KR20210072670A - Method for manufacturing semiconductor device - Google Patents

Abstract

The present invention relates to a method for manufacturing a semiconductor device comprising forming a metal-containing film using a co-reactant. More particularly, the method for manufacturing a semiconductor device comprises: providing a metal precursor on a substrate to form a preliminary film; and providing a reactant and a co-reactant as a nitrogen source on the preliminary film to form a metal nitride film. The co-reactant is an organometallic compound.

Description

Method for manufacturing semiconductor device

The present invention relates to a method for manufacturing a semiconductor device, and more particularly, to a method for manufacturing a semiconductor device including a method for forming a metal-containing film.

BACKGROUND ART Semiconductor devices are used in many electronic industries due to characteristics such as miniaturization, multifunctionality, and/or low manufacturing cost. The semiconductor device may include a memory device for storing data, a logic device for processing data, and a hybrid device capable of simultaneously performing various functions.

As the electronic industry is highly developed, the demand for high integration of semiconductor devices is increasing. Accordingly, various problems such as a decrease in a process margin of an exposure process for defining fine patterns occur, making it increasingly difficult to implement a semiconductor device. In addition, with the development of the electronic industry, the demand for high-speed semiconductor devices is also increasing. Various studies are being conducted to satisfy the demands for high integration and/or high speed of such semiconductor devices.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of manufacturing a semiconductor device including forming a metal-containing film using a co-reactant.

A method of manufacturing a semiconductor device according to a concept of the present invention includes providing a metal precursor on a substrate to form a preliminary film; and providing a reactant and a co-reactant serving as a nitrogen source on the preliminary layer to form a metal nitride layer. The co-reactant is an organometallic compound represented by the following formula (1),

[Formula 1]

M2 is selected from the group consisting of Sn, In and Ge, n is 2, 3 or 4, L1s are the same as or different from each other, L1s are each independently hydrogen, halogen, or a functional group of Formula 2 below, and L1 At least one of them is a functional group of the following formula (2),

[Formula 2]

x is 0 or an integer between 1 and 5, y is 0 or 1, wherein when x is 0, y is 1, and R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms. , or may be an aminoalkyl having 1 to 5 carbon atoms.

A method of manufacturing a semiconductor device according to another concept of the present invention includes forming an active pattern on a substrate; forming a gate electrode crossing the active pattern; and forming an active contact electrically connected to the active pattern and a gate contact electrically connected to the gate electrode. Forming the active contact and the gate contact may include: forming a first hole exposing the active pattern and a second hole exposing the gate electrode; and forming a first metal nitride film in the first and second holes, wherein forming the first metal nitride film includes: providing a first metal precursor on the substrate to form a first preliminary film; and providing a first reactant and a first co-reactant serving as a nitrogen source on the first preliminary layer, wherein the first co-reactant may be an organometallic compound represented by Formula 1 above.

A method of manufacturing a semiconductor device according to another concept of the present invention includes forming a first region including transistors; and forming a second region stacked on the first region. Forming the second region may include: forming a semiconductor layer on the first region; forming an active pattern on the semiconductor layer; and forming a capacitor electrically connected to the active pattern, wherein forming the capacitor includes forming a first electrode, forming a dielectric film on the first electrode, and forming a second capacitor on the dielectric film and forming two electrodes, wherein forming at least one of the first and second electrodes comprises: providing a metal precursor to form a preliminary film; and providing a reactant and a co-reactant serving as a nitrogen source on the preliminary layer. The co-reactant may be an organometallic compound represented by Formula 1 above.

In the method of forming a metal-containing film according to the present invention, a metal-containing film (eg, a metal nitride film having conductivity) may be deposited at a low temperature (eg, 150° C. to 400° C.) using a co-reactant. Since the metal-containing film can be formed at a low temperature, deterioration of the semiconductor device can be prevented and reliability can be improved.

Since the method of forming the metal nitride film according to the present invention does not use plasma, step coverage characteristics may be excellent. In addition, there is no need to use a highly reactive reactant, and a safe reactant such as ammonia may be used. In addition, since the metal nitride film formed by the method according to the present invention has a relatively low resistivity, electrical properties can be improved.

1 to 3 are conceptual views for explaining a method of forming a metal-containing film according to a comparative example of the present invention.
4 is a graph showing the Gibbs free energy according to the temperature of the metal nitridation reaction.
5 to 7 are conceptual views for explaining a method of forming a metal-containing film according to embodiments of the present invention.
8 is a graph of measuring the specific resistance of a TiN film according to an embodiment of the present invention and a specific resistance of TiN according to a comparative example.
9, 11, 13, and 15 are plan views illustrating a method of manufacturing a semiconductor device according to embodiments of the present invention.
10A, 12A, 14A, and 16A are cross-sectional views taken along line II′ of FIGS. 9, 11, 13 and 15, respectively.
10B, 12B, 14B, and 16B are cross-sectional views taken along line II-II' of FIGS. 9, 11, 13 and 15, respectively.
10C, 12C, 14C, and 16C are cross-sectional views taken along line III-III′ of FIGS. 9, 11, 13 and 15, respectively.
17 and 19 are plan views illustrating a method of manufacturing a semiconductor device according to embodiments of the present invention.
18 and 20 are cross-sectional views taken along line II′ of FIGS. 17 and 19 , respectively.
21 is a cross-sectional view illustrating a semiconductor device and a method of manufacturing the same according to embodiments of the present invention.

In the present specification, "substituted or unsubstituted" is one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an ether group, an alkenyl group, an aryl group, a hydrocarbon ring group, and a heterocyclic group. It may mean unsubstituted or substituted with the above substituents.

In this specification, the halogen atom may include fluorine, chlorine, iodine, and/or bromine.

In the present specification, the alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but may be an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include, but are not limited to, a methyl group and an ethyl group.

Unless otherwise defined in the chemical formulas of the present specification, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it may mean that a hydrogen atom is bonded to the position.

1 to 3 are conceptual views for explaining a method of forming a metal-containing film according to a comparative example of the present invention. 4 is a graph showing the Gibbs free energy according to the temperature of the metal nitridation reaction.

