JP6639253B2 - Functional component of mask for electroforming, method of manufacturing functional component of mask for electroforming - Google Patents

Description

  The present invention relates to a functional component suitable for an electroforming mask master used for manufacturing a metal mask by electroforming, and a method for manufacturing the same.

  For example, in an organic EL (Electro Luminescence) display or the like, a metal mask is used as a deposition mask for forming a fine pattern with high accuracy. As a method of manufacturing such a metal mask, a method of manufacturing by etching a metal foil and a method of manufacturing by electroforming are generally known.

  Among them, it is difficult to reduce the thickness of the metal foil as a material of the metal mask manufactured using the metal foil. For this reason, when used as a metal mask for vapor deposition, shadows are likely to occur due to the large thickness of the metal foil, and it has been difficult to form a fine pattern.

  On the other hand, in the production of a metal mask by electroforming, since the thin film is formed by electroplating, it is easy to reduce the thickness of the mask material film. In the production of a metal mask by electroforming, a mask for electroforming in which an electrode film having a desired pattern is formed on a glass substrate is used. A metal mask is manufactured by plating the electroforming mask master to form a plating film having a desired pattern and peeling the plating film from the electroforming mask master (see, for example, Patent Document 1). .

  However, in the past, such an electroforming mask master had insufficient adhesion between the glass substrate and the electrode film, so that the electrode film was peeled off from the glass substrate by forming the metal mask once or several times, There was a problem in durability.

In recent years, instead of the conventional nickel electroformed mask, an electroformed mask using a Ni—Fe alloy, which is a low thermal expansion metal, which is suitable for manufacturing a high-precision metal mask, has been developed (for example, Non-patented). Reference 1).
However, in the conventional nickel electroforming, the plating solution has a pH of about 4, whereas in the electroforming using a Ni—Fe alloy, the plating solution has a pH of 2.3 and is highly acidic. For this reason, in the conventional mask for electroforming, there has been a problem that the electrode film containing chromium as a main component is insufficient in acid resistance, and the pattern is easily chipped due to corrosion by a plating solution during electroforming.

JP-A-2002-55461

The journal of the Surface Finishing Society of Japan 62 (12), 702-707, 2011-12-01

The present invention has been made in view of the above-mentioned circumstances, and has excellent adhesion between an electrode film and a glass substrate, and also has excellent acid resistance of the electrode film, and is a functional component of an original mask for electroforming , and its production. It provides a method.

Functional components for electroforming mask precursor of the invention, a glass substrate, formed by formed in contact with the glass substrate, the adhesion layer mainly composed of chromium oxide, and is formed in contact said seal adhesive layer An electrode film having at least a conductive layer containing nitrogen in a concentration range of not less than 8 atom% and not more than 38 atom%.

  According to the functional component of the present invention, the adhesion between the electrode film and the glass substrate can be significantly improved by forming the adhesion layer containing chromium oxide as a main component between the conductive layer and the glass substrate. it can. Thus, for example, when a metal mask is formed by electroforming using a functional component as an electroforming mask master, even if the plated metal mask is separated from the functional component, the electrode film easily peels off from the glass substrate. There is no fear of damage or partial damage. This makes it possible to realize a functional component having sufficient strength to repeatedly produce a metal mask a plurality of times when the functional component is used as an electroforming mask master.

  Further, according to the functional component of the present invention, by forming the conductive layer from a material containing at least a main component of chromium and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less, the acid resistance of the conductive layer can be reduced. It can be greatly improved. By improving the acid resistance of the conductive layer, the corrosion of the conductive layer can be sufficiently suppressed even for a plating solution having a high acidity such as pH 2.3 used for electroforming using a Ni—Fe alloy. . Therefore, it is possible to perform electroforming using a Ni—Fe alloy that is a low thermal expansion metal, which is suitable for manufacturing a highly accurate metal mask.

The conductive layer may further include carbon.
Further, the carbon is contained in the conductive layer in a concentration range of 3 atom% or more and 18 atom% or less.
The thickness of the adhesion layer along the lamination direction is in the range of 10 nm or more and 50 nm or less.
Further, the conductive layer has a resistivity in a range of 0.8 × 10 ⁻⁶ Ω · m or more and 2.5 × 10 ⁻⁶ Ω · m or less.

  Further, the conductive layer has a thickness along a lamination direction of 100 nm or more and 500 nm or less.

