WO2001049898A1 - Procede de galvanoplastie, agent de pretraitement et tranche de semi-conducteurs et dispositif semi-conducteur utilisant cette derniere - Google Patents

Procede de galvanoplastie, agent de pretraitement et tranche de semi-conducteurs et dispositif semi-conducteur utilisant cette derniere Download PDF

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Publication number
WO2001049898A1
WO2001049898A1 PCT/JP2000/008166 JP0008166W WO0149898A1 WO 2001049898 A1 WO2001049898 A1 WO 2001049898A1 JP 0008166 W JP0008166 W JP 0008166W WO 0149898 A1 WO0149898 A1 WO 0149898A1
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metal
plating
metal plating
silane coupling
copper
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PCT/JP2000/008166
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English (en)
Japanese (ja)
Inventor
Toru Imori
Masashi Kumagai
Junnosuke Sekiguchi
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Nikko Materials Co., Ltd.
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Priority to JP2001550424A priority Critical patent/JP3670238B2/ja
Publication of WO2001049898A1 publication Critical patent/WO2001049898A1/fr
Priority to US10/767,697 priority patent/US7045461B2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the present invention relates to a method for metal plating on a surface of a material having low conductivity, a mirror-like object, a powder, or the like by electroless plating. Further, the present invention relates to an electroless plating method for forming copper wiring on a semiconductor wafer, and particularly to a method for forming fine vias or trenches formed on a semiconductor wafer without causing defects such as voids and seams. The present invention relates to an electroless plating method suitable for a semiconductor wafer that can be embedded. Background art
  • the electroless metal plating method is one of the methods for forming a metal film on a nonconductive base, and is used for forming printed wiring on a resin substrate.
  • a method called activation in which a noble metal such as palladium is preliminarily attached to a base as a catalyst, is generally used.
  • the loading method has been used. These methods have many problems such as high toxicity !, the use of Sn, and the complicated processing steps.
  • the method of separately treating the plating catalyst fixing agent and the plating catalyst that is, the precious metal that becomes the catalyst after the coupling agent is adsorbed on the object
  • aminosilane coupling In the method using a mixed solution of the agent and palladium chloride, plating cannot be performed uniformly depending on the material to be covered and the plating conditions for the same reason or because palladium does not show sufficient catalytic activity. there were.
  • the catalyst be applied to processing methods utilizing conventional S n C 1 2 It was difficult to fix noble metal ions.
  • the damascene method is used to form copper wiring. This is done by forming a wiring pattern on a silicon wafer, then forming a barrier layer and a seed layer by sputtering or CVD, and wiring with an electric plating. The process of embedding patterns and removing excess precipitated copper with CMP is common.
  • LSI wiring is formed on the surface of a semiconductor wafer such as silicon
  • a via / trench is formed to bury copper wiring, and titanium, tantalum, or the like is used to prevent copper from diffusing into silicon on the surface.
  • Niride is coated to a thickness of about 0.01 to 0.1 ⁇ by sputtering, a CVD method, or the like.
  • a thin copper layer is coated on the barrier metal layer by sputtering, a CVD method, or the like, as described above.
  • the barrier metal generally has a large electric resistance, and the difference in current density between the periphery of the contact provided on the peripheral portion of the wafer and the central portion is large when the copper is coated later. Small copper is applied (thinly coated).
  • the conventional sputtering method described above requires the seed layer on the inner wall of the via trench. Insufficient coverage can be obtained, causing defects (void-seam) during subsequent electrical plating. In addition, the CVD method has the problem that the coverage is improved but the cost is extremely high. Disclosure of the invention
  • the present invention is based on the above-mentioned circumstances, and is based on a novel metallization which can be suitably electrolessly applied to powders, mirror-like objects, and resin cloths, to which conventional electroless plating is difficult to apply.
  • the purpose of this is to provide a method for using this.
  • the present invention can suitably apply electroless plating to a semiconductor wafer such as a silicon wafer among mirror-like objects, and is a problem in the case of fine wiring of a semiconductor wafer. It is an object of the present invention to provide a metal plating method capable of solving a lack of layer coverage.
  • the inventor of the present invention can solve the above-mentioned technical problems by surface-treating an adherend with a liquid in which a silane coupling agent having a metal-capturing ability is previously mixed or reacted. This led to the present invention.
