JP2000007337A - Tantalum thin film and thin film consisting mainly of tantalum and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for chemically depositing a thin film containing tantalum on a substrate. SOLUTION: This method for chemically depositing a thin film containing tantalum on a substrate comprises charging (i) a substrate, (ii) a raw material precursor in a vapor state, and (iii) at least one kind of carrier gas into a deposition chamber and subsequently maintaining the temperature of the substrate in the chamber at about 70 deg.C to about 675 deg.C for such a sufficient period as depositing the thin film containing the tantalum on the substrate. The raw material precursor is expressed by the formula: Ta(I5-m-n-p)(Brm-p)(Cln-p)(Rp) [(m) is an integer of 0-5; (n) is an integer of 0-4; (p) is an integer of 0-4; R is selected from a group consisting of hydrogen and a lower alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tantalum thin film, a thin film mainly composed of tantalum, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION The evolution of computer integrated chips (ICs) has been driven by the need to increase speed, performance, and functionality. In order to achieve these objectives sufficiently, it was necessary to fundamentally change the architecture of the chip by introducing a multilayer wiring scheme utilizing the third (vertical) dimension of the chip to improve device performance. .
In this manner, the overall length of the interconnect and the size of the chip, ie, the increase in "area", are simultaneously minimized. It is predicted that these multilayer wiring systems will have an average of seven wiring layers in so-called ultra-large-scale integration (ULSI) within the next ten years. With the changes in chip architecture, the device dimensions of a single device have continued to shrink to accommodate more devices per chip, and the functionality of the chip has steadily improved. In this regard, device elements are expected to shrink from the current nominal 0.5 μm to less than 0.18 μm by 2000. However, the trend toward shrinking element dimensions faces significant performance issues with increasing RC delay (R is the resistance in the wiring structure, C is the capacitance in the wiring structure).

A large reduction in wire resistance R can be achieved by changing the currently used metallization architecture consisting of tungsten plugs and tungsten or aluminum wiring to a fully integrated copper-based metallization scheme. It is. Copper has a lower resistivity (bulk resistivity = 1.68 μΩ · cm) than aluminum and tungsten and should reduce RC delay by up to 40%. It is also predicted that the increase in electromigration and stress resistance will increase reliability and improve performance. However, a key issue in the realization of such a structurally stable, copper-based metallization architecture is the proper diffusion barrier that provides the performance required for sub-quarter-micron device technology. And the selection of an adhesion promoter. It is known that copper has high reactivity with silicon and diffuses at a high speed in silicon.
The presence of copper in silicon creates a deep trap level and significantly degrades device performance. Currently, titanium and titanium nitride technologies are used, however, as ever thinner liners are required to maximize the space utilization of actual conductors in ever-smaller device structures, Is not expected to provide the required performance. It has also been found that prior art deposition of copper on titanium nitride diffusion barriers and adhesion promoters is problematic, particularly if the titanium nitride is exposed to air prior to the copper deposition step.

[0004] Tantalum-based compounds have the potential to solve these problems. Tantalum and its binary and ternary nitrides are high heat resistant materials that are known to be stable to extremely high temperatures and have no reactivity with copper. Copper-tantalum contact is 550
It exhibits stability up to ° C., and at the normal temperatures used in the manufacture of microelectronic devices, the migration of copper in tantalum is very slow. In addition, a tantalum-based nitride has a higher melting point than tantalum. Tantalum nitride has a high melting point, such as Ta
The melting points of N and Ta ₂ N are 2050 ° C. and 3087 ° C., respectively.
It is. Due to these properties, sputtered tantalum nitride has been shown to act as a good diffusion barrier for copper-based technologies, with copper-
The stability of tantalum contacts has been demonstrated. More importantly, the demand for ever thinner liners has made tantalum-based alloys inherently more desirable than their titanium counterparts. This is because tantalum is a heavier (larger) ion than titanium, so that tantalum-based alloys have ULSI at very thin liner thicknesses compared to titanium alloys.
This may be because it should provide the required diffusion barrier performance of the structure. The increased performance at reduced liner thickness maximizes the available space for aluminum or copper conductors in ever-smaller device structures.

In this regard, ternary tantalum alloys such as TaN _x Si _y (x is greater than 0 and less than or equal to 2 and y is greater than 0 and less than or equal to 3) are highly desirable due to their unique structural properties. It might be. These compounds not only share the excellent diffusion barrier properties of binary tantalum alloys, but can also be grown in an amorphous state. The formation of an amorphous phase eliminates the presence of grain boundaries, thereby preventing the formation of potential diffusion paths for metals such as copper along such grain boundaries and ultimately forming TaN _x.
The barrier properties of the Si _y phase are improved. One of the important uses of pure tantalum is its ability to exclude oxygen. Pure tantalum is
Deposited directly on silicon and alloyed with silicon to form a tantalum silicide phase, TaSi _y (y is greater than 0,
When a phase is formed (a value of 3 or less as much as possible), a stable ohmic contact is formed. Traditionally, the formation of the tantalum silicide phase involves depositing pure tantalum on silicon,
Thereafter, it is necessary to perform one or more annealings at a high temperature (900 ° C.) to form a silicide phase. However, as the size of semiconductor devices is reduced to less than a quarter micron, the consumption of silicon from the substrate during the silicidation process is very inconvenient and creates significant problems, and the potential for current leakage This can lead to problems related to contact reliability in addition to problems related to device and device performance. Clearly, there is a need to develop a deposition method for growing tantalum silicide directly from the vapor phase without having to consume silicon from the underlying substrate.

[0006] Currently, the growth of tantalum and its binary and ternary nitrides is performed by conventional sputtering techniques. Unfortunately, these techniques rely on a line-of-sigh approach to metal deposition.
t approach allows for conformal (conformal) in rugged trench and via structures.
It is essentially impossible to achieve mal) step coverage. Therefore, there is a need for other process techniques for growing tantalum-based thin films used in sub-quarter micron devices. In this regard, chemical vapor deposition (CVD) is one of the most promising technologies. C
VD has the inherent potential of achieving conformal coverage in rugged via and hole structures by using the substrate surface as a catalyst for the deposition reaction. CVD has also demonstrated the ability to deposit pure and doped materials at industrially viable growth rates over large substrate areas, such as the standard 200 mm wafers currently used in the semiconductor industry. Many CVD methods have already been tried for the growth of tantalum and its nitrides. Tantalum pentachloride (TaC) in an atmosphere of hydrogen, nitrogen and argon
In inorganic CVD using l ₅ ), TaN and Ta ₂ N were deposited in a temperature range of 700 to 1000 ° C. (T. Takahashi, H. Itoh, S. Ozeki (O)
zeki), J. et al. , "Less-Common Met." 52:29 (1977
Year)). Obviously, the high processing temperatures required do not allow this deposition method to be used in real semiconductor devices. Tantalum TaCl ₅ - is completely dissociated chlorine bond, then the cause reliably produce nitride phase by reaction with ammonia requires a higher temperature. Obviously, these high processing temperatures do not allow the use of such CVD tantalum pentachloride based deposition methods in practical semiconductor devices. Also,
The presence of small amounts of chlorine (up to 5 at%) in tantalum-based thin films is very problematic, and the mobility of chlorine from the final nitride phase to the surrounding layers causes significant corrosion and reliability. Problems will arise.

[0007] Organometallic CVD processes involving the use of homoleptic dialkylamido tantalum complexes and tributyldiethyl tantalum type materials have been attempted (SC Sun, MH Tsai). (T
sai); T. Chiu, S.C. H. Chuan (C
huang), C.I. E. FIG. Tsai, "Proceedings of the IEDM"; SC Sun, M .;
H. Tsai, C.I. E. FIG. Tsai, H.S. T. Chu "Proceedings of the 12th International Conference on VLSI Multilayer Interconnection"
dings of the 12th International VLSI Multilevel In
terconnection Conference) "(VMIC, Tampa, FL, (1995)) p. 157; Fix, R.A. G. FIG. Gordon, D.A. M. Hoffman "Chem. Mater." Vol. 5, p. 614 (1993
Year)). However, metal organic CVD based deposition methods have not been very successful for various reasons. In the case of tantalum, metal-organic CVD routes have not been able to form pure tantalum thin films without carbon and oxygen contamination. In the case of nitrides, the low vapor pressure of the raw materials used in some cases has made the resulting production by metal-organic CVD processes worthless. On the other hand, the relative instability and short shelf life of precursors used in other cases have created difficulties in transport, handling and storage.

[0008]

However, any of the above methods has led to finding a metalorganic CVD process suitable for manufacturing that incorporates tantalum and its various nitrides and alloys into ULSI computer device structures. Not in. Therefore, in the art,
There is an urgent need for a method of forming a tantalum thin film and a tantalum-based thin film suitable for ULSI manufacturing in the manufacturing industry. In addition, in the art, there is a demand for a tantalum-based thin film of an electronics industry grade, that is, a tantalum-based thin film having an extremely high purity and an impurity concentration of less than 1 at% in terms of purity. Has a non-columnar structure, and is conformal to the complicated shape of the ULSI circuit.
In addition, the art can readily produce single or thin layers of pure tantalum thin films or tantalum-based thin films such as tantalum nitride, thin films including appropriately sized thin films of tantalum and various alloys thereof. A method is needed. Also, to prevent thermal damage to the device during processing, less than approximately 675 ° C,
There is a need for a method that is suitable for processing temperatures preferably below about 500 ° C.

