JP2006093550A - Method of forming vanadium content film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming a vanadium content film as a base layer having a sufficient characteristic by a CVD method. <P>SOLUTION: The vanadium content film is formed by the CVD method by using metal material gas and reducing gas such as TDEAV or TDMAV. Reducing gas deviates, can discharge H<SP>*</SP>radicals and H<SP>+</SP>ions, and is selected from tertiary butyl hydrazine, NH<SB>3</SB>and H<SB>2</SB>, for example. Reaction of metal material gas and reducing gas is performed in a temperature region where film forming speed depends on a substrate temperature. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a vanadium-containing film, and more particularly to a method for forming a vanadium-containing film useful as an underlayer by a CVD method.

  In wiring for manufacturing a semiconductor element (LSI, IC, etc.), it is common to form a barrier layer and / or an adhesion layer as a base layer in a contact hole or groove connecting a lower wiring and an upper wiring. This barrier layer is intended to prevent the wiring material and the insulating material from diffusing each other and the characteristics of the semiconductor element from deteriorating, and the adhesion layer is peeled off at the interface between the wiring material and the insulating material. For the purpose of preventing the occurrence, it is often provided between the wiring material and the insulating material.

  In recent years, it has been proposed to use copper having a lower resistivity as a wiring material in contact holes and grooves instead of conventional Al. In this case, a barrier layer is formed between the silicon oxide film or the like and the copper wiring in order to prevent copper from diffusing into an insulating layer such as a silicon oxide film that becomes a base layer of the copper wiring.

  Incidentally, a plating method has been conventionally used for forming the copper wiring. However, in recent years, with the shrinking of wiring scales such as LSIs, the size of contact holes and the like has become elongated, and there has been a problem that it is difficult for the plating solution to enter the interior of elongated holes with a high aspect ratio. It is difficult to form copper wiring.

  Therefore, as a copper wiring forming method replacing the plating method, a method using a gas typified by a CVD method is currently being studied.

  However, in the copper wiring formation process using the CVD method, the film formation is greatly influenced by the surface characteristics of the underlying material, and (1) it is difficult to form initial nuclei and takes time, and (2) island-like There is a problem that it is easy to grow, and it is difficult to form a continuous thin film. For this reason, when the hole diameter is 0.2 μm or less and the groove width is 0.2 μm or less, when the aspect ratio is 4 or more, voids are generated when filling holes or the like, and complete filling cannot be performed. . This makes it difficult to fill holes and grooves with a diameter of 0.1 μm or less, which makes it difficult to fill holes by plating, and may cause a serious problem in the future. Furthermore, the influence of the surface characteristics of the base material also leads to a problem that it is difficult to achieve close contact between the copper-containing film and the base layer such as a barrier layer.

  Therefore, in order to form a copper-containing film as a continuous thin film by the CVD method, it is necessary to accelerate the nucleation at the initial stage of the film formation process and to increase the nucleation density. The layer (adhesion layer) is important. At the same time, good adhesion between the underlying layer and the copper-containing film is also important for forming the copper-containing film.

  When a copper thin film formed by a CVD method is used as a wiring, a vanadium nitride film is formed by a reactive sputtering method or a CVD method in order to form a barrier layer having good adhesion to the thin film and low internal stress. It is known (see, for example, Patent Document 1). In this case, it is difficult for the reactive sputtering method to form a uniform thin film in elongated contact holes and grooves, and the CVD method uses bis (cyclopentadienyl) vanadium (III) as a source gas. In fact, a good barrier layer, for example, a barrier layer excellent in step coverage is not obtained.

On the other hand, in a method in which film-forming particles have a certain directionality, such as sputtering or vapor deposition, a film-forming part that is at an angle with the flight direction of the particle, or a film-forming part that is invisible from the particle source, for example, It is difficult to attach films to contact holes and sidewalls of trenches, and it is difficult to form uniform films (step coverage) on complex structures, especially as the structure becomes finer as technology advances. .
JP 2003-17437 A (Claims)

  Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and by using a specific raw material, it is possible to form a continuous copper-containing thin film with good characteristics, for example, by a post process by a CVD method. An object of the present invention is to provide a method for forming a vanadium-containing film, particularly a vanadium-containing film having excellent step coverage and having good adhesion to a copper-containing film.

