KR100709990B1 - Film forming material, film forming method and device - Google Patents

Abstract

The present invention provides a technique for producing a silicide film that can be sufficiently used for next-generation transistors by CVD.

In the film forming material for forming the silicide film consisting of one or two metal elements and Si selected from the group consisting of Co and Ni,

As the raw material of the metal element, one or two or more compounds selected from the group consisting of the following general formula [I] and general formula [II] are used.

General formula [Ⅰ]

(Wherein M is Co or Ni, n is 2 or 3, R ₁ , R ₂ , R ₃ is H or an alkyl group)

General formula [Ⅱ]

(Wherein M is Co or Ni, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ is H or an alkyl group)

Description

Film Forming Material, Film Forming Method and Device {FILM FORMING MATERIAL, FILM FORMING METHOD AND DEVICE}             

1 is a schematic diagram of a CVD apparatus.

* Explanation of symbols for main parts of drawings *

1a, 1b: container 2: heater (加熱器)

3: decomposition reaction furnace 4: Si substrate

5: flow controller

The present invention relates to a film forming material, a film forming method and a device.

The current progress in the semiconductor field is markedly shifting from large scale integration (LSI) to ultra large scale integrated circuits (ULSI). In order to improve the processing speed of the signal, miniaturization is in progress. As a wiring material, copper having a low resistance value is selected, and a gate oxide film is filled with a material having a very low dielectric constant between the wirings, and is becoming an ultrathin film. ) it was also started to be reviewed for a metal oxide film (金屬酸化膜) of HfO ₂ and so on in the SiO _2.

However, even if the above technical concept is adopted, the diffusion layer of the source and drain portions becomes extremely thin with the miniaturization, so that the resistance increases and it is difficult to improve the signal processing speed.

Therefore, studies have been made on metal silicides such as TiSi ₂ .

However, it is expected that there will be a limit to future performance improvements in TiSi ₂ .

It is thought that introduction of CoSi ₂ or NiSi ₂ is essential as a semiconductor in the future.

It is considered that the thin film of CoSi ₂ or NiSi ₂ can be easily produced by the sputtering technique.

However, sputtering is thought to cause physical damage to the semiconductor device, and there is a limit to uniform film formation on a large area. Therefore, CoSi is deposited by CVD (Chemical Vapor Deposition). _It is considered that development of a method for forming a film of ₂ or NiSi ₂ is expected.

Accordingly, an object of the present invention is to provide a technique capable of forming a silicide film called CoSi ₂ or NiSi ₂ by CVD.

It was found that what was chosen as the CVD material during the course of reviewing the above problem was important.

As a result of examination from this point of view, when a compound selected from the group consisting of the following general formula [I] and general formula [II] is used, a silicide film called CoSi ₂ or NiSi ₂ is used. ) Can be formed by CVD.

That is, in the film forming material for forming the silicide film which consists of one or two metal elements and Si chosen from the group which consists of Co and Ni,

As a raw material for the metal element, one or two or more compounds selected from the group consisting of the following general formula [I] and general formula [II] are used.

Further, in the film forming material for forming a silicide film composed of one or two metal elements and Si selected from the group consisting of Co and Ni,

As the raw material of the metal element, one or two or more compounds selected from the group consisting of the following general formula [I] and general formula [II] are used,

Si _x H _{(2x + 2)} (where x is an integer of 1 or more) and R _x SiH _(4-x) (where R is an alkyl group and x is an integer of 0 to 3). In the case of more than one, all R may be the same or may not be the same) is solved by the film-forming material, characterized in that one or two or more compounds selected from the group consisting of.

General formula [Ⅰ]

(Wherein M is Co or Ni, n is 2 or 3, R ₁ , R ₂ , R ₃ is H or an alkyl group. R ₁ , R ₂ , R ₃ may or may not be identical)

General formula [Ⅱ]

(Wherein M is Co or Ni, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ is H or an alkyl group. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ may or may not be identical)

In particular, in the film forming material for forming the silicide film composed of one or two metal elements and Si selected from the group consisting of Co and Ni,

As a raw material of the metal element, (Acac) ₂ Co, (Acac) ₂ Co hydrate (Water compound), (Acac) ₃ Co, (Acac) ₃ Co hydrate, (DPM) ₂ Co, (DPM) ₂ Co hydrate, ( DPM) ₃ Co, (DPM) ₃ Co hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Co, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Co, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Co, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Co, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni, (DPM) ₂ Ni hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni, [(nC ₄ H ₉ ) C ₅ H ₄ ] One or two or more compounds selected from the group consisting of ₂ Ni are solved by the film-forming material, characterized in that used.

