JP2004300579A - Material and method for depositing conductive barrier film, wired film depositing method, and ulsi - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive barrier film depositing material in which film deposition is performed even when a condition that the ratio (aperture/depth) of the aperture to the depth of a groove or a hole is 1/5-1/7 is required, and the thickness is ≤ 10 nm, copper diffusion prevention (barrier property) is excellent, the electric resistance is small, and adhesiveness to a copper film is excellent. <P>SOLUTION: The conductive barrier film depositing material is used to deposit a conductive Ti-Zr barrier film by the chemical vapor deposition, and contains Ti halide compound (TiCl<SB>4</SB>or the like) or metal organic compound with Ti, and Zr halide compound (ZrCl<SB>4</SB>or the like) or metal organic compound with Zr. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a conductive barrier film forming material, a conductive barrier film forming method, a wiring film forming method, and ULSI.

  At present, progress in the semiconductor field is remarkable, and it is moving from LSI to ULSI. In order to improve the signal processing speed, miniaturization is progressing. In particular, a conductive portion (wiring) for transmitting an electric signal is required to be thin. However, when the wiring is made thinner, the electric resistance naturally becomes higher. Therefore, a wiring material having a lower resistance has been demanded. For example, it has moved from a W wiring film to an Al wiring film. Then, in the next generation, a Cu wiring film is attracting attention.

  However, copper diffuses strongly into the silicon substrate. Therefore, it is difficult to form a wiring film as it is. Therefore, a conceivable means is to provide a diffusion prevention film (barrier film) on a substrate and form a copper film thereon. Titanium nitride, tungsten nitride, tantalum nitride, tantalum, or the like has been expected as a material for the barrier film.

  By the way, the above-mentioned materials have excellent performance, but relatively high electric resistance, and have a problem in adhesion to a substrate or a copper film, if attention is paid only to prevention of copper diffusion. Came.

  Further, as a result of further research and development, they came to the knowledge that a Ti-Zr-N film, a W-Ta-N film, etc. could solve the above-mentioned problems.

  By the way, the width of the copper wiring film required at present is 0.15 μm or less, and the ratio of the opening to the depth of the groove or hole (opening / depth) is 1/5 to 1/7. It is getting bigger. Accordingly, the ratio of the opening to the depth of the groove or hole (opening / depth) is also required for the Ti-Zr-N film, the W-Ta-N film, etc., as the base film of the copper wiring film. Must be satisfied. In addition, a requirement that the thickness of the base film be 10 nm or less is also required.

  Attempts have been made to form a Ti-Zr-N film, a W-Ta-N film, or the like satisfying such conditions by physical vapor deposition (PVD) such as sputtering. However, it has been found that this technique is very difficult and practically practically impossible.

  Therefore, the first problem to be solved by the present invention is that even if a condition such that the ratio of the opening and the depth of the groove or hole (opening / depth) is 1/5 to 1/7 is required. Moreover, even if the thickness is 10 nm or less, it is possible to form a film, and it is excellent in prevention of copper diffusion (barrier property), furthermore, has low electric resistance and excellent adhesion to a copper film. It is to provide a barrier film forming material.

  The second problem to be solved by the present invention is that even if a condition such that the ratio of the opening and the depth of the groove or hole (opening / depth) is 1/5 to 1/7 is required, A conductive barrier film that can be formed even if the thickness is 10 nm or less, is excellent in preventing copper diffusion (barrier property), has low electric resistance, and has excellent adhesion to a copper film. It is to provide a forming method.

  A third problem to be solved by the present invention is to provide an ULSI in which a copper wiring film is formed on a barrier film formed by the above-described method for forming a conductive barrier film.

  The first problem is a material for forming a conductive Ti-Zr-based barrier film by chemical vapor deposition (CVD), and includes a halogenated Ti-based compound and a halogenated Zr-based compound. The problem is solved by the conductive barrier film forming material described above.

  In particular, a material for forming a conductive Ti-Zr-based barrier film by CVD, comprising a halogenated Ti-based compound and a halogenated Zr-based compound, wherein the halogenated Ti-based compound and the halogenated Zr-based compound are And at least one of them is a liquid.

Furthermore, the problem is solved by a conductive barrier film forming material which is a material for forming a conductive Ti-Zr-based barrier film by CVD and is characterized by containing TiCl ₄ and ZrCl ₄ .

  A material for forming a conductive Ti-Zr-based barrier film by CVD, wherein the material comprises a metal organic compound having Ti and a metal organic compound having Zr. Will be resolved.

  In particular, a material for forming a conductive Ti-Zr-based barrier film by CVD, comprising a metal organic compound having Ti, a metal organic compound having Zr, and a solvent dissolving the metal organic compound. The problem is solved by the conductive barrier film forming material described above.

  In the present invention, the conductive barrier film forming material is particularly used for forming a conductive barrier film provided as a base film of a copper (including copper alloy) film (particularly, a copper (including copper alloy) wiring film). Material. That is, when a copper film is formed, it is a material for forming a barrier film provided to prevent diffusion and intrusion of copper into the substrate side. The barrier film formed of this material has high conductivity. It is shown.

  Examples of the metal organic compound having Ti in the conductive barrier film forming material include, for example, tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetrakisdipropylaminotitanium, tetrakismethylethylaminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino] Titanium, trisdimethylaminobis (trimethylsilyl) aminotitanium, biscyclopentadienylbisdimethylaminotitanium, cyclopentadienylcyclooctatetraenyltitanium, biscyclopentadienyltitanium diazide, and derivatives of the above compounds are preferred. No. Therefore, one or more compounds selected from these groups can be used.

  Examples of the metal organic compound having Zr in the conductive barrier film forming material include, for example, tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, bis Cyclopentadienyl bisdiethylaminozirconium and derivatives of the compounds are mentioned as being preferred. Therefore, one or more compounds selected from these groups can be used.

  The “derivative of the compound” is used to mean a derivative derived without impairing the basic skeleton of the compound, for example, by substituting H for F or attaching a side chain such as a methyl group to a cyclic compound. It is a thing.

By the way, when one (ZrCl ₄ ) is solid and the other (TiCl ₄ ) is liquid as in the case of a combination of TiCl ₄ and ZrCl ₄ , the handling by CVD becomes easy.

  Therefore, when both are solid, it is preferable to use a solvent in order to facilitate handling by CVD. Here, any solvent may be used as long as it can dissolve any compound. When a metal organic compound having Ti and a metal organic compound having Zr are used, examples of the solvent include dimethylethylamine, diethylmethylamine, triethylamine, tripropylamine, toluene, xylene, heptane, octane, nonane, and the like. Preferred are decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and the like. As the solvent when the metal organic compound having Ta and the metal organic compound having W are used, for example, dimethylethylamine, diethylmethylamine, triethylamine, tripropylamine, toluene, xylene, heptane, octane, nonane, decane, Preferred are undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, and the like.