Referring to FIG. 1 , a metal precursor MP may be provided on a substrate 100 to form a preliminary layer PL. A method of forming a metal-containing layer according to embodiments of the present invention may use an atomic layer deposition process (ALD) or a chemical vapor deposition process (CVD). During the atomic layer deposition process (ALD) or the chemical vapor deposition process (CVD), a process temperature may be 400° C. to 600° C., and a process pressure may be 0 Torr 100 Torr.

The metal precursor MP may be a metal halide compound including the first metal M1 or an organometallic compound including the first metal M1 . The first metal M1 may be selected from the group consisting of Ti, Ta, Co, W, Ru, Mo, Sn, Cu, and Al. For example, the metal halide compound may include TiCl4, WF6, HfCl4, NbCl5 or TaCl5. For example, the metal organic compound may include Pentakis(dimethylamino)tantalum (PDMAT) or tert-butylimido-tris-ethylmethylamido-tantalum (TBTEMT).

Referring to FIG. 2 , a reactant RT may be provided on the preliminary layer PL. The reactant RT may react with the preliminary layer PL. The reactant (RT) may be a nitrogen source compound containing a nitrogen atom. For example, the reactant RT may include at least one selected from the group consisting of NH3, N2H4, and N2.

The reactant RT may react with the preliminary layer PL to be substituted with the first metal M1 (ie, a substitution reaction). Alternatively, the reactant RT may react with the preliminary layer PL to reduce the first metal M1 (ie, a reduction reaction).

Referring to FIG. 3 , the preliminary layer PL and the reactant RT may react to form a metal-containing layer ML. All by-products produced during the reaction can be removed. Since the reactant RT includes a nitrogen atom, the metal-containing layer ML may be a metal nitride layer including the first metal M1 .

Referring to FIG. 4 , when TiCl4 is used as the metal precursor MP and NH3 is used as the reactant RT, they react to form a titanium nitride layer. The reduction reaction between TiCl4 and NH3 is as follows.

Looking at the reduction reaction between TiCl4 and NH3, it can be confirmed that the Gibbs free energy has a positive value in a low temperature section (eg, 400° C. or less). That is, the reduction reaction between TiCl4 and NH3 is a non-spontaneous reaction at a low temperature of 400°C or less.

On the other hand, it can be seen that the Gibbs free energy has a negative value in the high temperature section (eg, 400° C. or higher). That is, the reduction reaction between TiCl4 and NH3 is a spontaneous reaction at a high temperature of 400°C or higher.

At low temperatures, the substitution reaction between TiCl4 and NH3 may predominantly occur. Accordingly, at a low temperature, a metal nitride film such as Ti3N4(IV) is formed, and in this case, Ti may have an oxidation number of +4. When the oxidation number of Ti of the titanium nitride layer is +4, free electrons do not exist and the specific resistance may be very high. That is, the titanium nitride film formed at a low temperature may be substantially an insulator.

At high temperature, the reduction reaction between TiCl4 and NH3 may occur predominantly. Accordingly, at a high temperature, a metal nitride layer such as TiN(III) is formed, and in this case, Ti may have an oxidation number of +3. When the oxidation number of Ti of the titanium nitride layer is +3, free electrons exist and the specific resistance may be lowered. That is, the titanium nitride layer formed at a high temperature may be substantially a conductor.

As described above, in order to form a metal nitride film having conductivity (ie, a metal nitride film having a relatively low resistivity), a high-temperature deposition process must be performed. Therefore, the deposition temperature according to this comparative example may be adjusted to 400°C to 600°C. However, in a semiconductor process for forming a semiconductor device, when a deposition process is performed at a high temperature, the lower layer formed in the previous step may be exposed to a high temperature and deteriorate. This may cause a process defect, which may cause a problem in the reliability of the semiconductor device.

In order to perform a deposition process for forming a conductive metal nitride film at a relatively low temperature, plasma or a highly reactive reactant (eg, N2H4) may be used. However, it is difficult to use plasma in a region having a large aspect ratio due to poor step coverage characteristics. In addition, highly reactive reactants are dangerous and difficult to handle.

5 to 7 are conceptual views for explaining a method of forming a metal-containing film according to embodiments of the present invention.

Referring to FIG. 5 , the metal precursor MP may be provided on the substrate 100 to form a preliminary layer PL. A detailed description of the metal precursor MP and the preliminary layer PL may be the same as that described above with reference to FIG. 1 . The method of forming the metal-containing layer according to the present embodiment may use an atomic layer deposition process (ALD) or a chemical vapor deposition process (CVD). During the deposition process, the process pressure may be 0 Torr 100 Torr, and the process temperature may be 150°C to 600°C. Preferably, the deposition process according to the present embodiment may be performed at a low temperature of 150°C to 400°C.

Referring to FIG. 6 , a reactant RT and a co-reactant (CRT) may be provided on the preliminary layer PL. A detailed description of the reactant RT may be the same as described above with reference to FIG. 2 . Preferably, the reactant (RT) may be NH3.

The co-reactant CRT may serve as a catalyst for lowering activation energy of a reduction reaction between the preliminary layer PL and the reactant RT. For example, the co-reactant CRT may reduce the first metal M1 of the preliminary layer PL. Alternatively, the co-reactant (CRT) may increase the reducing power of the reactant (RT). Accordingly, the co-reactant CRT may help the reduction reaction between the preliminary layer PL and the reactant RT to proceed spontaneously even at a low temperature (eg, 150° C. to 400° C.).

For example, the co-reactant (CRT) may increase the reducing power of ammonia having a low reducing power. As a result, a reduction reaction in which ammonia reduces the preliminary layer PL proceeds even at a low temperature, thereby forming a conductive metal nitride layer.

In an embodiment, the reactant RT may be sequentially provided on the preliminary layer PL after the co-reactant CRT is provided. In another embodiment, the reactant RT and the co-reactant CRT may be simultaneously provided on the preliminary layer PL. In another embodiment, the reactant RT may be first provided on the preliminary layer PL and then the co-reactant CRT may be sequentially provided thereafter.

The co-reactant (CRT) may be an organometallic compound including the second metal (M2). Specifically, the co-reactant (CRT) may be an organometallic compound represented by Formula 1 below.

[Formula 1]

The M2 may be selected from the group consisting of Sn, In, and Ge. The n may be 2, 3 or 4. n may be the number of functional groups L1 coupled to M2. Since n is an integer between 2 and 4, L1 may be at least two or more.