The method of manufacturing a functional component of an electroforming mask master according to the present invention includes, on a glass substrate, a step of forming an adhesion layer containing chromium oxide as a main component in contact with the glass substrate ; A step of forming an electrode film having at least a conductive layer containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less, in contact with the adhesion layer, the main component being chromium.

  ADVANTAGE OF THE INVENTION According to the manufacturing method of the functional component of this invention, the adhesion between an electrode film and a glass substrate is significantly improved by forming the adhesion layer containing chromium oxide as a main component between the conductive layer and the glass substrate. Therefore, for example, when a metal mask is formed by electroforming using a functional component as an original mask for electroforming, even if the plated metal mask is separated from the functional component, the electrode film easily peels off from the glass substrate. There is no fear of damage or partial damage. Thereby, a highly accurate metal mask can be easily manufactured.

  According to the method for manufacturing a functional component of the present invention, the conductive layer is formed of a material containing at least a main component of chromium and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less. The acid resistance is greatly improved, and the corrosion of the conductive layer can be sufficiently suppressed even for a plating solution having a high acidity such as pH 2.3 used for electroforming using a Ni—Fe alloy. Therefore, it is possible to perform electroforming using a Ni—Fe alloy that is a low thermal expansion metal, which is suitable for manufacturing a highly accurate metal mask.

  The method further includes a step of forming a predetermined electrode pattern on the electrode film by etching the surface of the electrode film including at least the adhesion layer and the conductive layer using an etchant for chromium.

  Forming a non-conductive film having a predetermined pattern on a surface of the electrode film provided with at least the adhesion layer and the conductive layer.

  ADVANTAGE OF THE INVENTION According to this invention, the functional component excellent in the adhesiveness of an electrode film and a glass substrate, and also excellent in the acid resistance of a conductive layer, and its manufacturing method can be provided.

It is a principal part expanded sectional view which shows the functional component which concerns on embodiment of this invention. 1 is a flowchart illustrating step by step a method for manufacturing a functional component of the present invention and a method for manufacturing a metal mask using the same. It is an important section enlarged sectional view which explained a manufacturing method of a functional part of the present invention step by step. It is the principal part expanded sectional view which showed the process of manufacturing a metal mask using a functional component in steps. 9 is a graph showing a result of a verification example according to the present invention. 9 is a graph showing a result of a verification example according to the present invention.

  Hereinafter, a functional component and a method for manufacturing the functional component of the present invention will be described with reference to the drawings. Each embodiment described below is specifically described for better understanding of the gist of the invention, and does not limit the invention unless otherwise specified. In addition, in the drawings used in the following description, for convenience, in order to make the features of the present invention easy to understand, a portion that is a main part may be enlarged, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

(functional parts)
FIG. 1 is an enlarged sectional view of a main part showing a functional component according to an embodiment of the present invention.
The functional component 1 is a component suitable for an electroforming mask master used when a metal mask is manufactured by electroforming, and includes a glass substrate 10, an adhesion layer 11 on the glass substrate 10, and an adhesion layer 11. An electrode film 13 having the conductive layer 12 formed thereon is formed.

Although the constituent material of the glass substrate 10 is not particularly limited, for example, alkali-free glass, quartz glass, borosilicate glass (Tempax float manufactured by Schott), soda lime glass, white plate, or the like, or pure SiO ₂ Various glasses, such as a glass close to, and a glass containing a large amount of impurities (additives) other than SiO ₂ . In the present embodiment, soda lime glass is used as a constituent material of the glass substrate 10.

  The adhesion layer 11 is a film formed between the adhesion layer 11 and the conductive layer 12 in order to increase the adhesion between the conductive layer 12 formed thereon and the glass substrate 10. The constituent material of the adhesion layer 11 is mainly composed of chromium oxide. Further, it is more preferable to include chromium carbide and chromium nitride in addition to chromium oxide.

  Oxygen contained in the adhesion layer 11 is in a concentration range of 20 atom% or more and 50 atom% or less.

  The adhesion layer 11 is formed such that the thickness along the laminating direction is in the range of 10 nm or more and 50 nm or less. More preferably, the film is formed to have a thickness of 10 nm or more and 30 nm or less. If the thickness of the adhesion layer 11 is less than 10 nm, components of the glass substrate 10, for example, alkali components such as sodium, potassium, magnesium, and calcium may reach the conductive layer 12 and deteriorate the properties of the conductive layer 12. In view of the barrier property between the conductive layer 12 and the glass substrate 10, the thickness of the adhesion layer 11 is preferably 10 nm or more. If the glass substrate 10 is made of non-alkali glass containing no alkali component, borosilicate glass, quartz glass, or the like, the thickness of the adhesion layer 11 can be further reduced.