The second problem is solved by a method for forming a conductive barrier film, which comprises forming a conductive barrier film by CVD using the above-mentioned material for forming a conductive barrier film. When a halogenated Ti-based compound and a halogenated Zr-based compound, for example, TiCl ₄ and ZrCl ₄ are used, the conductive barrier film formed by CVD is a Ti—Zr-based film. When CVD is performed in a nitriding atmosphere (for example, an atmosphere such as ammonia), the Ti-Zr-based film is a Ti-Zr-N-based film. When a metal organic compound having Ti and a metal organic compound having Zr are used, the conductive barrier film formed by CVD is a Ti-Zr-based film. When CVD is performed in a nitriding atmosphere (for example, an atmosphere such as ammonia), the Ti-Zr-based film is a Ti-Zr-N-based film. When a metal organic compound having Ta and a metal organic compound having W are used, the conductive barrier film formed by CVD is a Ta-W based film. When CVD is performed in a nitriding atmosphere (for example, an atmosphere such as ammonia), the Ta-W-based film is a Ta-W-N-based film.

  Also, a method of forming a Ti-Zr-based conductive barrier film by CVD, comprising the steps of vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr, and a vapor pressure of 0.00001 to 760 torr And a step of vaporizing a Zr-based compound having the following formula:

  A method for forming a Ta—Ti-based conductive barrier film by CVD, comprising: vapor-forming a Ta-based compound having a vapor pressure of 0.00001 to 760 torr; and a vapor pressure of 0.00001 to 760 torr. And a step of vaporizing a Ti-based compound having the following.

  A method for forming a Ta-Zr-based conductive barrier film by CVD, comprising the steps of vaporizing a Ta-based compound having a vapor pressure of 0.00001 to 760 torr, and a vapor pressure of 0.00001 to 760 torr. And a step of vaporizing a Zr-based compound having the following formula:

  A method of forming a conductive barrier film by CVD, comprising: a Ti-based compound having a vapor pressure of 0.00001 to 760 torr, a Zr-based compound having a vapor pressure of 0.00001 to 760 torr, and 0.00001 to 760 torr. Vaporizing at least two compounds selected from a Ta-based compound having a vapor pressure and a W-based compound having a vapor pressure of 0.00001 to 2,000 torr; and Ti having a vapor pressure of 0.00001 to 760 torr. A method of forming a conductive compound into a gaseous phase.

  The step of forming a film by vaporizing a plurality of compounds may be performed simultaneously or at different times (in order, repeatedly in order, or alternately). When performed simultaneously, the formed conductive barrier film becomes a composite film in which a plurality of conductive barrier films are mixed in one layer. When CVD is performed in a nitriding atmosphere (for example, an atmosphere of ammonia or the like), the Ti-Zr-based conductive barrier film is a Ti-Zr-N-based conductive barrier film and a Ta-W-based conductive barrier film. The conductive barrier film is a Ta-W-N-based conductive barrier film, the Ta-Ti-based conductive barrier film is a Ta-Ti-N-based conductive barrier film, and a Ta-Zr-based conductive barrier film. The film is a Ta-Zr-N-based conductive barrier film. When film formation is performed in order, only one kind exists in one layer (however, since the thickness of the layer is thin, even if the film formation is performed in order, it is mixed in one layer. It can be said that this is the case)), which results in a laminated type composite film. For example, a composite film formed by laminating a Ti-N film and a Zr-N film, a composite film formed by laminating a Ta-N film and a W-N film, a Ta-N film and a Ti-N film, A composite film formed by laminating a Ta-N film and a Zr-N film, or a composite film formed by laminating a Ta-N film, a WN film, and a Ti-N film. Or a composite film formed by laminating a Zr-N film, a WN film, and a Ti-N film, a composite film formed by laminating a Zr-N film, a Ta-N film, and a Ti-N film, It may be a composite film formed by laminating a Zr-N film, a Ta-N film, a W-N film, and a Ti-N film.

  In the case of a laminated composite film, a Zr-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Zr-based film, and then a Ti-based compound having a vapor pressure of 0.00001 to 760 torr. Is preferably vaporized to form a Ti-based film. Also, after a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ta-based film, a W-based compound having a vapor pressure of 0.00001 to 2000 torr is vaporized to form a W-based film. Is preferably formed. Further, after a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ta-based film, a Ti-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ti-based film. Is preferably formed. Further, after a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ta-based film, a Zr-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Zr-based film. Is preferably formed. Also, a Ti compound having a vapor pressure of 0.00001 to 760 torr, a Zr compound having a vapor pressure of 0.00001 to 760 torr, a Ta compound having a vapor pressure of 0.00001 to 760 torr, and 0.00001 to 2000 torr After vapor-forming at least two compounds selected from W-based compounds having a vapor pressure of 0.1 to 750 torr, a Ti-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ti-based film. It is preferable to form a film. This is because, in the case of a laminated type composite film, when the Ti-based film is in the upper layer (particularly, the uppermost layer), the adhesion with the copper film provided thereon is better, and the copper film is less likely to be peeled off. .

  Examples of the Ti-based compound having a vapor pressure of 0.00001 to 760 torr in the method of forming a conductive barrier film include tetrafluorotitanium, tetrachlorotitanium, tetrabromotitanium, tetraioditanium, tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium. , Tetrakisdipropylaminotitanium, tetrakismethylethylaminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino] titanium, trisdimethylaminobis (trimethylsilyl) aminotitanium, biscyclopentadienylbisdimethylaminotitanium, cyclopentadienyl Preferred are cyclooctatetraenyltitanium, biscyclopentadienyltitaniumdiazide, and derivatives of the compounds. Therefore, one or more compounds selected from these groups can be used.

  Examples of the Zr-based compound having a vapor pressure of 0.00001 to 760 torr in the method for forming a conductive barrier film include tetrafluorozirconium, tetrachlorozirconium, tetrabromozirconium, tetraiodzirconium, zirconium tetraboron hydride, and tetrakisdimethylamino. Preferred examples include zirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and derivatives of the above compounds. Therefore, one or more compounds selected from these groups can be used.

  Examples of the Ta-based compound having a vapor pressure of 0.00001 to 760 torr in the method for forming a conductive barrier film include pentafluorotantalum, pentachlorotantalum, pentabromotantalum, pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, Preferred are tetrakis diethylamino tantalum, ethyl imido tris diethyl amino tantalum, butyl imido tris diethyl amino tantalum, pentakis methyl ethyl amino tantalum, tetrakis methyl butyl amino tantalum, and derivatives of the above compounds. Therefore, one or more compounds selected from these groups can be used.

  Examples of the W-based compound having a vapor pressure of 0.00001 to 2000 torr in the method for forming a conductive barrier film include hexafluorotungsten, hexachlorotungsten, hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, Butylimidobisbutylaminotungsten, bispropylcyclopentadienyltungsten dihydride, and derivatives of said compounds are mentioned as being preferred. Therefore, one or more compounds selected from these groups can be used.