Further, in the art, a method capable of producing the thin film sequentially and in situ, that is, while transferring a substrate coated with a tantalum-based thin film to another reaction chamber for further thin film deposition, air is used. Without having to touch
There is a need for a method capable of producing the above thin film. Generally, in prior art methods, a first layer is deposited in a first reaction chamber to produce a two-layer or multi-layer structure, and then is transferred to another reaction chamber, usually in a manner that exposes the substrate to air. It is necessary to transport and coat the next layer on the already grown layer. Prior art methods do not provide the flexibility of a single reaction chamber to deposit tantalum and its nitrides simply by controlling the operating parameters of the chamber. Also, prior art methods have tantalum and / or its nitrides in two or more chambers interconnected by vacuum load locks or central handlers so that samples can be transferred between reactors without exposure to air. It cannot be deposited. In particular, due in part to the high affinity of tantalum for oxygen and water, a method for sequentially depositing two or more layers of tantalum and its nitride in situ is desired. Normally, this affinity results in contamination of the surface of the tantalum-based thin film during transfer to a second reaction chamber where the layer is exposed to air in a manner that is coated with the next layer.

[0010]

SUMMARY OF THE INVENTION The present invention involves a method for chemically depositing a thin film containing tantalum on a substrate. The method, in a vapor deposition chamber: (i) a substrate; (ii) in a state of vapor formula _{(I): Ta (I 5} -mnp) (Br mp) (Cl np) (R p) (I) (M is an integer from 0 to 5, n is an integer from 0 to 4,
p is an integer from 0 to 4, R is selected from the group consisting of hydrogen and lower alkyl) and (ii)
i) introducing at least one carrier gas. The temperature of the substrate in the chamber is about 70 ° C. for a period sufficient to deposit a thin film containing tantalum on the substrate.
To about 675 ° C.

In one embodiment, the method further comprises depositing a second thin film comprising tantalum over the thin film deposited on the substrate to form a multilayer structure while the substrate is fixed in the chamber. To include. The second thin film containing tantalum is a pure tantalum thin film, a TaN _x thin film (x
Is greater than 0 and less than or equal to about 2), a TaSiy thin film (y is greater than 0 and less than or equal to about 3), and TaN.
_x Si _y thin film (x is a value greater than 0 and about 2 or less, y
Is greater than 0 and about 3 or less). In yet another embodiment, the method further comprises using a silicon substrate to add silicon to the tantalum-containing deposited thin film and reducing the substrate and the tantalum-containing deposited thin film to between about 700 ° C. and about 950 ° C. Heating.

[0012]

BRIEF DESCRIPTION OF THE DRAWINGS The foregoing summary, as well as the following detailed description of the preferred embodiment of the present invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, the drawings show a presently preferred embodiment. It should be understood, however, that the intention is not to limit the invention to the exact construction and means shown.

The present invention relates to a chemical precursor mainly comprising a halide and a conformal tantalum, TaN _x (x
Is preferably a tantalum nitride alloy containing any value greater than 0 and about 2 or less, TaSi _y (y is preferably 0 or less).
Tantalum silicide alloys containing any value greater than or equal to about 3 or less, and tantalum silicide alloys containing TaN _x Si _y (x and y are preferably as defined above) are used to chemically react on various special substrates. Related thermal and plasma methods of performing the deposition. The present invention
Either depositing a thin film such as a metallization layer in the form of a single-layer tantalum-based thin film on a substrate, or depositing a plurality of such thin films stacked on a substrate to form a multilayer structure. . Such thin films are useful in substrates having submicron components and structures, such as semiconductor substrates, such as silicon substrates and gallium arsenide substrates. These single or multilayer films can be deposited ex situ in different reactors, in situ in a single reactor, or a combination thereof. For example, several layers can be deposited in a single reactor and the next layer can be deposited in another reactor. If more than one reactor is used, the reactors are preferably interconnected via a leak proof transfer arm and a load lock so that sample transfer between different reactors is coated. This can be performed without exposing the substrate to air.

In microelectronics applications, the preferred substrate is intended to be an integrated circuit, such as holes, trenches, vias, etc., to make the necessary connections between the various conductivity materials forming the semiconductor device. It has a complicated shape formed by. The substrate is preferably, for example, silicon, silicon dioxide, silicon nitride,
It is formed by doping or a mixture thereof.
The substrate of the present invention is more preferably for ULSI circuits and is patterned with holes, trenches and other elements less than 1.0 microns in diameter, often less than 0.50 microns, and even less than 0.25 microns. Substrates having such small elements are known as "sub-quarter micron" substrates. Sub-quarter micron substrates that can be coated according to the present invention are generally defined as high aspect ratios (from a ratio of element depth to its diameter when viewed in cross section) of from about 3: 1 to about 6: 1 or more. ). As used herein, a sub-quarter micron substrate has an element diameter of less than about 0.25 microns and an element aspect ratio generally of about 3: 5.
More than one. Most substrates for ULSI circuits include elements having an aspect ratio of about 4: 1 or greater. Examples of coatable substrates include semiconductor substrates as described above, or hard protective films, for example, for aircraft parts and engines, automotive parts and engines, and cutting tools; decorative coatings for jewelry; Metals, glasses, plastics, or other polymers for applications including barrier layers and adhesion promoters for flat panel displays and solar cell devices are included. Suitable metal substrates include aluminum, beryllium, cadmium, cerium, chromium, cobalt, copper, gallium, gold, iron, lead, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, silver, stainless steel, steel, Includes iron, strontium, tin, titanium, tungsten, zinc, zirconium, their alloys and compounds such as silicides and carbides.

There is no practical limit to the type of substrate that can be used in the present method. However, it is preferred that the substrate be stable under the conditions used to deposit a thin film on the substrate. That is, the substrate is preferably from about 70 ° C to about 950 ° C, preferably from about 70 ° C to about 700 ° C, depending on the type of thin film to be deposited and the intended use of the coated substrate.
Stable up to temperature. According to the CVD method used in the method of the present invention, a conformal single-layer, two-layer or other multilayer thin film can be disposed on a sub-quarter micron substrate. Disposing a conformal coating of tantalum, tantalum nitride, tantalum silicide, and tantalum silicide nitride on a sub-quarter micron substrate having an element diameter of about 0.25 microns or less and an aspect ratio of about 6: 1 or more Can be. As used herein, “conformal film” refers to a film that uniformly covers a substrate having a complicated shape. The uniformity of the coating can be measured, for example, by examining the thickness of the coating along the walls and bottom of the hole in the substrate and determining the variation in the thickness of the coating. In the present invention, a sub-quarter micron substrate is characterized in that the thickness of the coating, measured at any point perpendicular to the wall or bottom surface of the hole on the substrate surface, is 25% of the thickness at any other point in the hole. If it is within the range of%, it is conformally coated. According to a preferred embodiment, the thickness variation of the coating is within 10%, in other words, at no point does the thickness of the coating exceed or fall below 10% of the average thickness of the coating. .

"Step coverage" as used herein, especially when referring to ULSI devices and coated substrates useful therein, refers to the thickness of the coating at the bottom of an element such as a trench or via. The ratio to the film thickness of the uppermost surface of the substrate adjacent to the substrate is multiplied by 100 to indicate the percentage. The method of the present invention reduces the step coverage in sub-quarter micron structures by about
Over 70% of conformally coated sub-quarter micron substrates are provided. In the present invention, a halide-based complex is used for low-temperature growth of tantalum and its nitride and / or its silicide alloy, depending on the reactants used. In situ, using a sequential CVD method using a single halide precursor, to smoothly and reversibly switch between tantalum and its nitride and / or silicide alloy by appropriately changing the processing conditions Can be. Further, there is provided a CVD method capable of sequentially depositing various pure tantalum layers or tantalum-based layers required for a specific application by utilizing various halide precursors.

The present invention provides a thin film containing tantalum,
Of pure tantalum thin film or thin film mainly composed of tantalum,
It includes a method of CVD on a substrate. This method
Introducing a substrate, a source precursor, and at least one carrier gas capable of acting as a carrier and / or a reactant into the deposition chamber. However, for convenience, this gas is generally referred to herein as at least one "carrier" gas. The raw material precursor is introduced in the vapor state and is preferably represented by the following formula: Ta (I _5-mnp ) (Br _mp ) (Cl _np ) (R _p ) (I) (m is 0 to 5) An integer, n is an integer from 0 to 4,
p may be an integer from 0 to 4, R may be hydrogen or lower alkyl, such as, and preferably, methyl or neopentyl. According to one preferred embodiment, the precursor of formula (I) is T
aBr ₅ or (CH ₃ ) ₃ TaBr ₂ and the substrate is UL
Silicon or silicon dioxide wafers useful in the manufacture of SI devices. Among other halides that can be used as raw material precursors, the bond configuration of tantalum pentabromide and tantalum pentaiodide and the related electronic environment are as follows:
It is completely different from tantalum pentabromide as used in the prior art. With these precursors of the present invention, the corresponding dissociation energies are much lower than for tantalum pentachloride, so that tantalum-based thin films can be deposited at much lower processing temperatures than required for tantalum pentachloride. .

Furthermore, the activation energy for diffusion of, for example, iodine or bromine is expected to be much higher than for chlorine, due to the fact that I or Br is much heavier than Cl. M. Seel and P.S. S. See Bagus, Phys. Rev. B28, 2023 (1983). Here, Si (111) of fluorine and chlorine
Studies on the interaction with have shown that the barrier for chlorine penetration into the silicon surface is much larger than for fluorine. This behavior was attributed to the chlorine atom being larger than the fluorine atom, and thus the ionicity of the chlorine atom and hence the Coulomb interaction. This property is due to the fact that certain concentrations of iodine or bromine require significantly higher thermal energy than chlorine to diffuse from the lattice of the film.
This has important implications for the effect of residual halide incorporation in tantalum-based thin films.

