WO2013039109A1

WO2013039109A1 - Device and method for forming electro-conductive substance

Info

Publication number: WO2013039109A1
Application number: PCT/JP2012/073343
Authority: WO
Inventors: 英一近藤; 正弘松原; 竹内　裕人; 満洋渡邉; 山本　敏; 直博菊川
Original assignee: 国立大学法人山梨大学; 株式会社フジクラ
Priority date: 2011-09-13
Filing date: 2012-09-12
Publication date: 2013-03-21
Also published as: JPWO2013039109A1; JP5785264B2; US20140193573A1

Abstract

This device for forming an electro-conductive substance is a device for forming an electro-conductive substance on the inside of a small hole. In the device, which introduces into a reaction container a fluid obtained by dissolving at least a metallic complex in a supercritical fluid or a subcritical fluid, a plate-shaped substrate is arranged in the fluid, which is continuously moved in a specific direction inside the reaction container, and an electro-conductive substance is formed on an inside wall of a small hole, which is provided on the substrate. The reaction container is provided with a first space into which the fluid is introduced, and a second space into which the fluid is introduced. A second face of the substrate is established perpendicularly with respect to the specific direction in which the fluid introduced into the first space moves, and a support member in which a small through hole is provided is arranged so that the fluid advances through the small hole in the substrate from the second face of the substrate toward a first face. The support member supports the first face of the substrate over the entirety thereof, and allows the fluid to pass into the second space.

Description

Conductive substance forming apparatus and method for forming the same

The present invention relates to an apparatus for forming a conductive material in a micropore provided in a substrate using a fluid obtained by dissolving a metal complex in a supercritical fluid or a subcritical fluid, and a method for forming the same.
The present application includes Japanese Patent Application No. 2011-199678 filed on September 13, 2011, Japanese Patent Application No. 2011-218300 filed on September 30, 2011, and Japanese Patent Application No. 2011-218300 filed on September 30, 2011. Claim priority based on Japanese Patent Application No. 2011-218301 and Japanese Patent Application No. 2011-218302 filed on Sep. 30, 2011, the contents of which are incorporated herein by reference.

In recent years, a technology for synthesizing materials without using environmentally hazardous materials such as organic solvents is required. 2. Description of the Related Art Conventionally, ultra-fine processing processes such as the manufacture of integrated circuits frequently use dry processes (vacuum processes) such as in a vacuum, a rare gas atmosphere, or a plasma discharge atmosphere.

The dry process has been developed as an extremely effective means since a single atom or molecule or its ion can be directly used for processing. However, the need for equipment for maintaining a vacuum environment and the need for a plasma generator are factors in increasing costs. On the other hand, in a wet process using a liquid such as plating or cleaning, a large amount of waste liquid is generated. Therefore, there is a problem that the cost required for the waste liquid treatment is large and the load on the environment is large.

A supercritical fluid using CO ₂ as a medium has an intermediate property between liquid and gas, has a surface tension of zero, and has a unique ability to dissolve other substances (solvent ability). Combines nature. Furthermore, it has the advantages of being chemically stable, inexpensive, harmless and low cost. In addition to these, there are many features that CO ₂ itself and substances dissolved in the CO ₂ fluid can be recycled by vaporization and reliquefaction.

Research and development using supercritical CO ₂ has been promoted, focusing on the wafer cleaning process in the integrated circuit manufacturing process. For example, in the cleaning process, a process focusing on the solvent ability and safety / recyclability of supercritical CO ₂ has been developed. Further, focusing on the fact that the surface tension is zero in supercritical CO ₂ , research and development of a microfabrication process for forming nano-level wiring has been performed (for example, Patent Document 1).

∙ Supercritical fluid has zero surface tension and a large diffusion coefficient, so even nano-scale micropores penetrate into the inside very well. If the supercritical fluid itself can be used as a reaction field for forming a thin film, it is possible to form and fill a material in an ultrafine structure, and to construct a low-cost clean process that replaces CVD and plating.

In recent years, with the development of small and highly functional electronic devices, high mounting density of LSI is required, and the current two-dimensional mounting technology is said to be close to the limit. For this reason, a three-dimensional mounting technique in which LSI chips are stacked and stacked is essential, and a through electrode that penetrates a semiconductor substrate in the vertical direction (stacking direction) has been put into practical use.

The through electrode is used for a wiring board (interposer) for mounting these LSIs at a high density in addition to the three-dimensional lamination of the LSI chips. There are two typical shapes of the through electrode, one in which the inside of the fine hole is completely filled with a conductive substance and one in which the conductive substance is deposited in a thin film on the inner wall of the fine hole. Due to the higher performance of LSIs, higher density of packages, and the increase in the number of pins associated with higher integration, more finer and narrower pitches are required for through-wires. The problem is how to completely fill the conductive material or how to deposit the conductive material uniformly and uniformly in thickness.

International Publication No. 2005/118910

The present invention has been devised in view of such a conventional situation, and the inside of a microscopic hole in which a conductive material can be uniformly and uniformly deposited in the microscopic hole provided in the substrate. It is a first object of the present invention to provide a conductive material forming apparatus.
In addition, the present invention provides a method for forming a conductive material in a microscopic hole, in which the conductive material can be deposited uniformly and uniformly in the microscopic hole provided in the substrate. Second purpose.

The conductive material forming apparatus according to the first aspect of the present invention includes a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived. A flat substrate having a first surface, a second surface, and fine holes, the reaction vessel being disposed in the fluid that continuously moves in a specific direction in the reaction vessel, and the first The fineness of the substrate is such that the second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the space moves and from the second surface of the substrate toward the first surface. A support member having a fine communication hole for supporting the first surface of the base body over the entire surface so that the fluid proceeds in the hole and allowing the fluid to pass through the second space. An apparatus for forming a conductive material.
The conductive substance forming apparatus according to the first aspect of the present invention has an introduction port configured to protrude into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the substrate. It is preferable to provide an introduction part for introducing the fluid into the reaction vessel.
The conductive substance forming apparatus according to the first aspect of the present invention includes a plurality of inlets configured to protrude into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the base. And an introduction part for introducing the fluid into the reaction vessel.

The method for forming a conductive material according to the second aspect of the present invention includes a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived. A flat substrate having a first surface, a second surface, and a fine hole disposed in the fluid that continuously moves in a specific direction in the reaction vessel; and A support member that supports the first surface, the second surface of the base body is perpendicular to a specific direction in which the fluid introduced into the first space moves, and The support member is arranged so that the fluid travels in the micropores of the substrate from the second surface of the substrate toward the first surface, and the fluid is transferred from the first space to the second space. To the inner wall of the micropores provided in the substrate To form a quality.
In the method for forming a conductive substance according to the second aspect of the present invention, it is preferable to use a semiconductor substrate or a glass substrate as the base.
In the method for forming a conductive substance according to the second aspect of the present invention, it is preferable that a reducing agent is dissolved in the fluid.

The conductive material forming apparatus according to the third aspect of the present invention includes a reaction vessel into which a fluid obtained by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a specific direction continuously in the reaction vessel. And a flat substrate having fine holes, and the substrate is arranged so that the fluid moves along both surfaces of the substrate.
In the conductive material forming apparatus according to the third aspect of the present invention, it is preferable that the base is arranged so that both surfaces of the base are parallel to the specific direction.
In the conductive material forming apparatus according to the third aspect of the present invention, it is preferable to dispose the base body so that both surfaces of the base body are not parallel to the specific direction.
The conductive material forming apparatus according to the third aspect of the present invention preferably includes a holding portion provided inside the reaction vessel, which holds an angle formed by both surfaces of the substrate with respect to the specific direction. .

According to a fourth aspect of the present invention, there is provided a method for forming a conductive substance comprising: a reaction vessel into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced; And a flat substrate disposed in the fluid moving in the direction, the fluid is moved along both surfaces of the substrate, and the conductive material is transferred to the inner walls of the micropores provided in the substrate. Form.
In the method for forming a conductive substance according to the fourth aspect of the present invention, a semiconductor substrate or a glass substrate is preferably used as the base.
In the method for forming a conductive substance according to the fourth aspect of the present invention, it is preferable that a reducing agent is dissolved in the fluid.

The conductive material forming apparatus according to the fifth aspect of the present invention includes a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived. A flat substrate having a first surface, a second surface, and fine holes, the reaction vessel being disposed in the fluid that continuously moves in a specific direction in the reaction vessel, and the first The fineness of the substrate is such that the second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the space moves and from the second surface of the substrate toward the first surface. And a support member that supports the first surface of the base so that the fluid travels in the hole.
The conductive substance forming apparatus according to the fifth aspect of the present invention has an inlet configured to protrude into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the base. It is preferable to provide an introduction part for introducing the fluid into the reaction vessel.
The conductive substance forming apparatus according to the fifth aspect of the present invention includes a plurality of inlets configured to protrude into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the substrate. It is preferable to have an introduction part for introducing the fluid into the reaction vessel.

The conductive material forming apparatus according to the sixth aspect of the present invention includes a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived. A flat substrate having a first surface, a second surface, and fine holes, the reaction vessel being disposed in the fluid that continuously moves in a specific direction in the reaction vessel, and the first The second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the space moves and from the second surface of the substrate toward the first surface, the first surface of the substrate. A support member that supports the first surface of the base body so that the fluid travels through the micropores, and has a guide path that is provided around the base body while the fluid passes through the second space; Is provided.
The conductive substance forming apparatus according to the sixth aspect of the present invention has an introduction port configured to protrude into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the base. It is preferable to provide an introduction part for introducing the fluid into the reaction vessel.
According to a sixth aspect of the present invention, there is provided the conductive substance forming apparatus including a plurality of inlets configured to protrude into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the substrate. It is preferable to have an introduction part for introducing the fluid into the reaction vessel.

In the conductive material forming apparatus according to the first aspect of the present invention, the fluid can be forcibly transported from both the first surface and the second surface of the substrate into the micropores. Therefore, according to the present invention, it is possible to provide a device for forming a conductive material in a microscopic hole, which can deposit a conductive material uniformly and uniformly in the microscopic hole provided in the substrate. it can.
In particular, the forming apparatus according to the first aspect of the present invention includes a support portion that supports the first surface of the substrate over the entire surface and has a fine communication hole through which the fluid passes into the second space. Since it is disposed, the differential pressure between the upper and lower surfaces of the substrate is increased, and it is possible to deposit the conductive material in the fine holes more reliably. In addition, it is possible to reduce the load on the substrate. As a result, breakage of the base body can be prevented, and blockage of the piping and equipment failure can be prevented. As a result, according to the forming apparatus according to the present invention, a stable operating state is possible, and the length of the fine holes provided in the base is increased by increasing the differential pressure while reducing the load on the base. Even in this case, it is possible to further extend the distance in which the conductive material can be uniformly deposited in the longitudinal direction of the micropores provided in the substrate.
Examples of the configuration of the fluid introduction portion include a case where a pipe-like introduction portion is connected to the reaction vessel so as to communicate with the first space α of the reaction vessel, and a case where the fluid introduction portion protrudes into the first space α of the reaction vessel and the introduction thereof. When the mouth is configured to be positioned in the vicinity of the second surface of the substrate, and the plurality of inlet ports are positioned in the vicinity of the second surface of the substrate. The case where it is comprised is mentioned.