The compound is decomposed at the time of forming the conductive barrier film (CVD) by one or more of thermal decomposition, photolysis, plasma decomposition, and reactive decomposition. Decomposition may be performed using any means. The decomposition of the compound at the time of forming the conductive barrier film is preferably performed in a reducing atmosphere. Alternatively, hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, hydrazine derivatives (eg, CH ₃ NHNH ₂ , (CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ , RNHNH ₂
(R is a functional group such as an alkyl group); silane; silane derivatives (for example, R _n SiY _4-n (R is a functional group such as an alkyl group; Y is H, F, Cl, Br or I) ), Borane, and borane derivatives (eg, R _n
Under an air flow (atmosphere) containing one or more selected from the group of BY _3-n (R is a functional group such as an alkyl group, Y is a borane derivative such as H, F, Cl, Br or I). Preferably, the decomposition of the compound is carried out. The conductive barrier film may be formed simultaneously with decomposition of a compound containing one or more selected from the group consisting of ammonia, hydrazine, hydrazine derivatives, and alkyl azides, or before and / or after decomposition of the compound. Decomposing the forming material is also a preferred method. Further, a compound containing one or more selected from the group consisting of methylhydrazine, dimethylhydrazine, ethylhydrazine, diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, and phenyl azide It is a preferable method to perform the decomposition of the conductive barrier film forming material simultaneously with the decomposition of the compound or before and / or after the decomposition of the compound.

  Further, the third problem is that a conductive barrier film forming step of forming a conductive barrier film by the above-described conductive barrier film forming method and a conductive barrier film formed by the conductive barrier film forming step are formed on the conductive barrier film. And a copper film forming step of forming a copper film.

  Further, the problem is solved by ULSI in which a copper wiring film is formed on a conductive barrier film formed by the above-described method for forming a conductive barrier film.

  Even if a condition such that the ratio of the opening and the depth of the groove or hole (opening / depth) is 1/5 to 1/7 is required, and the thickness is 10 nm or less, the film can be formed. It is possible to form a conductive barrier film which is excellent in preventing copper diffusion (barrier property), has low electric resistance, and is excellent in adhesion to a copper film.

The conductive barrier film forming material according to the present invention is a material for forming a conductive Ti-Zr-based barrier film by CVD (a conductive Ti-Zr-based material provided by CVD as a base film of a copper film, particularly, a copper wiring film). (A material for forming a barrier film), which contains a halogenated Ti-based compound and a halogenated Zr-based compound. In particular, it is in the form of a mixture containing a halogenated Ti-based compound and a halogenated Zr-based compound. Further, at least one of the halogenated Ti-based compound and the halogenated Zr-based compound is liquid and is in a solution form. Examples of the halogenated Ti-based compound include TiF ₄ , TiCl ₄ , TiBr ₄ , and TiI ₄ . As the halogenated Zr-based compound, for example, ZrF ₄
, ZrCl ₄ , ZrBr ₄ , ZrI _{4 and the} like. Among them, TiCl ₄
It is preferably in the form of a mixture containing (liquid) and ZrCl ₄ (solid). The ratio (molar ratio) between the halogenated Ti-based compound and the halogenated Zr-based compound is as follows: halogenated Ti-based compound: halogenated Zr-based compound = 9: 1 to 1: 9 (particularly, 6: 4 to 4: 6). ). Here, the ratio as described above is that when the ratio is less than 9: 1, the formed conductive Ti-Zr-based barrier film has almost no difference in performance from the Ti-based barrier film, and the characteristics as an alloy. On the other hand, when the ratio exceeds 1: 9, the formed conductive Ti-Zr-based barrier film has a low effect of preventing copper diffusion and cannot easily exhibit the characteristics as an alloy. Because it is.

  Further, the conductive barrier film forming material according to the present invention is a material for forming a conductive Ti—Zr-based barrier film by CVD (a conductive Ti—Zr film provided as a base film of a copper film, particularly, a copper wiring film by CVD). (A material for forming a Zr-based barrier film), which includes a metal organic compound having Ti and a metal organic compound having Zr. In particular, it is in the form of a mixture. If one or both of the metal organic compound having Ti and the metal organic compound having Zr are liquid, the mixture is in the form of a solution, so that no further addition is necessary. A solvent for dissolving the metal organic compound is further added to obtain a solution. Examples of the metal organic compound having Ti include, for example, tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetrakisdipropylaminotitanium, tetrakismethylethylaminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino] titanium, trisdimethylaminobis ( Trimethylsilyl) aminotitanium, biscyclopentadienylbisdimethylaminotitanium, cyclopentadienylcyclooctatetraenyltitanium, biscyclopentadienyltitanium diazide, and derivatives of the above compounds can be used. Examples of the metal organic compound having Zr include tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, And derivatives of the above compounds. Among them, those in the form of a mixture (solution form) containing tetrakisdimethylaminotitanium (liquid) and tetrakisdimethylaminozirconium (solid), and those in the form of a mixture containing tetrakisdimethylaminotitanium (liquid) and tetrakisdimethylaminozirconium (solid) (Solution form), a mixture containing tetrakismethylethylaminoaminotitanium (liquid) and tetrakismethylethylaminozirconium (liquid) (solution form), tetrakisdiethylaminotitanium (liquid) and tetrakisdiethylaminozirconium (liquid) In the form of a mixture (solution form) containing The ratio (molar ratio) of the metal organic compound having Ti and the metal organic compound having Zr is as follows: metal organic compound having Ti: metal organic compound having Zr = 9: 1 to 1: 9 (particularly, 6: 4 4: 4). Here, the ratio as described above is that when the ratio is less than 9: 1, the formed conductive Ti-Zr-based barrier film has almost no difference in performance from the Ti-based barrier film, and the characteristics as an alloy. On the other hand, when the ratio exceeds 1: 9, the formed conductive Ti-Zr-based barrier film has a low effect of preventing copper diffusion and cannot easily exhibit the characteristics as an alloy. Because it is. As the solvent, for example, dimethylethylamine, diethylmethylamine, triethylamine, tripropylamine, toluene, xylene, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and the like can be used. Among them, nonane, decane, undecane, dodecane, tridecane and tetradecane are preferred. The solvent is used such that the concentration of the metal organic compound is about 0.001 to 1 mol / l.

