JP2010132969A - Method of manufacturing structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a structure without using large-scale vacuum equipment and further without causing the waste of the material. <P>SOLUTION: The method of manufacturing a structure comprises: a stage where a first catalyst 31 is formed on a substrate 10; a stage where the projection pattern of second catalysts 32 is formed on the first catalyst 31 by printing; and a stage where an electroless plating film 40 is formed on the first catalyst 31 and the second catalysts 32. Alternatively, the first catalyst 31 is formed on the whole face of the substrate 10, or an adhesive layer 20 is formed on the surface of the substrate 10, and the first catalyst 31 is formed on the adhesive layer 20. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a structure. Specifically, the present invention relates to a method of manufacturing a structure by forming an electroless plating film on a convex pattern of a catalyst formed on a substrate.

  Conventionally, in order to perform shape control when a structure is formed on a metal surface, a process of forming a metal material by vacuum deposition or sputtering and a photolithography process for patterning the metal material are used. Furthermore, there are also methods for controlling the metal surface shape by performing an etching process by a dry or wet method a plurality of times, or by previously forming a substrate surface on which a metal is to be deposited, and then depositing the metal on the substrate by a vacuum process. (For example, refer to Patent Document 1).

  For example, in the gradation mask manufacturing method, the following steps are used as a method of forming regions having different film thicknesses on a transparent substrate in order to control transmittance. That is, a plurality of metal film forming steps, resist patterning by photolithography, and wet or dry etching steps (see, for example, Patent Document 2).

  There is also a method of using a lift-off method in which a resist is patterned by photolithography when a metal film is patterned on a substrate, the metal film is formed, and then the metal film is removed together with the resist (see, for example, Patent Document 3).

  In addition, a method of using an alloy plating layer as an etching stopper in patterning a copper plating layer by using a laminated structure of an alloy plating layer and a copper plating layer instead of forming a structure with the same material is also considered ( For example, see Patent Document 4.)

JP 2002-307398 A JP 09-146259 A Japanese Patent Laid-Open No. 06-104256 Japanese Patent Laid-Open No. 06-305270

  However, the conventional technology has the following problems. That is, a large-scale vacuum facility with a high degree of vacuum is required because the photoresist material is used a plurality of times and the metal film is formed by vacuum deposition and sputtering. Further, when using a photoresist material, it is applied by spin coating, but there is a problem that many materials are wasted.

  An object of the present invention is to provide a technique for manufacturing a structure without generating a waste of material without requiring a large-scale vacuum facility.

  The present invention includes a step of forming a first catalyst on a substrate, a step of forming a convex pattern of a second catalyst on the first catalyst by printing, and a step of forming the first catalyst on the first catalyst and the second catalyst. And a step of forming an electrolytic plating film.

  The present invention also includes a step of forming a convex pattern of a first catalyst on a substrate by printing, a step of forming a first electroless plating film on the convex pattern of the first catalyst, A step of forming a second catalyst on the top and side surfaces of the electrolytic plating film and a substrate on which the first electroless plating film is not formed; and a step of forming a second electroless plating film on the second catalyst The manufacturing method of the structure which has these.

  The present invention also includes a step of forming a first catalyst on a substrate, a step of forming a multi-step convex pattern of the second catalyst on the first catalyst, a first catalyst and a second catalyst. And a step of forming an electroless plating film on the catalyst.

  The present invention also includes a step of forming a convex pattern of a first catalyst on a substrate by printing, a step of forming a first electroless plating film on the convex pattern of the first catalyst, A structure having a step of forming a second catalyst on a substrate on which an electrolytic plating film is not formed, and a step of forming a second electroless plating film on the first electroless plating film and the second catalyst It is a manufacturing method of a body.

  The present invention also includes a step of forming a convex pattern of a first catalyst on a substrate by printing, a step of forming a first electroless plating film on the convex pattern of the first catalyst, It is a manufacturing method of a structure including a step of forming a second catalyst on a substrate on which an electrolytic plating film is not formed and a step of forming a second electroless plating film on the second catalyst.