  The method for forming a vanadium-containing film of the present invention is characterized in that a vanadium-containing film is formed on a film formation object by a CVD method using a tetravalent amide-based vanadium organometallic source gas and a reducing gas. . Thereby, it is a vanadium containing film | membrane which can form a continuous copper containing thin film at a post process, Comprising: While being excellent in level | step difference covering property, a vanadium containing film | membrane which has favorable adhesiveness with a copper containing film | membrane can be formed.

  The tetravalent amide-based vanadium organometallic raw material is preferably tetrakisdiethylaminovanadium (TDEAV), tetrakisdimethylaminovanadium (TDMV), or tetrakisethylmethylaminovanadium.

The reducing gas is preferably a gas that can be released to release H ^* radicals and H ⁺ ions. For example, a gas selected from hydrazine derivatives, NH ₃ , H ₂ , SiH ₄ and Si ₂ H ₆ is preferable. This hydrazine derivative is preferably one obtained by substituting one or two hydrogen atoms of hydrazine with a methyl group, an ethyl group, a linear or branched butyl group, and reacts with TDEAV, TDAV, or the like to perform nitriding. Tertiary butyl hydrazine (TBH) that can be promoted is particularly preferred.

  It is preferable that the reaction between the tetravalent amide-based vanadium organometallic source gas and the reducing gas is performed in a temperature range in which the film formation rate depends on the temperature of the film formation target to form a vanadium-containing film.

  According to the present invention, an underlayer (barrier layer and / or adhesive layer) suitable for forming a copper-containing film in a subsequent step can be obtained. That is, it is possible to obtain a barrier layer in which the wiring material and the insulating material do not diffuse each other, and an adhesion layer in which film peeling does not occur at the interface between the wiring material and the insulating material.

  In addition, the formation of initial nuclei can be easily performed in a short time in the subsequent CVD process using a copper-containing film, and the nucleation density is high, so a continuous copper-containing film can be easily formed. In addition, it is possible to efficiently form an underlayer that can be easily adhered to the obtained copper-containing film.

  Furthermore, it is possible to uniformly cover a complicated structure, for example, a hole or groove having a high aspect ratio, including the side wall portion, and the effect of excellent step coverage is achieved. As a result, the wiring material can be uniformly embedded in the hole or the like in a later process.

  First, one structural example of a CVD apparatus for carrying out the vanadium-containing film forming method of the present invention will be described with reference to the drawings.

The CVD apparatus shown in FIG. 1 includes a gas supply apparatus 1 for supplying a gas such as a carrier gas (for example, N ₂ , Ar, He) or a reducing gas (for example, NH ₃ , H ₂ ), and a film formation. It comprises a raw material supply device 2 for supplying raw materials, a reaction device 3 for forming a metal-containing film, and a discharge device 4 for discharging raw materials and gases.

  The gas supply device 1 controls the flow rate of each gas from a carrier gas source and a reducing gas source through a mass flow controller (indicated as MFC1 and MFC2 in the figure), and in the reactor 3 through a pipe. Has the function of transporting to

  The raw material supply device 2 has a function of transporting the raw material into the reaction chamber 301 of the reaction device 3 while controlling the supply flow rate and supply pressure of the raw material 202 in the raw material container 201. According to FIG. 1, this raw material supply apparatus can be used as a liquid or solid raw material at room temperature, for example, an organic metal material for forming a vanadium film such as TDEAV or TDMV, or a hydrazine derivative (for example, tertiary butyl hydrazine (TBH)). Etc.) is used to gasify the gas through the vaporizer 203 and introduce the gas into the reactor 3. In FIG. 1 showing one of the basic components of this raw material supply apparatus, the supply flow rate and supply pressure are indicated by mass flow controllers (indicated by L-MFC and MFC3 in FIG. 1) and pressure gauges (indicated by 204 and 205 in FIG. 1). ) Can be transported to the reaction chamber 301 while being controlled via the above-described control. Each component such as a raw material transport pipe and a valve from the raw material container 201 to the shower plate 302 of the reactor 3 is temperature-controlled. The temperature control range is preferably about room temperature to about 270 ° C. Thereby, it can control so that source gas does not liquefy and precipitate.

