JP4833434B2 - Plating solution holding member for electroplating equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a plating solution holding member for an electrolytic plating apparatus.
[0002]
[Prior art]
Attention has been attracted to electrolytic copper plating using an electrolytic plating apparatus as a technique for forming wiring on a semiconductor wafer, particularly as a technique for forming copper wiring on a semiconductor wafer in recent years.
[0003]
In a conventional general electroplating apparatus, a semiconductor wafer is immersed in a plating solution in a state where the plating solution is filled in the plating tank, and a film is formed by connecting a cathode to the semiconductor wafer and flowing electricity. It is like that.
[0004]
However, in order to form fine and uniform copper wiring using such a conventional apparatus, for example, it is necessary to flow a plating solution or to secure a certain distance between the cathode and the anode. For this reason, there was a tendency for the apparatus to become huge. Further, in the case of this conventional apparatus, a large amount of plating solution is required for one film formation, which is disadvantageous in achieving a reduction in the cost of the semiconductor.
[0005]
Therefore, recently, a next-generation electrolytic plating apparatus that can solve the above-mentioned problems has been proposed. This new electrolytic plating apparatus includes a plating solution supply unit, a cathode, an anode, a plating solution holding member, and the like. An anode is provided at the lower end of the plating supply unit. A slit for allowing the plating solution to pass therethrough is formed on the anode. A plating solution holding member made of porous alumina is provided on the lower surface side of the anode. On the other hand, the semiconductor wafer is supported in contact with the cathode. The upper surface of the semiconductor wafer and the lower surface of the plating solution holding member face each other with a slight gap therebetween.
[0006]
Therefore, the plating solution supplied to the plating solution supply unit passes through the slit of the anode and reaches the plating solution holding member, and then is supplied to the semiconductor wafer side through the pores of the plating solution holding member. By energizing the electrodes in this state, electrolytic plating is performed on the semiconductor wafer, and fine copper wiring is formed even in a static bath.
[0007]
And this inventor has already proposed the plating solution holding member using porous silicon carbide in order to eliminate the fault of porous alumina which is easy to be attacked by copper plating solution.
[0008]
[Problems to be solved by the invention]
However, in the case of a plating solution holding member made of porous silicon carbide, it was confirmed that for some reason, bubbles were generated on the surface of the member at the time of plating, thereby partially blocking the pores that are the passage of the plating solution. For this reason, there was a possibility that the plating solution was poorly passed, and the amount of the plating solution exuded from the lower surface of the plating solution holding member may vary. Therefore, it was concluded that in order to reliably form a plating layer with a uniform film thickness, it is necessary to investigate the cause and to take predetermined countermeasures.
[0009]
This invention is made | formed in view of said subject, The objective is to provide the plating solution holding member for electrolytic plating apparatuses which can form the plating layer of a uniform film thickness reliably.
[0010]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies to solve the above-mentioned problems. As a result, silicon carbide having a molecular structure with a small polarity is not so good in wettability with water. And found that bubbles are generated. Therefore, the inventor of the present application conducted further research under the hypothesis that good results would be obtained if the wettability of the portion where bubbles are likely to be generated in silicon carbide was obtained. I came up with the idea.
[0011]
That is, in the invention according to claim 1, the surface of the silicon carbide particles in the surface layer portion is covered with a substance having better wettability with respect to water than silicon carbide, and a porous silica layer is formed on the surface of the silicon carbide particles . Ri Do from quality silicon carbide plate, the thickness of the silica layer is 50 nm to 200 nm, wherein a depth of the porous silicon carbide plate surface of the portion to which the silica layer is formed is 100μm~300μm The gist is a plating solution holding member for an electrolytic plating apparatus.
[0012]
In the invention described in claim 2, the surface of the silicon carbide particles in the surface portion is covered by the highly hydrophilic material, Ri Do porous silicon carbide plate silica layer is formed on the surface of the silicon carbide particles, The thickness of the silica layer is 50 nm to 200 nm, and the depth of the portion where the silica layer is formed from the surface of the porous silicon carbide plate is 100 μm to 300 μm. The holding member is the gist thereof.
