KR20030009093A - Method of depositing an atomic layer, and method of depositing a thin layer and a metal layer using the same - Google Patents

Abstract

PURPOSE: A method for laminating an atomic layer and a method for laminating a thin film and a metal layer by using the same are provided to laminate the atomic layer and the thin film by using a metalorganic precursor or a tantalum halide precursor as a reactive material. CONSTITUTION: A silicon substrate(10) is located in the inside of a chamber. A predetermined pressure is applied to the inside of the chamber. The silicon substrate(10) is heated. A reactive material such as TBTDET is introduced on the silicon substrate(10). A part of the reactive material is chemically absorbed on the silicon substrate(10). An inert gas is injected into the silicon substrate(10). The remaining reactive material is removed from the silicon substrate(10). A mixed gas of H2, NH3, SiH4, and Si2H6 is injected into the silicon substrate(10). Ligand-combined elements are removed from chemically combined elements of the reaction material. An atomic layer(14) is laminated on the silicon substrate(10) by removing the ligand-combined elements.

Description

Method of depositing an atomic layer, and method of depositing a thin layer and a metal layer using the same}

The present invention relates to a method for forming a thin film and a method for forming a metal layer using atomic layer lamination, and more particularly, to an atomic layer and a thin film using a metallorganic precursor or a tantalum halide precursor as a reactant. It relates to a method of laminating.

BACKGROUND With the rapid spread of information media such as computers, semiconductor devices are also rapidly developing. In terms of its function, the semiconductor device is required to operate at a high speed and to have a large storage capacity. In response to these demands, manufacturing techniques have been developed in the direction of improving the degree of integration, reliability, response speed, and the like of the semiconductor device.

There is also a strict demand for the metal layer used as the metal wiring of the semiconductor device. Accordingly, in order to increase the density of devices formed on the substrate, the metal layer is formed in a multilayer structure. The metal layer is mainly formed using aluminum or tungsten. However, the aluminum or tungsten is not suitable for the multilayer structure because the resistivity is about 2.8 × 10E-8 Ωm and about 5.5 × 10E-8 Ωm, respectively. Therefore, recently, copper has been used as the metal layer of the multilayer structure having a relatively low specific resistance and good electromigration characteristics.

The copper shows very high mobility in silicon and silicon dioxide (SiO ₂ ). However, the copper oxidizes easily when reacted with the silicon and silicon dioxide. Therefore, it is desirable to prevent oxidation of the copper or the like using the barrier metal layer.

As the barrier metal layer, a titanium nitride layer (TiN layer) is widely used. However, the titanium nitrite layer is not suitable as the barrier metal layer of copper. That is, in order to prevent the mobility of the copper, the titanium nitride layer should have a thickness of at least 30 nm, and the resistance becomes high when the titanium nitride layer is formed at about 30 nm. This is because the resistance of the titanium nitride layer is proportional to the thickness, and the reactivity is high.

Therefore, application of a tantalum nitride layer as said barrier metal layer of copper is proposed. This is because the tantalum nitride layer can inhibit the mobility of copper even with a relatively thin thickness.

Examples of using the tantalum nitride layer as a barrier metal layer include US Pat. No. 6,204,204 (issued to Paranjpe et al.), US Pat. No. 6,153,519 (issued to Jain et al.) And US Pat. No. 5,668,054 (issued to Sun et. al.) and the like.

As disclosed in U.S. Patent No. 5,668,054 and the like, terbutylimido-tris-diethylamido tantalum: (NEt ₂ ) ₃ Ta = NBu ^t : hereinafter referred to as 'TBTDET' as a reaction material Chemical vapor deposition using a) is performed to deposit the tantalum nitride layer. The method performs the process at a temperature of at least 600 ° C. This is because the tantalum nitride layer has a resistivity value of 10,000 μΩ · cm or more when the method is performed at a temperature of about 500 ° C. In addition, the method incurs a thermal damage disadvantageous to the semiconductor device because the process is performed at a relatively high temperature. In addition, the chemical vapor deposition method is not suitable for the implementation of tantalum nitride layers having good step coverage.

Recently, an atomic layer deposition (ALD) method has been proposed as a technique to replace the above chemical vapor deposition. According to the atomic layer deposition method, it can be carried out at a lower temperature than the conventional thin film formation method, it is possible to implement excellent step coverage.

An example of a method for depositing tantalum nitride using the atomic layer deposition is described in US Pat. No. 6,203,613 (issued to Gates) and Kang et al. (Electrochemical and Solid-State Letters, 4 (4) C17 -C19 (2001).

