JP2014110258A - Method of manufacturing substrate with electrode and substrate with electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a substrate with high density electrodes capable of forming high density electrodes rapidly in a short period of time.SOLUTION: The method of manufacturing a substrate with electrodes includes: forming a metal seed film on a substrate; forming a resist film on the metal seed film; forming resist holes that penetrate the resist film; and depositing metallic fine particles whose average particle size is in a range of 1 to 50 nm into the resist holes by an electrophoresis method.

Description

  The present invention relates to a method for producing a substrate with a high-density electrode capable of forming a high-density electrode quickly (in a short time) and a substrate with a high-density electrode obtained by the method.

  A three-dimensional mounting technique using a through silicon via (TSV) is attracting attention because it can realize a highly integrated circuit (LSI) that is small, capable of high-speed, low-power computing.

For example, a method is disclosed in which a metal plating is applied to a through hole provided in an insulating substrate, a resin or a conductive paste is filled, and then a plated layer is formed so as to close the opening of the through hole. (Patent Document 1: Japanese Patent Laid-Open No. 2003-23251)
However, in the above-described method, the thermal contraction rate and thermal expansion rate of the resin or conductive resin paste are significantly different from those of the insulating substrate, and the resin layer is peeled off from the through hole or a void is generated, so there is a concern about the reliability of the wiring substrate. .

Therefore, a method of forming a base conductive layer on one surface of a core substrate having a through hole in order to suppress the peeling and voids, and then growing the base conductive layer by electrolytic plating to fill the through hole with the conductive material. Is disclosed. (Patent Document 2: JP 2006-147971 A)
However, in the above method, when the conductive material is filled in the through hole by electrolytic plating, there is an excess conductive material on the surface of the conductive material filled through hole substrate, which is removed by polishing or the like and removed. It is pointed out that it is necessary to remove the conductive material fine powder generated by the above.

Therefore, a resist having a through hole having a concentric axis with the through hole formed in the insulating substrate on the surface of at least one of the insulating substrate in which the through hole is formed, and having a smaller hole diameter than the through hole. A method for manufacturing a wiring substrate is disclosed in which a film is formed, a conductive material is filled in the through hole by electrolytic plating of copper, and then the resist film is removed. (Patent Document 3: JP 2012-80002 A)
On the other hand, since the metal deposition rate by plating treatment is slow and the productivity is poor, heat treatment is performed by attaching nano metal particles such as silver, gold, copper, etc. to the wall surface of the depression or the side wall of the through hole by the dispensing method or the ink jet method. A substrate with a through electrode in which a through electrode as a metal film is formed, a manufacturing method thereof, and a light emitting device using the substrate with a through electrode are disclosed. (Patent Document 4: JP 2010-123606 A)

JP 2003-23251 A JP 2006-147971 A JP 2012-80002 A JP 2010-123606 A

However, in the above-described conventional technology, in the Via first, Via middle, or Via last process, a plating technique such as copper is being used as a method for embedding a metal in the through silicon via (TSV). Since it is slow, it takes a long time to completely embed the TSV. For example, it has been reported that it takes 5 hours at an average current density of 1 A / cm ^2. Therefore, it is an obstacle to the practical use and spread of TSV.

  Also, when forming metal electrodes with nano metal particles by the dispensing method or ink jet method, since a solvent dispersion of nano metal particles is used, it is not possible to form electrodes precisely in the through-holes with a single application, and repeated application is required. In addition, a solvent removal process is required, and the packing density of the electrodes may be non-uniform. In addition, there is a limit to increasing the number of electrodes per unit area, and small, high-speed, low-power computing However, there has been a limit to three-dimensional mounting of integrated circuits (LSIs) that can be used.

  As a result of intensive studies on the above-mentioned problems, the present inventors have been able to easily deposit in Via by adopting an electrophoretic method using ultrafine metal colloidal particles, and have a high density in an extremely short time. The inventors have found that an electrode can be formed and have completed the present invention.

