JP5382797B2 - Method for manufacturing structure by electrochemical reaction using conductive composition - Google Patents

Description

The present invention relates to a manufacturing how structures by electrochemical reaction using a conductive composition.

  As a conductive composition for performing an electrochemical reaction, for example, a liquid plating solution or an etching solution is widely known. In contrast, the applicant has disclosed a gel-like plating composition in Japanese Patent Application Laid-Open No. 2008-266740. That is, in Japanese Patent Application Laid-Open No. 2008-266740, by adding a gelling agent to a plating solution, a solid gel-like plating composition having no fluidity is created and plated using the gel-like plating composition. It is disclosed to form a metal film on the body. Furthermore, it is disclosed that a patterned metal film can be obtained by placing a gel-like plating composition having an arbitrary pattern such as a sheet shape or a lattice shape on an object to be plated.

  Patterning of the gel-like plating composition is performed by cutting the sheet-like gel-like plating composition with, for example, a knife, but it may not be easy to pattern accurately. Moreover, it may not be easy to place the sheet-like gel-like plating composition after patterning on the object to be plated.

JP 2008-266740 A

The present invention aims to provide an easy manufacturing how the structure using the conductive composition of the gel state.

In order to achieve the above object, a method for manufacturing a structure according to an embodiment of the present invention includes a sol state of a conductive composition having a gelling agent, conductive ions for performing an electrochemical reaction, and a solvent. And a pattern forming step of forming the conductive composition in a sol state into a predetermined pattern shape on a substrate,
A gelling step of bringing the conductive composition having the predetermined pattern shape into a gel state; and an electrochemical reaction step of performing an electrochemical reaction using the conductive composition in the gel state. To do.

According to the present invention, it is possible to provide easy fabrication how the structure using the conductive composition of the gel state.

It is the figure seen from the horizontal direction of the dispenser apparatus which patterns the composition for plating. It is a perspective view for demonstrating the state which patterns the composition for plating on a board | substrate using a dispenser apparatus. It is the figure seen from the horizontal direction for demonstrating the state which patterns the composition for plating on a board | substrate using a dispenser apparatus, FIG. 3 (A) is in the state before patterning, FIG. 3 (B) is in patterning. FIG. 3C shows the state after patterning. It is the figure seen from the horizontal direction for demonstrating the state which patterns the composition for plating on a board | substrate using a photoresist pattern. It is the figure seen from the horizontal direction for demonstrating the state which patterns the composition for plating on a board | substrate using a screen printing apparatus. It is a cross-sectional schematic diagram for demonstrating the method of depositing a metal using the composition for plating. It is the schematic diagram seen from the side for demonstrating the method to deposit a metal using a prober. It is a cross-sectional schematic diagram for demonstrating the method of depositing a metal using the composition for plating. FIGS. 9A and 9B are schematic views for explaining the creation of a structure using an etching composition, FIG. 9A is a plan view of a substrate having a gel pattern before etching, and FIG. It is a cross-sectional schematic diagram including the board | substrate which has a gel pattern before the etching along the IXB-IXB line of A). FIGS. 10A and 10B are schematic views for explaining the production of a structure using an etching composition, FIG. 10A is a plan view of a substrate having a copper film pattern after etching, and FIG. It is a cross-sectional schematic diagram containing the board | substrate which has the copper film pattern after the etching along the XB-XB line of (A). It is the schematic diagram seen from the side for demonstrating the method to etch a metal using a prober.

<First Embodiment>
The conductive composition used in the method for manufacturing the structure according to the first embodiment of the present invention is a gel state containing a metal ion capable of being electroplated as a conductive ion for performing an electrochemical reaction. It is composition 2A for plating. The plating composition 2A has a gelling agent, a metal ion, and a solvent, and reversibly changes the gel state and the sol state. Here, the gel state means a state having no fluidity, and the sol state means a state having fluidity. In other words, the gel state is a state where the dispersoid network has a high viscosity and loses fluidity, and the entire system is in a solid state. The plating composition is in a gel state at room temperature and becomes a sol state by heating. It may be a plating composition that is in a sol state at room temperature and becomes a gel state upon cooling. That is, the plating composition reversibly changes between a sol state and a gel state, and at least when an electrochemical reaction is performed, the plating composition becomes a gel state.