  • a pretreatment agent is prepared by previously mixing or reacting a silane coupling agent having a functional group having a metal capturing ability with a noble metal compound,
  • a metal plating method characterized by electrolessly plating the object to be plated
  • silane coupling agent having an azole group is a silane coupling agent obtained by reacting an azole compound with an epoxysilane compound.
  • the azole group is an imidazole group (2) or
  • the noble metal compound is a palladium compound (1) to
  • a metal plating pretreatment agent comprising a liquid obtained by preliminarily mixing or reacting a silane coupling agent having a functional group having a metal capturing ability and a noble metal compound,
  • the present invention uses a specific silane coupling agent having the function of trapping a noble metal ion serving as a catalyst for electroless plating and the function of fixing the noble metal ion to a substance to be plated in the same molecule, and using a specific silane coupling agent. It is characterized by electroless plating after surface treatment of attached material.
  • a silane coupling agent By using such a silane coupling agent, not only can the plating process be shortened, but also the catalyst can be securely fixed to the adherend. Furthermore, as described above, it has been difficult to fix noble metal ions serving as a catalyst on a semiconductive mirror-like object such as a wafer.
  • Functional groups having a metal-capturing ability useful in the present invention include, but are not limited to, amino groups, carboxyl groups, azole groups, hydroxyl groups, mercapto groups, and the like.
  • an azole group is particularly preferred.
  • the azole group include imidazole, oxazolyl, thiazonole, selenazonole, pyrazole, isoxoxazole, isothiazole, triazole, oxazidazole, thiadiazole, tetrazole, oxatriazole, thiazoleazoreno, benzodazonolezo, benzoazonolezo, benzoazono, benzoazono, benzoazono, benzoazono, benzoazono And the like.
  • imidazole group is particularly preferred.
  • imidazole which is an azole compound, but is not a silane coupling agent
  • the adhesion of the plating to the adherend is very small, although the plating is performed with good uniformity.
  • the silane coupling agent used in the present invention is a compound having one S i XiX 2 X 3 group, and X, X 2 and X 3 mean an alkyl group, a halogen or an alkoxy group, and the like. Any functional group can be used as long as it can be fixed to an object.
  • X x 2 and x 3 may be the same or different.
  • a silane coupling agent obtained by a reaction between an azole compound and an epoxysilane compound can be exemplified (JP-A-6-256358).
  • Epoxy group-containing silane compounds to be reacted with such azole compounds include:
  • RR 2 represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and n represents 1 to 3.
  • the reaction between the azole compound and the epoxy group-containing silane compound can be performed under the conditions described in JP-A-6-256358. For example, at 80 to 200 ° C., 0.1 to 10 moles of an epoxy group-containing silane compound is added dropwise to 1 mole of the azole compound, and the mixture is reacted for 5 minutes to 2 hours. At this time, a solvent is not particularly required, but an organic solvent such as chloroform, dioxane, methanol, and ethanol may be used.
  • Noble metal compounds include chlorides, hydroxides, oxides, such as palladium, silver, platinum, and gold, which have a catalytic effect when depositing copper, nickel, etc. from the electroless plating solution on the surface of the adherend.
  • Examples include ammine complexes such as sulfates and ammonium salts. Palladium chloride is particularly preferred.
  • the noble metal compound is preferably used as an aqueous solution, and the concentration in the solution to be treated is preferably 20 to 30 Omg / L. According to the metal plating method of the present invention, the properties of the adherend are not limited.
  • inorganic materials such as glass and ceramics, plastic materials such as polyester, polyamide, polyimide, and fluororesin; insulating films such as films, sheets, tanada, and epoxy resins reinforced with glass cloth base materials as necessary It is applied to insulators with low conductivity, and objects with low conductivity such as semiconductors such as silicon wafers.
  • the method of the present invention can be preferably applied to the object to be plated whether it is a mirror-like object such as a transparent glass plate, a silicon wafer, or another semiconductor substrate, or a powder.
  • Such powders include glass beads, molybdenum disulfide powder, magnesium oxide powder, graphite powder, silicon carbide powder, dinoreconium oxide powder, alumina powder, silicon oxide powder, mica flake, glass fiber, And Teflon powder.
  • the semiconductor wafer referred to in the present invention includes not only silicon-based wafers but also compound semiconductor-based wafers such as gallium-arsenic, gallium-phosphorus, and indium-phosphorus.
  • the material of the surface to be covered of the semiconductor wafer is not limited.