The at least one carrier gas is preferably hydrogen, helium, oxygen, fluorine, neon, chlorine, argon, krypton, xenon, carbon monoxide, nitrogen, ammonia, hydrazine, nitrous oxide, and / or steam. It is. This gas can be changed according to the type of thin film to be formed. For example, suitable gases for forming a pure tantalum thin film are hydrogen, helium, oxygen, fluorine, neon, chlorine, argon, krypton, xenon, carbon monoxide, carbon dioxide, and water vapor. More preferred said at least one gas for the formation of a pure tantalum thin film is hydrogen, helium, xenon and / or argon, and even more preferred gas is hydrogen or hydrogen in combination with argon or xenon. The raw material precursor, at least one carrier gas, and the substrate are heated in the chamber at an internal reaction temperature of about
Maintained at 70 ° C to about 675 ° C, preferably at least 100 ° C. More preferably, a plasma having a plasma power density of about 0.01 to about 10 W / cm ² is provided to the chamber.
The frequency of this plasma is preferably from about 0 Hz to about 10 ⁸
Hz. These components are maintained under these conditions for a period sufficient to deposit a pure tantalum thin film or a tantalum-based thin film on the substrate. The deposition process usually takes about 30 seconds to about 30 minutes, depending on the type of tantalum-based thin film to be deposited, processing conditions and desired film thickness.

According to yet another embodiment of the present invention, a thin film of a tantalum nitride alloy is deposited on a substrate by CVD. A tantalum nitride alloy such as TaN _x (where x can be any value greater than 0 and less than or equal to about 2) comprises a substrate, a precursor of the above formula (I),
At least one carrier gas as listed above, most preferably a gas comprising nitrogen, such as, for example, nitrogen, ammonia or hydrazine, and a further nitrogen-containing reactant which is the same or different from said at least one carrier gas It is deposited by introducing a gas. The nitrogen-containing reactant gas is preferably selected from the group consisting of nitrous oxide, ammonia, nitrogen, and hydrazine. Preferably, the at least one carrier gas and the nitrogen-containing reactant gas are used in combination with hydrogen, nitrogen, argon, ammonia, and / or hydrazine. These components are deposited in the deposition chamber
Maintained at a temperature from about 70 ° C to about 675 ° C, preferably at least 100 ° C. To form a tantalum nitride alloy thin film,
The most preferred temperature in the chamber is from about 250 ° C to about 500 ° C. The substrate is maintained in the chamber for a period sufficient to deposit a tantalum nitride alloy thin film. To form a tantalum nitride alloy thin film, the compound of formula (I) is TaBr ₅
Or (CH ₃ ) ₃ TaBr ₂ and the substrate is ULS
Preferably, it is a silicon or silicon dioxide wafer useful in the manufacture of I-devices.

[0021] The tantalum nitride alloy is most preferably combined with hydrogen as the at least one carrier gas; hydrogen in combination with nitrogen, ammonia, argon, xenon and / or hydrazine; ammonia, argon and / or xenon. Nitrogen; one of ammonia combined with argon and / or xenon
Deposited using more than one seed. Preferably these components to the plasma power density of about 0 to 10 W / cm ^2, in a more preferred presence of a plasma of about 0.01 to about 10 W / cm ^2, a thin film of tantalum entities, i.e. tantalum nitride alloy film on a substrate Maintained in the chamber for a period sufficient to allow for deposition. In this example, the raw material precursor is T
Most preferably ABR _5, which is combined with at least one carrier gas and / or reactive gases, further nitrogen, ammonia, and / or with another nitrogen-containing reactant gas is either hydrazine, for ULSI device manufacturing Is deposited on a silicon or silicon dioxide wafer substrate. Multiple layers of pure tantalum thin film and / or tantalum nitride alloy thin film deposited alternately or sequentially may be added to the substrate, preferably while the substrate is held in a single deposition reactor. As the substrate and source precursor are supplied to the deposition chamber, the source precursor is in a vapor state. Thereafter, the suitable gas is supplied to form the thin film layers alternately or sequentially at a suitable deposition chamber temperature as described above. Either the tantalum metal thin film or the tantalum nitride alloy thin film is first deposited on the substrate, and then the layers can be alternately stacked or added in a predetermined order.

Alternatively, a plurality of such alternating or sequential layers of pure tantalum or tantalum nitride alloy may be deposited on the substrate while the substrate moves through a single deposition reactor. In addition, multiple layers may be added to the substrate while the substrate moves between two or more independent reactors, each used to deposit one or more tantalum or tantalum nitride alloy layers, depending on the particular application of the coated substrate. You can also. Either a pure tantalum thin film or a tantalum nitride thin film is first deposited on a substrate. The substrate moves from one reactor where one or more such layers are deposited to another where another layer is deposited. Preferably, the reactors are interconnected via leak-proof transfer arms and / or load locks, such that transfer of the sample between different reactors can be performed without exposing the coated substrate to air. Has become. In yet another preferred embodiment, a pure tantalum thin film or a tantalum nitride alloy thin film is deposited on a substrate to form a coated substrate, and then preferably the later deposited layers have a higher nitrogen concentration. A series of tantalum-based thin films, such as pure tantalum or tantalum nitride, are deposited on the coated substrate. The tantalum thin film and the tantalum nitride alloy thin film are formed as described above.

In the present invention, pure (electronics grade) tantalum thin films and tantalum nitride alloy thin films for use as diffusion barriers or adhesion interlayers, for example, in integrated circuit fabrication, particularly in ULSI fabrication, are produced by using the CVD method. You. The method of the present invention sends carefully selected precursors to a thermal CVD reactor or a plasma enhanced CVD reactor under suitable reaction conditions to achieve high quality tantalum based thin films. In addition to the above-described tantalum nitride alloy thin film, a tantalum silicide nitride alloy thin film and a tantalum silicide alloy thin film can also be produced by the present method described in more detail below. Such a thin film is, for example, a multilayer laminate of a two-layer thin film of tantalum and tantalum nitride, a two-layer thin film of tantalum and tantalum silicide nitride, and a multilayer thin film composed of a tantalum thin film and a tantalum nitride thin film alternately or sequentially. It is also possible to form the structure.

For producing the tantalum thin film and the tantalum-based thin film according to the present invention, thermal CVD or plasma-promoted CVD can be used. "Thermal CVD" refers to a CVD method in which all reactants are introduced into the CVD reactor in gaseous form and all of the energy required for bond breaking is supplied by thermal energy. "Plasma enhanced CVD"
All reactants are introduced into the CVD reactor in gaseous form, and a portion of the energy required for bond breaking is either within the glow discharge or at a plasma power density of about 0 to about 10
0 W / cm ² , preferably from about 0.01 to about 10 W / cm ² ,
More preferably, it refers to a CVD method provided by high-energy electrons formed in a plasma of less than 0.5 W / cm ² . Plasma enhanced CVD uses plasma enhanced C
Like VD, the dissociation of gas molecules is promoted by using high-energy electrons existing in the glow discharge. Plasma acceleration CV
D is a technique widely known in the art. But,
The low power density used in plasma enhanced CVD, as opposed to plasma enhanced CVD utilizing high plasma power density, prevents premature precursor decomposition in the gas phase and prevents undesirable thin film contamination. Also, since a low plasma power density is used, electrical damage to the thin film and substrate is prevented.

In the method of the present invention, any CVD reactor having the following basic components may be used: These components provide for the supply and control of the raw material precursors. Supply, vacuum chamber, pump to maintain a suitable reduced pressure, power supply to generate plasma discharge for plasma enhanced CVD, temperature controller, reactants and production resulting from process It is a gas or vapor handling function for measuring and controlling the flow rate of an object. The precursor supply device may be any of the following: a pressure-based bubbler or sublimator, a hot source mass flow controller, a liquid supply device, a direct liquid ejection device or similar device. In the deposition of the tantalum-based thin film according to the present invention, the raw material precursor is preferably contained in a reservoir. The reservoir heats, in combination with the resistive heating tape and associated power supply, to a temperature that is high enough to ensure sublimation or evaporation of the precursor, but not high enough to cause early decomposition of the precursor. be able to. The mass flow controller can be isolated from the reservoir by a high vacuum valve, and is preferably arranged to control the gas flow into the reservoir. If a conventional pressure and / or temperature mass flow controlled supply is used as a precursor supply into the CVD reaction chamber, a gas such as, for example, hydrogen, helium, argon, xenon, nitrogen acts as a carrier agent. sell. Alternatively, if a liquid supply is used to supply the precursor to the CVD reactor, such a gas may act as a pressurizing agent. Such a device may include a combination head of a micropump and a vaporizer. A suitable example of such a device is the MKS Direct Liquid Injector
ion system). Another example of a suitable raw material precursor supply device is, for example, an MKS Model 1150 MFC
And hot source mass flow controllers, which do not require the use of a carrier gas or pressurized gas. Yet another example is a solid feeder such as the MKS1153 system, which also does not require the use of a carrier gas or a pressurized gas.

