for producing a substrate with a film according to the present invention is a laminated film in which a laminated film having at least an inorganic film containing a noble metal and a first plated metal film formed on the inorganic film is formed on the substrate. A forming step, a first etching step of patterning the first plating metal film using a first etching solution, and a second etching step of patterning the inorganic film using a second etching solution. The second etching solution is characterized in that it does not substantially contain a component that oxidizes the first plating metal film.

In the present invention, it is preferable that the second etching solution contains at least one of an organic acid and an organic acid salt.

In the present invention, it is preferable that the second etching solution contains at least one of oxalic acid and sodium oxalate.

In the present invention, it is preferable that the first etching solution contains hydrogen peroxide, oxalic acid, and sodium oxalate.

In the present invention, it is preferable that the first plated metal film is formed by electroless plating.

In the present invention, the laminated film further has a second plated metal film formed by electrolytic plating on the first plated metal film, and in the first etching step, the first It is preferable to pattern the first plated metal film and the second plated metal film using an etching solution.

In the present invention, it is preferable that the first plated metal film has nickel.

In the present invention, it is preferable that the second plated metal film has copper.

According to the present invention, the amount of side etching can be effectively reduced.

It is a schematic cross-sectional view for demonstrating the manufacturing method of the substrate with a film which concerns on one Embodiment of this invention. It is a schematic cross-sectional view for demonstrating the manufacturing method of the substrate with a film which concerns on one Embodiment of this invention. It is a schematic cross-sectional view for demonstrating the manufacturing method of the substrate with a film which concerns on one Embodiment of this invention. It is a figure which shows the relationship between the 2nd etching time in Example 1 and the amount of residual components of a laminated film. It is a figure which shows the relationship between the over-etching time of the 1st etching process in Comparative Example 1 and the amount of residual components of a laminated film. It is a figure which shows the relationship between the over-etching time of the 1st etching process, and the side etching amount of a laminated film.

Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. Further, in each drawing, members having substantially the same function may be referred to by the same reference numerals.

The method for manufacturing a substrate with a film according to the present invention includes a laminated film forming step, a first etching step, and a second etching step. The laminated film forming step is a step of forming a laminated film having at least an inorganic film containing a noble metal and a first plated metal film formed on the inorganic film on a substrate. The first etching step is a step of patterning the first plated metal film using the first etching solution. The second etching step is a step of patterning the inorganic film using the second etching solution. In the present invention, the second etching solution substantially does not contain a component that oxidizes the first plating metal film.

In the present invention, after the first etching step of patterning the first plated metal film using the first etching solution, the second etching substantially contains no component that oxidizes the first plated metal film. By performing the second etching step of selectively patterning the inorganic film using the liquid, it is possible to suppress the side etching of the first plated metal film in the second etching step.

Therefore, according to the method for manufacturing a substrate with a film of the present invention, the amount of side etching can be effectively reduced.

Hereinafter, each step of the method for manufacturing a substrate with a film according to an embodiment of the present invention will be described in detail with reference to FIGS. 1 to 3.

(Laminate film forming process)
As shown in FIG. 1, a laminated film 6 is formed on the substrate 1. More specifically, first, the inorganic film 2 is formed on the substrate 1. Next, the first plated metal film 3 and the second plated metal film 4 are formed on the inorganic film 2 in this order, thereby forming the laminated film 6. In the present embodiment, both the first plated metal film 3 and the second plated metal film 4 are formed on the inorganic film 2, but the second plated metal film 4 may not be formed. Often, only the first plated metal film 3 may be formed on the inorganic film 2.

The material of the substrate 1 is not particularly limited, and for example, glass, ceramics, resin, or the like can be used. It is preferable to use glass from the viewpoint of weather resistance and thinning. Examples of the glass include soda-lime glass and non-alkali glass. Further, it may be aluminum silicate glass used as tempered glass.

The thickness of the substrate 1 is not particularly limited, and can be, for example, 10 μm or more and 300 μm or less. The thickness of the substrate 1 is preferably 20 μm or more, more preferably 50 μm or more, preferably 200 μm or less, and more preferably 100 μm or less.