Meanwhile, n may mean an oxidation number of the second metal M2. For example, when n is 2, the second metal M2 has an oxidation number of +2, when n is 3, the second metal M2 has an oxidation number of +3, and when n is 4, the second metal M2. (M2) may have an oxidation number of +4.

L1s may be the same or different from each other. Each of L 1 may independently be hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted amino group, or a substituted or unsubstituted aminoalkyl group. The substituted amino group may be an alkylamino group having 1 to 10 carbon atoms. The substituted aminoalkyl group may be an alkylaminoalkyl group having 2 to 15 carbon atoms.

More specifically, L1s may each independently be hydrogen, halogen (F, Cl, Br or I), or a functional group (or ligand) of Formula 2 below.

[Formula 2]

wherein x is 0 or an integer between 1 and 5, and y may be 0 or 1. In this case, if x is 0, y may be 1. R1, R2, R3 and R4 may each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or aminoalkyl having 1 to 5 carbon atoms.

Preferably, the second metal (M2) of the co-reactant (CRT) may be Sn. Hereinafter, a co-reactant (CRT) containing tin (Sn) will be specifically exemplified.

First, when tin (Sn) as the second metal (M2) has an oxidation number of +4, that is, when n is 4 in Formula 1, specific compounds are exemplified as follows. When n is 4 in Formula 1, the compound of Formula 1 may have four functional groups (four L1s) bonded to tin (Sn).

In Formula 1 (n=4), each of the four L1s may independently be an alkyl group having 1 to 4 carbon atoms (in Formula 2, x is an integer between 1 and 4, and y is 0). In this case, typically, the co-reactant (CRT) may include a compound of Formula 3 below.

[Formula 3]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tetra(ethyl)tin

Tetra(propyl)tin

Tetra(isopropyl)tin

Tetra(butyl)tin

Tetra(sec-butyl)tin

Dimethyl diethyl tin

Diethyl diisopropyl tin

Diisopropyl dimethyl tin

Dibutyl dimethyl tin

Tris(isopropyl) methyl tin

Tris(ethyl) methyl tin

Tris(methyl) ethyl tin

Tris(isopropyl) ethyl tin

Tris(methyl) butyl tin

Tris(ethyl) isopropyl tin

In Formula 1 (n=4), the four L1s may each independently be an alkylaminoalkyl group having 2 to 15 carbon atoms (in Formula 2, x is an integer between 1 and 4, and y is 1). In this case, typically, the co-reactant (CRT) may include a compound of Formula 4 below.

[Formula 4]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tetra(3-diethylaminopropyl) tin

Tetra(3-dimethylamino-2-methylpropyl) tin

Tetra(3-diisopropylamino propyl) tin

In Formula 1 (n=4), at least one of the four L1s may be an alkylaminoalkyl group, and at least one of the four L1s may be an alkyl group. In this case, typically, the co-reactant (CRT) may include a compound of Formula 5 below.

[Formula 5]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tris(3-dimethylaminopropyl)ethyl tin

Tris(3-diethylaminopropyl)methyl tin

Tris(3-diethylaminopropyl)ethyl tin

Bis(3-diethylaminopropyl)dimethyl tin

Bis(3-dimethylaminopropyl)dimethyl tin

In Formula 1 (n=4), each of the four L1s may independently be an alkylamino group having 1 to 10 carbon atoms (in Formula 2, x is 0 and y is 1). In this case, typically, the co-reactant (CRT) may include a compound represented by the following formula (6).

[Formula 6]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tetra(diethylamino)tin

Tetra(ethylmethylamino)tin

In Formula 1 (n=4), at least one of the four L1s may be an alkylamino group, and at least one of the four L1s may be an alkyl group. In this case, typically, the co-reactant (CRT) may include a compound of Formula 7 below.

[Formula 7]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tris(dimethylamino)butyltin

Tris(diethylamino)butyltin

Bis(dimethylamino) dibutyl tin

Bis(dimethylamino) dibutyl tin

Tributyl (dimethylamino) tin

In Formula 1 (n=4), one of the four L1s may be hydrogen, and the remaining three L1s may be an alkyl group. In this case, typically, the co-reactant (CRT) may include a compound of Formula 8 below.

[Formula 8]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tri(methyl)tin hydride

Tri (ethyl) tin hydride

Tri (propyl) tin hydride

Tri (isopropyl) tin hydride

Tri (butyl) tin hydride

Tri (sec-butyl)tin hydride

Dimethyl ethyl tin hydride

Diethyl isopropyl tin hydride

Diisopropyl methyl tin hydride

Dibutyl methyl tin hydride

Bis(isopropyl) methyl tin hydride

Bis (ethyl) methyl tin hydride

Bis (methyl) ethyl tin hydride

Bis (isopropyl) ethyl tin hydride

Bis (methyl) butyl tin hydride

Bis (ethyl) isopropyl tin hydride

In Formula 1 (n=4), one of the four L1s may be hydrogen, and the other three L1s may be an alkylaminoalkyl group. In this case, typically, the co-reactant (CRT) may include a compound of Formula 9 below.

[Formula 9]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tri(3-dimethylaminopropyl) tin hydride

Tri (3-diethylaminopropyl) tin hydride

Tri (3-dimethylamino-2-methylpropyl) tin hydride

Tri (3-diisopropylamino propyl) tin hydride

In Formula 1 (n=4), one of the four L1s may be hydrogen, at least one of the four L1s may be an alkylaminoalkyl group, and at least one of the four L1s may be an alkyl group. In this case, typically, the co-reactant (CRT) may include a compound represented by the following Chemical Formula 10.

[Formula 10]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Bis(3-dimethylaminopropyl)ethyl tin hydride

Bis(3-diethylaminopropyl)methyl tin hydride

Bis(3-diethylaminopropyl)ethyl tin hydride

(3-diethylaminopropyl)dimethyl tin hydride

(3-dimethylaminopropyl)dimethyl tin hydride

In Formula 1 (n=4), one of the four L1s may be hydrogen, and the other three L1s may be an alkylamino group. In this case, representatively, the co-reactant (CRT) may include a compound of Formula 11 below.