  • a low-conductive barrier selected from titanium, tantalum, tungsten, or a nitride thereof (nitride) formed by vapor deposition, sputtering, CVD, or the like.
  • the metal is used as the covering surface, and the method of the present invention can be preferably applied in any case.
  • the method of the present invention can also be preferably applied when the surface to be covered is silicon or its oxide film.
  • a pretreatment agent is prepared by preliminarily mixing or reacting a silane coupling agent having a functional group having the above-mentioned metal-capturing ability with a noble metal ion on a base to be electrolessly plated.
  • the pretreatment agent can be used after being dissolved in an appropriate solvent.
  • the solvent for example, water, methyl alcohol, ethyl alcohol, 2-propanol, acetone, toluene, ethylene glycolone, polyethylene glycolone, dimethinole formamide, dimethyl sulfoxide, dioxane, or a mixture thereof is used. Can be used.
  • water it is necessary to optimize the pH of the solution, particularly according to the object to be covered and the plating conditions.
  • the concentration of the silane coupling agent having a functional group having a metal-capturing ability in the pretreatment agent or the solution in which the pretreatment agent is dissolved is not limited to 0. It is preferably from 0.1 to 10% by weight. If the content is less than 0.001% by weight, the amount of the compound adhering to the surface of the substrate tends to be low, and it is difficult to obtain the effect. On the other hand, if the content is more than 10% by weight, the amount of adhesion is too large to make it difficult to dry, or to cause agglomeration of the powder.
  • a method such as dipping or brushing is generally used, and then the solvent is volatilized, but the method is not limited to this. If it is a method of attaching a silane coupling agent uniformly to the surface without any problem, for powders, there is a method in which the solvent is volatilized after the immersion treatment and the silane coupling agent contained in the solution is forcibly attached to the base surface. Another method is to dry the wet powder by filtering off the solvent after the treatment, because the silane coupling agent can be adsorbed on the substrate surface in the immersion treatment state due to the uniform film forming property of the silane coupling agent. It is possible. Depending on the state of adhesion, the washing step may be omitted only by washing with water. Room temperature is sufficient for pretreatment (surface treatment), but heating may be effective depending on the object to be covered.
  • the adherend Before performing the plating pretreatment, the adherend may be washed.
  • a conventional etching treatment with chromic acid or the like may be used.
  • plating can be performed by omitting the drying step and simply washing with water after surface treatment. However, at this time, it is necessary to sufficiently wash the water so as not to bring the catalyst into the plating solution.
  • electroless plating is performed after the above surface treatment.
  • metals such as copper, nickel, cobalt, tin, and gold can be deposited at this stage. At this time, it may be effective to treat with a solution containing a reducing agent before plating. In particular, in the case of copper plating, treatment with a dimethylamine-borane solution or the like as the reducing agent is preferable. It is also possible to form a metal thin film by performing electroless plating and to give a certain degree of conductivity to a non-conductive base, and then to perform electroplating or replacement plating with a base metal. .
  • the metal plating method of the present invention is applied to a semiconductor wafer, copper or nickel is applied after the catalyst is applied on the barrier metal by performing the surface treatment as described above, instead of the conventional seed layer film forming method.
  • a seed layer is formed by electroless plating. This method can solve the problem of insufficient coverage of the inner wall of vias and trenches in the case of fine wiring at a lower cost than the CVD method.
  • copper is electrolessly plated, it is possible not only to use it as a shield layer but also to continually embed the wiring with the electroless plating.
  • electroless plating when the catalyst is uniformly attached to the surface to be plated, the film grows evenly on the surface to be plated, and in the case of fine wiring, a seam is easily generated.
  • the catalyst when the catalyst is applied by the method of the present invention, the catalyst easily adheres to the inner wall of the fine wiring. Metals tend to precipitate more easily in places where the amount of catalyst attached is larger, and therefore, by using the method of the present invention, a bottom-up type deposit such as an electrolytic copper plating solution used for embedding fine wiring occurs. Thus, fine wiring can be buried without generating seams. Of course, after the seed layer is formed by electroless copper plating, it is also possible to bury the wiring by electrolytic copper plating.
  • a method of subjecting the wafer to surface treatment by immersion treatment and then volatilizing the solvent is generally used, but the method is not limited to this.
  • a silane coupling agent uniformly to the I just need.