In the method for forming a conductive material according to the second aspect of the present invention, the fluid can be forcibly transported from both the first surface and the second surface side of the substrate into the micropores. Therefore, according to the present invention, it is possible to provide a method for forming a conductive material in a microscopic hole, which allows the conductive material to be uniformly and uniformly deposited in the microscopic hole provided in the substrate. it can.
In particular, in the forming method according to the second aspect of the present invention, a support portion that supports the first surface of the substrate over the entire surface and that has a fine communication hole through which the fluid passes to the second space is provided. Since it is disposed, the differential pressure between the upper and lower surfaces of the substrate is increased, and it is possible to deposit the conductive material in the fine holes more reliably. In addition, it is possible to reduce the load on the substrate. As a result, breakage of the base body can be prevented, and blockage of the piping and equipment failure can be prevented. As a result, the forming method according to the present invention enables a stable operation state for a long time, and reduces the load on the substrate, while increasing the differential pressure, thereby reducing the length of the fine holes provided in the substrate. Even in the case of increasing the thickness, it contributes to further extending the distance in which the conductive material can be deposited uniformly and uniformly in the longitudinal direction of the micropores provided in the substrate.
In the method for forming a conductive substance according to the second aspect of the present invention, the substrate is preferably a semiconductor substrate or a glass substrate. By making the present invention applicable to a semiconductor substrate or a glass substrate, application to the above-described three-dimensional mounting (stacking) of LSIs, interposers, and the like can be expected. Further, it is desirable to use a fluid in which a reducing agent is further dissolved as an additive gas. By dissolving the reducing agent in the fluid, the raw material and the reducing agent can be simultaneously supplied into the micropores, and a uniform thin film can be formed.

In the conductive material forming apparatus of the third aspect of the present invention, the fluid is transported by both “flow” and “diffusion” toward the micropores. Therefore, it is considered that more fluid is transported into the micropores than in the case where only one side of the base body is exposed in the specific direction. Therefore, according to the present invention, it is possible to provide a conductive material forming apparatus capable of uniformly depositing a conductive material with a uniform thickness on a substrate.
Examples of a configuration in which the substrate is arranged so that the fluid moves along both surfaces of the substrate include a case where the substrate is arranged so that both surfaces of the substrate are parallel to the specific direction, and And the case where the substrate is arranged so that both surfaces of the substrate are not parallel to a specific direction. In order to dispose the substrate in this way, it is preferable to provide a holding portion that holds an angle formed by both surfaces of the substrate with respect to the specific direction, inside the reaction vessel. When the holding unit is used in this way, when the fluid moves along both surfaces of the substrate, the angle formed by both surfaces of the substrate with respect to the specific direction is maintained without obstructing the direction of the fluid. It becomes possible.

In the method for forming a conductive substance according to the fourth aspect of the present invention, the fluid is transported by both “flow” and “diffusion” toward the micropores. Therefore, compared with the case where both surfaces of the base are parallel to the specific direction, it is considered that more fluid is transported into the micropores. Therefore, according to the present invention, it is possible to provide a method for forming a conductive material capable of depositing a conductive material having a uniform thickness on a substrate.
In the method for forming a conductive substance according to the fourth aspect of the present invention, the substrate is preferably a semiconductor substrate or a glass substrate. By making the present invention applicable to a semiconductor substrate or a glass substrate, application to the above-described three-dimensional mounting (stacking) of LSIs, interposers, and the like can be expected. Further, it is desirable to use a fluid in which a reducing agent is further dissolved as an additive gas. By dissolving the reducing agent in the fluid, the raw material and the reducing agent can be simultaneously supplied into the micropores, and a uniform thin film can be formed.

In the conductive material forming apparatus of the fifth aspect of the present invention, the fluid can be forcibly transported into the micropores. Therefore, according to the present invention, it is possible to provide a device for forming a conductive material in a microscopic hole, which can deposit a conductive material uniformly and uniformly in the microscopic hole provided in the substrate. it can.
Examples of the configuration of the fluid introduction portion include a case where a pipe-like introduction portion is connected to the reaction vessel so as to communicate with the first space α of the reaction vessel, and a case where the fluid introduction portion protrudes into the first space α of the reaction vessel and the introduction thereof. When the mouth is configured to be positioned in the vicinity of the second surface of the substrate, and the plurality of inlet ports are positioned in the vicinity of the second surface of the substrate. The case where it is comprised is mentioned.

In the conductive material forming apparatus of the sixth aspect of the present invention, the fluid can be forcibly transported into the micropores. Therefore, according to the present invention, it is possible to provide a device for forming a conductive material in a microscopic hole, which can deposit a conductive material uniformly and uniformly in the microscopic hole provided in the substrate. it can.
Further, in the forming apparatus according to the sixth aspect of the present invention, since the support portion provided around the base is provided with a guide path through which the fluid passes to the second space, the load on the base is reduced. It is possible to plan. Therefore, the forming apparatus according to the sixth aspect of the present invention can prevent the base from being damaged, and can prevent the blockage of the piping and the failure of the equipment.
Examples of the configuration of the fluid introduction portion include a case where a pipe-like introduction portion is connected to the reaction vessel so as to communicate with the first space α of the reaction vessel, and a case where the fluid introduction portion protrudes into the first space α of the reaction vessel and the introduction thereof. When the mouth is configured to be positioned in the vicinity of the second surface of the substrate, and the plurality of inlet ports are positioned in the vicinity of the second surface of the substrate. The case where it is comprised is mentioned.

It is a figure which shows typically the example of 1 structure of the apparatus which concerns on this invention. In the apparatus shown in FIG. 1, it is a figure which shows typically an example of the internal structure of a reaction container. FIG. 3 is a diagram showing a positional relationship between a substrate and a support member provided with a fine communication hole in the substrate support of the reaction container of FIG. 2. In the apparatus shown in FIG. 1, it is a figure which shows typically an example of the internal structure of a reaction container. In the apparatus shown in FIG. 1, it is a figure which shows typically an example of the internal structure of a reaction container. It is a figure which shows typically the positional relationship of the base | substrate which has a micropore, and the flow direction of a fluid. It is a figure which shows typically the example of 1 structure of the apparatus which concerns on this invention. In the apparatus shown in FIG. 1, it is a figure which shows typically an example of the internal structure of a reaction container. It is a figure which shows the positional relationship of a base | substrate and a supporting member (O-ring) in the base | substrate support tool of reaction container. In the apparatus shown in FIG. 1, it is a figure which shows typically an example of the internal structure of a reaction container. In the apparatus shown in FIG. 1, it is a figure which shows typically an example of the internal structure of a reaction container. It is a figure which shows the positional relationship of a base | substrate and a supporting member (O-ring) in the base | substrate support tool of reaction container. It is a figure which shows the optical micrograph of the base | substrate cross section obtained in the 1st Example. It is a figure which shows the optical micrograph of the base | substrate cross section obtained in 2nd Example. It is a figure which shows typically the base | substrate cross section in which the electroconductive substance was formed by 3rd Example. It is a figure which shows typically the base | substrate cross section in which the electroconductive substance was formed by 4th Example. It is sectional drawing which shows the structure of the base | substrate used in 5th Example and 7th Example. It is a figure which shows typically the base | substrate cross section in which the electroconductive substance was formed by 6th Example.

[First embodiment]
The apparatus and method according to the first embodiment of the present invention will be described below.
In this specification, the supercritical fluid refers to a state in which a gas such as CO ₂ is kept above its critical point so that there is no difference between gas and liquid and the fluid is neither liquid nor gas.

FIG. 1 is a diagram schematically showing a configuration example of an apparatus according to the present invention.
This apparatus is a flow-type thin film deposition apparatus, and includes an H ₂ cylinder 1, a CO ₂ cylinder 2, a pressure regulator 3, a supply valve 4, a mixer 5, a liquid feed pump 6, a cooler 7, A raw material container 8, a raw material feed pump 9, a front valve 10, a mantle heater 11, a preheat pipe 12, a reaction container 13, a back pressure regulator (BPR) 14, and a constant temperature bath 15 are provided.
In this apparatus, CO ₂ at a constant pressure and flow rate is continuously supplied into the reaction vessel 13 in a supercritical state or a subcritical fluid, and a conductive material is formed on the inner wall of the fine holes provided in the substrate by the reducing agent H _2. (For example, Cu) is deposited and deposited to form a through electrode.

Material changes into gas, liquid and solid depending on temperature and pressure. A supercritical fluid is a state of a substance when temperature and pressure exceed a critical point. In this state, it has high density and low viscosity, that is, both liquid and gas properties. It has a diffusion coefficient intermediate between liquid and gas and has a surface tension of 0 (zero). From these facts, it can be said that the supercritical fluid has the same dissolving power as liquid and fluidity like gas. Therefore, nano-level permeability and high-speed reaction can be expected by using a supercritical fluid as a reaction solvent. Depending on the conditions, the same action and effect may be obtained even if a subcritical fluid is used instead of the supercritical fluid.

The H ₂ cylinder 1 contains H ₂ gas as a reducing agent, and the H ₂ gas is introduced into the mixer 5 through the pressure regulator 3 and the supply valve 4.
The CO ₂ cylinder 2 contains CO ₂ gas which is a medium of supercritical fluid. The CO ₂ gas is liquefied from the CO ₂ cylinder 2 by the cooler 7 and then pressurized by the liquid feed pump 8, and the mixer 5 Introduced into
H ₂ gas and CO ₂ gas are mixed by the mixer 5 and introduced into the reaction vessel 13.

The raw material container 8 contains a metal complex of a conductive material as a raw material. In this embodiment, the case where bisisobutyryl methanato copper (Cu (divm) ₂ ) is used is described as an example, but the present invention is not limited to this.
The metal complex is introduced into the reaction vessel 13 through the raw material feed pump 9. The supply of the raw material is controlled by a front valve 10 provided close to the gas supply port of the reaction vessel.

The reaction vessel 13 is preferably composed of, for example, a pressure- and heat-resistant vessel made of stainless steel, but is not limited thereto. This reaction vessel 13 can be produced, for example, by processing an autoclave (pressure defoaming device).
A preheat pipe 12 is provided in front of the reaction vessel 13, and a mantle heater 11 and a thermostatic layer 15 are provided in the preheat pipe 12 and the reaction vessel 13 to heat and hold the fluid at a predetermined temperature. And adjust the temperature.
A back pressure regulator (BPR) 14 is disposed downstream of the reaction vessel 13. After the reaction is completed in the reaction vessel 13, the supercritical fluid in the reaction vessel 13 is exhausted through the back pressure regulator 14.

FIG. 2 is a diagram schematically showing the internal configuration of the reaction vessel 13 in the apparatus according to the first embodiment of the present invention.
A substrate support 31 is provided inside the reaction vessel 13, and the substrate 20 is placed on the substrate support 31.
As the base body 20, for example, a semiconductor substrate such as silicon or a glass substrate is used. The base body 20 is provided with a fine hole 21 penetrating from the second surface toward the first surface.

In such an apparatus, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into the reaction vessel 13, and in the fluid that continuously moves in a specific direction in the reaction vessel 13, The substrate 20 is disposed, and a conductive material is formed on the inner wall of the micropore 21 provided in the substrate 20.