  First, a method of using the plating composition 2 as a plating composition 2A having a predetermined pattern shape in a gel state will be described. The plating composition 2 is discharged in a predetermined pattern shape onto the substrate through the opening in a heated sol state, for example, and cooled on the substrate, whereby the plating composition 2A in a gel state It becomes. That is, as shown in FIG. 1, the plating composition 2 is stored in the dispenser 11 of the dispenser device 10, and is controlled on the stage 14 from the opening 13 at the tip of the capillary 12 of the dispenser 11 by the control of the main body 10 </ b> A. It is discharged onto the substrate 20 arranged. The inside of the dispenser 11 and the capillary 12 are heated to, for example, 50 ° C. by a heating device (not shown). The heating temperature is appropriately selected depending on the plating composition 2, but is higher than room temperature and lower than 100 ° C., and preferably 40 ° C. or higher and lower than 80 ° C. in view of the stability and viscosity of the plating composition 2. is there.

  That is, in the state shown in FIG. 1, the plating composition 2, which is a conductive composition having a gelling agent, conductive ions for performing an electrochemical reaction, and a solvent, is heated to a sol state. It is in the solation process.

  In addition, as a sol formation process which makes the composition 2 for plating into a sol state, it may just hold | maintain at predetermined temperature. For example, in the case of the plating composition 2 having gelatin or the like that is in a sol state at room temperature and is in a gel state at a temperature lower than room temperature, there is no need for heating, and leaving it at room temperature itself is in the sol forming step. Equivalent to. Or if it is the composition 2 for plating which will be in a sol state by applying a pressure, a sol formation process is a process of applying a pressure. Furthermore, in the case of the plating composition 2 having so-called thixotropy that becomes a sol state by applying a shear stress, the sol formation step is a step of applying the shear stress. That is, it is the sol formation step that breaks the bonds of the molecules constituting the gel-forming plating composition 2.

  Furthermore, as the sol formation step, two or more selected from heating, pressure, or shear stress may be combined. In addition, although the composition 2 for plating which became the big lump cannot be conveyed in a pipe line, it can be conveyed in the pipe line by a pump by dividing | segmenting small (pulverization) with a mixer etc. That is, when supplying the plating composition 2 in a gel state to the dispenser 11, it may be in a sol state, but can be supplied in a gel state.

  The capillary 12 has an inner diameter of 0.1 mm and an outer diameter of 0.3 mm, for example, and is made of a fluororesin. The dispenser 11 can be moved in three directions, ie, an in-plane direction and a vertical direction of the substrate 20 by a driving mechanism (not shown). The movement of the dispenser 11, that is, the movement of the capillary 12, is controlled by the main body 10A. The stage 14 may move instead of the dispenser 11.

  FIG. 2 shows a state in which a large number of gel-like plating compositions 2A having a predetermined pattern shape are continuously formed on the substrate 20 at intervals D1. In the heating step, the plating composition 2 inside the sol-state dispenser 11 is formed into a predetermined pattern shape by a pattern formation step of discharging onto the substrate 20 through the opening 13 of the capillary 12 by pressurization of 0.2 MPa, for example. It becomes. The sol-state plating composition 2 discharged onto the substrate 20 at room temperature is in a gel state because the substrate 20 is deprived of heat, that is, naturally cooled (cooling step). The substrate 20 may be cooled to room temperature or lower by a cooling device, or heat from the plating composition 2 may be radiated through the stage 14 by being fixed to the stage 14 having a large heat capacity.

  Here, the plating composition 2A having a substantially hemispherical or substantially cylindrical pattern shape may be used alone, or by continuously forming the plating composition 2A as shown in FIG. A larger desired pattern, for example, a wiring pattern may be formed. In other words, the plating composition 2A having a pattern shape that is directly formed on the substrate by discharge may be formed so as to partially overlap each other.

  Further, as shown in FIGS. 3A to 3C, the plating composition 2 may protrude from the opening 13 in a state where the tip of the capillary 12 is close to the substrate 20. That is, as shown in FIG. 3A, a part of the plating composition 2 is in contact with the substrate 20 as shown in FIG. 3B in a state where the plating composition 2 is not dripped from the tip of the capillary 12. Up to the substrate 20 at the tip of the capillary 12. Thereafter, the tip of the capillary 12 is moved away from the substrate 20 as shown in FIG. By this method, a plating composition 2A having a diameter R1 smaller than the diameter R0 of the opening 13 of the capillary 12 may be formed.

  That is, when the plating composition 2 is dropped from the capillary 12, the plating composition 2 </ b> A formed on the substrate 20 has a larger area than the opening 13. However, in the above method, a finer pattern can be easily formed. Further, the plating composition 2 in a sol state is continuously discharged onto the substrate 20 while moving the capillary 12 in the state shown in FIG. Can also be formed. In the patterning using the dispenser 11, for example, a plating composition 2A having a diameter of 1 to 2000 μm and a height of 1 to 1000 μm can be easily obtained.