  According to the present invention, when forming a structure with an electroless plating film, a convex pattern serving as a catalyst for electroless plating is formed by printing, so that the structure is manufactured without applying photolithography, sputtering, or vapor deposition. become able to.

  Here, printing refers to the transfer of a catalyst pattern using a predetermined plate (a relief plate, a plate with a reverse offset, a screen, etc.), and a catalyst pattern using an application (ink discharge, etc.) that matches the pattern. Say to form.

  According to the present invention, it is possible to manufacture a structure without using a large-scale vacuum facility and without generating material waste.

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as an embodiment) will be described. The description will be given in the following order.
1. Outline of manufacturing method of structure according to this embodiment (features of manufacturing object and characteristics of manufacturing method, processing common to each embodiment)
2. First embodiment (method of manufacturing a structure having a number of steps of about 100 nm to 100 nm)
3. Second Embodiment (Method for producing a structure having several tens of meters to several μm)
4). Third embodiment (method for producing a plurality of step structures)
5). Fourth Embodiment (Method for manufacturing a structure having several tens of meters to several μm with good adhesion)
6). Fifth Embodiment (Method for Producing Stepped Structure of Different Materials)
7). Method for evaluating structure 8. Application examples

<1. Overview of Manufacturing Method of Structure according to Embodiment>
[Characteristics of manufacturing structure and manufacturing method]
The structure which is the target of the manufacturing method according to the present embodiment is a concavo-convex shape formed on a substrate, and is a structure mainly composed of metal concavo-convex. This embodiment is characterized in that such a structure is manufactured without using photolithography and without having to be processed in a high vacuum environment such as vacuum deposition or sputtering.

  Here, conventionally, a method of patterning a metal is performed by vacuum film formation and etching using a photoresist. In particular, when a fine structure is formed on a metal surface, the number of resist patterning and film formation increases, the process time increases, and a lot of resist, etchant, pure water, etc. are used, resulting in waste of materials. .

  This embodiment uses a fully additive method by combining catalyst patterning and electroless plating as a method for forming a fine structure on a metal surface, and does not require a vacuum apparatus for film formation, and resist or etching. This is a simple method with little environmental load that does not consume liquid.

[Common processing in each embodiment]
In the manufacturing method of the structure according to the present embodiment, alkali-free glass (for example, 1737 glass manufactured by Corning) is used as a substrate serving as a support base material. In addition, as long as there is no adverse effect on the substrate in the process of each embodiment described below, application to a resin, a film substrate, or the like is also possible.

  Prior to the production of a specific structure, the substrate serving as the support base is cleaned. The substrate is dried after alkali cleaning.

  Thereafter, an adhesion layer is formed on the surface of the substrate as necessary. The adhesion layer is for obtaining adhesion when an electroless plating catalyst material (for example, a solvent containing Pd (palladium) fine particles or a Pd complex) is formed on the substrate in a later step. In the case where sufficient adhesion between the substrate and the catalyst material can be ensured, the adhesion layer is unnecessary. In this embodiment, the case where an adhesion layer is formed is taken as an example.

  The adhesion layer is formed by depositing an amino silane coupling agent on the substrate by a vapor phase method. In the vapor phase method, a glass bottle containing an amino-based silane coupling agent serving as an adhesion layer is placed in a fluorine-based container or the like, and a substrate is placed in the container. And the adhesion layer of an amino-type silane coupling agent is formed in the board | substrate surface by heating the whole container by oven etc. under atmospheric pressure.

  In this embodiment, KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd. was used as the amino-based silane coupling agent, and the gas phase process conditions were a processing temperature of 120 ° C. and a processing time of within 12 hours. Note that the material for the adhesion layer, the processing temperature, and the processing time are not limited to these.