In the apparatus of the first embodiment of the present invention, the reaction vessel 13 includes a first space α into which the fluid F is introduced and a second space β into which the fluid is derived, and the first space α. The second surface 20a of the base body 20 is perpendicular to a specific direction in which the fluid F introduced into the base body moves, and the fluid F advances toward the second surface 20a of the base body 20 And a base support 31 (support portion) provided to support the first surface 20b of the base body 20 and provide a guide path 34 around the base body 20 through which the fluid F passes to the second space β. It is characterized by.

Here, the method of transporting substances in the fluid can be divided into “flow” and “diffusion”. If we compare the ink to the ink when the fluid is dropped into water as an image, the “flow” is similar to the state when the “diffusion” spreads without stirring when it is stirred with a stick.

FIG. 6 is a diagram schematically showing a positional relationship between the base body 20 having the fine holes 21 and the flow direction of the fluid F in the reaction vessel 13 in the first embodiment of the present invention. Below, the result of having considered beforehand the relationship with the flow direction of the fluid F in the reaction container 13 is described.

In FIG. 6A, only the second surface (upper surface) of the substrate 20 is exposed to the flow F in parallel with the flow direction of the fluid F, and the first surface (lower surface) is in contact with the inner surface of the reaction vessel 13. This is the case. In this case, it is considered that the raw material (fluid F) is transported to the micropores 21 only by diffusion.

FIG. 6B shows a case where both surfaces (upper and lower surfaces) of the base body 20 are arranged so as to be exposed to the flow F in parallel with the flow direction of the fluid F. In this case, the substrate 20 may be arranged at a position off the center in the reaction vessel 13 [FIG. 6 (b) shows 1 from the inner wall of the reaction vessel 13 drawn on the upper side with respect to the diameter of the reaction vessel 13. / 3, a configuration example in which the position is 2/3 from the inner wall of the reaction vessel 13 drawn on the lower side]. By disposing the substrate 20 at a position away from the center in the reaction vessel 13, the flow of fluid flowing on both surfaces of the substrate can be changed. On the side where the distance from the inner wall of the reaction vessel 13 is narrow, the “flow” toward the fine holes becomes active. Since “flow” is affected by the inner wall of the reaction vessel 13, it is possible to control the entry of fluid into the micropores of the substrate by appropriately adjusting the distance from the inner wall on the upper and lower surfaces of the substrate.

6C and 6D show a case where both surfaces (upper and lower surfaces) of the base body 20 are arranged so as to be exposed to the flow F in a non-parallel manner with respect to the flow direction of the fluid F. FIG. 6D shows a case where the flow direction of the fluid F and the second surface (upper surface) of the base 20 are perpendicular to each other. In any of the arrangements shown in FIGS. 6B to 6D, the raw material (fluid F) is transported to the micropores 21 by both “flow” and “diffusion”, so that the raw material is more than the former. Expected to be transported. In this case, the flow of the fluid flowing on both surfaces of the substrate on the second surface (upper surface) of the substrate positioned on the side facing the flow direction of the fluid F and on the first surface (back surface) of the substrate positioned on the opposite side. You can change the way. On the second surface (upper surface) of the substrate located on the side facing the flow direction of the fluid F, “flow” toward the micropores becomes active. By appropriately adjusting the angle formed by the second surface (upper surface) of the substrate located on the side facing the flow direction of the fluid F, it becomes possible to control the entry of the fluid into the micropores of the substrate.

Based on the above consideration, the first embodiment of the present invention is shown in FIGS. 2, 4, and 5 as an apparatus capable of depositing a conductive material uniformly and uniformly in the micropores 21. A device with a configuration was devised.
All of the apparatuses shown in FIGS. 2, 4 and 5 are arranged such that the flow direction is perpendicular to the base body 20, that is, the fine holes 21 and the flow direction are parallel to each other. In addition, the fluid travels in the micro holes 21 of the base 20 from the second surface 20a to the first surface 20b of the base, and the fluid also flows from the first surface 20b of the base. It was configured to proceed and to support the first surface 20b of the substrate. Thereby, the raw material can be transported more efficiently into the micropores 21.

Compared to the apparatus of FIG. 2 (when a pipe-shaped introduction part is connected to the reaction vessel so as to communicate with the first space α of the reaction vessel), FIG. 4 (projects into the first space α of the reaction vessel, When the introduction port is configured to be located in the vicinity of the second surface of the substrate, FIG. 5 (projects into the first space of the reaction vessel, and there are a plurality of introduction ports of the second surface of the substrate. In the case of the apparatus in the case of being arranged in the vicinity), the flow direction of the fluid with respect to the second surface of the base is more accurately perpendicular to the base 20 and the flow direction, that is, the fine holes 21 and the flow direction are more accurately. It becomes possible to guide the fluid to the inside of the micropore so that they are parallel to each other. As shown in FIG. 5 as compared to FIG. 4, it is more preferable that a plurality of fluid inlets be arranged because the induction effect is further improved.

That is, in the first embodiment of the present invention, the base body 20 is arranged so that the fluid F advances toward the second surface 20a of the base body 20, and the base body 20 is provided with a fine communication hole. Further, since the pressure difference between the upper part of the base and the lower part of the base becomes large and uniform, the fluid can be forcibly transported into the micropores. As a result, in the present invention, it is possible to deposit the conductive material uniformly and uniformly in the micropores provided in the substrate 20.

In any of the apparatuses shown in FIGS. 2, 4 and 5, the base 20 is attached to the base support 31 so that the second surface 20a is perpendicular to the fluid flow direction (spraying direction). It is attached. Further, the first surface 20b of the base body 20 is supported over the entire surface. The fluid F is supplied from the nozzle 33 toward the second surface 20a of the base body 20 arranged in this manner, and sprayed onto the second surface 20a of the base body 20. Thereby, the fluid which goes to the 2nd space (beta) from 1st space (alpha) can be forced to distribute | circulate the inside of a micropore, and raw material transport can be accelerated | stimulated. Further, in order to stably support the substrate 20, the reaction vessel 13 is a vertical type as shown in FIGS. 2, 4 and 5 (in FIGS. To express). That is, in the apparatus shown in FIGS. 2, 4, and 5, in the first space α and the second space β of the reaction vessel 13, the direction in which the fluid flows (solid arrow) is the direction of gravity. Has been placed.

In the forced transportation method as described above, it is considered that the pressure difference between the upper and lower surfaces of the substrate 20 promoted the covering property. This differential pressure is generated because the flow rate of the fluid F is different between the upper part of the base and the lower part of the base.

FIG. 4 is an enlarged view showing the periphery of the substrate 20 in the reaction vessel 13. Describing in the reaction vessel 13, the low flow rate region is from the inflow to the upper surface (second surface 20 a) of the substrate 20, and the high flow rate region is from the lower surface (first surface 20 b) of the substrate 20 to the outflow. As a result, a differential pressure is generated between the upper and lower surfaces of the substrate 20, and the fluid is considered to have circulated in the micropores.

Furthermore, in the apparatus according to the first embodiment of the present invention, the base support 31 (support portion) has a fine communication hole through which the fluid F passes into the second space β from which the fluid F is led out. Yes.
In the first embodiment, a glass filter is used as a support body having fine communication holes. However, the present invention is not limited to this. The glass filter is a laboratory instrument equipped with a filter for filtration made of glass fiber (glass fiber). GF / A is the most efficient general purpose filter paper that is most widely used for filtration of denatured proteins, and is also used for air pollution analysis.
By using a glass filter as a support for the substrate 20, it is considered that the gap between the substrate 20 and the jig is reduced and the differential pressure between the upper and lower surfaces of the substrate is increased. As a result, a coating promoting effect can be expected.

In the first embodiment of the present invention, as shown in FIGS. 2, 4, and 5, the first surface 20 b of the base 20 is supported over the entire surface, and fine communication holes are provided in the base support 31. The load applied to the base body 20 can be reduced by using the guide path through which the fluid passes. Thereby, breakage of the base 20 can be prevented, and blockage of the piping and equipment failure can be prevented.

The medium of the supercritical fluid is CO ₂ , inert gases such as Ar, H ₂ , and Xe, halogen gases such as CF ₄ , CHF ₃ , and CCl ₄ , NH ₃ , CH ₃ OH, H ₂ O, and the like The polar gas can be used.

However, particularly when a supercritical medium is not used as a reactant, CO ₂ is preferable from the viewpoints of safety, low environmental impact, cost, and solvent ability.
The critical point of CO ₂ is easy to handle because it reaches a critical temperature of 31.1 ° C. and a critical pressure of 7.382 MPa, which is in a supercritical state at a lower temperature and lower pressure than other supercritical fluids. In addition, CO ₂ is a non-toxic and non-flammable substance that also exists in the atmosphere, and does not become an environmental burden when discharged as a gas after being used as a reaction solvent.
Furthermore, compared with other thin film formation methods (evaporation method, sputtering, CVD, etc.), it is excellent in formation in the fine holes 21 due to the properties of high diffusion and zero surface tension. By applying this technology, it is possible to make ultrafine Cu wiring as an environmentally friendly organic solvent.

For the fluid, it is desirable to use an additive gas in which a reducing agent is further dissolved. By dissolving the reducing agent, the entry of fluid into the micropores is further promoted. In the present invention, although with H ₂ as the reducing agent, as the reducing agent, in addition to H _2, methanol, and the like.

The reaction pressure, is not particularly limited, (in the case of CO _2, more than 7.4 MPa) above the critical point of the medium may be a subcritical state if the ability to dissolve the starting material (ability solvent) But it doesn't matter. In the case of CO ₂ , the pressure is preferably 6 MPa or more in order to exert the solvent ability. For example, 10 to 15 MPa.

The reaction temperature may be optimized according to the type of the metal complex or reducing agent as the raw material, and is not particularly limited. For example, the melting point of the metal complex as the raw material is the lower limit, and the integrated circuit wiring process The upper limit is an allowable temperature of 400 ° C., and the temperature is determined within that range. As the temperature rises, the film thickness increases, but the depth into the hole tends to decrease and become non-uniform.

The speed of the fluid sprayed toward the substrate is not particularly limited, but if the flow rate is too slow, it is difficult to reliably feed the fluid into the fine holes. On the other hand, if the flow rate is too high, a strong pressure is applied to the substrate, which may damage the substrate.

In particular, the flow rate of CO ₂ that is a fluid medium is preferably 1.0 m1 / min or more. The flow rate of CO ₂ needs to be 1.0 m 1 / min at a minimum in order to suppress the influence of the pressure fluctuation of the pump and the pressure drop when adding low-pressure H ₂ gas.
In particular, the flow rate of CO ₂ that is a fluid medium is preferably 1 cm / min or more in terms of linear velocity. Here, the linear velocity can be obtained, for example, by dividing the volume flow rate of the liquid CO ₂ sent by the pump 6 by the cross-sectional area of the reaction vessel. In order to suppress the influence of the pressure fluctuation of the pump and the pressure drop at the time of adding the low-pressure H ₂ gas, the value is required at the minimum.

Further, the reaction time is not particularly limited, and may be appropriately determined so as to obtain a desired film thickness.