Further, in the film forming material for forming a silicide film composed of one or two metal elements and Si selected from the group consisting of Co and Ni,

As a raw material of the metal element, (Acac) ₂ Co, (Acac) ₂ Co hydrate (Water compound), (Acac) ₃ Co, (Acac) ₃ Co hydrate, (DPM) ₂ Co, (DPM) ₂ Co hydrate, ( DPM) ₃ Co, (DPM) ₃ Co hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Co, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Co, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Co, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Co, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni, (DPM) ₂ Ni hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni, [(nC ₄ H ₉ ) C ₅ H ₄ One or two or more compounds selected from the group consisting of ₂ Ni are used,

One selected from the group consisting of SiH ₄ , Me ₃ SiH, Me ₂ SiH ₂ , Me ₃ SiH, Et ₃ SiH, Et ₂ SiH ₂ , Et ₃ SiH, Si ₂ H ₆ , Si ₃ H ₈ as a raw material of Si Or a film forming material, characterized in that two or more compounds are used.

Moreover, the said subject is also solved by the film formation method characterized by forming an electroconductive silicide film using said film forming material and a reducing agent.

Or the above film forming material and H ₂ O, R ₃ N, R ₂ N-NR ₂ , RCHO, ROH (R is H or an alkyl group. When R is 2 or more, all R may or may not be the same.) It is also solved by a film forming method characterized by forming a conductive silicide film by using one or two or more selected from the group consisting of:

Or a film forming method characterized by forming a conductive silicide film using the above film forming material and H ₂ and H ₂ O.

Alternatively, the film forming method can be solved by forming a conductive silicide film using the above film forming material and alpha, beta -unsaturated alcohol.

In particular, the film forming material is a film forming material for forming a silicide film of a MOSFET by CVD, and the film forming method is a method of forming a conductive silicide film, particularly by CVD. When forming a film by CVD, the film forming materials are decomposed simultaneously or separately, respectively. In addition, decomposition is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser.

In addition, the above object is characterized by comprising a silicide film formed by the film forming method described above and comprising one or two metal elements and Si selected from the group consisting of Co and Ni. Resolved.

(Example)

The film forming material according to the present invention is a film forming material for forming a silicide film composed of one or two metal elements and Si selected from the group consisting of Co and Ni (particularly of MOSFETs). A film forming material for forming a silicide film by CVD, wherein one or two or more compounds selected from the group consisting of general formula [I] and general formula [II] are used as a raw material of the metal element It is a forming material. Further, in the film forming material for forming a silicide film composed of one or two metal elements selected from the group consisting of Co and Ni and Si (in particular, a film forming material for forming a silicide film of a MOSFET by CVD), As a raw material of the metal element, one or two or more compounds selected from the group consisting of general formula [I] and general formula [II] are used, and Si _x H _{(2x + 2)} (where x is Film formation material in which one or two or more compounds selected from the group consisting of one or more integers) and R _x SiH _(4-x) (wherein R is an alkyl group and x is an integer of 0 to 3) are used to be.

Particularly preferred compounds selected from the group consisting of the general formula [I] and general formula [II] include (Acac) ₂ Co, (Acac) ₂ Co hydrate, (Acac) ₃ Co, (Acac) ₃ Co hydrate, (DPM) ₂ Co, (DPM) ₂ Co hydrate, (DPM) ₃ Co, (DPM) ₃ Co hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Co, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Co, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Co, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Co, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni, (DPM) ₂ Ni hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni and [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Ni. Particularly preferred compounds selected from the group consisting of Si _x H _{(2x + 2)} and R _x SiH _(4-x) include SiH ₄ , Me ₃ SiH, Me ₂ SiH ₂ , Me ₃ SiH, Et ₃ SiH, Et _{2 SiH 2, Et 3 SiH, Si} 2 H 6, there may be mentioned Si ₃ H _8.