  • Room temperature is sufficient for performing the surface treatment, but heating can increase the adhesion speed and amount of the catalyst.
  • the heating temperature is preferably 30 to 80 ° C.
  • a solution in which the pretreatment agent is dissolved in an appropriate solvent can be used.
  • the drying step may be omitted only by washing with water.
  • the solvent used after the wafer surface treatment it is sufficient to heat the solvent to a temperature higher than the solvent's volatilization temperature and dry the surface.However, it is further heated at 60 to 120 ° C for 3 to 6 minutes. Is preferred.
  • the drying step can be omitted, and plating can be performed only by washing with water after surface treatment. However, in this case, it is necessary to perform sufficient washing with water to prevent the catalyst from being brought into the liquid.
  • the electroless copper plating solution contains formalin as a reducing agent. However, the use of formalin has tended to be avoided in recent years due to growing concerns over its impact on the environment. This problem can be solved by using an electroless nickel plating solution.
  • the electroless copper plating solution and the electroless nickel plating solution often contain an alkaline component as a raw material. Alkali components are the most unfavorable impurities in wiring materials, so raw materials that do not contain them must be used. For example, instead of sodium hydroxide used for pH adjustment, tetramethylammonium hydroxide oxide should be used. Further, dimethylamine-borane is preferably used as a reducing agent in the electroless nickel plating solution.
  • FIG. 1 is an SEM photographic image of the copper plating film formed on the silicon wafer obtained in Example 5.
  • FIG. 2 is an SEM photographic image of the copper plating film formed on the silicon wafer obtained in Comparative Example 6. BEST MODE FOR CARRYING OUT THE INVENTION
  • Example 1 to 4 and Comparative Examples 1 to 5 a cloth-like object to be plated was plated using the metal plating method of the present invention.
  • Example 5 to 8 and Comparative Examples 6 to 7 plating was performed on a semiconductor wafer using the metal plating method of the present invention.
  • Example 3 The nylon cloth was immersed in the plating pretreatment agent prepared in Example 1 at room temperature for 3 minutes, and thoroughly washed with running water. Thereafter, the nylon cloth was plated with an electroless nickel plating solution (nickel metal plating nickel plating solution FM-0) at 70 ° C. for 5 minutes. As a result, the nylon cloth was satisfactorily adhered to both sides in both uniformity and adhesion.
  • an electroless nickel plating solution nickel metal plating nickel plating solution FM-0
  • a palladium chloride aqueous solution was added to the aqueous solution containing 0.05% by weight of the silane coupling agent prepared in Example 1 at room temperature so as to have a concentration of 8 Omg ZL to prepare a pretreatment agent for plating.
  • a polyester cloth was immersed in the pretreatment agent for 3 minutes at room temperature, and the polyester cloth was sufficiently washed with running water. Then this polyester cloth Next, using an electroless nickel plating solution (Nikko Metal Plating's nickel plating solution FM-0), plating was performed at 70 ° C for 5 minutes. As a result, the polyester cloth was nickel-plated on one side with good uniformity and adhesion.
  • a cloth-like polyester resin was immersed in the pretreatment agent prepared in Example 1 for 3 minutes at room temperature, and thoroughly washed with running water. Next, the polyester cloth was immersed in a 3.7 g ZL aqueous solution of dimethylamine-borane heated to 60 ° C. for 3 minutes. Thereafter, the polyester cloth was plated at 70 ° C. for 10 minutes using an electroless copper plating solution (Nikko Metal Plating Copper Plating Solution PM-0). As a result, the polyester cloth was uniformly coated with copper on both sides in both uniformity and adhesion. Comparative Example 1
  • a silane coupling agent was obtained in the same manner as in Example 1. An aqueous solution containing only 0.2% by weight of this silane coupling agent alone was immersed in a cloth-like polyester resin at room temperature for 3 minutes. Next, this polyester cloth was immersed in an aqueous solution containing 30 mg ZL of palladium chloride for 3 minutes at room temperature, and then sufficiently washed with running water. Thereafter, the polyester cloth was plated at 70 ° C. for 5 minutes using an electroless nickel plating solution (nickel plating solution FM-0, manufactured by Mineral Metal Plating). As a result, the polyester cloth was hardly nickel-plated. Comparative Example 2
  • Nickel plating was carried out in the same manner as in Comparative Example 1 except that the cloth-like polyester resin was changed to a nylon cloth in Comparative Example 1. As a result, the nylon cloth was hardly nickel-plated. Comparative Example 3
  • a cloth-like polyester resin was immersed in an aqueous solution containing only 0.2% by weight of the same silane coupling agent as in Example 1 at room temperature for 3 minutes. Then this polyester The cloth was immersed in an aqueous solution containing 3 OmgZL of palladium chloride at room temperature for 3 minutes, and then sufficiently washed with running water. After that, the polyester cloth was immersed in 3.7 g ZL aqueous solution of dimethylamine-borane heated to 60 ° C for 3 minutes, and then electroless copper plating solution (Nikko Metal Plating copper plating solution PM-0) was used. It was fixed at 70 ° C for 10 minutes. As a result, the polyester resin cloth was hardly copper-plated. Comparative Example 4
  • Example 1 was repeated except that ⁇ -aminopropyltriethoxysilane (manufactured by Kanto Kagaku) was used in place of the silane coupling agent, which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane.