  After the adhesion layer is formed on the substrate by a vapor phase method, ultrasonic cleaning is performed with a solvent such as ethanol capable of dissolving the amino silane compound for the purpose of removing excess amino silane compound. Thereby, the amino silane compound which is not bonded to the substrate can be peeled off.

  In addition, the formation method of an adhesion layer is not restricted to this. For example, a film obtained by dissolving the amino silane coupling agent in an ethyl lactate solution is formed on a substrate using a coating method such as a spin coating method, and then heated at 120 ° C. using a hot plate or the like, A method of cleaning by the cleaning method is also conceivable.

  Confirmation after the adhesion layer is formed, for example, by evaluating the contact angle of water before and after the treatment, or by scoring the substrate surface in the region where the electroless plating film is not deposited and evaluating the step using an AFM (Atomic Force Microscope) It is also possible to do.

  Hereinafter, the manufacturing method of the structure of the present embodiment on the premise of the processing on the substrate will be described.

<2. First Embodiment>
[Method of manufacturing a structure having a number of steps of about 100 nm to 100 nm]
FIG. 1 is a schematic cross-sectional view for sequentially explaining the structure manufacturing method according to the first embodiment. First, as the processing for the substrate described above, the substrate 10 made of non-alkali glass is prepared, washed and dried, and the adhesion layer 20 is formed on the surface of the substrate 10 (FIGS. 1A to 1B). ).

  Next, the first catalyst 31 is formed on the substrate 10 on which the adhesion layer 20 is formed by printing (FIG. 1C). In the present embodiment, the first catalyst 31 is printed on the entire upper surface of the substrate 10 on which the adhesion layer 20 is formed by the reverse offset method.

  Here, printing refers to the transfer of a catalyst pattern using a predetermined plate (a relief plate, a plate with a reverse offset, a screen, etc.), and a catalyst pattern using an application (ink discharge, etc.) that matches the pattern. Say to form. That is, this is a method that can form a catalyst without using photolithography. Hereinafter, the definition of printing used in the description of each embodiment is the same.

  In the present embodiment, a solvent containing Pd nanoparticles is used as the first catalyst 31. Of course, it is a material that can serve as a catalyst for electroless plating, and it can be used as long as it contains a metal compound such as Au, Ag, Pd, metal fine particles (nano) particles, or a complex as long as it is suitable for the patterning method selected. Is possible.

  In the present embodiment, the reverse offset printing method is selected as the patterning method for the first catalyst 31. However, it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the second catalyst 32 is formed on the first catalyst 31 (FIG. 1D). The second catalyst 32 has a convex pattern corresponding to the step shape to be manufactured. In the present embodiment, the second catalyst 32 patterned in advance is printed on the first catalyst 31. Thereby, the convex pattern (step) of the second catalyst 32 based on the first catalyst 31 is formed.

  Here, the material of the second catalyst 32 is the same as that of the first catalyst 32. In the present embodiment, the reverse offset printing method is selected as the patterning method of the second catalyst 32, but it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Specific examples of the pattern of the second catalyst 32 formed in this embodiment are (1) a dot pattern having a diameter of 5 μm, a pitch of 10 μm, and (2) a line and space (L / S) each having a width of 5 μm.

  The thicknesses of the first catalyst 31 and the second catalyst 32 in the present embodiment are on the order of several nm to several tens of nm. For example, adjusting the concentration of Pd contained in the second catalyst 32 solution, changing the conditions for applying the catalyst to the blanket or letterpress of the reverse offset method, or aligning the same catalyst material during patterning It is possible to control the level difference of the convex pattern by forming a plurality of times.

