JP2019094520A - Fine pattern nickel film and method for manufacturing the same - Google Patents

Abstract

To provide a fine pattern nickel film having a fine and high density opening pattern, and a method for simply manufacturing the same.SOLUTION: A method for manufacturing a fine pattern nickel film comprises: forming a fine pattern nickel film 1 on a glass base material having a pattern formed on a chromium film 22 by electroless nickel plating and electrolysis nickel plating; plating copper having a sufficient thickness on the fine pattern nickel film; peeling the copper plated fine pattern nickel film from the glass base material; and selectively etching only the copper to obtain the fine pattern nickel film 1. The fine pattern nickel film 1 has a sheet-like nickel film 11 having a thickness T of 2-10 μm and a plurality of openings 12 formed in the surface of the nickel film, and the thickness T of the nickel film 11, the shortest interval G between the openings 12 and the minimum size D of the opening 12 have the relations of T/G≥1, T/D≥1 and D/G≥1.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a fine pattern nickel thin film having minute openings at a high density in an extremely thin sheet, which is used for a dustproof filter of a precision instrument, and a method of manufacturing the same.

  Metal meshes having minute openings are used in a wide range of applications, including dustproof filters for electronic devices and precision instruments, and it is generally desirable that the openings be minute and dense. Here, conventionally, the metal mesh has been manufactured by forming a thin film by electrolytic plating on a conductive substrate having a resist pattern mainly formed by photolithography (see, for example, Patent Document 1).

  In this method, the fineness and density of the pattern of metal mesh depend solely on the accuracy of photolithography. That is, in order to form a pattern of metal mesh in a minute and high density, it is necessary to form a fine resist pattern in photolithography.

  Here, for example, when the photoresist layer to be used is thick, the definition of the resist pattern that can be formed tends to be coarse, and in order to achieve high definition, thinning the photoresist layer is one of the means Conceivable. However, when the photoresist is thinned, the thickness of the mesh that can be formed by plating is also reduced, so that the risk of breakage increases in the process of peeling from the substrate.

  As shown in FIG. 4, while securing a high definition pattern by the thin photoresist layer 102 formed on the conductive base material 101, the plating 103 is formed thicker than the thickness of the photoresist layer 102 to obtain strength. In addition, if a phenomenon such as an overhang that the plating 103 rides on the photoresist layer 102 occurs, and the size of the opening of the pattern is deviated from that which was set, the distance between the openings increases. Therefore, the density of the openings is low, which is generally considered undesirable.

JP-A-11-323592

  In view of the above-mentioned circumstances, an object of the present invention is to provide a fine pattern nickel thin film having a fine and high density opening pattern and a simple manufacturing method thereof.