In one preferred embodiment, the precursor vapor (or precursor and carrier gas, depending on the feeder used) is transported into the CVD reactor, preferably via feed tubes, which are To prevent re-condensation of the precursor,
Using a combination of resistance heating tape and associated power supply,
Maintained at the same temperature as the reservoir. The CVD reactor can be an 8-inch wafer cold wall, stainless steel CVD reactor, preferably with plasma generating capability. The plasma can be generated by various sources such as DC plasma, high frequency plasma, low frequency plasma, high density plasma, electron cyclotron plasma, inductively coupled plasma, microwave plasma, and similar sources. Plasma can be used for two purposes. That is, it can be used for in-situ substrate cleaning prior to vapor deposition,
In the case of VD, it can be used for actual deposition. In the reactor, an electric bias is preferably applied to the substrate. This bias, DC, high radio frequency of the low radio frequency of less than 500kHz, from 500kHz to about 10 ⁶ kHz,
Alternatively, it can be obtained from microwave frequencies from about 10 ⁶ kHz to about 10 ⁸ kHz and similar sources.

Evacuation of the CVD deposition reactor can be accomplished using various pump systems. Two such systems are preferred. One is a pump system of a high vacuum (10 ^{@ 6} torr or higher), it can be used either cryogenic pump or turbomolecular pump. This system ensures a high vacuum reference pressure in the reactor. A vacuum system with a Roots blower or dry pump may be used to handle the high gas throughput during CVD. Both pump devices are preferably isolated from the CVD reactor by a high vacuum gate valve. The CVD reactor preferably includes a high vacuum load lock system, which is used to transport and load substrates into the reactor as large as approximately 300 mm wafers. Alternatively, connect the reactor to a central vacuum handler device,
The apparatus can also be used to transfer substrates between multiple CVD reactors and deposit tantalum and / or tantalum-based thin layers sequentially or alternately. After the raw material precursor is filled into the reservoir, it is heated to a temperature that is high enough to ensure sublimation or evaporation of the precursor, but not high enough to cause early decomposition of the precursor. Preferably, the raw precursor is heated to a temperature of about 50C to about 200C. When controlling the flow of the precursor into the CVD reactor using a normal pressure-type and / or temperature-type mass flow control type or solid source type supply device, the precursor in the reservoir is heated. Alternatively, for example, when using a liquid supply device such as an MKS direct liquid ejection device configured with a combination head of a micropump and a vaporizer, the liquid in the reservoir is kept at room temperature. In such a liquid supply device, the liquid in the reservoir is heated to a temperature that is high enough to reliably cause the sublimation or evaporation of the precursor, but not high enough to decompose the precursor early. No vaporizer head.

When a gas is used, any gaseous substance may be used if it is as follows. That is, a gaseous substance having substantially no reactivity with the raw material precursor, or reacting with the raw material precursor to be more easily transported to the reaction zone and / or decomposed more easily to obtain the desired tantalum A gaseous substance that forms an intermediate product that results in a thin film or a tantalum-based thin film. Exemplary carrier gases are as listed above. Thermal CVD and plasma enhanced CV
Particularly preferred as carrier gas for both D is hydrogen. The flow rate of the carrier gas may range from about 10 cm ³ / min (under standard conditions) to about 5 liters / min (under standard conditions) for both thermal CVD and plasma enhanced CVD, preferably from about 10 to about 100 cm 3 Over a range of ³ / min. In all of the above feeding schemes, the flow rate of the raw material precursor vapor can range from about 0.01 to about 2000 cm ³ / min (under standard conditions). Preferably, the flow rate of the raw material precursor vapor into the CVD chamber is from about 0.1 to about 100
cm ³ / min (under standard conditions).

For both thermal and plasma enhanced CVD of pure tantalum thin films, the carrier gas that can act as a reactant gas is preferably hydrogen. Particularly suitable carriers / both for both thermal CVD and plasma enhanced CVD of tantalum nitride thin films and other tantalum based thin films
The reactant gas is ammonia or hydrazine, alone or mixed with hydrogen. The flow rate of the carrier and / or reactant gas, which is a simple gas or a gas mixture, is
Preferably from about 10 cm ³ / min (under standard conditions) to about 10 liters / min (under standard conditions), more preferably about 100 liters / min (under standard conditions).
cm ³ / min (under standard conditions) to about 5 l / min (under standard conditions). The corresponding reactor pressure is preferably from 10 mTorr for low pressure CVD to 1000 Torr for atmospheric pressure CVD, more preferably from about 100 mTorr to 1 mTorr.
5 torr. For convenience, the gases discussed herein are referred to as "carrier" or "reactant" gases, but the action of these gases must not be misunderstood.
Indeed, in addition to transporting the raw precursor vapor into the reaction chamber, the carrier gas may also react within the chamber during the deposition process. Also, the so-called "reactant" gases introduced may contain inert components, in which case some or all of the reactant gases merely act to dilute the reactive atmosphere in the deposition chamber. Similarly, the carrier gas may also contain an inert component.

In one preferred embodiment of plasma enhanced CVD for forming a tantalum thin film, hydrogen is the carrier gas and no reactant gas is present. This is because the hydrogen plasma acts as a catalyst and decomposes the precursor on the substrate. In another preferred embodiment of plasma enhanced CVD for forming a tantalum thin film, hydrogen is simultaneously introduced as a carrier gas and a reactant gas into the deposition chamber. In another preferred embodiment for forming a tantalum thin film, hydrogen is introduced into the deposition chamber simultaneously with an inert gas such as neon, argon, krypton and / or xenon as at least one carrier gas. Preferably, hydrogen is introduced to act as a reactant and at least one of argon and xenon is introduced to act only as a carrier. But,
An inert gas may be introduced in a mixture with hydrogen, and the gas mixture introduced as at least one carrier gas may also act as a carrier and a reactant.

A pure tantalum thin film can be prepared by using the thermal CVD according to the present invention. To produce a pure tantalum thin film by thermal CVD, for example, hydrogen, argon and / or xenon can be introduced as at least one carrier gas and act as a reactant in a deposition chamber. Hydrogen or at least one of the inert gases can act as a carrier. In a preferred embodiment, in at least one carrier gas, argon acts as a carrier and hydrogen acts as a reactant. A tantalum-based thin film such as a tantalum nitride alloy can also be prepared using the plasma enhanced CVD according to the present invention. Tantalum nitride thin film is deposited by plasma enhanced CVD.
In one preferred embodiment for making in the N form, a nitrogen-containing reactant gas needs to be introduced into the chamber. Preferred nitrogen-containing reactant gases according to the present invention are nitrogen, ammonia and hydrazine. When the nitrogen-containing reactant gas is nitrogen, the nitrogen may act as the carrier and the nitrogen-containing reactant gas, and hydrogen or an inert gas such as argon or xenon is introduced simultaneously as at least one carrier, and And / or may act as a reactant. Preferably, at least one of hydrogen, nitrogen and an inert gas acts as at least one carrier gas. Hydrogen, nitrogen and / or an inert gas may be introduced simultaneously as a combined reactant gas. That is, hydrogen and / or an inert gas may be mixed with ammonia or hydrazine gas. The gas present in the deposition chamber during tantalum nitride thin film fabrication may be only nitrogen in combination with at least one of ammonia and hydrazine, where the nitrogen acts as at least one carrier gas, Any of the three gases is a nitrogen-containing reactant gas. In one preferred embodiment for producing TaN thin films by plasma enhanced CVD, hydrogen and nitrogen are introduced into the reaction chamber simultaneously with the source precursor.

A thin film mainly composed of tantalum can be formed by using the thermal CVD according to the present invention. For producing a tantalum-based thin film such as a tantalum nitride thin film by thermal CVD, for example, ammonia, nitrogen and / or hydrazine may be introduced into the deposition chamber as a nitrogen-containing reactant, acting as a carrier and / or a reactant. As such, at least one carrier gas, such as hydrogen, nitrogen, or an inert gas such as argon or xenon, may be added. In a preferred embodiment, hydrogen acts as a carrier and ammonia acts as a nitrogen-containing reactant gas. If the nitrogen-containing gas during the plasma enhanced CVD of the tantalum nitride thin film is ammonia or hydrazine, that gas is preferably introduced into the deposition chamber as a reactant gas, such as hydrogen and / or an inert gas such as argon or xenon. Preferably acts as a carrier. Hydrogen and / or an inert gas may be introduced simultaneously as a mixed reactant gas, for example, with ammonia and / or hydrazine gas.

[0033] Irrespective of whether thermal or plasma enhanced CVD is used to form the tantalum nitride thin film, the nitrogen containing reactant gas and at least one carrier gas and / or reactant gas which can act as a reactant gas. Regardless of the exact attributes of the carrier gas, it is important that at least one mole of nitrogen atoms be maintained in the reaction chamber per mole of tantalum in the reaction chamber if a stoichiometric equivalent of TaN is desired. If the nitrogen present in the deposition chamber is less than the chemical equivalent, _a thin film with high tantalum content such as tantalum metal or Ta ₂ N or TaNa (a <1) is deposited. This forms a mixed phase thin film, that is, a thin film having a pure tantalum phase and a nitride phase having a high tantalum content. Mixed phase thin films are preferred for certain applications, and methods of making such tantalum-based thin films and substrates coated with these thin films are within the scope of the present invention. On the other hand, when depositing a pure TaN thin film, ie, a thin film with a 1: 1 Ta to N molar ratio for a particular application, an appropriate amount of nitrogen atoms must be supplied to the deposition chamber.

