JP2011122244A - Conductive barrier film forming material, method for forming conductive barrier film, and method for forming wiring film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive barrier film forming material which can form a film even if conditions are required such as the ratio of the opening of a groove or a hole to the depth thereof (opening/depth) being 1/5 to 1/7 and even if the thickness is 10 nm or less, is excellent in preventing copper diffusion (barrier properties), has small electric resistance, and is excellent in adhesiveness with a copper film. <P>SOLUTION: The conductive barrier film forming material is a material for forming a conductive Ta-Zr-based barrier film as a substrate film of a copper film by chemical vapor deposition. The conductive barrier film forming material includes an organic metal compound having Ta and an organic metal compound having Zr. Alternatively, the conductive barrier film forming material further includes a solvent which dissolves one or both of the Ta-organic compound and the Zr-organic compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

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

  However, copper is heavily diffused into the silicon substrate. Therefore, it is difficult to obtain a wiring film as it is. Therefore, a conceivable means is to provide a diffusion prevention film (barrier film) on the substrate and form a copper film thereon. As a material of this barrier film, titanium nitride, tungsten nitride, tantalum nitride, tantalum, or the like has been expected as a candidate.

  By the way, the above materials are excellent in performance if only focusing on copper diffusion prevention, but the electrical resistance is relatively large, and it has been found that there is a problem in adhesion to the substrate and the copper film. I came.

  As a result of further research and development, the inventors have come to know that a Ti—Zr—N film, a W—Ta—N film and the like are likely to solve the above problems.

  By the way, the width | variety of the copper wiring film currently requested | required is 0.15 micrometer or less, and ratio (opening part / depth) of the opening part and depth of a groove | channel or a hole is 1/5-1/7. It is getting bigger. Therefore, the Ti—Zr—N film and the W—Ta—N film as the base film of the copper wiring film also have the above-described conditions for the ratio of the opening and depth of the groove or hole (opening / depth) as described above. Must satisfy. In addition, the requirement that the thickness as a base film is 10 nm or less is also required.

  An attempt has been made to form a Ti—Zr—N film, a W—Ta—N film, or the like that satisfies such conditions by physical vapor deposition (PVD) such as sputtering. However, it has been found that this method is very difficult and practical application is almost impossible.

  Accordingly, the first problem to be solved by the present invention is that even if the ratio of the opening to the depth of the groove or hole (opening / depth) is required to be 1/5 to 1/7. In addition, it is possible to form a film even if the thickness is 10 nm or less, and is excellent in copper diffusion prevention (barrier property), and has low electrical 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 when the ratio of the opening and depth of the groove or hole (opening / depth) is required to be 1/5 to 1/7, A conductive barrier film that can be formed even when the thickness is 10 nm or less, is excellent in preventing copper diffusion (barrier properties), has low electrical resistance, and has excellent adhesion to a copper film. It is to provide a forming method.

The first problem is
A material for forming a conductive Ta-Zr-based barrier film as a base film of a copper film by chemical vapor deposition,
Pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, ethylimidotrisdimethylaminotantalum, butyrimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutylaminotantalum A metal organic compound having one or more Ta selected from the group of derivatives of the compound;
From the group of tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and derivatives of said compounds It solves by the conductive barrier film forming material characterized by including the metal organic compound which has 1 type, or 2 or more types of Zr chosen.

The first problem is
A material for forming a conductive Ta-Zr-based barrier film as a base film of a copper film by chemical vapor deposition,
Pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, ethylimidotrisdimethylaminotantalum, butyrimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutylaminotantalum A metal organic compound having one or more Ta selected from the group of derivatives of the compound;
From the group of tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and derivatives of said compounds This is solved by a conductive barrier film forming material comprising a metal organic compound having one or two or more selected Zr and a solvent that dissolves one or both of the Ta organic compound and the Zr organic compound.

The second problem is
This is solved by a method for forming a conductive barrier film, wherein a conductive Ta—Zr-based barrier film is formed as a base film of a copper film by chemical vapor deposition using the conductive barrier film forming material.

  Preferably, the conductive barrier film forming method is characterized in that the step of forming a film by vaporizing and decomposing a Ta organic compound and a Zr organic compound is simultaneously performed to form a conductive barrier film. This is solved by the conductive barrier film forming method.

  Preferably, in the method for forming the conductive barrier film, the conductive barrier film is formed by performing the vapor deposition and decomposition of the Ta organic compound and the Zr organic compound in different steps. This is solved by the method for forming a conductive barrier film.

  Preferably, in the conductive barrier film forming method, the decomposition of the Ta organic compound and the Zr organic compound in forming the conductive barrier film is any one or more of thermal decomposition, photodecomposition, plasma decomposition, and reaction decomposition. This method is solved by the method for forming a conductive barrier film, which is characterized by the above.

  Preferably, the conductive barrier film forming method is characterized in that the Ta organic compound and the Zr organic compound are decomposed in a reducing atmosphere when forming the conductive barrier film. Solved.

  Preferably, in the method for forming a conductive barrier film, the decomposition of the Ta organic compound and the Zr organic compound in forming the conductive barrier film is hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, hydrazine. This is solved by a method for forming a conductive barrier film, which is performed in an atmosphere containing one or more selected from the group of derivatives, silanes, silane derivatives, borane, and borane derivatives.