  Further, for example, the plating composition 2 may be poured into an opening of a pattern formed on the substrate with a photoresist. That is, as shown in FIG. 4, the opening on the substrate surrounded by the wall of the photoresist 6 is filled with the plating composition 2A. Patterning with a photoresist is highly accurate and easy to miniaturize, and can increase the aspect ratio (resist height / opening area). For this reason, 2 A of plating compositions can be filled in the opening of a pattern smaller than the magnitude | size of the composition 2 for plating which can be formed with the dispenser 11. FIG. Further thicker plating composition 2A can be obtained. Moreover, the pattern by a photoresist can also form arbitrary patterns other than circular.

  In addition, as a method for discharging the plating composition 2 onto the substrate through the opening in order to form a pattern, it is one type of stencil printing method as shown in FIGS. 5 (A) to 5 (D). A screen printing method can also be used. In the screen printing method, first, as shown in FIG. 5A, the sol-state plating composition 2 is disposed on the screen 31 having the openings 32 of the screen printing apparatus 30. 5B to 5D, the squeegee 33 moves while pressing the inner surface (upper surface) of the screen 31. Then, the plating composition 2 is extruded onto the substrate 20 through the openings 32 of the screen 31, that is, discharged, and becomes a gel state pattern. The shape of the pattern is designed when creating the screen. In the screen printing method, the plating composition 2 is patterned on the substrate through the opening formed by the warp and the weft. By using a thin thread, pattern breakage due to the influence of the thread can be prevented. .

  As a method for discharging the plating composition 2 onto the substrate through the openings in order to obtain a pattern shape, a metal mask printing method that is the same as the screen printing method may be used. The metal mask printing method is different from the screen printing method in that a metal plate having an opening is used instead of the screen 31, but the other methods are the same.

  The screen printing method and the metal mask printing method are excellent in productivity because a large number of patterns can be formed at once on a wide area, compared to the method using the dispenser device 10.

  Furthermore, as a method for forming the plating composition 2 into a predetermined pattern shape, an ink jet method can also be preferably used. Furthermore, the ink jet method is not limited to a piezo method using a widely used piezoelectric element or a heat method (bubble jet (registered trademark) method) that generates bubbles in a nozzle by heating, and is electrostatic. A so-called super ink jet method using a strong force may be used. In the super ink jet system, since the dot diameter is 1 μm or less and the femtoliter can be discharged as the droplet size, a finer pattern can be formed.

  In addition, the pattern formation of the plating composition in the gel state on the same part of the substrate is not limited to once, but the height of the plating composition 2A formed on the substrate, that is, the thickness is insufficient Alternatively, the sol plating composition may be discharged and laminated a plurality of times. That is, you may discharge the plating composition 2 further on the plating composition 2A. Moreover, you may laminate | stack the gel plating composition from which electroconductive ion differs so that it may mention later.

  Next, the configuration of the plating composition 2 will be described. As already described, the plating composition 2 has a gelling agent, metal ions, and a solvent.

  The gelling agent is selected from materials in which the plating composition 2 is in a gel state at room temperature and becomes a sol state upon heating. For example, agar, gelatin, xanthan gum, carrageenan, roast bean gum (LBG) ), Guar gum, gellan gum, methylcellulose, hydroxypropylmethylcellulose, pectin, alginic acid, that is, each alone or a mixture of two or more.

  Among the gelling agents, it is desirable to use agar, gelatin, xanthan gum, carrageenan, roast bean gum, guar gum, and hydroxypropyl methylcellulose, particularly preferably carrageenan and roasted from the viewpoints of solation temperature and gel strength. It is preferable to use a mixture with bean gum.

  The content of the gelling agent is appropriately adjusted. For example, in the plating composition 2 for electrolytic copper plating, the content of the gelling agent is 1 to 5% by weight (10 g) based on the total amount of the composition. / L to 50 g / L).

  The metal ion capable of being deposited by plating is a metal ion used for known plating. For example, ions such as copper, nickel, gold, tin, silver, and palladium can be given.

  As the solvent, an aprotic organic solvent capable of dissolving a metal compound to form metal ions, for example, ether, tetrahydrofuran, toluene and the like can be used, but water is preferable from the viewpoint of versatility.

  The plating composition 2 may further have a conductive compound, an additive, a stabilizer, and the like included in a known plating solution. For example, in the case of a plating composition for copper plating, since the conductivity is improved by using sulfuric acid as the conductive compound, high-speed film formation with a larger current becomes possible.