A procedure for depositing a conductive material on the inner wall of the fine hole 21 provided in the base 20 using the apparatus of the first embodiment of the present invention shown in FIG. 1 will be described.
(1) First, the substrate 20 is sealed in the reaction vessel 13, and the reaction vessel 13 is connected to the line of the apparatus. At this time, as shown in FIG. 2, the fluid F advances toward the second surface 20a of the base body 20 with the second surface 20a of the base body 20 perpendicular to the flow direction of the fluid F. As described above, the first surface 20b of the base body 20 is attached to the base body support tool 31 that supports the entire surface. The base support 31 has a fine communicating hole for the fluid F in the second space β.
(2) Next, devices other than the mantle heater 11 and the thermostat 15 are activated, and it is checked whether there is any leakage from the reaction vessel 13 with the CO ₂ cylinder 2 and the H ₂ cylinder 2 opened (leak check). ).
(3) The thermostat 15 and the mantle heater 11 are activated and heated to the set temperature.

(4) In the raw material container 8, the conductive material (Cu (divm) ₂ ) and acetone are weighed and mixed.
(5) When the temperature is stabilized at the set temperature, (4) is flowed by the raw material feed pump 9 to start measurement of the predetermined deposition time. The fluid is sprayed from the nozzle toward the second surface of the substrate.
(6) Periodically confirm whether each device is operating normally, such as whether the pressure of the H ₂ pressure regulator 3 and the raw material are reliably fed during a predetermined deposition time.

(7) When the predetermined deposition time is reached, the raw material feed pump 9 and the reducing agent H ₂ supply sequencer are stopped and the cock of the H ₂ cylinder 1 is closed. The CO ₂ liquid feed pump 6 is operated for about 30 minutes.
(8) Stop the heating of the thermostat 15 and the mantle heater 11 and naturally cool to about 50 ° C.
(9) The CO ₂ cylinder 2 is closed, and the CO ₂ in the apparatus is exhausted by the back pressure regulator 14.
(10) Remove the reaction vessel 13 from the line and turn off the power to all the devices.
(11) Finally, the substrate 20 is taken out from the reaction vessel 13.

Thus, in the first embodiment of the present invention, the second surface 20a of the base body 20 is perpendicular to the fluid flow direction, and the fluid F is directed toward the second surface 20a of the base body 20. By disposing the base body 20 so as to proceed, the fluid can be forcibly transported into the micropores 21 and the conductive material can be uniformly deposited in the micropores 21 with a uniform thickness. Is possible.

Furthermore, in the first embodiment of the present invention, the base support tool 31 has a minute communication hole through which the fluid passes into the second space β. It is considered that the differential pressure between the upper and lower surfaces increases. As a result, it is possible to deposit the conductive material in the fine holes 21 more reliably.
In addition, a fine communication hole is provided in the base support 31 and the first surface 20b of the base 20 is supported over the entire surface, whereby the load on the base 20 can be reduced. Thereby, breakage of the base 20 can be prevented, and blockage of the piping and equipment failure can be prevented.

In the first embodiment described above, the case where the supercritical fluid is used as the fluid medium has been described as an example. However, the present invention is not limited to this, and the subcritical fluid is used as the fluid medium. The same applies when used.

[Second Embodiment]
Hereinafter, a preferred embodiment of the apparatus and method of the second embodiment of the present invention will be described.

FIG. 7 is a diagram schematically illustrating a configuration example of an apparatus according to the second embodiment of the present invention.
This apparatus is a flow-type thin film deposition apparatus, and includes an H ₂ cylinder 1, a CO ₂ cylinder 2, a pressure regulator 3, a supply valve 4, a mixer 5, a liquid feed pump 6, a cooler 7, A raw material container 8, a raw material feed pump 9, a front valve 10, a mantle heater 11, a preheat pipe 12, a reaction container 13, a back pressure regulator (BPR) 14, and a constant temperature bath 15 are provided.
In this apparatus, CO ₂ at a constant pressure and flow rate is continuously supplied into the reaction vessel 13 in a supercritical state or a subcritical fluid, and a conductive material is formed on the inner wall of the fine holes provided in the substrate by the reducing agent H _2. (For example, Cu) is deposited and deposited to form a through electrode.

In the second embodiment of the present invention, the H ₂ cylinder 1 contains H ₂ gas as a reducing agent, and the H ₂ gas is introduced into the mixer 5 through the pressure regulator 3 and the supply valve 4. .
The CO ₂ cylinder 2 contains CO ₂ gas which is a medium of supercritical fluid. The CO ₂ gas is liquefied from the CO ₂ cylinder 2 by the cooler 7 and then pressurized by the liquid feed pump 8, and the mixer 5 Introduced into
H ₂ gas and CO ₂ gas are mixed by the mixer 5 and introduced into the reaction vessel 13.

In the second embodiment of the present invention, the raw material container 8 contains a metal complex of a conductive material as a raw material. In the second embodiment, the case of using bisisobutyryl methanato copper (Cu (divm) ₂ ) is described as an example, but the present invention is not limited to this.
The metal complex is introduced into the reaction vessel 13 through the raw material feed pump 9. The supply of the raw material is controlled by a front valve 10 provided close to the gas supply port of the reaction vessel.

The reaction vessel 13 is preferably composed of, for example, a pressure- and heat-resistant vessel made of stainless steel, but is not limited thereto. This reaction vessel 13 can be produced, for example, by processing an autoclave (pressure defoaming device).
A preheat pipe 12 is provided in front of the reaction vessel 13 as necessary. Further, a mantle heater 11 and a thermostatic layer 15 are provided in the preheat pipe 12 and the reaction vessel 13 so that the fluid is brought to a predetermined temperature. The temperature can be adjusted while being heated and held.
A back pressure regulator (BPR) 14 is disposed downstream of the reaction vessel 13. After the reaction is completed in the reaction vessel 13, the supercritical fluid in the reaction vessel 13 is exhausted through the back pressure regulator 14.

A substrate support is provided inside the reaction vessel 13, and the substrate is placed on the substrate support.
As the base body 20, for example, a semiconductor substrate such as silicon or a glass substrate is used. The base body 20 is provided with fine holes 21.

In the apparatus according to the second embodiment, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into the reaction vessel 13, and the fluid continuously moving in a specific direction in the reaction vessel 13. In addition, a flat substrate 20 is disposed, and a conductive substance is formed on the inner wall of the fine hole 21 provided in the substrate 20.
In the apparatus according to the second embodiment of the present invention, both sides of the base 20 are made non-parallel to the specific direction, and the base 20 is moved so that the fluid moves along both sides of the base 20. It is characterized by arranging.

Also in the second embodiment, similarly to the first embodiment, the positional relationship between the base body 20 having the fine holes 21 and the flow direction of the fluid F in the reaction vessel 13 is schematically shown using FIG. it can. Since it overlaps with description of 1st embodiment, it abbreviate | omits below.

In the second embodiment of the present invention, it is possible to deposit the conductive material uniformly in the fine holes 21 with a uniform thickness. In particular, it is preferable that the flow direction is perpendicular to the base body 20, that is, the micro holes 21 are parallel to the flow direction. Thereby, the raw material can be transported more efficiently into the micropores 21.
In addition, by arranging the base body 20 so that the fluid moves along both surfaces of the base body 20, when the microhole 21 is a through hole, the raw material can be transported from both sides of the microhole 21. The conductive material can be deposited more efficiently in the inside of 21.

Also in the second embodiment, the medium of the supercritical fluid is CO ₂ , inert gases such as Ar, H ₂ , and Xe, halogen gases such as CF ₄ , CHF ₃ , and CCl ₄ , NH ₃ , CH Polar gases such as ₃ OH and H ₂ O can be used.

It is desirable to use a fluid in which a reducing agent is further dissolved as the additive gas. By dissolving the reducing agent, the entry of fluid into the micropores is further promoted.

A procedure for depositing a conductive substance on the inner wall of the fine hole 21 provided in the substrate 20 will be described using the apparatus shown in FIG.
(1) First, the substrate 20 is sealed in the reaction vessel 13, and the reaction vessel 13 is connected to the line of the apparatus. At this time, the base body 20 is disposed so that both surfaces of the base body 20 are not parallel to the fluid flow direction and the fluid moves along both surfaces of the base body 20.
(2) Next, devices other than the mantle heater 11 and the thermostat 15 are activated, and it is checked whether there is any leakage from the reaction vessel 13 with the CO ₂ cylinder 2 and the H ₂ cylinder 2 opened (leak check). ).
(3) The thermostat 15 and the mantle heater 11 are activated and heated to the set temperature.

(4) In the raw material container 8, the conductive material (Cu (divm) ₂ ) and acetone are weighed and mixed.
(5) After stabilizing at the set temperature, (4) is flowed by the raw material feed pump 9 to start measurement of a predetermined deposition time.
(6) Periodically confirm whether each device is operating normally, such as whether the pressure of the H ₂ pressure regulator 3 and the raw material are reliably fed during a predetermined deposition time.

(7) When the predetermined deposition time is reached, the raw material feed pump 9 and the reducing agent H ₂ supply sequencer are stopped and the cock of the H ₂ cylinder 1 is closed. The CO ₂ liquid feed pump 6 was operated for about 30 minutes.
(8) Stop the heating of the thermostat 15 and the mantle heater 11 and naturally cool to about 50 ° C.
(9) The CO ₂ cylinder 2 is closed, and the CO ₂ in the apparatus is exhausted by the back pressure regulator 14.
(10) Remove the reaction vessel 13 from the line and turn off the power to all the devices.
(11) Finally, the substrate 20 is taken out from the reaction vessel 13.

As described above, in the invention of the second embodiment, the conductive material is deposited uniformly and uniformly in the micropores 21 by disposing both surfaces of the base body 20 non-parallel to the fluid flow direction. Is possible. In particular, the base 20 and the flow direction are preferably perpendicular, that is, the micro holes 21 and the flow direction are parallel. Thereby, the raw material can be transported more efficiently into the micropores 21.

In the second embodiment described above, the case where a supercritical fluid is used as a fluid medium has been described as an example. However, the present invention is not limited to this, and a subcritical fluid is used as a fluid medium. The same applies when used.

[Third embodiment]
The apparatus and method according to the third embodiment of the present invention will be described below.

The apparatus of the third embodiment can be described using the same configuration as the apparatus of FIG. 1 of the first embodiment. Below, the characteristic part of 3rd embodiment of this invention is demonstrated.

FIG. 8 is a diagram schematically showing the internal configuration of the reaction vessel 13 in the third embodiment.
A substrate support 31 is provided inside the reaction vessel 13, and the substrate 20 is placed on the substrate support 31.
As the base body 20, for example, a semiconductor substrate such as silicon or a glass substrate is used. The base body 20 is provided with a fine hole 21 penetrating from the second surface toward the first surface.

In the apparatus of the third embodiment, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into the reaction vessel 13, and the fluid that continuously moves in a specific direction in the reaction vessel 13 is contained in the fluid. In addition, a flat substrate 20 is disposed, and a conductive substance is formed on the inner wall of the fine hole 21 provided in the substrate 20.
In the apparatus of the third embodiment, the reaction vessel 13 includes a first space α into which the fluid is introduced and a second space β into which the fluid is derived, and the fluid introduced into the first space. The second surface 20a of the substrate 20 is perpendicular to the specific direction in which the substrate 20 moves, and the second surface 20a of the substrate 20 is directed from the second surface 20a toward the first surface 20b in the fine holes 21 of the substrate 20. The first surface 20b of the base is supported so that the fluid proceeds.