[0013]
In the invention described in claim 3, the surface of the silicon carbide particles are oxidized in the surface portion, Ri Do porous silicon carbide plate which oxide layer on the surface of the silicon carbide particles are formed, the thickness of the oxide layer And a depth of the portion where the oxide layer is formed from the surface of the porous silicon carbide plate is 100 μm to 300 μm. To do.
[0014]
The “action” of the present invention will be described below.
According to the first aspect of the present invention, the plating solution holding member is made of a porous silicon carbide plate, and the surface of the silicon carbide particles in the surface layer portion of the porous silicon carbide plate has better wettability to water than silicon carbide. A silica layer is formed on the surface of the silicon carbide particles . For this reason, the plating solution is not water-repellent and bubbles are hardly generated on the surface of the member.
[0015]
According to invention of Claim 2, a plating solution holding member consists of a porous silicon carbide board, and the surface of the silicon carbide particle in the surface layer part of the porous silicon carbide board is coat | covered with the highly hydrophilic substance. A silica layer is formed on the surface of the silicon carbide particles . For this reason, as a result of improving the wettability with respect to water, the plating solution is not repellent and bubbles are hardly generated on the surface of the member.
[0016]
According to the third aspect of the present invention, the plating solution holding member is made of a porous silicon carbide plate, the surface of the silicon carbide particles in the surface layer portion of the porous silicon carbide plate is oxidized , and the surface of the silicon carbide particles is oxidized. A layer is formed . Silica, which is an oxide layer, has a molecular structure that is more polar than silicon carbide, and therefore has higher hydrophilicity and better wettability with water than silicon carbide. For this reason, the plating solution is not water-repellent and bubbles are hardly generated on the surface of the member.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an electrolytic copper plating apparatus 1 according to an embodiment of the present invention will be described in detail with reference to FIG.
[0018]
The cathode 2 constituting the electrolytic copper plating apparatus 1 is an annular member whose diameter increases toward the upper end side, and a flange 3 is formed on the lower end side thereof. The cathode 2 is formed using, for example, a conductive metal material. The diameter of the lower end side opening 4 of the cathode 2 is set to be slightly smaller than the diameter of a semiconductor wafer (for example, a silicon wafer) 5 that is an object to be plated. The semiconductor wafer 5 is pressed against the flange 3 from below by a stage (not shown). As a result, the outer peripheral portion of the upper surface side of the semiconductor wafer 5 is in close contact with the lower surface side of the flange 3, and the semiconductor wafer 5 is held in this state. At this time, since the cathode 2 has a so-called bottomed shape, the electrolytic copper plating solution 15 is accumulated in a region formed on the upper surface side of the semiconductor wafer 5.
[0019]
On the other hand, the holder 12 which comprises this electrolytic copper plating apparatus 1 is arrange | positioned in the state which adjoined above the cathode 2 at the time of use. An opening 13 is provided on the lower end side of the holder 12, and a plate-like anode 14 is attached in the vicinity of the opening 13. The anode 14 is formed in a circular shape using, for example, a conductive metal material. Slits 16 are provided at a plurality of locations of the anode 14 as a structure for allowing the copper plating solution 15 to pass from the upper surface side to the lower surface side. On the upper surface of the holder 12, a plating solution supply pipe 17 and a plating solution recovery pipe 18 are provided. The plating solution supply pipe 17 communicates between a space 19 defined by the holder 12 and the anode 14 and a plating solution tank (not shown). When the copper plating solution 15 is insufficient, the copper plating solution 15 is replenished into the space 19 through the plating solution supply pipe 17. The plating solution recovery pipe 18 plays a role of recovering the surplus when the amount of the copper plating solution 15 in the space 19 exceeds a certain amount. The recovered copper plating solution 15 is returned to the plating solution tank and reused.