  In addition, the plating composition may have a hardness adjusting agent in order to increase the gel strength when it is in a gel state. As the hardness adjusting agent, for example, potassium salt, calcium salt, magnesium salt, cesium salt, saccharide, etc., specifically, potassium salt such as potassium chloride and potassium sulfate, calcium salt such as calcium chloride and calcium lactate, magnesium chloride At least one selected from the group consisting of magnesium salts such as cesium chloride, saccharides such as sucrose, and more preferably potassium chloride, calcium lactate, sulfuric acid from the viewpoint of a wide range of hardness adjustment. Potassium is preferred. The content of the hardness adjusting agent can be used, for example, in the range of 0.05 to 1.0% by weight (0.5 g / L to 10 g / L) with respect to the total amount of the composition.

  Furthermore, the plating composition contains a plating surface conditioner such as a nonionic surfactant, chloride, gelatin, etc. from the viewpoint of smoothness of the plating surface, formation of a uniform plating film, and control of water separation. It is preferable to do. As plating surface conditioners, non-ionic surface activity such as polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene octylphenyl ether, etc., from the point of forming smooth plating surface and uniform plating film Examples thereof include at least one of agents, chlorides such as sodium chloride, potassium chloride and calcium chloride, and gelatin, preferably polyoxyethylene alkyl ether, sodium chloride and potassium chloride. Furthermore, it is more preferable to use polyoxyethylene alkyl ether alone or in combination with other plating surface conditioners from the viewpoint of ease of water separation control. The content of the plating surface conditioner varies depending on the plating method, gelling agent, etc., but is in the range of 0.001 to 0.5% by weight (0.01 g / L to 5 g / L) based on the total amount of the composition. Can be used.

  Next, an electrochemical reaction process for performing an electrochemical reaction for forming an electroplating film (metal film 3) as a structure using the plating composition 2A having a predetermined pattern shape will be described.

  As shown in FIG. 6A, when the conductive substrate 20A is used, the conductive substrate 20A is connected to the cathode of the power supply 40, and the plating composition 2A is connected to the anode via the probe 41 or the like. By applying a direct current, a metal ion deposition reaction (electroplating reaction) that is an electrochemical reaction proceeds on the conductive substrate 20A, and the metal ions that the plating composition 2A had on the conductive substrate 20A. Is deposited as the metal film 3. In order to manage the precipitation reaction more precisely, a reference electrode (not shown) may be arranged in the plating composition 2A in addition to the probe 41.

Current density during plating as in the case of using a known plating solution, for example in the plating composition 2A for copper sulfate plating is about 1~50mA / cm ^2, the deposition at a current density of 10 mA / cm ² If it does, a copper metal film | membrane with a film thickness of 2 micrometers can be obtained in 10 minutes.

  As shown in FIG. 6B, in the case where the substrate is a non-conductive substrate 20B such as a resin substrate, a ceramic substrate, or a silicon substrate, the conductive layer 42 is formed by conducting the surface in advance. Later, the plating composition 2A is formed. Although known surface conductive treatment methods such as sputtering and electroless plating can be used, direct plating (DP) pretreatment is preferable from the viewpoint of reducing environmental impact. In the DP pretreatment, a known catalytic treatment with Pd or copper is performed. Note that the conductive layer 42 formed by the surface conductive treatment is removed after the metal film 3 is formed.

  Further, as shown in FIG. 6C, a substrate 20A having a plating composition 2A on the surface is joined to the second substrate 20A1 through the plating composition 2A, and an electrochemical reaction is performed on the second substrate 20A1. Progression, that is, the metal film 3 as a structure may be formed on the second substrate 20A1. As will be described later, the second substrate 20A1 can be provided with not only an energization function but also a function of a soluble anode that supplies metal ions by a metal dissolution reaction.

  Further, as shown in FIG. 6D, after the rearrangement step of peeling the plating composition 2A from the substrate 20A having the plating composition 2A on the surface and rearranging it on the third substrate 20D, the third The metal film 3 may be formed on the substrate 20D.

  Further, as shown in FIG. 6 (E), a second conductive composition 4A in a gel state having conductive ions is disposed on the substrate 20A having the plating composition 2A on the surface via the plating composition 2A. Thus, the metal film 3 may be formed on the conductive substrate 20A. The second conductive composition 4A may have the same configuration as that of the plating composition 2A, that is, the same gelling agent, the same metal ion, and the same solvent, respectively, or may be different. The second conductive composition 4A can be prepared by a known technique in which the second conductive composition 4A is poured into a container having a flat bottom in a sol state, cooled to a gel state, and then cut. Although the second conductive composition 4A is in a gel state, it is easy to handle even if it is large, unlike the patterned plating composition 2A.