In the third embodiment as well, the positional relationship between the base 20 having the fine holes 21 and the flow direction of the fluid F in the reaction vessel 13 can be schematically shown using FIG. 6 as in the first embodiment. it can. Since it overlaps with description of 1st embodiment, it abbreviate | omits below.

In the third embodiment, an apparatus having the configuration shown in FIGS. 8, 10, and 11 has been devised as an apparatus capable of depositing a conductive material uniformly and uniformly in the micro holes 21. FIG.
8, 10, and 11 are all arranged so that the flow direction is perpendicular to the base body 20, that is, the fine holes 21 are parallel to the flow direction. In addition, the first surface 20b of the substrate is supported so that the fluid travels through the micro holes 21 of the substrate 20 from the second surface 20a of the substrate toward the first surface 20b. Configured. Thereby, the raw material can be transported more efficiently into the micropores 21.

Compared with the apparatus of FIG. 8 (when a pipe-shaped introduction part is connected to the reaction vessel so as to communicate with the first space α of the reaction vessel), FIG. 10 (projects into the first space α of the reaction vessel, When the introduction port is configured to be located in the vicinity of the second surface of the substrate, FIG. 11 (projects into the first space of the reaction vessel, and there are a plurality of introduction ports of the second surface of the substrate. In the case of the apparatus in the case of being arranged in the vicinity), the flow direction of the fluid with respect to the second surface of the base is more accurately perpendicular to the base 20 and the flow direction, that is, the fine holes 21 and the flow direction are more accurately. It becomes possible to guide the fluid to the inside of the micropore so that they are parallel to each other. As shown in FIG. 11 as compared with FIG. 10, it is more preferable that a plurality of fluid inlets be arranged because the induction effect is further improved. Furthermore, in the apparatus shown in FIG. 11, even when the area of the base is large and a large number of micropores are distributed on the base, the fluid is introduced uniformly into the plurality of micropores. Is also effective.

That is, in the third embodiment of the present invention, the base body 20 is arranged so that the fluid F advances toward the second surface 20a of the base body 20, so that the fluid is forcibly forced into the fine holes. Can be transported. As a result, in the third embodiment of the present invention, it is possible to deposit the conductive material uniformly and uniformly in the fine holes provided in the substrate 20.

In any of the apparatuses shown in FIGS. 8, 10, and 11, the base body 20 is attached to the base body support 31 so that the second surface 20a is perpendicular to the fluid flow direction (the spraying direction). It is attached. The first surface 20b of the base body 20 is sealed using a support member 32 made of an O-ring. The fluid F is supplied from the nozzle 33 toward the second surface 20a of the base body 20 arranged in this manner and sprayed onto the second surface 20a of the base body 20. Thereby, the fluid which goes to the 2nd space (beta) from the 1st space (alpha) can be forced to distribute | circulate the inside of a micropore, and raw material transport can be accelerated | stimulated.
Further, in order to stably support the substrate 20, the reaction vessel 13 is a vertical type as shown in FIGS. 8, 10, and 11 (in FIGS. To express). That is, in the apparatus shown in FIG. 8, FIG. 10, and FIG. 11, in the first space α and the second space β of the reaction vessel 13, the direction in which the fluid flows (solid arrow) is the direction of gravity. Has been placed.

Since the procedure for depositing the conductive material on the inner wall of the fine hole 21 provided in the substrate 20 in the third embodiment of the present invention is the same as that in the first embodiment, the description thereof is omitted.

In the third embodiment of the present invention, the second surface 20a of the base body 20 is perpendicular to the fluid flow direction, and the fluid F proceeds toward the second surface 20a of the base body 20. By disposing the base body 20 in this manner, the fluid can be forcibly transported into the micropores 21 and the conductive material can be uniformly deposited in the micropores 21 with a uniform thickness. .

In the third embodiment described above, the case where a supercritical fluid is used as a fluid medium has been described as an example. However, the present invention is not limited to this, and a subcritical fluid is used as a fluid medium. The same applies when used.

[Fourth embodiment]
The apparatus and method according to the fourth embodiment of the present invention will be described below.

The apparatus of the fourth embodiment can be described by using the apparatus of FIG. 1 of the first embodiment and the apparatus having the same configuration as that of FIGS. 8, 10 and 11 of the third embodiment. Below, the characteristic part of 4th embodiment of this invention is demonstrated.

FIG. 8 is a diagram schematically showing the internal configuration of the reaction vessel 13 in the apparatus of the present invention.
A substrate support 31 is provided inside the reaction vessel 13, and the substrate 20 is placed on the substrate support 31.
As the base body 20, for example, a semiconductor substrate such as silicon or a glass substrate is used. The base body 20 is provided with a fine hole 21 penetrating from the second surface toward the first surface.

In the apparatus of the fourth embodiment of the present invention, the reaction vessel 13 includes a first space α into which the fluid F is introduced and a second space β into which the fluid is led out, and the first space α. The second surface 20a of the base body 20 is perpendicular to a specific direction in which the fluid F introduced into the base body moves, and the fluid F advances toward the second surface 20a of the base body 20 And a base support 31 (support portion) provided to support the first surface 20b of the base body 20 and provide a guide path 34 around the base body 20 through which the fluid F passes to the second space β. It is characterized by.

In the fourth embodiment as well, the positional relationship between the base body 20 having the fine holes 21 and the flow direction of the fluid F in the reaction vessel 13 is schematically shown using FIG. 6 as in the first embodiment. it can. Since it overlaps with description of 1st embodiment, it abbreviate | omits below.

In the fourth embodiment of the present invention, an apparatus having the configuration shown in FIG. 12 has been devised as an apparatus capable of depositing a conductive material uniformly and uniformly in the micro holes 21.
Note that the fourth embodiment of the present invention will be described below with reference to FIGS. 8, 10 and 11 as in the third embodiment.
8, 10, and 11 are all arranged so that the flow direction is perpendicular to the base body 20, that is, the fine holes 21 are parallel to the flow direction. In addition to this, the first surface 20b of the substrate is supported so that the fluid travels in the micro holes 21 of the substrate 20 from the second surface 20a of the substrate toward the first surface 20b. Configured. Thereby, the raw material can be transported more efficiently into the micropores 21.

Compared with the apparatus of FIG. 8 (when a pipe-shaped introduction part is connected to the reaction vessel so as to communicate with the first space α of the reaction vessel), FIG. 10 (projects into the first space α of the reaction vessel, When the introduction port is configured to be located in the vicinity of the second surface of the substrate, FIG. 11 (projects into the first space of the reaction vessel, and there are a plurality of introduction ports of the second surface of the substrate. In the case of the apparatus in the case of being arranged in the vicinity), the flow direction of the fluid with respect to the second surface of the base is more accurately perpendicular to the base 20 and the flow direction, that is, the fine holes 21 and the flow direction are more accurately. It becomes possible to guide the fluid to the inside of the micropore so that they are parallel to each other. As shown in FIG. 11 as compared with FIG. 10, it is more preferable that a plurality of fluid inlets be arranged because the induction effect is further improved.

That is, in the fourth embodiment of the present invention, the base body 20 is arranged so that the fluid F proceeds toward the second surface 20a of the base body 20, so that the fluid is forcibly forced into the micro holes. Can be transported. As a result, in the present invention, it is possible to deposit the conductive material uniformly and uniformly in the micropores provided in the substrate 20.

In any of the devices according to the fourth embodiment of the present invention shown in FIGS. 8, 10, and 11, the base 20 has the second surface 20a perpendicular to the fluid flow direction (spraying direction). Thus, it is attached to the substrate support 31. The first surface 20b of the base body 20 is sealed using a support member 32 made of an O-ring. The fluid F is supplied from the nozzle 33 toward the second surface 20a of the base body 20 arranged in this manner and sprayed onto the second surface 20a of the base body 20. Thereby, the fluid which goes to the 2nd space (beta) from the 1st space (alpha) can be forced to distribute | circulate in a micropore, and raw material transport can be accelerated | stimulated.
Further, in order to stably support the substrate 20, the reaction vessel 13 is a vertical type as shown in FIGS. 8, 10, and 11 (in FIGS. To express). That is, in the apparatus shown in FIG. 8, FIG. 10, and FIG. 11, in the first space α and the second space β of the reaction vessel 13, the direction in which the fluid flows (solid arrow) is the direction of gravity. Has been placed.

Furthermore, in the apparatus according to the fourth embodiment of the present invention, in the base support 31 (support), a guide path through which the fluid passes is provided around the base 20 to the second space β from which the fluid F is led out. Is provided.
When the base body 20 is attached to the base body support 31 so as to be perpendicular to the flow direction of the fluid F, an O-ring 32 having a size that fits in the back surface of the base body 20 is used, and the fluid is only inside the fine holes 21. Is configured to forcibly transport the substrate 20, a load is applied to the support portion of the base 20, and the base 20 may be damaged. If broken glass flows in the line, it may cause blockage of the pipes and failure of the equipment.
Therefore, in the fourth embodiment of the present invention, as shown in FIGS. 8, 10 and 11, while supporting the back surface of the base 20, an O-ring 32 larger than the back surface is used as shown in FIG. As a result, a clearance is provided between the base body 20 and the O-ring 32 to provide a guide path 34 through which the fluid passes, thereby reducing the load on the base body 20. As a result, it is possible to prevent the base body 20 from being damaged and to prevent the blockage of the piping and the failure of the equipment.

Since the procedure for depositing the conductive material on the inner wall of the fine hole 21 provided in the substrate 20 in the fourth embodiment of the present invention is the same as that in the first embodiment, the description thereof is omitted.

In the fourth embodiment of the present invention, the second surface 20a of the base body 20 is perpendicular to the fluid flow direction, and the fluid F advances toward the second surface 20a of the base body 20. By disposing the base body 20 in this manner, the fluid can be forcibly transported into the micropores 21, and the conductive material can be uniformly deposited in the micropores 21 with a uniform thickness. .
Furthermore, in the fourth embodiment of the present invention, in the base support 31, the guide path 34 through which the fluid passes to the second space β is provided around the base 20, so that the load on the base 20 is reduced. It is possible. Thereby, breakage of the base 20 can be prevented, and blockage of the piping and equipment failure can be prevented.

In the fourth embodiment described above, the case where a supercritical fluid is used as a fluid medium has been described as an example. However, the present invention is not limited to this, and a subcritical fluid is used as a fluid medium. The same applies when used.

Examples performed to confirm the effects of the second embodiment of the present invention will be described below.
In this example, the configuration of the apparatus according to the second embodiment of the present invention was used.
Using the apparatus shown in FIG. 7, a conductive material was deposited on the inner walls of the micropores provided in the substrate. Specifically, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into a reaction vessel, and a flat substrate is arranged in the fluid that continuously moves in a specific direction in the reaction vessel. Then, a conductive substance was formed on the inner wall of the fine hole provided in the substrate.

