JP3665031B2 - Barrier metal film manufacturing apparatus and barrier metal film manufacturing method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus and a method for producing a barrier metal film formed on a surface of a substrate in order to eliminate metal diffusion with respect to the substrate and maintain metal adhesion when the metal film is formed on the surface of the substrate. About.
[0002]
[Prior art]
In semiconductors to which electrical wiring is applied, copper has been used as a wiring material due to switching speed, reduction of transmission loss, high density, and the like. When copper wiring is applied, a copper film is formed on the surface including the recesses using a vapor phase growth method, plating, or the like, on a substrate having wiring recesses on the surface.
[0003]
When depositing copper on the surface of the substrate, a barrier metal film (for example, tantalum, titanium, silicon, etc.) is preliminarily formed on the surface of the substrate in order to eliminate copper diffusion to the substrate and maintain copper adhesion. Nitride). When plating or the like is used, a copper shield layer is formed on the barrier metal film by a physical or chemical vapor deposition method and applied as an electrode. The barrier metal film is formed by physical vapor deposition such as sputtering.
[0004]
[Problems to be solved by the invention]
The recesses for wiring formed on the surface of the substrate tend to be small, and the barrier metal film is also required to be made thinner. However, since the barrier metal film is manufactured using a sputtering method, the directionality is not uniform. Therefore, in the case of a small concave portion, the inlet portion of the concave portion is formed before the inside is formed, and the filling property is improved. There were problems that became insufficient, and the damage was severe.
[0005]
The present invention has been made in view of the above situation, and has a barrier metal film that has excellent embeddability and can form a barrier metal film at a high speed in an extremely thin state and has excellent adhesion to a metal formed on the surface. An object of the present invention is to provide a barrier metal film manufacturing apparatus and a barrier metal film manufacturing method capable of forming a metal film.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, an apparatus for producing a barrier metal film according to the present invention includes a chamber in which a substrate is accommodated, a metal member to be etched provided in a chamber facing the substrate, and a halogen in the chamber. A source gas supply means for supplying a source gas, a nitrogen-containing gas supply means for supplying a gas containing nitrogen into the chamber, a source gas plasma is generated by plasmaizing the inside of the chamber, and the member to be etched with the source gas plasma The precursor of the metal component contained in the member to be etched and the source gas is generated by etching the plasma, and the inside of the chamber is turned into plasma to generate a nitrogen-containing gas plasma, and the metal nitride is formed between the precursor and the precursor. The generated plasma generating means and the substrate side temperature are made lower than the temperature of the plasma generating means side, and the metal nitride is formed. A control means for forming a barrier metal film on the surface of the substrate, a rare gas supply means for supplying a rare gas to the upper part of the substrate surface, and generating a rare gas plasma by converting the inside of the chamber into a plasma. Surface treatment plasma generating means for performing a surface treatment for removing atoms and relatively reducing the nitrogen content of the surface layer as compared with the inside of the base material of the barrier metal film is provided.
[0007]
Then, oxygen gas supply means for supplying oxygen gas into the chamber just before the formation of the outermost layer of the barrier metal film and plasma generation inside the chamber to generate oxygen gas plasma to form an oxide layer on the outermost layer of the barrier metal film And oxygen plasma generating means.
[0013]
  The apparatus further comprises hydrogen gas supply means for supplying hydrogen gas into the chamber, and hydroxyl group plasma generation means for generating hydrogen gas plasma by plasmaizing the inside of the chamber to form hydroxyl groups in the oxide layer.AndFeatures.
[0014]
The source gas containing halogen is a source gas containing chlorine. The nitrogen-containing gas containing nitrogen is a gas containing ammonia. In addition, the member to be etched is tantalum or tungsten, titanium, or silicon which is a halide forming metal.
[0015]
In order to achieve the above object, a barrier metal film manufacturing method according to the present invention supplies a source gas containing halogen and a nitrogen-containing gas into a chamber between a substrate and a metal member to be etched. Plasma is generated to generate source gas plasma, and the member to be etched is etched with source gas plasma to generate a precursor of the metal component and source gas contained in the member to be etched, and the inside of the chamber is converted to plasma to contain nitrogen While generating a gas plasma to generate metal nitride with the precursor, the temperature on the substrate side is lower than the temperature on the plasma generating means side, and the metal nitride is formed as a barrier metal film on the surface of the substrate A rare gas is supplied into the chamber above the substrate surface, and the inside of the chamber is turned into plasma to generate a rare gas plasma. Removing the surface layer of nitrogen atoms as compared with the internal matrix of the barrier metal film, characterized in that the surface treatment to relatively reduce the nitrogen content of the surface layer in plasma.
[0016]
Then, oxygen gas is supplied into the chamber just before the outermost layer formation of the barrier metal film is completed, and the inside of the chamber is turned into plasma to generate oxygen gas plasma to form an oxide layer on the outermost layer of the barrier metal film. To do.
[0022]
  Then, hydrogen gas is supplied into the chamber and the inside of the chamber is turned into plasma to generate hydrogen gas plasma to form hydroxyl groups in the oxide layer.AndFeatures.
[0023]
The source gas containing halogen is a source gas containing chlorine. The nitrogen-containing gas containing nitrogen is a gas containing ammonia. In addition, the member to be etched is tantalum or tungsten, titanium, or silicon which is a halide forming metal.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
A barrier metal film manufacturing apparatus and a barrier metal film manufacturing method according to a first embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a schematic side view of a barrier metal film manufacturing apparatus according to a first embodiment of the present invention, FIG. 2 is a sectional view of a substrate for explaining a barrier metal film, and FIGS. 3 and 4 are barriers in denitrification processing. 5 shows the conceptual situation of the metal film, FIG. 5 shows the conceptual situation of the barrier metal film in the oxide layer forming process, FIG. 6 shows the relationship between the contact angle of the copper particles and the oxygen concentration of the substrate, and FIG. The conceptual situation of the membrane is shown. FIG. 8 shows a schematic configuration representing another example of the rare gas supply means.
[0025]
As shown in FIG. 1, a support base 2 is provided in the vicinity of the bottom of a chamber 1 made of, for example, ceramics (made of an insulating material), and a substrate 3 is placed on the support base 2. . The support 2 is provided with temperature control means 6 as a control means including a heater 4 and a refrigerant flow means 5, and the support 2 is heated to a predetermined temperature (for example, the substrate 3 is set to 100 ° C. to 200 ° C. by the temperature control means 6. Maintained temperature).
[0026]
The upper surface of the chamber 1 is an opening, and the opening is closed by a metal member 7 (for example, W, Ti, Ta, TiSi, etc.) as a member to be etched. The inside of the chamber 1 closed by the metal member 7 is maintained at a predetermined pressure by the vacuum device 8. A plasma antenna 9 of a coiled winding antenna as plasma generating means is provided around the cylindrical portion of the chamber 1, and a matching unit 10 and a power source 11 are connected to the plasma antenna 9 to supply power.
[0027]
In the cylindrical portion of the chamber 1 below the metal member 7, a source gas containing chlorine as a halogen inside the chamber 1 (the chlorine concentration is diluted to about 10% with He, Ar, etc., preferably about 10%) Cl₂A nozzle 12 is connected as a raw material gas supply means for supplying gas. The raw material gas is sent to the nozzle 12 via the flow rate controller 13. While supplying the source gas from the nozzle 12 and entering the electromagnetic wave from the plasma antenna 9 into the chamber 1, Cl₂The gas is ionized and Cl₂Gas plasma is generated (plasma generating means). Note that fluorine (F), bromine (Br), iodine (I), and the like can be applied as the halogen contained in the source gas.
