KR20100082172A - Method for forming copper interconnection layer - Google Patents

Abstract

PURPOSE: A copper wiring formation method is provided to perform electroplating or electroless plating directly on ruthenium film surface and to perform preprocessing using a chemical technique. CONSTITUTION: A copper wiring formation method comprises next steps. The oxide film on the anti-diffusion film formed in a substrate is eliminated using aqueous solution and copper ion is reduced on the anti-diffusion film. A copper layer is formed on the anti-diffusion film on which the copper ion has been reduced. The aqueous solution comprises copper salt, reducing agent, complexing agent, Ph controlling agent. The anti-diffusion film is formed from ruthenium. The copper layer is formed using electroplating or electroless plating. The copper salt is copper sulfate pentahydrate. The Ph controlling agent is NaOH, KOH, TMAH(Tetramethylammonium hydroxide) or H3BO3.

Description

Method for forming copper interconnection layer

The present invention relates to a copper wiring forming method, and to a copper wiring forming method for forming a seed layer in the diffusion barrier film by a pretreatment step.

Increasingly, as line widths are reduced in metallization processes, the need for thinner, continuous seed layers for electroplating is growing. In the formation of the seed layer by conventional physical vapor deposition, the thickness of the seed layer formed on the side wall surface becomes thinner than the top or the bottom of the pattern due to the weak step coating property. Continuity is threatened. Therefore, various metal thin film forming technologies having very high step coverage from the formation process are actively researched, including electroless plating, chemical vapor deposition, and atomic layer vapor deposition.

Among these, electroless plating is a chemical reaction that forms a catalyst on the surface and then reduces metal ions on the surface of the catalyst using a reducing agent coexisting in the solution, and has excellent step spreadability and excellent thickness uniformity on a large-area substrate. Its various advantages have been actively studied. However, in order to initiate such electroless plating, there is a problem in that specific catalyst materials that can act as a catalyst for electroless plating must be formed in advance on the substrate. In general, in the case of the diffusion barrier film used as the substrate for forming the seed layer in the metal wiring of the semiconductor process, the current tantalum and the like do not have any catalytic activity against the electroless plating, and therefore, the formation of additional catalyst material has been required. .

In the case of the most actively used palladium catalysis process, discontinuous catalyst particle layers were formed on the surface through various chemical processes, and electroless plating was induced from these catalyst particles. However, in this case, the density and size of the catalyst particles have been an important constraint in the formation of thin films, and the interfacial energy between the substrate and the catalyst material and the complicated chemical mechanism of the catalysis process itself control the size and density of the catalyst layer. There have been many difficulties.

Meanwhile, ruthenium is one of the materials being studied as a diffusion barrier to replace tantalum in the future. In the case of ruthenium, very thin thin films can be easily formed even in high-difference patterns through chemical vapor deposition or atomic layer vapor deposition, and have an appropriate diffusion preventing performance and above all, an initial particle formation step with excellent adhesion to copper thin films. Since it has a high density at, the copper thin film can be formed through electroplating directly on ruthenium. However, due to the relatively high electrical resistance of ruthenium, nonuniformity of plating amount may appear on the wafer surface of large area, and even thin film can be formed by three-dimensional growth due to initial particle formation even by direct electroplating. There is a constraint on the minimum thickness.

Therefore, there has been a study to use copper electroless plating directly on the surface using ruthenium as a catalyst to use it as a seed layer. However, electroless plating using ruthenium as a catalyst has not been actively studied, and it is known that ruthenium does not have catalytic activity for initiating a plating reaction with respect to a conventional copper electroless plating solution. In addition, ruthenium is known to form a very thin natural oxide film in the air, the presence of such a natural oxide film is to increase the interfacial energy with the copper film to be formed to reduce the adhesion, and to reduce the particle density in the initial particle formation step Known. Therefore, many studies to date have further required a process of forcibly reducing ruthenium's natural oxide film through external current application.

Therefore, the problem to be solved by the present invention is to provide a method for forming a copper wiring that can easily and simply form a thin copper metal thin film by forming a continuous seed layer.

Copper wiring forming method according to the present invention for achieving the above object is: an aqueous solution containing a copper salt, a reducing agent, a complex forming agent and a pH adjusting agent to remove the oxide film on the diffusion barrier formed on the substrate and copper ions on the diffusion barrier Reducing; And forming a copper layer on the diffusion barrier layer in which the copper ions are reduced.

At this time, the diffusion barrier is formed of ruthenium, the copper layer is characterized in that the electroplating or electroless plating.

In addition, the copper salt is copper sulfate pentahydrate, the pH adjusting agent is NaOH, KOH, Tetramethylammonium hydroxide (TMAH) or H ₃ BO ₃ , the complexing agent is a compound containing citrate or citrate hydrate, the reducing agent is NaH ₂ PO ₂ , NH ₄ H ₂ PO ₂ , KH ₂ PO _{2 It} is characterized in that at least any one selected from a reducing agent consisting of salts of cations and hypophosphate ions.

Further, the temperature of the aqueous solution is 50 ~ 90 ℃, characterized in that the pH is 8-12.

According to the present invention, since a thin and continuous seed layer or a thin metal film can be formed on the diffusion barrier such as ruthenium, the seed layer continuity at the pattern side wall which can be seen in the seed layer formation using conventional physical vapor deposition. The problem can be solved, electrolytic plating or electroless plating can be performed directly on the surface of the ruthenium thin film, and since the pretreatment is performed using a chemical method, it is more useful for processing on a large-area substrate than electroplating.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following examples are only presented to understand the content of the present invention, and those skilled in the art will be capable of many modifications within the technical spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to these embodiments.