The reactor 3 is a shower for appropriately supplying the substrate S with the source gas, reducing gas and carrier gas supplied from the source supply device 2 and the carrier gas and reducing gas supplied from the gas supply device 1. A plate 302, a reaction chamber 301 for maintaining a film-forming atmosphere in the vicinity of the substrate S, a substrate mounting table 303 (provided with a heating means not shown) on which the substrate S can be installed and heated. A partition valve 304 for partitioning the atmosphere with the adjacent substrate transfer chamber and the like, and a pressure gauge 305 for monitoring the pressure of the film forming atmosphere. This shower plate 302 is made of metal (for example, stainless steel, Al, Al alloy, Hastelloy (registered trademark), Inconel (manufactured by Canada Inco (INCO)), etc.), and temperature controlled in the range of room temperature to 250 ° C. It is preferable to do. The reaction chamber 301 is made of metal (for example, stainless steel, Al, Al alloy, Hastelloy, Inconel, etc.), and is preferably temperature controlled in the range of room temperature to 250 ° C. The substrate mounting table 303 can be made of metal (eg, stainless steel, Al, Al alloy, Hastelloy, Inconel, etc.) or ceramics (eg, Al ₂ O ₃ , AlN, SiN, SiC, SiO _2, etc.). Ceramics are preferred, and among ceramics, it is preferable to produce AlN with good thermal conductivity and good temperature distribution even at high temperatures. The substrate mounting table 303 made of AlN can cope with heating at room temperature to 600 ° C. The partition valve 304 is made of metal (for example, stainless steel, Al, Al alloy, Hastelloy, Inconel, etc.), and a temperature monitor and heating means such as a heater are installed inside and outside the valve. The temperature can be controlled with this. The pressure gauge 305 uses a high temperature type.

  The discharge device 4 is a device that adjusts the atmosphere in the reaction chamber 301. The basic structure is composed of a pipe, a discharge valve 401, a pressure control valve 402, a raw material trap 403, and a vacuum pump 404, as illustrated in FIG. The components from the reaction chamber 301 to the vacuum pump 404 are temperature controlled, and the control range is preferably room temperature to 250 ° C. Based on the value of the pressure gauge 305 provided in the reaction chamber 301, the pressure control valve 402 can be opened and closed in conjunction with each other so as to have an arbitrary set value. Further, by providing the pipe 5 that can transport the raw material gas exiting the raw material supply device 2 to the raw material trap 403 of the discharge device 4, the raw material gas is stabilized when the supply amount of the raw material gas transported from the raw material supply device 2 is stabilized. Thus, it is possible to stably supply the source gas into the reaction chamber 301 by switching the transport route to the reaction chamber 301 side. Further, when the supply of the source gas is completed, the gas supply to the reaction chamber 301 can be immediately stopped by switching the source gas to the source trap 403 through the pipe 5. This raw material trap 403 is a device having a function of collecting the discharged raw material gas, and is effective in reducing the load on the vacuum pump 404 (clogging inside the pump) and reusing the raw material. In order to increase the exhaust capability of the vacuum pump 404 shown in FIG. 1, a second vacuum pump may be installed between the pressure control valve 402 and the vacuum pump 404.

  The raw material supply apparatus can be used in the present invention as long as it has a structure as shown in FIGS. In any configuration including FIG. 1, the supply flow rate and the supply pressure are indicated by mass flow controllers (indicated by L-MFC, MFC3, and MFC4 in FIGS. 2 to 4) and pressure gauges (204 and 205 in FIGS. 2 to 4). The raw material gas can be transported into the reaction chamber 301 while being controlled via Although the vaporizer is not shown, it can be provided at any time.

In the raw material supply apparatus 2 shown in FIG. 2, the raw material 202 in the raw material container 201 is transported to the reaction chamber 301 via a mass flow controller (L-MFC) by a pressurized gas (N ₂ , Ar, He, etc.) at a predetermined pressure. It is configured to be able to. The raw material supply apparatus 2 shown in FIG. 3 is configured so that a carrier gas and a reducing gas at a predetermined pressure can be transported into the reaction chamber 301 together with the raw material 202 in the raw material container 201 via the mass flow controller (MFC3). . The raw material supply apparatus 2 shown in FIG. 4 is configured so that the raw material 202 in the raw material container 201 can be transported into the reaction chamber 301 via the mass flow controller (MFC4).