  If the thickness of the adhesion layer 11 exceeds 50 nm, it takes a long time to form a film, and it is not preferable from the viewpoint of film strength. Therefore, the thickness of the adhesion layer 11 is formed to be in the range of 10 nm or more and 50 nm or less.

  The conductive layer 12 is made of a material containing chromium as a main component at least and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less. More preferably, conductive layer 12 contains nitrogen in a concentration range of 14 atom% or more and 38 atom% or less.

  When the conductive layer 12 contains nitrogen in the above-described concentration range with respect to chromium as a main component, acid resistance can be increased. For example, when a metal mask is manufactured by electroforming, a high acid resistance can be obtained even with respect to a plating solution for a Ni—Fe alloy having a lower pH than conventional electroforming with nickel. It is possible to manufacture a metal mask made of an Fe alloy.

  The thickness of the conductive layer 12 in the stacking direction is preferably in the range of 100 nm or more and 500 nm or less. If the thickness of the conductive layer 12 is less than 100 nm, the electric resistance increases when electroforming is performed, and there is a concern that the time required for manufacturing the metal mask may increase. On the other hand, when the thickness of the conductive layer 12 exceeds 500 nm, it takes time to form the conductive layer 12, and the manufacturing cost of the functional component 1 may increase.

Further, the conductive layer 12 preferably has a resistivity in the range of 0.8 × 10 ⁻⁶ Ω · m or more and 2.5 × 10 ⁻⁶ Ω · m or less. By making the resistivity of the conductive layer 12 equal to or less than 2.5 × 10 ⁻⁶ Ω · m, when the functional component 10 is used as a mask master for electroforming, it is efficiently plated on the electrode film 12 during electroforming. A film (metal mask) can be formed.

The conductive layer 12 preferably further contains carbon in addition to chromium as a main component and nitrogen as an additional element. The carbon content of the conductive layer 12 is preferably in the range of 3 atom% to 18 atom%.
When the conductive layer 12 contains carbon, the acid resistance of the conductive layer 12 can be further increased.

  By providing an opening in the form of a desired metal mask shape in a part of the functional component 1 including the electrode film 13 having the conductive layer 12 and the adhesion layer 11, an electrode pattern having an electrode pattern 14 having a predetermined shape is provided. Thus, a functional component 2 with a tag is formed. The electrode pattern 14 simulates the shape of a metal mask to be manufactured when the functional component 1 is used as an electroforming mask master used for manufacturing a metal mask by electroforming. It is formed by etching the electrode film 13 of the functional component 1 in an etching step in the manufacturing method.

  According to the functional component 1 of the present invention having the above configuration, the functional component 1 is electrically connected by forming the adhesion layer 11 containing chromium oxide as a main component between the conductive layer 12 and the glass substrate 10. When used as a casting mask master, the adhesion between the electrode film 13 having the conductive layer 12 and the adhesion layer 11 and the glass substrate 10 can be greatly improved.

  Thus, for example, when the functional component 1 is used as an electroforming mask master to form a metal mask by electroforming, even if the plated metal mask is separated from the functional component 1, the conductive layer 12 and the adhesion layer 11 are removed. There is no fear that the electrode film 13 having the electrode film easily peels off from the glass substrate 10 or is partially damaged. Thus, when the functional component 1 is used as a mask for electroforming, the functional component 1 having sufficient strength to repeatedly produce a metal mask can be realized.

  Further, according to the functional component 1 of the present invention, the conductive layer 12 is made of a material containing at least a main component of chromium and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less. Acid resistance can be greatly improved.

  By improving the acid resistance of the conductive layer 12, for example, the corrosion of the conductive layer 12 can be sufficiently suppressed even with a plating solution having a high acidity such as pH 2.3 used in electroforming using a Ni-Fe alloy. Can be. Therefore, it is possible to perform electroforming using a Ni—Fe alloy that is a low thermal expansion metal, which is suitable for manufacturing a highly accurate metal mask.