A conductive barrier film forming step of forming a conductive barrier film by the conductive barrier film forming method;
The wiring film forming method includes a copper film forming step of forming a copper film on the conductive barrier film formed by the conductive barrier film forming step.

  Film formation is possible even if the ratio of the opening to the depth of the groove or hole (opening / depth) is required to be 1/5 to 1/7 or the thickness is 10 nm or less. It is possible to form a conductive barrier film that is excellent in copper diffusion prevention (barrier property), has low electrical resistance, and has excellent adhesion to the copper film.

Schematic diagram of CVD equipment Schematic diagram of CVD equipment

The conductive barrier film forming material is a material for forming a conductive Ti-Zr-based barrier film by CVD (a conductive Ti-Zr-based barrier film provided by CVD as a base film for a copper film, particularly a copper wiring film) And a material containing 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. At least one of the halogenated Ti-based compound and the halogenated Zr-based compound is liquid and is in the form of a solution. Examples of the halogenated Ti compound include TiF ₄ , TiCl ₄ , TiBr ₄ , TiI _{4 and the} like. Examples of the halogenated Zr-based compound include ZrF ₄ , ZrCl ₄ , ZrBr ₄ , ZrI _{4 and the} like. Among them, those TiCl ₄ and (liquid) in the form of a mixture comprising a ZrCl ₄ (solid) are preferred. The ratio (molar ratio) between the halogenated Ti compound and the halogenated Zr compound is as follows: Halogenated Ti compound: Halogenated Zr compound = 9: 1 to 1: 9 (especially 6: 4 to 4: 6). ). Here, when the ratio is less than 9: 1, the formed conductive Ti—Zr-based barrier film is not significantly different from the Ti-based barrier film in terms of performance, and is an alloy feature. In contrast, when the ratio exceeds 1: 9, the formed conductive Ti-Zr-based barrier film has a low copper diffusion preventing effect, and it is difficult to exhibit the characteristics as an alloy. Because it is.

  The conductive barrier film forming material is a material for forming a conductive Ti-Zr-based barrier film by CVD (a conductive Ti-Zr-based barrier film provided by CVD as a base film for a copper film, particularly a copper wiring film) And a metal organic compound having Ti and a metal organic compound having Zr. In particular, 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 no further addition is necessary, but both are solid. A solvent for dissolving the metal organic compound is further added to form a solution. Examples of the metal organic compound having Ti include 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 metal organic compounds having Zr include tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, In addition, derivatives of the above compounds can be used. Above all, the form (solution form) of a mixture containing tetrakisdimethylaminotitanium (liquid) and tetrakisdimethylaminozirconium (solid), the form of a mixture containing tetrakisdiethylaminotitanium (liquid) and tetrakisdimethylaminozirconium (solid) (Solution form), tetrakismethylethylaminotitanium (liquid) and tetrakismethylethylaminozirconium (liquid) mixture form (solution form), tetrakisdiethylaminotitanium (liquid) and tetrakisdiethylaminozirconium (liquid) In the form of a mixture (solution form) containing The ratio (molar ratio) between 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 (in particular, 6: 4 ~ 4: 6). Here, when the ratio is less than 9: 1, the formed conductive Ti—Zr-based barrier film is not significantly different from the Ti-based barrier film in terms of performance, and is an alloy feature. In contrast, when the ratio exceeds 1: 9, the formed conductive Ti-Zr-based barrier film has a low copper diffusion preventing effect, and it is difficult to 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 these, nonane, decane, undecane, dodecane, tridecane, and tetradecane are preferable. In addition, a solvent is used so that the density | concentration of a metal organic compound may be about 0.001-1 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 for a copper film, particularly a copper wiring film) And a metal organic compound having Ta and a metal organic compound having W. In particular, in the form of a mixture. If one or both of the metal organic compound with Ta and the metal organic compound with W are liquid, the mixture will be in the form of a solution, so no further addition is required, but both are solid. A solvent for dissolving the metal organic compound is further added to form a solution. Examples of the metal organic compounds having Ta include pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, butyrimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutyl Amino tantalum and derivatives of the above compounds can be used. Examples of metal organic compounds having W include hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, butyrimidobisbutylaminotungsten, bispropylcyclopentadienyltungsten dihydride, and derivatives of the above compounds Can be used. Among them, 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), in the form of a mixture (solution form) containing tetrakisdiethylaminotantalum (liquid) and bispropylcyclopentadienyl tungsten dihydride (liquid), pentakismethylethylamino tantalum ( Liquid) and hexamethylethylaminoditungsten (solid) in the form of a mixture (solution form) are preferred. The ratio (molar ratio) between the metal organic compound having Ta and the metal organic compound having W is: metal organic compound having Ta: metal organic compound having W = 8: 2 to 2: 8, especially 6: 4 to 4: 6. Here, when the ratio is set to less than 8: 2, the formed conductive Ta—W-based barrier film is not significantly different from the Ta-based barrier film in terms of performance, and is an alloy feature. In contrast, when the ratio exceeds 2: 8, the formed conductive Ta-W barrier film is not significantly different from the W barrier film in terms of performance. This 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 these, nonane, decane, undecane, dodecane, tridecane, and tetradecane are preferable. In addition, a solvent is used so that the density | concentration of a metal organic compound may be about 0.001-1 mol / l.