  The conductive barrier film forming material is a material for forming a conductive Ta-W-based barrier film by CVD (a conductive Ta-W-based barrier film provided by CVD as a base film of a copper film, particularly, a copper wiring film). And a metal organic compound having Ta and a metal organic compound having W. In particular, it is in the form of a mixture. If one or both of the metal organic compound having Ta and the metal organic compound having W are liquid, the mixture is in a solution form, so that no further addition is necessary. A solvent for dissolving the metal organic compound is further added to obtain a solution. Examples of the metal organic compound having Ta include pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, butylimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, and tetrakismethylbutyl. Amino tantalum and derivatives of the above compounds can be used. Examples of the metal organic compound having W include hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, butylimidobisbutylaminotungsten, bispropylcyclopentadienyltungsten dihydride, and derivatives of the compound. Can be used. Among them, those in the form of a mixture (solution form) containing pentakisdimethylaminotantalum (solid), hexadimethylaminoditungsten (solid) and a solvent, tetrakisdiethylaminotantalum (liquid) and hexadiethylaminoditungsten (solid) In the form of a mixture (solution form), containing tetrakisdiethylaminotantalum (liquid) and bispropylcyclopentadienyltungsten dihydride (liquid), in the form of a mixture (solution form), pentakismethylethylaminotantalum ( Liquid) and hexamethylethylaminoditungsten (solid) in the form of a mixture (solution). The ratio (molar ratio) between the metal organic compound having Ta and the metal organic compound having W is as follows: metal organic compound having Ta: metal organic compound having W = 8: 2 to 2: 8, particularly 6: 4 to 4: 6. Here, the ratio as described above is such that when the ratio is less than 8: 2, the formed conductive Ta-W-based barrier film does not have a great difference in performance from the Ta-based barrier film, and has a feature as an alloy. On the other hand, when the ratio exceeds 2: 8, the formed conductive Ta-W-based barrier film has almost no difference in performance from the W-based barrier film, and has a feature as an alloy. It is because it is difficult to demonstrate. As the solvent, for example, dimethylethylamine, diethylmethylamine, triethylamine, tripropylamine, toluene, xylene, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and the like can be used. Among them, nonane, decane, undecane, dodecane, tridecane and tetradecane are preferred. The solvent is used such that the concentration of the metal organic compound is about 0.001 to 1 mol / l.

  In the method for forming a conductive barrier film according to the present invention, a conductive barrier film is formed by CVD using the above-described conductive barrier film forming material (the conductive barrier film is formed by CVD as a base film of a copper film, particularly, a copper wiring film). Formation). The thickness of the conductive barrier film thus formed is 5 to 500 nm, particularly 10 to 50 nm. That is, when the thickness of the conductive barrier film is too thin, less than 5 nm, the feature of the effect of preventing copper diffusion is difficult to be exhibited. Conversely, when the thickness exceeds 500 nm, most of the copper wiring portion is not formed. This is because it occupies an area.

  Further, the method of forming a conductive barrier film according to the present invention (a method of forming a conductive barrier film as a base film of a copper film, particularly a copper wiring film) is a method of forming a Ti-Zr-based conductive barrier film by CVD. And comprising a step of vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr and a step of vaporizing a Zr-based compound having a vapor pressure of 0.00001 to 760 torr. Here, the ratio (molar ratio) between Ti and Zr in the Ti—Zr-based conductive barrier film is Ti: Zr = 9: 1 to 1: 9 (particularly, 6: 4 to 4; 6). Here, when the ratio is set to be less than 9: 1, the formed conductive Ti-Zr-based barrier film has almost no difference in performance from the Ti-based barrier film, On the other hand, when the ratio exceeds 1: 9, the formed conductive Ti-Zr-based barrier film has a low effect of preventing copper diffusion and cannot exhibit the characteristics as an alloy. It depends. The thickness of the formed Ti-Zr-based conductive barrier film is 5 to 500 nm, particularly 10 to 50 nm. That is, when the thickness of the conductive barrier film is too thin, less than 5 nm, the feature of the effect of preventing copper diffusion is difficult to be exhibited. Conversely, when the thickness exceeds 500 nm, most of the copper wiring portion is not formed. This is because it occupies an area.

  The conductive barrier film forming method according to the present invention (a method of forming a conductive barrier film as a base film of a copper film, particularly a copper wiring film) is a method of forming a Ta-W based conductive barrier film by CVD. The method includes a step of vaporizing a Ta-based compound having a vapor pressure of 0.00001 to 760 torr and a step of vaporizing a W-based compound having a vapor pressure of 0.00001 to 2000 torr. Here, the ratio (molar ratio) of Ta and W in the Ta-W-based conductive barrier film is Ta: W = 8: 2 to 2: 8, particularly 6: 4 to 4: 6. Here, the ratio as described above is such that when the ratio is less than 8: 2, the formed conductive Ta-W-based barrier film does not have a great difference in performance from the Ta-based barrier film, and has a feature as an alloy. On the other hand, when the ratio exceeds 2: 8, the formed conductive Ta-W-based barrier film has almost no difference in performance from the W-based barrier film, and has a feature as an alloy. It is because it is difficult to demonstrate. The thickness of the formed Ta-W based conductive barrier film is 5 to 500 nm, particularly 10 to 50 nm. That is, when the thickness of the conductive barrier film is too thin, less than 5 nm, the feature of the effect of preventing copper diffusion is difficult to be exhibited. Conversely, when the thickness exceeds 500 nm, most of the copper wiring portion is not formed. This is because it occupies an area.

  Further, the method of forming a conductive barrier film according to the present invention (a method of forming a conductive barrier film as a base film of a copper film, particularly a copper wiring film) is a method of forming a Ta-Ti-based conductive barrier film by CVD. The method further includes a step of vaporizing a Ta-based compound having a vapor pressure of 0.00001 to 760 torr and a step of vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr. Here, the ratio (molar ratio) of Ta and Ti in the Ta—Ti-based conductive barrier film is Ta: Ti = 9: 1 to 1: 9, particularly 6: 4 to 4: 6. Here, when the ratio is set to be less than 9: 1, the formed conductive Ta-Ti-based barrier film has substantially no difference in performance from the Ta-based barrier film, and the characteristics as an alloy. On the other hand, when the ratio exceeds 1: 9, the formed conductive Ta-Ti-based barrier film has almost no difference in performance from the Ti-based barrier film, and has the characteristics as an alloy. It is because it is difficult to demonstrate. The thickness of the formed Ta-Ti-based conductive barrier film is 5 to 500 nm, particularly 10 to 50 nm. That is, when the thickness of the conductive barrier film is too thin, less than 5 nm, the feature of the effect of preventing copper diffusion is difficult to be exhibited. Conversely, when the thickness exceeds 500 nm, most of the copper wiring portion is not formed. This is because it occupies an area.

