Method of producing semiconductor device

Abstract

A method of producing semiconductor device for reducing a gas of halogenated product of a group IVa element with H2 by the ECR plasma CVD method to form a thin film of the group IVa element on a substrate is disclosed. This method includes forming an adhesion layer of the group IVa element in a contact hole including walls, to be in contact with the exposed substrate, the adhesion layer being formed by reducing with H2 a gas of halogenated product of the group IVa element in an ECR plasma CVD process, the group IVa element and H2 being used at a flow ratio of 0.4 and greater; forming a barrier layer in contact with the adhesion layer; and filling the contact hole with an electrically conductive material. The stable barrier metal is formed and an upper-layer metallization material is filled within the minute contact hole having a large aspect ratio.

Description

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to a method of metallization of a semiconductor device, and particularly to a method of producing a highly reliable contact part, which is adapted for improving conformality of a thin film of a group IVa element, above all a Ti film employed as a barrier metal, by the electron cyclotron resonance (ECR) plasma CVD method.

[0003] 2. Description of the Related Art

[0004] For filling a metallization material into a contact hole of recent VLSI or ULSI, particularly a contact hole for having substrate-contact with an impurity diffused region in an Si substrate, aluminum (Al) and tungsten (W) are broadly used as an electrically conductive material for filling.

[0005] In order to enhance the reliability of contact by these filling metals, the inner wall of the contact hole is covered with a barrier metal composed of the group IVa element before the filling. A barrier metal which has a two-layer structure consisting of a titanium (Ti) film and a titanium nitride (TiN) film is employed as the above-mentioned barrier metal. The barrier metal of two-layer structure is employed for providing a Ti film having capability of reducing a natural oxidation film on the substrate of the Si substrate so as to assure ohmic property, and for stacking a TiN film thereon to assure barrier property.

[0006] These Ti film and TiN film are formed generally by sputtering. The process of forming the latter TiN film is particularly called reactive sputtering, in which a Ti target is sputtered in a nitrogen-containing atmosphere.

[0007] However, with the sputtering method, the step coverage in a recent contact hole of high aspect ratio is insufficient. Grains of a film forming material sputtered out from the target are incident on the substrate with certain directionality. Therefore, the travelling grains are prevented from reaching deep inside of the hole by shadowing effect of the sidewalls of the contact hole itself.

[0008] Thus, the CVD method is expected to be promising as it is capable of forming the barrier metal with satisfactory coverage on the basis of chemical reactions of the surface in the contact hole.

[0009] The TiN film can be formed relatively easily by a known process using various material gases and the CVD method. For instance, an example of forming the TiN film based on methylhydrazine reduction of TiCl4 using a low pressure CVD device of parallel flat plate single-wafer processing is reported in Monthly Semiconductor World, January 1993, pages 145-151. The formation Gibbs energy in this reaction system of TiN at normal temperatures is approximately −209 kJ/mol (ΔG<0). The system is thermodynamically stable.

[0010] On the contrary, the reaction system of film formation of the Ti film by the CVD method is limited to H2 reduction of TiCl4 as far as it is known. In addition, the forming Gibbs energy in the reaction system as shown by the following formula is 209 kJ/mol (ΔG>0), which is very high, at temperatures within a range of 100 to 1000° C. for currently practical semiconductor processes.

TiCl4+2H2→Ti+4HCl

[0011] Therefore, film formation of the Ti film by the conventional CVD method has rarely been realized.

[0012] Recently, a technique of forming the Ti film by the ECR plasma CVD method utilizing ECR discharge of high dissociation efficiency of material gases has been proposed instead of the conventional heat CVD method.

[0013] However, the Ti film formation by this method is not satisfactory in reliability and reproducibility. For instance, if the Ti film grows into grains, not conformal, under certain conditions, the TiN film growing thereon inherits the surface profile of the Ti film, thus further increasing surface irregularities of the barrier metal. Consequently, problems arise, such as, generation of a crack in a corner part on the bottom of the contact hole, and difficulty in filling the contact hole with an upper-layer metallization material in the latter process. The Ti film is a critical component for assuring the ohmic property of the contact. The conformality of the Ti film is a requirement for assuring reliability of the contact part.

