KR101094951B1 - Semiconductor device with titanium nitride bottom electrode and method for manufacturing the same - Google Patents

Abstract

PURPOSE: A semiconductor device equipped with a titanium nitride film bottom electrode and a manufacturing method thereof are provided to prevent the loss of a contact plug by forming a wet barrier layer. CONSTITUTION: An etching stopping layer(32) and a separation film(33) are formed on a contact plug(31). A first titanium containing film which contains chlorine is formed on the separation film. A second titanium containing film which does not contain the chlorine is formed on the first titanium containing film. A bottom electrode(37A) which is composed of the second titanium containing film is formed in the inner side of an opening part(34). An exterior wall of the bottom electrode is exposed by eliminating a part of the first titanium containing film.

Description

A semiconductor device having a titanium nitride film lower electrode and a manufacturing method therefor {SEMICONDUCTOR DEVICE WITH TITANIUM NITRIDE BOTTOM ELECTRODE AND METHOD FOR MANUFACTURING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor device, and more particularly, to a semiconductor device having a titanium nitride film lower electrode and a method of manufacturing the same.

In the manufacturing process of a metal-insulator-metal (MIM) capacitor, a titanium nitride film (TiN) is mainly used as a lower electrode and an upper electrode.

1A and 1B illustrate a method of manufacturing a semiconductor device using a titanium nitride film TiN as a lower electrode according to the prior art.

As shown in FIG. 1A, after the etch stop layer 12 is formed on the contact plug 11, a separator 13 is formed on the etch stop layer 12. Thereafter, the separator 13 and the etch stop layer 12 are etched to form the open portion 14, and then the lower electrode 15 is formed using the titanium nitride layer TiN in the open portion 14.

As shown in FIG. 1B, the separator 13 is removed by performing a wet deep out process. Thus, the cylindrical lower electrode 15 is completed.

Although not shown, a dielectric film and an upper electrode are subsequently formed in sequence.

However, in the prior art, a bunker 17 is generated in which the chemical 16 flows along the interface between the etch stop layer 12 and the lower electrode 15 during the wet deep-out process, and the contact plug 11 is lost. there is a problem.

SUMMARY OF THE INVENTION An object of the present invention is to provide a semiconductor device and a method of manufacturing the same that can prevent bunkers from occurring during a wet deep-out process.

The semiconductor device manufacturing method of the present invention for achieving the above object comprises the steps of forming an etch stop layer and a separator layer having an open portion on the contact plug; Forming a first titanium-containing film containing chlorine on the separator including the open part; Forming a second titanium-containing film free of chlorine on the first titanium-containing film; Forming a lower electrode formed of the second titanium-containing film in the open part by separating a lower electrode; Removing the separator; And removing the first titanium-containing film to partially expose the outer wall of the lower electrode, and after exposing the outer wall of the lower electrode, forming a dielectric film on the entire surface including the lower electrode. step; And forming an upper electrode on the dielectric layer. The first titanium-containing film is formed at a higher temperature than the second titanium-containing film. The first titanium-containing film is formed using a chemical vapor deposition method, and the second titanium-containing film is formed using a metal organic atom layer deposition method. The first titanium-containing film is formed using titanium tetrachloride (TiCl ₄ ) gas. The second titanium-containing film is formed using a titanium organic source free of chlorine, and the titanium organic source includes any one selected from TDMAT, TEMAT or TDETAT. The first titanium-containing film is formed by forming a titanium film alone or by stacking a titanium film and a titanium nitride film, and the second titanium-containing film is formed of a titanium nitride film.

In addition, the semiconductor device of the present invention comprises a contact plug; A lower electrode formed on the contact plug and formed of a titanium nitride film containing no chlorine; A dielectric film formed on the lower electrode; An upper electrode formed on the dielectric layer; An etch stop layer surrounding the lower outer wall of the lower electrode; And a wet barrier film formed at an interface between the lower outer wall of the lower electrode and the etch stop layer and an interface between the lower electrode and the contact plug and containing a titanium nitride film containing chlorine.

The present invention described above can form a titanium nitride film containing no chlorine by depositing the metal organic atomic layer deposition method (MOALD) using a titanium organic source when forming the titanium nitride film used as the lower electrode and the upper electrode of the capacitor. This improves the leakage current characteristics of the dielectric film.