  A method for forming a conductive barrier film is a method in which a conductive barrier film is formed by CVD using the above-described conductive barrier film forming material (a conductive barrier film is formed by CVD as a base film of a copper film, particularly a copper wiring film). It is. The conductive barrier film thus formed has a thickness of 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, it is difficult to achieve the copper diffusion preventing effect, and conversely, when the thickness exceeds 500 nm, the majority of the copper wiring portion It will occupy the area.

  A method for forming a conductive barrier film (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. A step of vaporizing a Ti-based compound having a vapor pressure of 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) of 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 as described above, when the ratio is less than 9: 1, the formed conductive Ti—Zr-based barrier film is not significantly different from the Ti-based barrier film in terms of performance. On the contrary, when the ratio exceeds 1: 9, the formed conductive Ti-Zr-based barrier film has a low copper diffusion prevention effect, and it is difficult to exhibit the characteristics as an alloy. Because it is a thing. The thickness of the Ti—Zr-based conductive barrier film to be 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, it is difficult to achieve the copper diffusion preventing effect, and conversely, when the thickness exceeds 500 nm, the majority of the copper wiring portion It will occupy the area.

  A conductive barrier film forming method (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. A step of vaporizing a Ta-based compound having a vapor pressure of 00001 to 760 torr, and a step of vaporizing a W-based compound having a vapor pressure of from 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, when the ratio is set to less than 8: 2, the formed conductive Ta—W-based barrier film is not significantly different from the Ta-based barrier film in terms of performance, and is an alloy feature. In contrast, when the ratio exceeds 2: 8, the formed conductive Ta-W barrier film is not significantly different from the W barrier film in terms of performance. This 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, it is difficult to achieve the copper diffusion preventing effect, and conversely, when the thickness exceeds 500 nm, the majority of the copper wiring portion It will occupy the area.

  The method for forming a conductive barrier film (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—Ti based conductive barrier film by CVD. A step of vaporizing a Ta compound having a vapor pressure of 00001 to 760 torr, and a step of vaporizing a Ti 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 less than 9: 1, the formed conductive Ta—Ti barrier film is not significantly different from the Ta barrier film in terms of performance, and is an alloy feature. On the contrary, when the ratio exceeds 1: 9, the formed conductive Ta-Ti barrier film is not significantly different from the Ti barrier film in terms of performance, and has the characteristics as an alloy. This 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, it is difficult to achieve the copper diffusion preventing effect, and conversely, when the thickness exceeds 500 nm, the majority of the copper wiring portion It will occupy the area.

  A conductive barrier film forming method (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—Zr-based conductive barrier film by CVD. A step of vaporizing a Ta compound having a vapor pressure of 00001 to 760 torr, and a step of vaporizing a Zr compound having a vapor pressure of from 0.00001 to 760 torr. Here, the ratio (molar ratio) of 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, when the ratio is less than 9: 1, the formed conductive Ta—Zr-based barrier film is not significantly different from the Ta-based barrier film in terms of performance, and is an alloy feature. On the other hand, when the ratio exceeds 1: 9, the formed conductive Ta—Zr-based barrier film is not significantly different from the Zr-based barrier film in terms of performance, and has the characteristics as an alloy. This is because it is difficult to demonstrate. The thickness of the Ta—Zr-based conductive barrier film to be 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, it is difficult to achieve the copper diffusion preventing effect, and conversely, when the thickness exceeds 500 nm, the majority of the copper wiring portion It will occupy the area.

  A conductive barrier film forming method (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 conductive barrier film by CVD, and a vapor of 0.00001 to 760 torr. Of a Ti compound having a pressure, 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 a W compound having a vapor pressure of 0.00001 to 2000 torr. A step of vaporizing at least two compounds selected from the above, and a step of vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr. Here, the ratio (molar ratio) between components (Zr, Ta, W) other than Ti and Ti in the conductive barrier film is such that components other than Ti (Zr, Ta, W): Ti = 99: 1 to 1: 99, in particular 9: 1 to 1: 9. Here, if the ratio is less than 99: 1, the formed conductive barrier film has difficulty in controlling the film thickness of the final adhesion Ti film, and has the advantage of improving 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 characteristics of improving the barrier property. The formed conductive barrier film has a thickness of 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, it is difficult to achieve the copper diffusion preventing effect, and conversely, when the thickness exceeds 500 nm, the majority of the copper wiring portion It will occupy the area. The step of forming a film by vaporizing the plurality of compounds is performed simultaneously or at different times (in order, repeatedly in order, or alternately). When performed at the same time, the formed conductive barrier film becomes a composite film in which a plurality of layers are mixed in one layer. When the CVD is performed in a nitriding atmosphere (for example, an atmosphere such as ammonia), the Ti—Zr-based conductive barrier film is a Ti—Zr—N-based conductive barrier film, and the Ta—W-based conductive barrier film is used. 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 the Ta—Zr based conductive barrier. The film is a Ta—Zr—N based conductive barrier film. If the film formation is repeated in order, for example, only one type exists in one layer, but a composite film of a stacked type is obtained. For example, a composite film formed by stacking a Ti—N film and a Zr—N film, a composite film formed by stacking a Ta—N film and a W—N film, a Ta—N film and a Ti—N film, Or a composite film formed by stacking a Ta—N film and a Zr—N film, or a composite film formed by stacking a Ta—N film, a W—N film, and a Ti—N film. Or a composite film formed by stacking a Zr-N film, a W-N film, and a Ti-N film, or a composite film formed by stacking a Zr-N film, a Ta-N film, and a Ti-N film, It may be a composite film formed by stacking a Zr—N film, a Ta—N film, a W—N film, and a Ti—N film.