[0028]
In addition, the cylindrical portion of the chamber 1 below the metal member 7 has an ammonia gas (NH) as a nitrogen-containing gas inside the chamber 1._ThreeA nozzle 14 is connected as a nitrogen-containing gas supply means for supplying a gas. NH from nozzle 14_ThreeWhile supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, NH_ThreeGas is ionized and NH_ThreeGas plasma is generated (plasma generating means).
[0029]
Further, a rare gas nozzle 21 is provided as a rare gas supply means for supplying Ar gas as a rare gas into the chamber 1 above the surface of the substrate 3. Ar gas is supplied from the rare gas nozzle 21 and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 9, whereby Ar gas is ionized to generate Ar gas plasma (surface treatment plasma generating means). ).
[0030]
As a rare gas supply means, Cl₂When Ar gas is applied as the gas dilution gas, as shown in FIG.₂Gas) and dilution gas (Ar gas) where a control valve 22 is provided to generate Ar gas plasma when Cl gas is generated.₂A configuration in which the gas is stopped and only Ar gas is supplied from the nozzle 12 is also possible. Thereby, it is not necessary to provide the rare gas nozzle 21 in particular, which is advantageous in terms of space.
[0031]
Further, oxygen gas (O 2) is placed in the chamber 1 above the surface of the substrate 3.₂An oxygen gas nozzle 15 is provided as oxygen gas supply means for supplying (gas). O from the oxygen gas nozzle 15₂While supplying gas, an electromagnetic wave is incident on the inside of the chamber 1 from the plasma antenna 9.₂Gas is ionized and O₂Gas plasma is generated (oxygen plasma generating means).
[0032]
Further, hydrogen gas (H₂A hydrogen gas nozzle 16 is provided as hydrogen gas supply means for supplying (gas). Hydrogen gas nozzle 16 to H₂While supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, H₂Gas is ionized and H₂Gas plasma is generated (hydroxyl plasma generating means).
[0033]
In the barrier metal film manufacturing apparatus described above, the source gas is supplied from the nozzle 12 into the chamber 1 and electromagnetic waves are incident from the plasma antenna 9 into the chamber 1.₂The gas is ionized and Cl₂Gas plasma (raw material gas plasma) is generated. Cl₂An etching reaction occurs in the metal member 7 by the gas plasma, and a precursor (MxCly: M is a metal such as W, Ti, Ta, TiSi) 16 is generated. The metal member 7 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by plasma.
[0034]
Further, NH 14 is provided in the chamber 1 from the nozzle 14._ThreeWhile supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, NH_ThreeGas is ionized and NH_ThreeGas plasma is generated, and a reduction reaction occurs between the precursor 20 and metal nitride (MN) is generated. The metal nitride (MN) generated inside the chamber 1 is carried to the substrate 3 controlled at a low temperature, and MN is formed on the surface of the substrate 3 to generate a barrier metal film 23 (FIG. 2). reference).
[0035]
The reaction when the barrier metal film 23 is generated can be expressed by the following equation.
2MCl + 2NH_Three→ 2MN ↓ + HCl ↑ + 2H₂↑
Gases and etching products not involved in the reaction are exhausted from the exhaust port 17.
[0036]
After the barrier metal film 23 is generated, Ar gas is supplied from the rare gas nozzle 21 and electromagnetic waves are incident from the plasma antenna 9 into the chamber 1 to generate Ar gas plasma. Since the barrier metal film 23 of MN is formed on the surface of the substrate 3 as shown in FIG. 3, by generating Ar gas plasma, Ar gas plasma is generated.⁺Thus, the barrier metal film 23 on the surface of the substrate 2 is etched to remove nitrogen atoms (N) of the MN on the surface layer, so that the nitrogen content in the surface layer is relatively reduced as compared with the inside of the base material of the barrier metal film 23. Treatment (denitrification treatment) is performed.
[0037]
As shown in FIG. 3, in the barrier metal film 23, M and N are mixed in an amorphous state, and Ar⁺Thus, N having a small mass is preferentially removed, and the surface layer of the barrier metal film 23 (for example, at most half of the total film thickness: preferably about 1/3) is denitrified. As a result, as shown in FIG. 4, the barrier metal film 23 having a two-layer structure of the metal layer 23a and the MN layer 23b substantially composed of M is obtained. At this time, the entire thickness of the barrier metal film 23 remains as a single layer.
[0038]
Just before the formation of the outermost surface layer of the barrier metal film 23 is completed, a small amount of O is introduced into the chamber 1 from the oxygen gas nozzle 15.₂By supplying gas and introducing electromagnetic waves from the plasma antenna 9 into the chamber 1, O₂A gas plasma is generated. As a result, as shown in FIG. 5, an oxide layer 24 is formed on the surface of the metal layer 23a substantially composed of M. By forming the oxide layer 24, when a metal (for example, copper) is deposited (deposited) on the surface of the barrier metal film 23, the wettability of the metal is improved and the adhesion can be improved. .
[0039]
That is, as shown in FIG. 6, as the oxygen concentration of the substrate 3 increases, the contact angle θ of the copper particles (the minimum surface energy in the balance of surface tension when the substrate is solid and copper is liquid is taken. It has been confirmed that the angle is small. That is, as the oxygen concentration of the substrate 3 increases, the copper particles adhere to the surface of the substrate 3 in a state of being crushed (a good wettability state). For this reason, O₂By generating gas plasma and forming the oxide layer 24 on the surface of the metal layer 23a, it becomes possible to improve the wettability of the metal (copper) formed by increasing the oxygen concentration.
[0040]
After forming the oxide layer 24 on the surface of the metal layer 23a, the hydrogen gas nozzle 16 enters the chamber 1 with H.₂By supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, H₂A gas plasma is generated. As a result, hydroxyl groups (OH groups) are formed on the surface of the oxide layer 24 as shown in FIG. Thereby, hydrophilicity improves and it becomes possible to further improve the adhesiveness of the metal (copper) formed into a film.
[0041]
In the barrier metal film manufacturing apparatus having the above configuration, the barrier metal film 23 is formed by generating metal by plasma, so that the barrier metal film 23 can be formed in a uniform and thin film shape. For this reason, for example, even a small recess having a width of about several hundreds of nanometers provided on the substrate 3 is accurately formed even inside, and the barrier metal film 23 is formed at high speed in an extremely thin state with excellent embedding property. It becomes possible to do.
[0042]
Moreover, since the nitrogen atom was removed by Ar gas plasma and the denitrification treatment of the barrier metal film 23 was performed, the barrier metal film 23 having a two-layer structure of the metal layer 23a and the MN layer 23b substantially composed of M. In addition, the entire film thickness can be maintained as a single layer. For this reason, it is possible to maintain the adhesiveness with the metal deposited on the surface by the metal layer 23a without increasing the thickness of the barrier metal film 23, and to prevent the diffusion of the metal by the MN layer 23b. be able to. Therefore, it becomes possible to produce a barrier metal that can be deposited with good adhesion without diffusing the deposited metal.
[0043]
Also O₂Since the gas plasma is generated to form the oxide layer 24 on the surface of the metal layer 23a, the metal wettability is improved and the adhesion is improved when the metal is formed on the surface of the barrier metal film 23. be able to. In addition, H₂Since the gas plasma is generated to form a hydroxyl group (OH group) on the surface of the oxide layer 24, the hydrophilicity is improved and the adhesion of the metal to be formed can be further improved.
