JP3801582B2 - Barrier metal film fabrication method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
  In the present invention, when a metal film is formed on the surface of the substrate, the barrier metal film is formed on the surface of the substrate in order to eliminate the diffusion of the metal to the substrate and maintain the adhesion of the metal.Manufacturing methodRegarding the law.
[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 a physical vapor deposition method such as a diffusion method.
[0004]
Now, in the manufacture of semiconductors and the like, film formation using a plasma CVD (Chemical Vapor Deposition) apparatus is known. A plasma CVD apparatus is a gas that is introduced into a chamber, such as an organometallic complex that becomes a film material, is converted into a plasma state by a high frequency incident from a high frequency antenna, and the substrate surface chemistry is activated by active excited atoms / molecules in the plasma. It is an apparatus for forming a metal thin film or the like by promoting a natural reaction.
[0005]
On the other hand, the present inventors installed a member to be etched containing a metal component desired to be formed in a chamber, and etched the member to be etched with a plasma of a halogen gas to thereby obtain a precursor that is a halide of the metal component. In addition, a plasma CVD apparatus and a film forming method for forming only the metal component of the precursor on the substrate have been developed (see, for example, Patent Document 1).
[0006]
Using this plasma CVD apparatus, the present inventors adopted tantalum, tungsten, or the like as the member to be etched to generate a precursor which is a halide of the tantalum or tungsten component according to the same principle, and by using excited nitrogen. We have developed a barrier metal film production apparatus that generates metal nitride and deposits the metal nitride on a substrate to form a barrier metal film.
[0007]
[Patent Document 1]
JP 2003-147534 A
[0008]
[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. When a metal nitride is used as a barrier metal film, in order to achieve both diffusion resistance and adhesion, a metal nitride part and a metal part are provided, and there is a limit to thinning the barrier metal film. Was the current situation.
[0009]
The present invention has been made in view of the above situation, and 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 barrier metal film at a high speed in an extremely thin state with excellent embedding properties. And
[0010]
The inventors have obtained the following knowledge. That is, the film thickness can be reduced by using tantalum, tungsten, or the like as a barrier metal film with a single layer structure. However, tantalum and tungsten are refractory metals, and when film formation is performed at a low temperature, which is a film formation condition, crystals grow in a columnar shape and a crystal interface is formed in the film thickness direction, affecting the diffusion resistance. End up.
[0011]
Based on the above knowledge, the present invention intends to produce a barrier metal film capable of achieving both diffusion resistance and adhesion even when tantalum, tungsten, or the like is used as a barrier metal film with a single layer structure. To do.
[0023]
[Means for Solving the Problems]
  In order to solve the above-mentioned object, a barrier metal film manufacturing method of the present invention according to claim 1 is provided.
  A source gas containing halogen is supplied into a chamber provided with a substrate and a member to be etched made of a refractory metal, and a small amount of nitrogen is supplied.
  The inside of the chamber is turned into plasma to generate the raw material gas plasma mixed with the trace amount of nitrogen, and the member to be etched is etched with the raw material gas plasma to generate a precursor of the metal component and halogen contained in the member to be etched. ,
  The temperature on the substrate side is lower than the temperature of the member to be etched.while doingWhen depositing the precursor metal component on the substrate as a barrier metal,
  The supply amount of the small amount of nitrogen is set to 1 at% to 3 at% with respect to the amount of the metal component to be formed,
  The columnar interface in the film thickness direction of the crystal formed by film deposition was disturbed by replacing a part of the crystal formed by the film formation with the mixed nitrogen component.
It is characterized by that.
[0024]
  In order to solve the above-mentioned object, a barrier metal film manufacturing method of the present invention according to claim 2 is provided.
  A source gas containing halogen is supplied into a chamber provided with a substrate and a member to be etched made of a refractory metal, and a small amount of argon is supplied.
  The inside of the chamber is turned into plasma to generate a raw material gas plasma mixed with a small amount of argon, and the member to be etched is etched with the raw material gas plasma to generate a precursor of the metal component and halogen contained in the member to be etched. ,
  The temperature on the substrate side is lower than the temperature of the member to be etched.while doingWhen depositing the precursor metal component on the substrate as a barrier metal,
  The supply amount of the small amount of argon is set to 1 at% to 5 at% with respect to the supply amount of halogen,
  The small amount of argon component that has been converted to plasma causes a diffusive action on the crystal due to film formation, and disturbs the columnar interface in the film thickness direction of the crystal due to film formation.