  The step between the first catalyst 31 and the second catalyst 32 is used to control the step of the electroless plating film when the electroless plating film is formed in a post-process. After the second catalyst 32 is formed, it is activated by removing the protective film of the solvent and metal nanoparticles contained in the first catalyst 31, and promotes the electroless plating process performed in the subsequent process And

  In this embodiment, a hot plate is used under atmospheric pressure, and heat treatment is performed by heating the substrate 10 on which the catalyst is formed at about 200 ° C. for several minutes. For this activation, UV (ultraviolet) ozone treatment or the like may be used. In addition, this activation treatment is not particularly necessary when, for example, a palladium catalyst imparting agent (product name: OPC50 inducer) manufactured by Okuno Pharmaceutical Co., Ltd. is used as the catalyst material. This is a mixed solution of two products, and there is a recommended method of use. However, if the life of the solution is not considered, the pH (acid / alkalinity) may be adjusted in consideration of damage to the object to be plated. .

  Next, the substrate 10 on which the convex pattern of the second catalyst 32 is formed is immersed in an electroless plating solution. Thereby, the electroless plating film 40 is deposited on the first catalyst 31 and the second catalyst 32 (FIG. 1E).

  In this embodiment, Niboron MF (trade name: manufactured by World Metal Co., Ltd.), which is an autocatalytic Ni-B solution, was used as the electroless plating solution, and the substrate 10 was immersed at 60 ° C. for 1 minute. Under this condition, the thickness of the plating film is approximately 150 nm.

  When the surface of the electroless plating film 40 formed under these conditions was evaluated with AFM, VN-8000 (product name) manufactured by Keyence Corporation, the results shown in FIGS. 2 and 3 were obtained. 2 is a specific example of the pattern of the second catalyst 32. (1) An example of shape evaluation of an electroless plating film when a dot pattern having a diameter of 5 μm and a pitch of 10 μm is used, and FIG. (2) This is an example of shape evaluation of an electroless plating film when lines and spaces (L / S) each having a width of 5 μm are used. In either case, (a) is a three-dimensional image, (b) is a partial cross-sectional view, and (c) shows measured values of the pitch and height of the convex pattern.

  As shown in FIGS. 2 and 3, it was confirmed that a convex pattern having a thickness of about 20 nm was formed on the surface of the Ni plating film. In addition, as a result of baking the substrate 10 with the electroless plating film formed at 150 ° C. to 350 ° C. for 30 minutes or more using a vacuum furnace, the resistivity of the electroless plating film 40 is in the range of about 10 to 30 μΩ · cm. It became.

<3. Second Embodiment>
[Method for producing a structure having a level difference of several tens of meters to several μm]
FIG. 4 is a schematic cross-sectional view for sequentially explaining the method for manufacturing the structure according to the second embodiment. First, as the processing for the substrate described above, the substrate 10 made of non-alkali glass is prepared, washed and dried, and the adhesion layer 20 is formed on the surface of the substrate 10 (FIGS. 4A to 4B). ).

  Next, the convex pattern of the 1st catalyst 31 is formed by printing on the board | substrate 10 with which the contact | adherence layer 20 was formed (FIG.4 (c)). The first catalyst 31 has a convex pattern corresponding to the step shape to be manufactured. In this embodiment, the first catalyst 31 patterned in advance is formed on the substrate 10 on which the adhesion layer 20 is formed by the reverse offset printing method.

  In the present embodiment, a solvent containing Pd nanoparticles is used as the first catalyst 31. Of course, it is a material that can serve as a catalyst for electroless plating, and it can be used as long as it contains a metal compound such as Au, Ag, Pd, metal fine particles (nano) particles, or a complex as long as it is suitable for the patterning method selected. Is possible.

In the present embodiment, the reverse offset printing method is selected as the patterning method for the first catalyst 31. However, it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  A specific example of the pattern of the first catalyst 32 formed in the present embodiment is a line and space (L / S) having a width of 10 μm.

  Next, the substrate 10 on which the convex pattern of the first catalyst 31 is formed is immersed in an electroless plating solution. Thereby, the first electroless plating film 41 is deposited on the convex pattern of the first catalyst 31 (FIG. 4D). At this time, the first electroless plating film 41 is slightly deposited also on the side surface of the convex pattern of the first catalyst 31.