  Examples of the Ti compound having a vapor pressure of 0.00001 to 760 torr include, for example, 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. In addition, when these Ti compounds are metal organic compounds, they are used in a form dissolved in a solvent.

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

  Examples of Ta compounds having a vapor pressure of 0.00001 to 760 torr include pentafluorotantalum, pentachlorotantalum, pentabromotantalum, pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, and ethylimidotrisdiethylamino. Tantalum, butylimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutylaminotantalum, and derivatives of the above compounds can be used. When these Ta compounds are metal organic compounds, they are used in a form dissolved in a solvent.

  Examples of W compounds having a vapor pressure of 0.00001 to 2000 torr include hexafluorotungsten, hexachlorotungsten, hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, butyrimide bisbutylaminotungsten, bis Propylcyclopentadienyl tungsten dihydride and derivatives of the above compounds can be used. In addition, when these W type compounds are metal organic compounds, they are used in a form dissolved in a solvent.

  By using an apparatus as shown in FIGS. 1 and 2, a conductive barrier film is formed on the substrate. 1 and 2, 1 a and 1 b are containers in which a conductive barrier film forming material is placed, 2 is a vaporizer, 3 is a heater, 4 is a decomposition reactor, 5 is a silicon substrate, 6 is hydrogen, hydrogen plasma, A reactive 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, the mixed solution of TiCl ₄ and ZrCl ₄ is put in the container 1a and is sent to the vaporizer 2 by the pressurized gas. A carrier gas is sent to the vaporizer 2. The vaporized raw material is introduced into the decomposition reaction furnace 4 through a pipe. Further, a reaction gas is also introduced into the decomposition reaction furnace 4 as necessary. A silicon substrate 5 on which film formation is performed is placed in the reaction furnace 4, and the silicon substrate 5 is heated by the heating means 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 in the form of a solution. The decomposition of the compound during the formation of the conductive barrier film by the CVD is performed by any one or more of thermal decomposition, photodecomposition, plasma decomposition, and reaction decomposition. The decomposition of the compound in forming the conductive barrier film is performed in a reducing atmosphere. For example, hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, hydrazine derivatives (for example, CH ₃ NHNH ₂ , (CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ , RNHNH ₂ (R is an alkyl group, etc.) Hydrazine derivatives) such as 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)) Or decomposition | disassembly of a compound is performed under the airflow containing 2 or more types. 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 disassembled. A compound containing one or more selected from the group consisting of methyl hydrazine, dimethyl hydrazine, ethyl hydrazine, diethyl hydrazine, butyl hydrazine, phenyl hydrazine, ethyl azide, propyl azide, butyl azide and phenyl azide The conductive barrier film-forming material is decomposed simultaneously with the decomposition of the compound or before and / or after the decomposition of the compound.

  The wiring film forming method includes a conductive barrier film forming step of forming a conductive barrier film by the conductive barrier film forming method, and a copper film formed on the conductive barrier film formed by the conductive barrier film forming step. A copper film forming step to be formed. The ULSI according to the present invention is formed by forming a copper wiring film on the conductive barrier film formed by the conductive barrier film forming method.

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. This is solved by the conductive barrier film forming material. In particular, it is a material for forming a conductive Ti—Zr-based barrier film by CVD, and includes a halogenated Ti-based compound and a halogenated Zr-based compound, and the halogenated Ti-based compound and the halogenated Zr-based compound This is solved by a conductive barrier film forming material characterized in that at least one of them is a liquid. Furthermore, it is a material for forming a conductive Ti—Zr-based barrier film by CVD, which is solved by a conductive barrier film forming material comprising TiCl ₄ and ZrCl ₄ . Also, a conductive barrier film forming material characterized in that it is a material for forming a conductive Ti-Zr-based barrier film by CVD, comprising a metal organic compound having Ti and a metal organic compound having Zr. Solved. 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 for dissolving the metal organic compound. This is solved by the conductive barrier film forming material.

  The conductive barrier film forming material is a material for forming a conductive barrier film provided as a base film of a copper (including copper alloy) film (in particular, a copper (including copper alloy) wiring film). That is, when a copper film is formed, it is a material for forming a barrier film provided to prevent copper from diffusing and penetrating into the substrate side. The barrier film formed from this material has high conductivity. It is shown.