It is characterized by that.
[0026]
  To solve the above purposeClaim 3The barrier metal film production method of the present invention according to
  A site isolated from the chamberTrace amounts of nitrogenThe raw material gas containing the mixed halogen is turned into plasma,
  By excited source gas componentsHigh melting pointBy etching the metal member to be etched, the metal component of the member to be etchedhalogenAnd produce a precursor with
  By making the temperature on the substrate side lower than the temperature of the member to be etchedAt low temperature,The metal component of the precursor is deposited on the substrate as a barrier metal film.When,
  The supply amount of the small amount of nitrogen is set to 1 at% to 3 at% with respect to the amount of the metal component to be formed,
  A part of the crystal formed by the film formation is replaced by the small amount of nitrogen component mixed in, so thatThe columnar interface was disturbed
It is characterized by that.
[0027]
  In order to solve the above object, a barrier metal film manufacturing method of the present invention according to claim 4 is provided.
  The source gas containing halogen mixed with a small amount of argon is isolated from the chamber and turned into plasma,
  Etching a member to be etched made of a refractory metal with the excited source gas component generates a precursor of the metal component and halogen of the member to be etched in the gas phase,
  By lowering the temperature on the substrate side lower than the temperature of the member to be etched, the metal component of the precursor is deposited on the substrate as a barrier metal film at a low temperature.
  The supply amount of the small amount of argon is set to 1 at% to 5 at% with respect to the supply amount of halogen,
  The excited small amount of argon component causes a diffusive action on the crystal due to the film formation, and disturbs the columnar interface in the film thickness direction of the crystal due to the film formation.
It is characterized by that.
  And this invention which concerns on Claim 5 is
  In the barrier metal film preparation method according to any one of claims 1 to 4,
  It is characterized in that the metal component on the surface side of the barrier metal is increased by decreasing the subsequent supply amount stepwise or gradually with respect to the supply amount of nitrogen or argon at the initial stage of film formation.
  The present invention according to claim 6
  In the barrier metal film preparation method according to any one of claims 1 to 5,
  The halogen is chlorine.
  The present invention according to claim 7
  In the barrier metal film preparation method according to any one of claims 1 to 6,
  The refractory metal is tantalum, tungsten, or titanium.AndIt is characterized by doing.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a source gas containing halogen is supplied into a chamber provided with a substrate and a metal member to be etched, and a small amount of inert gas is supplied. A source gas plasma mixed in a minute amount is generated, and the member to be etched is etched with the source gas plasma to generate a precursor of the metal component and the source gas contained in the member to be etched, and the temperature on the substrate side is set to the member to be etched. The metal component of the precursor is deposited on the substrate as a barrier metal by lowering the temperature of the substrate, and the inert gas component is bonded to the metal crystal of the barrier metal to disturb the columnar interface.
[0029]
By binding an inert gas component to the metal crystal of the barrier metal and disturbing the columnar interface, the diffusion resistance of the barrier metal film composed of a single-layer metal component is improved.
[0030]
In addition, a source gas containing halogen is supplied into a chamber provided with a substrate and a metal member to be etched, and a trace amount of inert gas is supplied. The mixed material gas plasma is generated and the member to be etched is etched with the material gas plasma to generate a precursor of the metal component and the material gas contained in the member to be etched, and the substrate side temperature is set to the temperature of the member to be etched. The metal component of the precursor is deposited on the substrate as a barrier metal by making it lower than that, and the columnar interface is disturbed by causing a diffusion (sputtering) action on the metal crystal of the barrier metal by the plasma-induced inert gas component. It is a thing.
[0031]
A diffusion effect is generated in the metal crystal of the barrier metal by the inert gas component converted into plasma to disturb the columnar interface, thereby improving the diffusion resistance of the barrier metal film composed of a single-layer metal component.
[0032]
<First Embodiment>
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 concept showing a film formation state of a tantalum component, FIG. 3 is a concept showing a barrier metal film state, 4 shows the concept of the tantalum crystal state, FIG. 5 shows the relationship between the copper diffusion state and the ratio of the amount of nitrogen to tantalum, and FIG. 6 shows the supply state of nitrogen gas.