The metal raw material that can be used in the present invention is preferably a tetravalent amide-based vanadium organometallic raw material. For example, V [NR ¹ R ² ] ₄ , V [NR ¹ R ² ] ₃ · Cl, V [NR ¹ R ² ] ₂ · Cl ₂ , V [NR ¹ R ² ] · Cl _{3 and the} like can be used. Here, R ¹ and R ² may be the same or different, and C _n H _{2n + 1} (n = 0 to 4), C _m H _2m O (m = 0 to 4). ), CH ₂ OH or a phenyl group. Cl may be a halogen atom other than this. Among these metal raw materials, the above-described TDEAV and TDMV are more preferable.

Examples of the reducing gas include gases that can dissociate to release H ^* radicals and H ⁺ ions, such as hydrazine derivatives (eg, tertiary butyl hydrazine (TBH): (CH ₃ ) ₃ CNHNH ₂ ), NH _3. , H ₂ , SiH ₄ or the like can be used. Other hydrazine derivatives (eg, one or two H substituted with an alkyl group such as methyl, ethyl, butyl, etc.) can also be used. Of these reducing gases, gases (TBH and NH ₃ ) that can promote nitridation when reacting with the TDEAV gas to form a vanadium-containing film are preferable.

  Although the supply ratio of the reducing gas with respect to the organometallic raw material is not particularly limited, in the present invention, a desired purpose can be achieved with about 2 to 20.

As the carrier gas, it is possible to use for example argon, an inert gas such as rare gas or N _2, such as helium.

The film formation target that can be used in the present invention is not particularly limited as long as it is a semiconductor manufacturing substrate. For example, a SiO ₂ / Si substrate that may have holes and grooves formed therein is the following example. However, other than this, a Low-k substrate may be used. As this Low-k substrate, SiOC type (for example, trade name Black Diamond (manufactured by AMAT), Coral (manufactured by Novellus), Aurola (manufactured by ASM), Orion (manufactured by TRIKON), SiLK (manufactured by Dow Chemical) ), FLARE (Honeywell Electric Materials)), SiOF, HSQ, MSQ, NCS (Nano Crystal Silica (Fujitsu)), and the like.
Next, examples of the present invention performed using the above CVD apparatus will be described.

  In this example, a vanadium-containing film was formed under the following conditions using the CVD apparatus shown in FIG.

First, the partition valve 304 of the reaction apparatus 3 was opened, and the substrate S was transferred into the reaction chamber using a robot in a chamber adjacent to the reaction chamber 301. During this transfer, gas existing in the air such as carbon-containing gas (CO or CO ₂ ), oxygen-containing gas (O ₂ ), water (H ₂ O) or the like adheres to the surface of the substrate S during the transfer. In order to avoid diffusing inside the substrate, it is desirable to carry out in a vacuum.

  The substrate S transported into the reaction chamber 301 was placed on the substrate mounting table provided with heating means in the reaction chamber with the main surface of the substrate S being the shower plate 302 side and the back surface being the substrate mounting table 303 side. .

Next, N ₂ gas is controlled from the gas supply device 1 to a flow rate of 1500 sccm through the MFC 1 to flow into the reaction chamber 301, and the pressure in the reaction chamber is maintained at the film formation pressure so as to reach a predetermined substrate temperature. Heated. After 1 to 10 minutes, film formation was started according to the following film formation conditions.