As the fluid, a fluid in which a supercritical fluid of CO ₂ is used as a medium, Cu (divm) ₂ as a metal complex as a raw material of the conductive material, and H ₂ gas as a reducing agent is dissolved is used. Concentrations in the fluid were 2.92 × 10 ⁻² mol% (273 K) for Cu (divm) _{2 and} 1.53 mol% (273 K) for H ₂ gas.
As the substrate, a glass substrate (SiO ₂ ) having a fine hole at the center was used. The diameter of the micropore is 30 μm and the depth is 310 μm.

(First Example)
In the reaction vessel, both surfaces (upper and lower surfaces) of the substrate 20 are arranged so as to be exposed to the flow F in a direction not parallel to the flow direction of the fluid F, and a conductive substance is deposited on the inner wall of the micropore. . Here, the substrate is disposed so as to be substantially perpendicular to the fluid flow direction [arrangement of FIG. 6 (d)]. The reaction pressure was 10 MPa, the reaction temperature was 240 ° C., and the reaction time was 600 min.

(Second embodiment)
Also in this example, the configuration of the apparatus according to the second embodiment of the present invention was used.
In the reaction vessel, both surfaces (upper and lower surfaces) of the substrate 20 were arranged so as to be exposed to the flow F in parallel with the flow direction of the fluid F, and the conductive material was deposited on the inner walls of the micropores. Here, the substrate is disposed so as to be substantially perpendicular to the fluid flow direction [arrangement of FIG. 6B]. The reaction pressure was 10 MPa, the reaction temperature was 280 ° C., and the reaction time was 240 min.

(First comparative example)
In this comparative example, the configuration of the apparatus according to the second embodiment of the present invention was used.
In the reaction vessel, only the second surface (upper surface) of the substrate 20 is exposed to the flow F in parallel with the flow direction of the fluid F, and the first surface (lower surface) is disposed in contact with the inner surface of the reaction vessel 13. Then, a conductive substance was deposited on the inner wall of the micropore. The reaction pressure was 10 MPa, the reaction temperature was 280 ° C., and the reaction time was 240 min [arrangement of FIG. 6A].

The cross section of the substrate obtained as described above was observed. In addition, the film thickness of the deposited conductive material was measured.
A micrometer was used for film thickness measurement, and an optical microscope was used for observation.
The substrate was cut in half with a diamond cutter. At this time, an adhesive was applied to one surface to be cut. This is to prevent debris from entering the fine holes during cross-sectional polishing. After the adhesive was dried, the cross section was polished with sandpaper (# 1500 to # 10000) while observing with an optical microscope, and the cross section of the substrate was observed with an optical microscope.

FIG. 13 shows an optical micrograph of the cross section of the substrate of the first example, and FIG. 14 shows an optical micrograph of the cross section of the substrate of the second example. Here, a value obtained by dividing the depth at which the Cu film is formed by the diameter (30 μm) of the fine holes is referred to as an aspect ratio.

In the sample of the comparative example, the Cu film is formed in the hole of the microhole only from the second surface (upper surface) side of the substrate, but the depth of the Cu film formed from the entrance of the microhole is fine. It was about the same as the diameter of the hole (about 30 μm). Therefore, in the case of the comparative example, the aspect ratio was about 1.

On the other hand, in the first embodiment shown in FIG. 13, it can be seen that the Cu film is uniformly formed up to the center of the hole in a short deposition time of 60 minutes. It can be seen that the Cu film is formed to a sufficient thickness up to the central part of the hole with a film thickness of 2.1 μm. In the case of the first embodiment, the aspect ratio was approximately 10 (= 310/30).

Further, in the second embodiment shown in FIG. 14, the Cu film gradually becomes thinner toward the center of the hole, but it can be seen that the Cu film was formed to about 135 μm from both sides of the substrate. This is thought to be because the raw material concentration decreased as it went further and was not fully deposited.
Although the film thickness was not uniform at 5.6 μm on the substrate surface and 1.4 μm at the center of the hole, it can be seen that the Cu film can be sufficiently formed in the fine holes as compared with the first comparative example. In the case of the second embodiment, the aspect ratio was about 4 to 5 (= 135/30).

From the above results, by disposing the both surfaces (upper and lower surfaces) of the base body 20 so as to be exposed to the flow F in parallel or non-parallel to the flow direction of the fluid F, the conductive substance can reach the inside of the micropores. It became clear that it could be deposited. In particular, it has been confirmed that by arranging the base so as to be non-parallel to the fluid flow direction, it is possible to deposit the conductive material uniformly and uniformly to the inside of the micropores. It was.
This is probably because the fluid was transported to the micropores by both “flow” and “diffusion”, and the raw material could be transported more efficiently into the micropores.
In addition, by arranging the base so that the fluid moves along both sides of the base, the raw material can be transported from both sides of the micropore, and the conductive material is deposited more efficiently inside the micropore. I was able to.

(Third embodiment)
In this example, the configuration of the apparatus according to the third embodiment of the present invention was used.
Using the apparatus shown in FIG. 1, a conductive material was deposited on the inner walls of the micropores provided in the substrate. Specifically, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into a reaction vessel, and a flat substrate is arranged in the fluid that continuously moves in a specific direction in the reaction vessel. Then, a conductive substance was formed on the inner wall of the fine hole provided in the substrate.

As the fluid, a supercritical fluid of CO ₂ was used as a medium, a metal complex (Cu (divm) ₂ ) serving as a raw material for the conductive material, and a fluid obtained by dissolving H ₂ gas as a reducing agent were used. The metal complex is dissolved at a ratio of 500/25 using acetone as an auxiliary solvent.
Concentrations in the fluid were 2.92 × 10 ⁻² mol% (273 K) for (Cu (divm) ₂ ) and 1.53 mol% (273 K) for H ₂ gas.
As shown in FIG. 15, a glass substrate (SiO ₂ ) having a fine hole vertically penetrating between both main surfaces of the substrate and having a plate thickness of 0.75 mm (750 μm) is used as the substrate. Using. The diameter of the micropore is 25 μm.

In the reaction vessel, the substrate was disposed so as to be perpendicular to the fluid flow direction, and the lower surface of the substrate was sealed using a support member made of an O-ring. A fluid was sprayed from the nozzle toward the second surface of the substrate to deposit a conductive substance on the inner wall of the fine hole.
The total reaction pressure was 10 MPa (of which H ₂ gas pressure was 1 MPa), the reaction temperature was 280 ° C., the CO ₂ flow rate was 7.0 m 1 / min, and the reaction time was 60 min.

(Second comparative example)
In this comparative example, the configuration of the apparatus according to the third embodiment of the present invention was used.
The specification of the reaction vessel and the specification of the substrate were changed as follows, and a conductive substance was deposited on the inner wall of the fine hole.
As the reaction vessel, the one shown in FIG. 8 was used.
In the reaction vessel, both surfaces (upper and lower surfaces) of the substrate 20 are arranged so as to be exposed to the flow F in a direction not parallel to the flow direction of the fluid F, and a conductive substance is deposited on the inner wall of the micropore. . Here, the substrate is disposed so as to be substantially perpendicular to the fluid flow direction [arrangement of FIG. 6 (d)]. The reaction pressure was 10 MPa, the reaction temperature was 240 ° C., and the reaction time was 600 min.
The substrate used was a glass substrate (SiO ₂ ) having a fine hole penetrating perpendicularly between both main surfaces of the substrate at the center and having a plate thickness of 0.30 mm (300 μm). The diameter of the micropore is 30 μm.

The cross section of the substrate obtained as described above was observed. An optical microscope was used for observation.
The substrate was cut in half with a diamond cutter. At this time, an adhesive was applied to one surface to be cut. This is to prevent debris from entering the fine holes during cross-sectional polishing. After the adhesive was dried, the cross section was polished with a sandpaper (# 1500 to 10000) while observing with a microscope, and the cross section of the substrate was observed with an optical microscope.

FIG. 15 is a cross-sectional view of the substrate showing a state in which a conductive material is deposited in the fine holes according to the third embodiment. In FIG. 15, the upper side is the second surface of the substrate (fluid inlet side), and the lower side is the first surface of the substrate (fluid outlet side). As is clear from FIG. 15, the conductive material was deposited almost uniformly on the inner wall of the fine hole having a pore diameter of 25 μm up to a depth of 80% when viewed from the inlet side. The remaining 20% tended to become thinner toward the outlet side. From this result, it was succeeded in covering 80% of the total length with respect to the fine holes having an aspect ratio (hole depth (full length) / hole diameter) of 30.

Under the conditions of the second comparative example, it was found that the conductive material was uniformly deposited with a uniform thickness over the entire length direction of the fine holes. When the plate thickness is 0.30 mm (300 μm) on a glass substrate (SiO ₂ ) and the micropore diameter is 30 μm, the conductive material forming apparatus according to the present invention (FIGS. 8, 10 and 11) is used. Even without this, it was confirmed that the conductive material could be reliably formed on the inner wall of the micropore.

In the configuration of the apparatus according to the third embodiment of the present invention, the following points were clarified from the above-described examples and comparative examples.
(1) When the pore diameter is about 25-30 μm, the substrate is arranged so as to be perpendicular to the fluid flow direction, so that the inside of the micropore is uniform and uniformly conductive. It is possible to deposit material.
(2) Device configuration in which the first space α located on the fluid inlet side is higher than the second space β located on the fluid outlet side with respect to the micropores of the substrate (FIGS. 8, 10, By adopting 11), even in a substrate having a fine hole with an aspect of 30, it is possible to deposit a conductive material uniformly and uniformly to the inside of the fine hole.
(3) With the apparatus configuration shown in FIGS. 8, 10 and 11, even in the case of a fine hole having a hole diameter of 10 μm, if the fine hole extends perpendicularly from the second surface of the substrate, the thickness is uniform over the entire region. The conductive material can be uniformly deposited.

From the above results, according to the third embodiment of the present invention, the second surface of the base body is perpendicular to the specific direction in which the fluid introduced into the first space moves, and By supporting the first surface of the substrate so that the fluid proceeds in the micropores of the substrate from the second surface to the first surface, the inside of the micropores with an aspect ratio of 30 It was confirmed that the conductive material can be uniformly deposited with a uniform thickness.
By adopting a device configuration in which the second surface side of the substrate has a higher pressure than the first surface side of the substrate, the effect of forcibly transporting the fluid into the micropores is improved, and the fineness of the aspect ratio is high. Conductive material could be deposited efficiently inside the hole.

The fluid introduction part protrudes into the first space of the reaction vessel, and the introduction port is located in the vicinity of the second surface of the base, or in the first space of the reaction vessel. By adopting the configuration so that the plurality of inlets are positioned in the vicinity of the second surface of the base body, the above-described functions and effects are further enhanced. For example, in the case of the former configuration, it is preferable to dispose the fluid introduction portion at a position aimed at the entrance of the micropore because the amount of inflow that the fluid is forced to transport into the micropore can be increased. On the other hand, the latter configuration is effective when the substrate is applied to a substrate having a large area and a plurality of fine holes. According to the shape and area of the substrate, the fluid can be forcibly transported into each micropore evenly with respect to the plurality of micropores.