[0033]
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 base 2 is provided with a temperature control means 6 including a heater 4 and a refrigerant flow means 5, and the support base 2 is set to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 300 ° C.) by the temperature control means 6. ) Is controlled.
[0034]
The upper surface of the chamber 1 is an opening, and the opening is closed by a plate-like ceiling plate 7 made of an insulating material (for example, made of ceramics). A plasma antenna 8 for converting the inside of the chamber 1 into plasma is provided above the ceiling plate 7, and the plasma antenna 8 is formed in a planar ring shape parallel to the surface of the ceiling plate 7. A matching unit 9 and a power source 10 are connected to the plasma antenna 8 to supply a high frequency current. Plasma generating means is constituted by the plasma antenna 8, the matching unit 9 and the power source 10.
[0035]
An etched member 11 made of tantalum (Ta) as a halide forming metal is held on the upper side of the chamber 1, and the etched member 11 is not between the substrate 3 and the ceiling plate 7 with respect to the electric flow of the plasma antenna 8. They are arranged in a continuous state.
[0036]
For example, the member to be etched 11 includes a rod-shaped protrusion 12 and a ring part 13, and the protrusion 12 is provided on the ring part 13 so as to extend toward the center of the chamber 1. As a result, the member to be etched 11 is structurally discontinuous with respect to the circumferential direction that is the flow direction of electricity of the plasma antenna 8.
[0037]
In addition, as a structure which makes it a discontinuous state with respect to the electric flow of the plasma antenna 8, it is also possible to form a to-be-etched member in a grid | lattice form, or a net | network form.
[0038]
Around the cylindrical portion of the chamber 1, there are a plurality of nozzles 14 for supplying a source gas containing chlorine as a halogen gas into the chamber 1 at equal intervals in the circumferential direction (for example, 8 locations: 2 locations are shown in the figure). Is connected). The raw material gas is sent to the nozzle 14 via the flow rate controller 15. Gases that are not involved in film formation are exhausted from the exhaust port 16.
[0039]
The halogen contained in the source gas is fluorine (F₂), Bromine (Br₂) And iodine (I₂) And the like can be applied.
[0040]
The inside of the chamber 1 closed by the ceiling plate 7 is maintained at a predetermined pressure by the vacuum device 17.
[0041]
On the other hand, the cylindrical portion of the chamber 1 contains nitrogen (N₂) A nozzle 51 for supplying gas is connected. Nozzle 51 is connected to N through flow controller 52₂Gas is sent. The amount of nitrogen supplied (the amount adjusted by the flow rate controller 52) is controlled to 1 at% to 3 at% with respect to the amount of tantalum (Ta) to be deposited.
[0042]
In the above-described embodiment, the example in which the nozzles 51 are provided independently has been described. However, one or more of the nozzles 14 arranged in the circumferential direction of the chamber 1 are N.₂It is also possible to use a nozzle for supplying gas. A small amount of N is added to the raw material gas supplied from the nozzle 14.₂It is also possible to mix gases.
[0043]
In the barrier metal film manufacturing apparatus described above, the source gas 18 is supplied from the nozzle 14 into the chamber 1 and a small amount of N is supplied from the nozzle 51.₂Gas 53 is supplied. By making electromagnetic waves enter the chamber 1 from the plasma antenna 8, the chlorine gas in the raw material gas 18 is ionized to generate chlorine gas plasma. The plasma is generated in the region shown by the gas plasma 19. The reaction at this time can be expressed by the following formula.
Cl₂    → 2Cl^*        (1)
Where Cl^*  Represents a chlorine gas radical.
[0044]
When this gas plasma 19 acts on the member to be etched 11 made of tantalum (Ta), the member to be etched 11 is heated and an etching reaction occurs in tantalum. The reaction at this time is represented by the following formula, for example.
Ta (s) + Cl^*  → TaCl (g) (2)
Here, s represents a solid state and g represents a gas state. Formula (2) is a state in which tantalum is etched by the gas plasma 19 to be a precursor 20.