  • the polyester cloth was plated. As a result, the polyester resin cloth was hardly adhered. Comparative Example 5
  • Example 5 The same operation as in Example 1 was carried out except that imidazole was used in place of the equimolar reaction product of imidazole and V-dalicidoxypropyltrimethoxysilane in Example 1 and the concentration of palladium chloride was 30 OmgZL. Then, electroless nickel plating was performed on the polyester cloth. As a result, the polyester cloth had good plating coverage but poor adhesion.
  • imidazole was used in place of the equimolar reaction product of imidazole and V-dalicidoxypropyltrimethoxysilane in Example 1 and the concentration of palladium chloride was 30 OmgZL. Then, electroless nickel plating was performed on the polyester cloth. As a result, the polyester cloth had good plating coverage but poor adhesion.
  • Example 5 Example 5
  • Examples 5 to 8 and Comparative Examples 6 to 7 described below a silicon wafer having a fine via pattern and 30 nm of TaN sputtered thereon was used as an adherend.
  • the via pattern had a depth of lpm and a hole diameter of 0.18 ⁇ .
  • a palladium chloride aqueous solution was added at room temperature to an aqueous solution containing 0.05% by weight of the same silane coupling agent as in Example 1 at room temperature to prepare a pretreatment agent for plating.
  • the silicon wafer was immersed in the solution of the plating pretreatment agent at 60 ° C. for 10 minutes, and thoroughly washed with running water.
  • This silicon wafer is immersed in a 10 g ZL aqueous solution of dimethylamine-borane heated to 60 ° C for 15 minutes, and then sufficiently run under running water. Washed with water.
  • the silicon wafer was polished for 1 minute at 60 ° C using an electroless copper plating solution (Copper plating solution NKM-554 manufactured by Nikko Metal Plating Co., Ltd.). As a result, copper was plated over the entire surface of the silicon wafer with good adhesion. Further, the embedding into the fine via pattern was confirmed by cleaved cross-sectional SEM observation. As shown in FIG. 1, no voids and seams were observed, and the embedding was good.
  • a pretreatment for plating was prepared by adding a palladium chloride aqueous solution to an aqueous solution containing 0.05% by weight of the same silane coupling agent as in Example 1 at room temperature to a concentration of 20 OmgZL.
  • the silicon wafer was immersed in this plating pretreatment agent at 60 ° C for 5 minutes, and thoroughly washed with running water. Thereafter, the silicon wafer was plated at 65 ° C. for 4 seconds using an electroless plating solution (Ni-B, Nikko Metal Plating Co., Ltd.), and then thoroughly washed with running water.
  • the silicon wafer was plated at 60 ° C for 1 minute using an electroless copper plating solution (Copper plating solution NKM-554, manufactured by Nikko Metal Plating Co., Ltd.). As a result, copper was plated over the entire surface of the silicon wafer with good adhesion. Furthermore, the embedding into the fine via pattern was confirmed by cleavage cross-sectional SEM observation. As a result, no voids and seams were observed, and the embedding was good.
  • a palladium chloride aqueous solution was added to an aqueous solution containing 0.1% by weight of the same silane coupling agent as in Example 1 at room temperature so as to have a concentration of 15 OmgZL to prepare a pretreatment agent for plating.
  • the silicon wafer was immersed in this plating pretreatment agent at 60 ° C for 10 minutes, and thoroughly washed with running water.