[0044]
H₂It is also possible to omit the step of generating a gas plasma to form a hydroxyl group (OH group) on the surface of the oxide layer 24. Also O₂It is also possible to omit the step of generating gas plasma to form the oxide layer 24 on the surface of the metal layer 23a.
[0045]
Based on FIG. 9, a barrier metal film manufacturing apparatus and a barrier metal film manufacturing method according to a second embodiment of the present invention will be described. FIG. 9 shows a schematic configuration of a barrier metal film manufacturing apparatus according to the second embodiment of the present invention. In addition, the same code | symbol is attached | subjected to the same member as the member shown in FIG. 1, and the overlapping description is abbreviate | omitted. FIG. 10 shows a conceptual state of an example in which a barrier metal film is manufactured by the barrier metal film manufacturing apparatus according to the second embodiment of the present invention.
[0046]
The barrier metal film manufacturing apparatus of the second embodiment shown in FIG. 9 has a configuration in which the rare gas nozzle 21 is not provided in the barrier metal film manufacturing apparatus of the first embodiment shown in FIG. . In the first embodiment, Ar gas is supplied from the rare gas nozzle 21 to generate Ar gas plasma.⁺Thus, the barrier metal film 23 on the surface of the substrate 2 is etched to remove nitrogen atoms (N) of the MN on the surface layer, so that the nitrogen content in the surface layer is relatively reduced as compared with the inside of the base material of the barrier metal film 23. Although the treatment (denitrification treatment) has been carried out, in the second embodiment, when the denitrification treatment is carried out, the oxygen gas nozzle 15 supplies O 2.₂Supply gas O₂Generate gas plasma, O₂ ⁺Thus, the denitrification treatment is performed by etching the barrier metal film 23 on the surface of the substrate 2. After denitrification, O₂The oxide layer 24 (see FIG. 5) is formed by reducing the amount of gas. Other configurations and operations are the same as those of the first embodiment.
[0047]
In the second embodiment, the number of nozzles for supplying gas can be reduced, which is advantageous in terms of space.
[0048]
In the barrier metal film manufacturing apparatus of the second embodiment, O₂It is also possible to use only the formation of the oxide layer 24 (see FIG. 5) without using the gas plasma for etching. In this case, the barrier metal film 23 is only one layer of the MN layer 23b. For example, when the metal to be formed is a metal (for example, Al) with little problem in adhesion, the process of forming the metal layer 23a by etching can be omitted.
[0049]
Furthermore, in the barrier metal film manufacturing apparatus of the second embodiment, O₂The gas plasma is not used for etching but only for forming the oxide layer 24 (see FIG. 5), and after forming the MN layer 23b, NH from the nozzle 14 is used._ThreeThe gas supply is stopped and the precursor 20 NH_ThreeIt is also possible to stop the reaction by the gas plasma and form the metal layer 23a by laminating the metal component of the precursor 20 on the MN layer 23b as shown in FIG.
Reaction when the metal layer 23a is produced | generated from the metal component of the precursor 16 can be represented by following Formula.
2MCl → 2M ↓ + Cl₂↑
[0050]
A barrier metal film manufacturing apparatus and a barrier metal film manufacturing method according to a third embodiment of the present invention will be described with reference to FIG. FIG. 11 shows a schematic configuration of a barrier metal film manufacturing apparatus according to the third embodiment of the present invention. The same members as those in the barrier metal film manufacturing apparatus shown in FIG.
[0051]
As shown in FIG. 11, a support base 2 is provided near the bottom of the chamber 1, and a substrate 3 is placed on the support base 2. The support 2 is provided with temperature control means 6 as a control means including a heater 4 and a refrigerant flow means 5, and the support 2 is heated to a predetermined temperature (for example, the substrate 3 is set to 100 ° C. to 200 ° C. by the temperature control means 6. Maintained temperature). The upper surface of the chamber 1 is an opening, and the opening is closed by a metal member 7 (for example, W, Ti, Ta, TiSi, etc.). The inside of the chamber 1 closed by the metal member 7 is maintained at a predetermined pressure by the vacuum device 8. A plasma antenna 9 is provided around the cylindrical portion of the chamber 1, and a matching unit 10 and a power source 11 are connected to the plasma antenna 9 to supply power.
[0052]
A nozzle 12 through which a raw material gas is sent is connected to the cylindrical portion of the chamber 1 below the metal member 7. While supplying the source gas from the nozzle 12 and entering the electromagnetic wave from the plasma antenna 9 into the chamber 1, Cl₂The gas is ionized and Cl₂Gas plasma is generated (plasma generating means).
[0053]
Further, a rare gas nozzle 21 for supplying Ar gas is provided in the chamber 1, and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 9, whereby Ar gas is ionized and Ar gas plasma is generated. (Surface treatment plasma generating means). As a rare gas supply means, Cl₂When Ar gas is applied as the gas dilution gas, it is possible to supply only Ar gas from the nozzle 12 as in the first embodiment.
[0054]
Also, oxygen gas (O₂An oxygen gas nozzle 15 for supplying gas) is provided. By entering electromagnetic waves from the plasma antenna 9 into the chamber 1, O₂Gas is ionized and O₂Gas plasma is generated (oxygen plasma generating means). Further, hydrogen gas (H₂A hydrogen gas nozzle 16 for supplying gas) is provided. When electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 9, H₂Gas is ionized and H₂Gas plasma is generated (hydroxyl plasma generating means).
[0055]
On the other hand, slit-like openings 31 are formed at a plurality of locations around the bottom of the cylindrical portion of the chamber 1 (for example, four locations: only one location is shown in the figure). One end of each of the passages 32 is fixed. A cylindrical excitation chamber 33 made of an insulator is provided in the middle of the passage 32, and a coiled plasma antenna 34 is provided around the excitation chamber 33. The plasma antenna 34 is connected to a matching unit 35 and a power source 36. Then, power is supplied. The plasma antenna 34, the matching unit 35, and the power source 36 constitute excitation means. A flow rate controller 37 is connected to the other end side of the passage 32, and ammonia gas (NH) as a nitrogen-containing gas enters the passage 32 via the flow rate controller 37._ThreeGas).
[0056]
Further, NH is introduced into the passage 32 via the flow rate controller 37._ThreeGas is supplied to the excitation chamber 33 for NH_ThreeInject gas. By injecting electromagnetic waves from the plasma antenna 34 into the excitation chamber 33, NH_ThreeGas is ionized and NH_ThreeA gas plasma 38 is generated. Since a predetermined differential pressure is set between the pressure in the chamber 1 and the pressure in the excitation chamber 33 by the vacuum device 8, NH in the excitation chamber 33_ThreeExcited ammonia of the gas plasma 38 is sent from the opening 31 to the precursor (MxCly) 20 in the chamber 1.
[0057]
That is, the excitation means which excites the nitrogen-containing gas containing nitrogen in the excitation chamber 33 isolated from the chamber 1 is configured. As a result, the metal component of the precursor (MxCly) 20 and ammonia react to generate metal nitride (MN) (generation means). At this time, the metal member 7 and the excitation chamber 33 are maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by plasma.
[0058]
In the barrier metal film manufacturing apparatus described above, the source gas is supplied from the nozzle 12 into the chamber 1 and electromagnetic waves are incident from the plasma antenna 9 into the chamber 1.₂Gas plasma (raw material gas plasma) is generated. Cl₂An etching reaction occurs in the metal member 7 by the gas plasma, and a precursor (MxCly) 20 is generated. The metal member 7 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by plasma.
[0059]
NH in excitation chamber 33_ThreeExcited ammonia of the gas plasma 38 is sent from the opening 31 to the precursor (MxCly) 20 in the chamber 1, so that metal nitride (MN) is generated inside the chamber 1, and the generated metal nitride (MN) ) Is carried to the substrate 3 controlled at a low temperature, and a barrier metal film 23 is generated on the surface of the substrate 3. Gases and etching products not involved in the reaction are exhausted from the exhaust port 17.
[0060]
After the barrier metal film 23 is generated, Ar gas is supplied from the rare gas nozzle 21 and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 9 to generate Ar gas plasma.⁺Thus, the barrier metal film 23 on the surface of the substrate 2 is etched to remove nitrogen atoms (N) of the MN on the surface layer, so that the nitrogen content in the surface layer is relatively reduced as compared with the inside of the base material of the barrier metal film 23. Treatment (denitrification treatment) is performed. As a result, the barrier metal film 23 having a two-layer structure of the metal layer 23a and the MN layer 23b substantially composed of M is obtained (see FIG. 4).
[0061]
Just before the formation of the outermost surface layer of the barrier metal film 23 is completed, a small amount of O is introduced into the chamber 1 from the oxygen gas nozzle 15.₂By supplying gas and introducing electromagnetic waves from the plasma antenna 9 into the chamber 1, O₂A gas plasma is generated. As a result, an oxide layer 24 is formed on the surface of the metal layer 23a substantially composed of M (see FIG. 5). By forming the oxide layer 24, when a metal (for example, copper) is deposited (deposited) on the surface of the barrier metal film 23, the wettability of the metal is improved and the adhesion can be improved. .
[0062]
After forming the oxide layer 24 on the surface of the metal layer 23a, the hydrogen gas nozzle 16 enters the chamber 1 with H.₂By supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, H₂A gas plasma is generated. Thereby, a hydroxyl group (OH group) is formed on the surface of the oxide layer 24 (see FIG. 7). Thereby, hydrophilicity improves and it becomes possible to further improve the adhesiveness of the metal (copper) formed into a film.
[0063]
In the barrier metal manufacturing apparatus described above, as in the first embodiment, the barrier metal film 23 is excellent in embeddability and can be formed at a high speed in an extremely thin state. In addition, it is possible to maintain the adhesion with the metal deposited on the surface while maintaining the total film thickness as a single layer, eliminating the diffusion of the deposited metal, and forming the film with good adhesion. It is possible to produce a barrier metal that can be used.
[0064]
In addition, when a metal is formed on the surface of the barrier metal film 23, the wettability of the metal is improved, the adhesion can be improved, and the hydrophilicity is improved. It becomes possible to further improve the adhesion.
[0065]
And NH_ThreeSince the gas plasma 38 is generated in the excitation chamber 33 isolated from the chamber 1, NH_ThreeThe influence of the gas plasma 38 does not reach the surface of the substrate 3.
[0066]
H₂It is also possible to omit the step of generating a gas plasma to form a hydroxyl group (OH group) on the surface of the oxide layer 24. Also O₂It is also possible to omit the step of generating gas plasma to form the oxide layer 24 on the surface of the metal layer 23a.
[0067]
It is also possible to adopt a configuration in which the rare gas nozzle 21 is not provided in the barrier metal film manufacturing apparatus of the third embodiment shown in FIG. In the third embodiment, Ar gas is supplied from the rare gas nozzle 21 to generate Ar gas plasma.⁺Thus, the barrier metal film 23 on the surface of the substrate 2 is etched to remove nitrogen atoms (N) of the MN on the surface layer, so that the nitrogen content in the surface layer is relatively reduced as compared with the inside of the base material of the barrier metal film 23. The treatment (denitrification treatment) is performed. In this case, when the denitrification treatment is performed, the oxygen gas nozzle 15 supplies O 2.₂Supply gas O₂Generate gas plasma, O₂ ⁺Thus, the barrier metal film 23 on the surface of the substrate 2 is etched to perform a denitrification process. After denitrification, O₂The oxide layer 24 (see FIG. 5) is formed by reducing the amount of gas.
[0068]
In this case, the number of nozzles for supplying gas can be reduced, which is advantageous in terms of space.
[0069]
O₂It is also possible to use only the formation of the oxide layer 24 (see FIG. 5) without using the gas plasma for etching. In this case, the barrier metal film 23 is only one layer of the MN layer 23b. For example, when the metal to be formed is a metal (for example, Al) with little problem in adhesion, the process of forming the metal layer 23a by etching can be omitted.
[0070]
In addition, O₂The gas plasma is not used for etching but only for forming the oxide layer 24 (see FIG. 5), and after forming the MN layer 23b, NH is formed._ThreeBy stopping the power supply to the gas and the power source 36, the precursor (MxCly) 20 is conveyed to the substrate 3 controlled to a temperature lower than that of the metal member 7. The precursor (MxCly) 20 carried to the substrate 3 is made only into metal (M) ions by a reduction reaction and applied to the substrate 3, and a metal layer 23a is laminated on the MN layer 23b of the substrate 3 to form the metal layer 23a. It can also be formed (see FIG. 10).
[0071]
A barrier metal film manufacturing apparatus and a barrier metal film manufacturing method according to a fourth embodiment of the present invention will be described with reference to FIGS. 12 is a schematic side view of the barrier metal film manufacturing apparatus according to the fourth embodiment of the present invention, FIG. 13 is a view taken along line XIII-XIII in FIG. 12, and FIG. 14 is a line XIV-XIV in FIG. Arrow view is shown. The same members as those shown in FIGS. 1 to 11 are denoted by the same reference numerals, and redundant description is omitted.
[0072]
The upper surface of the chamber 1 is an opening, and the opening is closed by a disk-shaped ceiling plate 41 made of an insulating material (for example, made of ceramics). A member to be etched 42 made of metal (for example, W, Ti, Ta, TiSi, etc.) is sandwiched between the opening on the upper surface of the chamber 1 and the ceiling plate 41. The member to be etched 42 is provided with a ring portion 43 that is sandwiched by an opening on the upper surface of the chamber 1. A plurality of (44 in the illustrated example) portions 44 are provided in the circumferential direction.
[0073]
The protruding portion 44 is attached to the ring portion 43 integrally or detachably. Between the ceiling plate 41 and the inside of the chamber 1, there is a notch 45 (space) formed between the protrusions 44. The ring portion 43 is grounded, and the plurality of protrusions 44 are electrically connected and maintained at the same potential. The member to be etched 42 is provided with temperature control means (not shown) such as a heater, and the temperature is controlled to about 200 ° C. to 400 ° C., for example.
[0074]
In addition, it is also possible to arrange | position the 2nd projection part shorter than the projection part 44 in the radial direction between the projection parts 44, and also arrange | position a short projection part between the projection part 44 and the 2nd projection part. It is also possible. In this way, the area of the metal member to be etched can be ensured while suppressing the induced current.
[0075]
Above the ceiling plate 41 is provided a planar winding plasma antenna 46 for converting the inside of the chamber 1 into plasma, and the plasma antenna 46 is formed in a planar ring shape parallel to the surface of the ceiling plate 41. The plasma antenna 46 is connected to the matching unit 10 and the power source 11 to be fed. Since the member to be etched 42 has a plurality of protrusions 44 in the circumferential direction on the inner peripheral side of the ring part 43 and there are notches 45 (spaces) formed between the protrusions 44, the plasma antenna The protrusions 44 are arranged between the substrate 3 and the ceiling plate 41 in a discontinuous state with respect to the direction of electricity flow 46.