[0045]
The member to be etched 11 is heated by generating the gas plasma 19 (for example, 300 ° C. to 700 ° C.), and the temperature of the substrate 3 is lower than the temperature of the member to be etched 11 by the temperature control means 6 (for example, 100 ° C. to 100 ° C. 300 ° C). As a result, the precursor 20 is adsorbed on the substrate 3. The reaction at this time is represented by the following formula, for example.
TaCl (g) → TaCl (ad) (3)
Here, ad represents an adsorption state.
[0046]
As shown in FIG. 2A, TaCl adsorbed on the substrate 3 is chlorine gas radical Cl.^*A part of the barrier metal film is formed by being reduced to a Ta component. The reaction at this time is represented by the following formula, for example.
TaCl (ad) + Cl^*  → Ta (s) + Cl₂  ↑ ・ ・ （４）
[0047]
Further, as shown in FIG. 2B, a part of the gasified TaCl generated in the above equation (2) is adsorbed on the substrate 3 (see the above equation (3)) before the chlorine gas radical Cl.^*Is reduced to tantalum in a gas state. The reaction at this time is represented by the following formula, for example.
TaCl (g) + Cl^*  → Ta (g) + Cl₂  ↑ ・ ・ （５）
Thereafter, the Ta component in the gas state is formed on the substrate 3 to form a part of the barrier metal film.
[0048]
Since Ta has a melting point of about 3000 ° C., when it is formed on the substrate 3 set to a temperature lower than the temperature of the member to be etched 11 (for example, 100 ° C. to 300 ° C.), as shown in FIG. The Ta crystal grows in a columnar shape to form the barrier metal film 22 in which the columnar crystal 54 exists in the film thickness direction. When a metal (for example, Cu) film 55 is formed in this state, Cu diffuses to the substrate 3 side through the interface of the columnar crystals 54.
[0049]
In this embodiment, a small amount of nitrogen (N₂) Since the gas is supplied, as shown in FIG. 4, a part of Ta atoms in the Ta crystal lattice is replaced with N atoms, and the nitrogen component is bonded to the Ta crystals of the barrier metal film 22. The columnar interface is disturbed.
[0050]
For this reason, the columnar crystal 54 in the film thickness direction is chemically changed to form a crystal interface also in the plate width direction of the substrate 3, and even if it is a Ta barrier metal film 22 composed of a single layer. The diffusion of Cu to the substrate 3 side can be suppressed.
[0051]
The amount of nitrogen supplied in a minute amount (the amount adjusted by the flow rate controller 52) is controlled to 1 at% to 3 at% with respect to the amount of tantalum (Ta) formed. As shown in FIG. 5, when the amount of nitrogen is less than 1 at%, the columnar interface is not sufficiently disturbed and the amount of diffusion of Cu exceeds the allowable limit. Moreover, even if the nitrogen amount exceeds 3 at%, the diffusion suppression by Ta becomes insufficient, and the diffusion amount of Cu exceeds the allowable limit.
[0052]
Therefore, the amount of nitrogen supplied in a minute amount is set to 1 at% to 3 at% with respect to the amount of tantalum (Ta) to be deposited, and as shown in the figure, the range is 1.5 at% to 2.5 at%. It is less than half of the allowable limit, and is preferable because it has the least amount of Cu diffusion.
[0053]
The amount of diffusion of Cu is estimated by, for example, applying a voltage between the Cu film after film formation and the substrate 3 and then the resistance value (current value) at that time.
[0054]
An example of the supply status of nitrogen gas supplied in a minute amount will be described with reference to FIG.
[0055]
As shown by a solid line in FIG. 6, nitrogen gas can be supplied in a uniform amount from the start of the formation of the barrier metal film 22. By supplying a uniform amount, nitrogen gas can be supplied with a simple flow rate control.
[0056]
As shown by a dotted line in FIG. 6, a predetermined amount of nitrogen gas can be supplied for a predetermined time from the start of the formation of the barrier metal film 22, and the nitrogen gas amount can be decreased and supplied at a predetermined time. As a result, the amount of Ta in the vicinity of the surface of the barrier metal film 22 can be increased to improve the adhesion while maintaining the diffusion resistance.