According to the method of the steel or the like, the tantalum nitride layer having a specific resistance value of about 400 μΩ · cm can be formed by the atomic layer deposition method using the TBTDET. At this time, the lamination is performed at a temperature of about 260 ℃. As described above, according to the method of steel or the like, the tantalum nitride layer having a low specific resistance can be easily formed at a relatively low temperature.

However, in the method of steel or the like, hydrogen radicals formed by the plasma increasing method are used as reducing agents. Thus, a power source is applied in the chamber when performing the lamination. Thus, the teaching method has process variables such as control of the power source. Thus, although the method of steel or the like can form a thin film having a low resistivity at a relatively low temperature, process variables such as control of the power source are added. In addition, the method of demoting may damage the substrate because the power source is applied directly to the site where the substrate is placed.

Therefore, there is a need for a new method of forming tantalum nitrite layers that can be performed at low temperatures, has low resistivity, is easy to implement good step coverage, and has simple process parameters.

It is a first object of the present invention to provide an atomic layer deposition method having simple process parameters.

It is a second object of the present invention to provide a method for laminating TaN thin films using atomic layer deposition having simple process parameters.

It is a third object of the present invention to provide a method for laminating TaN thin films using atomic layer lamination having simple process parameters as barrier metal layers.

A fourth object of the present invention is to provide a metal layer stacking method having a TaN thin film formed by using an atomic layer stack having simple process parameters as a barrier metal layer.

1A to 1D are cross-sectional views illustrating a method of forming a thin film using atomic layer stacking according to an embodiment of the present invention.

2 is a graph showing the results of confirming the XRD of the thin film formed according to an embodiment of the present invention.

3 is a graph showing a specific resistance of a thin film when H ₂ is applied as a reducing gas.

4 is a cross-sectional view illustrating a TaN thin film formed according to an embodiment of the present invention.

5 is a cross-sectional view showing a metal layer formed according to an embodiment of the present invention.

The present invention for achieving the first object,

a) introducing a metal precursor on the substrate as a reactant comprising a metal element and binding elements chemically bonded to the metal element, some of the binding elements comprising ligand binding elements ligand binding to the metal element; ;

b) chemically adsorbing a portion of the reactant onto the substrate;

c) removing from the substrate a reactant that is not chemically adsorbed in the reactant; And

d) removing the ligand binding elements from the chemically adsorbed reactants from among the chemically adsorbed reactant elements to form a solid material containing the metal element on the substrate.

The present invention for achieving the second object,

a) introducing a gaseous tantalum amine derivative or tantalum helide precursor as a reactant onto the substrate;

b) chemically adsorbing a portion of the reactant onto the substrate;

c) introducing an inert gas onto the substrate to remove from the substrate a reactant that is not chemically adsorbed in the reactant;

d) an element having a ligand bond included in the chemically adsorbed reaction material by introducing any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof on the substrate; Removing them from the reaction material to form a solid material containing TaN; And

e) repeating said a) -d) at least once to form said solid material into a TaN thin film.

The present invention for achieving the third object,

a) forming an insulating layer on the substrate;

b) etching a portion of the insulating layer to form an opening through which the surface of the substrate is exposed;

c) continuously introducing a gaseous tantalum amine derivative or tantalum helide precursor as a reactant material on the substrate surface, the insulating layer and the opening sidewalls;

d) continuously chemically adsorbing a portion of the reactant material on the substrate surface, the insulating layer and the opening sidewalls;

e) continuously introducing an inert gas on the substrate surface, the insulating layer and the opening sidewalls to remove from the substrate surface, the insulating layer and the opening sidewalls a reaction material which is not chemically adsorbed in the reaction material;

f) the chemically adsorbed reaction by introducing any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof continuously on the substrate surface, the insulating layer and the opening sidewall Removing the elements having a ligand bond included in the material from the reaction material to form a solid material containing TaN; And

g) repeating c) -f) at least once to continuously form said solid material into a TaN thin film on said substrate surface, insulating layer and opening sidewalls.

The present invention for achieving the fourth object,

a) forming an insulating layer on the lower structure formed on the substrate;

b) etching a portion of the insulating layer to form an opening through which the surface of the lower structure is exposed;

c) continuously introducing a gaseous tantalum amine derivative or tantalum helide precursor as a reactant material on the underlying structure surface, insulating layer and opening sidewalls;

d) continuously chemically adsorbing a portion of the reactant material on the underlying structure surface, insulating layer and opening sidewalls;

e) continuously introducing an inert gas onto the bottom surface, the insulating layer and the opening sidewall to remove from the bottom surface, the insulating layer and the opening sidewall the reaction material which is not chemically adsorbed in the reaction material;

f) chemically adsorbed by introducing any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H ₆ and compounds thereof continuously on the surface of the lower structure, the insulating layer and the opening sidewalls; Removing the elements having ligand bonds included in a reactant from the reactant to form a solid material containing TaN;

g) repeating c) -f) at least once to continuously form said solid material into a TaN thin film on said underlying structure, insulating layer and opening sidewalls; And

h) filling the opening with a metal material and simultaneously forming a metal layer including the metal material on the TaN thin film.