  In the present embodiment, Niboron MF (trade name: manufactured by World Metal Co., Ltd.), which is an autocatalytic Ni—B solution, was used as the electroless plating solution, and the substrate 10 was immersed under conditions of 60 ° C. for 3 minutes. Under this condition, the thickness of the plating film is about 450 nm.

  Next, the second catalyst 32 is formed on the entire surface of the substrate 10 on which the first electroless plating film 41 is deposited by the reverse offset printing method (FIG. 4E). That is, the second catalyst 32 is formed not only on the surface of the first electroless plating film 41 but also on a portion where the first electroless plating film 41 is not deposited. Thus, even if there is a convex shape due to the first electroless plating film 41, the reverse offset printing method uses a soft base material such as a silicone resin to press the second so as to adjust to the surface irregularities. The catalyst 32 can be printed.

  In the present embodiment, the reverse offset printing method is selected as the patterning method of the second catalyst 32, but it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the substrate 10 on which the second catalyst 32 is formed is immersed in an electroless plating solution. Thereby, the second electroless plating film 42 is deposited on the second catalyst 32 (FIG. 4F). In the present embodiment, the substrate 10 is immersed in the electroless plating solution Niboron MF at 60 ° C. for 1 minute, so that the second film having a thickness of about 150 nm is formed on the second catalyst 32 printed by pattern printing. The electroless plating film 42 is deposited.

  The substrate 10 on which the second electroless plating film 42 is formed under these conditions is baked at 150 ° C. to 350 ° C. for 30 minutes or more using a vacuum furnace, and then the surface of the second electroless plating film 42 is obtained. Was evaluated with AFM, VN-8000 (product name) manufactured by Keyence Corporation. 5A and 5B are diagrams showing the evaluation results, where FIG. 5A shows a three-dimensional image, FIG. 5B shows a partial cross-sectional view, and FIG. 5C shows measured values of the pitch and height of the convex pattern.

  As shown in FIG. 5, it was confirmed that a convex pattern having a step of about 450 nm was formed on the surface of the Ni plating film as the second electroless plating film.

  In the present embodiment, the material of the first electroless plating film 41 and the material of the second electroless plating film 42 are the same, but different materials may be used. For example, it is also conceivable to form a coil using either the first electroless plating film 41 or the second electroless plating film 42 as a magnetic material and the other as a non-magnetic material. Further, an insulating film (not shown) may be interposed between the first electroless plating film 41 and the second electroless plating film 42 to achieve electrical insulation.

<4. Third Embodiment>
[Method for producing a plurality of step structures]
FIG. 6 is a schematic cross-sectional view for sequentially explaining the method for manufacturing the structure according to the third embodiment. First, as the processing for the substrate described above, the substrate 10 made of non-alkali glass is prepared, washed and dried, and the adhesion layer 20 is formed on the surface of the substrate 10 (FIGS. 6A to 6B). ).

  Next, the first catalyst 31 is formed by printing on the substrate 10 on which the adhesion layer 20 is formed (FIG. 6C). In the present embodiment, the first catalyst 31 is printed on the entire upper surface of the substrate 10 on which the adhesion layer 20 is formed by the reverse offset method.

  In the present embodiment, a solvent containing Pd nanoparticles is used as the first catalyst 31. Of course, it is a material that can serve as a catalyst for electroless plating, and it can be used as long as it contains a metal compound such as Au, Ag, Pd, metal fine particles (nano) particles, or a complex as long as it is suitable for the patterning method selected. Is possible.

  In the present embodiment, the reverse offset printing method is selected as the patterning method for the first catalyst 31. However, it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the multistage second catalyst 32 is formed on the first catalyst 31 by the reverse offset printing method (FIG. 6D). The material of the second catalyst 32 is the same as that of the first catalyst 31. The second catalyst 32 has a multi-stage convex pattern corresponding to the step shape to be manufactured. In the present embodiment, the second catalyst 32 has two stages.