[0057]
As indicated by a one-dot chain line in FIG. 6, the nitrogen gas can be supplied in a state of gradually decreasing from the initial stage of the formation of the barrier metal film 22. Thereby, the amount of Ta on the surface side of the barrier metal film 22 can be gradually increased with respect to the substrate 3 side to improve the adhesion while maintaining the diffusion resistance.
[0058]
By forming the barrier metal film 22 with the barrier metal manufacturing apparatus described above, the columnar interface can be disturbed by binding a nitrogen component to the Ta crystal of the barrier metal. Therefore, diffusion of Cu can be suppressed and the diffusion resistance of the barrier metal film 22 composed of a single layer Ta component can be improved.
[0059]
<Second Embodiment>
FIG. 7 is a schematic side view of a barrier metal film manufacturing apparatus according to the second embodiment of the present invention, FIG. 8 is a concept showing a film formation state of a tantalum component, and FIG. 9 is an argon with respect to copper diffusion state and chlorine content. The relationship with the proportion of quantity is shown. The same members as those shown in FIG. 1 are denoted by the same reference numerals, and redundant description is omitted.
[0060]
The barrier metal film manufacturing apparatus according to the second embodiment has the same apparatus configuration as the barrier metal film manufacturing apparatus shown in FIG. Then, Ar gas is sent to the nozzle 51 via the flow rate controller 52. The amount of Ar supplied (the amount adjusted by the flow rate controller 52) is Cl of chlorine gas which is a raw material gas.₂The amount is controlled to 1 at% to 5 at%.
[0061]
In the barrier metal film manufacturing apparatus described above, the source gas 18 is supplied from the nozzle 14 into the chamber 1 and a small amount of Ar gas 61 is supplied from the nozzle 51. By making electromagnetic waves enter the chamber 1 from the plasma antenna 8, the chlorine gas in the raw material gas 18 is ionized to generate chlorine gas plasma. Also, Ar gas is ionized to generate a small amount of Ar gas plasma.
[0062]
The member to be etched 11 is heated by generating the gas plasma 19 (for example, 200 ° C. to 400 ° C.), and the temperature of the substrate 3 is further lowered by the temperature control means 6 (for example, 100 ° C. to 100 ° C.). 200 ° C.). As a result, the precursor 20 is adsorbed on the substrate 3.
[0063]
As shown in FIG. 8A, TaCl adsorbed on the substrate 3 is chlorine gas radical Cl.^*A part of the barrier metal film is formed by being reduced to a Ta component. Further, as shown in FIG. 2B, a part of the gasified TaCl is adsorbed on the substrate 3 before being adsorbed on the substrate 3.^*After this, the tantalum in the gas state is reduced to the gaseous tantalum, and the Ta component in the gas state is formed on the substrate 3 to form a part of the barrier metal film.
[0064]
Since Ta has a melting point of about 3000 ° C., when it is formed on the substrate 3 set at a temperature lower than the temperature of the member to be etched 11 (for example, 100 ° C. to 300 ° C.), the Ta crystal becomes columnar. Thus, the barrier metal film 22 is grown and has columnar crystals 54 in the film thickness direction. When a metal (for example, Cu) film 55 is formed in this state, Cu diffuses to the substrate 3 side through the interface of the columnar crystals 54.
[0065]
In the present embodiment, since a small amount of Ar gas is supplied into the chamber 1 to generate Ar gas plasma, Ar gas radical Ar^*As a result, a diffusion effect occurs in the Ta columnar crystal 54 and the columnar interface is disturbed.
[0066]
For this reason, the columnar crystal 54 in the film thickness direction is physically changed and the columnar crystal 54 is broken, and even if it is a Ta barrier metal film 22 composed of a single layer, it is on the Cu substrate 3 side. Can be prevented from spreading.
[0067]
The amount of Ar supplied in a minute amount (the amount adjusted by the flow controller 52) is Cl of chlorine gas which is a raw material gas.₂The amount is controlled to 1 at% to 5 at%. As shown in FIG. 9, when the amount of Ar is less than 1 at%, the diffusion effect is insufficient and the columnar interface is not sufficiently disturbed, and the amount of diffusion of Cu exceeds the allowable limit. Moreover, even if the amount of Ar exceeds 5 at%, the amount of diffusion increases and diffusion suppression by Ta becomes insufficient, and the amount of diffusion of Cu exceeds the allowable limit.