According to the method of the present invention, a thin film having a low specific resistance can be easily formed at a relatively low temperature. In particular, since the process can be performed using removal gases activated by a remote plasma method, process variables due to plasma formation can be excluded.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, a metal precursor and a coupling element chemically bonded to the metal element as a reaction material, a portion of the binding elements on the substrate containing a metallic precursor containing a ligand binding element ligand-binding with the metal element To be introduced.

The reactant material is introduced into the chamber, ie on the substrate, on which the substrate is placed. In addition, the metal element of the reaction material includes Ta. Here, examples of the metal precursor which is the reactant including Ta may include an organic metal precursor or a tantalum halide precursor. Specifically, the organometallic precursor includes a tantalum amine derivative, and terbutylimido-tris-diethylamido tantalum (TBTDET: (NEt ₂ ) ₃ Ta = NBu ^t ), Ta ( NR ₁ ) (NR ₂ R ₃ ) ₃ , wherein R ₁ , R ₂ , R ₃ are the same or different from each other as H or a C ₁ -C ₆ alkyl group, Ta (NR ₁ R ₂ ) ₅ , where R ₁ R ₂ is the same as or different from each other as H or a C ₁ -C ₆ alkyl group or Ta (NR ₁ R ₂ ) _x (NR ₃ R ₄ ) _5-x , where R ₁ , R ₂ , R ₃ , R ₄ is H or a C ₁ -C ₆ alk group, same or different from each other) or tertiaryamylimido-tris-dimethylamido tantalum: Ta (= NC (CH ₃ ) ₂ C ₂ H ₅ ) (N (CH ₃ ) ₂ ) ₃ ), and the like. The tantalum halide precursor is exemplified by such TaF _5, TaCl _5, TaBr ₅ or TaI _5.

A portion of the reactant is then chemically adsorbed onto the substrate. At this time, the reactant is introduced in a gaseous state. In addition, some of the reactants are chemically adsorbed on the substrate, and others are physically adsorbed. Accordingly, the reaction material which is not chemically adsorbed in the reaction material is removed from the substrate. In this case, the removal may include, for example, ligand exchange of the ligand binding elements or deposition by the ligand exchange.

The chemically non-adsorbed reactants, that is, the physically adsorbed reactants, are removed using an inert gas. The inert gas is used, preferably, there may be mentioned an Ar or N ₂ and the like.

Subsequently, among the binding elements of the chemically adsorbed reactant, the ligand binding elements are removed from the chemically adsorbed reactant to form a solid material containing the metal element on the substrate.

The ligand binding elements are removed using any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and mixtures thereof. Preferably, the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H ₆ and mixtures thereof is activated and used in a remote plasma manner.

Here, the atomic layer deposition is performed at a constant pressure of 0.3-10 Torr. Preferably, the atomic layer deposition is performed at a pressure of 0.3 Torr or 5 Torr.

The atomic layer deposition is performed at a temperature of 650 ° C. or less. In addition, when activating materials for removing the ligand binding element, it is possible to form a thin film using the atomic layer stack even at a temperature of less than 300 ℃.

In addition, when the atomic layer deposition is repeatedly performed, a TaN thin film is formed. Therefore, the TaN thin film can be actively applied as a barrier metal layer of the copper metal layer.

Hereinafter, with reference to the accompanying drawings will be described in detail the atomic layer deposition method of the present invention.

1A to 1D are cross-sectional views illustrating an atomic layer deposition method. First, the substrate 10 made of a silicon material is placed in the chamber. Then, the chamber is formed to have the aforementioned pressure state. In addition, the substrate 10 is heated to have the above-mentioned temperature.

Referring to FIG. 1A, TBTDET is introduced as reactant 12 on a substrate lying in the chamber. As a result, a part of the reaction material 12 is chemically adsorbed on the substrate 10.

Referring to FIG. 1B, an inert gas is introduced onto the substrate. Accordingly, the reactants that are not chemically adsorbed among the reactants 12 are removed from the substrate 10.

Referring to FIG. 1C, any one of a removal gas selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and mixtures thereof is introduced onto the substrate 10.