  That is, the composition of the gelling agent or the like is determined so that the second conductive composition 4A can maintain its own shape. The shape of the second conductive composition 4A is not limited to a rectangular parallelepiped or the like, and is preferably a shape that can easily maintain its own shape. Or you may use the jig | tool which has the function to hold | maintain the shape of 4 A of 2nd electroconductive compositions. Alternatively, the sheet made of the second conductive composition 4A can be used by being attached to a holding frame as a jig. Furthermore, you may arrange | position the jig | tool as a reinforcing material for maintaining a shape inside the 2nd conductive composition 4A. A jig as a reinforcing material uses, for example, a mesh metal as a core. These jigs may be made of a conductor to provide an electrode function, and may be used as an insoluble anode or a soluble anode. In addition, a spacer may be provided in a portion without the plating composition 2A, or a convex portion having a spacer function may be provided. That is, the spacer may be provided later using, for example, an O-ring, but it is necessary to arrange the spacer so that it can be easily removed.

  In the above case, it is only necessary that at least one of the conductive ions of the plating composition 2A or the second conductive composition 4A has a metal ion for plating deposition. For example, if the plating composition 2A has metal ions, the metal film 3 can be formed on the substrate 20A even if the second conductive composition 4A does not have metal ions. Since the second conductive composition 4A is in a gel state similar to the plating composition 2A, the contact state between the two is good and the contact resistance is low. Furthermore, even if the solvent is volatilized and the conductivity of the surface is deteriorated with the passage of time after the formation of the plating composition 2A, the conductivity is improved because the solvent can be supplied from the second conductive composition 4A. . For this reason, it is preferable that 2nd electroconductive composition 4A has the same solvent as plating composition 2A.

  On the other hand, as shown in FIG. 6F, the second conductive composition 4B may be disposed on a plurality of plating compositions 2A having a predetermined pattern shape. Further, even if the plating composition 2A has a small volume and does not have metal ions necessary for depositing a metal film having a desired film thickness, the second conductive composition 4B does not contain metal ions. If so, the metal ions of the second conductive composition 4B are supplied to the interface between the plating composition 2A and the substrate 20A, so that a metal film having a desired film thickness can be deposited. . Furthermore, even if the plating composition 2A does not have any metal ions, a desired metal film can be deposited by receiving the supply of metal ions from the second conductive composition 4B.

  Further, by using a soluble metal on the anode side, that is, a metal that dissolves by electrolysis and supplies metal ions, metal ions generated by anodic dissolution can be supplied to the conductive composition 2A. For example, by using a soluble metal plate 20E, for example, a copper plate, instead of the probe 41 as shown in FIG. 6F, not only the metal ions of the conductive composition 2A but also the second conductive material from the metal plate. The metal film 3 can be formed using metal ions supplied to the conductive compositions 2A and 4B via the conductive composition 4B.

  As the soluble metal, various known compositions in normal electroplating, such as phosphorus-containing copper in the case of copper, sulfur-containing nickel in the case of nickel, and the like can be used.

  When the soluble metal is used as the anode, the metal ion from the soluble metal even if the plating composition 2A does not have a metal ion necessary for depositing a metal film having a desired film thickness. However, since it is supplied to the interface between the plating composition 2A and the substrate 20A, a metal film having a desired film thickness can be deposited.

  Further, as shown in FIG. 6D, when the plating composition 2A is peeled from the substrate 20A having the plating composition 2A on the surface, one end of a rod-like body that can control the movement of the plating composition 2A, for example, It can be rearranged at the tip of the prober probe. That is, as shown in FIG. 7, the plating composition 2A is rearranged at the tip of the probe 51 of the prober 50, and the power source 40 is arranged between the probe 51 and the substrate 20D as the third substrate on the stage 52. To do. The prober 50 can control the movement of the relative relationship between the probe 51 and the substrate to be plated 20D on the stage 52 in three directions XYZ. For this reason, a plurality of metal films 3 patterned in the shape of the plating composition 2A can be formed at desired locations on the substrate 20D. That is, a plurality of patterned metal films 3 can be formed on the substrate 20D by using one plating composition 2A by controlling the position of the probe 51 of the prober 50 and the power source 40. Furthermore, by replacing the substrate on the stage 52, the metal film 3 can be formed on the plurality of substrates using one plating composition 2A.

  As shown in FIG. 6C, even when the metal film 3 is formed by bonding the substrate 20A having the plating composition 2A on the surface to the second substrate 20C via the plating composition 2A, A metal film can be formed on another substrate by separating the plating composition 2A from the second substrate 20C and bonding it to another substrate.