When the thickness of the substrate 1 is at least the above lower limit value, it is possible to make it more difficult for the substrate 1 to warp or wrinkle due to the stress of the first plated metal film 3. In addition, the substrate 1 can be made less likely to be damaged. When the thickness of the substrate 1 is not more than the above upper limit value, the flexibility of the substrate 1 can be improved, and it can be more preferably used for a display having a curved surface or the like.

The inorganic film 2 contains at least a precious metal. The noble metal is not particularly limited, and for example, gold, silver, platinum, palladium, ruthenium and the like can be used. Further, in the present embodiment, the inorganic film 2 is a black layer. However, in the present invention, the inorganic film 2 may be a layer of another color.

Examples of such an inorganic film 2 include tin chloride, zinc chloride, copper chloride and the like that are easily adsorbed on the substrate 1, sodium gold sulfite, silver chloride, silver nitrate, hexachloroplatinum (IV) acid hexahydrate, and palladium chloride. , Ruthenium chloride and the like are added. In addition to the noble metal described above, the inorganic film 2 may contain a metal such as nickel, cobalt, or copper that serves as a catalyst for electroless plating.

The method for forming the inorganic film 2 is not particularly limited, and for example, the inorganic film 2 can be formed by the following method. Specifically, the substrate 1 is immersed in a solution containing one or more of tin, zinc, and copper, the metal ions are adsorbed on the surface of the substrate 1, and then the substrate 1 is immersed in an aqueous solution containing a noble metal. To do. As a result, metal ions such as tin, zinc, and copper are replaced with noble metal ions due to the difference in ionization tendency, and a film containing a noble metal or a noble metal compound is formed on the substrate 1. The inorganic film 2 formed in this way is an oxide film. The substrate 1 on which this film is formed may be immersed in a reducing solution. In this case, the noble metal near the surface of the film can be reduced to have a catalytic action of electroless plating. However, even in this case as well, since only the noble metal near the surface of the film is reduced, the inorganic film 2 can be etched using the second etching solution described later.

The thickness of the inorganic film 2 is not particularly limited, and can be, for example, 0.03 μm or more and 1.0 μm or less. The thickness of the inorganic film 2 is preferably 0.05 μm or more, more preferably 0.07 μm or more, preferably 0.7 μm or less, and more preferably 0.5 μm or less. When the thickness of the inorganic film 2 is at least the above lower limit value, the formation rate of the first plated metal film 3 can be further increased. Further, when the thickness of the inorganic film 2 is not more than the above upper limit value, it is not necessary to increase the amount of precious metal more than necessary, which is more preferable from the viewpoint of economy.

The first plated metal film 3 can be formed by, for example, electroless plating. Further, the second plated metal film 4 can be formed by, for example, electrolytic plating or electroless plating.

The first plated metal film 3 preferably contains copper or nickel. Copper and nickel are preferable because they are metal materials capable of fine etching. Copper has a low electrical resistance, and in electroless plating, a uniform film thickness is formed. Nickel has good adhesion to the inorganic film 2.

The thickness of the first plated metal film 3 is not particularly limited, and can be, for example, 0.05 μm or more and 5.0 μm or less. The thickness of the first plated metal film 3 is preferably 0.1 μm or more, more preferably 0.2 μm or more, preferably 1.0 μm or less, and more preferably 0.5 μm or less. When the thickness of the first plated metal film 3 is equal to or greater than the above lower limit value, when the second plated metal film 4 is formed on the first plated metal film 3 by electrolytic plating, the second plated metal film 3 is formed. The film thickness of 4 can be made even more uniform. Further, when the thickness of the first plated metal film 3 is not more than the above upper limit value, the film forming time can be further shortened, thereby further increasing the production efficiency and further reducing the manufacturing cost. it can.

The second plated metal film 4 is not particularly limited, but is preferably low in electrical resistance in consideration of its use as an electrode, and copper or nickel is preferable from this viewpoint. The volume resistivity is 3 μΩ · cm for electroless plated copper and electrolytic plated copper, and 8 μΩ · cm for electroplated nickel. Further, copper and nickel are preferable because they are metal materials capable of fine etching as described above.