(Method of manufacturing functional components)
Next, a method of manufacturing the functional component having the above-described configuration will be described.
FIG. 2 is a flowchart illustrating step by step a method for manufacturing a functional component according to the present invention and a method for manufacturing a metal mask using the same. FIG. 3 is an enlarged cross-sectional view of a main part, illustrating step by step the method of manufacturing a functional component according to the present invention.
When manufacturing the functional component 1, first, the glass substrate 10 is prepared. Examples of the glass substrate 10 include, for example, alkali-free glass, quartz glass, borosilicate glass (Tempax float manufactured by Schott), soda lime glass, white plate, and the like, and impurities close to pure SiO ₂ and other than SiO _2. Glass containing a large amount of (additive) can be used. In the present embodiment, soda lime glass is used as a constituent material of the glass substrate 10.

  Then, as shown in FIG. 3A, as a pretreatment, the processing surface 10a on which the adhesion layer 11 is formed on the glass substrate 10 is polished to smooth the processing surface 10a (preprocessing step S1). In the pretreatment step S1, the processing surface 10a of the glass substrate 10 is polished using, for example, a polishing pad P and a polishing liquid containing cerium oxide as a main component. This polishing step can be performed any number of times. Further, the glass substrate 10 after the polishing treatment is cleaned by using a known cleaning method to remove a polishing liquid or the like attached to the substrate surface. As a method of cleaning the glass substrate 10, it is common to perform cleaning with pure water after cleaning with a detergent.

  Next, as shown in FIG. 3B, the adhesion layer 11 is formed on the processed surface 10a of the glass substrate 10 that has been subjected to the pretreatment (adhesion layer forming step S2). The adhesion layer 11 contains chromium oxide as a main component. Further, it is also preferable to include chromium carbide and chromium nitride in addition to chromium oxide.

Oxygen contained in the adhesion layer 11 is in a concentration range of 20 atom% or more and 50 atom% or less.
Further, the adhesion layer 11 is formed such that the thickness along the lamination direction is in the range of 10 nm or more and 50 nm or less.

As a method for forming the adhesion layer 11 in the adhesion layer forming step S2, it is preferable to use a sputtering method in consideration of mass productivity and the like. In this case, it is preferable to use a mixed gas of an argon gas, a nitrogen gas and a carbon dioxide gas as the sputtering gas, and the flow ratio can be set so as to obtain a desired film thickness and adhesion of the film. In particular, conditions such as the nitrogen gas flow rate are set so that the nitrogen concentration in the film falls within the prescribed range. Note that a sputtering device having a known structure can be used.
By the sputtering method using such an argon gas, a nitrogen gas, and a carbon dioxide gas, the adhesion layer 11 containing chromium oxide as a main component can be formed on the surface 10a to be processed of the glass substrate 10.

Next, as shown in FIG. 3C, a conductive layer 12 is formed on the adhesion layer 11 (conductive layer forming step S3). Thereby, the functional component 1 in which the electrode film 13 having the conductive layer 12 and the adhesion layer 11 is formed on the glass substrate 10 is obtained.
The conductive layer 12 is made of a material containing chromium as a main component at least and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less. As a method for forming the conductive layer 12 in the conductive layer forming step S3, it is preferable to use a sputtering method in consideration of mass productivity and the like. In this case, it is preferable to use a mixed gas of an argon gas and a nitrogen gas as the sputtering gas, and the flow rate ratio can be set so as to obtain a desired film thickness and film adhesion. In particular, conditions such as the nitrogen gas flow rate are set so that the nitrogen concentration in the film falls within the prescribed range. Note that a sputtering device having a known structure can be used.

The conductive layer 12 is preferably formed so that the thickness along the stacking direction is in the range of 100 nm or more and 500 nm or less. The conductive layer 12 has a resistivity in the range of 0.8 × 10 ⁻⁶ Ω · m or more and 2.5 × 10 ⁻⁶ Ω · m or less in order to facilitate formation of a metal mask by electroforming. You.

  The conductive layer 12 preferably further contains carbon in addition to chromium as a main component and nitrogen as an additional element. The carbon content of the conductive layer 12 is preferably in the range of 3 atom% to 18 atom%. In order to make the conductive layer 12 contain carbon, a sputtering gas used for forming the conductive layer 11 by a sputtering method can be realized by adding carbon dioxide gas as a carbon source in addition to argon gas and nitrogen gas.