In addition, a thermal CV for forming a tantalum nitride thin film is used.
Regardless of whether D or plasma enhanced CVD is used, and regardless of the precise attributes of the nitrogen-containing reactant gas and the carrier gas and / or reactant gas, a Ta-based thin film with a high nitrogen content can be used. If desired, an excess of nitrogen atoms per mole of tantalum in the reaction chamber;
That is, it is important to maintain more than one mole of nitrogen atoms in the reaction chamber. If too much nitrogen is present in the deposition chamber, a thin film with a high nitrogen content, such as TaN _z (z> 1), is deposited. This forms a mixed phase thin film, that is, a thin film having a pure tantalum phase, a nitride phase having a high tantalum content, and a nitride phase having a high nitrogen content.
In some embodiments of the present method, preferably using either thermal CVD or plasma enhanced CVD, the method of forming a pure tantalum thin film or a tantalum nitride alloy thin film using any of the above carrier gases and / or reactive gases may include silicon. The containing compound, preferably in the vapor state, is supplied to the reaction chamber. By adding silicon,
A tantalum silicide phase, preferably TaSi _y (y is any value greater than 0 and less than 3), or a tantalum nitride silicide phase, preferably TaN _x Si _y (x is a value greater than 0 and less than about 2; y is (A value greater than 0 and about 3 or less) is formed. This silicon-containing compound is preferably a halide-based compound of the formula (II): Si (I _4-mnp ) (Br _mp ) (Cl _np ) (R _p ) (II) (m from 0 An integer up to 4, n is an integer from 0 to 4,
p is an integer from 0 to 4, and R is defined as in the above formula (I). )

The plasma used for plasma enhanced CVD may be generated by any of the above plasma sources.
The frequency of the plasma can range from 0 Hz to about 10 ⁸ kHz or more, preferably from about 1 MHz to about 10 ⁸ kHz.
Over the range of ⁶ kHz. The plasma power density is preferably about 0.01 to 10 W / cm ² , more preferably 0.01 to 0.5
W / cm ² range. An electric bias as described above can be applied to the substrate. Corresponding power density preferably about 0.001 W / cm ² from 10 ³ W / cm ^2, more preferably ranges from 0.001 W / cm ² of 10 W / cm ^2.

Another method of adding silicon to a tantalum or tantalum nitride alloy thin film deposited according to the present invention is as follows:
A silicon-based or polysilicon-based substrate is used. After the tantalum or tantalum nitride thin film is formed, the temperature of the substrate in the reactor is typically high enough to allow silicon to react with the tantalum or tantalum nitride phase in the thin film, preferably about 700 ° C. Or about 950 ° C
To be raised. As a result, silicon from the substrate reacts with tantalum in the thin film formed on the substrate to form a tantalum silicide phase or a tantalum silicide nitride phase. The type and amount of silicide phase added to the film depends on the type of reactant gas and / or carrier gas used and the processing temperature as described above. In these cases, such as a halide-based compound of general formula (II),
Without using a silicon-containing compound in a vapor state,
A silicide phase can be provided. Advantageously, the tantalum thin film and the tantalum-based thin film formed according to the present invention have a columnar or non-columnar structure. The tantalum thin film and the tantalum-based thin film of the present invention have excellent ohmic contact characteristics when manufactured as a ULSI circuit. In addition, these tantalum thin films and tantalum-based thin films have excellent adhesion properties when fabricated as ULSI circuits and act as good barriers to metal diffusion.

In general, the tantalum-based thin film according to the present invention has a ratio of nitrogen to tantalum of about 0 to 2 and a ratio of silicon to tantalum, whether formed by thermal CVD or plasma enhanced CVD. Is approximately 0 to 3. According to the present invention,
While allowing independent fabrication of pure tantalum and tantalum-based thin films, the method of the present invention also provides for an in situ sequential CVD process. In this method, a single tantalum precursor deposition mode is smoothly and reversibly switched between a pure tantalum thin film formation mode and a tantalum nitride thin film formation mode by switching a reactant gas that can also act as a carrier gas. Can be switched. Thus, in one preferred embodiment of the method of the present invention, the deposition reactor is provided with hydrogen and a plasma power density of about 0.01 W / cm ^2.
The vapor from the compound of formula (I) can be charged in the presence of a plasma of from about 0.5 W / cm ² to about 0.5 W / cm ² . As described above, these reaction conditions result in the formation of a pure tantalum thin film on the substrate. The plasma can then be turned off and the reactant gas switched from hydrogen to a nitrogen-containing reactant gas such as ammonia. These altered reaction conditions result in the deposition of a thin film of TaN _x (x is as defined above) on the previously deposited pure tantalum thin film, thereby forming a bilayer thin film on the substrate.

In another preferred embodiment of the method of the present invention, the deposition reactor is provided with hydrogen and a plasma power density of about 0.01 W / c.
m ² to about 0.5 W / cm ^{2 with} a plasma,
Vapor from the compound of formula (I) is charged to form a pure tantalum thin film on the substrate. Then turn off the plasma,
A nitrogen-containing reactant gas such as ammonia can be introduced with the vapor of another raw material precursor according to formula (I).
Due to these modified reaction conditions, a thin film of TaN _x is deposited on the pure tantalum thin film that was first deposited, thereby forming the bilayer thin film of the present invention. In situ, a pure tantalum thin film is formed by using a sequential CVD method together with one kind of raw material precursor and one kind of silicon-containing compound in a vapor state and switching a reactant gas which can also act as a carrier gas. When, and TaSi _x, TaN _x S
i _y can be switched smoothly and reversibly. Thus, in one preferred embodiment of the method of the invention,
Hydrogen and plasma power density of about 0.01 W /
in the presence of a plasma of from about ² cm ² to about 0.5 W / cm ² , filled with vapors from the raw material precursor according to formula (I);
A pure tantalum thin film is formed on the substrate. The plasma is then turned off and the reactant gas is switched from hydrogen to a nitrogen-containing reactant gas such as ammonia, which can also act as a carrier gas. Along with the nitrogen-containing reactant gas, a vapor of the silicon-containing compound of formula (II) is also introduced into the deposition reactor. With these modified reaction conditions, a thin film of TaN _x Si _y (x and y are independently greater than 0 and about 2 or less) is deposited on the initially deposited pure tantalum thin film, and A two-layer thin film is formed.

In another preferred embodiment of the method of the present invention, the deposition reactor is charged with hydrogen and a plasma power density of about 0.01 W / c.
m ² to about 0.5 W / cm ^{2 with} a plasma,
The vapor of the raw material precursor according to the formula (I) is filled to form a pure tantalum thin film on the substrate. The plasma is then turned off and the reactant gas is switched from hydrogen to a nitrogen-containing reactant gas such as ammonia. Instead of the first raw material precursor, the vapor of another raw material precursor according to formula (I) can be introduced into the deposition reactor together with the vapor of the silicon-containing compound according to formula (II). With these modified reaction conditions, TaN _x S
A thin film of i _y (x and y are as defined above) is deposited to form a two-layer thin film. Based on the present disclosure, it should be understood that in any of the above embodiments, a reversal or other modification of the procedure is possible. For example, it is also possible to first deposit a thin film of either tantalum nitride, tantalum silicide, or tantalum silicide nitride on the substrate, and then deposit a tantalum thin film or other tantalum-based thin film. Preferably, a pure tantalum thin film is first deposited in contact with a substrate, which is preferably a silicon substrate or a silicon-containing substrate. In accordance with the present disclosure, it should be appreciated that more than two layers of different compositions can be deposited on a substrate without having to remove the substrate from the reaction zone. Based on this disclosure, it should be appreciated that the method of the present invention can utilize any suitable CVD technique, alone or in combination, for making tantalum or tantalum-based thin films. For example, a pure tantalum thin film is deposited by thermal CVD using a hydrogen carrier gas, and then tantalum nitride is deposited by plasma enhanced CVD using hydrogen and nitrogen as at least one carrier gas and / or a nitrogen-containing reactant gas. A two-layer thin film may be formed on a substrate by depositing a thin film.

As described above, in-situ deposition of tantalum and tantalum-based two-layer and multilayer thin films requires
This is very convenient for fabricating LSI devices. The method of the present invention allows the formation of a bi-layer or multi-layer film without the need to transfer the partially coated substrate between reaction chambers to risk exposure to air. The ability to make bi- or multi-layer films in a single reaction chamber minimizes the risk of contamination of the films. This contamination can occur during transfer of the partially coated substrate between reaction chambers. Contamination is particularly problematic for tantalum and tantalum-based thin films. The reason for this is that tantalum is generally reactive with oxygen, and even small amounts of such contamination can impair the usefulness of tantalum or tantalum-based coatings in ULSI devices. .

In the method of the present invention, a selected tantalum perhalide compound is used as a raw material precursor that can be converted into a high-quality tantalum thin film and a tantalum-based thin film by thermal CVD or plasma enhanced CVD. Similarly, the present invention provides electronics grade tantalum nitride thin films by reacting the same precursor precursor of a tantalum perhalide compound with a nitrogen-containing reactant gas. Also, the same precursor may be obtained by mixing at least one carrier gas and / or reactant gas, a vapor of a silicon-containing compound, and / or a nitrogen-containing reactant that is the same as or different from the at least one carrier gas and / or reactant gas. By reacting with the gas, electronics grade tantalum silicide and / or tantalum silicide nitride is provided. Exemplary chemical equations for the method of the present invention are summarized as follows. Here, TaBr ₅ and SiI ₄ are included as exemplary tantalum raw material precursors and silicon-containing compounds. Plasma enhanced CVD or thermal CVD: TaBr ₅ + H ₂ → Ta + HBr (III) (major by-product) Plasma enhanced CVD: TaBr ₅ + H ₂ + N ₂ → TaN _x + HBr (IV) (major by-product) Thermal CVD: _{TaBr 5 + NH 3 + H 2} → TaN x + HBr + NH 4 Br (V) ( major byproduct) plasma enhanced CVD or thermal _{CVD: TaBr 5 + SiI 4 +} H 2 → TaSi x + HBr + HI (VI) ( (Major by-product) Plasma enhanced CVD: TaBr ₅ + SiI ₄ + H ₂ + N ₂ → TaN _x Si _y + HBr + HI (VII) (Major by-product) Thermal CVD: TaBr ₅ + SiI ₄ + H ₂ → TaSi _x + HBr + HI (VIII) (major by-product) Thermal CVD: TaBr ₅ + SiI ₄ + NH ₃ + H ₂ → TaN _x + HBr + NH ₄ Br (IX) (major by-product)

[0042]

The invention, together with the modes and compositions of pure tantalum and other tantalum-based thin films deposited by the method of the invention, and their structural and electrical properties, are described by way of the following non-limiting examples. explain.