Substrate: 8-inch wafer (SiO ₂ / Si)
When TDEAV (tetrakisdiethylaminovanadium: V [N (C ₂ H ₅ ) ₂ ] ₄ ) is used as the organometallic raw material:
TDEAV supply amount: 84mg / min
TDEAV carrier N ₂ : 400 sccm
Reducing gas (TBH, NH ₃ ) flow rate: 22 sccm
Supply molar ratio of reducing gas to organometallic raw material: 4
Carrier N ₂ : 1500sccm
Substrate temperature: 300-550 ° C
Deposition pressure: 340Pa
Deposition time: 1-60 min
When TDMV (tetrakisdimethylaminovanadium: V [N (CH ₃ ) ₂ ] ₄ ) is used as the organometallic raw material:
TDMV supply: 56 mg / min
TDMV carrier N ₂ : 400 sccm
Reducing gas (TBH, NH ₃ ) flow rate: 22 sccm
Supply molar ratio of reducing gas to organometallic raw material: 4
Carrier N ₂ : 1500sccm
Substrate temperature: 200-450 ° C
Deposition pressure: 340Pa
Deposition time: 1-60 min

  5A and 5B show the results of forming the vanadium-containing film under the above film forming conditions and summing up the substrate temperature dependence of the film deposition rate in the Arrhenius plot. Based on FIG. 5, combinations of metal raw materials and reducing gases that have a temperature region in which the film formation rate depends on the substrate temperature (so-called surface reaction rate limiting) are shown in Table 1 below. In Table 1, ◯ indicates that the activation energy has an inclination within the range of the substrate temperature (deposition temperature). That is, it shows that the film formation rate depends on the substrate temperature.

(Table 1)

  5 (a) and 5 (b) and Table 1, it can be seen that there is a surface reaction-controlled temperature range in any metal raw material. In addition, when the reducing gas is used, the surface reaction-controlled temperature range becomes narrower than when the reducing gas is not used. As is apparent from FIGS. 5A and 5B, a temperature range in which the film deposition rate does not depend on the substrate temperature is excluded, and a practical film deposition rate (0.1 nm / min or more) is ensured. It can be seen that the temperature that can be used is 300 to 500 ° C. when using TDEAV, and 200 to 400 ° C. when using TDMV.

The step coverage was evaluated using holes having a diameter of 0.2 μm and a depth of 1 μm at 300 ° C. and 350 ° C. in the surface reaction-controlled temperature range obtained in Example 1. In this case, the TDMAV and TDEAV as metal source, also with NH ₃ and TBH as nitride raw material is a reducing gas, was formed according to the method of Example 1. For comparison, a film was similarly formed when no reducing gas was used, and the step coverage was evaluated. The result is shown as a cross-sectional SEM photograph in FIG.

  As is apparent from FIG. 6, it can be seen that side coating with a coverage of 50% or more can be realized by forming a film at a predetermined temperature using TDMV or TDEAV and a reducing gas. That is, according to the vanadium-containing film forming method of the present invention, films having substantially the same thickness were formed on the top, bottom, and side surfaces of the hole, and the top of the hole was not covered. From the results of FIG. 6, the relationship between the combination of raw materials and the step coverage is summarized as shown in Table 2 below. In Table 2, it shows that the step coverage is relatively improved in the order of x → Δ → ○ → ◎.

(Table 2)

  Therefore, it can be seen from FIG. 6 and Table 2 that the step coverage is improved by using the reducing gas. This is because the surface adsorption of the reducing gas promotes the surface reaction.

A vanadium-containing film was formed using the CVD apparatus shown in FIG. As a substrate for forming the film, an 8-inch wafer (SiO ₂ / Si) on which a silicon oxide film was formed was used.

The partition valve 304 of the reaction apparatus 3 was opened, and the substrate S was transferred into the reaction chamber using a robot in a chamber adjacent to the reaction chamber 301. During this transfer, gas existing in the air such as carbon-containing gas (CO or CO ₂ ), oxygen-containing gas (O ₂ ), water (H ₂ O) or the like adheres to the surface of the substrate S during the transfer. Or in vacuum to avoid diffusing inside the substrate.

  The substrate S transported into the reaction chamber 301 was placed on the substrate mounting table provided with heating means in the reaction chamber with the main surface of the substrate S being the shower plate 302 side and the back surface being the substrate mounting table 303 side. . The substrate mounting table was always kept at a predetermined film forming temperature.

Next, N ₂ gas is controlled from the gas supply device 1 to a flow rate of 1500 sccm through the MFC 1 to flow into the reaction chamber 301, the pressure in the reaction chamber is maintained at a predetermined film formation pressure, and the substrate temperature is set to 350 ° C. It heated so that it might become. After 0 to 10 minutes, film formation was started according to the following film formation conditions 1 and 2.