OBJECT AND SUMMARY OF THE INVENTION

[0014] It is an object of the present invention to provide a method of producing semiconductor device which is adapted for improving conformality of the Ti film formed by the ECR plasma CVD method and for raising reliability of the contact part.

[0015] According to the present invention, there is provided a method of producing semiconductor device including the steps of: forming an insulating layer on a substrate; forming a contact hole in the insulating layer to expose a selected portion of the substrate, the contact hole being defined by walls of the insulating layer; forming an adhesion layer of a group IVa element in the contact hole including the walls, to be in contact with the exposed substrate, the adhesion layer being formed by reducing with H2 a gas of halogenated product of the group IVa element in an ECR plasma CVD process, the group IVa element and H2 being used at a flow ratio of 0.4 and greater; forming a barrier layer in contact with the adhesion layer; and filling the contact hole with an electrically conductive material.

[0016] If the flow ratio of the group IVa element to H2 is smaller than 0.4, grain growth of Ti is observed in a fine contact hole. Although the upper limit of the flow ratio is not particularly defined, an excessively large flow ratio may lower the reduction capability of H2, disturbing achievement of practical film forming speed. Therefore, the flow ratio is selected in a range approximately up to 2.

[0017] After a thin film of the group IVa element is formed, a nitride film of the group IVa element may be continuously formed on the thin film.

[0018] The nitride film may be formed by the CVD method or in a self-aligned manner by annealing the thin-film of the group IVa element in a nitrogen-containing atmosphere.

[0019] The group IVa element includes three types, that is, Ti, zirconium (Zr) and hafnium (Hf). Forming the Ti film using a TiCl4 gas is particularly effective.

[0020] In an experiment, when the flow ratio of a TiCl/H2 mixed gas was set to 0.4 or greater, conformal formation of the Ti film was possible. On the contrary, at a flow ratio of the TiCl/H2 mixed gas of 0.4 or smaller, grain growth of Ti was observed. The reason for the above results is conceivably as follows. As an excessive amount of by-products, such as HCl, are generated near the bottom of the fine contact hole in the atmosphere containing an excessive amount of H2, vapor pressures in a micro ambient is lowered and release thereof is restricted. Consequently, individual Ti crystalline nuclei grow extraordinarily. From the above phenomenon, it is conceivable that the quantity balance of the by-products from the viewpoint of the vapor pressure can be improved at the flow ratio of 0.4 and greater, and that other Ti crystalline nuclei are sequentially formed on the substrate before the individual crystalline nuclei grow extraordinarily, thus realizing conformality.

[0021] As the Ti film is thus formed conformally, even when a TiN film is stacked on the Ti film by the CVD method, a film inheriting the property of the underlying film can be grown. Thus, the risk of generating the crack in the corner part of the contact hole is eliminated.

[0022] If the Ti film is annealed in a nitrogen-containing atmosphere, the TiN film is formed conformally and in a self-aligned manner.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIGS. 1A to 1D are cross-sectional views of an example of a series of processes, sequentially shown, in which the method of the present invention is applied to filling a contact hole. FIG. 1A shows a state in which the contact hole is closed with an SiO2 interlayer insulating film. FIG. 1B shows a state in which a Ti film is formed conformally by the ECR plasma CVD method. FIG. 1C shows a state in which a TiN film is formed conformally. FIG. 1D shows a state in which the contact hole is uniformly filled with an upper-layer metallization film.

[0024] FIGS. 2A to 2C are cross-sectional views of another example of a series of processes, sequentially shown, in which the method of the present invention is applied to filling the contact hole. FIG. 2A shows a state in which a conformal Ti film is formed to cover the contact hole. FIG. 2B shows a state in which a conformal TiN film and a TiSi2 layer are formed in a self-aligned manner by nitriding anneal. FIG. 2C shows a state in which the contact hole is uniformly filled with an upper-layer metallization film.