[0020]
A plating solution holding plate 21 as a plating solution holding member is provided in the opening 13 of the holder 12 so as to be in contact with the lower surface side of the anode 14. The plating solution holding plate 21 has substantially the same size and the same shape (that is, a disc shape) as the anode 14. The plating solution holding plate 21 includes a flange portion 21a that protrudes laterally from the outer peripheral portion. The flange portion 21 a is supported by a support portion 13 a provided in the opening 13 of the holder 12. A rubber annular packing 22 as a seal member is interposed between the lower surface of the flange portion 21a and the upper surface of the support portion 13a.
[0021]
The plating solution holding plate 21 also serves to prevent the copper plating solution 15 from flowing out from the lower surface side when the holder 12 is transferred by holding the copper plating solution 15 in its pores. Note that the lower surface of the plating solution holding plate 21 is opposed to the upper surface of the semiconductor wafer 5 with a slight gap therebetween. Specifically, in the present embodiment, the size of the gap is set to about 1 mm.
[0022]
Next, the material of the plating solution holding plate 21 used in this embodiment will be described in detail.
The plating solution holding plate 21 of the present embodiment is a porous ceramic plate, and specifically, a porous silicon carbide plate (porous SiC plate) P1 is used. The reason why porous silicon carbide is selected is that porous silicon carbide is superior in corrosion resistance and electrical conductivity as compared with porous alumina, and is extremely convenient as a material for the plating solution holding plate 21.
[0023]
The porosity of the plating solution holding plate 21 is preferably 20% to 50%, and more preferably 30% to 45%. The average pore diameter is preferably 10 μm to 60 μm, and more preferably 20 μm to 50 μm.
[0024]
If the porosity is less than 20%, the copper plating solution 15 becomes difficult to flow smoothly due to an increase in pressure loss, and the ease of the copper plating solution 15 leaching varies from place to place. That is, the amount of the copper plating solution 15 supplied from the lower surface side of the plating solution holding plate 21 becomes non-uniform, and as a result, the film thickness of the copper plating layer may become non-uniform. Conversely, if the porosity exceeds 50%, an increase in pressure loss can be avoided, but the property of holding the copper plating solution 15 is impaired. Therefore, even in this case, the thickness of the plating layer may be nonuniform.
[0025]
If the average pore diameter is less than 10 μm, the copper plating solution 15 becomes difficult to flow smoothly due to an increase in pressure loss, so that the ease with which the copper plating solution 15 exudes varies depending on the location. That is, the amount of the plating solution 15 supplied from the lower surface side of the plating solution holding plate 21 becomes non-uniform, and as a result, the film thickness of the copper plating layer may become non-uniform. Conversely, when the average pore diameter exceeds 60 μm, an increase in pressure loss can be avoided, but the property of holding the copper plating solution 15 is impaired. Therefore, even in this case, the film thickness of the copper plating layer may be non-uniform.
[0026]
The volume resistivity of the plating solution holding plate 21 is preferably 10 ¹ Ωm to 10 ⁵ Ωm, and more preferably 10 ² Ωm to 10 ⁴ Ωm.
If it is intended to realize a material having a volume resistivity of less than 10 ¹ Ωm, it becomes difficult to select materials and set firing conditions, and the manufacturing cost of the plating solution holding plate 21 may increase. In addition, the porosity of the plating solution holding plate 21 may be impaired, and the basic performance of plating solution holding property may be impaired. On the other hand, if it exceeds 10 ⁵ Ωm, the electrical conductivity becomes too low, and the plating solution holding plate 21 may not substantially function as the anode 14. Therefore, there is a possibility that a strong and stable electric field cannot be applied to the copper plating solution 15 near the upper surface of the semiconductor wafer 5.
[0027]
The density of the plating solution holding plate 21 is 1.6 g / cm ^{3 to} 2.5 g / cm ³ , the bending strength is 30 MPa to 150 MPa, the Young's modulus is 50 GPa to 200 GPa, and the thermal conductivity is 50 W / m · K to 150 W / It may be m · K. Further, as the porous silicon carbide constituting the plating solution holding plate 21, high purity porous silicon carbide is preferably used. Specifically, porous silicon carbide having a concentration of heavy metal as an impurity of 0.5% or less is preferably used.
[0028]
Silicon carbide particles 23 in the surface layer portion of porous silicon carbide plate P1 are coated with a substance having better wettability with respect to water than silicon carbide. Specifically, in the present embodiment, the surface of the silicon carbide particles in the surface layer portion of the porous silicon carbide plate P1 is oxidized, and a layer made of silicon oxide (silica: SiO ₂ ) (hereinafter referred to as a silica layer 24). ) Is formed. The reason for selecting silica is that silica has a molecular structure having a larger polarity than silicon carbide, and therefore has higher hydrophilicity and better water wettability than silicon carbide. A silicon-based ceramic compound other than silica that exhibits a molecular structure having a polarity greater than that of silicon carbide can be used, but it is desirable that it does not contain metal impurities such as aluminum as much as possible.
[0029]
The thickness of the silica layer 24 is preferably 50 nm to 200 nm. This is because if the silica layer 24 is too thin, the hydrophilicity is not sufficiently high and the wettability with respect to water cannot be sufficiently improved. On the other hand, if the silica layer 24 is to be thickened, not only is it difficult to set the conditions for the oxidation treatment, but there is a risk that the proper physical properties (for example, conductivity and strength) inherent to silicon carbide may be impaired.
[0030]
The depth d1 from the surface of the portion where the silica layer 24 is formed in the porous silicon carbide plate P1 is preferably 100 μm to 300 μm. Further, it is desirable that the silica layer 24 is formed only on the surface layer portion and not in the inner region. If the depth d1 is too small, the wettability to water may not be sufficiently improved. On the other hand, if the depth d1 is increased, not only is it difficult to set the conditions for the oxidation treatment, but there is a possibility that the proper physical properties of silicon carbide are impaired.
[0031]
Here, a method for manufacturing the plating solution holding plate 21 of the present embodiment will be described. First, one or more silicon carbide powders as raw materials are prepared. And after mix | blending a solvent, a binder, etc. with silicon carbide powder, this is mixed well. The mixture is then dried and then the dried mixture is granulated. And it shape | molds using the granule obtained by the said granulation process as a material, and produces a disk-shaped molded object. In this case, it is preferable to set the conditions so that the density distribution at the time of molding falls within the range of ± 0.05 g / cm ³ . In the present embodiment, a hydrostatic press is adopted as a pressing method for realizing this. Next, the molded body obtained by the molding process is fired at normal pressure at a temperature of about 2000 ° C. to 2300 ° C. in an inert atmosphere to sinter the molded body (ie, porous silicon carbide). A plate P1) is obtained. In this case, it is preferable to set conditions so that the in-plane temperature distribution of the molded body during firing is within ± 1 ° C. Finally, a treatment for oxidizing the porous silicon carbide plate P1 is performed, and the surface of the silicon carbide particles 23 in the surface layer portion is changed to silica, whereby the plating solution holding plate 21 is completed.
[0032]
Examples of the oxidation treatment include dry treatment such as heating the porous silicon carbide plate P1 in an oxidizing atmosphere, wet treatment using an oxidizing agent, and the like.
When performing the dry oxidation treatment, the heating temperature is preferably set to 500 ° C. or higher, particularly about 800 ° C. to 1200 ° C. If the heating temperature is too low, the oxidation reaction of silicon carbide does not proceed, and there is a possibility that a sufficiently thick silica layer 24 cannot be formed. On the other hand, if the heating temperature is too high, not only does the energy loss increase and the cost increases, but the formation of the silica layer 24 extends to the inside of the porous silicon carbide plate P1 due to excessive oxidation reaction, resulting in a decrease in physical properties. Will lead to.
[0033]
In the case of performing the dry oxidation treatment, the heating time is preferably set to 0.1 hour or longer, particularly about 0.5 hour to 5 hours. If the heating time is too short, the silica layer 24 having a sufficient thickness may not be formed. Conversely, if the heating time is too long, the formation of the silica layer 24 extends to the inside of the porous silicon carbide plate P1, which may lead to a decrease in physical properties.
[0034]
Next, a method of using the electrolytic copper plating apparatus 1 using the plating solution holding plate 21 configured as described above will be described.
In the case of the electrolytic copper plating apparatus 1, a certain amount of the copper plating solution 15 supplied through the plating solution supply pipe 17 is accumulated in the space 19. The copper plating solution 15 supplied to the space 19 passes through the slit 16 of the anode 14 and reaches the plating solution holding plate 21. The copper plating solution 15 is further supplied to the upper surface side of the semiconductor wafer 5 through the pores of the plating solution holding plate 21. Therefore, by conducting current between the anode 14 and the cathode 2 in this state, electrolytic copper plating is performed while still bathing. Then, a copper plating layer is deposited so as to fill a wiring groove dug in advance on the upper surface side of the semiconductor wafer 5, and as a result, a copper wiring having a desired pattern shape is formed.
[0035]
【Example】
[Production of Example 1]
In the production of Example 1, GC # 240 (manufactured by Shinano Denki Co., Ltd., average particle size 57 μm) and GMF-15H2 (manufactured by Taiheiyo Random Co., Ltd., average particle size 0.5 μm) were used as the raw material silicon carbide powder in a weight ratio. Was 7: 3. Then, these two types of silicon carbide powders were further mixed with water and an acrylic resin as a binder, which were mixed well using a pot mill. The uniform mixture obtained by the mixing step was dried for a predetermined time to remove water to some extent, and then an appropriate amount of the dried mixture was collected and granulated with a spray dryer.
[0036]
And the granule obtained by the said granulation process was used as a material, and the hydrostatic pressure press was performed by the pressure of about 100 MPa-130 MPa, and the disk-shaped molded object was produced. Next, the molded body obtained by the molding step was fired at normal pressure at a temperature of 2100 ° C. to 2200 ° C. in an argon atmosphere. The porous silicon carbide plate P1 obtained by firing was set in a heating furnace and baked as a dry oxidation treatment in the atmosphere. Here, the heating temperature was set to 1000 ° C., and the heating time was set to 3 hours. As a result, a disk-shaped plating solution holding plate 21 made of porous silicon carbide in which the silicon carbide particles 23 in the surface layer portion were covered with the silica layer 24 was obtained. The coating thickness of the silica layer 24 was 100 nm to 150 nm, and the depth d1 of the oxidized portion was 150 μm to 200 μm.
[0037]
Moreover, in the plating solution holding plate 21 (specifically, the region excluding the surface layer portion) of Example 1 obtained in this way, the porosity is about 25%, the average pore diameter is about 15 μm, and the volume resistivity is 10 ^The resistance was ³ Ωm, the density was 2.4 g / cm ³ , the bending strength was 130 MPa, the thermal conductivity was 140 W / m · K, and the heavy metal concentration was 0.5% or less.
[Production of Example 2]
In the production of Example 2, GC # 240 (manufactured by Shinano Denki Co., Ltd., average particle size 57 μm) and GMF-15H2 (manufactured by Taiheiyo Random Co., Ltd., average particle size 0.5 μm) are used as raw material silicon carbide powder in a weight ratio. Was 9: 1. And these two types of silicon carbide powders were further mixed with water and an acrylic resin as a binder, and granulated at the same time while thoroughly mixing them using a universal mixer.
[0038]
And the granule obtained by the said mixing and granulation process was used as a material, and the hydrostatic pressure press was performed by the pressure of about 50 MPa, and the disk-shaped molded object was produced. Next, the molded body obtained by the molding step was fired at normal pressure at a temperature of 2250 ° C. in an argon atmosphere. The porous silicon carbide plate P1 obtained by firing was set in a heating furnace and baked as a dry oxidation treatment in the atmosphere. Here, the heating temperature was set to 1200 ° C., and the heating time was set to 4 hours. As a result, a disk-shaped plating solution holding plate 21 made of porous silicon carbide in which the silicon carbide particles 23 in the surface layer portion were covered with the silica layer 24 was obtained. The coating thickness of the silica layer 24 was 100 nm to 200 nm, and the depth d1 of the oxidized portion was 200 μm to 300 μm.
[0039]
Moreover, in the plating solution holding plate 21 (specifically, the region excluding the surface layer portion) of Example 2 obtained in this way, the porosity is about 40%, the average pore diameter is about 30 μm, and the volume resistivity is 10 ^The resistance was ³ Ωm, the density was 1.9 g / cm ³ , the bending strength was 50 MPa, the thermal conductivity was 80 W / m · K, and the heavy metal concentration was 0.5% or less.
[Comparative example]
Except that only the oxidation treatment was not performed after the firing step, a disk-shaped plating solution holding plate 21 made of porous silicon carbide was basically produced according to the same procedure as in Example 1. Therefore, in the comparative example, the coating thickness of the silica layer 24 was approximately 0 nm, and the depth d1 of the oxidized portion was 0 μm.
[Method and result of evaluation test]
Here, the following was performed as an evaluation test. That is, water (ion exchange water having a conductivity of 1 ± 0.5 μs / cm ² ) was dropped on each plating solution holding plate 21, and the wetting angle (contact angle) θ was measured after 30 seconds. In addition, the contact angle measuring device (The product made by ERMA, brand name: G-1-1000) was used for the measurement.
[0040]
As a result, θ = 40 ° in Example 1, θ = 35 ° in Example 2, and θ = 44 ° in the comparative example. As is clear from the above, it was confirmed that Examples 1 and 2 in which the silica layer 24 was formed had better wettability with respect to water than the comparative example.
[0041]
Then, when the electrolytic copper plating was actually carried out using the plating solution holding plate 21 of Examples 1 and 2, there was no appearance of bubbles on the surface of the member, and the pores that were the passages of the copper plating solution 15 were partially It was not blocked. Therefore, the amount of the copper plating solution 15 leached from the lower surface of the plating solution holding plate 21 becomes uniform, and it is possible to form a copper wiring with a uniform film thickness on the semiconductor wafer 5.
[0042]
Therefore, according to the example of the present embodiment, the following effects can be obtained.
(1) The plating holding plate 21 of the above embodiment is made of a porous silicon carbide plate P1, and the silicon carbide particles 23 in the surface layer portion thereof are covered with a silica layer 24 having better wettability with respect to water than silicon carbide. Therefore, the copper plating solution 15 is not water repellent and bubbles are hardly generated on the surface of the member. For this reason, it is possible to prevent the occurrence of a bad place of the copper plating solution 15, and the amount of the copper plating solution 15 leached from the lower surface of the plating solution holding plate 21 is less likely to vary. Therefore, it is possible to reliably form a copper plating layer (that is, copper wiring) having a uniform film thickness.
[0043]
(2) In the said Example, the silica layer 24 is formed there by oxidizing the surface of the silicon carbide particle 23 in a surface layer part. In addition, since the above-described dry oxidation treatment does not require chemicals or the like, wettability can be improved relatively easily and inexpensively. Therefore, cost increase of the plating solution holding plate 21 is also prevented.
[0044]
(3) In the said Example, it heats on suitable temperature and time conditions in the case of a dry-type oxidation process. Therefore, the necessary and sufficient silica layer 24 can be reliably formed without accompanying a decrease in suitable physical properties and an increase in cost.
[0045]
In addition, you may change embodiment of this invention as follows.
The silicon carbide particles 23 in the surface layer portion may be changed to silica not only on the surface but also inside thereof.
[0046]
It is also possible to coat the silicon carbide particles 23 in the surface layer portion with the silica layer 24 by a method such as CVD.
-The layer made of a substance having higher hydrophilicity than silicon carbide (good wettability to water) is not limited to a layer made of a silicon-based ceramic compound typified by silica. For example, other ceramic compounds not containing silicon The layer which consists of may be sufficient. Moreover, the layer which consists of nonmetallic materials other than a ceramic compound may be sufficient.
[0047]
The electrolytic plating apparatus 1 of the embodiment can be used not only when performing electrolytic copper plating but also when performing electrolytic nickel plating or electrolytic gold plating, for example.
[0048]
The object to be plated is not limited to the semiconductor wafer 5 made of silicon, gallium arsenide, or the like, and may be, for example, a ceramic, metal, or plastic substrate.
[0049]
The electroplating apparatus 1 of the embodiment can be used not only for the formation of wiring, but also for the formation of external connection terminals in semiconductors such as bumps, for example. Furthermore, the electroplating apparatus 1 is not only used for forming a metal layer for the purpose of flowing electricity as in the case of the wiring, but is used for forming a metal layer that is not specifically intended for flowing electricity. It does not matter.
[0050]
The upper surface of the plating solution holding plate 21 may be disposed in a non-contact state with respect to the lower surface of the anode 14.
Next, in addition to the technical ideas described in the claims, the technical ideas grasped by the embodiment described above are listed below.
[0051]
(1) An anode having a structure through which a plating solution can pass, a cathode in contact with an object to be plated, and a porous plating solution holding member arranged on the object to be plated side of the anode, and the plating solution Is supplied to the object to be plated through the anode and the plating solution holding member, the plating solution holding member is made of a porous silicon carbide plate, and carbonized in a surface layer portion of the porous silicon carbide plate. An electrolytic plating apparatus, wherein the silicon particles are coated with a substance having a molecular structure having a polarity greater than that of silicon carbide molecules. Therefore, according to the invention described in this technical idea 1, it is possible to provide an electrolytic plating apparatus that can reliably form a plating layer having a uniform film thickness.
[0052]
(2) A method for manufacturing a plating solution holding member according to any one of claims 3 and 1, wherein the porous silicon carbide plate is heated in an oxidizing atmosphere, whereby the porous Forming an oxide layer on the surface of the silicon carbide particles in the surface layer portion of the silicon carbide plate;
[0053]
(3) A method for producing a plating solution holding member according to any one of claims 3 and 1, wherein the porous silicon carbide plate is 0 in an oxidizing atmosphere at 800 ° C to 1200 ° C. Forming an oxide layer on the surface of the silicon carbide particles in the surface layer portion of the porous silicon carbide plate by heating for 5 hours to 5 hours.
[0054]
【The invention's effect】
As described in detail above, according to the first to third aspects of the invention, it is possible to provide a plating solution holding member for an electrolytic plating apparatus that can reliably form a plating layer having a uniform film thickness.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view of an electrolytic copper plating apparatus according to an embodiment of the present invention.
FIG. 2 is a conceptual diagram showing a state of a surface layer portion of a plating solution holding plate constituting the electrolytic copper plating apparatus.
FIG. 3 is a diagram for explaining an evaluation test method of an example and a comparative example.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Electrolytic copper plating apparatus as an electroplating apparatus, 2 ... Cathode, 5 ... Semiconductor wafer as to-be-plated object, 14 ... Anode, 21 ... Plating solution holding plate as a plating solution holding member, 23 ... Silicon carbide particle, 24 ... silica layer, P1 ... porous silicon carbide plate.

Claims (3)

The surface of the silicon carbide particles in the surface portion is covered by a good material wettability for water than silicon carbide, Ri Do porous silicon carbide plate silica layer is formed on the surface of the silicon carbide particles, the silica layer The plating solution holding member for an electrolytic plating apparatus , wherein the thickness of the part is 50 nm to 200 nm, and the depth from the surface of the porous silicon carbide plate in the portion where the silica layer is formed is 100 μm to 300 μm . The surface of the silicon carbide particles in the surface portion covered by highly hydrophilic material, Ri Do porous silicon carbide plate silica layer on the surface of the silicon carbide particles are formed, the thickness of the silica layer 50nm~ A plating solution holding member for an electroplating apparatus , wherein the depth from the surface of the porous silicon carbide plate at 200 nm and where the silica layer is formed is 100 μm to 300 μm . The surface of the silicon carbide particles in the surface portion is oxidized, Ri Do porous silicon carbide plate which oxide layer on the surface of the silicon carbide particles are formed, the thickness of the oxide layer is 50 nm to 200 nm, the oxidation A plating solution holding member for an electrolytic plating apparatus, wherein the depth of the portion where the layer is formed from the surface of the porous silicon carbide plate is 100 μm to 300 μm .

Images