JP2017141482A - Functional parts, methods for producing functional parts - Google Patents

Abstract

The present invention provides a functional component that has excellent adhesion between an electrode film and a glass substrate and also has an excellent acid resistance of a conductive layer, and a method for manufacturing the same. [Solution] A glass substrate, an adhesion layer formed on the glass substrate and containing chromium oxide as a main component, and an adhesion layer formed on the adhesion layer, in which at least the main component is chromium, and the content is 8 atom%. As described above, an electrode film having at least a conductive layer containing nitrogen in a concentration range of 38 atom % or less is provided. [Selection diagram] Figure 1

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 manufacturing method thereof.

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

  Among these, it is difficult to reduce the thickness of the metal foil used as a material for the metal mask manufactured using the metal foil. For this reason, when it used as a metal mask for vapor deposition, since the thickness of metal foil was thick, it was easy to produce a shadow and it was difficult to form a fine pattern film.

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

  However, conventionally, such an electroforming mask original plate has insufficient adhesion between the glass substrate and the electrode film, so that the electrode film is peeled off from the glass substrate by forming the metal mask once or several times. There was a problem with durability.

In recent years, instead of the conventional nickel electroforming mask, an electroforming mask using a Ni—Fe alloy, which is a low thermal expansion metal, suitable for manufacturing a highly accurate metal mask has been developed (for example, non-patent). 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 becomes more acidic. For this reason, the conventional electroforming mask original plate has a problem that the acid resistance of the electrode film mainly composed of chromium is insufficient, and pattern chipping is likely to occur due to corrosion by a plating solution during electroforming.

JP 2002-55461 A

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

  This invention is made | formed in view of the above-mentioned situation, and provides the functional component which was excellent in the adhesiveness of an electrode film and a glass substrate, and was excellent also in the acid resistance of an electrode film, and its manufacturing method. is there.

  The functional component of the present invention includes a glass substrate, an adhesion layer formed on the glass substrate, mainly composed of chromium oxide, and at least a major component formed on the adhesion layer. And 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.

  According to the functional component of the present invention, the adhesion between the electrode film and the glass substrate can be greatly improved by forming an adhesion layer mainly composed of chromium oxide between the conductive layer and the glass substrate. it can. Thus, for example, when a functional part is used as an electroforming mask master and a metal mask is formed by electroforming, the electrode film is easily peeled off from the glass substrate even if the plated metal mask is peeled off from the functional part. There is no concern that some will be damaged. Thereby, when a functional component is used for an electroforming mask master, a functional component having sufficient strength to repeatedly manufacture a metal mask can be realized.

  Further, according to the functional component of the present invention, the conductive layer 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. 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 becomes possible to perform electroforming using a Ni—Fe alloy which is a low thermal expansion metal suitable for manufacturing a highly accurate metal mask.

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

  The conductive layer has a thickness in the range of 100 nm or more and 500 nm or less along the stacking direction.

  The method for producing a functional component according to the present invention includes a step of forming an adhesion layer containing chromium oxide as a main component on a glass substrate, and at least a main component is chromium on the adhesion layer, and is at least 8 atom% and 38 atom. And a step of forming a conductive layer containing nitrogen in a concentration range of not more than%.

  According to the method for producing a functional component of the present invention, the adhesion between the electrode film and the glass substrate is greatly improved by forming an adhesion layer mainly composed of chromium oxide between the conductive layer and the glass substrate. Therefore, for example, when a functional part is used as an electroforming mask master and a metal mask is formed by electroforming, the electrode film is easily peeled off from the glass substrate even if the plated metal mask is peeled off from the functional part. There is no concern that some will be damaged. Thereby, a highly accurate metal mask can be manufactured easily.

  According to the method for manufacturing a functional component of the present invention, the conductive layer 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. 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 becomes possible to perform electroforming using a Ni—Fe alloy which is a low thermal expansion metal suitable for manufacturing a highly accurate metal mask.

  The method further includes the step of etching the surface of the electrode film provided with at least the adhesion layer and the conductive layer using a chromium etchant to form a predetermined electrode pattern on the electrode film.

  The method further includes the step of forming a nonconductive film having a predetermined pattern on the surface of the electrode film having at least the adhesion layer and the conductive layer.