  Examples of the metal organic compound having Ti in the conductive barrier film forming material include tetrakisdimethylaminotitanium, tetrakisdiethylaminotitanium, tetrakisdipropylaminotitanium, tetrakismethylethylaminotitanium, bisdimethylaminobis [bis (trimethylsilyl) amino]. Preferred are titanium, trisdimethylaminobis (trimethylsilyl) aminotitanium, biscyclopentadienylbisdimethylaminotitanium, cyclopentadienylcyclooctatetraenyltitanium, biscyclopentadienyltitanium diazide, and derivatives of the above compounds. Can be mentioned. Accordingly, 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 tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, bis Preferred examples include cyclopentadienylbisdiethylaminozirconium and derivatives of the above compounds. Accordingly, one or more compounds selected from these groups can be used.

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

By the way, when one (ZrCl ₄ ) is solid and the other (TiCl ₄ ) is liquid like a combination of TiCl ₄ and ZrCl ₄ , 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, the solvent used should just be what can melt | dissolve any compound. In addition, as the solvent when the metal organic compound having Ti and the metal organic compound having Zr are used, for example, dimethylethylamine, diethylmethylamine, triethylamine, tripropylamine, toluene, xylene, heptane, octane, nonane, Preferred are decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and the like. Examples of the solvent when a metal organic compound having Ta and a metal organic compound having W are used include 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, wherein the conductive barrier film is formed by CVD using the conductive barrier film forming material. 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, there is a method of forming a Ti-Zr-based conductive barrier film by CVD, a step 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 forming a Zr-based compound having a gas phase into a vapor phase.

  Also, a method of forming a Ta—Ti conductive barrier film by CVD, which comprises vaporizing a Ta 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 forming a Ti-based compound having a gas phase into a vapor phase.

  Also, a method of forming a Ta—Zr-based conductive barrier film by CVD, wherein a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized, and a vapor pressure of 0.00001 to 760 torr. And a step of forming a Zr-based compound having a gas phase into a vapor phase.

  Also, a method of forming a conductive barrier film by CVD, which is 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. A step of vaporizing at least two compounds selected from Ta-based compounds having a vapor pressure and W-based compounds having a vapor pressure of 0.00001 to 2000 torr; and Ti having a vapor pressure of 0.00001 to 760 torr And a process for forming a gas-based compound into a gas phase.

  The step of forming a film by vaporizing the plurality of compounds may be performed simultaneously or at different times (in order, repeatedly in order, or alternately). When performed at the same time, the formed conductive barrier film becomes a composite film in which a plurality of layers are mixed in one layer. When the CVD is performed in a nitriding atmosphere (for example, an atmosphere such as ammonia), the Ti—Zr-based conductive barrier film is a Ti—Zr—N-based conductive barrier film, and the Ta—W-based conductive barrier film is used. 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 the Ta—Zr based conductive barrier. The film is a Ta—Zr—N based conductive barrier film. When film formation is performed sequentially, there is only one kind in one layer (however, since the thickness of the layer is thin, it is mixed in one layer even if film formation is performed in order) It can also be said that this is a laminated type composite film. For example, a composite film formed by stacking a Ti—N film and a Zr—N film, a composite film formed by stacking a Ta—N film and a W—N film, a Ta—N film and a Ti—N film, Or a composite film formed by stacking a Ta—N film and a Zr—N film, or a composite film formed by stacking a Ta—N film, a W—N film, and a Ti—N film. Or a composite film formed by stacking a Zr-N film, a W-N film, and a Ti-N film, or a composite film formed by stacking a Zr-N film, a Ta-N film, and a Ti-N film, It may be a composite film formed by stacking a Zr—N film, a Ta—N film, a W—N film, and a Ti—N film.

  In the case of a laminated type 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. It is preferable to form a Ti-based film by vaporizing. Further, a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ta-based film, and then a W-based compound having a vapor pressure of 0.00001 to 2000 torr is vaporized to form a W-based film. It is preferable to form a film. Further, a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ta-based film, and then 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. Further, a Ta-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Ta-based film, and then a Zr-based compound having a vapor pressure of 0.00001 to 760 torr is vaporized to form a Zr-based film. It is preferable to form a film. Further, 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 forming a film by vaporizing at least two compounds selected from W-based compounds having a vapor pressure of 0.1 to 760 torr, a Ti-based film is formed by vaporizing a Ti-based compound having a vapor pressure of 0.00001 to 760 torr. It is preferable to form a film. This is because in the case of a laminated type composite film, the Ti-based film in the upper layer (especially, the uppermost layer) has better adhesion to the copper film provided thereon, and the copper film is difficult to peel off. .

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

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

  Examples of the Ta compound having a vapor pressure of 0.00001 to 760 torr in the conductive barrier film forming method include pentafluorotantalum, pentachlorotantalum, pentabromotantalum, pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, Preferred examples include tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, butylimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutylaminotantalum, and derivatives of the above compounds. Accordingly, 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 conductive barrier film forming method include hexafluorotungsten, hexachlorotungsten, hexadimethylaminoditungsten, hexamethylethylaminoditungsten, hexadiethylaminoditungsten, Preferred are butyrimidobisbutylaminotungsten, bispropylcyclopentadienyltungsten dihydride, and derivatives of the above compounds. Accordingly, one or more compounds selected from these groups can be used.