In addition, the present invention forms a titanium film containing chlorine and a titanium nitride film containing chlorine by using chemical vapor deposition at the interface between the lower electrode and the etch stop layer, thereby preventing bunkers from losing contact plugs during the wet dipout process. have.

1A and 1B illustrate a method of manufacturing a capacitor using a titanium nitride film according to the prior art as a lower electrode.
2 is a view for explaining a metal organic atomic layer deposition (MOALD) method of the titanium nitride film according to an embodiment of the present invention.
3 is a diagram illustrating a semiconductor device using a titanium nitride film (MOALD-TiN) according to an embodiment of the present invention.
4A to 4F illustrate a method of manufacturing a semiconductor device using a titanium nitride film (MOALD-TiN) according to an embodiment of the present invention.
5 is a diagram illustrating another example of a semiconductor device using a titanium nitride film (MOALD-TiN) according to an embodiment of the present invention.
6 is a view showing a capacitor according to a comparative example of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to facilitate a person skilled in the art to easily carry out the technical idea of the present invention. .

The present invention forms a wet barrier (Wet barrier) in order to prevent the occurrence of bunkers during the wet deep-out process of the cylindrical or pillar-type capacitor manufacturing process. The wet barrier film is an inter-layer formed at the interface between the lower electrode and the etch stop film. The wet barrier film inhibits the flow of a solution (or chemical) during the wet deep out process. This prevents bunkers due to loss of contact plugs and the like.

In addition, the present invention uses a titanium nitride film (TiN) as the lower electrode (and / or upper electrode) to improve the electrical characteristics of the capacitor. Preferably, the titanium nitride layer TiN is formed by atomic layer deposition (ALD) using a titanium organic source to prevent chlorine (Cl) from being contained. This improves the leakage current characteristics of the dielectric film due to residual chlorine.

Atomic Layer Deposition (ALD) is a method of sequentially depositing a plurality of monoatomic layers by sequentially injecting and purging a source material and a reactant into a chamber.

In the embodiment described later, the titanium nitride film is formed using atomic layer deposition (ALD). The titanium nitride film by the atomic layer deposition method (ALD) is referred to as 'ALD-TiN'. In the atomic layer deposition method, the titanium source uses a titanium organic source. As described above, the atomic layer deposition method (ALD) using a titanium organic source is called a metal organic atomic layer deposition method (MOALD), and the titanium nitride film by the metal organic atomic layer deposition method (MOALD) is called 'MOALD-TiN'. . Titanium organic sources include chlorine-free source materials. Titanium organic sources are also known as titanium organic precursors. For example, the titanium organic source is TEMAT {Tetrakis (ethylmethylamio) titanium, Ti [N (C ₂ H ₅ ) CH ₃ ] ₄ }, TDMAT {Tetrakis (dimethylamino) titanium, Ti (N (CH ₃ ) ₂ ) ₄ } , Precursors such as TDEAT {Tetrakis (diethylamino) titanium, Ti [N (C ₂ H ₅ ) ₂ ] ₄ }, and the like.

2 is a view for explaining a metal organic atomic layer deposition (MOALD) method of the titanium nitride film according to an embodiment of the present invention.

Referring to FIG. 2, the atomic layer deposition method of the titanium nitride film is a titanium organic source injection step (Ti 'Ti'), a purge step (Fig. 'Purge'), a nitrogen injection step (Fig. ) And the unit cycle consisting of the purge step (reference numeral 'purge'), that is, (Ti / purge / nitrogen / purge) is repeated M times.

First, the titanium organic source injection step is to supply the titanium organic source into the chamber on which the substrate on which the titanium nitride film is to be deposited is mounted, and the titanium organic source is adsorbed on the substrate surface by the supply of the titanium organic source. Titanium organic sources include any one selected from TDMAT, TEMAT or TDETAT. Titanium organic sauce is injected for 1-15 seconds. The substrate on which the titanium nitride film is to be deposited may include a silicon substrate (Si), a silicon oxide film (SiO ₂ ), a metal film, or a dielectric film having a high dielectric constant. Preferably, the substrate may include any one selected from a zirconium oxide layer (ZrO ₂ ), an aluminum oxide layer (Al ₂ O ₃ ), or a structure in which a zirconium oxide layer and an aluminum oxide layer are stacked (Al ₂ O ₃ / ZrO ₂ ). The deposition temperature is maintained at a relatively low temperature of 200 ℃ to 350 ℃.