As mentioned above, although the apparatus and method of 3rd embodiment of this invention were demonstrated, this invention is not limited to this, In the range which does not deviate from the meaning of invention, it can change suitably. In addition, the third embodiment of the present invention has the purpose of “a conductive material into a micropore in which a conductive material can be deposited uniformly and uniformly in a micropore provided in a substrate. However, the conductive material may be deposited on the surface of the substrate as well as the conductive material is deposited in the micropores.

(Fourth embodiment)
In this example, the configuration of the apparatus according to the fourth embodiment of the present invention was used.
Using the apparatus shown in FIG. 1, a conductive material was deposited on the inner walls of the micropores provided in the substrate. Specifically, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into a reaction vessel, and a flat substrate is arranged in the fluid that continuously moves in a specific direction in the reaction vessel. Then, a conductive substance was formed on the inner wall of the fine hole provided in the substrate. As a result, the fluid traveling from the first space α to the second space β passes through the microscopic holes provided in the base body, and a gap (guide path) provided between the base body and the support member made of the O-ring is also provided. It was configured to pass.

As the fluid, a supercritical fluid of CO ₂ was used as a medium, a metal complex (Cu (divm) ₂ ) serving as a raw material for the conductive material, and a fluid obtained by dissolving H ₂ gas as a reducing agent were used. The metal complex is dissolved at a ratio of 500/25 using acetone as an auxiliary solvent.
Concentrations in the fluid were 2.92 × 10 ⁻² mol% (273 K) for (Cu (divm) ₂ ) and 1.53 mol% (273 K) for H ₂ gas.
As shown in FIG. 7, a glass substrate (SiO ₂ ) having a fine hole penetrating vertically between both main surfaces of the substrate and having a plate thickness of 1.0 mm (1000 μm) is used as the substrate. Using. The diameter of the micropore is 20 μm.

In the reaction vessel, the substrate was disposed so as to be perpendicular to the fluid flow direction, and the lower surface of the substrate was sealed using a support member made of an O-ring. A fluid was sprayed from the nozzle toward the second surface of the substrate to deposit a conductive substance on the inner wall of the fine hole.
The reaction pressure was 10 MPa (of which the H ₂ gas pressure was 1 MPa), the reaction temperature was 200 ° C., the CO ₂ flow rate was 2.0 m 1 / min, and the reaction time was 60 minutes.

(Fifth embodiment)
In this example, the configuration of the apparatus according to the fourth embodiment of the present invention was used.
A conductive material was deposited on the inner walls of the micropores under the same production conditions as in the fourth example except that the substrate was changed to the specifications described below.
In this example, as a substrate, a glass substrate (SiO ₂ ) having a plurality of fine holes (reference symbols a to g) bent inside the substrate as shown in FIG. 17 and having a plate thickness of 0.30 mm (300 μm). ) Was used. The diameter of the micropore is 10 μm. Each micropore is composed of two parts extending perpendicularly from both main surfaces of the substrate and a part connected to the two parts and extending in parallel with both main surfaces of the substrate, and the length of the latter is 1.7 mm. . In other words, this fine hole has two bent portions (cranks).

(Third comparative example)
In this comparative example, the configuration of the apparatus according to the fourth embodiment of the present invention was used.
The specification of the reaction vessel was changed as follows, and a conductive substance was deposited on the inner wall of the micropore.
As the reaction vessel, the same reaction vessel as in the fourth example was used except that an O-ring smaller than the substrate was used in the configuration shown in FIG. The same substrate as in the fourth example was used.
That is, by configuring the first surface 20b side of the base body 20 to be supported by the O-ring 32, the fluid that travels from the first space α to the second space β passes only through the micro holes provided in the base body. It was.

(Fourth comparative example)
In this comparative example, the configuration of the apparatus according to the fourth embodiment of the present invention was used.
The specification of the reaction vessel and the specification of the substrate were changed as follows, and a conductive substance was deposited on the inner wall of the fine hole.
As the reaction vessel, the same reaction vessel as in the fourth example was used except that an O-ring smaller than the substrate was used in the configuration shown in FIG. That is, by configuring the first surface 20b side of the base body 20 to be supported by the O-ring 32, the fluid traveling from the first space α to the second space β passes only through the micro holes provided in the base body. It was.
As the substrate, the same one as in the fifth example was used. That is, as shown in FIG. 17, a glass substrate (SiO ₂ ) having a plurality of fine holes (reference symbols a to g) provided inside the substrate and having a plate thickness of 0.30 mm (300 μm) was used.

FIG. 16 is a cross-sectional view of the substrate showing a state in which a conductive substance is deposited in the fine holes according to the fourth embodiment. In FIG. 16, the upper side is the second surface (fluid inlet side) of the substrate, and the lower side is the first surface (fluid outlet side) of the substrate. As is clear from FIG. 16, the conductive material was deposited in a uniform thickness almost uniformly up to a depth of 80% when viewed from the inlet side with respect to the inner wall of the fine hole having a hole diameter of 20 μm. The remaining 20% tended to become thinner toward the outlet side. From this result, it succeeded in covering about 80% of the total length with respect to the fine hole having the aspect ratio (hole depth (full length) / hole diameter) of 50.

In the fifth example, with respect to the substrate shown in FIG. 17, the conductive material was deposited almost uniformly on the micropores extending vertically from the second surface (fluid inlet side) of the substrate. Furthermore, the portion extending in parallel with both main surfaces of the substrate located at the tip of the vertically extending fine hole portion (that is, beyond the first bent portion (crank portion)) is electrically conductive over the entire area. The material was deposited almost uniformly. However, there is a slight amount of conductive material in the vertically extending micropores located on the other surface (fluid outlet side) of the substrate (beyond the second bend (crank)). It was confirmed that it was in an attached state.

Under the conditions of the third comparative example, the conductive material could be deposited only up to about half the depth when viewed from the entrance of the micropore.

Under the conditions of the fourth comparative example, the conductive material could be deposited only near the entrance of the micropores, that is, to the same depth as the pore diameter.

The following points were clarified from the results of the examples and the comparative examples using the apparatus of the fourth embodiment of the present invention described above.
(1) When the hole diameter of the micropore is about 20 μm, the base is arranged so as to be perpendicular to the fluid flow direction, and the first space located on the fluid inlet side with respect to the micropore of the base By adopting an apparatus configuration in which α is higher than the second space β located on the fluid outlet side (FIGS. 8, 10, and 11), even in a substrate having a fine hole with an aspect of 50, It is possible to deposit the conductive material uniformly and uniformly to the inside of the hole.
(2) In the case of a fine hole that changes the longitudinal direction inside the substrate, if there is only one bent part (crank part), the fine hole extends to the area beyond the bent part (crank part). Fluid can be poured into the interior. If there are two or more bent portions (crank portions), the method according to the present invention has a limit.
(3) With the apparatus configuration shown in FIGS. 8, 10, and 11, even in the case of a fine hole having a hole diameter of 10 μm, if the fine hole extends perpendicularly from the second surface of the substrate, the thickness is uniform over the entire region. In this way, a conductive material can be deposited. Further, the device configuration shown in FIGS. 8, 10 and 11 has a thickness of up to a region beyond the bent portion (crank portion) following the vertically extending micro hole, even if the hole diameter is 10 μm. It has the ability to deposit a conductive material uniformly and uniformly.

From the above results, according to the fourth embodiment of the present invention, the second surface of the base body is perpendicular to the specific direction in which the fluid introduced into the first space moves, and By supporting the first surface of the substrate so that the fluid proceeds in the micropores of the substrate from the second surface to the first surface, the inside of the micropores having an aspect ratio of 50 It was confirmed that the conductive material can be uniformly deposited with a uniform thickness. Further, it has been found that even when a bent portion (crank portion) exists in the fine hole, the conductive material can be deposited up to a region beyond the bent portion (crank portion).
In addition, according to the fourth embodiment of the present invention, the second surface side of the base is set to a pressure higher than that of the first surface of the base, and the fluid from the first space α to the second space β is provided on the base. By adopting a configuration that passes through the fine holes and also passes through the gap (guide path) provided between the base and the support member consisting of the O-ring, the base is supported and the base is damaged. In addition, the problem that the broken base body flows into the line and the piping is blocked or the equipment breaks down has been solved.

Examples performed to confirm the effects of the first embodiment of the present invention will be described below.
In the following examples, the configuration of the apparatus according to the first embodiment of the present invention was used.
<Sixth embodiment>
In this example, the configuration of the apparatus according to the first embodiment of the present invention was used.
Using the apparatus shown in FIGS. 1 and 2, a conductive substance was deposited on the inner walls of the micropores provided in the substrate. Specifically, a fluid obtained by dissolving a metal complex in a supercritical fluid is introduced into a reaction vessel, and a flat substrate is arranged in the fluid that continuously moves in a specific direction in the reaction vessel. Then, a conductive substance was formed on the inner wall of the fine hole provided in the substrate. As a result, the fluid traveling from the first space α to the second space β passes through the micro holes provided in the base body from the second surface side of the base body, and is finely contained in the support member on which the base body is placed. It was set as the structure supplied to the inside of a fine hole also from the 1st surface side of a base | substrate through a communicating hole.

As the fluid, a supercritical fluid of CO ₂ was used as a medium, a metal complex (Cu (divm) ₂ ) serving as a raw material for the conductive material, and a fluid obtained by dissolving H ₂ gas as a reducing agent were used. The metal complex is dissolved at a ratio of 500/25 using acetone as an auxiliary solvent.
Concentrations in the fluid were 2.92 × 10 ⁻² mol% (273 K) for (Cu (divm) ₂ ) and 1.53 mol% (273 K) for H ₂ gas.
As shown in FIG. 18, a glass substrate (SiO ₂ ) having a fine hole penetrating perpendicularly between both main surfaces of the substrate and having a plate thickness of 1.0 mm (1000 μm) is used as the substrate. Using. The diameter of the micropore is 20 μm.

In the reaction vessel, the substrate is arranged so as to be perpendicular to the fluid flow direction, and a substrate holder (support member) 40 for holding the substrate is disposed and sealed over the entire lower surface of the substrate. .
As a substrate holder (support member) 40 for holding the substrate, a glass filter (GF / A) having a communication hole 41 was used. GF / A is the most efficient general purpose filter paper that is most widely used for filtration of denatured proteins, and is also used for air pollution analysis. The size of GF / A is 4.7 cm, the particle retention capacity is 1.6 μm, the load is strong, and the filtration rate (fast basis weight) is 53 g / m ² .
A fluid was sprayed from the nozzle toward the second surface of the substrate to deposit a conductive substance on the inner wall of the fine hole. The reaction pressure was 10 MPa (of which the H ₂ gas pressure was 1 MPa), the reaction temperature was 200 ° C., the CO ₂ flow rate was 2.0 ml / min, and the reaction time was 60 min.

<Seventh embodiment>
In this example, the configuration of the apparatus according to the first embodiment of the present invention was used.
A conductive substance was deposited on the inner wall of the fine hole under the same production conditions as in the sixth example except that the substrate was changed to the specification described below.
In this example, as a substrate, a glass substrate (SiO ₂ ) having a plurality of fine holes (reference symbols a to g) bent inside the substrate as shown in FIG. 17 and having a plate thickness of 0.30 mm (300 μm). ) Was used. The diameter of the micropore is 10 μm. Each micropore is composed of two parts extending perpendicularly from both main surfaces of the substrate and a part connected to the two parts and extending in parallel with both main surfaces of the substrate, and the length of the latter is 1.7 mm. . In other words, this fine hole has two bent portions (cranks).