[0076]
The cylindrical portion of the chamber 1 includes a nozzle 12 for supplying a raw material gas into the chamber 1, and NH inside the chamber 1._ThreeA nozzle 14 for supplying gas, a rare gas nozzle 21 for supplying Ar gas into the chamber 1, and an O in the chamber 1₂The oxygen gas nozzle 15 for supplying gas and the inside of the chamber 1 have H₂A hydrogen gas nozzle 16 for supplying gas is provided.
[0077]
In the barrier metal film manufacturing apparatus described above, the source gas is supplied from the nozzle 12 to the inside of the chamber 1, and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 46.₂The gas is ionized and Cl₂Gas plasma (raw material gas plasma) is generated. A member to be etched 42, which is a conductor, is present below the plasma antenna 46, but Cl is formed between the member to be etched 42 and the substrate 3, that is, below the member to be etched 42, by the following action.₂Gas plasma is generated stably.
[0078]
Cl under the etched member 42₂The effect | action which gas plasma generate | occur | produces is demonstrated. As shown in FIG. 14, the electric flow A of the planar ring-shaped plasma antenna 46 crosses the projection 44, and at this time, an induced current b is generated on the surface of the projection 44 facing the plasma antenna 46. . Since the notched portion 45 (space) exists in the member to be etched 42, the induced current b flows to the lower surface of each protrusion 44 and flows in the same direction as the electric current A of the plasma antenna 46. Flow a (Faraday shield).
[0079]
For this reason, when the member 42 to be etched is viewed from the substrate 3 side, there is no flow in the direction to cancel the electric flow A of the plasma antenna 46, and the ring portion 43 is grounded and the projection 44 is the same. It is maintained at a potential. As a result, even if the member to be etched 42, which is a conductor, is present, the electromagnetic wave is reliably incident from the plasma antenna 46 into the chamber 1, and the Cl is formed below the member 42 to be etched.₂Gas plasma is generated stably.
[0080]
Cl₂The gas plasma causes an etching reaction in the member 42 to be etched, and a precursor (MxCly: M is a metal such as W, Ti, Ta, TiSi) 20 is generated.
[0081]
Then, NH from the nozzle 14 into the chamber 1_ThreeWhile supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 46, NH_ThreeGas is ionized and NH_ThreeGas plasma is generated, and a reduction reaction occurs between the precursor 20 and metal nitride (MN) is generated. The metal nitride (MN) generated inside the chamber 1 is carried to the substrate 3 controlled at a low temperature, and MN is formed on the surface of the substrate 3 to generate a barrier metal film 23 (FIG. 2). reference).
[0082]
After the barrier metal film 23 is generated, Ar gas is supplied from the rare gas nozzle 21 and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 46 to generate Ar gas plasma, thereby causing a barrier on the surface of the substrate 2. The metal film 23 is etched to remove the MN nitrogen atoms (N) in the surface layer, and a process (denitrification process) is performed to relatively reduce the nitrogen content in the surface layer compared to the inside of the base material of the barrier metal film 23. Is done.
[0083]
Just before the formation of the outermost surface layer of the barrier metal film 23 is completed, a small amount of O is introduced into the chamber 1 from the oxygen gas nozzle 15.₂By supplying gas and introducing electromagnetic waves from the plasma antenna 46 into the chamber 1, O₂A gas plasma is generated. As a result, an oxide layer 24 (see FIG. 5) is formed on the surface of the metal layer 23a (see FIG. 5) substantially composed of M. By forming the oxide layer 24, when a metal (for example, copper) is deposited (deposited) on the surface of the barrier metal film 23, the wettability of the metal is improved and the adhesion can be improved. .
[0084]
After an oxide layer 24 (see FIG. 5) is formed on the surface of the metal layer 23a (see FIG. 5), H is introduced into the chamber 1 from the hydrogen gas nozzle 16.₂By supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 46, H₂A gas plasma is generated. Thereby, a hydroxyl group (OH group) is formed on the surface of the oxide layer 24 (see FIG. 7). Thereby, hydrophilicity improves and it becomes possible to further improve the adhesiveness of the metal (copper) formed into a film.
[0085]
H₂It is possible to omit the step of generating a gas plasma to form a hydroxyl group (OH group) on the surface of the oxide layer 24 (see FIG. 7). Also O₂It is also possible to omit the step of generating gas plasma to form the oxide layer 24 (see FIG. 5) on the surface of the metal layer 23a (see FIG. 5). Furthermore, the metal layer 23a can be laminated to form the barrier metal film 23, or the barrier metal film 23 without the metal layer 23a can be formed.
[0086]
In addition to the configuration of the member to be etched 42 and the plasma antenna 46 that are the configuration for generating the precursor 20, a nozzle configuration similar to that of the second embodiment (see FIG. 9) in which the rare gas nozzle 21 is omitted may be used. It is. In addition to the configuration of the member to be etched 42 and the plasma antenna 46, a configuration similar to that of the third embodiment (see FIG. 11) including the excitation chamber 33 and the like instead of the nozzle 14 can be used.
[0087]
In the barrier metal film manufacturing apparatus having the above configuration, the barrier metal film 23 can be formed uniformly and in a thin film shape. For this reason, for example, even a small recess having a width of about several hundreds of nanometers provided on the substrate 3 is accurately formed even inside, and the barrier metal film 23 is formed at high speed in an extremely thin state with excellent embedding property. It becomes possible to do.
[0088]
Since the member to be etched 42 has a plurality of protrusions 44 in the circumferential direction on the inner peripheral side of the ring part 43 and there are notches 45 (spaces) formed between the protrusions 44. The induced current generated in the member to be etched 42 flows in the same direction as the flow of electricity in the plasma antenna 46 when viewed from the substrate 3 side. As a result, even if the member to be etched 42, which is a conductor, exists under the plasma antenna 46, electromagnetic waves are reliably incident from the plasma antenna 46 into the chamber 1, and Cl₂Gas plasma can be generated stably.
[0089]
A barrier metal film manufacturing apparatus and a barrier metal film manufacturing method according to a fifth embodiment of the present invention will be described with reference to FIG. FIG. 15 shows a schematic side view of a barrier metal film manufacturing apparatus according to the fifth embodiment of the present invention. The same members as those shown in FIGS. 1 to 14 are denoted by the same reference numerals, and redundant description is omitted.
[0090]
The opening at the top of the chamber 1 is closed by a ceiling plate 41. An etched member 48 made of metal (for example, W, Ti, Ta, TiSi, etc.) is provided on the lower surface of the ceiling plate 41, and the etched member 48 has a quadrangular pyramid shape. Slit-like openings 51 are formed at a plurality of locations around the upper portion of the cylindrical portion of the chamber 1 (for example, four locations: one location is shown in the figure). One end of each is fixed. A cylindrical excitation chamber 53 made of an insulator is provided in the middle of the passage 52, and a coiled plasma antenna 54 is provided around the excitation chamber 53. The plasma antenna 54 includes a matching unit 57 and a power source 58. Connected to supply power.