  Further, the method for forming a conductive barrier film according to the present invention (a method for forming a conductive barrier film as a base film of a copper film, particularly a copper wiring film) is a method of forming a Ta-Zr-based conductive barrier film by CVD. And comprising a step of vaporizing a Ta-based compound having a vapor pressure of 0.00001 to 760 torr and a step of vaporizing a Zr-based compound having a vapor pressure of 0.00001 to 760 torr. Here, the ratio (molar ratio) between Ta and Zr in the Ta—Zr-based conductive barrier film is Ta: Zr = 9: 1 to 1: 9, particularly 6: 4 to 4: 6. Here, the ratio as described above is that when the ratio is less than 9: 1, the formed conductive Ta-Zr-based barrier film has substantially no difference in performance from the Ta-based barrier film, and the characteristics as an alloy. On the other hand, when the ratio exceeds 1: 9, the formed conductive Ta-Zr-based barrier film has almost no difference in performance from the Zr-based barrier film, and has a feature as an alloy. It is because it is difficult to demonstrate. The thickness of the formed Ta-Zr-based conductive barrier film is 5 to 500 nm, particularly 10 to 50 nm. That is, when the thickness of the conductive barrier film is too thin, less than 5 nm, the feature of the effect of preventing copper diffusion is difficult to be exhibited. Conversely, when the thickness exceeds 500 nm, most of the copper wiring portion is not formed. This is because it occupies an area.

  The method for forming a conductive barrier film according to the present invention (a method for forming a conductive barrier film as a base film for a copper film, particularly a copper wiring film) is a method for forming a conductive barrier film by CVD. A Ti-based compound having a vapor pressure of 0.000001 to 760 torr, a Zr-based compound having a vapor pressure of 0.00001 to 760 torr, a Ta-based compound having a vapor pressure of 0.00001 to 760 torr, and a vapor pressure of 0.00001 to 2000 torr And a gas phase of a Ti-based compound having a vapor pressure of 0.00001 to 760 torr. Here, the ratio (molar ratio) between the components (Zr, Ta, W) other than Ti and Ti in the conductive barrier film is such that the components (Zr, Ta, W) other than Ti: Ti = 99: 1 to 1: 99, especially 9: 1 to 1: 9. Here, when the ratio is set as above, if the ratio is less than 99: 1, the formed conductive barrier film has difficulty in controlling the thickness of the final adhesion Ti film, and has a feature of improving the adhesion. On the other hand, when the ratio exceeds 1:99, the formed conductive barrier film is not much different from the Ti film, and it is difficult to exhibit the feature of improving the barrier property. The thickness of the formed conductive barrier film is 5 to 500 nm, particularly 10 to 50 nm. That is, when the thickness of the conductive barrier film is too thin, less than 5 nm, the feature of the effect of preventing copper diffusion is difficult to be exhibited. Conversely, when the thickness exceeds 500 nm, most of the copper wiring portion is not formed. This is because it occupies an area. The step of forming a film by vaporizing the plurality of compounds is performed at the same time or at different times (in order, repeatedly in order, or alternately). When performed simultaneously, the formed conductive barrier film becomes a composite film in which a plurality of conductive barrier films are mixed in one layer. When CVD is performed in a nitriding atmosphere (for example, an atmosphere of ammonia or the like), the Ti-Zr-based conductive barrier film is a Ti-Zr-N-based conductive barrier film and a Ta-W-based conductive barrier film. The conductive barrier film is a Ta-W-N-based conductive barrier film, the Ta-Ti-based conductive barrier film is a Ta-Ti-N-based conductive barrier film, and a Ta-Zr-based conductive barrier film. The film is a Ta-Zr-N-based conductive barrier film. If film formation is repeatedly performed in order, for example, only one kind is present in one layer, but a composite film of a stacked type is obtained. For example, a composite film formed by laminating a Ti-N film and a Zr-N film, a composite film formed by laminating a Ta-N film and a W-N film, a Ta-N film and a Ti-N film, A composite film formed by laminating a Ta-N film and a Zr-N film, or a composite film formed by laminating a Ta-N film, a WN film, and a Ti-N film. Or a composite film formed by laminating a Zr-N film, a WN film, and a Ti-N film, a composite film formed by laminating a Zr-N film, a Ta-N film, and a Ti-N film, It may be a composite film formed by laminating a Zr-N film, a Ta-N film, a W-N film, and a Ti-N film.

  Examples of the Ti-based compound having a vapor pressure of 0.00001 to 760 torr include tetrafluorotitanium, tetrachlorotitanium, tetrabromotitanium, tetraioditanium, tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetrakisdipropylaminotitanium, Tetrakismethylethylaminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino] titanium, trisdimethylaminobis (trimethylsilyl) aminotitanium, biscyclopentadienylbisdimethylaminotitanium, cyclopentadienylcyclooctatetraenyltitanium, bis Cyclopentadienyl titanium diazide and derivatives of the above compounds can be used. When these Ti compounds are metal organic compounds, they are used in a form dissolved in a solvent.

  Examples of the Zr-based compound having a vapor pressure of 0.00001 to 760 torr include tetrafluorozirconium, tetrachlorozirconium, tetrabromozirconium, tetraiodzirconium, zirconiumtetraboron hydride, tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdi Propylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and derivatives of the above compounds can be used. When these Zr-based compounds are metal organic compounds, they are used in a form dissolved in a solvent.

  Examples of Ta-based compounds having a vapor pressure of 0.00001 to 760 torr include pentafluorotantalum, pentachlorotantalum, pentabromotantalum, pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, and ethylimidotrisdiethylamino. Tantalum, butyl imido tris diethyl amino tantalum, pentakis methyl ethyl amino tantalum, tetrakis methyl butyl amino tantalum, and derivatives of the above compounds can be used. When these Ta-based compounds are metal organic compounds, they are used in a form dissolved in a solvent.

  Examples of the W-based compound having a vapor pressure of 0.00001 to 2000 torr include hexafluorotungsten, hexachlorotungsten, hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, butylimidobisbutylaminotungsten, bis Propylcyclopentadienyltungsten dihydride and derivatives of the above compounds can be used. When these W-based compounds are metal organic compounds, they are used in a form dissolved in a solvent.

  Then, a conductive barrier film is formed on the substrate by using an apparatus as shown in FIGS. 1 and 2, reference numerals 1a and 1b denote containers in which a material for forming a conductive barrier film is placed, 2 denotes a vaporizer, 3 denotes a heater, 4 denotes a decomposition reactor, 5 denotes a silicon substrate, 6 denotes hydrogen and hydrogen plasma, A reaction gas such as ammonia or silane, 7 is a gas flow controller, and 8 is a liquid flow controller.

In the case where the apparatus shown in FIG. 1 is used, a mixed solution of TiCl ₄ and ZrCl ₄ is put in a container 1 a and sent to a vaporizer 2 by a pressurized gas. Further, a carrier gas is sent to the vaporizer 2. Then, the vaporized raw material is introduced into the decomposition reaction furnace 4 through a pipe. Also, a reaction gas is introduced into the decomposition reaction furnace 4 as needed. A silicon substrate 5 on which a film is formed is placed in the reaction furnace 4, and the silicon substrate 5 is heated by the heating unit 3. Then, TiCl ₄ and ZrCl ₄ introduced into the decomposition reaction furnace 4 are decomposed near the silicon substrate 5 to form a conductive Ti—Zr barrier film on the surface. When ammonia is supplied as a reaction gas, a conductive Ti—Zr—N barrier film is formed on the surface of the silicon substrate 5.