  ADVANTAGE OF THE INVENTION According to this invention, the functional component which was excellent in the adhesiveness of an electrode film and a glass substrate, and was excellent also 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. It is the flowchart which demonstrated in steps the manufacturing method of the functional component of this invention, and the manufacturing method of a metal mask using the same. It is the principal part expanded sectional view which demonstrated the manufacturing method of the functional component of this invention in steps. It is the principal part expanded sectional view which showed the process of manufacturing a metal mask using a functional component in steps. It is a graph which shows the result of the example of verification concerning the present invention. It is a graph which shows the result of the example of verification concerning the present invention.

  Hereinafter, the functional component of the present invention and the method of manufacturing the functional component 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 present invention unless otherwise specified. In addition, in the drawings used in the following description, in order to make the features of the present invention easier to understand, there is a case where a main part is shown in an enlarged manner for convenience, and the dimensional ratio of each component is the same as the actual one. Not necessarily.

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

The constituent material of the glass substrate 10 is not particularly limited. For example, non-alkali glass, quartz glass, borosilicate glass (Tempax float made by Schott), soda lime glass, white plate, etc., or pure SiO ₂ Various glasses such as glass containing a large amount of impurities (additives) other than SiO ₂ from glass close to glass can be mentioned. 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 improve the adhesion between the conductive layer 12 formed on the glass substrate 10 and the glass substrate 10. The constituent material of the adhesion layer 11 is mainly composed of chromium oxide. Furthermore, it is more preferable to contain chromium carbide and chromium nitride in addition to chromium oxide.

  The oxygen contained in the adhesion layer 11 has a concentration range of 20 atom% or more and 50 atom% or less.

  The adhesion layer 11 is formed so that the thickness along the stacking direction is in the range of 10 nm or more and 50 nm or less. More preferably, it is formed so that the thickness is in the range 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 characteristics of the conductive layer 12. From the viewpoint 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. In addition, if the alkali free glass, borosilicate glass, quartz glass, etc. which do not contain an alkali component are used as the glass substrate 10, the thickness of the contact | adherence layer 11 can also be made still thinner.

  When the thickness of the adhesion layer 11 exceeds 50 nm, it takes 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 at least a main component of chromium and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less. More preferably, the conductive layer 12 contains nitrogen in a concentration range of 14 atom% or more and 38 atom% or less.

  By including nitrogen in the above-described concentration range with respect to the main component chromium as the conductive layer 12, it is possible to enhance acid resistance. For example, when producing a metal mask by electroforming, high acid resistance can be obtained even for a plating solution for Ni—Fe alloy having a pH lower than that of electroforming with nickel as in the prior art. Enables production of metal masks with Fe alloys.

  Moreover, it is preferable to make the thickness along the lamination direction of the conductive layer 12 into the range of 100 nm or more and 500 nm or less. When the thickness of the conductive layer 12 is less than 100 nm, there is a concern that the electrical resistance increases when electroforming is performed, and the time required for manufacturing the metal mask increases. On the other hand, if the thickness of the conductive layer 12 exceeds 500 nm, it takes a long time to form the conductive layer 12, which may increase the manufacturing cost of the functional component 1.

The conductive layer 12 preferably has a resistivity in the range of 0.8 × 10 ⁻⁶ Ω · m to 2.5 × 10 ⁻⁶ Ω · m. By setting the resistivity of the conductive layer 12 to 2.5 × 10 ⁻⁶ Ω · m or less, when the functional component 10 is used as an electroforming mask master, 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 the main component chromium and the additional element nitrogen. The carbon-containing concentration of the conductive layer 12 is preferably in a concentration range of 3 atom% or more and 18 atom% or less.
By containing carbon in the conductive layer 12, the acid resistance of the conductive layer 12 can be further increased.

  An electrode pattern provided with an electrode pattern 14 having a predetermined shape by providing an opening in the shape of a desired metal mask shape in a part of the functional component 1 including the electrode layer 13 having the conductive layer 12 and the adhesion layer 11. The attached functional component 2 is formed. The electrode pattern 14 represents the shape of a metal mask to be manufactured when the functional component 1 is used as an electroforming mask original plate used when a metal mask is manufactured by electroforming. In the etching process in the manufacturing method, the electrode film 13 of the functional component 1 is etched.