(Fifth comparative example)
In this comparative example, the configuration of the apparatus according to the first embodiment of the present invention was used.
Similar to the third comparative example, the specification of the reaction vessel was changed as follows, and a conductive substance was deposited on the inner wall of the micropore.
As the reaction vessel, the same reaction vessel as in the sixth example was used except that an O-ring smaller than the substrate was used in the configuration shown in FIG. The same substrate as in the sixth example was used. That is, by configuring the first surface 20b side of the base body 20 to be supported by the O-ring 32, the fluid traveling from the first space α to the second space β passes only through the micro holes provided in the base body. It was.

(Sixth comparative example)
In this comparative example, the configuration of the apparatus according to the first embodiment of the present invention was used.
As in the fourth comparative example, the specification of the reaction vessel and the specification of the substrate were changed as follows, and a conductive substance was deposited on the inner wall of the micropore.
As the reaction vessel, the same reaction vessel as in the fourth example was used except that an O-ring smaller than the substrate was used in the configuration shown in FIG. That is, by configuring the first surface 20b side of the base body 20 to be supported by the O-ring 32, the fluid traveling from the first space α to the second space β passes only through the micro holes provided in the base body. It was.
As the substrate, the same one as in the fifth example was used. That is, as shown in FIG. 17, a glass substrate (SiO ₂ ) having a plurality of fine holes (reference symbols a to g) provided inside the substrate and having a plate thickness of 0.30 mm (300 μm) was used.

FIG. 18 is a cross-sectional view of the substrate showing a state in which a conductive substance is deposited in the fine holes according to the sixth embodiment. In FIG. 18, the upper side is the second surface (fluid inlet side) of the substrate, and the lower side is the first surface (fluid outlet side) of the substrate. As is clear from FIG. 18, the conductive material was deposited almost uniformly on the inner wall of the fine hole having a hole diameter of 15 μm to a depth of 85% when viewed from the inlet side. The remaining 20% tended to become thinner toward the outlet side. From this result, it has succeeded in covering about 85% of the total length with respect to the fine holes having an aspect ratio (hole depth (full length) / hole diameter) of 100.

In the seventh example, with respect to the substrate shown in FIG. 17, the conductive material was deposited almost uniformly on the micropores extending vertically from the second surface (fluid inlet side) of the substrate. Furthermore, the portion extending in parallel with both main surfaces of the substrate located at the tip of the vertically extending fine hole portion (that is, beyond the first bent portion (crank portion)) is electrically conductive over the entire area. The material was deposited almost uniformly. In addition to this, the conductive material is also applied to the portion of the fine hole extending vertically (located beyond the second bent portion (crank portion)) located on the other surface (fluid outlet side) of the substrate. Was confirmed to be deposited almost uniformly.

In the condition of the fifth comparative example, the conductive material could be deposited only up to about half the depth when viewed from the entrance of the micropore.

Under the conditions of the sixth comparative example, the conductive material could be deposited only near the entrance of the micropores, that is, up to the same depth as the pore diameter.

From the comparison between the example and the comparative example using the configuration of the apparatus of the first embodiment of the present invention described above, the following points became clear.
(1) When the hole diameter of the micropore is about 15 μm, the base is arranged so as to be perpendicular to the fluid flow direction, and the first space located on the fluid inlet side with respect to the micropore of the base By adopting an apparatus configuration in which α is higher than the second space β located on the fluid outlet side (FIGS. 2, 4, and 5), even in a substrate having a fine hole with an aspect of 100, It is possible to deposit the conductive material uniformly and uniformly to the inside of the hole.
(2) In the case of a fine hole that changes the longitudinal direction inside the substrate, if there is only one bent part (crank part), the fine hole extends to the area beyond the bent part (crank part). Fluid can be poured into the interior. Even if there are two or more bent portions (crank portions), according to the method according to the present invention, it is possible to cause the fluid to travel over the entire region in the longitudinal direction of the fine holes.
(3) With the device configuration shown in FIGS. 2, 4 and 5, even in the case of a fine hole having a hole diameter of 10 μm, the fine hole extending vertically is not limited to the fine hole extending vertically from the second surface of the substrate. It has the ability to deposit a conductive material uniformly and uniformly to a region beyond the subsequent bent portion (crank portion) and further to a region reaching the first surface side of the substrate.

From the above results, according to the first embodiment of the present invention, the second surface of the base body is perpendicular to the specific direction in which the fluid introduced into the first space moves, and By supporting the first surface of the substrate so that the fluid proceeds in the micropores of the substrate from the second surface toward the first surface, the inside of the micropores having an aspect ratio of 100 It was confirmed that the conductive material can be uniformly deposited with a uniform thickness. In addition, even if a bent portion (crank portion) exists in the minute hole, the conductive material is applied to the region beyond the bent portion (crank portion) and further to the region reaching the first surface side of the substrate. It has been found that it can be deposited.
Further, according to the first embodiment of the present invention, the base is provided with a fluid from the first space α to the second space β with the second surface side of the base being at a higher pressure than the first surface side of the base. The substrate is supported by adopting a structure that passes through the minute holes and is also supplied from the first surface side of the substrate through the minute communication holes incorporated in the support member on which the substrate is placed. The problem that the load was applied to the location, the base was damaged, the broken base flowed into the line and the piping was blocked, or the equipment failed was also solved.

The apparatus and method of the present invention have been described above, but the present invention is not limited to this and can be appropriately changed without departing from the spirit of the invention.

The present invention can be widely applied to an apparatus and a method for forming a conductive material on the inner wall of a fine hole provided in a substrate using a fluid obtained by dissolving a metal complex in a supercritical fluid. In addition, the conductive substance formed in the fine hole using the method of the present invention can be used as the through wiring.

1 H ₂ cylinder, 2 CO ₂ cylinder, 3 pressure regulator, 4 supply valve, 5 mixer, 6 feed pump, 7 cooler, 8 feed container, 9 feed pump, 10 front valve, 11 mantle heater, 12 Preheat piping, 13 reaction vessel, 14 back pressure regulator (BPR), 15 thermostatic bath, 20 substrate, 21 micropores, 31 substrate support (support), 32 O-ring (support member), 33 nozzle (introduction of fluid) Part), 34 guide path, 40 substrate support (support member), 41 communicating hole, α first space, β second space.

Claims

A conductive material forming apparatus comprising:
A reaction vessel comprising a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived;
A flat substrate disposed in the fluid that continuously moves in a specific direction in the reaction vessel and having a first surface, a second surface, and micropores;
The substrate so that the second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the first space moves and from the second surface of the substrate toward the first surface A support member having a fine communication hole that supports the first surface of the substrate over the entire surface so that the fluid travels in the fine holes, and the fluid passes through the second space;
An apparatus for forming a conductive substance, comprising:
Providing an inlet for projecting into the first space of the reaction vessel and configured to be located in the vicinity of the second surface of the substrate, and for introducing the fluid into the reaction vessel. The apparatus for forming a conductive material according to claim 1.
A plurality of inlets configured to project into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the substrate, and to introduce an introduction portion for introducing the fluid into the reaction vessel The conductive material forming apparatus according to claim 1, further comprising:
A method of forming a conductive material, comprising:
A reaction vessel comprising a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is led out, and continuous identification in the reaction vessel Preparing a flat substrate having a first surface and a second surface and a fine hole disposed in the fluid moving in the direction of, and a support member for supporting the first surface of the substrate;
The second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the first space moves, and from the second surface of the substrate toward the first surface. The support member is arranged so that the fluid travels in the micropores of the base;
Moving the fluid from the first space to the second space;
A method for forming a conductive material, comprising: forming a conductive material on an inner wall of the fine hole provided in the base.
The method for forming a conductive substance according to claim 4, wherein a semiconductor substrate or a glass substrate is used as the substrate.
6. The method for forming a conductive substance according to claim 4, wherein a reducing agent is dissolved in the fluid.
A conductive material forming apparatus comprising:
A reaction vessel into which a fluid obtained by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced;
A flat substrate disposed in the fluid that continuously moves in a specific direction in the reaction vessel and having micropores;
With
An apparatus for forming a conductive substance, wherein the substrate is arranged so that the fluid moves along both surfaces of the substrate.
8. The conductive substance forming apparatus according to claim 7, wherein the base is disposed so that both surfaces of the base are parallel to the specific direction.
8. The conductive substance forming apparatus according to claim 7, wherein the base is disposed so that both surfaces of the base are non-parallel to the specific direction.
10. The apparatus according to claim 7, further comprising: a holding unit that holds an angle formed by both surfaces of the base with respect to the specific direction and is provided inside the reaction vessel. Conductive substance forming device.
A method for forming a conductive material, comprising:
A reaction vessel into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced; and a flat plate disposed in the fluid that continuously moves in a specific direction in the reaction vessel. Prepare the substrate and
Moving the fluid along both sides of the substrate;
A method for forming a conductive material, comprising: forming a conductive material on an inner wall of the fine hole provided in the base.
The method for forming a conductive substance according to claim 11, wherein a semiconductor substrate or a glass substrate is used as the substrate.
The method for forming a conductive substance according to claim 11 or 12, wherein a reducing agent is dissolved in the fluid.
A conductive material forming apparatus comprising:
A reaction vessel comprising a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived;
A flat substrate disposed in the fluid that continuously moves in a specific direction in the reaction vessel and having a first surface, a second surface, and micropores;
The substrate so that the second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the first space moves and from the second surface of the substrate toward the first surface A support member for supporting the first surface of the base so that the fluid travels in the micropores of
An apparatus for forming a conductive substance, comprising:
Providing an inlet for projecting into the first space of the reaction vessel and configured to be located in the vicinity of the second surface of the substrate, and for introducing the fluid into the reaction vessel. The apparatus for forming a conductive material according to claim 14.
A plurality of inlets configured to project into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the substrate, and to introduce an introduction portion for introducing the fluid into the reaction vessel 15. The conductive material forming apparatus according to claim 14, further comprising:
A conductive material forming apparatus comprising:
A reaction vessel comprising a first space into which a fluid formed by dissolving at least a metal complex in a supercritical fluid or a subcritical fluid is introduced, and a second space from which the fluid is derived;
A flat substrate disposed in the fluid that continuously moves in a specific direction in the reaction vessel and having a first surface, a second surface, and micropores;
The second surface of the substrate is perpendicular to the specific direction in which the fluid introduced into the first space moves, and from the second surface of the substrate toward the first surface, Supporting the first surface of the base so that the fluid travels in the micropores of the base, and passing the fluid to the second space and having a guide path provided around the base A member,
An apparatus for forming a conductive substance, comprising:
Providing an inlet for projecting into the first space of the reaction vessel and configured to be located in the vicinity of the second surface of the substrate, and for introducing the fluid into the reaction vessel. The conductive material forming apparatus according to claim 17.
A plurality of inlets configured to project into the first space of the reaction vessel and to be positioned in the vicinity of the second surface of the substrate, and to introduce an introduction portion for introducing the fluid into the reaction vessel The conductive material forming apparatus according to claim 17, further comprising: