Mixed gas supply device, metal nitride film manufacturing device and metal nitride film manufacturing method

Abstract

The present invention aims to provide a method for producing a metal nitride film with a high film forming speed and excellent productivity. A method for producing a metal nitride film is provided, wherein the metal nitride film is formed on at least a portion of the surface of a substrate to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material, wherein the nitrogen-containing compound raw material contains hydrazine and ammonia.

Description

Technical Field

[0001] The present invention relates to a mixed gas supply device, a metal nitride film manufacturing device and a metal nitride film manufacturing method. Background Art

[0002] Metal nitride films are widely used for many purposes due to their physical, chemical, electrical and mechanical properties. For example, silicon nitride films (SiN) are used for gate insulating films, sidewall spacers, etc. when forming transistors. In addition, titanium nitride films (TiN), tantalum nitride films (TaN) and tungsten nitride films (WN) are used for barrier films for wiring of integrated circuits, etc.

[0003] In particular, in recent years, the miniaturization of three-dimensional transistor structures such as Fin-FET (Fin Field-Effect Transistor) in cutting-edge logic and the high integration of 3D-NAND have been further promoted. As the horizontal and vertical dimensions of integrated circuits continue to shrink, thin film formation technology with sub-nanometer film thickness control and good coverage characteristics is required.

[0004] Generally, the metal nitride film is formed by simultaneously or alternately supplying a raw material gas (metal compound raw material) and a reaction gas (nitrogen-containing compound raw material) into a processing chamber (chamber). Specifically, in the processing chamber, the metal compound adsorbed on the surface of the substrate to be processed (substrate) chemically reacts with the nitrogen-containing compound by thermal energy to form a thin film on the surface of the substrate to be processed.

[0005] The method of forming a thin film by alternately supplying raw material gas and reaction gas into a processing chamber is called atomic layer deposition (ALD). In the ALD method, a film is formed on the surface of the substrate to be processed in atomic layers, so that On the other hand, the productivity (i.e., film formation speed) of the ALD method is inferior to that of the chemical vapor deposition method (CVD).

[0006] In addition, although the ALD method is known to be a plasma-assisted method that can realize film formation at a relatively low temperature by supplying a reaction gas in a plasma-activated state, it has major disadvantages such as damage to a substrate (substrate) as a base and inability to obtain good step coverage. Therefore, it is desired to form a metal nitride film at a low temperature by a general ALD method and to develop raw materials and film formation processes for film formation.

[0007] However, in the formation of silicon nitride films, it is generally known to use ammonia (NH3) as a reaction gas (Non-Patent Document 1 and Patent Document 1). In addition, in the formation of silicon nitride films, it is known that the film can be formed at a low temperature by using an amine compound or a hydrazine compound instead of ammonia. Specifically, Non-Patent Document 2 discloses a method for manufacturing a silicon nitride film using hydrazine (N2H4) as a reaction gas.

[0008] On the other hand, it is known that ammonia (NH3) is also used as a reaction gas in the formation of metal nitride films other than silicon nitride films. Specifically, non-patent document 3 discloses a method for manufacturing a titanium nitride film using titanium tetrachloride (TiC4) as a raw material gas and ammonia (NH3) as a reaction gas.

[0009] In addition, it is known that hydrazine compounds can also be used as a substitute for ammonia in the formation of metal nitride films other than silicon nitride films. Specifically, Patent Document 2 discloses a method for manufacturing a titanium nitride film using titanium tetrachloride (TiC4) as a raw material gas and monomethylhydrazine (MMH: NH2NH2Me) as a reaction gas.

[0010] Patent Document 1: Japanese Patent Publication No. 2002-343793

[0011] Patent Document 2: Japanese Patent Publication No. 2010-248624

[0012] Non-patent document 1: M. Tanaka et al., J. Electrochem. Soc. 147, 2284 (2000)

[0013] Non-patent document 2: S. Morishita et al., Appl. Surf. Sci. 112, 198 (1997)

[0014] Non-patent document 3: CHAhn et al., METALS AND MATERIALS International., vol. 7, No. 6, 621 (2001)

[0015] However, as shown in Non-Patent Document 1, Patent Document 1 and Non-Patent Document 3, when ammonia is used as a reaction gas in the formation of a metal nitride film, there are problems of slow film formation speed and low productivity. In particular, when the film formation temperature is set to a low temperature (specifically, less than 350° C. in the formation of a titanium nitride film), not only the film formation speed is significantly reduced, but also oxygen enters the film, thereby causing a problem of deterioration of the film quality.