TDEAV was used as a raw material, and TBH, NH ₃ , and H ₂ were used as reducing gases.

Film forming condition 1:
TDEAV supply amount: 84mg / min
TDEAV carrier N ₂ : 400 sccm
Reducing gas (TBH, NH ₃ , H ₂ ) flow rate: 80 sccm
Carrier N ₂ : 1500sccm
Deposition pressure: 340Pa
Deposition time: 10-60 min
Deposition temperature: 350 ° C
Film thickness: 100nm

Film formation condition 2:
TDEAV supply amount: 84mg / min
TDEAV carrier _N 2: _400sccm
Carrier N ₂ : 1580 sccm
Deposition pressure: 340Pa
Deposition time: 50 min
Deposition temperature: 350 ° C
Film thickness: 100nm

  The electric resistivity of the vanadium-containing film produced according to the film formation condition 1 was 2500 to 3000 μΩ · cm, and the electric resistivity of the vanadium-containing film produced under the film formation condition 2 was 1200 to 1500 μΩ · cm. Table 3 below shows the results of examining the composition of the vanadium-containing film prepared according to the above film formation conditions 1 and 2 by the XPS method.

(Table 3)

As can be seen from Table 3, a film having higher vanadium and nitrogen contents is obtained when the reducing gas is used than when the reducing gas is not used, and nitriding is promoted particularly in the case of NH ₃ and TBH.

  The method described in Example 3 was repeated except that TDMV was used instead of TDEAV as a raw material. The film forming conditions at that time are shown below.

Film forming condition 1:
TDMV supply: 56 mg / min
TDMV carrier N ₂ : 400 sccm
Reducing gas (TBH, NH ₃ , H ₂ ) flow rate: 80 sccm
Carrier N ₂ : 1580 sccm
Deposition pressure: 340Pa
Deposition time: 5-60 min
Deposition temperature: 250 ° C
Film thickness: 100nm

Film formation condition 2:
TDMV supply: 56 mg / min
TDMV carrier N ₂ : 400 sccm
Carrier _N 2: _1580sccm
Deposition pressure: 340Pa
Deposition time: 50 min
Deposition temperature: 250 ° C
Film thickness: 100nm

  The electric resistivity of the vanadium-containing film produced according to the TDMV film formation condition 1 was 1200 to 3000 μΩ · cm, and the electric resistivity of the vanadium-containing film produced under the film formation condition 2 was 1000 to 1500 μΩ · cm. . Table 4 below shows the results of examining the composition of the vanadium-containing film produced according to the above film formation conditions 1 and 2 by the XPS method.

(Table 4)

As is clear from Table 4, a film having a high nitrogen content is obtained when the reducing gas is used compared with the case where the reducing gas is not used, but nitriding is promoted particularly in the case of NH ₃ and TBH. You can see that.

(Application example 1)
The substrate on which the vanadium-containing film obtained in Examples 3 and 4 was formed was not released to the atmosphere so that its surface was not oxidized, and passed through a transfer chamber (under vacuum) provided next to the reaction chamber. Then, it was transferred to a reaction chamber for forming a copper-containing film and placed on a substrate mounting table maintained at a predetermined temperature. Similarly, the SiO ₂ / Si substrate on which no vanadium-containing film was formed was also placed on the reaction chamber substrate mounting base for forming the copper-containing film. These substrates were heated to a substrate temperature of 170 ° C. while supplying H ₂ gas with a controlled flow rate and keeping the pressure in the reaction chamber constant. The pressure and substrate heating temperature in this case were the same as the conditions for forming the copper-containing film to be performed later. The H ₂ gas used here also has an effect of removing the oxide film on the substrate surface.

  Next, in a hydrogen atmosphere, a known hexafluoroacetylacetonato copper (I) trimethylvinylsilane (Cu (hfac) TMVS) is introduced as a raw material for forming a copper film, and copper is formed at a film forming pressure of 300 Pa and a film forming time of 1 minute. A containing film was formed.