Referring to FIG. 1D, among the binding elements of the chemically adsorbed reactants on the substrate 10, the ligand-bound elements 12a are removed by the introduction of the removal gas. The removal may be by ligand exchange of the ligand binding elements. As a result, the atomic layer 14 containing TaN is laminated on the substrate 10.

2 is a graph showing the results of confirming the XRD of the thin film formed according to an embodiment of the present invention. 2 shows that TaN is crystalline when the atomic layer deposition is performed using NH ₃ , SiH ₄ , and mixtures thereof as the removal gas. The graph shown in FIG. 2 shows the results of the process performed under the process conditions of heating the substrate at 400 ° C.

In FIG. 2, when NH ₃ is used as the removal gas (C), when SiH ₄ is used as the removal gas (A), and when these compounds are used as the removal gas (B), the TaN peak is (111). It was confirmed that this appeared. From this, it was confirmed that TaN was contained in the atomic layer.

The reaction mechanism of the atomic layer stack of the present invention containing TaN is as follows. As the reaction material (NEt ₂ ) ₃ Ta = NBu ^t is chemically adsorbed on the substrate. Then, the reaction material which is not chemically adsorbed by the inert gas is removed. The removal is purification with the inert gas. Subsequently, any one of the removal gases selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof is introduced onto the substrate. Then, the gas removed by the elements having the binding among the _{(NEt 2) 3 Ta = NBu} t is removed. That is, since the reaction force that the removal gas reacts with the ligand binding element is greater than the binding force to which the ligand binding element is bound, the element having the ligand bond can be removed. At this time, since Ta = N has a double bond, it is not affected by the removal gas. Therefore, by removing the ligand binding element, an atomic layer thin film containing Ta = N is laminated on the substrate.

In the lamination of the atomic layer thin film, a reaction mechanism using a reducing agent is disclosed in the aforementioned steel. However, according to the above steel, it is thought that the ligand-binding element is substituted for the hydrogen radical by using a reducing agent instead of removing the ligand-binding element using the removal gas as in the present invention.

In addition, the reaction material (NEt ₂ ) ₃ Ta = NBu ^t is completely decomposed at a temperature of 650 ° C. Therefore, when the temperature is 650 ° C. or higher, the atomic layer stacking is not performed. When the temperature is 300 ° C. or less, the reactant is not decomposed. Therefore, it is used after activating the removal gas. The activation is preferably made by a remote plasma method. In addition, when the temperature is about 300-650 ° C., the reaction material partially decomposes. Therefore, even in the atomic layer deposition in the above temperature range, the removal gas can be more easily promoted when used after activating the removal gas.

The thin film formation method using the atomic layer stacking can easily form a thin film having a low specific resistance at a relatively low temperature. In particular, the method can eliminate process variables due to plasma formation since it uses removal gases activated by a remote plasma method. Thus, it is possible to implement atomic layer stacking which can be carried out at low temperatures, has low specific resistance, is easy to implement excellent step coverage, and has simple process parameters.

Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

Example 1

After placing the substrate in the chamber, the pressure in the chamber was adjusted to 5 Torr. In addition, the substrate was heated to about 450 ℃. In addition, the TBTDET was introduced at a flow rate of about 10 g / min into the chamber having the pressure and temperature atmosphere, and a part thereof was chemically adsorbed onto the substrate. The reactants that were not chemically adsorbed were removed from the chamber using an inert gas. Then, NH ₃ activated by a remote plasma method was introduced at a flow rate of about 100 sccm to remove the ligand-binding element of the chemically adsorbed reactant. Accordingly, an atomic layer containing TaN was formed on the substrate as a thin film. XRD analysis was performed on the thin film obtained by performing the above process. Similarly to FIG. 2, a peak having a (111) orientation was observed, and the resistivity value was 1,254 μΩ · cm.

Example 2

Except that the substrate was heated at 500 ° C in the same manner as in Example 1 to form an atomic layer consisting of TaN as a thin film. The resistivity of the obtained TaN layer was measured, and the measured resistivity value was 1,035 µΩ · cm. In addition, when XRD analysis was performed on the thin film, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2.

Example 3

Except that the substrate was heated at 550 ℃ to form a thin film of the atomic layer consisting of TaN in the same manner as in Example 1. The resistivity of the obtained TaN layer was measured, and the measured resistivity value was 1,117 µΩ · cm. In addition, when XRD analysis was performed on the thin film, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2.

Example 4

Except that the substrate was heated at 600 ° C in the same manner as in Example 1 to form an atomic layer consisting of TaN as a thin film. The resistivity of the obtained TaN layer was measured, and the measured resistivity value was 721 µΩ · cm. In addition, when XRD analysis was performed on the thin film, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2.