[0068]
Therefore, the amount of Ar supplied in a minute amount is Cl of chlorine gas which is a raw material gas.₂The amount is set at 1 at% to 5 at% with respect to the amount, and as shown in the figure, the range of 1.5 at% to 4.5 at% is less than half of the allowable limit, and the amount of diffusion of Cu is the smallest.
[0069]
As described above, the amount of diffusion of Cu is estimated from, for example, a resistance value (current value) when a voltage is applied between the Cu film after film formation and the substrate 3.
[0070]
As in the case of the nitrogen gas described above, the supply status of the example shown in FIG. 6 can be applied to the amount of Ar supplied in a minute amount.
[0071]
By producing the barrier metal film 22 with the barrier metal producing apparatus described above, Ar gas radical Ar is formed on the Ta crystal of the barrier metal.^*Can cause a diffusion effect to disturb the columnar interface. Therefore, diffusion of Cu can be suppressed and the diffusion resistance of the barrier metal film 22 composed of a single layer Ta component can be improved.
[0072]
Another embodiment of the barrier metal film manufacturing apparatus will be described with reference to FIGS. 10 to 12 show a schematic configuration of a barrier metal film manufacturing apparatus according to another embodiment of the present invention.
[0073]
In the apparatus shown in FIG. 10, the ceiling plate 60 is made of a member to be etched, and a coil-shaped plasma antenna 62 is installed around the outside of the side wall of the cylindrical portion of the chamber 1 to generate plasma.
[0074]
The apparatus shown in FIG. 11 has a configuration in which the ceiling plate 65 is made of a member to be etched, the substrate 3 side is grounded, and power is supplied to the ceiling plate 65 to generate capacitive plasma.
[0075]
The apparatus shown in FIG. 12 is provided with a cylindrical passage (external plasma generation chamber) 66 communicating with the inside of the chamber 1, and a coiled plasma antenna 67 is installed around the passage 66. The generated plasma is used for film formation.
[0098]
【The invention's effect】
  The barrier metal film production method of the present invention according to claim 1 comprises:
  A source gas containing halogen is supplied into a chamber provided with a substrate and a member to be etched made of a refractory metal, and a small amount of nitrogen is supplied.
  The inside of the chamber is turned into plasma to generate the raw material gas plasma mixed with the trace amount of nitrogen, and the member to be etched is etched with the raw material gas plasma to generate a precursor of the metal component and halogen contained in the member to be etched. ,
  The temperature on the substrate side is lower than the temperature of the member to be etched.while doingWhen depositing the precursor metal component on the substrate as a barrier metal,
  The supply amount of the small amount of nitrogen is set to 1 at% to 3 at% with respect to the amount of the metal component to be formed,
  The columnar interface in the film thickness direction of the crystal formed by film deposition was disturbed by replacing a part of the crystal formed by the film formation with the mixed nitrogen component.
It is characterized by that.
[0099]
  For this reason, it is possible to provide a barrier metal film manufacturing method that is excellent in embeddability and capable of forming a barrier metal film at a high speed in an extremely thin state. Even if it exists, it becomes possible to produce the barrier metal film which can make diffusion resistance and adhesiveness compatible.
  Further, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion using nitrogen.
[0100]
  The barrier metal film production method of the present invention according to claim 2 comprises:
  A source gas containing halogen is supplied into a chamber provided with a substrate and a member to be etched made of a refractory metal, and a small amount of argon is supplied.
  The inside of the chamber is turned into plasma to generate a raw material gas plasma mixed with a small amount of argon, and the member to be etched is etched with the raw material gas plasma to generate a precursor of the metal component and halogen contained in the member to be etched. ,
  The temperature on the substrate side is lower than the temperature of the member to be etched.while doingWhen depositing the precursor metal component on the substrate as a barrier metal,
  The supply amount of the small amount of argon is set to 1 at% to 5 at% with respect to the supply amount of halogen,
  The small amount of argon component that has been converted to plasma causes a diffusive action on the crystal due to film formation, and disturbs the columnar interface in the film thickness direction of the crystal due to film formation.
It is characterized by that.
[0101]
  For this reason, it is possible to provide a barrier metal film manufacturing method that is excellent in embeddability and capable of forming a barrier metal film at a high speed in an extremely thin state. Even if it exists, it becomes possible to produce the barrier metal film which can make diffusion resistance and adhesiveness compatible.
  Moreover, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion by using argon.
[0104]
  Claim 3The barrier metal film production method of the present invention according to
  A site isolated from the chamberTrace amounts of nitrogenThe raw material gas containing the mixed halogen is turned into plasma,
  By excited source gas componentsHigh melting pointBy etching the metal member to be etched, the metal component of the member to be etchedhalogenAnd produce a precursor with
  By making the temperature on the substrate side lower than the temperature of the member to be etchedAt low temperature,The metal component of the precursor is deposited on the substrate as a barrier metal film.When,
  The supply amount of the small amount of nitrogen is set to 1 at% to 3 at% with respect to the amount of the metal component to be formed,
  A part of the crystal formed by the film formation is replaced by the small amount of nitrogen component mixed in, so thatThe columnar interface was disturbed
It is characterized by that.
[0105]
  For this reason, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion without exposing the substrate to plasma.
  Further, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion using nitrogen.
[0106]
  Claim 4The barrier metal film production method of the present invention according to
  A site isolated from the chamberA small amount of argonThe raw material gas containing the mixed halogen is turned into plasma,
  By excited source gas componentsHigh melting pointBy etching the metal member to be etched, the metal component of the member to be etchedhalogenAnd produce a precursor with
  By making the temperature on the substrate side lower than the temperature of the member to be etchedAt low temperature,The metal component of the precursor is deposited on the substrate as a barrier metal film.When,
  The supply amount of the small amount of argon is set to 1 at% to 5 at% with respect to the supply amount of halogen,
  ExcitedThe trace amount of argonBy ingredientsCrystal by film formationCause a diffusion effectIn the film thickness direction of the crystalThe columnar interface was disturbed
It is characterized by that.
[0107]
  For this reason, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion without exposing the substrate to plasma.
  Moreover, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion by using argon.
  And the barrier metal film preparation method of the present invention according to claim 5 comprises:
  In the barrier metal film preparation method according to any one of claims 1 to 4,
  It is characterized in that the metal component on the surface side of the barrier metal is increased by decreasing the subsequent supply amount stepwise or gradually with respect to the supply amount of nitrogen or argon at the initial stage of film formation.
  For this reason, it becomes possible to produce a barrier metal film capable of achieving both high diffusion resistance and adhesion.
  Moreover, the barrier metal film manufacturing method of the present invention according to claim 6 comprises:
  In the barrier metal film preparation method according to any one of claims 1 to 5,
  The halogen is chlorine.
  For this reason, it becomes possible to produce a barrier metal film that can achieve both diffusion resistance and adhesion using inexpensive chlorine gas.
  Moreover, the barrier metal film manufacturing method of the present invention according to claim 7 is
  In the barrier metal film preparation method according to any one of claims 1 to 6,
  The refractory metal is tantalum, tungsten, or titanium.AndIt is characterized by doing.
  Therefore, tantalum or tungsten, titaniumTheIt becomes possible to produce a barrier metal film capable of achieving both diffusion resistance and adhesion as components.
[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 conceptual diagram showing a film formation state of a tantalum component.
FIG. 3 is a conceptual diagram showing the state of a barrier metal film.
FIG. 4 is a conceptual diagram showing a crystal state of tantalum.
FIG. 5 is a graph showing the relationship between the diffusion state of copper and the ratio of the amount of nitrogen to tantalum.
FIG. 6 is a graph showing the supply status of nitrogen gas.
FIG. 7 is a schematic side view of a barrier metal film manufacturing apparatus according to a second embodiment of the present invention.
FIG. 8 is a conceptual diagram showing a film formation state of a tantalum component.
FIG. 9 is a graph showing the relationship between the copper diffusion state and the ratio of the argon amount to the chlorine amount.
FIG. 10 is a schematic configuration diagram of a barrier metal film manufacturing apparatus according to another embodiment of the present invention.
FIG. 11 is a schematic configuration diagram of a barrier metal film manufacturing apparatus according to another embodiment of the present invention.
FIG. 12 is a schematic configuration diagram of a barrier metal film manufacturing apparatus according to another embodiment of the present invention.