The decomposition of the compound during the formation of the conductive barrier film (CVD) is performed by any one or more of thermal decomposition, photodecomposition, plasma decomposition, and reaction decomposition. Any means may be used for the decomposition. The decomposition of the compound during the formation of the conductive barrier film is preferably performed in a reducing atmosphere. Alternatively, hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, hydrazine derivatives (for example, CH ₃ NHNH ₂ , (CH ₃ ) ₂ NNH ₂ , CH ₃ NHNHCH ₃ , RNHNH ₂ (R is an alkyl group, etc.) Hydrazine derivatives) such as 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 Y _3-n (where R is a functional group such as an alkyl group, Y is a borane derivative such as H, F, Cl, Br, or I)) Or it is preferable that decomposition | disassembly of a compound is performed under the airflow (atmosphere) containing 2 or more types. In addition, the conductive barrier film is formed 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. It is also a preferred method to decompose the forming material. A compound containing one or more selected from the group consisting of methyl hydrazine, dimethyl hydrazine, ethyl hydrazine, diethyl hydrazine, butyl hydrazine, phenyl hydrazine, ethyl azide, propyl azide, butyl azide and phenyl azide It is preferable to decompose the conductive barrier film-forming material simultaneously with the decomposition of the compound or before and / or after the decomposition of the compound.

  A conductive barrier film forming step of forming a conductive barrier film by the conductive barrier film forming method, and a copper film forming step of forming a copper film on the conductive barrier film formed by the conductive barrier film forming step It solves by the wiring film formation method characterized by comprising.

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

  The present invention is particularly useful in the semiconductor field.

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

[Reference 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 put 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 pressure gas. Since the vaporizer 2 was heated to 120 ° C., the TiCl ₄ and ZrCl ₄ vaporized here were introduced into the decomposition reaction furnace 4 together with the carrier gas (N ₂ ). At this time, 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 500 ° C.
After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ti—Zr—N film. The film thickness was 0.05 μm, and the film resistivity was 300 μΩcm. On this conductive Ti—Zr—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.
Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. In addition, the Ti—Zr—N film and the copper film were neatly formed at a place where the ratio of the opening to the depth of the hole was 1/6.

[Reference Example 2]
The apparatus of FIG. 1 was used. A mixed solution of tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium (mixing molar ratio is the former: latter = 1: 1) is put in the container 1a. Nothing is put in the container 1b.
Then, tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium were introduced into the vaporizer 2 by the pressure gas. Since the vaporizer 2 was heated to 100 ° C., the tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium vaporized here were introduced into the decomposition reaction furnace 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.
The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 500 ° C. After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ti—Zr—N film. The film thickness was 0.05 μm, and the film resistivity was 400 μΩcm.
On this conductive Ti—Zr—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. In addition, the Ti—Zr—N film and the copper film were neatly formed at a place where the ratio of the opening to the depth of the hole was 1/6.

[Reference Example 3]
The apparatus of FIG. 1 was used. Mixed solution of pentakisdimethylaminotantalum and hexadimethylaminoditungsten (mixing molar ratio is former: latter = 1: 1. Since both are solid, decane was used as a solvent. Pentakisdimethylaminotantalum / decane = 0. 1 mol / l) is put in the container 1a. Nothing is put in the container 1b.
Then, pentakisdimethylaminotantalum and hexadimethylaminoditungsten were introduced into the vaporizer 2 by the pressure gas. Since the vaporizer 2 is heated to 70 ° C., the pentakisdimethylaminotantalum and hexadimethylaminoditungsten vaporized here are introduced into the decomposition reactor 4 together with the carrier gas (N 2). At this time, hydrogen and ammonia as reaction gases were introduced into the decomposition reaction furnace 4.
A silicon substrate 5 is placed in the decomposition reaction furnace 4 and heated to 480 ° C. After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ta-W-N film. The film thickness was 0.03 μm, and the film resistivity was 800 μΩcm.
On this conductive Ta—W—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. Also, the Ta—W—N film and the copper film were neatly formed at a place where the ratio of the opening to the depth of the hole was 1/6.

[Reference Example 4]
The apparatus of FIG. 2 was used. First, tetrakisdimethylaminotitanium was put in the container 1a, and helium was flowed at a rate of 30 ml / min as a carrier gas to vaporize it. The container 1a is heated to 40 ° C.
Further, tetrakisdiethylaminozirconium was put in the container 1b, and helium was flowed at a rate of 50 ml / min as a carrier gas to be vaporized. The container 1b is heated to 40 ° C. The vaporized raw material was introduced into the decomposition reactor 4 through each pipe. In addition, hydrogen and ammonia as reaction gases were introduced into the decomposition reaction furnace 4.
The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 500 ° C. After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ti—Zr—N film. The film thickness was 0.05 μm, and the film resistivity was 300 μΩcm.
On this conductive Ti—Zr—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. In addition, the Ti—Zr—N film and the copper film were neatly formed at a place where the ratio of the opening to the depth of the hole was 1/6.