  • the silicon wafer was immersed in a 10 g ZL aqueous solution of dimethylamine-borane heated to 60 ° C. for 15 minutes, and then sufficiently washed with running water.
  • the silicon wafer was plated at 60 ° C for 30 seconds using an electroless copper plating solution (Copper plating solution NKM-554 manufactured by Nikko Metal Plating Co., Ltd.), and then washed thoroughly with running water. did.
  • a copper plating solution is placed on the silicon wafer.
  • dm 2 plating equivalent to ⁇ was performed at room temperature.
  • copper was plated over the entire surface of the silicon wafer with good adhesion.
  • a palladium chloride aqueous solution was added to an aqueous solution containing 0.05% by weight of the same silane coupling agent as in Example 1 at room temperature to a concentration of 10 OmgZL to prepare a pretreatment agent for plating.
  • the silicon wafer was immersed in this pretreatment agent at 60 ° C. for 5 minutes, and thoroughly washed with running water.
  • the silicon wafer was plated at 65 ° C for 4 seconds using an electroless nickel plating solution (nickel plating solution Ni-B manufactured by Mineral Metal Plating Co., Ltd.), and then thoroughly washed with running water.
  • the silicon wafer was treated with a SnCl 2 aqueous hydrochloric acid solution, immersed in a PdCl 2 aqueous solution, and then sufficiently washed with running water. Next, the wafer was plated at 60 ° C. for 1 minute using a non-electrolytic copper plating solution (Nikko Metal Plating Co., Ltd., copper plating solution N KM—554). As a result, little copper was deposited on the silicon wafer. Industrial applicability
  • the novel plating method of the present invention it is possible to perform electroless plating on a substrate such as a powder or a resin cloth, which has conventionally been impossible to perform plating, with a simple process. It becomes possible. Furthermore, according to the plating method of the present invention, noble metal ions serving as a catalyst can be fixed even on a semiconductive mirror-like object such as a semiconductor wafer, which has been difficult in the past. Sticking can be performed easily. At the same time, this can solve the problem of insufficient power barrier of the seed layer on the inner wall of the via / trench at the time of forming the LSI fine wiring.

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  • Electroplating Methods And Accessories (AREA)

Abstract

On décrit un procédé de galvanoplastie qui consiste à mélanger ou à faire réagir un composé de métal noble faisant office de catalyseur avec un agent de couplage silane contenant un groupe fonctionnel capable de piéger un métal, en vue de préparer un agent de prétraitement, à soumettre un article devant être traité à un traitement de surface avec l'agent de prétraitement puis à soumettre l'article prétraité au dépôt autocatalytique. Le procédé permet de préparer sans défaut des produits métallisés par galvanoplastie à partir d'une poudre, d'une matière de résine et d'un article comportant une surface miroir tel qu'une tranche de semi-conducteurs, qui ont été difficilement métallisés de manière classique jusqu'à présent. De plus, le fait d'utiliser le procédé selon l'invention pour réaliser le câblage fin sur la surface d'une tranche de semi-conducteurs assure le recouvrement satisfaisant d'une couche d'amorce sur la paroi interne d'une tranchée d'interconnexion. En tant qu'agent de couplage silane, un composé comportant un groupe azole, et plus particulièrement, un groupe imidazole est judicieusement utilisé.
PCT/JP2000/008166 2000-01-07 2000-11-20 Procede de galvanoplastie, agent de pretraitement et tranche de semi-conducteurs et dispositif semi-conducteur utilisant cette derniere WO2001049898A1 (fr)

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JP2001550424A JP3670238B2 (ja) 2000-01-07 2000-11-20 金属めっき方法、前処理剤、それを用いた半導体ウェハー及び半導体装置
US10/767,697 US7045461B2 (en) 2000-01-07 2004-01-29 Metal plating method, pretreatment agent, and semiconductor wafer and semiconductor device obtained using these

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WO2004024984A1 (fr) * 2002-09-10 2004-03-25 Nikko Materials Co., Ltd. Procede de galvanoplastie et agent de pre-traitement
JP2006513325A (ja) * 2003-01-23 2006-04-20 アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド 触媒を用いた無電解めっきによりパターン化された絶縁体上に金属層を形成する方法
EP1681372A1 (fr) * 2003-10-17 2006-07-19 Nikko Materials Company, Limited Solution de cuivrage par depot autocatalytique et procede de cuivrage par depot autocatalytique
WO2006095589A1 (fr) * 2005-03-10 2006-09-14 Nippon Mining & Metals Co., Ltd. Substrat de resine, substrat pour composant electronique comportant un placage non-electrolytique, et procede de fabrication d’un substrat pour composant electronique
WO2006095590A1 (fr) * 2005-03-10 2006-09-14 Nippon Mining & Metals Co., Ltd. Matière de remplissage pour résine, matériau de base de résine contenant ladite matière et matériau substrat de composant électronique
JP2007063661A (ja) * 2005-04-25 2007-03-15 Hitachi Chem Co Ltd 無電解ニッケルめっき用前処理液、無電解ニッケルめっきの前処理方法無電解ニッケルめっき方法、並びに、プリント配線板及び半導体チップ搭載用基板の製造方法
KR100717336B1 (ko) * 2005-11-30 2007-05-10 한국기계연구원 갈바니 치환을 이용한 금속층의 무전해 도금방법
CN100348775C (zh) * 2002-04-23 2007-11-14 日矿金属株式会社 无电镀敷法和在其上形成金属镀层的半导体晶片
JPWO2005073431A1 (ja) * 2004-01-29 2008-04-24 日鉱金属株式会社 無電解めっき前処理剤、それを用いる無電解めっき方法、及び無電解めっき物
CN100454501C (zh) * 2003-02-17 2009-01-21 阿尔齐默股份有限公司 表面涂布的方法、用该方法在微电子器件中制造互连的方法,以及集成电路
WO2009038135A1 (fr) * 2007-09-18 2009-03-26 Nippon Mining & Metals Co., Ltd. Procédé pour supporter une nanoparticule métallique, et substrat portant une nanoparticule métallique
JP2010168612A (ja) * 2009-01-21 2010-08-05 Fujitsu Ltd 無電解めっき物の製造方法
JP2011091427A (ja) * 2005-09-15 2011-05-06 Jx Nippon Mining & Metals Corp 微細スルーホールを有するプリント配線基板およびその製造方法
WO2012010655A1 (fr) * 2010-07-21 2012-01-26 Saint-Gobain Isover Procédé de métallisation de fibres minérales et leur utilisation
JPWO2010029635A1 (ja) * 2008-09-11 2012-02-02 パイオニア株式会社 金属配線の形成方法、及び金属配線を備えた電子部品
US8182873B2 (en) 2003-06-09 2012-05-22 Nippon Mining & Metals Co., Ltd. Method for electroless plating and metal-plated article
US8404035B2 (en) 2003-10-17 2013-03-26 Nippon Mining & Metals Co., Ltd. Electroless copper plating solution
JP2013151758A (ja) * 2008-03-07 2013-08-08 Japan Science & Technology Agency 複合材料
EP2791388A4 (fr) * 2011-12-15 2015-08-19 Henkel IP & Holding GmbH Placage électrolytique d'argent sur du graphite

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TWI573687B (zh) * 2013-12-31 2017-03-11 財團法人工業技術研究院 積層板及其製作方法
TWI672175B (zh) * 2017-10-20 2019-09-21 國立清華大學 自吸附觸媒組成物、自吸附觸媒組成物的製造方法以及無電鍍基板的製造方法
CN111826643B (zh) * 2020-07-14 2023-05-12 华东理工大学 一种改性金属表面活化镀铜提高镀层结合力的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100348775C (zh) * 2002-04-23 2007-11-14 日矿金属株式会社 无电镀敷法和在其上形成金属镀层的半导体晶片
WO2004024984A1 (fr) * 2002-09-10 2004-03-25 Nikko Materials Co., Ltd. Procede de galvanoplastie et agent de pre-traitement
US7867564B2 (en) 2002-09-10 2011-01-11 Nippon Mining & Metals Co., Ltd. Metal plating method and pretreatment agent