The film forming method according to the present invention is a method of forming a conductive silicide film using the film forming material and the reducing agent described above (in particular, a method of forming a conductive silicide film by CVD). Or the above film forming material and H ₂ O, R ₃ N, R ₂ N-NR ₂ , RCHO, ROH (R is H or an alkyl group. When R is 2 or more, all R may or may not be the same.) It is a method of forming a conductive silicide film using one or two or more selected from the group consisting of (in particular, a method of forming a conductive silicide film by CVD). Or a method of forming a conductive silicide film (particularly a method of forming a conductive silicide film by CVD) using the above-described film forming material and H ₂ and H ₂ O. Or a method of forming a conductive silicide film (particularly, a method of forming a conductive silicide film by CVD) using the above-described film forming material and alpha, beta -unsaturated alcohol.

When forming a film by CVD, the film forming materials are decomposed simultaneously or separately, respectively. In addition, decomposition is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser.

The device according to the present invention includes a silicide film formed by the above-described film forming method and composed of one or two metal elements and Si selected from the group consisting of Co and Ni.

A concrete Example is given to the following and it demonstrates in more detail.

Example 1

1 is a schematic diagram of a film deposition apparatus (CVD). In the drawings, 1a and 1b are raw material containers, 2 are heaters, 3 are decomposition reactors, 4 are Si (semiconductor) substrates, 5 are flow controllers. (流 量 制 御 器).

The container 1a contains (Acac) ₂ Co (Acac is an acetylacetonate group) and is heated to 140 ° C. Then, hydrogen gas is introduced at a rate of 300 ml / min as a carrier gas. Vaporized (Acac) ₂ Co is introduced into the decomposition reactor 3 through a pipe along with the carrier gas. At this time, the inside of the apparatus is evacuated to 10 to 15 Torr. In addition, the board | substrate 4 is heated at 350 degreeC.

When (Acac) ₂ Co was introduced into the decomposition reactor 3, SiH ₄ was introduced at a rate of 20 ml / min as a reaction gas.

As a result, a film was formed on the substrate 4.

The film was examined by XPS (X-ray photoelectron analysis) to confirm the presence of Co and Si. Moreover, as a result of irradiation with X-rays, it was confirmed that it was a CoSi ₂ film.

And this was suitable for next generation semiconductor devices.

Example 2

The film forming apparatus CVD of FIG. 1 is used. The container 1a contains (DPM) ₂ Ni (DPM is a dipivalolmethanate group) and is heated to 160 ° C. Hydrogen gas flows in at a rate of 80 ml / min as a carrier gas. The container 1b contains H ₂ O, and hydrogen gas flows in at a rate of 5 ml / min as a carrier gas. Vaporized (DPM) ₂ Ni and H ₂ O are introduced into the decomposition reactor 3 via piping together with the carrier gas. At this time, the inside of the apparatus is exhausted at 0.1 to 1 Torr. In addition, the board | substrate 4 is heated at 550 degreeC.

When introducing ₂ Ni and H ₂ O (DPM) into the decomposition reactor 3, SiH ₄ was introduced at a rate of 20 ml / min as a reaction gas.

As a result, a film was formed on the substrate 4.

When the film was examined by XPS, the presence of Ni and Si was confirmed. Moreover, as a result of irradiation with X-rays, it was confirmed that it was a NiSi ₂ film.

And this was suitable for next generation semiconductor devices.

(Examples 3 to 21)

Examples for ₂ Co instead of _{(Acac) 1 (Acac) 2} Co _{hydrate, (Acac) 3 Co, (} Acac) 3 Co _{hydrate, (DPM) 2 Co, (} DPM) 2 Co hydrate, (DPM) ₃ Co, (DPM) ₃ Co hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Co, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Co, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Co, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Co, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni, (DPM) ₂ Ni hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Ni The same was done.

As a result, the same silicide film was formed, which was suitable for the next generation semiconductor device.