The thickness of the second plated metal film 4 is, for example, 0.1 μm or more and 5.0 μm or less. The thickness of the second plated metal film 4 is preferably 0.3 μm or more, more preferably 0.5 μm or more, preferably 3.0 μm or less, and more preferably 2.0 μm or less. When the thickness of the second plated metal film 4 is at least the above lower limit value, the conductivity as an electrode can be further enhanced. When the thickness of the second plated metal film 4 is not more than the above upper limit value, the film forming time can be further shortened, thereby further increasing the production efficiency and further reducing the manufacturing cost.

When the first plated metal film 3 is made of electroless plated copper and the second plated metal film 4 is made of electrolytic plated copper, a laminated film 6 having a uniform thickness and a low resistivity can be obtained in a short time. Further, since both the first plated metal film 3 and the second plated metal film 4 are made of copper, microfabrication by etching becomes easy.

When the first plated metal film 3 is made of electroless plated copper and the second plated metal film 4 is made of electroless plated copper, both are made of copper, so that fine processing by etching becomes easy.

When the first plated metal film 3 is made of electroless plated copper and the second plated metal film 4 is made of electroless plated nickel or electrolytic plated nickel, the surface is made of nickel, so that the corrosion resistance is excellent.

When the first plated metal film 3 is made of electroless plated nickel and the second plated metal film 4 is made of electrolytically plated copper, the resistivity of the laminated film 6 can be lowered. Further, the laminated film 6 having a uniform thickness can be formed. In addition, an inexpensive plating bath can be used, and the low-resistance laminated film 6 can be formed inexpensively and with good productivity.

When the first plated metal film 3 is made of electroless plated nickel and the second plated metal film 4 is made of electroless plated nickel or electrolytic plated nickel, both are made of nickel, so that fine processing by etching is easy. become. Moreover, since the surface is composed of nickel, it has excellent corrosion resistance.

(First etching process)
Next, the resist film 5 is formed on the laminated film 6. The resist film 5 can be formed of a resist material used in a general photolithography method. The resist film 5 has a pattern corresponding to the pattern of the electrode film formed by etching the laminated film 6.

Next, after forming the resist film 5, the substrate 1 is immersed in the first etching solution to etch the first plated metal film 3 and the second plated metal film 4 in the laminated film 6. At this time, the time point at which the first plated metal film 3 and the second plated metal film 4 are removed in the portion where the resist film 5 is not formed in the plan view is set as the end point of etching. Since the laminated film 6 is etched in order from the upper layer to the lower layer, the first etching is performed by setting the time point at which the first plated metal film 3 and the second plated metal film 4 are removed as the end point of etching. Over-etching on the plated metal film 3 and the second plated metal film 4 can be suppressed. Therefore, according to this method, the first plated metal film 3 and the second plated metal film 4 can be etched with an appropriate overetching time. Further, according to this method, even when only the first plated metal film 3 is provided on the inorganic film 2, only the first plated metal film 3 can be etched with an appropriate overetching time. .. It should be noted that confirmation that the first plated metal film 3 and the second plated metal film 4 have been removed can be performed, for example, by a reflective optical sensor, a transmissive optical sensor, visual inspection, or the like.

FIG. 2 is a schematic cross-sectional view showing the laminated film 6 after the first etching step. As shown in FIG. 2, the first plated metal film 3 and the second plated metal film 4 are side-etched so as to recede inward from the lower outer end portion 5a of the resist film 5. The amount of side etching (SE amount) is the horizontal distance from the lower outer end portion 5a of the resist film 5 to the upper outer end portion 6a of the laminated film 6.

The first etching solution is not particularly limited, but preferably contains an oxidizing agent, and more preferably contains at least one of an organic acid and an organic acid salt.

The oxidizing agent is an oxidizing agent that oxidizes the first plated metal film 3 and the second plated metal film 4. The oxidizing agent is not particularly limited, and examples thereof include hydrogen peroxide, ferric chloride, and cupric chloride. When hydrogen peroxide is used as the oxidizing agent, it is preferable to use at least one of an organic acid and an organic acid salt in combination.

The organic acid or organic acid salt functions as a complexing agent for dissolving the first plated metal film 3 and the second plated metal film 4 as a metal complex. Examples of such organic acids and acid salts include oxalic acid, acetic acid, citric acid, maleic acid, glycolic acid, succinic acid, tartaric acid, fumaric acid, salicylic acid, malic acid, pivalic acid, and salts thereof. .. These may be used alone or in combination of two or more. Among them, the organic acid and the organic acid salt are preferably oxalic acid or oxalate. Examples of the oxalate include sodium oxalate, ammonium oxalate and the like.