  Comparing the sample with and without the vanadium-containing film obtained in this film formation process, the vanadium-containing film is formed as a barrier layer according to Examples 3 and 4 before forming the copper-containing film. Thus, it was confirmed from the SEM photograph that the initial nucleus formation was promoted and the nucleus density of the initial nucleus was increased in a short time.

  Moreover, it was confirmed by SEM, XPS, and fluorescent X-ray analysis (XRF) that a copper-containing film was formed.

  For a copper-containing film with a film thickness of 100 nm obtained under the same conditions as above (however, the film formation time was 10 minutes) As a result of a tape test in which 9 portions were drawn at equal intervals in the X-Y direction, an adhesive tape was attached to the surface, and then peeled off, no peeling from the surface of the vanadium-containing film was observed. Note that when the copper-containing film was formed directly on the substrate without forming the vanadium-containing film, the copper-containing film was easily peeled from the substrate surface.

  According to the present invention, it is possible to obtain a vanadium-containing film (a barrier layer and / or an adhesion layer) that can form a continuous copper-containing film in a subsequent process using a specific raw material, and to obtain the obtained copper-containing film. A vanadium-containing film that can be easily adhered to the film can be efficiently formed. In addition, it has excellent step coverage that evenly covers complex structures such as holes and trenches with high aspect ratios, including the side walls, and as a result, a copper-containing film is formed inside the holes in the subsequent process. It becomes possible to embed uniformly. Therefore, the vanadium-containing film forming method of the present invention is a technique that can be applied when forming a metal film, particularly a metal wiring, when manufacturing a semiconductor element (LSI, IC, etc.).

The layout figure which shows typically the example of 1 structure of the CVD apparatus for enforcing the formation method of this invention. The layout which shows another embodiment of the raw material supply apparatus of the CVD apparatus shown in FIG. 1 typically. FIG. 6 is a layout diagram schematically showing still another embodiment of the raw material supply apparatus of the CVD apparatus shown in FIG. 1. FIG. 6 is a layout diagram schematically showing still another embodiment of the raw material supply apparatus of the CVD apparatus shown in FIG. 1. It is a graph which shows the substrate temperature dependence of the film | membrane deposition rate with respect to the vanadium containing film | membrane obtained in Example 1, (a) when TDEAV is used as a metal raw material, (b) is the case where TDMV is used as a metal raw material It is. The cross-sectional SEM photograph which shows the level | step difference covering property of the vanadium containing film | membrane obtained by changing a metal raw material and reducing gas according to Example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas supply apparatus 2 Raw material supply apparatus 201 Raw material container 202 Raw material 203 Vaporizer 3 Reactor 301 Reaction chamber 302 Shower plate 303 Substrate installation stand 304 Partition valve 4 Discharge apparatus 401 Discharge valve 402 Pressure control valve 403 Raw material trap 404 Vacuum pump

Claims (7)

  A method for forming a vanadium-containing film, wherein a vanadium-containing film is formed on a film formation object by a CVD method using a tetravalent amide-based vanadium organometallic source gas and a reducing gas.   2. The method for forming a vanadium-containing film according to claim 1, wherein the tetravalent amide-based vanadium organometallic raw material is tetrakisdiethylaminovanadium, tetrakisdimethylaminovanadium, or tetrakisethylmethylaminovanadium. 3. The method for forming a vanadium-containing film according to claim 1, wherein the reducing gas is a gas that can be released to release H ^* radicals or H ⁺ ions. The method for forming a vanadium-containing film according to claim ₃ , wherein the reducing gas is a gas selected from a hydrazine derivative, NH ₃ , H ₂ , SiH _4, and Si ₂ H ₆ .   The method for forming a vanadium-containing film according to claim 4, wherein the hydrazine derivative is obtained by replacing one or two hydrogen atoms of hydrazine with a methyl group, an ethyl group, a linear or branched butyl group.   The method for forming a vanadium-containing film according to claim 4, wherein the hydrazine derivative is tertiary butyl hydrazine.   The vanadium-containing film is formed by performing the reaction between the tetravalent amide-based vanadium organometallic raw material gas and the reducing gas in a temperature range in which a film formation speed depends on the temperature of the object to be formed. Item 7. A method for forming a vanadium-containing film according to any one of Items 1 to 6.

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