JP2006513325A (ja) * 2003-01-23 2006-04-20 アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド 触媒を用いた無電解めっきによりパターン化された絶縁体上に金属層を形成する方法
CN100454501C (zh) * 2003-02-17 2009-01-21 阿尔齐默股份有限公司 表面涂布的方法、用该方法在微电子器件中制造互连的方法,以及集成电路
US8182873B2 (en) 2003-06-09 2012-05-22 Nippon Mining & Metals Co., Ltd. Method for electroless plating and metal-plated article
KR100767943B1 (ko) 2003-10-17 2007-10-17 닛코킨조쿠 가부시키가이샤 무전해 구리도금액 및 무전해 구리도금방법
US8404035B2 (en) 2003-10-17 2013-03-26 Nippon Mining & Metals Co., Ltd. Electroless copper plating solution
EP1681372A4 (fr) * 2003-10-17 2008-07-16 Nippon Mining Co Solution de cuivrage par depot autocatalytique et procede de cuivrage par depot autocatalytique
EP1681372A1 (fr) * 2003-10-17 2006-07-19 Nikko Materials Company, Limited Solution de cuivrage par depot autocatalytique et procede de cuivrage par depot autocatalytique
US7713340B2 (en) 2004-01-29 2010-05-11 Nippon Mining & Metals Co., Ltd. Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating
JPWO2005073431A1 (ja) * 2004-01-29 2008-04-24 日鉱金属株式会社 無電解めっき前処理剤、それを用いる無電解めっき方法、及び無電解めっき物
JP4711415B2 (ja) * 2004-01-29 2011-06-29 Ｊｘ日鉱日石金属株式会社 無電解めっき前処理剤、それを用いる無電解めっき方法、及び無電解めっき物
JP5072094B2 (ja) * 2005-03-10 2012-11-14 Ｊｘ日鉱日石金属株式会社 樹脂用フィラー、それを配合した樹脂基材、及び電子部品基材
WO2006095590A1 (fr) * 2005-03-10 2006-09-14 Nippon Mining & Metals Co., Ltd. Matière de remplissage pour résine, matériau de base de résine contenant ladite matière et matériau substrat de composant électronique
WO2006095589A1 (fr) * 2005-03-10 2006-09-14 Nippon Mining & Metals Co., Ltd. Substrat de resine, substrat pour composant electronique comportant un placage non-electrolytique, et procede de fabrication d’un substrat pour composant electronique
US8043705B2 (en) 2005-03-10 2011-10-25 Nippon Mining & Metals Co., Ltd. Resin substrate material, electronic component substrate material manufactured by electroless plating on the same, and method for manufacturing electronic component substrate material
JP2007063661A (ja) * 2005-04-25 2007-03-15 Hitachi Chem Co Ltd 無電解ニッケルめっき用前処理液、無電解ニッケルめっきの前処理方法無電解ニッケルめっき方法、並びに、プリント配線板及び半導体チップ搭載用基板の製造方法
JP2011091427A (ja) * 2005-09-15 2011-05-06 Jx Nippon Mining & Metals Corp 微細スルーホールを有するプリント配線基板およびその製造方法
KR100717336B1 (ko) * 2005-11-30 2007-05-10 한국기계연구원 갈바니 치환을 이용한 금속층의 무전해 도금방법
US8318313B2 (en) 2007-09-18 2012-11-27 Jx Nippon Mining & Metals Corporation Method for supporting metal nanoparticles and metal nanoparticles-carrying substrate
WO2009038135A1 (fr) * 2007-09-18 2009-03-26 Nippon Mining & Metals Co., Ltd. Procédé pour supporter une nanoparticule métallique, et substrat portant une nanoparticule métallique
JP5514548B2 (ja) * 2007-09-18 2014-06-04 Ｊｘ日鉱日石金属株式会社 ナノ金属粒子担持方法及びナノ金属粒子担持基板
JP2013151758A (ja) * 2008-03-07 2013-08-08 Japan Science & Technology Agency 複合材料
JPWO2010029635A1 (ja) * 2008-09-11 2012-02-02 パイオニア株式会社 金属配線の形成方法、及び金属配線を備えた電子部品
JP2010168612A (ja) * 2009-01-21 2010-08-05 Fujitsu Ltd 無電解めっき物の製造方法
WO2012010655A1 (fr) * 2010-07-21 2012-01-26 Saint-Gobain Isover Procédé de métallisation de fibres minérales et leur utilisation
EP2791388A4 (fr) * 2011-12-15 2015-08-19 Henkel IP & Holding GmbH Placage électrolytique d'argent sur du graphite
US10361016B2 (en) 2011-12-15 2019-07-23 Henkel IP & Holding GmbH Electroless plating of silver onto graphite
US10923249B2 (en) 2011-12-15 2021-02-16 Henkel IP & Holding GmbH Electroless plating of silver onto graphite

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