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

  As a result, for example, when the metal mask is formed by electroforming using the functional component 1 as an electroforming mask master, the conductive layer 12 and the adhesion layer 11 can be formed even if the plated metal mask is peeled off from the functional component 1. There is no concern that the electrode film 13 having the electrode film 13 is easily peeled off from the glass substrate 10 or is partially damaged. Thereby, when the functional component 1 is used for the electroforming mask master, the functional component 1 having sufficient strength to repeatedly manufacture a metal mask can be realized.

  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 for a plating solution having a high acidity such as pH 2.3 used for electroforming using a Ni—Fe alloy. Can do. Therefore, it becomes possible to perform electroforming using a Ni—Fe alloy which is a low thermal expansion metal suitable for manufacturing a highly accurate metal mask.

(Functional parts manufacturing method)
Next, a method for 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 method. FIG. 3 is an enlarged cross-sectional view of a main part illustrating the method for manufacturing a functional component according to the present invention step by step.
When manufacturing the functional component 1, first, the glass substrate 10 is prepared. Examples of the glass substrate 10 include, for example, non-alkali glass, quartz glass, borosilicate glass (Schott Tempax float), soda lime glass, white plate, etc., and impurities other than SiO ₂ from glass close to pure SiO _2. A 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.

  And as shown to Fig.3 (a), the to-be-processed surface 10a which forms the contact | adherence layer 11 in the glass substrate 10 is grind | polished as pre-processing, and the to-be-processed surface 10a is smoothed (pre-processing process S1). In the pretreatment step S1, for example, the processing surface 10a of the glass substrate 10 is polished using the polishing pad P and a polishing liquid mainly composed of cerium oxide. This polishing step can be performed any number of times. Furthermore, the glass substrate 10 after the polishing treatment is cleaned using a known cleaning method, and the polishing liquid and the like adhering to the substrate surface is removed. As a method for cleaning the glass substrate 10, it is common to perform cleaning with pure water after cleaning with a detergent.

  Next, as shown in FIG.3 (b), the contact | adherence layer 11 is formed in the to-be-processed surface 10a of the glass substrate 10 which performed the pre-process (adhesion layer formation process S2). The adhesion layer 11 is mainly composed of chromium oxide. Furthermore, it is also preferable to contain chromium carbide and chromium nitride in addition to chromium oxide.

The oxygen contained in the adhesion layer 11 has a concentration range of 20 atom% or more and 50 atom% or less.
The adhesion layer 11 is formed so that the thickness along the stacking direction is in the range of 10 nm to 50 nm.

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. In this case, it is preferable to use a mixed gas of argon gas, nitrogen gas, and carbon dioxide gas as the sputtering gas, and the flow rate ratio can be set so that a desired film thickness and film adhesion can be obtained. In particular, conditions such as a nitrogen gas flow rate are set so that the nitrogen concentration in the film falls within the range of the regulations. Note that a sputtering apparatus having a known structure can be used.
By the sputtering method using such argon gas, nitrogen gas, and carbon dioxide gas, the adhesion layer 11 mainly composed of chromium oxide can be formed on the processing surface 10a 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 at least a main component of chromium 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. In this case, it is preferable to use a mixed gas of argon gas and nitrogen gas as the sputtering gas, and the flow rate ratio can be set so that a desired film thickness and film adhesion can be obtained. In particular, conditions such as a nitrogen gas flow rate are set so that the nitrogen concentration in the film falls within the range of the regulations. Note that a sputtering apparatus 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 to 500 nm. In order to facilitate the formation of a metal mask by electroforming, 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. The

  The conductive layer 12 preferably further contains carbon in addition to the main component chromium and the additional element nitrogen. The carbon-containing concentration of the conductive layer 12 is preferably in a concentration range of 3 atom% or more and 18 atom% or less. The inclusion of carbon in the conductive layer 12 can be realized by adding carbon dioxide gas as a carbon source in addition to argon gas and nitrogen gas as a sputtering gas used when the conductive layer 11 is formed by sputtering.