[0091]
A flow rate controller 55 is connected to the other end side of the passage 52, and a raw material gas containing chlorine in the passage 52 via the flow rate controller 55 (He, Ar, etc., the chlorine concentration is ≦ 50%, preferably 10%) Cl diluted to a degree₂Gas). By making electromagnetic waves enter the excitation chamber 53 from the plasma antenna 54, Cl₂The gas is ionized and Cl₂Gas plasma (raw material gas plasma) 56 is generated. Cl₂Excitation chlorine is sent into the chamber 1 from the opening 51 by the generation of the gas plasma 56, and the member 48 to be etched is etched by the excitation chlorine.
[0092]
The cylinder portion of the chamber 1 has NH inside the chamber 1._ThreeA nozzle 14 for supplying gas, a rare gas nozzle 21 for supplying Ar gas into the chamber 1, and an O in the chamber 1₂The oxygen gas nozzle 15 for supplying gas and the inside of the chamber 1 have H₂A hydrogen gas nozzle 16 for supplying gas is provided. In addition, a plasma antenna 9, a matching unit 10 and a power source 11 are provided around the chamber 1, and NH_ThreeGas plasma, Ar gas plasma, O₂Gas plasma and H₂A gas plasma is generated.
[0093]
In the barrier metal film manufacturing apparatus described above, the source gas is supplied into the passage 52 via the flow rate controller 55 and the source gas is sent into the excitation chamber 53. By making electromagnetic waves enter the excitation chamber 53 from the plasma antenna 54, Cl₂The gas is ionized and Cl₂Gas plasma (raw material gas plasma) 56 is generated. Since a predetermined differential pressure is set between the pressure in the chamber 1 and the pressure in the excitation chamber 53 by the vacuum device 8, Cl in the excitation chamber 53₂Excited chlorine of the gas plasma 56 is sent from the opening 51 to the member to be etched 48 in the chamber 1. An etching reaction occurs in the member to be etched 48 by the excited chlorine, and the precursor 20 is generated inside the chamber 1. At this time, the member to be etched 48 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by the heater 50 provided on the ceiling plate 41.
[0094]
Then, NH from the nozzle 14 into the chamber 1_ThreeWhile supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, NH_ThreeGas is ionized and NH_ThreeGas plasma is generated, and a reduction reaction occurs between the precursor 20 and metal nitride (MN) is generated. The metal nitride (MN) generated inside the chamber 1 is carried to the substrate 3 controlled at a low temperature, and MN is formed on the surface of the substrate 3 to generate a barrier metal film 23 (FIG. 2). reference).
[0095]
After the barrier metal film 23 is generated, Ar gas is supplied from the rare gas nozzle 21 and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 9, thereby generating Ar gas plasma, and a barrier on the surface of the substrate 2. The metal film 23 is etched to remove the MN nitrogen atoms (N) in the surface layer, and a process (denitrification process) is performed to relatively reduce the nitrogen content in the surface layer compared to the inside of the base material of the barrier metal film 23. Is done.
[0096]
Just before the formation of the outermost surface layer of the barrier metal film 23 is completed, a small amount of O is introduced into the chamber 1 from the oxygen gas nozzle 15.₂By supplying gas and introducing electromagnetic waves from the plasma antenna 9 into the chamber 1, O₂A gas plasma is generated. As a result, an oxide layer 24 (see FIG. 5) is formed on the surface of the metal layer 23a (see FIG. 5) substantially composed of M. By forming the oxide layer 24, when a metal (for example, copper) is deposited (deposited) on the surface of the barrier metal film 23, the wettability of the metal is improved and the adhesion can be improved. .
[0097]
After an oxide layer 24 (see FIG. 5) is formed on the surface of the metal layer 23a (see FIG. 5), H is introduced into the chamber 1 from the hydrogen gas nozzle 16.₂By supplying gas and making electromagnetic waves enter the chamber 1 from the plasma antenna 9, H₂A gas plasma is generated. Thereby, a hydroxyl group (OH group) is formed on the surface of the oxide layer 24 (see FIG. 7). Thereby, hydrophilicity improves and it becomes possible to further improve the adhesiveness of the metal (copper) formed into a film.
[0098]
H₂It is possible to omit the step of generating a gas plasma to form a hydroxyl group (OH group) on the surface of the oxide layer 24 (see FIG. 7). Also O₂It is also possible to omit the step of generating gas plasma to form the oxide layer 24 (see FIG. 5) on the surface of the metal layer 23a (see FIG. 5). Furthermore, the metal layer 23a can be laminated to form the barrier metal film 23, or the barrier metal film 23 without the metal layer 23a can be formed.
[0099]
Other than the configuration of the member to be etched 48, the opening 51, the passage 52, the excitation chamber 53, the plasma antenna 54, the flow rate controller 55, the matching unit 57, the power source 58, and the like, which are configurations for generating the precursor 20, A nozzle configuration similar to that of the second embodiment (see FIG. 9) in which the rare gas nozzle 21 is omitted may be used. In addition to the configuration for generating the precursor 20, a configuration similar to that of the third embodiment (see FIG. 11) including the excitation chamber 33 and the like instead of the nozzle 14 may be used.
[0100]
In the barrier metal film manufacturing apparatus having the above configuration, the barrier metal film 23 can be formed uniformly and in a thin film shape. For this reason, for example, even a small recess having a width of about several hundreds of nanometers provided on the substrate 3 is accurately formed even inside, and the barrier metal film 23 is formed at high speed in an extremely thin state with excellent embedding property. It becomes possible to do.
[0101]
Then, in the excitation chamber 53 isolated from the chamber 1, Cl₂Since the gas plasma 56 is generated, the substrate 3 is Cl.₂It is no longer exposed to the gas plasma 56, and the substrate 3 is Cl.₂Damage due to the gas plasma 56 does not occur.
[0102]
In the excitation chamber 53, Cl₂As a means for generating the gas plasma 56, that is, a means for exciting the raw material gas to use as a raw material for excitation, microwaves, lasers, electron beams, radiated light, etc. can be used. The metal filament is heated to a high temperature. It is also possible to produce a precursor. Also, Cl₂The configuration for isolating the gas plasma 56 from the substrate 3 may be other configurations such as isolating the chamber 1 in addition to the configuration in which the excitation chamber 53 is provided in the passage 52.
[0103]
A barrier metal film manufacturing apparatus and a barrier metal film manufacturing method according to the sixth embodiment of the present invention will be described with reference to FIG. FIG. 16 shows a schematic side view of a barrier metal film manufacturing apparatus according to the sixth embodiment of the present invention. The same members as those shown in FIGS. 1 to 15 are denoted by the same reference numerals, and redundant description is omitted.
[0104]
The barrier metal film manufacturing apparatus according to the sixth embodiment is different from the barrier metal film manufacturing apparatus according to the first embodiment shown in FIG. 1 in that a plasma antenna 9 is provided around the cylindrical portion of the chamber 1. Instead, the matching unit 10 and the power source 11 are connected to the metal member 7 to supply power to the metal member 7.
[0105]
The cylinder portion of the chamber 1 has NH inside the chamber 1._ThreeA nozzle 14 for supplying gas, a rare gas nozzle 21 for supplying Ar gas into the chamber 1, and an O in the chamber 1₂The oxygen gas nozzle 15 for supplying gas and the inside of the chamber 1 have H₂A hydrogen gas nozzle 16 for supplying gas is provided. By feeding the metal member 7, NH_ThreeGas plasma, Ar gas plasma, O₂Gas plasma and H₂A gas plasma is generated. NH_ThreeGas plasma, Ar gas plasma, O₂Gas plasma and H₂In order to generate gas plasma, it is also possible to separately provide a coiled plasma antenna in the cylindrical portion of the chamber 1 and connect the plasma antenna to a power source via a matching unit.