[0025] FIGS. 3A and 3B are cross-sectional views of a comparative example of filling the contact hole, sequentially shown. FIG. 3A shows a state in which a granular Ti film has grown within the contact hole. FIG. 3B shows a state in which a TiN film having large surface irregularities has grown on the Ti film.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

EXAMPLE 1

[0027] The present example is of the contact hole filling process. In this example, a Ti film was formed by the ECR plasma CVD method at a TiCl4/H2 flow ratio of 0.8, and then a TiN film was continuously formed similarly by the ECR plasma CVD method. Finally, the contact hole was filled with a Al-1% Si film. This process will be explained with reference to FIGS. 1A to 1D.

[0028] A sample wafer used in this example has a contact hole 3 with a diameter of approximately 0.3 μm opened in an SiO2 interlayer insulating film 2 with a thickness of approximately 1 μm deposited on an Si substrate 1, as shown in FIG. 1A. Therefore, the contact hole 3 exhibits an aspect ratio of 3 or greater. However, the aspect ratio is expressed in a compressed manner in FIGS. 1A to 1D.

[0029] The wafer was set on an ECR plasma CVD device, and a Ti film with a thickness of 2 to 10 nm was formed under the following conditions.

TiCl4 flow rate          24 SCCM
H2 flow rate             30 SCCM
gas pressure             0.12 Pa
microwave power          2.8 kW (2.45 GHz)
film forming temperature 420° C.

[0030] By setting the above conditions, a Ti film 4c for conformally covering the inner wall surface of the contact hole was formed, as shown in FIG. 1B. The subscript “c” indicates conformality hereinbelow.

[0031] Next, a TiN film was continuously formed in the same device. Exemplary film forming conditions are shown as follows.

TiCl4 flow rate          20 SCCM
H2 flow rate             26 SCCM
N2 flow rate             6 SCCM
gas pressure             0.23 Pa
microwave power          2.8 kW (2.45 GHz)
film forming temperature 420° C.

[0032] In this process, a TiN film 5c reflecting the profile of the conformal underlying Ti film 4c and being similarly conformal was formed, as shown in FIG. 1C. Cracks and defects at the corner part of the bottom of the contact hole 3 were not observed.

[0033] The contact hole 3 thus having a satisfactory barrier metal formed thereto was uniformly filled with an upper-layer metallization film 6, as shown in FIG. 1D. As the upper-layer metallization film 6 in this example, an Al-1% Si film formed by high-temperature sputtering or a tungsten (W) film formed by the blanket CVD method can be used. In either case, satisfactory results were obtained.

EXAMPLE 2

[0034] In the present example, a Ti film was conformally formed, and then the Ti film was annealed in a nitrogen-containing atmosphere to form a TiN film in a self-aligned manner. This process will be described with reference to FIGS. 2A to 2C. Reference numerals of FIGS. 2A to 2C are partly the same as those of FIGS. 1A to 1D.

[0035] First, a wafer as shown in FIG. 2A, having a TiN film 4c formed thereon in a manner similar to Example 1, was set on an annealing device and was nitrided at annealing temperatures of 500 to 900° C. for annealing time of 30 to 120 seconds in an N2 atmosphere or an ammonium (NH3) atmosphere.

[0036] By this nitriding anneal, the Ti film 4c was changed into a TiN film 7c on an SiO2 interlayer insulating film 2, as shown in FIG. 2B.

[0037] A major part of the Ti film 4c was changed into the TiN film 7c on the bottom of the contact hole 3, and a titanium/silicide (TiSi2) layer 8 was formed in a self-aligned manner on the boundary face with the Si substrate 1. This TiN/TiSi2 two-layer structure was generated for the following reasons. Since TiN having a formation Gibbs energy of −336.6 kJ/mol is thermodynamically more stable than TiSi2 having a formation Gibbs energy of −134.4 kJ/mol, the nitriding of the Ti film on the bottom of the contact hole 3 precedes the silicification thereof, and the resulting TiN film 7c serves as a barrier to external diffusion of Si. By this process, formation of the barrier metal and ohmic contact were simultaneously achieved.