[Explanation of symbols]
1 chamber
2 Support stand
3 Substrate
4 Heater
5 Refrigerant distribution means
6 Temperature control means
7, 65 Ceiling board
8, 62, 67 Plasma antenna
9 Matching device
10 Power supply
11 Member to be etched
12 Protrusion
13 Ring part
14 nozzles
15, 51 Flow controller
16 Exhaust port
17 Vacuum equipment
18 Source gas
19 Gas plasma
20 Precursor
51 nozzles
55 Membrane
66 Passage

Claims (7)

A source gas containing halogen is supplied into a chamber provided with a substrate and a member to be etched made of a refractory metal, and a small amount of nitrogen is supplied.
The inside of the chamber is turned into plasma to generate the raw material gas plasma mixed with the trace amount of nitrogen, and the member to be etched is etched with the raw material gas plasma to generate a precursor of the metal component and halogen contained in the member to be etched. ,
While the temperature of the substrate side to be lower than the temperature of the etched member, when to be deposited on the substrate the metal component of the precursor as a barrier metal,
The supply amount of the small amount of nitrogen is set to 1 at% to 3 at% with respect to the amount of the metal component to be formed,
A method for producing a barrier metal film, comprising replacing a part of a crystal formed by film formation with the minute amount of nitrogen component mixed therein to disturb a columnar interface in a film thickness direction of the crystal formed by film formation. A source gas containing halogen is supplied into a chamber provided with a substrate and a member to be etched made of a refractory metal, and a small amount of argon is supplied.
The inside of the chamber is turned into plasma to generate the raw material gas plasma mixed with the trace amount of argon, and the member to be etched is etched with the raw material gas plasma to generate a precursor of the metal component and halogen contained in the member to be etched. ,
While the temperature of the substrate side to be lower than the temperature of the etched member, when to be deposited on the substrate the metal component of the precursor as a barrier metal,
The supply amount of the small amount of argon is set to 1 at% to 5 at% with respect to the supply amount of halogen,
A barrier metal film manufacturing method, characterized in that a diffusive action is produced in a crystal formed by film formation by the trace amount of argon component formed into plasma, thereby disturbing a columnar interface in the film thickness direction of the crystal formed by film formation. A source gas containing halogen mixed with a trace amount of nitrogen is isolated from the chamber and turned into plasma,
Etching a member to be etched made of a refractory metal with the excited source gas component generates a precursor of the metal component and halogen of the member to be etched in the gas phase,
By lowering the temperature on the substrate side lower than the temperature of the member to be etched, the metal component of the precursor is deposited on the substrate as a barrier metal film at a low temperature.
The supply amount of the small amount of nitrogen is set to 1 at% to 3 at% with respect to the amount of the metal component to be formed,
A method for producing a barrier metal film, comprising replacing a part of a crystal formed by film formation with the minute amount of nitrogen component mixed therein to disturb a columnar interface in a film thickness direction of the crystal formed by film formation. The source gas containing halogen mixed with a small amount of argon is isolated from the chamber and turned into plasma,
Etching a member to be etched made of a refractory metal with the excited source gas component generates a precursor of the metal component and halogen of the member to be etched in the gas phase,
By lowering the temperature on the substrate side lower than the temperature of the member to be etched, the metal component of the precursor is deposited on the substrate as a barrier metal film at a low temperature.
The supply amount of the small amount of argon is set to 1 at% to 5 at% with respect to the supply amount of halogen,
A barrier metal film manufacturing method, characterized in that a diffusive action is produced in a crystal by film formation by the excited small amount of argon component to disturb a columnar interface in the film thickness direction of the crystal by film formation. In the barrier metal film preparation method according to any one of claims 1 to 4,
A barrier metal film manufacturing method characterized by increasing the metal component on the surface side of the barrier metal by gradually or gradually decreasing the subsequent supply amount with respect to the initial supply amount of nitrogen or argon. In the barrier metal film preparation method according to any one of claims 1 to 5,
A method for producing a barrier metal film, wherein the halogen is chlorine. In the barrier metal film preparation method according to any one of claims 1 to 6,
The barrier metal film production method which is characterized in that the high melting point metal, tantalum or tungsten, and titanium emissions.

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