[0016] On the other hand, as shown in Non-Patent Document 2 and Patent Document 2, when a hydrazine compound (specifically, hydrazine, monomethylhydrazine, etc.) is used as a reaction gas during the formation of a metal nitride film, the film formation speed is faster than when ammonia is used, and a lower film formation temperature can be achieved. However, since the hydrazine compound is highly toxic and reactive, it needs to be handled with care, and since the hydrazine compound is a liquid material with a relatively low vapor pressure, it is difficult to maintain a sufficient supply amount and safely supply it into the processing chamber when replacing ammonia as a reaction gas. Summary of the invention

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a mixed gas supply apparatus capable of safely and stably supplying a mixed gas containing a nitrogen-containing compound raw material which is useful as a reaction gas when forming a nitride film.

[0018] Another object of the present invention is to provide an apparatus for producing a metal nitride film and a method for producing a metal nitride film that have a high film forming speed and excellent productivity.

[0019] In order to solve the above-mentioned problems, the present invention provides the following mixed gas supply device, metal nitride film manufacturing device and metal nitride film manufacturing method.

[0020] (1) A mixed gas supply device for supplying a mixed gas containing a hydrazine compound and ammonia as a nitrogen-containing compound raw material, comprising:

[0021] a raw material container for containing the hydrazine compound;

[0022] A heater, located around the raw material container, for heating the raw material container;

[0023] A heater adjustment device for adjusting the output power of the heater;

[0024] An introduction path for introducing a carrier gas into the raw material container;

[0025] an outlet path for outlet the gas containing the hydrazine compound from the raw material container;

[0026] A dilution gas supply path for supplying dilution gas;

[0027] an ammonia supply path for supplying the ammonia;

[0028] A mixed gas outlet path connected to the outlet path to outlet the mixed gas;

[0029] a dilution gas flow control device, located in the dilution gas supply path, for controlling the flow rate of the dilution gas supplied to the dilution gas supply path;

[0030] an ammonia flow control device, located in the ammonia supply path, and controlling the flow rate of ammonia supplied to the ammonia supply path;

[0031] a mixed gas flow meter located in the mixed gas outlet path and measuring the flow rate of the mixed gas outlet to the mixed gas outlet path; and

[0032] a calculation device that calculates the flow rate of the hydrazine compound contained in the mixed gas based on the flow rate of the dilution gas, the flow rate of the ammonia, and the flow rate of the mixed gas,

[0033] The ammonia supply path is connected to at least any one of the introduction path, the outlet path, and the mixed gas outlet path.

[0034] The dilution gas supply path is connected to one or both of the introduction path and the outlet path.

[0035] (2) The mixed gas supply device according to (1), wherein:

[0036] A bypass path is further provided, the bypass path branching from the introduction path and merging with the discharge path without passing through the raw material container.

[0037] (3) The mixed gas supply device according to (1) or (2), comprising:

[0038] A first pressure gauge, located in the outlet path, for measuring the pressure in the raw material container;

[0039] a switch valve capable of adjusting the opening degree, located in the outlet path or the mixed gas outlet path; and

[0040] The pressure regulating device adjusts the opening of the on-off valve based on the measurement value of the first pressure gauge.

[0041] (4) The mixed gas supply device according to (3), comprising:

[0042] A storage tank, located on the mixed gas outlet path, storing the mixed gas;

[0043] a second pressure gauge for measuring the pressure in the storage tank; and

[0044] A flow path selection device selects the open / closed states of the ammonia supply path and the derivation path based on the measurement values ​​of the first pressure gauge and the second pressure gauge.