When the CVD raw material to be used is a metal organic compound, the containers 1a and 1b contain not only the metal organic compound but also a solvent and are made into a solution form. The decomposition of the compound at the time of forming the conductive barrier film by the CVD is performed by one or more of thermal decomposition, photolysis, plasma decomposition, and reactive decomposition. The decomposition of the compound at the time of forming the conductive barrier film is performed under a reducing atmosphere. For example, hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, hydrazine derivatives (eg, CH ₃ NHNH ₂ , (CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ , RNHNH ₂ (R is an alkyl group, etc.) Hydrazine derivatives), silanes, silane derivatives (eg, R _n SiY _4-n (R is a functional group such as an alkyl group, Y is a silane derivative such as H, F, Cl, Br or I)) , Borane, and borane derivatives (for example, R _n BY _{3 -n} (R is a functional group such as an alkyl group, Y is a borane derivative such as H, F, Cl, Br or I)) Alternatively, the compound is decomposed in an air stream containing two or more kinds. The conductive barrier film forming material simultaneously with the decomposition of a compound containing one or more selected from the group consisting of ammonia, hydrazine, hydrazine derivatives, and alkyl azides, or before and / or after the decomposition of the compound; Is decomposed. Further, a compound containing one or more selected from the group consisting of methylhydrazine, dimethylhydrazine, ethylhydrazine, diethylhydrazine, butylhydrazine, phenylhydrazine, ethyl azide, propyl azide, butyl azide, and phenyl azide The decomposition of the conductive barrier film-forming material is performed simultaneously with the decomposition of the compound or before and / or after the decomposition of the compound.

  The method of forming a wiring film according to the present invention includes a conductive barrier film forming step of forming a conductive barrier film by the conductive barrier film forming method, and a conductive barrier film formed by the conductive barrier film forming step. And a copper film forming step of forming a copper film. The ULSI according to the present invention is obtained by forming a copper wiring film on a conductive barrier film formed by the above-described method for forming a conductive barrier film.

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

[Example 1]
The apparatus of FIG. 1 was used. A mixed solution of TiCl ₄ and ZrCl ₄ (mixing molar ratio is TiCl ₄ : ZrCl ₄ = 1: 1) is placed in the container 1a. Nothing is put in the container 1b.
Then, TiCl ₄ and ZrCl ₄ were led to the vaporizer 2 by the pumping gas. Since the carburetor 2 is heated to 120 ° C., to be introduced into the decomposition reactor 4 together with a carrier gas (N ₂₎ and TiCl ₄ and ZrCl ₄ vaporized here. At this time, ammonia was introduced into the decomposition reaction furnace 4 as a reaction gas. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 500 ° C.

  After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was found to be a Ti-Zr-N film. The film thickness was 0.05 μm, and the film resistivity was 300 μΩcm. A copper thin film for wiring was formed on the conductive Ti-Zr-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.

  Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. In addition, the Ti-Zr-N film and the copper film were formed neatly in a place where the ratio of the opening to the depth of the hole was 1/6.

[Example 2]
The apparatus of FIG. 1 was used. A mixed solution of tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium (molar ratio: former: latter = 1: 1) is placed in the container 1a. Nothing is put in the container 1b.
Then, tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium were led to the vaporizer 2 by the pumping gas. Since the vaporizer 2 was heated to 100 ° C., the vaporized tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium were introduced into the decomposition reactor 4 together with the carrier gas (N ₂ ). At this time, hydrogen, ammonia, and monomethylhydrazine were introduced into the decomposition reactor 4 as reaction gases.

  A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 500 ° C. After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was found to be a Ti-Zr-N film. The film thickness was 0.05 μm, and the resistivity of the film was 400 μΩcm.

  A copper thin film for wiring was formed on the conductive Ti-Zr-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. In addition, the Ti-Zr-N film and the copper film were formed neatly in a place where the ratio of the opening to the depth of the hole was 1/6.

[Example 3]
The apparatus of FIG. 1 was used. A mixed solution of pentakisdimethylaminotantalum and hexadimethylaminoditungsten (the molar ratio of the former: the latter = 1: 1. Since both are solids, decane was used as a solvent; pentakisdimethylaminotantalum / decane = 0. 1 mol / l) is contained in the container 1a. Nothing is put in the container 1b.
Then, pentakisdimethylaminotantalum and hexadimethylaminoditungsten were led to the vaporizer 2 by the pumping gas. Since the vaporizer 2 was heated to 70 ° C., the pentakisdimethylamino tantalum and hexadimethylaminoditungsium vaporized here were introduced into the decomposition reaction furnace 4 together with the carrier gas (N ₂ ). At this time, hydrogen and ammonia were introduced into the decomposition reactor 4 as reaction gases.

  A silicon substrate 5 is placed in the decomposition reaction furnace 4 and is heated to 480 ° C. After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was a Ta-W-N film. The film thickness was 0.03 μm, and the resistivity of the film was 800 μΩcm.

  A copper thin film for wiring was formed on the conductive Ta-W-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. Also, the Ta-W-N film and the copper film were formed neatly in the place where the ratio of the opening to the depth of the hole was 1/6.

[Example 4]
The apparatus of FIG. 2 was used. First, tetrakisdimethylaminotitanium was placed in a container 1a, and helium was flowed as a carrier gas at a flow rate of 30 ml / min to evaporate. Note that the container 1a is heated to 40 ° C.
Further, tetrakisdiethylaminozirconium was placed in the container 1b, and helium was flowed as a carrier gas at a flow rate of 50 ml / min to evaporate. In addition, the container 1b is heated to 40 degreeC. The vaporized raw material was introduced into the decomposition reaction furnace 4 through each pipe. In addition, hydrogen and ammonia were introduced into the decomposition reactor 4 as reaction gases.

  A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 500 ° C. After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was found to be a Ti-Zr-N film. The film thickness was 0.05 μm, and the film resistivity was 300 μΩcm.

  A copper thin film for wiring was formed on the conductive Ti-Zr-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. In addition, the Ti-Zr-N film and the copper film were formed neatly in a place where the ratio of the opening to the depth of the hole was 1/6.

[Example 5]
The apparatus of FIG. 2 was used. First, a pentachlorotantalum diethylsulfide duct was placed in the container 1a, and helium was flowed as a carrier gas at a flow rate of 30 ml / min to evaporate. Note that the container 1a is heated to 90 ° C.
The vaporized pentachlorotantalum diethylsulfide duct was introduced into the decomposition reactor 4 via a pipe. At the same time, hydrogen, ammonia and hexafluorotungsten were introduced into the decomposition reactor 4. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 500 ° C.

  After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was a Ta-W-N film. The film thickness was 0.03 μm, and the resistivity of the film was 900 μΩcm. A copper thin film for wiring was formed on the conductive Ta-W-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.

  Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. Also, the Ta-W-N film and the copper film were formed neatly in the place where the ratio of the opening to the depth of the hole was 1/6.

[Example 6]
The apparatus of FIG. 2 was used. First, zirconium tetraboron hydride was placed in a container 1a, and helium was flowed as a carrier gas at a flow rate of 30 ml / min to vaporize. Note that the container 1a is heated to 40 ° C.
Also, a mixture of tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum was placed in a container 1b, and hydrogen was vaporized as a carrier gas at a flow rate of 70 ml / min. Note that the container 1b is heated to 60 ° C. The vaporized raw material was introduced into the decomposition reactor 4 via a pipe. Ammonia was introduced into the decomposition reactor 4 as a reaction gas.

  The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 550 ° C. After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was a Ta-Zr-N film. The film thickness was 0.05 μm, and the resistivity of the film was 700 μΩcm.

  A copper thin film for wiring was formed on the conductive Ta-Zr-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. In addition, the Ta-Zr-N film and the copper film were formed neatly in a place where the ratio between the opening of the hole and the depth was 1/6.

[Example 7]
The apparatus of FIG. 2 was used. First, tetrakisdiethylaminozirconium was put into the container 1a, and helium was flowed as a carrier gas at a flow rate of 50 ml / min to evaporate. Note that the container 1a is heated to 60 ° C.
Also, a mixture of tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum was placed in a container 1b, and hydrogen was vaporized as a carrier gas at a flow rate of 70 ml / min. Note that the container 1b is heated to 60 ° C. The vaporized raw material was introduced into the decomposition reactor 4 via a pipe. Ammonia was introduced into the decomposition reactor 4 as a reaction gas.

  The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 550 ° C. After the film was formed by CVD under the above conditions, the substrate was taken out and examined. As a result, the film was a Ta-Zr-N film. The film thickness was 0.05 μm, and the resistivity of the film was 800 μΩcm.

  A copper thin film for wiring was formed on the conductive Ta-Zr-N barrier film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent. In addition, the Ta-Zr-N film and the copper film were formed neatly in a place where the ratio between the opening of the hole and the depth was 1/6.

Example 8
The apparatus of FIG. 2 was used. First, a mixture of tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum was placed in a container 1a, and helium was flowed as a carrier gas at a flow rate of 70 ml / min to evaporate. Note that the container 1a is heated to 60 ° C. The vaporized tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum were introduced into the decomposition reactor 4 via a pipe. At this time, ammonia was introduced into the decomposition reaction furnace 4 as a reaction gas. The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 550 ° C.

  After film formation by CVD under the above conditions, film formation by CVD was subsequently performed under the following conditions. That is, tetrakisdimethylaminotitanium was placed in the container 1b, and hydrogen was vaporized as a carrier gas at a flow rate of 40 ml / min. In addition, the container 1b is heated to 40 degreeC. The vaporized tetrakisdimethylaminotitanium was introduced into the decomposition reactor 4 via a pipe. At this time, ammonia was introduced into the decomposition reaction furnace 4 as a reaction gas. The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 550 ° C.

  After the film formation by the two-step CVD was performed, the substrate was taken out and examined. As a result, a Ta-N film having a thickness of 0.04 μm was formed on the surface of the substrate, and a Ti film having a thickness of 0.01 μm was formed thereon. The -N film was laminated. A copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane on the stacked barrier film of the conductive Ta-N film and the Ti-N film.

  Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent.

[Example 9]
The apparatus of FIG. 1 was used. A mixed solution in which pentakisdimethylaminotantalum and hexadimethylaminoditungsten are dissolved in decane is placed in the container 1a. Then, pentakisdimethylamino tantalum and hexadimethylaminoditungsten were led to the vaporizer 2. Since the vaporizer 2 was heated to 70 ° C., the pentakisdimethylaminotantalum and hexadimethylaminoditungsium vaporized here were introduced into the decomposition reaction furnace 4 via piping. At this time, ammonia was introduced into the decomposition reaction furnace 4 as a reaction gas. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and is heated to 480 ° C. After film formation by CVD under the above conditions, film formation by CVD was subsequently performed under the following conditions.
That is, tetrakisdimethylaminotitanium was placed in the container 1 b, and hydrogen was flowed as a carrier gas at a flow rate of 40 ml / min and led to the vaporizer 2. Since the vaporizer 2 was heated to 40 ° C., the tetrakisdimethylaminotitanium vaporized here was introduced into the decomposition reactor 4 via a pipe. At this time, ammonia was introduced into the decomposition reaction furnace 4 as a reaction gas. The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 550 ° C.

  After the film formation by the two-stage CVD was performed, the substrate was taken out and examined. As a result, a Ta-W-N film having a thickness of 0.04 μm was formed on the surface of the substrate, and a thickness of 0.01 μm was formed thereon. A Ti-N film was laminated. A copper thin film for wiring was formed on the laminated barrier film of the conductive Ta-W-N film and the Ti-N film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.

  Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent.

[Example 10]
The apparatus of FIG. 1 was used. A mixed solution of tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium is placed in a container 1a. Then, tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium were led to the vaporizer 2. Since the vaporizer 2 was heated to 100 ° C., the vaporized tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium were introduced into the decomposition reactor 4 via piping. At this time, hydrogen and ammonia were simultaneously flowed. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 500 ° C.
After film formation by CVD under the above conditions, film formation by CVD was subsequently performed under the following conditions. That is, a mixed solution of pentakisdimethylamino tantalum and hexadimethylaminoditungsten dissolved in decane is placed in the container 1b. Then, pentakisdimethylamino tantalum and hexadimethylaminoditungsten were led to the vaporizer 2. Since the vaporizer 2 was heated to 70 ° C., the pentakisdimethylaminotantalum and hexadimethylaminoditungsium vaporized here were introduced into the decomposition reaction furnace 4 via piping. At this time, hydrogen and ammonia were simultaneously flowed. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and is heated to 480 ° C.
After film formation by CVD under the above conditions, film formation by CVD was subsequently performed under the following conditions. The container 1a was replaced with another container containing only tetrakisdimethylaminotitanium, and the tetrakisdimethylaminotitanium was led to the vaporizer 2. Since the vaporizer 2 was heated to 100 ° C., the tetrakisdimethylaminotitanium vaporized here was introduced into the decomposition reactor 4 via a pipe. At this time, hydrogen and ammonia were simultaneously flowed. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 500 ° C.