Example 1 Pure tantalum thin films were prepared by plasma enhanced CVD in a standard CVD deposition reaction chamber. The raw material precursor was tantalum pentabromide having a sublimation temperature in the range of 140 ° C to 200 ° C. Operating reaction pressure in deposition reactor 100
Thin films were prepared under millitorr to 10 torr. The carrier gas was hydrogen, with flow rates ranging from 10 cm ³ / min (under standard conditions) to 100 cm ³ / min (under standard conditions).
Hydrogen was also selected as the reactant gas, and flow rates ranged from 100 cm ³ / min (under standard conditions) to 1000 cm ³ / min (under standard conditions). Substrate temperature from 300 ° C to 500
° C range. RF plasma was used and its power density ranged from 0.1 W / cm ² to 0.25 W / cm ² .
The thin films were deposited on silicon and silicon dioxide wafer substrates.

The resulting tantalum thin film was metallic, continuous, and mirror-like. Figure 1 shows 450 ° C, hydrogen flow 8
The X-ray diffraction analysis of a tantalum thin film grown at 00 cm ³ / min (under standard conditions), a sublimation temperature of 160 ° C., a power density of hydrogen of 0.35 W / cm ² , and a working pressure of 700 mTorr in a reaction chamber is shown. The thickness of the formed thin film measured in a direction perpendicular to the plane of the thin film on the silicon wafer substrate was 350 Å. The X-ray diffraction analysis in FIG. 1 shows a plurality of diffraction peaks corresponding to the polycrystalline tantalum phase. X-ray photoelectron spectroscopy was performed on the same sample using a Physical Electronics Model 10-360 spherical condenser analyzer. 83.8e
The analyzer was calibrated accordingly with the _V7 gold _{f7 / 2} line as the reference line. Resolution 0.8 using 5eV pass energy
All spectra were obtained at eV. Primary X of 300W at 15keV
A line beam (MgKa, 1274 eV) was used. The pressure of the analysis chamber is in the range of 10 ^-10 torr, analysis results were standardized using a sample of high purity sputtered tantalum. Sputtering was performed prior to data collection to clean all samples. Composition similar to CVD thin film,
By choosing the chemical environment and binding standards, high precision X-ray photoelectron spectroscopy could be performed. The results of the analysis are based on the expectation that, even if chemical and structural changes occur during the cleaning process, the changes are basically the same between the standard and the thin film produced by CVD.
FIG. 2 shows the X-ray photoelectron spectrum, which shows that the contamination level of the pure tantalum phase is below the detection limit of 1 at% of X-ray photoelectron spectroscopy.

Further, the chemical composition of the same thin film was examined by Auger electron spectroscopy using a Physical Electronics Model 15-110B cylindrical mirror analyzer. The analyzer was calibrated accordingly with the 83.8 eV gold f _7/2 line as the reference line. A full spectrum was obtained using a pass energy of 23.5 eV. A primary electron energy of 5 keV at 1 mA was used. The pressure of the analysis chamber is in the range of 10 ^-10 torr, analysis results were standardized using a sample of high purity sputtered tantalum. Sputtering was performed prior to data collection to clean all samples. By choosing similar compositions, chemical environments and bonding standards as the CVD thin films, high precision Auger electron spectroscopy could be performed. As in the case of X-ray photoelectron spectroscopy, the analysis results show that, even if chemical and structural changes occur during the cleaning process, the changes are basically the same between the standard and the thin film made by plasma enhanced CVD. It is based on expectations. In the Auger electron spectrum shown in FIG. 3, the contamination level is below the detection limit of 1 at% of Auger electron spectroscopy, confirming the results of X-ray photoelectron spectroscopy on the purity of the tantalum phase. In the resistivity measurement by the four needle method,
The resistivity of the thin film was 117 μΩ · cm.

Rutherford backscattering spectra were obtained using a 2 MeV He ⁺ beam and calibrated with a high purity gold, carbon thin film and silicon bulk sample.
The Rutherford backscattering spectrum is shown in FIG. These measurement results show that heavy elements, especially tantalum thin films,
That is, the fact that there is no contamination of an element having an atomic number greater than 13 supports the results of Auger electron spectroscopy and X-ray photoelectron spectroscopy regarding the purity of the tantalum phase. Specifically, these Rutherford backscattering spectra indicated that the bromine in the thin film was less than 3 at%. Next, the properties of the tantalum thin film on the silicon substrate were examined. The tantalum thin film was observed to adhere well to silicon or silicon dioxide. Cross-sectional scanning electron microscope analysis was performed on the step coverage of the thin film. "Conformal coverage" refers to a thin film or coating that uniformly covers a substrate having a complex shape. The degree of uniformity of the coating can be measured, for example, by examining the thickness of the coating along the walls and bottom of the hole in the substrate and determining the variation in the thickness of the coating. This measurement yields a value for step coverage. This value is the ratio of the thickness at the bottom of the hole to the thickness in the field outside the hole in the substrate. Cross section scanning electron microscopy, Zeiss
This was performed using a DSM940 microscope with a primary electron beam of 20 KeV and a beam current of 4 μA. FIG. 5 shows a cross-sectional scanning electron micrograph of a 350 Å thick tantalum thin film. This photograph shows conformal step coverage for a 0.25 μm via with an aspect ratio (defined as via height divided by its diameter) of 4. The micrograph of FIG.
This shows that the step coverage of the tantalum thin film deposited using plasma enhanced CVD on a substrate with a nominal trench diameter of 0.25 μm and an aspect ratio of 4: 1 exceeded 80%. FIG. 5 also shows that the plasma enhanced CVD used in the method of the present invention provides a conformal coating with high step coverage, even after the deposition time is extended to form a thick tantalum nitride thin film. This thin film was formed using hydrogen and tantalum pentabromide.

Example 2 A pure TaN _x thin film was prepared by a thermal CVD method in a standard CVD deposition reaction chamber. The raw material precursor is
It was tantalum pentabromide having a sublimation temperature in the range of 140 ° C to 200 ° C. Operating pressure in the deposition reactor is reduced from 100 mTorr to 1
At 0 Torr, a thin film was prepared using hydrogen as a carrier gas. Hydrogen flow rate from 10 cm ³ / min (under standard conditions) to 1
00 cm ³ / min (under standard conditions). The nitrogen-containing reactant gas was ammonia, with flow rates ranging from 100 cm ³ / min (under standard conditions) to 1000 cm ³ / min (under standard conditions). Substrate temperatures and reactor temperatures ranged from 250 ° C to 500 ° C. The thin films were deposited on silicon and silicon dioxide wafer substrates. The produced tantalum nitride thin film was metallic, continuous, and mirror-like. 425
An X-ray diffraction analysis was performed on a TaN _1.2 thin film having a sublimation temperature of 170 ° C. grown at a temperature of 600 ° C. and a flow rate of ammonia of 600 cm ³ / min (under standard conditions). The working pressure of the reactor was 950 mTorr. FIG. 6 shows an X-ray diffraction pattern for a thin film deposited on a silicon substrate at a thickness of 1900 Å. This X-ray diffraction pattern shows a substantially amorphous TaN
A diffraction peak corresponding to the _1.2 phase was shown. X-ray photoelectron spectroscopy was performed using a Physical Electronics Model 10-360 spherical condenser analyzer. 83.8 eV gold f
_The analyzer was calibrated accordingly with the _7/2 line as the reference line.
All spectra were obtained at a resolution of 0.8 eV using a pass energy of 5 eV. A primary X-ray beam (MgKa, 1274 eV) of 300 W at 15 keV was used. The pressure of the analysis chamber is in the range of 10 ^-10 torr, analysis results were standardized using a high purity sputtered TaN sample. Sputtering was performed prior to data collection to clean all samples. By selecting similar compositions, chemical environments and bonding standards as the CVD thin films, high precision X-ray photoelectron spectroscopy analysis could be performed. The results of the analysis are based on the expectation that, even if chemical and structural changes occur during the cleaning process, the changes are basically the same between the standard and the thin film produced by CVD. FIG. 7a shows the X-ray photoelectron spectrum of the same sample, where the contamination level of the pure TaN _1.2 phase is 1a of X-ray photoelectron spectroscopy.
It is shown to be below the detection limit of t%. Fig. 7b
As shown in the figure, the high-resolution X-ray photoelectron spectrum of the N peak in TaN showed a binding energy of 398.2 eV corresponding to the nitride phase.