  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 this is exposed and developed to form a resist pattern 15 having an opening 15a. . The shape of the resist pattern 15 only needs to be a 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, the electrode film 13 is etched by etching the portion of the electrode film 13 exposed at the opening 15a of the resist pattern 15 using an etchant for chromium, for example, an etchant mainly composed of cerium ammonium nitrate. 13 is formed to be a predetermined electrode pattern 14.

  Finally, as shown in FIG. 3F, if the resist pattern 15 on the electrode film 13 is stripped using a known stripping method (resist removal step S6), the conductive electrode film 13 is predetermined. Thus, the functional component 2 with the electrode pattern including the functional component 1 in which the conductive layer 12 is firmly bonded to the glass substrate 10 through the adhesion layer 11 can be obtained.

When such a functional part 2 with an electrode pattern is used as an electroforming mask original plate when producing a metal mask by electroforming, and when producing a metal mask, as shown in FIG. Electroplating (electroplating) is performed using the plate or the Ni—Fe metal plate S as the anode and the electrode film 13 of the functional component 2 with the electrode pattern as the cathode (electroforming step S11). As the electrolytic solution (plating solution) W used for electroforming, for example, Ni-SO ₄ , NiCl ₂ , H ₃ BO ₃ , FeSO ₄ , malonic acid, etc. as a main component and Ni- having a high acidity of about pH 2.3. Fe plating solution is used.

  In such an electroforming step S11, as in the functional component 1 (functional component 2 with electrode pattern) of the present invention, the conductive layer 12 has a concentration of at least a main component of chromium and a concentration of 8 atom% or more and 38 atom% or less. By comprising 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 when a highly acidic Ni—Fe plating solution having a pH of about 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 that is a Ni—Fe metal plating layer is formed on the electrode film 13 of the functional component 2 with the electrode pattern. A mask M is formed.

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

  By using the functional component 1 (functional component 2 with 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 The adhesion of is greatly improved. Thus, when the functional component 1 is used as an electroforming mask master and a metal mask is formed by electroforming, the electrode film 13 can be easily removed from the glass substrate 10 even if the plated metal mask is peeled off from the functional component 1. There is no concern of exfoliation or partial damage. Therefore, it becomes possible to manufacture a metal mask repeatedly several times.

  In the above-described embodiment, an example is shown 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. It is also possible to form an insulating resist pattern in the portion to be formed, and form a metal mask by electroforming in the portion where the electrode film 13 is exposed without forming this resist pattern. In this case, there is no need to etch the electrode film to form an electrode pattern on the electrode film.

  As mentioned above, although some embodiment of this invention was described, these embodiment is shown as an example and is not intending limiting the range of invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit 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 the equivalents thereof.

Hereinafter, verification examples for verifying the effects of the present invention will be described.
(Verification example 1)
Soda lime glass was used as the glass substrate. After cleaning the glass substrate with detergent and pure water, the DC sputtering method is used to form an adhesion layer and a conductive layer (main layer for the purpose of energization during electroforming) under the following conditions, and functional parts Got. Moreover, the case where the adhesion layer (chromium oxide film) was formed and the case where it was not formed were set and compared with Examples 1-4 and Comparative Examples 1-2.

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

"Conductive layer (nitrogen-added chromium film)"
Sputtering gas: Ar / N ₂ (in 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: 2.0kW
Target: Cr / φ8 inch The conductive layer (nitrogen-added chromium film) formed thereby has a thickness of about 150 nm, and Table 2 shows the composition analysis of the adhesion layer by Auger electron spectroscopy (AES). FIG. 5 shows a graph of the relationship between the amount of nitrogen added to the conductive layer and the resistivity.

  Next, a positive photosensitive resist is applied on the electrode film composed of the formed conductive layer and adhesive layer with a spin coater so as to have a film thickness of 1 μm, and exposure and development are sequentially performed to form a resist pattern. did. Then, using the resist pattern as a mask, the chromium film was etched with a chromium etching solution containing cerium ammonium nitrate as a main component, and the resist was removed to obtain an electroforming mask original plate (functional part with an electrode pattern).