[Formula 11]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tri(diethylamino)tin hydride

Tri(ethylmethylamino)tin hydride

In Formula 1 (n=4), one of the four L1s may be hydrogen, at least one of the four L1s may be an alkylamino group, and at least one of the four L1s may be an alkyl group. In this case, typically, the co-reactant (CRT) may include a compound of Formula 12 below.

[Formula 12]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Bis(diethylamino) butyl tin hydride

(dimethylamino) dibutyl tin hydride

When tin (Sn) as the second metal (M2) has an oxidation number of +3, that is, when n is 3 in Formula 1, specific compounds are exemplified as follows. When n is 3 in Formula 1, the compound of Formula 1 may have three functional groups (three L1s) bonded to tin (Sn).

In Formula 1 (n=3), three L1s may each independently be an alkyl group having 1 to 4 carbon atoms (in Formula 2, x is an integer between 1 and 4, and y is 0). In this case, representatively, the co-reactant (CRT) may include a compound of Formula 13 below.

[Formula 13]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tri (ethyl)tin

Tri(propyl)tin

Tri (isopropyl) tin

Tri (butyl)tin

Tri (sec-butyl)tin

Dimethyl ethyl tin

Diethyl isopropyl tin

Diisopropyl methyl tin

Dibutyl methyl tin

Bis(isopropyl) methyl tin

Bis (ethyl) methyl tin

Bis (methyl) ethyl tin

Bis (isopropyl) ethyl tin

Bis (methyl) butyl tin

Bis (ethyl) isopropyl tin

In Formula 1 (n=3), three L1s may each independently be an alkylaminoalkyl group having 2 to 15 carbon atoms (in Formula 2, x is an integer between 1 and 4, and y is 1). In this case, representatively, the co-reactant (CRT) may include a compound of Formula 14 below.

[Formula 14]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tri (3-diethylaminopropyl) tin

Tri (3-dimethylamino-2-methylpropyl) tin

Tri (3-diisopropylamino propyl) tin

In Formula 1 (n=3), at least one of the three L1s may be an alkylaminoalkyl group, and at least one of the three L1s may be an alkyl group. In this case, typically, the co-reactant (CRT) may include a compound of Formula 15 below.

[Formula 15]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Bis(3-dimethylaminopropyl)ethyl tin

Bis(3-diethylaminopropyl)methyl tin

Bis(3-diethylaminopropyl)ethyl tin

(3-diethylaminopropyl)dimethyl tin

(3-dimethylaminopropyl)dimethyl tin

In Formula 1 (n=3), three L1s, each independently, may be an alkylamino group having 1 to 10 carbon atoms (in Formula 2, x is 0 and y is 1). In this case, typically, the co-reactant (CRT) may include a compound of Formula 16 below.

[Formula 16]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Tri(diethylamino)tin

Tri(ethylmethylamino)tin

In Formula 1 (n=3), at least one of the three L1s may be an alkylamino group, and at least one of the three L1s may be an alkyl group. In this case, representatively, the co-reactant (CRT) may include a compound of Formula 17 below.

[Formula 17]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Bis(diethylamino) butyl tin

(dimethylamino) dibutyl tin

When tin (Sn) as the second metal (M2) has an oxidation number of +2, that is, when n is 2 in Formula 1, specific compounds are exemplified as follows. When n is 2 in Formula 1, the compound of Formula 1 may have two functional groups (two L1s) bonded to tin (Sn).

In Formula 1 (n=2), two L1s, each independently, may be an alkyl group having 1 to 4 carbon atoms (in Formula 2, x is an integer between 1 and 4, and y is 0). In this case, representatively, the co-reactant (CRT) may include a compound of Formula 18 below.

[Formula 18]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Di (ethyl)tin

Di(propyl)tin

Di (isopropyl)tin

Di (butyl)tin

Di (sec-butyl)tin

Ethyl methyl tin

Ethyl isopropyl tin

Isopropyl methyl tin

Butyl methyl tin

Ethyl isopropyl tin

In Formula 1 (n=2), two L1s, each independently, may be an alkylaminoalkyl group having 2 to 15 carbon atoms (in Formula 2, x is an integer between 1 and 4, and y is 1). In this case, representatively, the co-reactant (CRT) may include a compound of Formula 19 below.

[Formula 19]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Di (3-diethylaminopropyl) tin

Di (3-dimethylamino-2-methylpropyl) tin

Di (3-diisopropylamino propyl) tin

In Formula 1 (n=2), one of the two L1s may be an alkylaminoalkyl group, and the other of the two L1s may be an alkyl group. In this case, representatively, the co-reactant (CRT) may include a compound of Formula 20 below.

[Formula 20]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

(3-dimethylaminopropyl)ethyl tin

(3-diethylaminopropyl)methyl tin

(3-diethylaminopropyl)ethyl tin

In Formula 1 (n=2), two L1s, each independently, may be an alkylamino group having 1 to 10 carbon atoms (in Formula 2, x is 0 and y is 1). In this case, typically, the co-reactant (CRT) may include a compound represented by the following Chemical Formula 21.

[Formula 21]

In addition, the co-reactant (CRT) may include at least one of the following compounds.

Bis(diethylamino)tin

Bis(ethylmethylamino)tin

In Formula 1 (n=2), one of the two L1s may be an alkylamino group, and the other of the two L1s may be an alkyl group. In this case, representatively, the co-reactant (CRT) may include a compound of Formula 22 below.

[Formula 22]

In addition, the co-reactant (CRT) may include the following compounds.

(diethylamino) butyl tin

In another embodiment, the second metal M2 of the co-reactant CRT may be In. A co-reactant (CRT) containing indium (In) having an oxidation number of +3 may include the following compounds:

,

,

, 또는

, or

triethyl indium.

The co-reactant (CRT) including indium (In) having an oxidation number of +1 may include the following compound.

R5 may be hydrogen or an alkyl group having 1 to 5 carbon atoms.

In another embodiment, the second metal M2 of the co-reactant CRT may be Ge. A co-reactant (CRT) containing germanium (Ge) having an oxidation number of +4 may include the following compounds:

, 또는

, or

The co-reactant (CRT) including germanium (Ge) having an oxidation number of +2 may include at least one of the following compounds.

R1 to R4 may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms.