The invention according to claim 1 includes a sheet-like nickel thin film having a thickness T of 2 to 10 μm, and a plurality of openings formed in the surface of the nickel thin film, and the shortest distance G between the openings The fine pattern nickel thin film is characterized in that the thickness T and the minimum dimension D of the opening are in the relationship of T / GG1, T / D ≧ 1, and D / G ≧ 1.
The invention according to claim 2 is characterized in that in the fine pattern nickel thin film according to claim 1, a conductive material is coated on the surface.
The invention according to claim 3 is that, in the method for producing a fine pattern nickel thin film, a chromium film having a thickness of 0.05 to 1 μm is formed in a predetermined pattern on one side of a 1 to 10 mm thick flat glass. Applying a palladium chloride aqueous solution having a pH adjusted to a predetermined range on the pattern surface of the glass substrate having the patterned surface, and selectively adsorbing the chromium film on the chromium film, and reducing the palladium chloride as a reducing agent First reduction step of reducing the palladium to palladium, first washing step of washing the glass substrate with water, first drying step of drying the glass substrate, and electroless nickel plating on the chromium film. Electroless nickel plating step of depositing a nickel layer by 1 to 2 μm, second washing step of washing the glass substrate with water, second drying step of drying the glass substrate, electrolytic nickel plating An electrolytic nickel plating step of laminating a second nickel layer to a thickness of 1 to 8 μm on the first nickel layer, and peeling a nickel thin film composed of the first nickel layer and the second nickel layer from the glass substrate And a peeling step, wherein the thickness T of the nickel thin film, the shortest distance G between the openings, and the minimum dimension D of the openings are such that T / G ≧ 1, T / D ≧ 1, and D / G ≧ 1. It is characterized by being in a relationship.
The invention according to claim 4 is characterized in that, in the method for producing a fine pattern nickel thin film according to claim 3, the pH is 5.5 to 6.5.
The invention according to claim 5 is the method for producing a fine pattern nickel thin film according to any one of claims 3 or 4, wherein the pattern is formed after the second drying step and before the electrolytic nickel plating step. And a water repellent treatment step of forming a water repellent film on the entire surface.
The invention according to claim 6 is the method for producing a fine pattern nickel thin film according to any one of claims 3 to 5, wherein the second nickel is applied after the electrolytic nickel plating step and before the peeling step. It is characterized by comprising a copper plating step of forming copper plating with a thickness of 10 μm or more on the layer, and an etching step of dissolving only copper and not dissolving nickel after the peeling step.
The invention according to claim 7 is the method for producing a fine pattern nickel thin film according to any one of claims 3 to 5, wherein the surface of the first nickel layer and the second nickel layer is after the peeling step. And a coating step of coating the conductive material.
The invention according to claim 8 is the method for producing a fine pattern nickel thin film according to claim 6, wherein a conductive material is coated on the surfaces of the first nickel layer and the second nickel layer after the etching step. A coating step to be carried out.

  According to the invention of claims 1 to 4, in forming the first nickel layer exclusively on the chromium film and the thickness of the nickel thin film being as thin as 2 to 10 μm, in electroless nickel plating and electrolytic nickel plating, Most precipitates in the longitudinal direction (perpendicular to the pattern surface of the glass substrate) and anisotropic plating with little lateral deposition is promoted, so it is possible to shorten the minimum distance between adjacent openings. As a result, it becomes possible to form a fine and high density opening pattern, and it is possible to improve the filtering function as various filters including dustproof filters of precision equipment.

  In addition, since a glass substrate patterned with a chromium film is used as a matrix, it is more economical than that patterned with a conventional photoresist, and can be used repeatedly, which is economical.

  According to the invention of claim 5, by forming the water repellent film on the entire pattern surface of the glass substrate, the deposition of plating other than in the longitudinal direction on the first nickel layer is suppressed, and anisotropic plating is further promoted. Therefore, it is possible to further shorten the minimum distance between adjacent openings, and to form a finer and denser opening pattern.

  According to the invention of claim 6, after the electrolytic nickel plating step, the copper plating layer is formed thick enough to close and unify the opening on the second nickel layer, and it is integrally peeled off from the glass substrate By doing this, the copper plating layer acts as a reinforcing plate, and it becomes possible to prevent permanent deformation and breakage of the fine pattern nickel thin film at the time of peeling.

  According to the inventions of claim 3, claim 7 and claim 8, the fine pattern nickel thin film has a very large specific surface area as compared with the conventional filter because the openings are formed in a fine and high density pattern. As a result, when the surface is coated with a conductive material layer or the like, the functional improvement due to its synergy is obtained.

According to an embodiment of the present invention, a front view of a schematic of a fine pattern thin nickel film and (a), a sectional view of the X ₁ -X ₁ (b). It is a general | schematic manufacturing flowchart of the fine pattern nickel thin film based on embodiment of this invention. It is a general | schematic manufacturing-process figure of the fine pattern nickel thin film based on embodiment of this invention. It is a schematic manufacturing-process figure of the conventional metal mesh.

  Embodiments of the present invention will be described with reference to the attached drawings. In the drawings, the size, interval, number, and other details of the configuration of each part in the drawings are expressed by being greatly simplified and omitted from actual objects to aid in visual recognition and understanding.