Example 5

After placing the substrate in the chamber, the pressure in the chamber was adjusted to 0.3 Torr. In addition, the substrate was heated to about 500 ℃. In addition, the TBTDET was introduced at a flow rate of about 10 g / min into the chamber having the pressure and temperature atmosphere, and a part thereof was chemically adsorbed onto the substrate. The reactants that were not chemically adsorbed were removed from the chamber using an inert gas. In addition, NH ₃ activated by a remote plasma method was introduced at a flow rate of about 500 sccm to remove the ligand-binding element of the chemically adsorbed reactant. Accordingly, an atomic layer containing TaN was formed on the substrate as a thin film. As a result of performing the XRD analysis on the thin film obtained by performing the above process, similar to that described with reference to FIG. 2, a peak having a (111) orientation was observed, and the resistivity value was 1,744 μΩ · cm.

Example 6

An atomic layer composed of TaN was formed in a thin film in the same manner as in Example 5 except that the substrate was heated at 550 ° C. The resistivity of the obtained TaN layer was measured, and the measured resistivity value was 1,301 µΩ · cm. In addition, when XRD analysis was performed on the thin film, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2.

Example 7

Except that the substrate was heated at 600 ℃ to form a thin film of the atomic layer consisting of TaN in the same manner as in Example 5. The resistivity of the obtained TaN layer was measured, and the measured resistivity value was 1,304 µΩ · cm. In addition, when XRD analysis was performed on the thin film, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2.

Example 8

After placing the substrate in the chamber, the pressure in the chamber was adjusted to 5 Torr. In addition, the substrate was heated to about 400 ℃. In addition, the TBTDET was introduced at a flow rate of about 10 g / min into the chamber having the pressure and temperature atmosphere, and a part thereof was chemically adsorbed onto the substrate. The reactants that were not chemically adsorbed were removed from the chamber using an inert gas. In addition, NH ₃ activated by a remote plasma method was introduced at a flow rate of about 500 sccm to remove the ligand-binding element of the chemically adsorbed reactant. Accordingly, an atomic layer containing TaN was formed on the substrate as a thin film. As a result of performing the XRD analysis on the thin film obtained by performing the above process, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2, and the specific resistance value was 924.5 μΩ · cm.

Example 9

Except that the substrate was heated at 450 ℃ to form an atomic layer consisting of the TaN thin film in the same manner as in Example 8. The resistivity of the obtained TaN layer was measured, and the measured resistivity value was 685 µΩ · cm. In addition, when XRD analysis was performed on the thin film, a peak having a (111) orientation was observed similarly to that described with reference to FIG. 2.

Example 10

After placing the substrate in the chamber, the pressure in the chamber was adjusted to 1 Torr. In addition, the substrate was heated to about 250 ℃. The tertiary millimido-tris-dimethylamido tantalum was introduced into the chamber having the pressure and temperature atmosphere at a flow rate of about 10 g / min, and a part thereof was chemically adsorbed onto the substrate. The reactants that were not chemically adsorbed were removed from the chamber using an inert gas. In addition, NH ₃ activated by a remote plasma method was introduced at a flow rate of about 500 sccm to remove the ligand-binding element of the chemically adsorbed reactant. Accordingly, an atomic layer containing TaN was formed on the substrate as a thin film. As a result of performing XRD analysis on the thin film obtained by performing the above process, a peak having (111) orientation was observed similarly as described with reference to FIG. 2.

Comparative example

Then, as disclosed in the above-mentioned steel and the like, a thin film was formed using H ₂ as a reducing gas. The lamination process was performed as follows. The pressure was adjusted to 0.3 Torr and the substrate was heated to about 400 ° C. The TBTDET was introduced at a flow rate of about 10 g / min, and the NH ₃ was introduced at a flow rate of 500 sccm. The thin film formed under the above conditions showed the result as shown in FIG. 3. That is, it was confirmed that the specific resistance of the thin film increased as the flow rate of the reducing gas H ₂ increased.

Hereinafter, a method of forming a TaN thin film will be described.

The TaN thin film is formed under the same process conditions to which the atomic layer deposition method is applied. In this case, any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof may be removed using the inert gas to remove the chemically unreacted reactants. Can be used repeatedly to remove elements having ligand bonds. This is to completely remove impurities present in the TaN thin film. The TaN thin film may be formed by repeatedly performing the atomic layer deposition method. That is, by repeatedly performing the atomic layer deposition, the atomic layer is formed of a TaN thin film having a predetermined thickness. The thickness of the thin film is different depending on the number of repetitions. Therefore, the thickness of the thin film can be accurately controlled by adjusting the number of repetitions. In addition, since the thin film formation uses the atomic layer deposition method, a thin film having good step coverage can be formed. In addition, after the TaN thin film is formed, the TaN thin film is post-treated using any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof activated by a remote plasma method. can do. This is also to completely remove impurities present in the TaN thin film.