In the present invention, the first etching solution preferably contains hydrogen peroxide, oxalic acid, and oxalate. When these combinations are used in the first etching solution, the first plated metal film 3 and the second plated metal film 4 are more reliably etched while the amount of side etching is further reduced effectively. Can be done. As the oxalate, sodium oxalate is preferable.

In this case, the concentration of hydrogen peroxide is not particularly limited, but is preferably 2% by mass or more, more preferably 2.5% by mass or more, still more preferably 3.5% by mass or more, and preferably 5% by mass or less. Is. When the concentration of hydrogen peroxide is at least the above lower limit value, the amount of side etching (SE amount) can be further reduced. When the concentration of hydrogen peroxide is not more than the above upper limit value, the promotion of autolysis of hydrogen peroxide can be further suppressed, and the rapid temperature rise can be further suppressed.

The total amount of the concentrations of oxalic acid and oxalate is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.4% by mass or more, and preferably 1.0% by mass or less. , More preferably 0.8% by mass or less, still more preferably 0.6% by mass or less. When the total amount of the concentrations of oxalic acid and oxalate is not more than the above lower limit value, the etching rate can be further increased, and for example, the time required to complete the etching can be further shortened. Further, when the total amount of the concentrations of oxalic acid and oxalate is not more than the above upper limit value, the amount of side etching (SE amount) can be further reduced.

The concentration of oxalic acid is preferably 0.025% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, preferably 0.25% by mass or less, and more preferably 0.2. It is mass% or less, more preferably 0.15 mass% or less. When the concentration of oxalic acid is at least the above lower limit value, the etching rate can be further increased, and for example, the time required to complete the etching can be further shortened. Further, when the concentration of oxalic acid is not more than the above upper limit value, the amount of side etching (SE amount) can be further reduced. The concentration of oxalic acid shall be determined by the concentration of oxalic acid dihydrate.

The concentration of oxalate is preferably 0.075% by mass or more, more preferably 0.15% by mass or more, still more preferably 0.3% by mass or more, preferably 0.75% by mass or less, and more preferably 0. It is 6% by mass or less, more preferably 0.45% by mass or less. When the concentration of oxalate is at least the above lower limit value, the etching rate can be further increased, and for example, the time required to complete the etching can be further shortened. Further, when the concentration of oxalate is not more than the above upper limit value, the amount of side etching (SE amount) can be further reduced.

The first etching solution may contain ethylene glycol, a surfactant, or the like. When ethylene glycol is contained, its concentration can be, for example, 1.4% by mass or more and 2.1% by mass or less.

The temperature of the first etching solution at the time of performing the first etching is preferably in the range of 50 ° C. or higher and 70 ° C. or lower.

(Second etching process)
After the first etching step, the substrate 1 is washed. The substrate 1 can be washed with, for example, pure water. The substrate 1 may be used as it is in the second etching step without cleaning, but it is desirable to perform the second etching step through the cleaning step.

After cleaning, the substrate 1 is immersed in a second etching solution to perform a second etching step of etching the inorganic film 2 in the laminated film 6.

FIG. 3 is a schematic cross-sectional view showing the laminated film 6 after the second etching step. As shown in FIG. 3, in the second etching step, the side etching of the first plated metal film 3 and the second plated metal film 4 is suppressed. On the other hand, the inorganic film 2 is etched and patterned by the second etching solution. As a result, the film-attached substrate 10 is formed.

In the present invention, the second etching solution substantially does not contain a component that oxidizes the first plating metal film 3 and the second plating metal film 4. In addition, "substantially free of components that oxidize the plating metal film" means that the etching rate of the second etching solution in a single layer of the first plating metal film 3 and the second plating metal film 4 It means that each is 0.01 μm / min or less. When only the first plated metal film 3 is provided, it is assumed that the component that oxidizes the first plated metal film 3 is substantially not contained.