  Next, as shown in FIG. 3D, a resist pattern 15 is formed on the functional component 1 including the electrode film 13 having the conductive layer 12 and the adhesion layer 11 (resist pattern forming step S4). As a method of forming the resist pattern 15 in the resist pattern forming step S4, a resist is uniformly applied on the electrode film 13, and the resist is exposed and developed to form the resist pattern 15 having the opening 15a. . The shape of the resist pattern 15 may be any shape as long as it imitates the shape of a metal mask manufactured by electroforming.

  Next, as shown in FIG. 3E, a predetermined electrode pattern 14 is formed on the electrode film 13 by wet etching using the resist pattern 15 as an etching mask (etching step S5).

  In the etching step S5, a portion of the electrode film 13 exposed at the opening 15a of the resist pattern 15 is etched using an etching solution for chromium, for example, an etching solution containing cerium ammonium nitrate as a main component. 13 is formed so as to be a predetermined electrode pattern 14.

  Finally, as shown in FIG. 3 (f), if the resist pattern 15 on the electrode film 13 is peeled off using a known peeling method (resist removing step S6), the conductive electrode film 13 has a predetermined shape. Thus, a functional component 2 with an electrode pattern including the functional component 1 in which the conductive pattern 12 is firmly bonded to the glass substrate 10 via the adhesion layer 11 with the electrode pattern 14 formed thereon can be obtained.

Such a functional component 2 with an electrode pattern is used as an electroforming mask master when a metal mask is manufactured by electroforming, and when manufacturing a metal mask, as shown in FIG. Electroforming (electroplating) is performed using the plate or the Ni—Fe metal plate S as an anode and the electrode film 13 of the functional component 2 with an electrode pattern as a cathode (electroforming step S11). As an electrolytic solution (plating solution) W used for electroforming, for example, Ni— having a high acidity of about pH 2.3 and containing NiSO ₄ , NiCl ₂ , H ₃ BO ₃ , FeSO ₄ , malonic acid, or the like as a main component is used. An Fe plating solution is used.

  In such an electroforming step S11, as in the functional component 1 (functional component 2 with an electrode pattern) of the present invention, the conductive layer 12 has a concentration of at least 8 atom% and not more than 38 atom% in which at least the main component is chromium. By using a material containing nitrogen in the range, the acid resistance of the conductive layer 12 is greatly improved, and the conductive layer 12 is corroded even if a Ni—Fe plating solution having a high acidity of about pH 2.3 is used. There is no concern.

  By supplying a predetermined current for a predetermined time in the electroforming step S11, as shown in FIG. 4A, a metal, which is a Ni—Fe metal plating layer, is formed on the electrode film 13 of the functional component 2 having the electrode pattern. A mask M is formed.

  Then, as shown in FIG. 4B, by peeling the formed metal mask M from the electrode film 13, the metal mask M having the through hole V to which the electrode pattern 14 formed on the electrode film 13 is transferred. Can be obtained (mask stripping step S12). Further, the functional component 2 with the electrode pattern after the metal mask M is peeled can be repeatedly used as a master for electroforming again in the production of the metal mask M by electroforming.

  By using the functional component 1 (the functional component 2 having an electrode pattern) in which the adhesion layer 11 mainly composed of chromium oxide is formed between the conductive layer 12 and the glass substrate 10, the electrode film 13 and the glass substrate 10 Greatly improves the adhesion. Thus, when the metal mask is formed by electroforming using the functional component 1 as an electroforming mask master, even if the plated metal mask is separated from the functional component 1, the electrode film 13 can be easily removed from the glass substrate 10. There is no fear of exfoliation or partial damage. Therefore, a metal mask can be repeatedly manufactured a plurality of times.

  In the above-described embodiment, an example is described in which the resist pattern 15 is formed on the electrode film 13 and the electrode pattern 14 is formed using the resist pattern 15 as an etching mask. A metal mask can be formed by electroforming in a portion where the electrode film 13 is exposed without forming this resist pattern. In this case, it is not necessary to form an electrode pattern on the electrode film by etching the electrode film.

  Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in other various forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and their modifications are included in the scope and gist of the invention, and are also included in the invention described in the claims and equivalents thereof.

Hereinafter, a verification example in which the effect of the present invention is verified will be described.
(Verification example 1)
Soda lime glass was used as a glass substrate. After cleaning the glass substrate using a detergent and pure water, the adhesion layer and the conductive layer (main layer for the purpose of conducting electricity during electroforming) are formed under the following conditions by using the DC sputtering method. I got Further, a comparison was made between Examples 1 to 4 and Comparative Examples 1 and 2, with and without the formation of the adhesion layer (chromium oxide film).