  Further, as described above, when the substrate 20A has a soluble anode function of supplying metal ions by a metal dissolution reaction, the amount is not limited to the amount of metal ions contained in the plating composition 2A. A desired number of metal films 3 can be formed. Furthermore, a desired thickness and a desired number of metal films 3 can be formed even if the plating composition 2 does not contain metal ions. That is, the plating composition 2A can form a desired metal film pattern without patterning the deposition surface in order to define the region where the metal film is formed. A desired metal film pattern can be formed on a plurality of different substrates using the substrate 20A on which the same plating composition 2A is formed.

  In other words, the plating composition 2A can fix the electrolyte for electrochemical reaction to a desired portion. The substrate 20A on which the patterned plating composition 2A is formed is an imprint plate having a gel electrolyte as an ink holding member. By using this, a metal based on minimal manufacturing by a so-called imprint plating method is used. Precipitation, that is, creation of a structure can be realized.

  In particular, by the probe 51 of the prober 50 provided with the patterned plating composition 2A, metal deposition based on minimal manufacturing can be realized without patterning at a desired position on the substrate.

<Modification of the first embodiment>
Hereinafter, modifications of the first embodiment of the present invention will be described. Since this modification is similar to the first embodiment, the same description is omitted.

  The conductive composition used in the method for manufacturing the structure according to the first embodiment was a plating composition 2A for electroplating. On the other hand, as shown in FIGS. 8A and 8B, a plating composition 2B for electroless plating or a displacement plating film 3C capable of forming an electroless plating film 3B as a structure is formed. A plating composition 2C for displacement plating that can be formed into a film can also be used. The plating composition 2B can be appropriately configured with reference to a known electroless plating solution, and the plating composition 2C can be appropriately configured with reference to a known displacement plating solution.

  Alternatively, the structure may be formed by electroplating or electroless plating using a metal film made of a plating composition as a base film. Since the metal film prepared from the plating composition in the preceding step is patterned, a patterned structure can be obtained without using a mask or the like during the subsequent step of electroplating or electroless plating. For example, by using a metal film prepared from a plating composition as a catalyst layer, a structure composed of a patterned electroless plating film can be obtained without masking in the subsequent electroless plating without masking. . Even if the metal film prepared from the plating composition does not function as a catalyst, a structure composed of an electroless plating film patterned in a maskless manner by performing a catalyzing process by electroless plating in a subsequent step. Can be obtained.

<Second Embodiment>
Next, an etching composition 7A, which is a conductive composition used in the structure manufacturing method of the second embodiment, will be described. Since the structure manufacturing method and the like of the present embodiment are similar to the structure manufacturing method and the like of the first embodiment, the same components are denoted by the same reference numerals and description thereof is omitted.

  The conductive composition used in the structure manufacturing method of the present embodiment is an etching composition 7A for performing a metal dissolution reaction that is an electrochemical reaction. That is, by using the etching composition 7A, the metal layer on the surface of the substrate to be etched, for example, a part of the copper wiring pattern of the wiring board can be dissolved.

  Etching composition 7A has a gelling agent, conductive ions, and a solvent in the same manner as plating composition 2A and the like, but is a composition for performing a metal dissolution reaction. It differs only in that it does not need to have metal ions. The etching composition 7A can be appropriately configured with reference to a known etching solution.

  For example, as shown in FIG. 9A, the etching composition 7A (gel pattern before etching) in a gel state is formed in a pattern that leaves a meander pattern on the surface of the conductive substrate 20C. The patterning of the etching composition 7A can use the same method as the plating composition 2A. 9B, the copper laminate 20E in which the copper film 20E1 is bonded to the resin substrate 20E2 is bonded to the conductive substrate 20C via the etching composition 7A. Thereafter, by applying a direct current between the copper film 20E1 and the conductive substrate 20C by the power source 40, the portion of the copper film 20E1 in contact with the etching composition 7A becomes copper ions, and the etching composition Move to the object 7A side. That is, the copper film 20E1 is pattern etched.

  After the etching, the copper laminate 20E is separated from the conductive substrate 20C as indicated by the arrow in FIG. As shown in FIG. 10A, the separated copper laminate 20E becomes a structure 8 having a copper film (a copper film pattern after etching) 20E1 having a meander pattern on the resin substrate 20E2. The conductive substrate 20C on which the etching composition 7A is formed can be reused, that is, used for etching another copper laminate.

  Further, as shown in FIG. 11, by disposing the etching composition 7A at the tip of the probe 51 of the prober 50, for example, only a part of the metal wiring of the wiring board having fine metal wiring on the surface thereof. It is also possible to dissolve and cut. The etching composition 7A disposed at the tip of the probe 51 of the prober 50 can be used for etching a plurality of times.