  Therefore, the second catalyst 32a, which is the lower stage patterned in advance, is printed on the first catalyst 31, and the second catalyst 32b, which is the upper stage patterned in advance, is printed on the pattern of the second catalyst 32a. It is formed by printing twice. Thereby, the 2nd catalyst 32 used as the multi-step convex pattern based on the 1st catalyst 31 is formed.

  In the present embodiment, the second catalyst 32 has two stages. However, the second catalyst 32 may have three or more stages, and can be formed by printing the number of times corresponding to the number of stages. Further, the shape of the stacked second catalyst 32 is not limited to that shown in the figure, and can correspond to a more complicated surface shape.

  In the present embodiment, the reverse offset printing method is selected as the patterning method of the second catalyst 32, but it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the substrate 10 on which the multi-step convex pattern of the second catalyst 32 is formed is immersed in an electroless plating solution. As a result, the electroless plating film 40 is deposited on the first catalyst 31 and the second catalyst 32 in multiple stages (FIG. 6E). The deposition conditions for the electroless plating film 40 in the present embodiment are the same as those in the first embodiment.

  In the present embodiment as described above, it is possible to manufacture structures having various shapes depending on the convex pattern shape of the second catalyst 32.

<5. Fourth Embodiment>
[Method of manufacturing a structure having a step of several tens of meters to several μm with good adhesion]
FIG. 7 is a schematic cross-sectional view for sequentially explaining the manufacturing method of the structure according to the fourth embodiment. The structure manufacturing method according to the fourth embodiment is similar to that of the second embodiment, but is formed only at a portion where the first electroless plating film is not formed at the time of patterning the second catalyst. It is different from the embodiment.

  First, as the processing for the substrate described above, the substrate 10 made of non-alkali glass is prepared, washed and dried, and the adhesion layer 20 is formed on the surface of the substrate 10 (FIGS. 7A to 7B). ).

  Next, a convex pattern of the first catalyst 31 is formed by printing on the substrate 10 on which the adhesion layer 20 is formed (FIG. 7C). The first catalyst 31 has a convex pattern corresponding to the step shape to be manufactured. In this embodiment, the first catalyst 31 patterned in advance is formed on the substrate 10 on which the adhesion layer 20 is formed by the reverse offset printing method.

  In the present embodiment, a solvent containing Pd nanoparticles is used as the first catalyst 31. Of course, it is a material that can serve as a catalyst for electroless plating, and it can be used as long as it contains a metal compound such as Au, Ag, Pd, metal fine particles (nano) particles, or a complex as long as it is suitable for the patterning method selected. Is possible.

  In the present embodiment, the reverse offset printing method is selected as the patterning method for the first catalyst 31. However, it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the substrate 10 on which the convex pattern of the first catalyst 31 is formed is immersed in an electroless plating solution. Thereby, the 1st electroless plating film | membrane 41 precipitates on the convex pattern of the 1st catalyst 31 (FIG.7 (d)). At this time, the first electroless plating film 41 is slightly deposited also on the side surface of the convex pattern of the first catalyst 31.

  Next, the second catalyst 32 is formed on the substrate 10 other than the portion where the first electroless plating film 41 is deposited, that is, the portion where the adhesion layer 20 is exposed by the reverse offset printing method (FIG. 7E). ). Thereby, the second catalyst 32 is formed only on the surface of the substrate 10 where the first electroless plating film 41 is not formed. Here, even if there is a convex shape due to the first electroless plating film 41, the reverse offset printing method uses a soft base material such as a silicone resin to press, so that the concave portion formed between the electroless plating film 41 Even so, the second catalyst 32 can be printed.