R1 to R4 may each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms.

R1 and R3 may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms. R2 and R4 may each independently represent an alkylamino group having 1 to 10 carbon atoms or an alkyl group having 1 to 5 carbon atoms.

R1 to R6 may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms.

R1 and R2 may each independently be an alkylsilyl group having 1 to 10 carbon atoms.

R1 and R2 may each independently be an alkylsilyl group having 1 to 10 carbon atoms.

Referring to FIG. 7 , the preliminary layer PL and the reactant RT may react and the first metal M1 may be reduced to form a metal-containing layer ML. The metal-containing layer ML may be a metal nitride layer including the first metal M1 . The metal nitride layer may have a relatively low resistivity, and thus may be substantially conductive.

Both the reduction reaction by-product and the oxidized co-reactant (CRT) can be removed. In other words, the second metal M2 of the co-reactant CRT may be removed without remaining in the metal-containing layer ML. Removal of by-products and co-reactants (CRTs) may include purging the gas within the process chamber. As described above, the co-reactant (CRT) may serve as a catalyst in the formation reaction of the metal-containing layer (ML).

In an embodiment, the metal-containing layer ML may not include the second metal M2 . Alternatively, in another embodiment, the second metal M2 of the co-reactant CRT is diffused into the preliminary layer PL while the preliminary layer PL is being reduced, so that the metal-containing layer ML is formed with the second metal M2 . may be included in a trace amount. In this case, the content of the second metal M2 in the metal-containing layer ML may be 0.1 at% to 10 at%.

As described above in the comparative example of the present invention, if the metal nitride film is formed using a reduction reaction without a co-reactant (CRT), a process temperature of 500° C. or higher is required. On the other hand, in the method of forming the metal nitride film according to embodiments of the present invention, the reduction of the preliminary film PL may be accelerated even when the co-reactant CRT is at a low temperature (eg, 150° C. to 400° C.). Since the method according to the present invention is carried out at a low temperature, it is possible not to damage the underlying layer formed in the previous step. Accordingly, the reliability of the semiconductor device can be improved.

The method for forming a metal nitride film according to the present invention may have excellent step coverage characteristics because plasma is not used. Therefore, it can be used on areas with a large aspect ratio. Furthermore, according to the present invention, it is possible to form a metal nitride film at a low temperature using a safe reactant such as ammonia without the need to use a highly reactive reactant.

In another embodiment of the present invention, a process temperature for forming the metal-containing layer ML may be performed at 400° C. to 600° C. In this case, the electrical properties of the metal-containing film (ie, the metal nitride film) may be further improved, and the specific resistance may be lowered.

In another embodiment of the present invention, although not shown, the reactant RT provided in FIG. 6 may not include a nitrogen atom. In other words, the reactant RT may not be a nitrogen source. Specifically, the reactant (RT) may be hydrogen (H2). In this case, the metal-containing layer ML may be formed of a metal layer (eg, a titanium layer) made of only the first metal M1 .

<Experimental example>

As a comparative example, as described above with reference to FIGS. 1 to 3 , a TiN film was deposited through an ALD process using TiCl4 as the metal precursor (MP) and NH3 as the reactant (RT). The process temperature was 450°C.

As an example, as described above with reference to FIGS. 5 to 7 , TiCl4 is used as the metal precursor (MP), the compound of the following Chemical Formula 7 is used as the co-reactant (CRT), and NH3 is used as the reactant (RT) A TiN film was deposited using an ALD process. The process temperature was 350 degreeC.

[Formula 7]

As a result of performing XPS analysis of the TiN film formed according to the example, the atomic percent of Ti was about 48 at% and the atomic percent of N was about 46 at%. In other words, it was confirmed that the number of Ti atoms and the number of N atoms of the TiN film had a ratio of about 1:1, and that Ti of the TiN film had an oxidation number of +3. An atomic ratio of N to Ti of the TiN film formed according to embodiments of the present invention may be 0.9 to 1.1.

Specific resistances were measured for the TiN film formed according to Comparative Example and the TiN film formed according to Example, and the results are shown in FIG. 8 . Referring to FIG. 8 , it can be seen that the specific resistance of the TiN film according to the embodiment of the present invention is lower than that of the TiN film according to the comparative example.

Although the TiN film according to the embodiment was deposited at a low temperature (350° C.), the specific resistance was lower than that of the TiN film according to the comparative example deposited at a high temperature (450° C.). That is, it can be confirmed that the TiN film according to the embodiment is in a better reduced state than the TiN film according to the comparative example. This means that, when the co-reactant according to the present invention is used, the reduction reaction between TiCl4 and NH3 is actively proceeded even at a low temperature.

9, 11, 13, and 15 are plan views for explaining a method of manufacturing a semiconductor device according to embodiments of the present invention. 10A, 12A, 14A, and 16A are cross-sectional views taken along line II′ of FIGS. 9, 11, 13 and 15, respectively. 10B, 12B, 14B, and 16B are cross-sectional views taken along line II-II' of FIGS. 9, 11, 13 and 15, respectively. 10C, 12C, 14C, and 16C are cross-sectional views taken along line III-III′ of FIGS. 9, 11, 13 and 15, respectively.

9 and 10A to 10C , a substrate 100 may be provided. For example, the substrate 100 may be a silicon substrate, a germanium substrate, or a silicon on insulator (SOI) substrate. The first trenches TR1 extending in the second direction D2 may be formed by patterning the upper portion of the substrate 100 . The first trenches TR1 may define first and second active patterns FN1 and FN2 on the substrate 100 . The first and second active patterns FN1 and FN2 may be arranged along the first direction D1 .

A second trench TR2 defining the first active region PR and the second active region NR may be formed by patterning the upper portion of the substrate 100 . While the second trench TR2 is formed, the active patterns FN1 and FN2 in the region where the second trench TR2 is formed may be removed. A first active pattern FN1 may be provided on the first active region PR, and a second active pattern FN2 may be provided on the second active region NR. The second trench TR2 may be deeper than the first trenches TR1 .

A device isolation layer ST filling the first and second trenches TR1 and TR2 may be formed. The device isolation layer ST may be formed using silicon oxide. Specifically, forming the device isolation layer ST includes forming an insulating layer filling the first and second trenches TR1 and TR2 on the substrate 100 , and the first and second active patterns FN1 . , FN2) may include recessing the insulating film until the upper portions are exposed.