"Adhesion layer (chromium oxide film)"
Sputtering gas: Ar / N ₂ / CO ₂ 0/60/10 (scom)
CD power: 1.7 kW
Target: Cr / φ8 inch Adhesive layer thickness: 30 nm
The adhesion layer thus formed has a thickness of about 30 nm. Table 1 shows a composition analysis of the adhesion layer by Auger electron spectroscopy (AES).

"Conductive layer (nitrogen-added chromium film)"
Sputtering gas: Ar / N ₂ (in the order of Comparative Examples 1-2 and Examples 1-4) 53/0, 30/48, 52/4, 50/8, 47/16, 40/32 (scom)
CD power: 2.0 kW
Target: Cr / φ8 inch The conductive layer (nitrogen-added chromium film) thus formed has a thickness of about 150 nm, and the composition analysis of the adhesion layer by Auger electron spectroscopy (AES) is shown in Table 2. FIG. 5 is a graph showing the relationship between the amount of nitrogen added to the conductive layer and the resistivity.

  Next, a positive photosensitive resist is applied by a spin coater so as to have a thickness of 1 μm on the electrode film formed of the formed conductive layer and the adhesion layer so as to have a thickness of 1 μm, and is sequentially subjected to exposure and development to form a resist pattern. did. Then, using the resist pattern as a mask, the chromium film was etched with a chromium etchant containing cerium ammonium nitrate as a main component, and the resist was removed to obtain an electroforming mask master (a functional component with an electrode pattern).

The Ni-Fe alloy was electroformed (plated) on the prepared electroforming mask master under the following conditions, and the plating resistance was evaluated. As a composition of the plating solution, a Ni-Fe plating solution containing NiSO ₄ , NiCl ₂ , H ₃ BO ₃ , FeSO ₄ , malonic acid, and saccharic acid and having a high acidity of about pH 2.3 was used. The liquid temperature was 50 ° C. An iron plate and an electric nickel plate were used for the anode. A DC stabilized power supply was used as a power supply, and constant current electrolysis was performed at a current density of 4 A / dm ² . After electrolysis to a film thickness of 20 μm, the resulting electrodeposited film was sufficiently washed with water and mechanically peeled off from the mask for electroforming (Comparative Example 1, Examples 1 to 5, with or without an adhesion layer (chromium oxide film)). Then, the damage of the conductive layer (and the adhesion layer) of the mask for electroforming was observed, and the number of times the electrode film could withstand without peeling was evaluated. (The reason why the film thickness is set to 20 μm is that the film thickness generally assumed as an electroformed mask is about 5 to 30 μm). Table 3 shows the evaluation of the plating resistance of Comparative Examples 1 and 2 and Examples 1 to 4.

According to the evaluation of plating resistance shown in Table 3, by forming an adhesion layer and adding nitrogen to the conductive layer, plating resistance is greatly improved, and formation of a metal mask by multiple electroformings is performed. It was confirmed that an electroforming mask master that could withstand the above was obtained.
Comparative Example 2 indicates that the resistance of the electrode film was too high, and the electrode film was damaged immediately after the energization, and the energization could not be maintained.

(Verification example 2)
In Examples 5 to 8, soda lime glass was used as a glass substrate. After cleaning the glass substrate with a detergent and pure water, an electrode film including an adhesion layer and a conductive layer (a main layer for conducting electricity during electroforming) is formed under the following conditions using a DC sputtering method. Then, a functional component was obtained. Further, with respect to Examples 5 to 8, a case where an adhesion layer (chromium oxide film) was formed and a case where it was not formed were set and compared.

"Adhesion layer (chromium oxide film)"
Sputtering gas: Ar / N ₂ / CO ₂ 0/60/10 (scom)
CD power: 1.7 kW
Target: Cr / φ8 inch Adhesive layer thickness: 30 nm
The adhesion layer thus formed has a thickness of about 30 nm. Table 4 shows a composition analysis of the adhesion layer by Auger electron spectroscopy (AES).

"Conductive layer (chromium film containing nitrogen and carbon)"
Sputtering _{gas: Ar / N 2 / CO 2} ( in the order of Example 5~8) 47/16 / 0,47 / 16 / 1.5,45 / 16 / 3,45 / 16/6 (scom)
CD power: 2.0 kW
Target: Cr / φ8 inches The conductive layer (the chromium film added with nitrogen and carbon) formed by this method has a thickness of about 150 nm. Table 5 shows the composition analysis of the adhesion layer by Auger electron spectroscopy (AES). FIG. 6 is a graph showing the relationship between the amount of carbon added to the conductive layer and the resistivity.