An object of this invention is to provide the manufacturing method of the board | substrate with a high-density electrode which can form a high-density electrode rapidly (short time), and a high-density board | substrate with an electrode.
[1] After forming a metal seed film on the substrate, forming a resist film on the metal seed film, and then forming a resist hole penetrating the resist film, the average particle diameter is in the range of 1 to 50 nm A method for manufacturing a substrate with an electrode, in which metal fine particles in the above are deposited in resist holes by electrophoresis.
[2] The diameter is in the range of 0.05 to 50 μm, the depth from the resist film surface is in the range of 1 to 100 μm, and the substrate unit surface is in the range of 1 to 64,000,000 pieces / mm ^2. [1] The method for manufacturing a substrate with an electrode according to [1].
[3] After forming a resist film on the substrate, a resist hole penetrating the resist film and a through hole penetrating the base material or a deep hole drilled into the base material are integrally formed, and then a metal seed film And then depositing metal fine particles having an average particle diameter in the range of 1 to 50 nm in at least through holes or deep holes by electrophoresis.
[4] The diameter is in the range of 0.05 to 50 μm, the depth from the resist film surface is in the range of 1 to 100 μm, and the density of through holes or deep holes in the substrate unit surface is 1 to 64,000, [3] The method for producing a substrate with an electrode according to [3], wherein the resist hole and the through hole or the deep hole are integrally formed so as to be in a range of 000 pieces / mm ² .
[5] The metal fine particles having a zeta potential in the range of −80 to −20 mV are used [1]
The manufacturing method of a substrate with electrodes of [4].
[6] The method for producing a substrate with an electrode according to [1] to [5], wherein the metal fine particles are fine particles containing at least one metal selected from silver, copper, gold, platinum, palladium, ruthenium, manganese and nickel.
[7] The method for producing a substrate with an electrode according to [1], wherein metal fine particles are deposited by electrophoresis in a current range of 0.1 to 100 mA / cm ² and a voltage range of 1 to 100V.
[8] A substrate, a metal seed film on the substrate, a resist film on the metal seed film, and an electrode, the electrode being cylindrical and having a diameter in the range of 0.05 to 50 μm and a height In which metal fine particles having an average particle diameter in the range of 1 to 50 nm are deposited by electrophoretic method in a range of 1 to 100 μm, an electrode density in the range of 1 to 64,000,000 pieces / mm ² A substrate with electrodes.
[9] The substrate with an electrode according to [8], wherein the metal fine particles are fine particles containing at least one metal selected from silver, copper, gold, platinum, palladium, ruthenium, manganese and nickel.
[10] The substrate with an electrode according to [8] or [9], wherein a through hole or a deep hole is formed in the substrate, and the electrode is formed in the through hole or the deep hole.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the board | substrate with a high density electrode which can form a high density electrode rapidly (short time), and a high density board | substrate with an electrode can be provided.
Moreover, it is excellent in productivity and production efficiency compared with the metal plating method and the nano metal fine particle coating method.

The model figure of the apparatus used in the Example is shown. The SEM photograph of the board | substrate with an electrode produced in Example 1 is shown.

Hereinafter, first, the manufacturing method of the board | substrate with an electrode which concerns on this invention is demonstrated.
Manufacturing method of substrate with electrode
Substrate The substrate used in the present invention is not particularly limited as long as it has an insulating property and can be used for three-dimensional mounting (technology), and a conventionally known substrate can be used.

For example, a glass substrate, a silicon substrate, a silicon carbide substrate, a diamond substrate, an α-alumina substrate, an epoxy resin substrate, a polyester resin substrate, a fluororesin substrate, and the like can be given.
In this invention, since it is excellent in intensity | strength and expansion / contraction rate is small, a silicon substrate is used suitably.

Formation of metal seed film A metal seed film is formed on the substrate.
As the metal, silver, copper, gold, platinum, palladium, nickel, manganese or the like is used. Among these, gold, silver, and copper are preferable in the present invention, although they vary depending on the type of metal fine particles for electrode formation. Furthermore, P, W, etc. may be included.

Examples of the method for forming the metal seed film include a sputtering method, a chemical vapor deposition (CVD) method, an electrolytic plating method, and an electroless plating method.
In the present invention, it is preferable to use a sputtering method because a quick and uniform thickness can be easily obtained.

The thickness of the metal seed film is preferably in the range of 0.5 to 500 nm, more preferably 1 to 400 nm.
If the thickness of the metal seed film is within the above range, it is possible to suppress the diffusion of the electrode metal to the substrate, and it has excellent adhesion to the substrate. Can be formed.