  FIG. 1 is a schematic front view (a) and a side sectional view (b) of a fine pattern nickel thin film 1 according to an embodiment.

  The fine pattern nickel thin film 1 is composed of a sheet-like nickel thin film 11 having a thickness T of 2 to 10 μm and a pattern of a plurality of openings 12 formed in the surface of the nickel thin film 11.

  Here, the relationship between the shortest distance G between the adjacent openings 12 and the minimum dimension D of the openings 12 is set such that the ratio of D to G is 1 or more (D / G ≧ 1). That is, when D is 5 μm, G is 5 μm or less. In this way, when a metal mesh is used for a filter, a high filtering function can be exhibited. If D / G is less than 1, the distance between the openings 12 is wider than the openings 12, and the density of the openings 12 is reduced, which is not preferable because the filtering function of the metal mesh is reduced.

  The relationship between the minimum dimension D of the opening 12 and the thickness T of the nickel thin film 11 is set such that the ratio of T to D is 1 or more (T / D / 1). That is, when T is 5 μm, D is 5 μm or less, and the maximum value of D is 10 μm. Here, in the present embodiment, the opening 12 is circular, and in this case, D refers to the diameter of the circle. If T / D is less than 1, the thickness of the nickel thin film 11 is larger than that of T, the opening 12 is larger, and the filtering function of the metal mesh is also deteriorated.

  Furthermore, the relationship between G and T is set such that the ratio of T to G is equal to or more (T / G ≧ 1). That is, when T is 2 μm, G is 2 μm or less, and the maximum value of G is 10 μm. When T / G is less than 1, the distance between the openings 12 is large compared to T in the thickness of the nickel thin film 11 This is not preferable because the filtering function of the metal mesh is also degraded.

  In the present embodiment, the minimum values of G and D are 1 μm respectively. If it is smaller than this range, it will be extremely difficult to properly manufacture in the manufacturing process described below. That is, the maximum values of T / G and T / D are 10, and the maximum value of D / G is also 10.

  From the above, the fine pattern nickel thin film 1 has many openings 12 formed with high density in the surface of the nickel thin film 11. Also, since T is as thin as 2 to 10 μm, both D and G are set to be correspondingly small.

  Next, a method of manufacturing the fine pattern nickel thin film 1 will be described based on FIGS. 2 and 3.

  First, the glass substrate 2 is prepared (step S1 in FIG. 2, (a) in FIG. 3). The glass substrate 2 has a pattern surface in which a chromium film 22 having a thickness of 0.05 to 1 μm is formed in a predetermined pattern on one side of a flat plate-like glass 21 having a thickness of 1 to 10 mm. The surface of the glass substrate 2 is sufficiently cleaned in advance with an acid / alkaline aqueous solution and water so as to prevent adhesion of dirt and foreign matter.

  Next, an aqueous palladium chloride solution is applied to the pattern surface (step S2). At this time, the concentration of the aqueous solution of palladium chloride is 0.03 wt%, and the pH is adjusted to 5.5 to 6.5 with the aqueous solution of potassium hydroxide, thereby selectively forming palladium chloride on the chromium film 22 Is adsorbed.

  Next, an aqueous solution of a reducing agent is applied to the pattern surface of the glass substrate 2 to reduce palladium chloride to palladium (step S3). As a reducing agent, sodium hypophosphite is used in the present embodiment.

  Next, the glass substrate is washed with water, and the glass substrate 2 is dried using a hot plate or a dryer (first drying process step S4). Drying conditions are 60 to 80 ° C. and 2 to 5 minutes. Thereby, the palladium remaining on the glass plate 21 is washed away, and the portion where palladium is adsorbed and the portion where it is not adsorbed are clarified.

  Next, the first nickel layer 31 is deposited to a thickness of 1 to 2 μm on the chromium film 22 by electroless nickel plating (electroless nickel plating step in step S5 in FIG. 2 and (b) in FIG. 3). In electroless nickel plating, the glass substrate 2 is immersed for 5-10 minutes while maintaining a pH of 4 to 6 and a temperature of 70 to 80 ° C. in a plating bath containing nickel sulfate or nickel chloride as a metal salt. At this time, palladium on the chromium film 22 acts as a catalyst, and the metal salt is reduced to precipitate an alloy of nickel and phosphorus on the palladium. When the treatment is further continued, nickel itself acts as a catalyst to deposit and deposit nickel.

  Next, the glass substrate 2 is washed with water, and the glass substrate 2 is dried using a hot plate or a dryer (second drying process step S6). Drying conditions are 60 to 80 ° C. and 20 minutes or more. Thereby, the adhesion between the electroless nickel plating and the chromium film 22 is enhanced to prevent the delamination.

  Next, the second nickel layer 32 is laminated to a thickness of 1 to 8 μm on the first nickel layer 31 by electrolytic nickel plating (electrolytic nickel plating step in step S7 of FIG. 2, (c) in FIG. 3). Electrolytic nickel plating uses a nickel sulfamate bath or a nickel sulfate bath.

  Here, the reason which used electroless nickel plating and electrolytic nickel plating together is demonstrated. First, since the chromium film 22 has low electric conductivity compared to nickel and is not suitable as an electrode of electrolytic nickel plating, electroless nickel plating is first performed to form the first nickel layer 31. Further, the electroless nickel plating has a slower deposition rate of nickel as compared to the electrolytic nickel plating, so the second nickel layer is formed by the electrolytic nickel plating in order to enhance the productivity.

  Next, electrolytic copper plating is formed on the second nickel layer 32 to a thickness of 10 μm or more (Copper plating step: step S8 in FIG. 2, (d) in FIG. 3). At this time, the thickness of the plating is performed to such an extent that the copper plating film spreads sideways simultaneously with the lamination of the plating and the opening 12 is closed and integrated.

  Next, it peels from the glass base material 2 with the copper plating layer 4, the 1st nickel layer 31, and the 2nd nickel layer 32 (peeling process step S9 of FIG. 2, (e) of FIG. 3).

  Next, only the copper is selectively dissolved and the plating film peeled off from the glass substrate 2 is etched so as not to dissolve the nickel (etching step S10 in FIG. 2). At this time, as the copper selective etching solution, an ammoniacal alkaline solution or a mixed solution of hydrogen peroxide water and sulfuric acid as the main components is used as the etching solution.

  According to the present invention, the first nickel layer 31 is formed exclusively on the chromium film 22 and the thickness T of the nickel thin film 11 is as thin as 2 to 10 μm. Precipitates in the longitudinal direction (perpendicular to the pattern surface of the glass substrate 2) and promotes anisotropic plating with less precipitation in the lateral direction, so it is possible to shorten the minimum distance between adjacent openings 12 As a result, it is possible to form many openings 12 at high density, and function improvement as various filters including dustproof filters for precision equipment can be achieved.

  In addition, since the glass substrate 2 patterned with the chromium film 22 is used as a matrix, it is more economical than that patterned with the conventional photoresist, and can be used repeatedly, which is economical.

  Also, after the electrolytic nickel plating process, the copper plating layer 4 is formed thick enough to close and unify the opening 12 on the second nickel layer 32 and peel it integrally from the glass substrate 2 The copper plating layer acts as a reinforcing plate, and it becomes possible to prevent permanent deformation and breakage of the fine pattern nickel thin film 1 at the time of peeling.

  The embodiment of the present invention has been described above, but the scope of the present invention is not limited to the above embodiment, and extends to other embodiments that can be regarded as the same.