A Ni—Fe alloy was electroformed (plated) on the produced electroforming mask original plate under the following conditions, and the plating resistance was evaluated. As the composition of the plating solution, 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 source was used as the power source, 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 is washed thoroughly with water and mechanically peeled off from the electroforming mask master (Comparative Example 1, Examples 1 to 5, presence or absence of adhesion layer (chromium oxide film)) Then, the damage of the conductive layer (and the adhesion layer) of the electroforming mask original plate was observed, and the number of times that the electrode film could withstand without peeling was evaluated. (The reason for setting the film thickness to 20 μm is that the film thickness generally assumed as an electroforming mask is about 5 to 30 μm). Table 3 shows the evaluation of the plating resistance of Comparative Examples 1-2 and Examples 1-4.

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

(Verification example 2)
As Examples 5 to 8, soda lime glass was used as a glass substrate. After the glass substrate is washed with detergent and pure water, an electrode film comprising an adhesion layer and a conductive layer (main layer for the purpose of energization during electroforming) is formed under the following conditions using a DC sputtering method. And got functional parts. Moreover, the case where the adhesion layer (chromium oxide film) was formed and the case where it was not formed were set and compared with Examples 5 to 8.

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

"Conductive layer (nitrogen, carbon-added chromium film)"
Sputtering gas: Ar / N ₂ / CO ₂ (in order of Examples 5 to 8) 47/16/0, 47/16 / 1.5, 45/16/3, 45/16/6 (scom)
CD power: 2.0kW
Target: Cr / φ8 inch The conductive layer (nitrogen, carbon-added chromium film) formed thereby has a thickness of about 150 nm, and Table 5 shows the composition analysis of the adhesion layer by Auger electron spectroscopy (AES). FIG. 6 shows a graph of 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 with a spin coater so as to have a film thickness of 1 μm, exposed, and developed in order to form a resist pattern. Then, using the resist pattern as a mask, the chromium film was etched with a chromium etching solution containing cerium ammonium nitrate as a main component, and the resist was removed to obtain an electroforming mask original plate (functional part with an electrode pattern). It is also possible to form a non-conductive film such as a resist on the formed electrode film and then perform desired patterning and use it as an electroforming glass original plate in that state.

A Ni—Fe alloy was electroformed (plated) on the produced electroforming mask original plate under the following conditions, and the plating resistance was evaluated. As the composition of the plating solution, 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 source was used as the power source, 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 is washed thoroughly with water and mechanically peeled off from the electroforming mask master (Examples 5 to 8, presence / absence of adhesion layer (chromium oxide film)). The damage of the conductive layer (and adhesion layer) of the mask original plate was observed and evaluated by the number of times the electrode film could withstand without peeling. (The reason for setting the film thickness to 20 μm is that the film thickness generally assumed as an electroforming 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 the plating resistance shown in Table 6, by forming an adhesion layer and adding nitrogen and carbon to the electrode layer, the plating resistance is greatly improved, and a metal mask by multiple times of electroforming. It was confirmed that an electroforming mask original plate that can withstand the formation of is obtained.

1 Functional parts (mask mask 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)

  A glass substrate, an adhesion layer formed on the glass substrate, the main component of which is chromium oxide, and at least a main component formed on the adhesion layer, which is 8 atom% or more and 38 atom% A functional component comprising an electrode film having at least a conductive layer containing nitrogen in the following concentration range.   The functional component according to claim 1, wherein the conductive layer further contains carbon.   The functional component 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.   The functional component according to claim 1, wherein the adhesion layer has a thickness in a range of 10 nm or more and 50 nm or less along a stacking direction. 5. The conductive layer according to claim 1, wherein a resistivity of the conductive layer is in a range of 0.8 × 10 ⁻⁶ Ω · m to 2.5 × 10 ⁻⁶ Ω · m. Functional parts.   6. The functional component according to claim 1, wherein the conductive layer has a thickness in the range of 100 nm or more and 500 nm or less along the stacking direction.   A step of forming an adhesion layer containing chromium oxide as a main component on a glass substrate; and a conductive layer containing at least a main component of chromium on the adhesion layer and containing nitrogen in a concentration range of 8 atom% or more and 38 atom% or less. And a step of forming a layer.   8. The method 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 a chromium etchant. The manufacturing method of the functional component as described.   8. The method of manufacturing a functional component according to claim 7, further comprising a step of forming a non-conductive film having a predetermined pattern on the surface of the electrode film including at least the adhesion layer and the conductive layer.

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