Next, the purge step is a purge step of removing the excess titanium organic source remaining after the adsorption reaction, wherein the purge gas uses argon (Ar) which is an inert gas that does not react with the titanium organic source. The purge step may also remove excess titanium organic sources by pumping. The purge step lasts for 1 to 100 seconds, with longer purge times being advantageous.

Next, the nitrogen injection step is a step of depositing a titanium nitride film by supplying a reactant and reacting with the adsorbed titanium organic source. The reactant nitrogen may include ammonia (NH ₃ ) gas or nitrogen (N ₂ ) gas activated by plasma. Preferably it may be activated by a remote plasma (Remote plasma). Remote plasma can be used to prevent the substrate from being physically damaged by the plasma. Remote plasma is generated using 50 to 3600W of power.

Next, the purge step is a step of purging the reaction by-products and the remaining reactants after the reaction. The purge step uses argon (Ar), which is an inert gas. Also, the purge step may use pumping.

As described above, the titanium nitride film is deposited in atomic layer units having excellent step coverage by repeating the (Ti / purge / nitrogen / purge) M cycles consisting of a titanium organic source injection step → purge step → nitrogen injection step → purge step. do. Preferably, the thickness of the unit cycle is controlled by controlling the number of repetitions (M).

According to the embodiment described above, chlorine does not remain in the film by using a titanium organic source free of chlorine (Cl) as the source material when the titanium nitride film is deposited.

3 is a diagram illustrating a semiconductor device using a titanium nitride film (MOALD-TiN) according to an embodiment of the present invention.

Referring to FIG. 3, the contact plug 31 and the contact plug 31 are formed on the lower electrode 37A and the lower electrode 37A formed of a titanium nitride film (MOALD-TiN) by a metal organic atomic layer deposition method. The etch stop layer 32 surrounding the formed dielectric layer 38, the upper electrode 39 formed on the dielectric layer 38, the lower outer wall of the lower electrode 37A, and the lower outer wall and etch stop layer 32 of the lower electrode 37A. The wet barrier film patterns 35B and 36B are formed at the interface between the bottom electrode 37 and the interface between the lower electrode 37A and the contact plug 31 and include a titanium nitride film (CVD-TiN) by chemical vapor deposition. The wet barrier film pattern includes a first wet barrier film pattern 35B and a second wet barrier film pattern 36B. The first wet barrier film pattern 35B is CVD Ti, and the second wet barrier film pattern 36B is formed of CVD TiN.

4A to 4F illustrate a method of manufacturing a semiconductor device using a titanium nitride film (MOALD-TiN) according to an embodiment of the present invention.

As shown in FIG. 4A, a contact plug 31 is formed. The contact plug 31 is called a storage node contact plug (SNC). The contact plug 31 includes polysilicon. Although not shown, as is well known, the contact plug 31 is formed in the contact hole formed in the interlayer insulating film on the substrate.

An etch stop layer 32 is formed on the contact plug 31. The etch stop layer 32 includes a nitride film such as silicon nitride film (Si ₃ N ₄ ).

The separator 33 is formed on the etch stop layer 32. The separator 33 includes an oxide film such as BPSG. The separator 33 is also called a mold layer.

The separation layer 33 is etched so that the etching stops at the etch stop layer 32 using the photoresist pattern not shown. Subsequently, the etch stop film 32 is etched. As a result, an open portion 34 exposing the contact plug 31 is formed. The open part 34 is a region providing a space in which the lower electrode is to be formed, and may have a shape of a hole.

As shown in FIG. 4B, the wet barrier films 35 and 36 are formed on the entire surface including the open part 34. The wet barrier films 35 and 36 serve to prevent the chemical from flowing along the interface between the lower electrode and the etch stop layer 32 during the subsequent wet dipout process. The wet barrier films 35 and 36 are conductive for electrical connection between the lower electrode and the contact plug 31. And, as will be described later, the wet barrier films 35 and 36 are deposited at a temperature higher than that of the lower electrode.

The wet barrier films 35 and 36 are formed of a material containing titanium. For example, the wet barrier films 35 and 36 may be formed by forming a titanium film Ti alone or by stacking a titanium film Ti and a titanium nitride film TiN. The titanium film and the titanium nitride film are formed by chemical vapor deposition (CVD). Hereinafter, it will be referred to as 'CVD Ti' and 'CVD TiN'. In forming CVD Ti and CVD TiN, a titanium source uses titanium tetrachloride (TiCl ₄ ), and the deposition temperature is in the range of 400 to 700 ° C. In this embodiment, the wet barrier film has a double structure of the first wet barrier film 35 using CVD Ti and the second wet barrier film 36 using CVD TiN. CVD Ti and CVD TiN used as the first wet barrier film 35 and the second wet barrier film 36 preferably control the chlorine concentration in the film to 50% or less (3 to 50%).