[0106]
In the barrier metal film manufacturing apparatus described above, the source gas is supplied from the nozzle 12 to the inside of the chamber 1, and electromagnetic waves are incident on the inside of the chamber 1 from the metal member 7.₂The gas is ionized and Cl₂Gas plasma (raw material gas plasma) is generated. Cl₂An etching reaction occurs in the metal member 7 by the gas plasma, and a precursor (MxCly) 20 is generated. At this time, the metal member 7 is maintained at a temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by a temperature control means (not shown).
[0107]
Then, NH from the nozzle 14 into the chamber 1_ThreeWhile supplying gas, electromagnetic waves are incident on the inside of the chamber 1 from the metal member 7, so that NH_ThreeGas is ionized and NH_ThreeGas plasma is generated, and a reduction reaction occurs between the precursor 20 and metal nitride (MN) is generated. The metal nitride (MN) generated inside the chamber 1 is carried to the substrate 3 controlled at a low temperature, and MN is formed on the surface of the substrate 3 to generate a barrier metal film 23 (FIG. 2). reference).
[0108]
After the barrier metal film 23 is generated, Ar gas is supplied from the rare gas nozzle 21 and electromagnetic waves are incident on the inside of the chamber 1 from the metal member 7, thereby generating Ar gas plasma, and the barrier on the surface of the substrate 2. The metal film 23 is etched to remove the MN nitrogen atoms (N) in the surface layer, and a process (denitrification process) is performed to relatively reduce the nitrogen content in the surface layer compared to the inside of the base material of the barrier metal film 23. Is done.
[0109]
Just before the formation of the outermost surface layer of the barrier metal film 23 is completed, a small amount of O is introduced into the chamber 1 from the oxygen gas nozzle 15.₂By supplying gas and making electromagnetic waves enter the chamber 1 from the metal member 7, O₂A gas plasma is generated. As a result, an oxide layer 24 (see FIG. 5) is formed on the surface of the metal layer 23a (see FIG. 5) substantially composed of M. By forming the oxide layer 24, when a metal (for example, copper) is deposited (deposited) on the surface of the barrier metal film 23, the wettability of the metal is improved and the adhesion can be improved. .
[0110]
After an oxide layer 24 (see FIG. 5) is formed on the surface of the metal layer 23a (see FIG. 5), H is introduced into the chamber 1 from the hydrogen gas nozzle 16.₂By supplying gas and making electromagnetic waves enter the chamber 1 from the metal member 7, H₂A gas plasma is generated. Thereby, a hydroxyl group (OH group) is formed on the surface of the oxide layer 24 (see FIG. 7). Thereby, hydrophilicity improves and it becomes possible to further improve the adhesiveness of the metal (copper) formed into a film.
[0111]
H₂It is possible to omit the step of generating a gas plasma to form a hydroxyl group (OH group) on the surface of the oxide layer 24 (see FIG. 7). Also O₂It is also possible to omit the step of generating gas plasma to form the oxide layer 24 (see FIG. 5) on the surface of the metal layer 23a (see FIG. 5). Furthermore, the metal layer 23a can be laminated to form the barrier metal film 23, or the barrier metal film 23 without the metal layer 23a can be formed.
[0112]
Further, except for the configuration of the metal member 7, the matching unit 10, the power source 11, and the like that are the configuration for generating the precursor 20, the same nozzle configuration as that of the second embodiment (see FIG. 9) in which the rare gas nozzle 21 is omitted. It is also possible. In addition to the configuration for generating the precursor 20, a configuration similar to that of the third embodiment (see FIG. 11) including the excitation chamber 33 and the like instead of the nozzle 14 may be used.
[0113]
In the barrier metal film manufacturing apparatus having the above configuration, the barrier metal film 23 can be formed uniformly and in a thin film shape. For this reason, for example, even a small recess having a width of about several hundreds of nanometers provided on the substrate 3 is accurately formed even inside, and the barrier metal film 23 is formed at high speed in an extremely thin state with excellent embedding property. It becomes possible to do.
[0114]
Further, since the metal member 7 itself is applied as an electrode for generating plasma, a plasma antenna is not required around the cylindrical portion of the chamber 1, and the degree of freedom of the surrounding configuration can be increased.
[0115]
【The invention's effect】
The barrier metal film manufacturing apparatus of the present invention includes a chamber in which a substrate is accommodated, a metal member to be etched provided in a chamber facing the substrate, and a source gas that supplies a source gas containing halogen in the chamber A supply means, a nitrogen-containing gas supply means for supplying a gas containing nitrogen into the chamber, and generating a source gas plasma by converting the inside of the chamber into plasma, and etching the member to be etched by the source gas plasma. A plasma generating means for generating a precursor of a metal component and a raw material gas contained in the member, generating a nitrogen-containing gas plasma by converting the inside of the chamber into a plasma, and generating a metal nitride with the precursor; The barrier metal film is formed on the surface of the substrate by lowering the substrate side temperature lower than the plasma generating means side temperature. The control means for film formation, the rare gas supply means for supplying the rare gas to the upper part of the substrate surface, the inside of the chamber is turned into plasma to generate the rare gas plasma, and nitrogen atoms on the surface layer are removed with the rare gas plasma. Since the surface treatment plasma generating means for performing a surface treatment that relatively reduces the nitrogen content of the surface layer compared to the inside of the base material of the barrier metal film is provided, the metal nitride layer and the metal layer are formed without increasing the film thickness. A barrier metal film made of can be produced. As a result, the barrier metal film can be formed at high speed in an extremely thin state with excellent embedding properties, and the barrier metal film can be formed with excellent adhesion to the metal formed on the surface. A metal film manufacturing apparatus can be obtained.
[0116]
Then, oxygen gas supply means for supplying oxygen gas into the chamber just before the formation of the outermost layer of the barrier metal film and plasma generation inside the chamber to generate oxygen gas plasma to form an oxide layer on the outermost layer of the barrier metal film Since the oxygen plasma generating means is further provided, the wettability when the metal is attached to the surface by the oxide layer can be improved, and the adhesion can be improved.
[0122]
The apparatus further comprises hydrogen gas supply means for supplying hydrogen gas into the chamber and hydroxyl group plasma generation means for generating hydrogen gas plasma by generating plasma in the chamber to form hydroxyl groups in the oxide layer. By doing so, it is possible to improve hydrophilicity, and it is possible to further improve the adhesion when a metal is attached to the surface.
[0123]
In the barrier metal film manufacturing method of the present invention, a source gas containing halogen and a nitrogen-containing gas are supplied into a chamber between a substrate and a metal member to be etched, and the inside of the chamber is turned into plasma to generate source gas plasma. The precursor is generated by etching the member to be etched with source gas plasma to generate a precursor of the metal component and source gas contained in the member to be etched, and generating nitrogen-containing gas plasma by converting the inside of the chamber into plasma. And forming a metal nitride as a barrier metal film on the surface of the substrate by lowering the temperature on the substrate side than the temperature on the plasma generating means side, while forming a chamber above the substrate surface. A rare gas is supplied into the chamber, and the inside of the chamber is turned into a plasma to generate a rare gas plasma. Since the surface treatment is performed to remove and relatively reduce the nitrogen content of the surface layer compared to the inside of the base material of the barrier metal film, the barrier made of the metal nitride layer and the metal layer without increasing the film thickness A metal film can be produced. As a result, the barrier metal film can be formed at high speed in an extremely thin state with excellent embedding properties, and the barrier metal film can be formed with excellent adhesion to the metal formed on the surface. A metal film manufacturing method can be obtained.