  Furthermore, it is also possible to use an etching composition that uses a chemical etching reaction instead of an electrolytic etching reaction.

  The various methods described in the first embodiment can also be used in this embodiment. For example, the etching composition 7 can also be formed using a screen printing method or a metal mask printing method.

  Similarly to the first embodiment, it is only possible to pattern-etch a plurality of metal films on the same substrate using the substrate on which the etching composition 7A is formed or the probe 51 provided. In addition, the metal films on a plurality of different substrates can be pattern etched.

  In other words, the etching composition 7A can fix the electrolyte for electrochemical reaction at a desired portion. The substrate or probe 51 on which the patterned etching composition 7A is formed is an imprint plate using a gel electrolyte as an ink holding member, and by using this, a minimal manufacturable by a so-called imprint etching method. Metal melting based on charing can be realized.

  In particular, by using the probe 51 of the prober 50 in which the patterned etching composition 7A is disposed, it is possible to achieve metal melting based on minimal manufacturing without patterning at a desired position on the substrate.

<Notes on implementation>
Note that the various electrochemical reactions described above may involve hydrogen generation as a side reaction. The conductive composition 2A or the like is suitable for an electrochemical reaction with less hydrogen generation because the gel deteriorates due to hydrogen generation. For example, high-concentration copper sulfate plating for electroplating, gold plating for electroless plating, and copper plating for displacement plating are particularly suitable for reactions with the conductive composition 2A and the like.

  In addition, the electrochemical reaction has a higher traveling speed when the temperature is higher, and a high-quality plated film may be formed at high speed. For this reason, you may heat when performing an electrochemical reaction, if the plating composition 2A grade | etc., Is the temperature range which does not sol.

  The gel-state plating composition 2A and the like are harder to dry than the plating solution, but may be used in combination with means for preventing drying. In particular, when heated, drying is promoted, so it is preferable to use a means for preventing drying. As a means for preventing the drying, in order to keep the atmosphere in a high humidity state, the plating composition 2A is put in a small box immediately after being stored and used in a sealed narrow space, for example, immediately after being discharged onto the substrate. It is preferable to store in a sealed state. Further, it is preferable to store the inside of the box together with a nonwoven fabric impregnated with water in order to obtain a saturated water vapor pressure.

  In addition, when plating composition 2A etc. have dried, a solvent can also be replenished by the method of making it contact with the solution (plating liquid) which removed the gelatinizer from the said method or plating composition 2A. Similarly to the solvent, when the metal ions in the plating composition 2A are depleted by an electrochemical reaction, they can be replenished.

  It should be noted that the surface of the gel-like plating composition 2A and the like is easily dried at room temperature as compared with the inside. Even when only the surface of the plating composition 2A is dried, the contact resistance with the probe 41 and the like is increased, which hinders the electrochemical reaction. In the case of using a gel whose surface is easy to dry, it is preferable to use a means for preventing drying, and the plating composition 2A is put into a small box immediately after being used in a closed narrow space, for example, after being discharged onto the substrate. It is preferable to store in a sealed state. Further, it is preferable to store the inside of the box together with a nonwoven fabric impregnated with water in order to obtain a saturated water vapor pressure. When the gel whose surface is easy to dry is dried, the contact resistance can be reduced by wetting the patterned plating composition 2A and the second conductive compositions 4A and 4B in a gel state with a solvent. Alternatively, the probe 41, the second substrate 20 </ b> A <b> 1, the soluble metal plate 20 </ b> E, the copper-plated plate 20 </ b> C, and the like that are in contact with the gel-state plating composition 2 </ b> A may be wetted with a solvent. Alternatively, the contact resistance can be reduced by applying pressure to the gel and moving the internal solvent to the surface. Further, when the probe 41 is used, the contact resistance can be reduced by inserting the tip portion of the probe 41 to the inside which is not dried.

  In the case of the chemically unstable plating composition 2, the components contained may be stored separately and discharged separately through the opening to create the plating composition 2 </ b> A. For example, in the plating composition 2B for electroless plating, the reducing agent-containing composition and the metal ion-containing composition may be separately ejected.

  Furthermore, the electrochemical reaction using the plating composition 2A is not easily affected by oxygen in the air. For this reason, the anaerobic plating reaction which could not be performed only in a nitrogen atmosphere can be performed in the air. For example, the electroless copper plating reaction using the electroless plating composition 2B having divalent iron ions as the reducing agent and copper ions as the metal ions can be performed in the atmosphere.

  The present invention is not limited to the above-described embodiment, and various changes and modifications can be made without departing from the scope of the present invention.