A conductive film, for example, a titanium nitride film 37, which is used as a lower electrode on the second wet barrier film 36, is formed. The titanium nitride film 37 is formed by metal organic atomic layer deposition (MOALD) using a titanium organic source to prevent chlorine from remaining in the film.

As described above, the CVD Ti used as the first wet barrier film 35 and the CVD TiN used as the second wet barrier film 36 are formed by chemical vapor deposition (CVD) and used as a lower electrode. The titanium nitride film 37 is formed by the metal organic atomic layer deposition method (ALD). Hereinafter, the titanium nitride film 37 is referred to as 'MOALD-TiN 37'.

Chemical Vapor Deposition (CVD) is superior to atomic layer deposition (ALD), so it has excellent film density. Therefore, the first wet barrier film 35 and the second wet barrier film 36 are excellent in interfacial properties to prevent infiltration of chemicals flowing along the interface during the subsequent wet dipout process.

Since MOALD-TiN 37 uses a chlorine-free titanium organic source, diffusion of chlorine ions into the subsequent dielectric film does not occur fundamentally. The metal organic atomic layer deposition method for forming the MOALD-TiN 37 proceeds at a temperature of 200 to 350 캜. Titanium organic sources use precursors such as TEMAT, TDMAT and TDEAT. The reactants include ammonia (NH ₃ ) gas or nitrogen (N ₂ ) gas activated by plasma.

As shown in FIG. 4C, the lower electrode separation process is performed. The lower electrode separation process is a process of selectively removing the MOALD-TiN 37 and remaining only in the open part 34. Preferably, the lower electrode separation process may proceed to an etchback process, or may sequentially proceed with the CMP process and the etchback process. By the lower electrode separation process as described above, the lower electrode 37A having a cylindrical shape is formed in the open part 34. The lower electrode 37A is formed of MOALD-TiN (37 in FIG. 3B). In the lower electrode separation process, some of the first wet barrier film and the second wet barrier film are also simultaneously removed. Therefore, the first wet barrier film pattern 35A and the second wet barrier film pattern 36A remain outside the lower electrode 37A.

As shown in FIG. 4D, the wet deep out is performed. The wet deep-out process is performed using a BOE (Buffered Oxide Etchant) solution. As a result, all of the separator 33 formed of the oxide film is removed.

The BOE solution may flow along the interface with the etch stop layer 32 during the wet dip-out process. However, in the present invention, the first wet barrier layer pattern 35A and the second wet barrier layer pattern 36A are dense. The substance prevents the BOE solution from flowing through the interface. As a result, bunkers due to the loss of the contact plug 31 do not occur.

As described above, by applying the first wet barrier layer pattern 35A and the second wet barrier layer pattern 36A, the titanium nitride layer using titanium tetrachloride (TiCl ₄ ) as a source has the ability to prevent chemical penetration.

In other words, the first wet barrier film pattern 35A and the second wet barrier film pattern 36A interface with the etch stop film 32. CVD Ti and CVD TiN, which are used as the first wet barrier film pattern 35A and the second wet barrier film pattern 36A, were formed using titanium tetrachloride (TiCl ₄ ) as a source, and thus high temperature deposition characteristics of 400 to 700 ° C. As a result, the bonding property of the interface is good, which is effective in preventing bunker generation.

However, when the dielectric film is subsequently deposited, since the interface that meets the dielectric film becomes the second wet barrier film pattern 36A, leakage current degradation of the dielectric film due to residual chlorine occurs.

In order to prevent this, the present invention partially removes the first wet barrier film pattern 35A and the second wet barrier film pattern 36A as follows.

As shown in FIG. 4E, the first wet barrier film pattern 35A and the second wet barrier film pattern 36A are partially removed to prevent bunker generation before the dielectric film is deposited. Accordingly, as shown by reference numerals 35B and 36B, the first wet barrier film pattern 35B and the second wet barrier film pattern 36B that expose the outer wall of the lower electrode 37A remain. The outer wall of the lower electrode 37A exposed is at a position higher than that of the etch stop film 32. Wet etching is used to partially remove the first wet barrier film pattern 35A and the second wet barrier film pattern 36A. Wet etching uses a mixture of sulfuric acid and fruit water 5: 1 (H ₂ SO ₄ : H ₂ O ₂ = 5: 1). When performing wet etching, the lower electrode 37A and the etch stop layer 32 are not etched.