  For example, after the second drying step, before the electrolytic nickel plating step, a water repellent treatment step is performed to form a water repellent film on the entire pattern surface. According to this, by forming the water repellent film on the entire pattern surface of the glass substrate, the deposition of the plating other than in the longitudinal direction on the first nickel layer is suppressed, and the anisotropic plating is further promoted. Furthermore, it is possible to shorten the minimum distance between the adjacent openings 12, and it is possible to form a finer and denser opening pattern.

  The steps from the copper plating step (step S8) to the etching step (step S10) are not necessarily performed if it is possible to safely peel the fine pattern nickel thin film 1 from the glass substrate 2 alone.

  Further, in the present embodiment, the opening 12 is circular, but the present invention is not limited to this, and it may be triangular, square or other polygonal shape.

  Further, the reducing agent used in the electroless nickel plating step is not limited to sodium hypophosphite, but other substances having a reducing action such as dimethylamine borane and formaldehyde can also be used. Here, the plating deposited when sodium hypophosphite is used is an alloy of nickel and boron.

  Further, the fine pattern nickel thin film 1 has the openings 11 formed in a fine and high density pattern, so that the specific surface area is extremely large as compared with the conventional filter, so a conductive material layer etc. is formed on the surface. In the case of coating, the synergetic effect is very great. For example, when coated with silver, Ti or copper, an antimicrobial function is obtained, and when coated with titanium oxide, a photoactive function is obtained.

  Further, the chromium film 22 is not generally chromium alone, and the surface of chromium may be coated with chromium oxide as a protective film. Therefore, by removing the chromium oxide film with a fluorine-based processing solution before step S2, the selectivity of palladium chloride adsorption can be further enhanced, and the adhesion of the first nickel layer 31 can be improved. .

  The fine-patterned nickel thin film 1 of the present invention is used for dust filters for electric devices and precision instruments, filters for fuel cells, filters for precision filtration of various liquids, filters for electrolyte separation by electrophoresis, bacteria and virus removal, etc. It can be widely used as a medical filter to be used, a biofilter utilizing electrostatic adsorption, an electromagnetic wave shield and the like.

DESCRIPTION OF SYMBOLS 1 Fine pattern nickel thin film 11 Nickel sheet 12 Opening 2 Glass base 21 Glass plate 22 Chromium film 31 1st nickel layer 32 2nd nickel layer 4 Copper plating layer

The invention according to claim 1 includes a sheet-like nickel thin film having a thickness T of 2 to 10 μm, and a plurality of openings formed in the surface of the nickel thin film, and the shortest distance G between the openings The fine pattern nickel thin film is characterized in that the thickness T and the minimum dimension D of the opening are in the relationship of T / GG1, T / D ≧ 1, and D / G ≧ 1.
The invention according to claim 2 is characterized in that in the fine pattern nickel thin film according to claim 1, silver, Ti, copper or titanium oxide is coated on the surface.
The invention according to claim 3 is that, in the method for producing a fine pattern nickel thin film, a chromium film having a thickness of 0.05 to 1 μm is formed in a predetermined pattern on one side of a 1 to 10 mm thick flat glass. Applying a palladium chloride aqueous solution having a pH adjusted to a predetermined range on the pattern surface of the glass substrate having the patterned surface, and selectively adsorbing the chromium film on the chromium film, and reducing the palladium chloride as a reducing agent First reduction step of reducing the palladium to palladium, first washing step of washing the glass substrate with water, first drying step of drying the glass substrate, and electroless nickel plating on the chromium film. Electroless nickel plating step of depositing a nickel layer by 1 to 2 μm, second washing step of washing the glass substrate with water, second drying step of drying the glass substrate, electrolytic nickel plating An electrolytic nickel plating step of laminating a second nickel layer to a thickness of 1 to 8 μm on the first nickel layer, and peeling a nickel thin film composed of the first nickel layer and the second nickel layer from the glass substrate And a peeling step, wherein the thickness T of the nickel thin film, the shortest distance G between the openings, and the minimum dimension D of the openings are such that T / G ≧ 1, T / D ≧ 1, and D / G ≧ 1. It is characterized by being in a relationship.
The invention according to claim 4 is characterized in that, in the method for producing a fine pattern nickel thin film according to claim 3, the pH is 5.5 to 6.5.
The invention according to claim 5 is the method for producing a fine pattern nickel thin film according to any one of claims 3 or 4, wherein the pattern is formed after the second drying step and before the electrolytic nickel plating step. And a water repellent treatment step of forming a water repellent film on the entire surface.
The invention according to claim 6 is the method for producing a fine pattern nickel thin film according to any one of claims 3 to 5, wherein the second nickel is applied after the electrolytic nickel plating step and before the peeling step. It is characterized by comprising a copper plating step of forming copper plating with a thickness of 10 μm or more on the layer, and an etching step of dissolving only copper and not dissolving nickel after the peeling step.
The invention according to claim 7 is the method for producing a fine pattern nickel thin film according to any one of claims 3 to 5, wherein the surface of the first nickel layer and the second nickel layer is after the peeling step. And a coating step of coating the conductive material.
The invention according to claim 8 is the method for producing a fine pattern nickel thin film according to claim 6, wherein silver, Ti, copper is formed on the surface of the first nickel layer and the second nickel layer after the etching step. Or a coating step of coating titanium oxide .