[0038] On the TiN film 7c which was conformally formed, the contact hole 3 was stably filled with the upper-layer metallization film 6, as shown in FIG. 2C. Thus, low-resistance contact was realized.

COMPARATIVE EXAMPLE

[0039] In the present comparative example, a Ti film was formed at a TiCl4/H2 flow rate of 0.2, and a TiN film was subsequently formed thereon. This process will be explained with reference to FIGS. 3A and 3B.

[0040] First, the wafer as previously shown in FIG. 1A was set on an ECR plasma CVD device, and a Ti film with a thickness of 2 to 10 nm was formed under the following conditions.

TiCl4 flow rate          6 SCCM
H2 flow rate             30 SCCM
gas pressure             0.12 Pa
microwave power          2.8 kW (2.45 GHz)
film forming temperature 420° C.

[0041] Under the above conditions, a conformal Ti film 4c was formed in the extreme vicinity of the upper surface of the SiO2 interlayer insulating film 2 the opening end of the contact hole 3, as shown in FIG. 3A. However, a granular Ti film 4g grew on the sidewall surface to the bottom. The subscript “g” indicates that the Ti film is granular. The above phenomenon is generated conceivably because an excessive amount of H2 in the film forming gas prevents reaction by-products from being released, causing Ti crystal nuclei to grow extraordinarily.

[0042] If a TiN film was subsequently formed thereon by the ECR plasma CVD method, a conformal TiN film 5c grew on the conformal Ti film 4c, as shown in FIG. 3B. However, a granular TiN film 5g grew on the granular Ti film 4g, intensifying the surface irregularities. Also, a crack was generated in the corner part on the bottom of the contact hole 3.

[0043] The upper-layer metallization film, not shown, was not filled uniformly on such a non-uniform barrier metal, and sufficient ohmic contact was not achieved. Also, a leak current was increased by the crack.

[0044] The present invention is described above on the basis of the two examples. However, it is to be understood that the present invention is not limited to these examples, and that details of the structure of the sample wafer and the film forming conditions may be suitably modified.

[0045] For instance, the structure of the barrier metal is not limited to the above-described Ti/TiN two-layer structure. A Ti/TiN/Ti three-layer structure having another Ti film stacked on the two-layer structure may also be employed.

[0046] In the above embodiment, the contact hole filling process is explained. A similar filling process is effective for a via hole.

[0047] As is clear from the above description, according to the present invention, a conformal Ti film can be formed stably by the ECR plasma CVD method. Thus, a barrier metal can be stably formed and an upper-layer metallization material can be filled even within a fine contact hole having a large aspect ratio. Consequently, a semiconductor device having highly reliable metallization can be produced.

Claims

1. A method of producing semiconductor device comprising the steps of: forming an insulating layer on a substrate; forming a contact hole in the insulating layer to expose a selected portion of the substrate, the contact hole being defined by walls of the insulating layer; forming an adhesion layer of a group IVa element in the contact hole including the walls, to be in contact with the exposed substrate, the adhesion layer being formed by reducing with H2 a gas of halogenated product of the group IVa element in an ECR plasma CVD process, the group IVa element and H2 being used at a flow ratio of 0.4 and greater; forming a barrier layer in contact with the adhesion layer; and filling the contact hole with an electrically conductive material.

2. The method of producing semiconductor device as claimed in claim 1, wherein the barrier layer is composed of nitride of the group IVa element.

3. The method of producing semiconductor device as claimed in claim 2, wherein the nitride of the group IVa element is formed into a film continuously on the adhesion layer.

4. The method of producing semiconductor device as claimed in claim 3, wherein the nitride of the group IVa element is deposited by a CVD process.

5. The method of producing semiconductor device as claimed in claim 2, wherein the nitride of the group IVa element is formed in a self-aligned manner by annealing the barrier layer of the group IVa element in a nitrogen-containing atmosphere.

6. The method of producing semiconductor device as claimed in claim 1, wherein the group IVa element is Ti and the gas of halogenated product is TiCl4.