As described above, when the first wet barrier layer pattern 35A and the second wet barrier layer pattern 36A are selectively removed to expose the outer wall of the lower electrode 37A, the lower electrode 37A is deposited during the dielectric film deposition. And the dielectric film form an interface. As a result, since the lower electrode 37A is formed of MODALD-TiN containing no chlorine, the leakage current characteristic of the dielectric film due to chlorine is prevented.

The remaining first wet barrier layer pattern 35B and the second wet barrier layer pattern 36B remain only at the interface between the lower electrode 37A, the contact plug 31, and the etch stop layer 32. Since the first wet barrier film pattern 35B and the second wet barrier film pattern 36B are conductive materials such as CVD Ti and CVD TiN, the contact plug 31 and the lower electrode 37A are electrically connected to each other.

As shown in FIG. 4F, the dielectric film 38 is formed on the entire surface including the lower electrode 37A. The dielectric film 38 is formed using atomic layer deposition (ALD).

The upper electrode 39 is formed on the dielectric film 38 using a titanium nitride film. The titanium nitride film used as the upper electrode 39 is deposited using a metal organic atomic layer deposition method (MOALD) using a titanium organic source containing no chlorine so as not to contain chlorine.

Subsequently, a metal film may be formed to electrically connect the upper electrode 39. The metal film includes a tungsten film.

Through a series of processes as described above, a cylindrical capacitor having a lower electrode and an upper electrode using MOALD-TiN containing no chlorine is produced.

5 is a diagram illustrating another example of a semiconductor device using MOALD-TiN according to an embodiment of the present invention. 4 is a case where a pillar type capacitor is applied.

Referring to FIG. 5, a pillar type lower electrode 45 is formed on the contact plug 41. An etch stop layer 42 surrounding the lower portion of the lower electrode 45 is formed on the contact plug 41. The first wet barrier film 43 and the second wet barrier film 44 are formed at the interface between the lower electrode 45 and the etch stop film 42. The dielectric layer 46 and the upper electrode 47 are formed on the lower electrode 45. The lower electrode 45 and the upper electrode 47 are formed of MOALD-TiN. The first and second wet barrier films 43 and 44 are formed of CVD Ti and CVD TiN, respectively.

In another embodiment, the lower electrode may have a flat plate shape.

According to the above-described embodiment, when the titanium nitride film is used as the lower electrode and the upper electrode of the MIM capacitor, it is possible to form a titanium nitride film that does not contain chlorine by depositing the metal organic atomic layer deposition method (MOALD) using a titanium organic source. have. This improves the leakage current characteristics of the capacitor.

In addition, the present invention forms a wet barrier film at a high temperature by chemical vapor deposition at the interface between the lower electrode and the etch stop layer, thereby preventing bunkers from losing contact plugs during the wet dipout process.

6 is a view showing a capacitor according to a comparative example of the present invention.

Referring to FIG. 6, in a capacitor including a lower electrode 51, a dielectric layer 52, and an upper electrode 53, the lower electrode 51 and the upper electrode 53 use titanium tetrachloride (TiCl ₄ ) as a source. Titanium nitride film (CVD-TiN) by chemical vapor deposition (CVD) is applied.

However, CVD-TiN Because formed by the titanium tetrachloride (TiCl ₄₎ as the source, membrane chloride ion (Cl ^-) in a becoming much residue, the residual chlorine ion (Cl ^-) enters by diffusion into the dielectric layer 52 . Chlorine ions (Cl ⁻ ) are diffused into the dielectric film 52 during a subsequent process such as the deposition process of the dielectric film 52.

As described above, the chlorine ions Cl ⁻ diffused into the dielectric layer 52 deteriorate leakage current characteristics of the dielectric layer 52 as they act as defects and mobile charges.

Recently, when the semiconductor device is scaled down and the thickness of the dielectric film 52 is minimized in order to lower the effective oxide film thickness T _ox , the leakage current deterioration characteristic due to residual chlorine is intensified.