Claims (8)

A sheet-like nickel thin film having a thickness T of 2 to 10 μm,
And a plurality of openings formed in the surface of the nickel thin film,
The shortest distance G between the openings, the thickness T, and the minimum dimension D of the openings have a relationship of T / GG1, T / D ≧ 1, and D / G ≧ 1.
A fine pattern nickel thin film characterized by The surface is coated with a conductive substance,
The fine pattern nickel thin film according to claim 1, characterized in that A pH of the glass substrate having a pattern surface in which a chromium film having a thickness of 0.05 to 1 μm is formed in a predetermined pattern on one side of a 1 to 10 mm thick plate-like glass has a predetermined pH Applying an aqueous solution of palladium chloride adjusted to the range of (1), and selectively adsorbing onto the chromium film;
Reducing the palladium chloride to palladium with a reducing agent;
A first washing step of washing the glass substrate with water;
A first drying step of drying the glass substrate;
An electroless nickel plating step of depositing a first nickel layer by 1 to 2 μm on the chromium film by electroless nickel plating;
A second washing step of washing the glass substrate with water;
A second drying step of drying the glass substrate;
An electrolytic nickel plating step of laminating a second nickel layer on the first nickel layer by 1 to 8 μm by electrolytic nickel plating;
Peeling off a nickel thin film composed of the first nickel layer and the second nickel layer from the glass substrate;
Equipped with
The thickness T of the nickel thin film, the shortest distance G between the openings, and the minimum dimension D of the openings have a relationship of T / G ≧ 1, T / D ≧ 1, and D / G ≧ 1.
A method of producing a fine pattern nickel thin film, characterized in that The pH is 5.5 to 6.5,
The method for producing a fine pattern nickel thin film according to claim 3, characterized in that A water repellent treatment step of forming a water repellent film on the entire pattern surface after the second drying step and before the electrolytic nickel plating step;
The method for producing a fine-patterned nickel thin film according to any one of claims 3 or 4, comprising: A copper plating step of forming copper plating with a thickness of 10 μm or more on the second nickel layer after the electrolytic nickel plating step and before the peeling step;
After the peeling step, an etching step in which only copper is dissolved and nickel is not dissolved;
The method for producing a fine pattern nickel thin film according to any one of claims 3 to 5, comprising: After the peeling step, a coating step of coating a conductive material on the surfaces of the first nickel layer and the second nickel layer,
The method for producing a fine pattern nickel thin film according to any one of claims 3 to 5, characterized by comprising. After the etching step, coating a conductive material on the surfaces of the first nickel layer and the second nickel layer;
The method for producing a fine pattern nickel thin film according to claim 6, comprising the method.

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