First, a substrate on which an insulating layer pattern having an opening is formed is placed in a chamber. Then, an atomic layer containing TaN is laminated on the substrate in the same manner as the above-described atomic layer deposition method. In this case, the atomic layer is continuously formed on the substrate surface, the insulating layer and the sidewall of the opening. Then, the atomic layer deposition method is repeated. Accordingly, as shown in FIG. 4, the TaN thin film 44 is continuously formed on the surface of the substrate 40, the insulating layer 42, and the sidewall of the opening.

The TaN thin film may be easily applied not only to a substrate on which an insulating layer pattern having the opening is formed, but also to a multilayer wiring structure formed on the substrate.

Hereinafter, a wiring layer forming method including the TaN thin film will be described.

First, a substrate on which an insulating layer pattern having an opening is formed is placed in a chamber. The opening has an aspect ratio of about 11: 1. Then, the periphery of the substrate is formed at a pressure of 0.3 Torr. In addition, the substrate is heated to about 450 ℃. Subsequently, the TBTDET is introduced at a flow rate of about 10 g / min as the reaction material. Thus, a portion of the reactant chemically adsorbs on the substrate. Ar is introduced as the inert gas at a flow rate of about 100 sccm to remove the chemically adsorbed reaction material from the substrate. Subsequently, 500 sccm of NH ₃ activated by the remote plasma system and SiH ₄ are introduced at a flow rate of about 100 sccm. Introduction of the NH ₃ and SiH ₄ removes the ligand binding element of the chemically adsorbed reactant. Thus, an atomic layer containing TaN is laminated on the substrate. In this case, the process of removing the chemically adsorbed reaction material using the inert gas, and the process of removing the element having a ligand bond using the NH ₃ , and SiH ₄ may be repeatedly performed. This is to completely remove impurities present in the TaN thin film. In addition, introduction of the reactant, the inert gas, and the removal gas is repeated about 600 times under the process conditions. Thus, as the atomic layers are continuously stacked, TaN thin films are continuously formed on the opening sidewalls, the insulating layer, and the substrate surface exposed to the bottom of the openings. In addition, after the TaN thin film is formed, the TaN thin film is post-treated using any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof activated by a remote plasma method. can do. This is also to completely remove impurities present in the TaN thin film.

The TaN thin film has excellent step coverage because it is formed by atomic layer stacking. In addition, a low temperature process can be performed. In addition, the processing conditions of the TaN thin film have a simple process variable because the atomic layer deposition adopts the remote plasma method.

The TaN thin film may be applied as a barrier metal layer of a metal layer. In particular, it can be actively applied as a barrier metal layer of a copper metal layer.

Specifically, the TaN thin film is formed on the insulating layer pattern having the opening formed on the substrate by the TaN thin film forming method using the atomic layer stacking. Accordingly, as shown in FIG. 5, the TaN thin film 54 is continuously formed on the substrate 50, the opening sidewalls, and the insulating layer 52 pattern. In addition, a copper metal layer 56 is formed on the TaN thin film 54. The copper metal layer 56 is mainly formed by a conventional thin film forming method.

In this manner, the TaN thin film can be easily formed as the barrier metal layer of the copper metal layer. Therefore, it is possible to maximize the characteristics of the copper.

In addition, the method can be actively applied to the formation of a thin film containing Al, Ru, Si.

Therefore, according to the present invention, an atomic layer containing a metal element having a low specific resistance can be easily formed at a relatively low temperature. In addition, the atomic layer deposition has simple process parameters. Therefore, there is an effect that the atomic layer deposition can be easily performed. That is, the remote plasma system is adopted to activate the gas used for the atomic layer deposition. As described above, not only the advantages of the atomic layer stacking but also simple process parameters can be expected to effectively apply the atomic layer stacking to thin film formation.

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the present invention without departing from the spirit and scope of the present invention described in the claims below. I can understand that you can.