(Examples 22 to 40)

(Acac) ₂ Co, (Acac) ₂ Co hydrate, (Acac) ₃ Co, (Acac) ₃ Co hydrate, (DPM) ₂ Co, (DPM) ₂ Co hydrate instead of (DPM) ₂ Ni in Example 2, (DPM) ₃ Co, (DPM) ₃ Co hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Co, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Co, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Co, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Co, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Ni The same was done.

As a result, the same silicide film was formed, which was suitable for the next generation semiconductor device.

(Examples 41 to 44)

In Example 2, instead of H ₂ O, Me ₃ N, MeHN-NH ₂ , MeCHO, and EtOH were used.

As a result, the same silicide film was formed, which was suitable for the next generation semiconductor device. Moreover, the decomposition temperature at the time of film-forming was 20-50 degreeC low compared with the case of Example 2. As shown in FIG.

(Example 45)

In Example 2, CH ₃ CH = CHCH ₂ OH was used instead of H ₂ O to make the same.

As a result, the same silicide film was formed, which was suitable for the next generation semiconductor device. In addition, the decomposition temperature at the time of film-forming was low compared with the case of Example 2.

(Examples 46 to 53)

In Example 1, instead of SiH ₄ , Me ₃ SiH, Me ₂ SiH ₂ , Me ₃ SiH, Et ₃ SiH, Et ₂ SiH ₂ , Et ₃ SiH, Si ₂ H ₆ , and Si ₃ H ₈ were used.

As a result, the same silicide film was formed, which was suitable for the next generation semiconductor device.

(Examples 54 to 56)

Instead of dissolving the compound as a heating means in Example 1, the same was accomplished by means of plasma, light and laser irradiation.

As a result, the same silicide film was formed, which was suitable for the next generation semiconductor device.

A silicide film called CoSi ₂ or NiSi ₂ can be formed by CVD.

Claims (33)

In the film forming material for forming the silicide film which consists of one or two metal elements selected from the group which consists of Co and Ni, and Si, A film-forming material, characterized in that one or two or more compounds selected from the group consisting of the following general formula [I] are used as raw materials for the metal elements. General formula [Ⅰ]

(Wherein M is Co or Ni, n is 2 or 3, R ₁ , R ₂ , R ₃ is H or an alkyl group. R ₁ , R ₂ , R ₃ may or may not be the same) The method of claim 1, A film forming material, characterized in that one or two or more compounds selected from the group consisting of the following general formula [II] are further used as a raw material of the metal element. General formula [Ⅱ]