In order to prevent leakage current degradation of the dielectric film 52 due to residual chlorine, the present invention applies a metal organic atomic layer deposition method (MOALD) to form a titanium nitride film using a titanium organic source free of chlorine. In addition, a wet barrier film using CVD Ti and CVD TiN is applied to prevent bunkers.

Although the technical idea of the present invention has been described in detail according to the above preferred embodiment, it should be noted that the above-described embodiment is for the purpose of description and not of limitation. In addition, it will be understood by those of ordinary skill in the art that various embodiments are possible within the scope of the technical idea of the present invention.

31: contact plug 32: etch stop film
33: separator 34: open portion
35B: first wet barrier film pattern 36B: second wet barrier film pattern
37: MOALD-TiN 37A: Lower electrode
38 dielectric layer 39 upper electrode

Claims (16)

Forming an etch stop layer and a separator layer having an open portion on the contact plug;
Forming a first titanium-containing film containing chlorine on the separator including the open part;
Forming a second titanium-containing film free of chlorine on the first titanium-containing film;
Forming a lower electrode formed of the second titanium-containing film in the open part by separating a lower electrode;
Removing the separator; And
Partially removing the first titanium-containing film to expose an outer wall of the lower electrode;
≪ / RTI >
Claim 2 has been abandoned due to the setting registration fee. The method of claim 1,
And the first titanium-containing film is formed by chemical vapor deposition.
Claim 3 was abandoned when the setup registration fee was paid. The method of claim 1,
And the first titanium-containing film is formed using titanium tetrachloride (TiCl ₄ ) gas.
Claim 4 was abandoned when the registration fee was paid. The method of claim 1,
The first titanium-containing film is formed by forming a titanium film alone or by stacking a titanium film and a titanium nitride film.
Claim 5 was abandoned upon payment of a set-up fee. The method of claim 1,
And the second titanium-containing film is formed using a metal organic atomic layer deposition method.
Claim 6 was abandoned when the registration fee was paid. The method of claim 1,
And the second titanium-containing film is formed by using a titanium organic source free of chlorine. Claim 7 was abandoned upon payment of a set-up fee. The method of claim 6,
The titanium organic source is a semiconductor device manufacturing method comprising any one selected from TDMAT, TEMAT or TDETAT.
Claim 8 was abandoned when the registration fee was paid. The method of claim 1,
And the second titanium-containing film is formed of a titanium nitride film.
Claim 9 was abandoned upon payment of a set-up fee. The method of claim 1,
The first titanium-containing film is formed by laminating a titanium film and a first titanium nitride film using a chemical vapor deposition method, and the second titanium-containing film is formed as a second titanium nitride film using a metal organic atomic layer deposition method. .
Claim 10 was abandoned upon payment of a setup registration fee. 10. The method of claim 9,
And the titanium film and the first titanium nitride film are formed using a gas containing chlorine, and the second titanium nitride film is formed using a titanium organic source containing no chlorine. Claim 11 was abandoned upon payment of a setup registration fee. The method of claim 1,
And the first titanium-containing film is formed at a higher temperature than the second titanium-containing film.
Claim 12 was abandoned upon payment of a registration fee. The method of claim 1,
Exposing the outer wall of the lower electrode by partially removing the first titanium-containing film;
A method of manufacturing a semiconductor device by wet etching.
Claim 13 was abandoned upon payment of a registration fee. The method according to any one of claims 1 to 12,
After exposing the outer wall of the lower electrode,
Forming a dielectric film on the entire surface including the lower electrode; And
Forming an upper electrode on the dielectric layer
A semiconductor device manufacturing method further comprising.
Claim 14 was abandoned when the registration fee was paid. The method of claim 13,
The upper electrode,
A semiconductor device manufacturing method comprising a titanium nitride film formed by a metal organic atomic layer deposition method using a titanium organic source free of chlorine.
Contact plugs;
A lower electrode formed on the contact plug and formed of a titanium nitride film containing no chlorine;
A dielectric film formed on the lower electrode;
An upper electrode formed on the dielectric layer;
An etch stop layer surrounding the lower outer wall of the lower electrode; And
Wet barrier film including a titanium nitride film formed on the interface between the lower outer wall of the lower electrode and the etch stop layer and the interface between the lower electrode and the contact plug and containing chlorine
A semiconductor device comprising a.
Claim 16 was abandoned upon payment of a setup registration fee. 16. The method of claim 15,
The wet barrier film is a semiconductor device in which a titanium film containing chlorine and a titanium nitride film containing chlorine are stacked.

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