Gate electrodes GE crossing the first and second active patterns FN1 and FN2 and extending in the first direction D1 may be formed. Gate dielectric layers GI may be formed under the gate electrodes GE. Gate spacers GS may be formed on both sides of each of the gate electrodes GE. Gate capping layers CP may be formed on the gate electrodes GE.

Specifically, forming the gate electrodes GE includes forming sacrificial patterns crossing the first and second active patterns FN1 and FN2 , and gate spacers GS on both sides of the sacrificial patterns. and replacing the sacrificial patterns with gate electrodes GE.

The gate electrodes GE may include at least one of a conductive metal nitride (eg, titanium nitride or tantalum nitride) and a metal (eg, titanium, tantalum, cobalt, tungsten, ruthenium, molybdenum, tin, copper, or aluminum). may contain one. Forming the gate electrodes GE may include the method of forming the metal-containing layer ML according to the exemplary embodiments described above with reference to FIGS. 5 to 7 .

The gate dielectric layers GI may include a high-k material having a higher dielectric constant than that of the silicon oxide layer. The gate spacers GS may include at least one of SiCN, SiCON, and SiN. The gate capping layers CP may include at least one of SiON, SiCN, SiCON, and SiN.

First source/drain regions SD1 may be formed on upper portions of the first active patterns FN1 . Second source/drain regions SD2 may be formed on the second active patterns FN2 . The first and second source/drain regions SD1 and SD2 may be formed on both sides of each of the gate electrodes GE. The first source/drain regions SD1 may be doped with a p-type impurity, and the second source/drain regions SD2 may be doped with an n-type impurity.

The first and second source/drain regions SD1 and SD2 are epitaxial patterns and may be formed by a selective epitaxial growth process. Specifically, after partially recessing the first and second active patterns FN1 and FN2 on both sides of each of the gate electrodes GE, the first and second active patterns FN1 and FN2 are removed. An epitaxial growth process may be performed on the recessed regions.

A first interlayer insulating layer 110 may be formed on the entire surface of the substrate 100 . The first interlayer insulating film 110 may be formed of a silicon oxide film or a silicon oxynitride film. A top surface of the first interlayer insulating layer 110 may be formed to be coplanar with top surfaces of the gate spacers GS and top surfaces of the gate capping layers CP.

11 and 12A to 12C , a second interlayer insulating layer 120 may be formed on the first interlayer insulating layer 110 . First holes HO1 passing through the first and second interlayer insulating layers 110 and 120 may be formed. Second holes HO2 passing through the second interlayer insulating layer 120 and the gate capping layers CP may be formed.

Each of the first holes HO1 may be formed between the gate electrodes GE adjacent to each other. Each of the first holes HO1 may expose the first source/drain area SD1 or the second source/drain area SD2 . The second holes HO2 may be formed on the isolation layer ST filling the second trench TR2 . Each of the second holes HO2 may expose at least a portion of the top surface of the gate electrode GE.

13 and 14A to 14C , a first metal-containing layer ML1 and a second metal-containing layer ML2 may be formed to sequentially fill the first and second holes HO1 and HO2 . Specifically, the first metal-containing layer ML1 may be conformally formed on the substrate 100 . The first metal-containing layer ML1 may include a metal nitride layer, for example, at least one of a titanium nitride layer, a tungsten nitride layer, and a tantalum nitride layer. Forming the first metal-containing layer ML1 may include the method of forming the metal-containing layer ML according to the exemplary embodiments described above with reference to FIGS. 5 to 7 .

The first and second holes HO1 and HO2 may have a relatively large aspect ratio. If plasma is used in the deposition process for forming the first metal-containing layer ML1, since the plasma has poor step coverage characteristics, the first metal-containing layer ML1 is formed in the first and second holes HO1 and HO2. There is a problem that it is difficult to form formally. However, in the method of forming the metal-containing layer according to the present exemplary embodiment, the first metal-containing layer ML1 may be conformally formed in the first and second holes HO1 and HO2 at a low temperature without using plasma.

A second metal-containing layer ML2 may be formed on the first metal-containing layer ML1 . The second metal-containing layer ML2 may include a metal layer, for example, titanium, tantalum, cobalt, tungsten, ruthenium, molybdenum, tin, copper, or aluminum. Forming the second metal-containing layer ML2 may include the method of forming the metal-containing layer ML according to the exemplary embodiments described above with reference to FIGS. 5 to 7 . The second metal-containing layer ML2 may be formed to completely fill the first and second holes HO1 and HO2 .

At least one of the first metal-containing layer ML1 and the second metal-containing layer ML2 may include the second metal M2 of the co-reactant CRT described with reference to FIGS. 5 to 7 . The content of the second metal M2 of at least one of the first metal-containing layer ML1 and the second metal-containing layer ML2 may be 0.1 at% to 10 at%.

15 and 16A to 16C , a planarization process is performed on the first metal-containing layer ML1 and the second metal-containing layer ML2 until the top surface of the second interlayer insulating layer 120 is exposed. , active contacts AC and gate contacts GC may be formed in the first holes HO1 and the second holes HO2 , respectively. Each of the active contacts AC and the gate contacts GC may include a first barrier pattern BM1 and a first conductive pattern FM1 .

A third interlayer insulating layer 130 may be formed on the second interlayer insulating layer 120 . By patterning the third interlayer insulating layer 130 , third holes HO3 may be formed in the third interlayer insulating layer 130 .

Lines IL filling the third holes HO3 may be formed. Each of the interconnections IL may include a second barrier pattern BM2 and a second conductive pattern FM2 .

Forming the interconnections IL may include forming a third metal-containing layer on the substrate 100 and forming a fourth metal-containing layer on the third metal-containing layer. Forming the third metal-containing layer and the fourth metal-containing layer may include the method of forming the metal-containing layer ML according to embodiments of the present invention described above with reference to FIGS. 5 to 7 . The third metal-containing layer may include a metal nitride layer, and the fourth metal-containing layer may include a metal layer. A planarization process may be performed on the third metal-containing layer and the fourth metal-containing layer to form a second barrier pattern BM2 and a second conductive pattern FM2 , respectively.