[Reference Example 5]
The apparatus of FIG. 2 was used. First, pentachloro tantalum diethyl sulfide adduct was put into the container 1a, and helium was flowed at a rate of 30 ml / min as a carrier gas to be vaporized. The container 1a is heated to 90 ° C.
The vaporized pentachlorotantalum diethyl sulfide adduct was introduced into the cracking reactor 4 via a pipe. At the same time, hydrogen, ammonia and hexafluorotungsten were introduced into the decomposition reactor 4. The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 500 ° C.
After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ta-W-N film. The film thickness was 0.03 μm, and the film resistivity was 900 μΩcm. On this conductive Ta—W—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.
Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. Also, the Ta—W—N film and the copper film were neatly formed at a place where the ratio of the opening to the depth of the hole was 1/6.

[Reference Example 6]
The apparatus of FIG. 2 was used. First, a mixture of tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum was placed in the container 1a, and helium was allowed to flow as a carrier gas at a flow rate of 70 ml / min for vaporization. The container 1a is heated to 60 ° C. Vaporized tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum were introduced into the decomposition reactor 4 via piping. At this time, ammonia was introduced into the decomposition reactor 4 as a reaction gas. A silicon substrate 5 is placed in the decomposition reactor 4 and 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 flowed as a carrier gas at a flow rate of 40 ml / min for vaporization. The container 1b is heated to 40 ° C. The vaporized tetrakisdimethylaminotitanium was introduced into the decomposition reactor 4 via a pipe. At this time, ammonia was introduced into the decomposition reactor 4 as a reaction gas. A silicon substrate 5 is placed in the decomposition reactor 4 and 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 0.04 μm thick Ta—N film was formed on the substrate surface, and a 0.01 μm thick Ti film was formed thereon. The -N film was laminated. A copper thin film for wiring was formed on the laminated barrier film of the conductive Ta—N film and the Ti—N film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.
Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent.

[Reference Example 7]
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, pentakisdimethylaminotantalum and hexadimethylaminoditungsten were introduced into the vaporizer 2. Since the vaporizer 2 was heated to 70 ° C., the pentakisdimethylaminotantalum and hexadimethylaminoditungsten vaporized here were introduced into the decomposition reaction furnace 4 through a pipe. At this time, ammonia was introduced into the decomposition reactor 4 as a reaction gas. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and 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 put 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 reaction furnace 4 through a pipe. At this time, ammonia was introduced into the decomposition reactor 4 as a reaction gas. A silicon substrate 5 is placed in the decomposition reactor 4 and heated to 550 ° C.
After the two-stage CVD film formation, the substrate was taken out and examined. A 0.04 μm thick Ta—W—N film was formed on the substrate surface, and a 0.01 μm thick film was formed thereon. The Ti—N film was laminated. A copper thin film for wiring was formed on the laminated barrier film of this conductive Ta—W—N film and Ti—N film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.
Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent.

[Example 1]
The apparatus of FIG. 2 was used. First, zirconium tetraboron hydride was put into the container 1a, and helium was flowed at a rate of 30 ml / min as a carrier gas to be vaporized. The container 1a is heated to 40 ° C.
Further, a mixture of tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum was placed in the container 1b, and hydrogen was flowed as a carrier gas at a flow rate of 70 ml / min to vaporize. The container 1b is heated to 60 ° C. The vaporized raw material was introduced into the decomposition reactor 4 through a pipe. Ammonia was introduced into the decomposition reactor 4 as a reaction gas.
A silicon substrate 5 is placed in the decomposition reactor 4 and heated to 550 ° C. After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ta—Zr—N film. The film thickness was 0.05 μm, and the film resistivity was 700 μΩcm.
On this conductive Ta—Zr—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. Also, the Ta—Zr—N film and the copper film were neatly formed at a place where the ratio between the opening and the depth of the hole was 1/6.

[Example 2]
The apparatus of FIG. 2 was used. First, tetrakisdiethylaminozirconium was put into the container 1a, and helium was flowed at a rate of 50 ml / min as a carrier gas to be vaporized. The container 1a is heated to 60 ° C.
Further, a mixture of tetrakisdiethylaminotantalum and ethylimidotrisdimethylaminotantalum was placed in the container 1b, and hydrogen was flowed as a carrier gas at a flow rate of 70 ml / min to vaporize. The container 1b is heated to 60 ° C. The vaporized raw material was introduced into the decomposition reactor 4 through a pipe. Ammonia was introduced into the decomposition reactor 4 as a reaction gas.
A silicon substrate 5 is placed in the decomposition reactor 4 and heated to 550 ° C. After film formation by CVD under the above conditions, when the substrate was taken out and examined, the film was a Ta—Zr—N film. The film thickness was 0.05 μm, and the film resistivity was 800 μΩcm.
On this conductive Ta—Zr—N barrier film, a copper thin film for wiring was formed by CVD using hexafluoroacetylacetone copper trimethylvinylsilane. Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent. Also, the Ta—Zr—N film and the copper film were neatly formed at a place where the ratio between the opening and the depth of the hole was 1/6.