  In the present embodiment, the reverse offset printing method is selected as the patterning method of the second catalyst 32, but it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the substrate 10 on which the second catalyst 32 is formed is immersed in an electroless plating solution. Thereby, the second electroless plating film 42 is deposited on the second catalyst 32, and the second electroless plating film 42 is also formed on the first electroless plating film 41 (FIG. 7 (f)). That is, the first electroless plating film 41 along with the second catalyst 32 also functions as a catalyst, and the second electroless plating film 42 is deposited on the entire surface of the substrate 10.

  In the present embodiment, since the first electroless plating film 41 and the second electroless plating film 42 are formed in direct contact with each other, compared to a case where a film of another material is interposed therebetween. Thus, the adhesion of the structure can be increased. In addition, after performing the said heat processing to the 2nd electroless plating film | membrane 42 obtained by this embodiment, as a result of performing a tape peeling test, favorable adhesiveness was shown.

<6. Fifth Embodiment>
[Method of manufacturing a step structure made of different materials]
FIG. 8 is a schematic cross-sectional view for sequentially explaining the method for manufacturing the structure according to the fifth embodiment. First, as the processing for the substrate described above, the substrate 10 made of non-alkali glass is prepared, washed and dried, and the adhesion layer 20 is formed on the surface of the substrate 10 (FIGS. 8A to 8B). ).

  Next, a convex pattern of the first catalyst 31 is formed by printing on the substrate 10 on which the adhesion layer 20 is formed (FIG. 8C). The first catalyst 31 has a convex pattern corresponding to the step shape to be manufactured. In this embodiment, the first catalyst 31 patterned in advance is formed on the substrate 10 on which the adhesion layer 20 is formed by the reverse offset printing method.

  In the present embodiment, a solvent containing Pd nanoparticles is used as the first catalyst 31. Of course, it is a material that can serve as a catalyst for electroless plating, and it can be used as long as it contains a metal compound such as Au, Ag, Pd, metal fine particles (nano) particles, or a complex as long as it is suitable for the patterning method selected. Is possible.

  In the present embodiment, the reverse offset printing method is selected as the patterning method for the first catalyst 31. However, it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the substrate 10 on which the convex pattern of the first catalyst 31 is formed is immersed in an electroless plating solution. Thereby, the 1st electroless plating film | membrane 41 precipitates on the convex pattern of the 1st catalyst 31 (FIG.8 (d)). At this time, the first electroless plating film 41 is slightly deposited also on the side surface of the convex pattern of the first catalyst 31.

  Next, the second catalyst 32 is formed on the substrate 10 other than the portion where the first electroless plating film 41 is deposited, that is, the portion where the adhesion layer 20 is exposed by the reverse offset printing method (FIG. 8E). ). Thereby, the second catalyst 32 is formed only on the surface of the substrate 10 where the first electroless plating film 41 is not formed. Here, even if there is a convex shape due to the first electroless plating film 41, the reverse offset printing method uses a soft base material such as a silicone resin to press, so that the concave portion formed between the electroless plating film 41 Even so, the second catalyst 32 can be printed.

  In the present embodiment, the reverse offset printing method is selected as the patterning method of the second catalyst 32, but it may be selected from various coating methods such as a relief printing method and an ink jet method, or a printing method.

  Next, the substrate 10 on which the second catalyst 32 is formed is immersed in an electroless plating solution. At this time, an electroless plating solution different from that used when the first electroless plating film 41 is deposited is used. For example, electroless plating for precipitating the first electroless plating film 41 is performed with the liquid A, and the first electroless plating film 41 is formed on the first catalyst 31. Next, the first electroless plating film 41 does not serve as a catalyst, and electroless plating using the second catalyst 32 as a catalyst is used as the B solution, and the second electroless plating film is formed on the second catalyst 32. 42 is formed. This makes it possible to obtain a structure in which electroless plating films 41 and 42 made of different materials are patterned on the same substrate 10.

  In the present embodiment, for example, one of the first electroless plating film 41 and the second electroless plating film 42 is a magnetic body, and the other is a non-magnetic body. Forming is also conceivable. Further, an insulating film (not shown) may be interposed between the first electroless plating film 41 and the second electroless plating film 42 to achieve electrical insulation.