Claims (35)

a) a metal precursor comprising a metal element and binding elements chemically bonded to the metal element, and a portion of the binding elements comprises a metallic precursor comprising a ligand binding element ligand-binding with the metal element. Introducing to; b) chemically adsorbing a portion of the reactant onto the substrate; c) removing from the substrate a reactant that is not chemically adsorbed in the reactant; And d) removing the ligand binding elements from the chemically adsorbed reactants among the chemically adsorbed reactant elements to form a solid material containing the metal element on the substrate; An atomic layer lamination method. The atomic layer deposition method of claim 1, wherein the metal element included in the reactive material comprises Ta. The method of claim 1, wherein the reactant comprises an organic metal precursor or a tantalum halide precursor. The method of claim 3, wherein the organometallic precursor is a tantalum amine derivative. The method of claim 4, wherein the tantalum amine derivative is terbutylimido-tris-diethylamido tantalum (TBTDET: (NEt ₂ ) ₃ Ta = NBu ^t ), Ta (NR ₁ ) ( NR ₂ R ₃ ) ₃ , wherein R ₁ , R ₂ , R ₃ are the same or different from each other as H or a C ₁ -C ₆ alkyl group, Ta (NR ₁ R ₂ ) ₅ , wherein R ₁ , R ₂ are H or a C ₁ -C ₆ alk group same or different from each other) or Ta (NR ₁ R ₂ ) _x (NR ₃ R ₄ ) _5-x , where R ₁ , R ₂ , R ₃ , R ₄ is H or A C ₁ -C ₆ alkali group, the same or different from each other); The method of claim 3, wherein the tantalum halide precursor, TaF _5, TaCl _5, TaBr ₅ or TaI atomic layer depositing method comprising the _five. The method of claim 1, wherein the reactant material is introduced in a gaseous state. The method of claim 1, wherein the chemically unreacted reactant is removed using an inert gas. The method of claim 8, wherein the inert gas is Ar or N ₂ . The method of claim 1, wherein the ligand binding element is removed using any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and mixtures thereof. . The atomic layer of claim 1, wherein the ligand binding element is removed using any one selected from the group consisting of activated H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and mixtures thereof. Lamination method. 12. The method of claim 11, wherein the activation is by remote plasma. The method of claim 1, wherein the solid material is TaN. The method of claim 1, wherein a) -d) is carried out at a temperature of 650 ℃ or less. The method of claim 1, wherein a) -d) maintains a constant pressure of 0.3-10 Torr. a) introducing a gaseous tantalum amine derivative or tantalum halide precursor as a reactant onto the substrate; b) chemically adsorbing a portion of the reactant onto the substrate; c) introducing an inert gas onto the substrate to remove from the substrate a reactant that is not chemically adsorbed in the reactant; d) an element having a ligand bond included in the chemically adsorbed reaction material by introducing any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof on the substrate; Removing them from the reaction material to form a solid material containing TaN; And e) repeating the a) -d) at least once to form the solid material into a TaN thin film. 17. The method of claim 16, wherein the tantalum amine derivative is terbutylimido-tris-diethylamido tantalum (TBTDET: (NEt ₂ ) ₃ Ta = NBu ^t ), Ta (NR ₁ ) ( NR ₂ R ₃ ) ₃ , wherein R ₁ , R ₂ , R ₃ are the same or different from each other as H or a C ₁ -C ₆ alkyl group, Ta (NR ₁ R ₂ ) ₅ , wherein R ₁ , R ₂ are H or a C ₁ -C ₆ alk group same or different from each other) or Ta (NR ₁ R ₂ ) _x (NR ₃ R ₄ ) _5-x , where R ₁ , R ₂ , R ₃ , R ₄ is H or C ₁ -C ₆ Alkyl group is the same or different from each other), the method for forming a thin film using atomic layer lamination. 17. The method of claim 16 wherein the tantalum halide precursor, TaF _5, TaCl _5, TaBr ₅ or the thin film forming method using the atomic layer depositing comprises a TaI _5. The method of claim 16, wherein the H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof are activated by a remote plasma method. The method of claim 16, wherein the a) to d) are performed at a temperature of about 650 ° C. or less. 17. The method of claim 16, wherein the a) -d) maintains a constant pressure of 0.3-10 Torr. 17. The method of claim 16, wherein the steps c) -d) are repeated at least once before performing step e). The method according to claim 16, wherein any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof activated by a remote plasma method after performing step e) is used. A thin film forming method using atomic layer deposition, characterized in that the TaN thin film is post-processed. a) forming an insulating layer on the substrate; b) etching a portion of the insulating layer to form an opening through which the surface of the substrate is exposed; c) continuously introducing a gaseous tantalum amine derivative or tantalum halide precursor as a reactant on the substrate surface, the insulating layer and the opening