[Example 3]
The apparatus of FIG. 1 was used. A mixed solution of tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium is placed in the container 1a. Then, tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium were introduced into the vaporizer 2. Since the vaporizer 2 was heated to 100 ° C., the tetrakisdimethylaminotitanium and tetrakisdimethylaminozirconium vaporized here were introduced into the decomposition reaction furnace 4 through a pipe. At the same time, hydrogen and ammonia were allowed to flow simultaneously. The decomposition reaction furnace 4 contains a silicon substrate 5 and is 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 in which pentakisdimethylaminotantalum and hexadimethylaminoditungsten are dissolved in decane is placed in the container 1b. Then, pentakisdimethylaminotantalum and hexadimethylaminoditungsten were introduced into the vaporizer 2. Since the vaporizer 2 was heated to 70 ° C., the pentakisdimethylaminotantalum and hexadimethylaminoditungsten vaporized here were introduced into the decomposition reaction furnace 4 through a pipe. At the same time, hydrogen and ammonia were allowed to flow simultaneously. A silicon substrate 5 is placed in the decomposition reaction furnace 4 and 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 1 a was replaced with another container containing only tetrakisdimethylaminotitanium, and the tetrakisdimethylaminotitanium was introduced into the vaporizer 2. Since the vaporizer 2 was heated to 100 ° C., the tetrakisdimethylaminotitanium vaporized here was introduced into the decomposition reaction furnace 4 through a pipe. At the same time, hydrogen and ammonia were allowed to flow simultaneously. The decomposition reaction furnace 4 contains a silicon substrate 5 and is heated to 500 ° C.
After the film formation by the above three-stage CVD, the substrate was taken out and examined. As a result, a Ti-Zr-N film having a thickness of 0.01 μm was formed on the surface of the substrate, and a thickness of 0.02 μm was formed thereon. The Ta—W—N film and a Ti—N film having a thickness of 0.01 μm were laminated on the outermost surface. A copper thin film for wiring was formed on the laminated barrier film of the conductive Ti—Zr—N film, Ta—W—N film, and Ti—N film by CVD using hexafluoroacetylacetone copper trimethylvinylsilane.
Thereafter, whether or not copper was diffused in the silicon substrate was examined by SIMS analysis, and it was confirmed that copper was not diffused in the silicon substrate. Moreover, when the adhesion test of the copper thin film was attempted by sticking and peeling of the tape, peeling of the copper thin film was not observed, and the adhesion was excellent.

1a, 1b Container 2 Vaporizer 4 Decomposition reactor 5 Silicon substrate

Claims (9)

A material for forming a conductive Ta-Zr-based barrier film as a base film of a copper film by chemical vapor deposition,
Pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, ethylimidotrisdimethylaminotantalum, butyrimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutylaminotantalum A metal organic compound having one or more Ta selected from the group of derivatives of the compound;
From the group of tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and derivatives of said compounds A conductive barrier film-forming material comprising a metal organic compound having one or two or more selected Zr. A material for forming a conductive Ta-Zr-based barrier film as a base film of a copper film by chemical vapor deposition,
Pentachlorotantalum diethylsulfide adduct, pentakisdimethylaminotantalum, tetrakisdiethylaminotantalum, ethylimidotrisdiethylaminotantalum, ethylimidotrisdimethylaminotantalum, butyrimidotrisdiethylaminotantalum, pentakismethylethylaminotantalum, tetrakismethylbutylaminotantalum A metal organic compound having one or more Ta selected from the group of derivatives of the compound;
From the group of tetrakisdimethylaminozirconium, tetrakisdiethylaminozirconium, tetrakisdipropylaminozirconium, tetrakismethylethylaminozirconium, biscyclopentadienylbisdimethylaminozirconium, biscyclopentadienylbisdiethylaminozirconium, and derivatives of said compounds A metal organic compound having one or two or more selected Zr;
A conductive barrier film-forming material comprising a solvent that dissolves one or both of the Ta organic compound and the Zr organic compound.   A method for forming a conductive Ta-Zr-based barrier film as a base film for a copper film by chemical vapor deposition using the conductive barrier film-forming material according to claim 1 or 2. .   4. The method of forming a conductive barrier film according to claim 3, wherein the Ta barrier compound and the Zr organic compound are vaporized and decomposed to form a conductive barrier film simultaneously.   4. The method of forming a conductive barrier film according to claim 3, wherein the conductive barrier film is formed when the steps of depositing and vaporizing the Ta organic compound and the Zr organic compound are different.   The decomposition of the Ta organic compound and the Zr organic compound during the formation of the conductive barrier film is performed by any one or more of thermal decomposition, photodecomposition, plasma decomposition, and reaction decomposition. 5. Any one of the conductive barrier film forming methods.   The method for forming a conductive barrier film according to any one of claims 3 to 6, wherein the Ta organic compound and the Zr organic compound are decomposed in a reducing atmosphere when forming the conductive barrier film.   Group of hydrogen, hydrogen plasma, nitrogen, nitrogen plasma, ammonia, ammonia plasma, hydrazine, hydrazine derivative, silane, silane derivative, borane, and borane derivative when decomposition of Ta organic compound and Zr organic compound in formation of conductive barrier film The method for forming a conductive barrier film according to any one of claims 3 to 7, wherein the method is performed in an atmosphere containing one or more selected from the group consisting of: 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 3 to 8,
A wiring film forming method comprising: a copper film forming step of forming a copper film on the conductive barrier film formed by the conductive barrier film forming step.