<7. Structure Evaluation Method>
The metal structure obtained by the manufacturing method according to the present embodiment can be analyzed by the following method.
1. The catalyst material can be detected by observing the vicinity of the substrate surface with a transmission electron microscope (TEM).
2. Whether the formed electroless plating film contains an organic compound or a eutectoid metal is present, secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), electron beam microanalyzer (EPMA) ) And the like.

<8. Application example>
Although this embodiment is mainly to form a metal surface structure, the applicable field of the present invention is to form a concavo-convex structure on the metal surface, and various materials can be used as long as they are obtained by electroless plating. It is applicable to. For example, Ni, Co, Cu, Sn, Ag, Au, Pt, Pd, In, Sn, Rh and metals that can be co-deposited with these metal materials, such as B, P, Fe, Zn, Cd, W, Cr, Mn, Re, Ti, S, V, etc. can be used. In addition, in a field where these electroless plating films can be applied, for example, a fine mold for producing an optical element, electrodes such as capacitors, solar cells, displays, electronic devices, or metal surface structures are required. It can be applied in a wide variety of technical fields.

It is a schematic cross section explaining the manufacturing method of the structure concerning a 1st embodiment in order. Specific Example of Second Catalyst Pattern (1) It is a diagram showing a shape evaluation example of an electroless plating film when a dot pattern with a diameter of 5 μm and a pitch of 10 μm are used. Specific example of pattern of second catalyst (2) It is a figure showing an example of shape evaluation of an electroless plating film when a line and space (L / S) each having a width of 5 μm is used. It is a schematic cross section explaining the manufacturing method of the structure concerning a 2nd embodiment in order. It is a figure which shows the example of shape evaluation of the pattern of the 2nd catalyst in 2nd Embodiment. It is a schematic cross section explaining the manufacturing method of the structure concerning a 3rd embodiment in order. It is a schematic cross section explaining the manufacturing method of the structure concerning a 4th embodiment in order. It is a schematic cross section explaining the manufacturing method of the structure concerning a 5th embodiment in order.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Board | substrate, 20 ... Adhesion layer, 31 ... 1st catalyst, 32 ... 2nd catalyst, 40 ... Electroless plating film | membrane, 41 ... 1st electroless plating film | membrane, 42 ... 2nd electroless plating film | membrane

Claims (7)

Forming a first catalyst on a substrate;
Forming a convex pattern of a second catalyst on the first catalyst by printing;
Forming the electroless plating film on the first catalyst and the second catalyst. Forming a convex pattern of a first catalyst on a substrate by printing;
Forming a first electroless plating film on the convex pattern of the first catalyst;
Forming a second catalyst on the upper surface and side surfaces of the first electroless plating film and the substrate on which the first electroless plating film is not formed;
Forming a second electroless plating film on the second catalyst. Forming a first catalyst on a substrate;
Forming a multi-stage convex pattern of the second catalyst on the first catalyst by printing;
Forming the electroless plating film on the first catalyst and the second catalyst. Forming a convex pattern of a first catalyst on a substrate by printing;
Forming a first electroless plating film on the convex pattern of the first catalyst;
Forming a second catalyst on the substrate on which the first electroless plating film is not formed;
And a step of forming a second electroless plating film on the first electroless plating film and the second catalyst. Forming a convex pattern of a first catalyst on a substrate by printing;
Forming a first electroless plating film on the convex pattern of the first catalyst;
Forming a second catalyst on the substrate on which the first electroless plating film is not formed;
Forming a second electroless plating film on the second catalyst. The method for manufacturing a structure according to claim 1, wherein the first catalyst is formed on the entire surface of the substrate. The method for manufacturing a structure according to any one of claims 1 to 5, wherein an adhesion layer is formed on a surface of the substrate, and the first catalyst is formed on the adhesion layer.

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