(Wherein M is Co or Ni, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ is H or an alkyl group. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ may or may not be identical) delete The method of claim 2, (Acac) ₂ Co, (Acac) ₂ Co hydrate, (Acac) ₃ Co, (Acac) ₃ Co hydrate, (DPM) ₂ Co, (DPM) ₂ Co hydrate, (DPM) ) ₃ Co, (DPM) ₃ Co hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Co, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Co, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Co, [(nC ₄ H ₉ ) C ₅ H ₄ ] ₂ Co, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni, (DPM) ₂ Ni hydrate, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [(iC ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni, [(nC ₄ H ₉ ) C ₅ H ₄ ] A film forming material, characterized in that one or two or more compounds selected from the group consisting of ₂ Ni are used. The method according to claim 1 or 2, Si _x H _{(2x + 2)} (where x is an integer of 1 or more) and R _x SiH _(4-x) (wherein R is an alkyl group and x is an integer of 0 to 3; when R is two or more) All R may be the same or may not be the same) A film forming material, characterized in that one or two or more compounds selected from the group consisting of. The method of claim 4, wherein Si _x H _{(2x + 2)} (where x is an integer of 1 or more) and R _x SiH _(4-x) (wherein R is an alkyl group and x is an integer of 0 to 3; when R is two or more) All R may be the same or may not be the same) A film forming material, characterized in that one or two or more compounds selected from the group consisting of. The method according to claim 1 or 2, One selected from the group consisting of SiH ₄ , Me ₃ SiH, Me ₂ SiH ₂ , Me ₃ SiH, Et ₃ SiH, Et ₂ SiH ₂ , Et ₃ SiH, Si ₂ H ₆ , Si ₃ H ₈ as a raw material of Si Or a film forming material, characterized in that two or more compounds are used. The method of claim 4, wherein One selected from the group consisting of SiH ₄ , Me ₃ SiH, Me ₂ SiH ₂ , Me ₃ SiH, Et ₃ SiH, Et ₂ SiH ₂ , Et ₃ SiH, Si ₂ H ₆ , Si ₃ H ₈ as a raw material of Si Or a film forming material, characterized in that two or more compounds are used. The method according to claim 1 or 2, A film forming material for forming a silicide film of a MOSFET by CVD. In the film formation method for forming the silicide film which consists of one or two metal elements selected from the group which consists of Co and Ni, and Si, A film forming method comprising forming a conductive silicide film using the film forming material of claim 1 or 2 and a reducing agent. In the film formation method for forming the silicide film which consists of one or two metal elements selected from the group which consists of Co and Ni, and Si, The film forming material according to claim 1 or 2 and H ₂ O, R ₃ N, R ₂ N-NR ₂ , RCHO, ROH (R is H or an alkyl group. When R is 2 or more, all R are the same or And a conductive silicide film is formed using one or two or more selected from the group consisting of (not necessarily the same). In the film formation method for forming the silicide film which consists of one or two metal elements selected from the group which consists of Co and Ni, and Si, A film forming method comprising forming a conductive silicide film using the film forming material of claim 1 or 2 and H ₂ and H ₂ O. In the film formation method for forming the silicide film which consists of one or two metal elements selected from the group which consists of Co and Ni, and Si, A film forming method comprising forming a conductive silicide film by using the film forming material of claim 1 or 2 and alpha, beta -unsaturated alcohol. The method of claim 10, A conductive silicide film is formed by CVD. The method of claim 11, A conductive silicide film is formed by CVD. The method of claim 12, A conductive silicide film is formed by CVD. The method of claim 13, A conductive silicide film is formed by CVD. The method of claim 10, A film forming method comprising decomposing the film forming material simultaneously or separately. The method of claim 11, A film forming method comprising decomposing the film forming material simultaneously or separately. The method of claim 12, A film forming method comprising decomposing the film forming material simultaneously or separately. The method of claim 13, A film forming method comprising decomposing the film forming material simultaneously or separately. The method according to any one of claims 14 to 17, A film forming method comprising decomposing the film forming material simultaneously or separately. The method of claim 10, A film forming method, wherein the film forming material is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser. The method of claim 11, A film forming method, wherein the film forming material is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser. The method of claim 12, A film forming method, wherein the film forming material is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser. The method of claim 13, A film forming method, wherein the film forming material is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser. The method according to any one of claims 14 to 17, A film forming method, wherein the film forming material is decomposed using at least one method selected from the group consisting of heat, plasma, light, and laser. An element comprising a silicide film formed by the film forming method according to claim 10 and comprising one or two metal elements selected from the group consisting of Co and Ni and Si. A device comprising a silicide film formed by the film forming method according to claim 11 and composed of one or two metal elements and Si selected from the group consisting of Co and Ni. An element comprising a silicide film formed by the film forming method according to claim 12 and comprising one or two metal elements selected from the group consisting of Co and Ni and Si. An element comprising a silicide film formed by the film forming method according to claim 13 and comprising one or two metal elements selected from the group consisting of Co and Ni and Si. A silicide film formed by the film forming method according to any one of claims 14 to 17 and comprising one or two metal elements selected from the group consisting of Co and Ni and Si. A device to say. The method of claim 1, (Acac) ₂ Co, (Acac) ₂ Co hydrate, (Acac) ₃ Co, (Acac) ₃ Co hydrate, (DPM) ₂ Co, (DPM) ₂ Co hydrate, (DPM) ) ₃ Co, (DPM) ₃ Co hydrate, (Acac) ₂ Ni, (Acac) ₂ Ni hydrate, (DPM) ₂ Ni, (DPM) ₂ Ni hydrate selected from the group consisting of A film forming material, characterized in that used.

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