By forming this metal seed film, a high-density electrode can be rapidly formed by electrophoresis by forming this metal seed film.
Forming a resist film Then, a resist film on the metal seed layer. The thickness of the resist film is preferably approximately the same as the required height of the electrode described later or the depth of the hole, and is preferably in the range of 1 to 100 μm, more preferably 2 to 80 μm. The resist hole is a hole that penetrates the resist film and reaches the metal seed film, and may penetrate the metal seed film and reach the substrate, or may further penetrate the substrate.

  When the thickness of the resist film is thin, the electrode layer to be formed and the resist film are not sufficiently adhered, and an electrode with high reliability may not be obtained. Further, if the resist film is thick, the thickness of the electrode is increased, and the number of stacked substrates with electrodes may be reduced or the economy may be lowered.

Examples of the resist constituting the resist film include organic resins such as acrylic resins and epoxy resins. As a method for forming the resist film, known means can be employed without particular limitation, and a spin coating method or the like can be employed.
(First aspect)
In the first aspect, after forming a metal seed film on the substrate, a resist film is formed on the metal seed film, and then a resist hole penetrating the resist film is formed.

A resist hole having a hole diameter of 0.05 to 50 μm, preferably 2 to 30 μm is formed in the resist film in which the resist hole is formed. Within this range, it is possible to create a uniform and highly accurate hole, which is large enough to obtain a high-speed integrated circuit. If the diameter of the resist hole is too small, it is difficult to form a uniform and highly accurate resist hole, and even if an electrode is formed, the desired conductivity cannot be obtained, and an integrated circuit having high-speed response can be obtained. There may not be. If the diameter of the resist hole is too large, the electrode density is lowered and it is not suitable for use in a highly integrated circuit.

Resist holes, 1～64,000,000 pieces / mm ² with respect to the unit area of the resist film, preferably is preferably formed by 10～50,000,000 pieces / mm ^2.
If the density of the resist holes is low, the number of electrodes is small and it is not suitable for a high-density highly integrated circuit. If the density of resist holes is too high, the number of holes themselves will increase, making it difficult to form isolated holes, and an electrode having sufficient electrical conductivity and strength may not be formed.

The depth of the resist hole can be appropriately changed according to the thickness of the resist film as long as it penetrates the resist film, but the depth is in the range of 1 to 100 μm from the resist film surface.
The method of forming the resist hole is not particularly limited, but it is optimal to mask the hole portion and form it by photolithography.

Metal fine particles are deposited in the resist holes thus formed. A method for depositing metal fine particles will be described later.
(Second aspect)
In the second aspect, after a resist film is formed on the substrate, a resist hole penetrating the resist film and a through hole penetrating the base material or a deep hole drilled to the inside of the base material are integrally formed. After forming the metal seed film, metal fine particles are deposited. The method for forming the resist film is the same as described above.

Formation of Through Holes / Deep Holes In the second aspect, the thickness of the resist film can be reduced as required.
Next, the hole diameter is 0.05 to 50 μm, preferably 2 to 30 μm, and the hole density is 1 to 64,000,000 holes / mm ² , preferably 10 to 50,000,000 holes on the substrate and the resist film. / Mm ² hole is formed. The hole may be a through hole that penetrates the resist film and also penetrates the substrate, or a deep hole that is drilled to the inside of the base material without penetrating.

  Note that when a through-hole or a deep hole previously formed on the substrate is used, a resist hole corresponding to the through-hole or deep hole may be formed. In some cases, the formation of the resist film and the formation of the resist hole can be omitted.

The diameter of the through hole / deep hole and the resist hole is preferably 0.05 to 50 μm, more preferably 2 to 30 μm.
If through-holes / deep holes and resist holes are small, it is difficult to form uniform and accurate through-holes (resist holes). Even if electrodes are formed, the desired conductivity cannot be obtained, resulting in high-speed response. An integrated circuit having the same may not be obtained. If the through hole / deep hole and the resist hole are too large, the electrode density may be insufficient.

  The depth of each of the through hole and the resist hole / deep hole is appropriately selected according to the thickness of the resist film, the metal seed film, and the substrate, and is in the range of 1 to 100 μm, and further 2 to 80 μm from each surface. Is preferred. If the depth of the through hole and the resist hole / deep hole is shallow, there is a case where the electrode layer is insufficiently adhered and a highly reliable electrode cannot be obtained. Even if the depth of the through hole / deep hole and resist hole is too deep, the thickness of the electrode is increased, the number of laminated substrates with electrodes is reduced, and the economy is lowered. The reference for the depth is from the upper surface of the substrate, the upper surface of the resist film, and the like.

Next, the density of through-holes / deep holes and resist holes per surface of the substrate unit is in the range of 1 to 64,000,000 / mm ² , preferably 10 to 50,000,000 / mm ^2. preferable. If the pore density is too high, it is difficult to form an isolated hole, and thus an isolated electrode may not be formed.

In this way, metal fine particles are deposited in the formed resist holes, through holes and deep holes.
Deposition of metal fine particles The metal fine particles used in the present invention are not particularly limited as long as an electrode can be formed by electrophoresis described later, but at least one metal selected from silver, copper, gold, platinum, palladium, ruthenium, manganese, nickel It is preferable that the fine particles contain.

  Specifically, it may be a single component metal fine particle or a composite metal fine particle (alloy fine particle). As composite metal fine particles (alloy fine particles), Pd · Ag, Pd · Cu, Ag · Pd, Ru · Au, Au · Ag, Ag · Cu, Ag · Sn, Cu · Sn, Pt · Au, Pt · Pd, Pt.Cu, Pt.Ag, etc. are mentioned.

The average particle diameter of the metal fine particles is preferably in the range of 1 to 50 nm, more preferably 2 to 20 nm.
It is difficult to obtain metal fine particles having an average particle diameter of less than 1 nm, and even if obtained, they may easily become oxides or ions, resulting in insufficient performance and durability as electrodes. There is a case.

  If the average particle size of the metal fine particles is too large, the particles may settle during electrophoresis, which will be described later, or the interparticle voids may increase, leading to a decrease in electrode density and insufficient conductivity.

  The average particle size of the metal fine particles in the present invention is measured with a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd .: Microtrac UPA) using a metal fine particle dispersion having a metal concentration of 0.1% by weight. The particle diameter at the frequency D50 of the volume conversion particle diameter was defined as the average particle diameter.

Such metal fine particles preferably have a zeta potential in the range of −80 to −20 mV, more preferably −70 to −30 mV.
When the zeta potential of the metal fine particles is less than −80 mV (minus is large), the deposition rate of the metal fine particles becomes too fast during electrophoresis, and a uniform and dense electrode may not be obtained.

  When the zeta potential of the metal fine particles exceeds −20 mV (approaching 0), the volume velocity of the metal fine particles becomes slow during electrophoresis, and the rapid electrode forming effect of the present invention may not be sufficiently obtained.

  In the electrophoresis method, when the voltage is increased to increase the deposition rate, ionization may occur depending on the type of metal fine particles. If the zeta potential of the metal fine particles is within the above range, a uniform and high-density electrode can be formed in a short time.

  In the above, the zeta potential varies depending on the type and particle diameter of the metal fine particles, but in order to adjust the zeta potential, the metal fine particle dispersion liquid may be subjected to surface treatment with a surface treatment agent or may remain during preparation. There are methods such as adjusting the ionic impurity content, for example, adsorbing carboxylic acid, anionic surfactant, polymer resin, etc., or adding electrolyte increases the zeta potential, carboxylic acid, anionic When a surfactant, a polymer resin, or the like is adsorbed or the electrolyte is reduced with an ion exchange resin or the like, the zeta potential can be lowered (minus is large). Further, when the particle size of the metal fine particles used is small, the zeta potential tends to be low (minus is large).

In the present invention, the zeta potential was measured using a Zetasizer Nano ZS90 manufactured by Malvern using a 0.1 wt% dispersion of metal fine particles.
The metal fine particles described above are in the average particle diameter range, and conventionally known metal fine particles can be used as long as they have a zeta potential in the above range.

  The metal fine particles are deposited by forming a predetermined resist hole on the substrate in an insulating container containing the metal fine particle dispersion, or a substrate having the predetermined through-hole / deep hole as an anode, A cathode (carbon electrode) spaced apart by a distance of 2 mm is disposed oppositely, and a predetermined voltage is applied to the cathode (carbon electrode) and adjusted so that a predetermined current flows. Alternatively, it is deposited in the through hole.

The dispersion medium is not particularly limited and includes water. Moreover, as solid content concentration, it is 0.1 to 20 weight%, Preferably it is 0.5 to 15 weight%.
The separation distance can be changed by voltage, current, etc., but is preferably in the range of about 0.5 to 20 cm, more preferably 1 to 10 cm.

In this invention, it is preferable that the said voltage exists in the range of 1-100V, Furthermore, 2-20V.
If the voltage is weak, sufficient current does not flow and the deposition rate of the metal fine particles is insufficient, and even if the voltage is too strong, a uniform and dense electrode may not be obtained although the deposition rate is high.

Further, current 0.1~100mA / cm ^2, more preferably in the range of 0.3~50mA / cm ^2.
If the current is low, the deposition rate of the metal fine particles becomes insufficient, and even if the current is too large, the deposition rate is high and a uniform and dense electrode may not be obtained.

The electrophoresis time varies depending on the amount of electrode formation, voltage, current, etc., but is generally within a few minutes to 1 hour, and is extremely short compared with the conventional plating method.
The formed electrode is usually dried and may be used as it is, or may be subjected to atomic hydrogen reduction or baking, baking, UV irradiation, plasma baking, etc. in the atmosphere or under an inert gas as necessary. good. When these treatments are performed, the sintering of the particles is promoted and the conductivity is improved.

Next, the substrate with electrode according to the present invention will be described.
[Substrate with electrode]
The substrate with an electrode according to the present invention comprises a substrate, a metal seed film on the substrate, and an electrode on the metal seed film, and the diameter of the electrode is in the range of 1 to 50 μm and the height is 1 to 100 μm. The electrode has an electrode density in the range of 1 to 64,000,000 / mm ² , and an electrode in which metal fine particles having an average particle diameter in the range of 1 to 50 nm are deposited by electrophoresis. It is said.

The substrate described above can be used as the substrate substrate. As described above, in the present invention, a silicon substrate can be suitably used because it can be used for a three-dimensional mounting technique, has excellent strength, and has a small expansion / contraction rate.

A metal seed film is formed on the metal seed film substrate. As the metal, silver, copper, gold, platinum, palladium or the like is used. In the present invention, gold, silver, and copper are preferable, although they vary depending on the type of electrode-forming metal fine particles. The thickness of the metal seed film is preferably in the range of 0.5 to 500 nm, more preferably 1 to 400 nm.

The electrode electrode is composed of the metal fine particles described above. The electrode preferably has a diameter in the range of 0.05 to 50 μm, preferably 2 to 30 μm.

  If the diameter of the electrode is small outside this range, it is difficult to form a uniform and accurate through hole (resist hole). In some cases, an integrated circuit having responsiveness cannot be obtained.

If the diameter of the electrode is too large, it is possible to create a uniform and highly accurate hole, but it is large enough to obtain a high-speed response integrated circuit.
The height of the electrode is preferably in the range of 1 to 100 μm, more preferably 2 to 80 μm.
If the height of the electrode is too low, the conductivity becomes insufficient, which may not be preferable for high integration.
Even if the height of the electrode is too high, the current may not flow uniformly because the distance between the metal fine particle dispersion and the metal plating film is long, and the uniformity of metal particle deposition is poor, resulting in a uniform film. An electrode may be difficult to obtain.

The density of such electrodes is preferably in the range of 1 to 64,000,000 pieces / mm ² , preferably 10 to 50,000,000 pieces / mm ² . If the density is too high, an isolated electrode may not be formed.
[Example]
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
[Example 1]
Preparation of metal fine particle (1) dispersion 30 g of trisodium citrate hydrate (manufactured by Kanto Chemical Co., Inc .: special grade) was dissolved in 100 g of pure water.
Separately, 20 g of ferrous sulfate (manufactured by Kanto Chemical Co., Ltd .: special grade) was dissolved in 100 g of pure water, and mixed with the above-mentioned trisodium citrate aqueous solution. Next, an aqueous solution in which 100 g of pure water and 10 g of silver nitrate (manufactured by Kanto Chemical Co., Ltd.) were dissolved was mixed, stirred for 10 hours, centrifuged, and the supernatant was removed to collect the sediment.

  Pure water is added to the sediment to prepare a dispersion liquid having a concentration of 15% by weight as silver, and impure so that the electric conductivity becomes 50 μS / cm or less using an ion exchange resin (manufactured by Mitsubishi Chemical Corporation: SMUPB). Minute removal was performed. Thereafter, the mixture was centrifuged for 10 minutes with a centrifuge (10000G), and the supernatant was collected to prepare a dispersion of metal fine particles (1) composed of silver having a concentration of 10.4% by weight as silver. At this time, the pH of the dispersion was 4.5.

With respect to the obtained metal fine particles (1) made of silver, the average particle diameter and the zeta potential were measured, and the results are shown in the table.
Production of Substrate with Electrode (1) A silicon substrate ( manufactured by Fujimi Electronics Co., Ltd .: silicon wafer, 6 inches φ) was cut into 1 cm × 2 cm, and a gold seed film having a thickness of 350 nm was formed thereon by sputtering.

Next, a resist film made of an acrylic resin is applied on the gold seed film by spin coating, and then cured to form, and then holes having a diameter of 10 μm and a depth of 5 μm are formed in 110 rows × 110 columns. did. At this time, the number of holes is 12100 (density is 60.5 / mm ² ).

  Next, the metal fine particle (1) dispersion is added to a glass beaker to such an extent that the silicon substrate can be immersed, and a gold seed film and a resist film formed on the silicon substrate prepared above are used as an anode, and a carbon electrode Was used as a cathode, and was immersed 3 cm apart.

Next, the electrode was connected to a direct current power source, and electrophoresis was performed for 1 minute under conditions of a voltage of 4.3 V and a current of 1 mA / cm ² . A model diagram of the apparatus at this time is shown in FIG.
Next, the anode substrate was taken out, thoroughly washed with pure water, and dried in an N ₂ gas stream to produce a substrate (1) with electrode.

For the obtained substrate with electrode (1), the diameter and height of the electrode were measured, the uniformity of the electrode was evaluated according to the following criteria, and the results are shown in the table. An SEM photograph is shown in FIG.
The diameter and height of the electrode, the depth of the resist film, and the like were measured by observing the surface and cross section using a scanning electron microscope (manufactured by Hitachi, Ltd .: S-2000).

The uniformity of the electrode was evaluated according to the following criteria by observing the surface of the electrode during the above measurement.
The surface of the electrode is smooth: ○
There are unevenness and cracks on the electrode surface: ×
[Example 2]
Production of substrate with electrode (2) In Example 1, the substrate with electrode (2) was prepared in the same manner except that electrophoresis was carried out for 0.5 minutes under the conditions of a voltage of 10.7 V and a current of 3 mA / cm ^2. Manufactured.

With respect to the obtained substrate with electrode (2), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Example 3]
Production of substrate with electrode (3) In Example 1, the substrate with electrode (3) was prepared in the same manner except that electrophoresis was performed for 1 minute under the conditions of a voltage of 2.5 V and a current of 0.5 mA / cm ^2. Manufactured.

For the obtained substrate with electrodes (3), the diameter, height and uniformity of the electrodes were measured, and the results are shown in the table.
[Example 4]
Preparation of metal fine particle (2) dispersion In Example 1, except that 40 g of trisodium citrate hydrate (manufactured by Kanto Chemical Co., Ltd .: special grade) was used, the concentration as silver was 10.4 wt. A dispersion of metal fine particles (2) composed of% silver was prepared. At this time, the pH of the dispersion was 4.0.

With respect to the obtained metal fine particles (2) made of silver, the average particle diameter and the zeta potential were measured, and the results are shown in the table.
Production of Substrate with Electrode (4) A substrate with electrode (4) was produced in the same manner as in Example 1 except that the metal fine particle (2) dispersion was used.

For the obtained substrate with electrode (4), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Example 5]
Preparation of metal fine particle (3) dispersion In Example 1, except that 20 g of trisodium citrate hydrate (manufactured by Kanto Chemical Co., Ltd .: special grade) was used, the concentration as silver was 10.4 wt. A dispersion of metal fine particles (3) composed of% silver was prepared. At this time, the pH of the dispersion was 5.0.

With respect to the obtained metal fine particles (3) composed of silver, the average particle diameter and the zeta potential were measured, and the results are shown in the table.
Production of Substrate with Electrode (5) A substrate with electrode (5) was produced in the same manner as in Example 1 except that the dispersion of metal fine particles (3) was used.

For the obtained substrate with electrodes (5), the diameter, height and uniformity of the electrodes were measured, and the results are shown in the table.
[Example 6]
Preparation of metal fine particle (4) dispersion 10 g of polyvinylpyrrolidone (Mw 1500) was dissolved in 100 g of pure water.

  Separately, 20 g of copper sulfate hydrate (manufactured by Kanto Chemical Co., Ltd .: special grade) was dissolved in 100 g of pure water and mixed with the above-mentioned aqueous solution of revinyl pyrrolidone. Then, after mixing for 19 hours under a hydrogen stream, impurities were removed using an ion exchange resin (SMUNUPB manufactured by Mitsubishi Chemical Corporation) so that the electric conductivity was 50 μS / cm or less. Next, it is concentrated on a rotary evaporator, diluted with pure water to a concentration of 10.4% by weight as copper, and a dispersion of metal fine particles (4) made of copper with a concentration of 10.4% by weight as copper is obtained. Prepared. At this time, the pH of the dispersion was 3.5.

The obtained copper metal fine particles (4) were measured for average particle diameter and zeta potential, and the results are shown in the table.
Production of Substrate with Electrode (6) A substrate with electrode (6) was produced in the same manner as in Example 1 except that the metal fine particle (4) dispersion was used.

For the obtained substrate with electrodes (6), the diameter, height and uniformity of the electrodes were measured, and the results are shown in the table.
[Example 7]
Production Example 1 of Electrode Substrate (7) In Example 1, Ag-Pd colloid solution (manufactured by JGC Catalysts & Chemicals Co., Ltd .: standard Ag-Pd colloid, average particle diameter 3 nm, Ag-Pd concentration 3.0 wt%, zeta potential) A substrate with electrode (7) was produced in the same manner except that -50 mV) was used.

For the obtained substrate with electrode (7), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Example 8]
Preparation of Metal Fine Particle (5) Dispersion 10 g of ion exchange resin (MMNUPB manufactured by Mitsubishi Chemical) was added to 100 g of the metal fine particle (1) dispersion prepared in the same manner as in Example 1, and the electric conductivity was 30 μS / cm. Impurities and the surface treatment agent (citric acid) were removed until the following concentration was obtained, thereby preparing a metal fine particle (5) dispersion having a concentration of 10.4% by weight as silver. At this time, the pH of the dispersion was 3.8.

With respect to the obtained metal fine particles (5) composed of silver, the average particle diameter and the zeta potential were measured, and the results are shown in the table.
Production of Substrate with Electrode (8) A substrate with electrode (8) was produced in the same manner as in Example 1 except that the metal fine particle (5) dispersion was used.

For the obtained substrate with electrode (8), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Example 9]
Preparation of metal fine particle (6) dispersion 1 g of polyvinylpyrrolidone (molecular weight: 55,000) as a surface treating agent was added to 100 g of metal fine particle (1) dispersion prepared in the same manner as in Example 1, and stirred for a whole day and night. A metal fine particle (6) dispersion having a concentration of 10.3 wt% was prepared. At this time, the pH of the dispersion was 4.5.

With respect to the obtained metal fine particles (6) comprising silver, the average particle diameter and the zeta potential were measured, and the results are shown in the table.
Production of Substrate with Electrode (9) A substrate with electrode (9) was produced in the same manner as in Example 1 except that the metal fine particle (6) dispersion was used.

For the obtained substrate with electrode (9), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Example 10]
Manufacture of substrate with electrode (10) A silicon substrate ( manufactured by Fujimi Electronics Co., Ltd .: silicon wafer, 6 inch φ) is cut into 1 cm × 2 cm, and a resist film having a thickness of 5 μm made of acrylic resin is formed thereon. Next, holes having a diameter of 10 μm and a depth of 20 μm were formed by plasma etching. The density at this time is 60.5 pieces / mm ² . Next, a 350 nm thick silver seed film was formed by sputtering.

Hereinafter, a substrate with electrode (10) was produced in the same manner as in Example 1 except that the metal fine particle (6) dispersion was used and the electrophoresis time was set to 2 minutes.
For the obtained substrate with electrode (10), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Comparative Example 1]
Production of substrate with electrode (R1) In the same manner as in Production Example 1, a gold seed film and a resist film were formed on a silicon substrate, and then a hole was formed.

Subsequently, it was immersed in an Ag plating solution (50 g / L of sulfuric acid, 200 g / L of silver nitrate, and 50 mg / L of chloride ions) for 1 minute under the condition of 1 mA / cm ² . A substrate with electrodes (R1) was produced.
With respect to the obtained substrate with electrode (R1), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Comparative Example 2]
Production of Substrate with Electrode (R2) In Comparative Example 1, a substrate with electrode (R2) was produced in the same manner except that it was immersed in an Ag plating solution for 2.5 hours.

With respect to the obtained substrate with electrode (R2), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.
[Comparative Example 3]
Preparation of metal fine particle (R1) dispersion In Example 1, except that 18 g of trisodium citrate hydrate (manufactured by Kanto Chemical Co., Ltd .: special grade) was dissolved, the concentration of Ag was 10.4 wt%. A metal fine particle (R1) dispersion made of silver was prepared. At this time, the pH of the dispersion was 5.0.
The obtained metal fine particles (R1) made of silver were measured for average particle diameter and zeta potential, and the results are shown in the table.

Production of substrate with electrode (R3) A substrate with electrode (R3) was produced in the same manner as in Example 1 except that the metal fine particle (R1) dispersion was used.

  For the obtained substrate with electrode (R3), the diameter, height and uniformity of the electrode were measured, and the results are shown in the table.

Claims (10)

  After forming a metal seed film on the substrate, forming a resist film on the metal seed film, and then forming a resist hole penetrating the resist film, a metal having an average particle diameter in the range of 1 to 50 nm A method of manufacturing a substrate with an electrode, wherein fine particles are deposited in a resist hole by electrophoresis. The resist has a diameter in the range of 0.05 to 50 μm, a depth from the resist film surface in the range of 1 to 100 μm, and a range of 1 to 64,000,000 pieces / mm ² of the substrate unit surface. The method for producing a substrate with an electrode according to claim 1, wherein holes are formed.   After forming a resist film on the substrate, a resist hole penetrating the resist film and a through hole penetrating the base material or a deep hole drilled into the base material are integrally formed, and then a metal seed film is formed. Then, a method for producing a substrate with an electrode, wherein metal fine particles having an average particle diameter in the range of 1 to 50 nm are deposited in at least through holes or deep holes by electrophoresis. The diameter is in the range of 0.05 to 50 μm, the depth from the resist film surface is in the range of 1 to 100 μm, and the density of through holes or deep holes on the substrate unit surface is 1 to 64,000,000 / to be in the range of mm ^2, the resist hole and method for producing a substrate with electrode as claimed in claim 3, characterized by integrally forming a through-hole or deep hole. The method for producing a substrate with an electrode according to any one of claims 1 to 4, wherein the metal fine particles having a zeta potential in a range of -80 to -20 mV are used.   The electrode-attached substrate according to claim 1, wherein the metal fine particles are fine particles containing at least one metal selected from silver, copper, gold, platinum, palladium, ruthenium, manganese, and nickel. Manufacturing method. ^2. The method for producing a substrate with an electrode according to claim 1, wherein metal fine particles are deposited by electrophoresis in a current range of 0.1 to 100 mA / cm ² and a voltage range of 1 to 100V. It consists of a substrate, a metal seed film on the substrate, a resist film on the metal seed film, and an electrode, the electrode is cylindrical and has a diameter in the range of 0.05 to 50 μm, and a height of 1 to It is an electrode in which metal fine particles in an area of 100 μm, an electrode density in a range of 1 to 64,000,000 pieces / mm ² and an average particle diameter in a range of 1 to 50 nm are deposited by electrophoresis. A substrate with electrodes.   9. The electrode-attached substrate according to claim 8, wherein the metal fine particles are fine particles containing at least one metal selected from silver, copper, gold, platinum, palladium, ruthenium, manganese, and nickel.   The substrate with an electrode according to claim 8 or 9, wherein a through hole or a deep hole is formed in the substrate, and the electrode is formed in the through hole or the deep hole.