  After the film formation by the three-stage CVD was performed, the substrate was taken out and examined. As a result, a 0.01 μm thick Ti—Zr—N film was formed on the substrate surface, and a 0.02 μm thick film was formed thereon. And a Ti-N film having a thickness of 0.01 μm on the outermost surface. A copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane on the laminated barrier film of the conductive Ti—Zr—N film, Ta—W—N film, and Ti—N film.

  Thereafter, whether or not copper was diffused into the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused into the silicon substrate. Further, when an adhesion test of the copper thin film was performed by attaching and detaching the tape, no peeling of the copper thin film was observed, and the adhesion was excellent.

  It is particularly useful in the semiconductor field.

Schematic diagram of CVD equipment Schematic diagram of CVD equipment Katsumi Utaka

Claims (24)

A material for forming a conductive Ti-Zr-based barrier film by chemical vapor deposition,
A halogenated Ti-based compound,
A material for forming a conductive barrier film, comprising a halogenated Zr-based compound. A material for forming a conductive Ti-Zr-based barrier film by chemical vapor deposition,
A halogenated Ti-based compound,
A halogenated Zr-based compound,
A material for forming a conductive barrier film, wherein at least one of the halogenated Ti-based compound and the halogenated Zr-based compound is a liquid. A material for forming a conductive Ti-Zr-based barrier film by chemical vapor deposition,
TiCl ₄ ,
ZrCl ₄
And a conductive barrier film forming material. A material for forming a conductive Ti-Zr-based barrier film by chemical vapor deposition,
A metal organic compound having Ti,
A conductive barrier film forming material, comprising: a metal organic compound having Zr. A material for forming a conductive Ti-Zr-based barrier film by chemical vapor deposition,
A metal organic compound having Ti,
A metal organic compound having Zr,
And a solvent for dissolving the metal organic compound.   Metal organic compounds having Ti are tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetrakisdipropylaminotitanium, tetrakismethylethylaminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino] titanium, trisdimethylaminobis (trimethylsilyl) amino Titanium, biscyclopentadienyl bisdimethylaminotitanium, cyclopentadienylcyclooctatetraenyltitanium, biscyclopentadienyltitanium diazide, and one or more compounds selected from the group of derivatives of the above compounds The conductive barrier film forming material according to claim 4 or 5, wherein:   The metal organic compound having Zr is tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and the above The conductive barrier film forming material according to claim 4, wherein the material is one or two or more compounds selected from the group of compound derivatives.   The conductive barrier film forming material according to any one of claims 1 to 7, which is a material for forming a conductive barrier film provided as a base film of a copper film.   A method for forming a conductive barrier film, comprising forming a conductive barrier film by chemical vapor deposition using the conductive barrier film forming material according to any one of claims 1 to 8. A method for forming a Ti-Zr-based conductive barrier film by chemical vapor deposition,
Vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr;
Vaporizing a Zr-based compound having a vapor pressure of 0.00001 to 760 torr. A method for forming a Ta-Ti-based conductive barrier film by chemical vapor deposition,
Vaporizing a Ta-based compound having a vapor pressure of 0.00001 to 760 torr;
Vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr. A method for forming a Ta-Zr-based conductive barrier film by chemical vapor deposition,
Vaporizing a Ta-based compound having a vapor pressure of 0.00001 to 760 torr;
Vaporizing a Zr-based compound having a vapor pressure of 0.00001 to 760 torr. A method of forming a conductive barrier film by chemical vapor deposition,
Ti compound having a vapor pressure of 0.00001 to 760 torr, Zr compound having a vapor pressure of 0.00001 to 760 torr, Ta compound having a vapor pressure of 0.00001 to 760 torr, and vapor of 0.00001 to 2000 torr Vaporizing at least two compounds selected from W-based compounds having a pressure;
Vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr.   14. The method for forming a conductive barrier film according to claim 10, wherein a step of forming a film by vaporizing a plurality of compounds is performed simultaneously.   14. The conductive barrier film forming method according to claim 10, wherein the step of forming a film by vaporizing the compound is performed at different times.   The conductive compound according to any one of claims 10 to 15, wherein the decomposition of the compound at the time of forming the conductive barrier film is performed by any one or more of heat decomposition, photo decomposition, plasma decomposition, and reactive decomposition. Barrier film forming method.   The method for forming a conductive barrier film according to any one of claims 10 to 16, wherein the decomposition of the compound at the time of forming the conductive barrier film is performed in a reducing atmosphere.   A compound selected from the group consisting of hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, a hydrazine derivative, silane, a silane derivative, borane, and a borane derivative when the compound is decomposed during formation of the conductive barrier film. 18. The method for forming a conductive barrier film according to claim 10, wherein the method is performed in an atmosphere containing two or more kinds.   Ti-based compounds having a vapor pressure of 0.00001 to 760 torr are tetrafluorotitanium, tetrachlorotitanium, tetrabromotitanium, tetraioditanium, tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetrakisdipropylaminotitanium, tetrakismethylethyl Aminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino] titanium, trisdimethylaminobis (trimethylsilyl) aminotitanium, biscyclopentadienylbisdimethylaminotitanium, cyclopentadienylcyclooctatetraenyltitanium, biscyclopentadi The conductive material according to any one of claims 10 to 18, wherein the compound is one or more compounds selected from the group consisting of enyl titanium diazide and a derivative of the compound. Rear film forming method.   Zr-based compounds having a vapor pressure of 0.00001 to 760 torr are tetrafluorozirconium, tetrachlorozirconium, tetrabromozirconium, tetraiodzirconium, zirconiumtetraboron hydride, tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylamino Zirconium, tetrakismethylethylaminozirconium, biscyclopentadienyl bisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and one or more compounds selected from the group of derivatives of the above compounds The method for forming a conductive barrier film according to any one of claims 10 to 18, wherein:   Ta-based compounds having a vapor pressure of 0.00001 to 760 torr are pentafluorotantalum, pentachlorotantalum, pentabromotantalum, pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, 11. A compound selected from the group consisting of butyl imido tris diethyl amino tantalum, pentakis methyl ethyl amino tantalum, tetrakis methyl butyl amino tantalum, and one or more compounds selected from the group of derivatives of the compound. Item 18. The method for forming a conductive barrier film according to any one of Items 18.   W-type compounds having a vapor pressure of 0.00001 to 2000 torr are hexafluorotungsten, hexachlorotungsten, hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, butylimidobisbutylaminotungsten, bispropylcyclo 19. The method for forming a conductive barrier film according to claim 13, wherein the conductive barrier film is one or more compounds selected from the group consisting of pentadienyltungsten dihydride and a derivative of the compound. A conductive barrier film forming step of forming a conductive barrier film by the conductive barrier film forming method according to any one of claims 9 to 22,
A copper film forming step of forming a copper film on the conductive barrier film formed in the conductive barrier film forming step. 23. An ULSI comprising a copper wiring film formed on a conductive barrier film formed by the conductive barrier film forming method according to claim 9.

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