At least one of the interconnections IL may include a via VI. The interconnection IL may be electrically connected to at least one of the active contacts AC and the gate contacts GC through the via VI.

17 and 19 are plan views illustrating a method of manufacturing a semiconductor device according to embodiments of the present invention. 18 and 20 are cross-sectional views taken along line II′ of FIGS. 17 and 19 , respectively.

17 and 18 , the device isolation layer 102 defining active patterns ACT may be provided on the substrate 100 . The substrate 100 may be a silicon substrate, a germanium substrate, or a silicon on insulator (SOI) substrate. The device isolation layer ST may be formed using silicon oxide.

In a plan view, each of the active patterns ACT may have a bar shape. Each of the active patterns ACT may have a long axis in the third direction D3 . The third direction D3 may intersect both the first direction D1 and the second direction D2 . All of the first to third directions D1 , D2 , and D3 may be directions parallel to the upper surface of the substrate 100 .

Gate lines GL crossing the active patterns ACT may be formed in the substrate 100 . The gate lines GL may extend in the second direction D2 and may be arranged along the first direction D1 . The gate lines GL may be formed to be buried in the substrate 100 .

The gate lines GL may include at least one of a conductive metal nitride (eg, titanium nitride or tantalum nitride) and a metal (eg, titanium, tantalum, cobalt, tungsten, ruthenium, molybdenum, tin, copper, or aluminum). may contain one. Forming the gate lines GL may include the method of forming the metal-containing layer ML according to the exemplary embodiments described above with reference to FIGS. 5 to 7 .

The gate dielectric layers GI may be interposed between the gate lines GL and the active patterns ACT. The gate dielectric layers GI may include a high-k material having a higher dielectric constant than that of the silicon oxide layer.

First capping patterns CP1 may be respectively formed on the gate lines GL. Top surfaces of the first capping patterns CP1 may be substantially coplanar with the top surface of the substrate 100 . For example, the first capping patterns CP1 may include at least one of SiON, SiCN, SiCON, and SiN.

A first source/drain region SD1 and second source/drain regions SD2 spaced apart from each other with the first source/drain region SD1 interposed therebetween are formed in each of the active patterns ACT. can be The first source/drain region SD1 may be formed between a pair of adjacent gate lines GL. The second source/drain regions SD2 may be respectively formed on both sides of the pair of gate lines GL. That is, the second source/drain regions SD2 may be spaced apart from each other with the pair of gate lines GL interposed therebetween. The first source/drain region SD1 may have the same conductivity type as that of the second source/drain region SD2 .

19 and 20 , the first interlayer insulating layer 110 covering the active patterns ACT may be formed on the substrate 100 . The first interlayer insulating film 110 may be formed of a silicon oxide film or a silicon oxynitride film.

Bit lines BL may be formed in the first interlayer insulating layer 110 . The bit lines BL may extend in the first direction D1 and may be arranged in the second direction D2 . Each of the bit lines BL may be electrically connected to the first source/drain region SD1 . The bit lines BL may include at least one of a conductive metal nitride and a metal. Forming the bit lines BL may include the method of forming the metal-containing layer ML according to the exemplary embodiments described above with reference to FIGS. 5 to 7 .

The second capping patterns CP2 may be respectively formed on the bit lines BL. For example, the second capping patterns CP2 may include at least one of SiON, SiCN, SiCON, and SiN.

Contacts CT that pass through the first interlayer insulating layer 110 and are respectively connected to the second source/drain regions SD2 may be formed on the substrate 100 . Landing pads LP may be respectively formed on the contacts CT. The contacts CT and the landing pads LP may include at least one of a conductive metal nitride and a metal. Forming the contacts CT and the landing pads LP may include the method of forming the metal-containing layer ML according to the exemplary embodiments described above with reference to FIGS. 5 to 7 . .

Capacitors CAP may be respectively formed on the landing pads LP. Forming the capacitor CAP includes forming the first electrode LEL1 on the landing pad LP, forming the dielectric film DIL on the first electrode LEL1, and on the dielectric film DIL. It may include forming the second electrode LEL2 on the . The first electrode LEL1 may be electrically connected to the second source/drain region SD2 through the landing pad LP and the contact CT.

In a plan view, the first electrodes LEL1 may be arranged in a zig zag shape along the first direction D1 as shown in FIG. 19 . The first electrodes LEL1 may be arranged in a line along the third direction D3 .

The first electrode LEL1 and the second electrode LEL2 may include at least one of a conductive metal nitride and a metal. Forming the first electrode LEL1 and the second electrode LEL2 may include the method of forming the metal-containing layer ML according to the embodiments of the present invention described above with reference to FIGS. 5 to 7 . have.

At least one of the first electrode LEL1 and the second electrode LEL2 may include the second metal M2 of the co-reactant CRT described above with reference to FIGS. 5 to 7 . The content of the second metal M2 of at least one of the first electrode LEL1 and the second electrode LEL2 may be 0.1 at% to 10 at%.

21 is a cross-sectional view illustrating a semiconductor device and a method of manufacturing the same according to embodiments of the present invention. In the present embodiment, detailed descriptions of technical features overlapping with those previously described with reference to FIGS. 9 to 20 are omitted, and differences will be described in detail.

Referring to FIG. 21 , a logic region LC that is a result of FIGS. 15 and 16A to 16C may be provided. The logic region LC may include logic transistors constituting a logic circuit of a semiconductor device.

A fourth interlayer insulating layer 140 may be formed on the logic region LC. A memory region MC as a result of FIGS. 19 and 20 may be formed on the fourth interlayer insulating layer 140 . The memory area MC may be formed to be stacked on the logic area LC. The memory area MC may include memory cells in which DRAM devices are disposed.

Specifically, the semiconductor layer 200 of the memory region MC may be formed on the fourth interlayer insulating layer 140 . The semiconductor layer 200 may be substantially the same as the substrate 100 described with reference to FIGS. 17 to 20 . Memory transistors and capacitors CAP electrically connected thereto may be formed on the semiconductor layer 200 . A detailed description thereof may be substantially the same as that described above with reference to FIGS. 17 to 20 .