The chemical composition of this thin film was investigated by Auger electron spectroscopy using a Physical Electronics Model 15-110B cylindrical mirror analyzer. 83.8 eV gold f
_The analyzer was calibrated accordingly with the _7/2 line as the reference line. Two
All spectra were obtained using a pass energy of 3.5 eV. A primary electron energy of 5 keV at 1 mA was used. The pressure of the analysis chamber is in the range of 10 ^-10 torr,
Analysis results were standardized using high purity sputtered TaN samples. Sputtering was performed prior to data collection to clean all samples. By choosing similar compositions, chemical environments and bonding standards as the CVD thin films, high precision Auger electron spectroscopy could be performed. As in the case of X-ray photoelectron spectroscopy, the analysis results show that even if chemical and structural changes occur during the cleaning process, those changes are basically the same between the standard and the thin film made by thermal CVD. It is based on expectations. FIG. 8 shows the results of Auger electron spectroscopy, in which the contamination levels were below the detection limit of 1 at% of Auger electron spectroscopy, confirming the results of X-ray photoelectron spectroscopy on the purity of the TaN phase. Have been. In the resistivity measurement by the four-needle method, the resistivity of the thin film was 2 × 10 ⁴ μΩ · cm.
Rutherford backscattering spectra were obtained using a 2 MeV He ⁺ beam and calibrated with a high purity sputtered TaN thin film and a bulk silicon sample.
The measurement results of Rutherford backscattering for the thin film are shown in FIG. These measurements confirm the results of Auger electron spectroscopy and X-ray photoelectron spectroscopy on the purity of the TaN phase, especially in the absence of heavy element contamination in the TaN _1.2 thin film. Specifically, from these Rutherford backscattering spectra, bromine in the thin film is 1a
It was shown to be less than t%.

The properties of the TaN _1.2 thin film on the silicon substrate were examined. It was observed that the tantalum nitride thin film adhered well to silicon or silicon dioxide. Cross-sectional scanning electron microscope analysis was performed on the step coverage of the thin film. Cross-sectional scanning electron microscopy was performed on a Zeiss DSM940 microscope using a 20 KeV primary electron beam and a beam current of 4 μA. FIG. 10 shows a cross-sectional scanning electron micrograph of a 1900 Å thick TaN thin film formed on silicon as described above. This photo shows an aspect ratio of 0.25μ
Conformal step coverage in mvia is shown. The micrograph in FIG. 10 shows that the nominal diameter of the trench is 0.25 μm and its aspect ratio is 4: 1.
It shows that the step coverage of tantalum nitride thin films deposited using VD and the method of the present invention is over 80%. The micrographs show that using thermal CVD and the method of the present invention provides a conformal coating with high step coverage, even after extending the deposition time to form a thick tantalum nitride thin film. .
This thin film was prepared from tantalum pentabromide as a raw material precursor and ammonia as a reactant gas.

Example 3 A plasma enhanced chemical vapor deposition was performed using TaBr ₅ as a tantalum raw material precursor. 140 ° C to 200 ° C depending on combination of heating tape and associated power supply during CVD process
This raw material precursor was placed in a sublimator heated to a temperature of 1.9 mm. The mass flow controller separated from the sublimator by the high vacuum valve was controlled to set the flow rate of the hydrogen carrier gas into the sublimator at 10 to 100 cm ³ / min (under standard conditions). Next, a mixture of the raw material precursor vapor and the hydrogen carrier gas was fed into the CVD reactor. The temperature of all transport and supply tubes and high vacuum isolation valves was maintained in the range of 140 ° C. to 200 ° C. using a combination of heating tape and an associated power supply to prevent precursor recondensation.

The vapor deposition was performed in a stainless steel CVD reactor with a cold wall of a 6-inch wafer. This reactor was equipped with a diode-type and parallel-plate-type plasma device comprising two electrodes. The upper electrode functioning as the active electrode was driven by a high frequency (13.56 MHZ) power supply. This electrode was configured with a "mesh" type pattern to provide a non-convergent flow of reactants to the substrate. Hydrogen plasma with a plasma power density in the range of 0.1 to 0.5 W / cm ² is used for substrate cleaning before deposition in situ, and hydrogen plasma with a power density of 0.1 to 0.25 W / cm ² during actual deposition It was used. Down,
Place a substrate (wafer) on the grounded plasma electrode,
This substrate was heated from 350 ° C. to 500 ° C. by a resistance heater. To maintain the cleanliness of the process, the reactor is periodically baked in a nitrogen or argon atmosphere is less than 0.3 torr, then 1 hour at 0.99 ° C., and under reduced pressure in the pump to below 10 ^-6 Torr. The pump stack consisted of two pump packages. The first was a low temperature pump and the second was a Roots blower pump isolated from the reactor by a high vacuum gate valve. The reason for using the low-temperature pump type package was to secure a high vacuum reference pressure in the reactor. On the other hand, the roots blower type package was used in order to appropriately cope with a high gas throughput during actual CVD. A high vacuum load lock system was used to transfer and load 6 inch wafers into the reactor. Finally, hydrogen (H ₂ ) gas was supplied into the reactor using a side wire. The flow rate of hydrogen was 100-1000 l / min and was controlled by a mass flow controller and associated isolation valves. The produced tantalum thin film was metallic, continuous, and mirror-like. Their structural and electrical properties, and chemical composition were determined by X-ray diffraction, X-ray photoelectron spectroscopy, Rutherford backscattering, four-needle, and cross-sectional scanning electron microscopy as described in Examples I and II above. Was analyzed in detail. As a result of these analyses, the tantalum thin film exhibited characteristics unique to the tantalum thin film as described in Example I.

Example 4 Thermal CV using tantalum pentabromide as a chemical precursor
By method D, a tantalum nitride thin film of the formula TaN was deposited. The operations were performed under processing conditions similar to those described in Example 3 for the deposition of pure tantalum, except that no plasma was used during the actual deposition.
In this example, the substrate is heated from 250 ° C to 5 ° C by a resistance heater.
Heated to processing temperature of 00 ° C. Ammonia was used as the nitrogen-containing reactant gas and carrier gas. The mass flow controller and associated isolation valve controlled the flow of NH ₃ in the side line from 100 to 1000 l / min. The tantalum nitride thin film thus produced was metallic, continuous, and mirror-like. Their structural and electrical properties, and chemical composition, were determined by X-ray diffraction, X-ray diffraction,
In-depth analysis was performed by line photoelectron spectroscopy, Rutherford backscattering, four-needle, and cross-sectional scanning electron microscopy. As a result of these analyses, the thin film exhibited characteristics unique to the tantalum nitride thin film described in Example 2 above.

Example 5 Tantalum pentabromide was used as a raw material precursor, and two layers of pure tantalum and tantalum nitride were sequentially deposited in situ. First, the plasma promoting C described in the third embodiment is used.
Pure tantalum layers were grown using VD with argon as the carrier gas. Next, the plasma was turned off and the gas switched from argon to ammonia, which also acts as a nitrogen-containing reactant gas. Then, a tantalum nitride layer was grown on the tantalum layer by using the thermal CVD of the method described in the fourth embodiment. As a result of analyzing these thin films as described above, these thin films exhibited the properties of tantalum and tantalum nitride as described in Examples 1 and 2. Under some conditions, it was possible to dope the tantalum layer with nitrogen during the deposition of tantalum nitride. An example of this is illustrated by the thin film formed in Example 2, which is illustrated in the Auger electron spectrum as shown in FIG.

The thin films produced by the method of the present invention have been found to have electronic grade purity, and are therefore suitable for use, for example, in microelectronic applications where purity requirements are very stringent. The carbon and oxygen impurity levels in the thin films made by the claimed method of the present invention are less than 1 at%. The thin film prepared by the method of the present invention includes
Little or no halogen is incorporated. Here, halogen is iodine, bromine, chlorine, or fluorine. Thus, according to the method of the present invention,
A thin film containing less than about 5 at%, more preferably less than about 1 at% of halogen is obtained. Pure tantalum thin films and other tantalum-based thin films formed according to the present invention have been found to have a desirable low resistivity, in part because of their high purity. The resistivity of the thin film of the present invention is about 50 to about 5000 μΩcm, preferably about
It is 50 to about 1000 μΩ · cm, more preferably about 40 to about 150 μΩ · cm.

In contrast to prior art chemical vapor deposition methods,
According to the method of the present invention, a thin film having a purity of an electronic industrial grade can be obtained by containing little or no carbon, oxygen, fluorine or halide. In contrast to sputtering techniques, our invention provides excellent coverage which is an essential feature in the manufacture of microelectronic devices. It will be appreciated by those skilled in the art that changes may be made to the embodiments described above without departing from their broad inventive concepts. Therefore, it is to be understood that the invention is not limited to the particular embodiments disclosed, but rather includes modifications within the spirit and scope of the invention as defined by the appended claims.

[Brief description of the drawings]

FIG. 1 illustrates an X-ray diffraction pattern of a tantalum thin film prepared by a plasma CVD reaction of TaBr ₅ and hydrogen in Example 1, according to an embodiment of the method of the present invention.

FIG. 2 shows an X-ray photoelectron spectrum of the tantalum thin film of Example 1.

FIG. 3 shows an Auger electron spectrum of the tantalum thin film of Example 1.

FIG. 4 shows a Rutherford backscattering spectrum of the tantalum thin film of Example 1.

FIG. 5 is an enlarged cross-sectional scanning electron microscope image of a silicon substrate on which an oxide via pattern having a diameter of 0.25 μm and an aspect ratio of 4: 1 is formed, and a conformal tantalum film of Example 1 is further deposited. It is.