2, 2A,... Plating composition, 2B, electroless plating composition, 2C, displacement plating composition, 3 ... metal film, 4A, 4B ... conductive composition, 6 ... photoresist, 7A ... etching 8 ... structure, 10 ... dispenser device, 10A ... main body, 11 ... dispenser, 12 ... capillary, 13 ... opening, 14 ... stage, 20, 20A-20D ... substrate, 30 ... screen printing device, 31 ... Screen, 32 ... Opening, 33 ... Squeegee, 40 ... Power supply, 41 ... Probe, 42 ... Conductive layer, 50 ... Prober, 51 ... Probe, 52 ... Stage

Claims (21)

A solating step of bringing a conductive composition having a gelling agent, a conductive ion for performing an electrochemical reaction, and a solvent into a sol state;
A pattern forming step in which the conductive composition in a sol state has a predetermined pattern shape on a substrate;
A gelation step of bringing the conductive composition of the predetermined pattern shape into a gel state;
And an electrochemical reaction step of performing an electrochemical reaction using the conductive composition in a gel state.   The method for manufacturing a structure according to claim 1, wherein the conductive composition is heated in the sol formation step, and the conductive composition is cooled in the gelation step.   3. The method for manufacturing a structure according to claim 1, wherein pressure is applied to the conductive composition in the sol formation step.   The method for producing a structure according to any one of claims 1 to 3, wherein a shear stress is applied to the conductive composition in the sol formation step.   5. The structure according to claim 1, wherein, in the pattern forming step, the conductive pattern in the sol state is discharged from an opening to form the predetermined pattern shape. 6. Body production method   6. The structure manufacturing method according to claim 5, wherein the opening is an opening of a capillary.   6. The structure manufacturing method according to claim 5, wherein the opening is an opening of a screen for screen printing or an opening of a metal mask for metal mask printing.   The method for manufacturing a structure according to any one of claims 1 to 6, wherein in the pattern formation step, the predetermined pattern shape is obtained by using a photoresist pattern formed on a substrate.   The method for manufacturing a structure according to any one of claims 1 to 8, wherein the solvent is water.   The substrate having the conductive composition in a gel state in the gelation step and the second substrate are joined via the conductive composition, and the electrochemical reaction step is performed on the second substrate. The method for producing a structure according to any one of claims 1 to 9, wherein the method is performed as described above. Further comprising a rearrangement step of peeling the conductive composition in a gel state in the gelation step from the substrate and rearranging the conductive composition on a third substrate;
The method for manufacturing a structure according to any one of claims 1 to 9 , wherein the electrochemical reaction step is performed on the third substrate. A disposing step of disposing the conductive composition in a gel state in the gelling step on one end of a rod-shaped body whose movement can be controlled from the substrate;
A rearrangement step of controlling the movement of the rod-shaped body and rearranging the conductive composition on a third substrate,
The method for manufacturing a structure according to any one of claims 1 to 9 , wherein the electrochemical reaction step is performed on the third substrate.   The method for producing a structure according to claim 12, wherein the rod-like body is a prober of a prober. The conductive ions have metal ions;
The method for manufacturing a structure according to claim 1, wherein the electrochemical reaction is a precipitation reaction of the metal ions. The electrochemical reaction is a precipitation reaction of metal ions,
The method for manufacturing a structure according to any one of claims 1 to 13, wherein the metal ions are supplied to the solvent by a metal dissolution reaction. The method for manufacturing a structure according to any one of claims 1 to 13 , wherein the electrochemical reaction is a metal dissolution reaction. A second conductive composition in a gel state having conductive ions is disposed on the conductive composition having the predetermined pattern shape to be in a gel state in the gelation step, and the conductive composition and the A second conductive composition arranging step of bringing the second conductive composition into electrical contact with the second conductive composition;
In the electrochemical reaction step structure according to any one of the second conductive composition via and applying a current to the conductive composition according to claim 1 to claim 13 Manufacturing method.   The method for manufacturing a structure according to claim 17, wherein the second conductive composition is disposed on the plurality of the conductive compositions having the predetermined pattern shape. The conductive ion of at least one of the conductive composition or the second conductive composition has a metal ion,
The method for producing a structure according to claim 17 or 18, wherein the electrochemical reaction is a precipitation reaction of the metal ions. The electrochemical reaction is a precipitation reaction of metal ions,
The method for manufacturing a structure according to claim 17 , wherein the metal ions are supplied to the solvent by a metal dissolution reaction. The method for manufacturing a structure according to claim 17 or 18, wherein the electrochemical reaction is a metal dissolution reaction.

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