The second etching solution preferably contains at least one of an organic acid and an organic acid salt. The organic acid or organic acid salt functions as a complexing agent for dissolving the inorganic film 2 as a metal complex. Examples of such organic acids and acid salts include oxalic acid, acetic acid, citric acid, maleic acid, glycolic acid, succinic acid, tartaric acid, fumaric acid, salicylic acid, malic acid, pivalic acid, and salts thereof. .. These may be used alone or in combination of two or more. Among them, the organic acid and the organic acid salt are preferably oxalic acid and oxalate. Examples of the oxalate include sodium oxalate, ammonium oxalate and the like.

In the present invention, the second etching solution preferably contains oxalic acid and oxalate. When these combinations are used in the second etching solution, the inorganic film 2 can be etched more reliably while reducing the amount of side etching more effectively. As the oxalate, sodium oxalate is preferable.

The concentration of oxalic acid is preferably 0.25% by mass or more, more preferably 0.35% by mass or more, still more preferably 0.4% by mass or more, preferably 0.7% by mass or less, and more preferably 0.6. It is mass% or less, more preferably 0.55 mass% or less. When the concentration of oxalic acid is at least the above lower limit value, the etching rate can be further increased, and for example, the time required to complete the etching can be further shortened. Further, when the concentration of oxalic acid is not more than the above upper limit value, the solubility of the chemical can be further enhanced. The concentration of oxalic acid shall be determined by the concentration of oxalic acid dihydrate.

The concentration of oxalate is preferably 0.75% by mass or more, more preferably 1.15% by mass or more, still more preferably 1.35% by mass or more, preferably 2.25% by mass or less, and more preferably 1. It is 85% by mass or less, more preferably 1.65% by mass or less. When the concentration of oxalate is at least the above lower limit value, the etching rate can be further increased, and for example, the time required to complete the etching can be further shortened. Further, when the concentration of oxalate is not more than the above upper limit value, the solubility of the chemical can be further enhanced.

The temperature of the second etching solution at the time of performing the second etching is preferably 35 ° C. or higher, preferably 65 ° C. or lower. When the temperature of the second etching solution is equal to or higher than the above lower limit value, the etching rate can be further increased, and for example, the time required to complete the etching can be further shortened. Further, in this case, the solubility of the chemical can be further improved. When the temperature of the second etching solution is not more than the above upper limit value, fluctuations in the amount and concentration of the solution due to evaporation can be further suppressed. Further, in this case, the temperature control cost can be further reduced.

In the present invention, since the second etching solution does not substantially contain a component that oxidizes the first plating metal film 3 and the second plating metal film 4, the first plating metal is used in the second etching step. The film 3 and the second plated metal film 4 are less likely to be oxidized. Therefore, even if an organic acid or an organic acid salt is added, the first plated metal film 3 and the second plated metal film 4 are difficult to dissolve as a metal complex and are difficult to be etched. On the other hand, since the inorganic film 2 containing at least a noble metal has already been oxidized as described above, it is dissolved as a metal complex and etched by adding an organic acid or an organic acid salt. Therefore, in the second etching step, the inorganic film 2 can be selectively etched, and the side etching of the first plated metal film 3 and the second plated metal film 4 can be suppressed.

Therefore, according to the method for manufacturing a substrate with a film of the present invention, the amount of side etching can be effectively reduced.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
A glass substrate (product name: OA-10G manufactured by Nippon Electric Glass Co., Ltd.) was used as the substrate. A laminated film composed of an inorganic film, a first plated metal film, and a second plated metal film was formed on one surface of this substrate. The inorganic film was formed by the method described above.

An electroless nickel plating film was formed as the first plating metal film, and the thickness was 0.25 μm.

An electrolytic copper plating film was formed as the second plating metal film, and the thickness was 1.0 μm.

A resist film patterned by a photolithography method was formed on the laminated film formed as described above. The line width of the resist film was 12 μm.

Next, after preparing a first etching solution having 0.12% by mass of oxalic acid dihydrate, 0.37% by mass of sodium oxalate as a oxalate, and 4.1% by mass of hydrogen peroxide, 65 The first etching step was performed by keeping the temperature constant at ° C., immersing the film-attached substrate after forming the resist film in an etching solution tank filled with the first etching solution, and shaking the film-attached substrate.

The etching time (over-etching time) after the first plated metal film and the second plated metal film were removed was 0.75 minutes, after which the substrate with the film was taken out and washed with pure water.