FIG. 6 illustrates an X-ray diffraction pattern of a TaN _x thin film produced by a thermal CVD reaction of TaBr ₅ and ammonia in Example 2, according to an embodiment of the method of the present invention.

FIG. 7a shows an X-ray photoelectron spectrum of the thin film of Example 2.

FIG. 7b shows an X-ray photoelectron spectrum of the thin film of Example 2.

FIG. 8 shows an Auger electron spectrum of the thin film of Example 2.

FIG. 9 shows a Rutherford backscattering spectrum of the thin film of Example 2.

FIG. 10 is an enlarged view of a silicon substrate on which a via pattern of an oxide having a diameter of 0.25 μm and an aspect ratio of 4: 1 is formed and a conformal thin film of Example 2 is further deposited by a cross-sectional scanning electron microscope. is there.

FIG. 11 includes a tantalum layer coated with a TaN _x layer, i
5 shows an Auger electron spectrum of a tantalum-based two-layer thin film grown in situ, and the tantalum layer is made of TaB.
The TaN _x layer was formed by a plasma enhanced CVD reaction of r ₅ and hydrogen, and the TaN _x layer was deposited by a thermal CVD reaction of TaBr ₅ and ammonia.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C23C 16/42 C23C 16/42 16/50 16/50 (71) Applicant 598095857 The Research Foundation of State University of New York State University Plaza, Albany, New York, United States of America. Arkles Bluebird Lane, Dorsetshire, Pennsylvania, United States of America 428 (72) Inventor Alan E. Kaloeros Forest Haven Drive, Slingerlands, New York, United States 203 F-term (reference) 4G048 AA01 AA06 AB01 AC08 AD02 AE05 AE06 AE07 4K030 AA02 AA03 AA06 AA09 AA11 AA16 AA17 AA18 BA17 BA29 BA35 JA38 CA18 JA10 LA15

Claims (26)

[Claims] 1. A method for chemical vapor deposition of a thin film containing tantalum on a substrate, comprising: (a) in a deposition chamber: (i) a substrate; I _5-mnp ) (Br _mp ) (Cl _np ) (R _p ) (I) (m is an integer from 0 to 5, n is an integer from 0 to 4,
wherein p is an integer from 0 to 4, and R is selected from the group consisting of hydrogen and lower alkyl); and (iii) introducing at least one carrier gas; ) Raising the temperature of the substrate in the chamber to about 70 degrees for a period sufficient to deposit a thin film comprising tantalum on the substrate;
C. to about 675.degree. C. 2. The method of claim 2, wherein the at least one carrier gas comprises:
Hydrogen, helium, oxygen, fluorine, neon, chlorine, argon, krypton, xenon, carbon monoxide, carbon dioxide,
The method according to claim 1, wherein the method is selected from the group consisting of nitrogen, ammonia, hydrazine, nitrous oxide, and water vapor. 3. The method according to claim 1, wherein the flow rate of the at least one gas is greater than 0 and less than or equal to about 10 liters / minute. 4. A plasma power density of about 0.01 W / d for a period sufficient to deposit a thin film comprising tantalum on said substrate.
The method according to claim 1, further comprising introducing a plasma of from about cm ^{2 to} about 10 W / cm ² into the chamber. 5. The method according to claim 4, wherein the frequency of the DC bias, the plasma is between about 0 Hz and about 10 ⁸ kHz. 6. An electrical device comprising at least one of a DC bias, a low RF bias less than 500 kHz, a high RF bias from 500 kHz to 10 ⁶ kHz, or a microwave frequency bias from 10 ⁶ kHz to about 10 ⁸ kHz. The method according to claim 1, further comprising applying a bias to the substrate. 7. The method according to claim 6, wherein the power density of the electrical bias is greater than 0 watts / cm ^{2 and} less than or equal to about 10 ³ watts / cm ² . 8. The method according to claim 7, wherein the power density of the electrical bias is greater than 0 watts / cm ^{2 and} less than or equal to about 10 watts / cm ² . 9. The method according to claim 1, wherein said substrate comprises a material selected from the group consisting of metal, glass, plastic, and polymer. 10. The method according to claim 1, wherein the substrate is aluminum, beryllium, cadmium, cerium, chromium, cobalt, copper, gallium, gold, iron, lead, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, silver, stainless steel, The method according to claim 9, wherein the metal is a metal selected from the group consisting of steel, iron, strontium, tin, titanium, tungsten, zinc, zirconium, and alloys and compounds thereof. 11. The method according to claim 1, wherein said temperature of said substrate in said chamber is maintained at about 250 ° C. to about 500 ° C. 12. The method according to claim 1, wherein said raw material precursor is tantalum pentabromide. 13. The method according to claim 1, wherein said at least one carrier gas is hydrogen. 14. The thin film comprising tantalum is a pure tantalum thin film; the at least one carrier gas comprises:
Hydrogen, helium, oxygen, fluorine, neon, chlorine, argon, krypton, xenon, carbon monoxide, carbon dioxide,
And the temperature of the substrate in the chamber is from about 100 ° C. to about 6 ° C.
The method according to claim 1, which is maintained at 75 ° C. 15. The thin film containing tantalum is TaSi _y
A thin film (y is greater than 0 and less than or equal to about 3); step (a) further comprises: (iv) introducing a silicon-containing compound in a vapor state into the chamber; The method according to claim 1, wherein the at least one carrier gas is selected from the group consisting of hydrogen, helium, oxygen, fluorine, neon, chlorine, argon, krypton, xenon, carbon monoxide, carbon dioxide, and water vapor. . 16. The compound containing silicon is represented by the formula (II): Si (I _4-mnp ) (Br _mp ) (Cl _np ) (R _p ) (II) wherein m is an integer from 0 to 4, and n is An integer from 0 to 4,
p is an integer from 0 to 4 and R is selected from the group consisting of hydrogen and lower alkyl). 17. The thin film comprising tantalum is a TaN _x thin film, where x is greater than 0 and less than or equal to about 2; Step (a) comprises: (iv) the same or different from the at least one carrier gas 2. The method according to claim 1, further comprising the step of introducing a reactant gas comprising nitrogen into the chamber. 18. The method according to claim 17, wherein said reactant gas comprising nitrogen is selected from the group consisting of nitrous oxide, ammonia, nitrogen, and hydrazine. 19. The thin film containing tantalum is made of TaN _x S
i _y thin film (x is a value greater than 0 and less than or equal to about 2 and y is a value greater than 0 and less than or equal to about 3); step (a) comprises: (V) introducing a reactant gas containing nitrogen, the same or different from the at least one carrier gas, into the chamber; wherein the at least one carrier gas is hydrogen, helium, Oxygen, fluorine, neon, chlorine, argon, krypton, xenon,
The method according to claim 1, wherein the method is selected from the group consisting of nitrogen, ammonia, hydrazine, nitrous oxide, carbon monoxide, carbon dioxide, and water vapor. 20. The compound containing silicon is represented by the formula (II): Si (I _4-mnp ) (Br _mp ) (Cl _np ) (R _p ) (II) wherein m is an integer from 0 to 4, and n is An integer from 0 to 4,
20. The method according to claim 19, wherein p is an integer from 0 to 4 and R is selected from the group consisting of hydrogen and lower alkyl. 21. The method according to claim 1, wherein (c) while the substrate is fixed in the chamber, on the thin film deposited on the substrate to form a multilayer structure; The method further includes the step of depositing a second thin film containing tantalum, wherein the second thin film containing tantalum is a pure tantalum thin film, a TaN _x thin film (x is a value larger than 0 and about 2 or less), a TaSi _y thin film ( y is greater than 0 and less than or equal to about 2), and a method selected from the group consisting of TaN _x Si _y thin films. 22. The method according to claim 22, wherein the second thin film is a pure tantalum thin film, and the step (c) comprises: introducing the raw material precursor in a vapor state and the at least one carrier gas into the chamber. And said at least one
The species carrier gas is hydrogen, helium, oxygen, fluorine,
Selecting from the group consisting of neon, chlorine, argon, krypton, xenon, carbon monoxide, carbon dioxide, and water vapor;
Maintaining the temperature at 0 ° C. 23. The method according to claim 23, wherein the second thin film is a TaN _x thin film (x is a value greater than 0 and about 2 or less), and the step (c) comprises: Introducing at least one carrier gas; and a reactant gas comprising nitrogen, the same or different from said at least one gas; and maintaining said chamber at a temperature of about 100 ° C to about 675 ° C. 22. The method according to claim 21, further comprising: 24. The method according to claim 24, wherein the second thin film is a TaSi _y thin film (y
Is greater than 0 and less than or equal to about 3); step (c) is: in the chamber: the raw material precursor in vapor state; hydrogen, helium, oxygen, fluorine, neon, chlorine, argon, krypton, 22. The method according to claim 21, further comprising the step of introducing the at least one carrier gas selected from the group consisting of xenon, carbon monoxide, carbon dioxide, and water vapor; and a compound comprising silicon, which is in a vapor state. . 25. The second thin film is a TaN _x Si _y thin film (x is a value greater than 0 and about 2 or less, and y is a value greater than 0 and about 3 or less), and step (c) includes: In: the raw material precursor in a vapor state; the at least one carrier gas; a silicon-containing compound in a vapor state; and a nitrogen-containing reaction that is the same or different from the at least one carrier gas. The method according to claim 21, further comprising the step of introducing a body gas. 26. The method as claimed in claim 26, wherein the substrate comprises silicon; and The method according to claim 1, further comprising the step of heating to a temperature.