First, the ruthenium is grown to a thickness of 500 으로서 as a diffusion barrier film through physical vapor deposition on the Si substrate, and the ruthenium surface is pretreated to remove the oxide film formed on the ruthenium surface and reduce it to copper ions. At this time, the constitution and process conditions of the pretreatment aqueous solution are shown in Table 1 below.

Usage Kinds density Cu source CuSO ₄ · 5H ₂ O 2.49 g reducing agent NaH ₂ PO ₂ · H ₂ O 2.12 g Complexing agent Na ₃ C ₃ H ₅ O (COO) ₃ 2.91 g pH regulator
H ₃ BO ₃ 6.18 g NaOH 2.65 g PH of solution 10.0

That is, the present invention provides primary phosphate ions as the reducing agent: ^- thin, the process proceeds to the using the progress in the formation of a very thin copper film to the removal of the oxide film on the initial at the same time, and then electroless plating on this surface (hypophosphite H ₂ PO ₂₎ To form a continuous thin film. Hypophosphate ions are materials that are used as reducing agents in many electroless platings and reduce metal ions by releasing electrons through reaction paths such as

^{_{H 2 PO 2 - + H 2}} O -> H 2 PO 3 - + 2H + + 2e -

These hypophosphate ions are used as reducing agents in many electroless platings, such as cobalt and gold, because the reaction is accelerated by using a metal surface as a catalyst. However, it is known that hypophosphite ions have activity on electroless plating reactions on ruthenium surfaces but not on electroless plating on copper surfaces. Therefore, even though the potential of the electrode shifts toward the cathode through the oxidation reaction of the diphosphate ions on the ruthenium surface, the copper on the surface can no longer act as a catalyst. There will be limits. This also results in no continuous electroless plating reaction on the already formed copper surface, which can suppress further particle growth reactions and possibly lead to the formation of thin films. Through this property, the copper film is formed very thin on the surface and then used as a catalyst for subsequent electroless plating.

Pretreatment of the ruthenium surface is performed by immersing the substrate on which the ruthenium diffusion barrier film is formed in an aqueous solution maintained at 70 ° C for 10 minutes. The pretreatment process removes the oxide film on ruthenium and reduces the ruthenium surface to copper ions.

The pretreated substrate is washed with deionized water and then immersed in a copper electroless plating solution or a copper electrolytic plating solution to form a copper layer, that is, a copper thin film layer on a ruthenium thin film in which copper ions are reduced.

Table 2 below shows the composition of the copper electroless plating solution.

Usage Kinds density Cu source CuSO ₄ · 5H2O 0.63 g reducing agent HCHO 0.29 g Complexing agent EDTA (ethylenediamine-
tetraacetic acid) 1.58 g pH regulator KOH 2.70 g Surfactants Polyethyleneglycol 0.36 mg

1 is a graph showing the sheet resistance of the ruthenium surface when the ruthenium surface is subjected to electroless plating after the pretreatment of the ruthenium surface according to the embodiment of the present invention, and FIG. Electron micrograph.

Referring to FIG. 1, since copper has a lower specific resistance than ruthenium, when the copper thin film is formed on the ruthenium surface through electroless plating, the sheet resistance of the thin film tends to decrease rapidly. It can be seen that through the normal formation.

Referring to FIG. 2, it can be seen that the copper thin film is successfully formed on the ruthenium thin film. The copper thin film thus formed has excellent interfacial properties and adhesion with the ruthenium thin film.

The present invention is to form a thin and continuous seed layer or metal thin film on the diffusion barrier such as ruthenium in the increasingly fine metal wiring process, through the process to form a seed layer having a very high step coverage in the fine pattern Alternatively, electrolytic plating or electroless plating may be performed directly on the surface of the ruthenium thin film. This solves the seed layer continuity problem at the pattern sidewalls that may occur in conventional physical vapor deposition, and eliminates the early-stage particle formation process that other thin film formation techniques on ruthenium may face. It is expected to be an excellent solution to the limitations of process technology. In addition, since the pretreatment is performed using a chemical method, it is suitable for the process technology in a large area substrate in the future compared to the electroplating.

 The present invention is not limited to the above embodiments, and it is apparent that many modifications are possible by those skilled in the art within the technical spirit of the present invention.

1 is a graph showing the sheet resistance of the ruthenium surface when the electroless plating is performed after pretreatment of the ruthenium surface according to an embodiment of the present invention; And

2 is an electron micrograph of the copper thin film surface and cross section formed according to an embodiment of the present invention.

Claims (9)

Removing an oxide film on the diffusion barrier film formed on the substrate with an aqueous solution containing a copper salt, a reducing agent, a complex forming agent, and a pH adjusting agent, and reducing copper ions on the diffusion barrier film; Forming a copper layer on the diffusion barrier film is reduced copper ions. The method of claim 1, wherein the diffusion barrier layer is formed of ruthenium. The method of claim 1, wherein the copper layer is formed by electroplating or electroless plating. The method of claim 1, wherein the copper salt is copper sulfate pentahydrate. The method of claim 1, wherein the pH adjusting agent is NaOH, KOH, Tetramethylammonium hydroxide (TMAH) or H ₃ BO ₃ characterized in that the copper wiring forming method. The method of claim 1, wherein the complexing agent is a compound including citrate or citrate hydrate. The method of claim 1, wherein the reducing agent is at least one selected from NaH ₂ PO ₂ , NH ₄ H ₂ PO ₂ , KH ₂ PO _2, and a reducing agent consisting of a salt of a cation and a hypophosphate ion. . The method of claim 1, wherein the temperature of the aqueous solution is 50 ~ 90 ℃ copper wiring forming method. The method of claim 1, wherein the pH of the aqueous solution is a copper wiring forming method, characterized in that 8 to 12.

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