Next, a second etching solution containing 0.5% by mass of oxalic acid dihydrate and 1.5% by mass of sodium oxalate, which is an oxalate, was prepared, kept at a constant temperature at 45 ° C., and after the above washing. The substrate with the film was immersed in an etching solution tank filled with the second etching solution, and the substrate with the film was shaken to perform the second etching step.

Residual components of the laminated film other than below the resist film were confirmed by appearance observation by SEM (Scanning Electron Microscope) and component analysis by EPMA (Electron Probe Micro Analyzer).

FIG. 4 is a diagram showing the relationship between the second etching time in Example 1 and the amount of residual components of the laminated film. From FIG. 4, it can be seen that when the second etching step is carried out for 2.5 minutes, the residual components of the laminated film are removed.

The amount of side etching (SE amount) shown in FIG. 3 was 3.3 μm in Example 1. The amount of side etching (SE amount) is determined by measuring the line width of the resist film and the line width of the second plated metal film after etching using an optical microscope, and from the line width of the resist film to the second plating after etching. It was calculated as 1/2 of the value obtained by subtracting the line width of the metal film.

(Comparative Example 1)
In Comparative Example 1, the first etching step was performed until there were no residual components of the laminated film other than below the resist film, and the second etching step was not performed.

FIG. 5 is a diagram showing the relationship between the overetching time of the first etching step in Comparative Example 1 and the amount of residual components of the laminated film. The over-etching time is the etching time after confirming that the first plated metal film and the second plated metal film have been removed.

From FIG. 5, it can be seen that in Comparative Example 1, the residual component was removed by performing the overetching of the first etching for 1.75 minutes.

The amount of side etching (SE amount) shown in FIG. 3 was 4.7 μm in Comparative Example 1.

Note that FIG. 6 is a diagram showing the relationship between the over-etching time of the first etching step and the side etching amount of the laminated film.

From FIG. 6, it can be seen that the side etching amount is 3.3 μm when the over-etching time of the first etching step is 0.75 minutes. At this time, since the over-etching time of the first etching step in Example 1 is 0.75 minutes, the side etching amount in Example 1 substantially corresponds to the over-etching amount of the first etching step, and is the second. It can be seen that side etching is hardly performed in the etching process of.

As a result, in the production method of the present invention in which the inorganic film is etched with the second etching solution which does not substantially contain the components that oxidize the first plated metal film and the second plated metal film, the amount of side etching is effective. It can be seen that it can be made smaller. Further, in the second etching step, since the side etching of the first plated metal film and the second plated metal film is not blurred, it is possible to set a time with a margin for removing the residual component, and the productivity is improved. You can also do it.

1 ... Substrate 2 ... Inorganic film 3 ... First plated metal film 4 ... Second plated metal film 5 ... Resist film 5a ... Lower outer end of resist film 6 ... Laminated film 6a ... Upper outer end of laminated film 10 … Substrate with film

Claims (8)

A laminated film forming step of forming a laminated film having an inorganic film containing at least a noble metal and a first plated metal film formed on the inorganic film on a substrate.
The first etching step of patterning the first plating metal film using the first etching solution, and
A second etching step of patterning the inorganic film using the second etching solution, and
With
A method for producing a substrate with a film, wherein the second etching solution does not substantially contain a component that oxidizes the first plated metal film. The method for producing a substrate with a film according to claim 1, wherein the second etching solution contains at least one of an organic acid and an organic acid salt. The method for producing a substrate with a film according to claim 1 or 2, wherein the second etching solution contains at least one of oxalic acid and sodium oxalate. The method for producing a substrate with a film according to any one of claims 1 to 3, wherein the first etching solution contains hydrogen peroxide, oxalic acid, and sodium oxalate. The method for manufacturing a substrate with a film according to any one of claims 1 to 4, wherein the first plated metal film is formed by electroless plating. The laminated film further has a second plated metal film formed by electrolytic plating on the first plated metal film.
The film according to any one of claims 1 to 5, wherein in the first etching step, the first plating metal film and the second plating metal film are patterned using the first etching solution. Manufacturing method of attached substrate. The method for producing a substrate with a film according to any one of claims 1 to 6, wherein the first plated metal film has nickel. The method for producing a substrate with a film according to claim 6 or 7, wherein the second plated metal film has copper.

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