  Next, a positive photosensitive resist was applied on the formed electrode film to a thickness of 1 μm by a spin coater, exposed, and developed sequentially to form a resist pattern. Then, using the resist pattern as a mask, the chromium film was etched with a chromium etchant containing cerium ammonium nitrate as a main component, and the resist was removed to obtain an electroforming mask master (a functional component with an electrode pattern). After a non-conductive film such as a resist is formed to a predetermined thickness on the formed electrode film, desired patterning is performed, and in this state, it can be used as a glass master for electroforming.

The Ni-Fe alloy was electroformed (plated) on the prepared electroforming mask master under the following conditions, and the plating resistance was evaluated. As a composition of the plating solution, a Ni-Fe plating solution containing NiSO ₄ , NiCl ₂ , H ₃ BO ₃ , FeSO ₄ , malonic acid, and saccharic acid and having a high acidity of about pH 2.3 was used. The liquid temperature was 50 ° C. An iron plate and an electric nickel plate were used for the anode. A DC stabilized power supply was used as a power supply, and constant current electrolysis was performed at a current density of 4 A / dm ² . After electrolysis to a film thickness of 20 μm, the obtained electrodeposited film was sufficiently washed with water, and mechanically peeled off from an electroforming mask master (Examples 5 to 8, with or without an adhesion layer (chromium oxide film)). The damage of the conductive layer (and the adhesion layer) of the mask master was observed, and the number of times the electrode film could withstand without peeling was evaluated. (The reason why the film thickness is set to 20 μm is that the film thickness generally assumed as an electroformed mask is about 5 to 30 μm). Table 6 shows the evaluation of the plating resistance of Examples 5 to 8.

  According to the evaluation of plating resistance shown in Table 6, the plating resistance was greatly improved by forming an adhesion layer and adding nitrogen and carbon to the electrode layer. It has been confirmed that an electroforming mask master plate that can withstand the formation of the film was obtained.

1 Functional parts (Mask original for electroforming)
2 Functional component with electrode pattern 10 Glass substrate 11 Adhesion layer 12 Conductive layer 13 Electrode film 14 Electrode pattern

Claims (9)

And the glass substrate, formed by formed in contact with the glass substrate, the adhesion layer mainly composed of chromium oxide, and a is formed in contact with the said seal adhesive layer, at least main component chromium, 8 atom% As described above, a functional component of an original mask for electroforming , comprising an electrode film having at least a conductive layer containing nitrogen in a concentration range of 38 atom% or less. The functional part of the mask for electroforming according to claim 1, wherein the conductive layer further contains carbon. The functional component of the mask for electroforming according to claim 2, wherein the carbon is contained in the conductive layer in a concentration range of 3 atom% or more and 18 atom% or less. 4. The functional component of the electroforming mask master according to claim 1, wherein the adhesion layer has a thickness along a stacking direction of 10 nm or more and 50 nm or less. 5. 5. The conductive layer according to claim 1, wherein the resistivity is in a range of 0.8 × 10 ⁻⁶ Ω · m or more and 2.5 × 10 ⁻⁶ Ω · m or less. ^6. Functional parts of the original master for electroforming masks . The functional component of an electroforming mask master according to any one of claims 1 to 5, wherein the conductive layer has a thickness in a stacking direction of 100 nm or more and 500 nm or less. Forming a contact layer containing chromium oxide as a main component on the glass substrate in contact with the glass substrate; and forming, on the contact layer, at least a main component of chromium and a concentration of 8 atom% or more and 38 atom% or less. process and method for producing a functional part of the mask original plate for electroforming which comprising the forming range of at least having an electrode film a conductive layer containing nitrogen in contact with the adhesion layer. 8. The method according to claim 7, further comprising the step of: etching a surface of the electrode film including at least the adhesion layer and the conductive layer using an etchant for chromium to form a predetermined electrode pattern on the electrode film. A method for producing a functional component of the electroforming mask master according to the above . 8. The functional component of the electroforming mask master according to claim 7, further comprising a step of forming a non-conductive film having a predetermined pattern on a surface of the electrode film including at least the adhesion layer and the conductive layer. Production method.

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