Meanwhile, while the memory region MC is formed on the logic region LC, the logic transistors in the logic region LC may be exposed under a manufacturing process condition of the memory region MC. For example, when the memory region MC undergoes a process condition of high temperature (about 450° C. or higher), the logic transistors of the logic region LC may also be exposed to high temperature. In this case, the logic transistors may be deteriorated by high temperature. It may cause a big problem in the reliability of the semiconductor device.

According to embodiments of the present invention, a metal-containing layer may be formed at a low temperature (eg, 150° C. to 400° C.) using a reducing agent. For example, when forming a metal-containing layer of each of the gate lines GL, the bit lines BL, the contacts CT, the landing pads LP, and the capacitors CAP of the memory area MC , the process temperature may be maintained at a low temperature by using the method for forming a metal-containing film according to embodiments of the present invention. As a result, deterioration of the logic transistors in the logic region LC may be prevented and reliability of the semiconductor device may be improved.

As described above, embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention may be embodied in other specific forms without changing the technical spirit or essential features thereof. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (20)

providing a metal precursor on the substrate to form a preliminary film; and
Providing a reactant and a co-reactant as a nitrogen source on the preliminary film to form a metal nitride film,
The co-reactant is an organometallic compound represented by the following formula (1),
[Formula 1]

M2 is selected from the group consisting of Sn, In and Ge, n is 2, 3 or 4,
L1s are the same as or different from each other, L1s are each independently hydrogen, halogen, or a functional group of Formula 2 below, and at least one of L1s is a functional group of Formula 2 below,
[Formula 2]

x is 0 or an integer between 1 and 5, y is 0 or 1, wherein if x is 0, y is 1,
R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or aminoalkyl having 1 to 5 carbon atoms.
According to claim 1,
M2 is Sn. A method of manufacturing a semiconductor device.
According to claim 1,
After providing the co-reactant on the preliminary layer, the method of manufacturing a semiconductor device further comprising removing the co-reactant.
According to claim 1,
The method for manufacturing a semiconductor device, wherein the metal precursor includes a metal halide compound or a metal organic compound.
According to claim 1,
The reactant is a method of manufacturing a semiconductor device comprising at least one selected from the group consisting of NH3, N2H4, and N2.
According to claim 1,
A method of manufacturing a semiconductor device wherein the content of M2 in the metal nitride layer is 0.1 at% to 10 at%.
According to claim 1,
Forming the metal nitride layer is a method of manufacturing a semiconductor device using an atomic layer deposition process (ALD) or a chemical vapor deposition process (CVD).
According to claim 1,
A process temperature for forming the metal nitride film is 150°C to 400°C.
According to claim 1,
A process pressure for forming the metal nitride layer is 0 Torr and 100 Torr.
According to claim 1,
The metal precursor is a titanium precursor,
An atomic ratio of nitrogen to titanium of the metal nitride film is 0.9 to 1.1.
forming an active pattern on the substrate;
forming a gate electrode crossing the active pattern; and
Comprising forming an active contact electrically connected to the active pattern and a gate contact electrically connected to the gate electrode,
Forming the active contact and the gate contact comprises:
forming a first hole exposing the active pattern and a second hole exposing the gate electrode; and
and forming a first metal nitride film in the first and second holes;
Forming the first metal nitride film includes:
providing a first metal precursor on the substrate to form a first preliminary film; and
It comprises providing a first reactant and a first co-reactant as a nitrogen source on the first preliminary film,
The first co-reactant is an organometallic compound represented by the following formula (1),
[Formula 1]

M2 is selected from the group consisting of Sn, In and Ge, n is 2, 3 or 4,
L1s are the same as or different from each other, L1s are each independently hydrogen, halogen, or a functional group of Formula 2 below, at least one of L1s is a functional group of Formula 2
[Formula 2]

x is 0 or an integer between 1 and 5, y is 0 or 1, wherein if x is 0, y is 1,
R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or aminoalkyl having 1 to 5 carbon atoms.
12. The method of claim 11,
M2 is Sn. A method of manufacturing a semiconductor device.
12. The method of claim 11,
The first reactant includes at least one selected from the group consisting of NH3, N2H4, and N2.
12. The method of claim 11,
A method of manufacturing a semiconductor device wherein the content of M2 in the first metal nitride layer is 0.1 at% to 10 at%.
12. The method of claim 11,
Further comprising forming wirings electrically connected thereto on the active contact and the gate contact,
Forming the wirings includes forming a second metal nitride film,
Forming the second metal nitride film includes:
providing a second metal precursor on the substrate to form a second preliminary layer; and
and providing a second reactant and a second co-reactant as a nitrogen source on the second preliminary film,
The second co-reactant is the same as or different from the first co-reactant, and is an organometallic compound represented by the formula (1).
forming a first region comprising transistors; and
forming a second region laminated on the first region;
Forming the second region comprises:
forming a semiconductor layer on the first region;
forming an active pattern on the semiconductor layer; and
Comprising forming a capacitor electrically connected to the active pattern,
Forming the capacitor includes forming a first electrode, forming a dielectric film on the first electrode, and forming a second electrode on the dielectric film,
Forming at least one of the first and second electrodes comprises:
providing a metal precursor to form a preliminary film; and
comprising providing a reactant and a co-reactant as a nitrogen source on the preliminary film,
The co-reactant is an organometallic compound represented by the following formula (1),
[Formula 1]

M2 is selected from the group consisting of Sn, In and Ge, n is 2, 3 or 4,
L1s are the same as or different from each other, L1s are each independently hydrogen, halogen, or a functional group of Formula 2 below, and at least one of L1s is a functional group of Formula 2 below,
[Formula 2]

x is 0 or an integer between 1 and 5, y is 0 or 1, wherein if x is 0, y is 1,
R1, R2, R3 and R4 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or aminoalkyl having 1 to 5 carbon atoms.
17. The method of claim 16,
M2 is Sn. A method of manufacturing a semiconductor device.
17. The method of claim 16,
The reactant is a method of manufacturing a semiconductor device comprising at least one selected from the group consisting of NH3, N2H4, and N2.
17. The method of claim 16,
At least one of the first and second electrodes has an M2 content of 0.1 at% to 10 at%.
17. The method of claim 16,
A process temperature for forming at least one of the first and second electrodes is 150°C to 400°C.

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