sidewalls; d) continuously chemically adsorbing a portion of the reactant material on the substrate surface, the insulating layer and the opening sidewalls; e) continuously introducing an inert gas on the substrate surface, the insulating layer and the opening sidewalls to remove from the substrate surface, the insulating layer and the opening sidewalls a reaction material which is not chemically adsorbed in the reaction material; f) the chemically adsorbed reaction by introducing any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof continuously on the substrate surface, the insulating layer and the opening sidewall Removing the elements having a ligand bond included in the material from the reaction material to form a solid material containing TaN; And g) repeating c) -f) at least once to continuously form the solid material into a TaN thin film on the substrate surface, the insulating layer and the opening sidewalls. Way. The method of claim 24, wherein the tantalum amine derivative is terbutylimido-tris-diethylamido tantalum (TBTDET: (NEt ₂ ) ₃ Ta = NBu ^t ), Ta (NR ₁ ) ( NR ₂ R ₃ ) ₃ , wherein R ₁ , R ₂ , R ₃ are the same or different from each other as H or a C ₁ -C ₆ alkyl group, Ta (NR ₁ R ₂ ) ₅ , wherein R ₁ , R ₂ are H or a C ₁ -C ₆ alk group same or different from each other) or Ta (NR ₁ R ₂ ) _x (NR ₃ R ₄ ) _5-x , where R ₁ , R ₂ , R ₃ , R ₄ is H or C ₁ -C ₆ Alkyl group is the same or different from each other), the method for forming a thin film using atomic layer lamination. 25. The method of claim 24 wherein said tantalum halide precursor is TaF _5, TaCl _5, TaBr ₅ TaI ₅ or the thin film forming method using the atomic layer depositing comprises a. The atomic layer of claim 24, wherein the insulating layer is a thin film containing an oxidizing material, and the H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof are activated by a remote plasma method. Thin film formation method using lamination. 25. The method of claim 24, wherein the steps e) -f) are repeated at least once before performing step g). The method according to claim 24, wherein any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof activated by a remote plasma method after performing step g) is used. A thin film forming method using atomic layer deposition, characterized in that the TaN thin film is post-processed. a) forming an insulating layer on the lower structure formed on the substrate; b) etching a portion of the insulating layer to form an opening through which the surface of the lower structure is exposed; c) continuously introducing a gaseous tantalum amine derivative or tantalum halide precursor as a reactant on the bottom structure surface, the insulating layer and the opening sidewalls; d) continuously chemically adsorbing a portion of the reactant material on the underlying structure surface, insulating layer and opening sidewalls; e) continuously introducing an inert gas onto the bottom surface, the insulating layer and the opening sidewall to remove from the bottom surface, the insulating layer and the opening sidewall the reaction material which is not chemically adsorbed in the reaction material; f) chemically adsorbed by introducing any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H ₆ and compounds thereof continuously on the surface of the lower structure, the insulating layer and the opening sidewalls; Removing the elements having ligand bonds included in a reactant from the reactant to form a solid material containing TaN; g) repeating c) -f) at least once to continuously form said solid material into a TaN thin film on said underlying structure, insulating layer and opening sidewalls; And h) filling the opening with a metal material and simultaneously forming a metal layer including the metal material on the TaN thin film. The method of claim 30, wherein the tantalum amine derivative is terbutylimido-tris-diethylamido tantalum (TBTDET: (NEt ₂ ) ₃ Ta = NBu ^t ), Ta (NR ₁ ) ( NR ₂ R ₃ ) ₃ , wherein R ₁ , R ₂ , R ₃ are the same or different from each other as H or a C ₁ -C ₆ alkyl group, Ta (NR ₁ R ₂ ) ₅ , wherein R ₁ , R ₂ are H or a C ₁ -C ₆ alk group same or different from each other) or Ta (NR ₁ R ₂ ) _x (NR ₃ R ₄ ) _5-x , where R ₁ , R ₂ , R ₃ , R ₄ is H or A C ₁ -C ₆ alk group, the same or different from each other). The method of claim 30, wherein the tantalum halide precursor is TaF _5, TaCl _5, TaBr _5, or the metal layer forming method comprising the TaI _5. The method of claim 30, wherein the metal layer is selected from the group consisting of Cu, Al, Ru and Si materials, wherein the H ₂ , NH ₃ , SiH ₄ , Si ₂ H ₆ and their compounds are remote plasma Activated by the method of forming a metal layer. 31. The method of claim 30, wherein the steps e) -f) are repeated at least once before performing step g). 31. The method of claim 30, wherein any one selected from the group consisting of H ₂ , NH ₃ , SiH ₄ , Si ₂ H _6, and compounds thereof activated by a remote plasma method between steps g) and h). The post-treatment of the TaN thin film using a metal layer forming method.