[0124]
Then, oxygen gas was supplied into the chamber just before the outermost layer formation of the barrier metal film was completed, and the inside of the chamber was turned into plasma to generate oxygen gas plasma so that an oxide layer was formed on the outermost layer of the barrier metal film. The wettability when a metal is adhered to the surface by the oxide layer can be improved, and the adhesion can be improved.
[0130]
Then, hydrogen gas is supplied into the chamber, and the inside of the chamber is turned into plasma to generate hydrogen gas plasma to form hydroxyl groups in the oxide layer, so that hydrophilicity can be improved and metal is attached to the surface. It becomes possible to further improve the adhesiveness in the case of making it.
[Brief description of the drawings]
FIG. 1 is a schematic side view of a barrier metal film manufacturing apparatus according to a first embodiment of the present invention.
FIG. 2 is a cross-sectional view of a substrate illustrating a barrier metal film.
FIG. 3 is a conceptual diagram of a barrier metal film in a denitrification process.
FIG. 4 is a conceptual diagram of a barrier metal film in a denitrification process.
FIG. 5 is a conceptual diagram of a barrier metal film in an oxide layer forming process.
FIG. 6 is a graph showing the relationship between the contact angle of copper particles and the oxygen concentration of the substrate.
FIG. 7 is a conceptual diagram of a barrier metal film in a hydroxyl group forming process.
FIG. 8 is a schematic configuration diagram illustrating another example of a rare gas supply unit.
FIG. 9 is a schematic configuration diagram of a barrier metal film manufacturing apparatus according to a second embodiment of the present invention.
FIG. 10 is a conceptual diagram of an example in which a barrier metal film is manufactured by the barrier metal film manufacturing apparatus according to the second embodiment of the present invention.
FIG. 11 is a schematic side view of a barrier metal film manufacturing apparatus according to a third embodiment of the present invention.
FIG. 12 is a schematic side view of a barrier metal film manufacturing apparatus according to a fourth embodiment of the present invention.
13 is a view taken along line XIII-XIII in FIG.
14 is a view taken along line XIV-XIV in FIG.
FIG. 15 is a schematic side view of a barrier metal film manufacturing apparatus according to a fifth embodiment of the present invention.
FIG. 16 is a schematic side view of a barrier metal film manufacturing apparatus according to a sixth embodiment of the present invention.
[Explanation of symbols]
1 chamber
2 Support stand
3 Substrate
4,50 heater
5 Refrigerant distribution means
6 Temperature control means
7 Metal parts
8 Vacuum equipment
9, 34, 46, 54 Plasma antenna
10, 35, 57 Matching device
11, 36, 58 Power supply
12 nozzles
13, 37, 55 Flow controller
14 nozzles
15 Oxygen gas nozzle
16 Hydrogen gas nozzle
17 Exhaust port
20 Precursor (MxCly)
21 Noble gas nozzle
22 Control valve
23 Barrier metal film
24 Oxide layer
31, 51 opening
32,52 passage
33,53 Excitation room
38 NH_ThreeGas plasma
41 Ceiling board
42,48 Member to be etched
43 Ring member
44 Protrusion
45 Notch
56 Cl₂Gas plasma (raw material gas plasma)

Claims (12)

A chamber containing a substrate;
A member to be etched provided in a chamber at a position facing the substrate;
A source gas supply means for supplying a source gas containing halogen into the chamber;
Nitrogen-containing gas supply means for supplying a gas containing nitrogen into the chamber;
The inside of the chamber is turned into plasma to generate source gas plasma, and the member to be etched is etched with source gas plasma to generate a precursor of the metal component and source gas contained in the member to be etched, and the inside of the chamber is Plasma generating means for generating nitrogen-containing gas plasma to generate metal nitride with the precursor;
Control means for lowering the temperature on the substrate side to be lower than the temperature on the plasma generating means side and forming a metal nitride as a barrier metal film on the surface of the substrate;
A rare gas supply means for supplying a rare gas to the top of the substrate surface;
The inside of the chamber is turned into plasma to generate a rare gas plasma, and the surface nitrogen treatment is performed to relatively reduce the nitrogen content of the surface layer as compared with the inside of the base material of the barrier metal film by removing nitrogen atoms on the surface layer with the rare gas plasma. A barrier metal film production apparatus comprising a surface treatment plasma generating means. In claim 1,
Oxygen gas supply means for supplying oxygen gas into the chamber just before the outermost layer formation of the barrier metal film is completed,
An apparatus for producing a barrier metal film, further comprising oxygen plasma generating means for generating an oxygen gas plasma by converting the inside of the chamber into plasma and generating an oxygen gas plasma on the outermost layer of the barrier metal film. Oite to claim 2,
Hydrogen gas supply means for supplying hydrogen gas into the chamber;
Internal barrier metal film production apparatus, wherein the plasma to this with further a hydroxyl group plasma generation means to form a hydroxyl group on the oxide layer to generate hydrogen gas plasma chamber. In any one of Claims 1 thru | or 3 ,
The barrier metal film manufacturing apparatus, wherein the halogen-containing source gas is a chlorine-containing source gas. In any one of Claims 1 thru | or 4 ,
A barrier metal film manufacturing apparatus, wherein the nitrogen-containing gas containing nitrogen is a gas containing ammonia. In any one of Claims 1 thru | or 5 ,
A barrier metal film manufacturing apparatus, wherein the member to be etched is tantalum or tungsten, titanium or silicon which is a halide forming metal. Supplying a source gas containing halogen and a nitrogen-containing gas in a chamber between the substrate and the metal member to be etched;
The inside of the chamber is turned into plasma to generate a source gas plasma, and the member to be etched is etched with the source gas plasma to generate a precursor of the metal component and source gas contained in the member to be etched, and the inside of the chamber is plasma. To generate a nitrogen-containing gas plasma to generate metal nitride with the precursor,
The substrate side temperature is made lower than the plasma generating means side temperature to form a metal nitride as a barrier metal film on the substrate surface, while supplying a rare gas into the chamber above the substrate surface,
Surface treatment that reduces the nitrogen content of the surface layer relative to the inside of the base material of the barrier metal film by converting the inside of the chamber into plasma and generating rare gas plasma, removing nitrogen atoms on the surface layer with the rare gas plasma. A method for producing a barrier metal film, characterized by comprising: In claim 7 ,
Supply oxygen gas into the chamber just before the formation of the outermost layer of the barrier metal film,
A method for producing a barrier metal film, wherein the inside of a chamber is converted into plasma to generate oxygen gas plasma to form an oxide layer on the outermost layer of the barrier metal film. In claim 8 ,
Supply hydrogen gas into the chamber,
The barrier metal film production method comprising the hydroxyl group formed child oxide layer to generate hydrogen gas plasma into plasma inside the chamber. In any one of claims 7 to 9,
A method for producing a barrier metal film, wherein the source gas containing halogen is a source gas containing chlorine. In any one of claims 7 to 10,
A method for producing a barrier metal film, wherein the nitrogen-containing gas containing nitrogen is a gas containing ammonia. In any one of claims 7 to 11,
A method for producing a barrier metal film, wherein the member to be etched is tantalum or tungsten, titanium or silicon which is a halide forming metal.

Images