[0045] (5) The mixed gas supply device according to any one of (1) to (3), wherein:

[0046] The computing device has a function of calculating a difference between a calculated value and a set value of the flow rate of the hydrazine compound and updating a set value of the heater adjusting device based on the difference.

[0047] (6) The mixed gas supply device according to any one of (1) to (3), wherein:

[0048] The calculation device has a function of calculating a difference between a calculated value of the content ratio of the hydrazine compound contained in the mixed gas and a set value, and updating set values ​​of the dilution gas flow rate control device and the ammonia flow rate control device based on the difference.

[0049] (7) The mixed gas supply device according to (3), wherein:

[0050] The calculation device has a function of calculating a difference between a calculated value of the content ratio of the hydrazine compound contained in the mixed gas and a set value, and updating a set value of the pressure regulating device based on the difference.

[0051] (8) The mixed gas supply device according to any one of (1) to (7), wherein:

[0052] The concentration of H2O contained in the nitrogen-containing compound raw material is 0.1 ppm or less.

[0053] (9) The mixed gas supply device according to any one of (1) to (8), wherein:

[0054] The concentration of H2O contained in the hydrazine compound is 10 ppm or less.

[0055] (10) The mixed gas supply device according to any one of (1) to (9), wherein:

[0056] The hydrazine compound is hydrazine (N2H4).

[0057] (11) A metal nitride film manufacturing apparatus, which forms a metal nitride film on at least a portion of a surface of a substrate to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material, wherein:

[0058] A mixed gas supply device according to any one of (1) to (10) is provided.

[0059] (12) A method for producing a metal nitride film, comprising forming a metal nitride film on at least a portion of a surface of a substrate to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material, wherein:

[0060] The nitrogen-containing compound raw material comprises hydrazine and ammonia.

[0061] (13) The method for producing a metal nitride film according to (12), comprising:

[0062] A preparation step of placing the substrate to be processed in a processing chamber and controlling the surface temperature of the substrate to be processed to a desired temperature; and

[0063] The film forming process repeats the following cycle:

[0064] The cycle comprises:

[0065] The step of supplying the metal compound raw material into the processing chamber;

[0066] a step of stopping the supply of the metal compound raw material;

[0067] The step of supplying the nitrogen-containing compound raw material into the processing chamber; and

[0068] The step of stopping the supply of the nitrogen-containing compound raw material.

[0069] (14) The method for producing a metal nitride film according to (13), wherein:

[0070] The cycle further includes a step of supplying the ammonia or the ammonia diluted with an inert gas into the processing chamber.

[0071] (15) The method for producing a metal nitride film according to (13) or (14), wherein:

[0072] In the step of supplying the nitrogen-containing compound raw material into the processing chamber,

[0073] The ammonia is introduced into a raw material container which is heated to a desired temperature and contains the hydrazine, and a mixed gas of the hydrazine and the ammonia discharged from the raw material container is used as the nitrogen-containing compound raw material.

[0074] (16) The method for producing a metal nitride film according to (15), wherein:

[0075] In the step of supplying the nitrogen-containing compound raw material into the processing chamber,

[0076] The adjusted mixed gas is stored in a storage tank, and the mixed gas output from the storage tank is used as the nitrogen-containing compound raw material.

[0077] (17) The method for producing a metal nitride film according to (15) or (16), wherein:

[0078] The content ratio of the hydrazine to the ammonia in the mixed gas is 1:99 to 50:50 in terms of volume flow ratio.

[0079] The mixed gas supply device of the present invention can safely and stably supply a mixed gas containing a nitrogen-containing compound raw material useful as a reaction gas when forming a nitride film.

[0080] In addition, the metal nitride film manufacturing apparatus and the metal nitride film manufacturing method of the present invention have a high film forming speed and excellent productivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0081] Figure 1 It is a system diagram schematically showing the structure of one embodiment of the metal nitride film manufacturing apparatus of the present invention.

[0082] Figure 2 It is a system diagram schematically showing the structure of a first embodiment of the mixed gas supply device of the present invention.

[0083] Figure 3 It is a system diagram schematically showing the structure of a second embodiment of the mixed gas supply device of the present invention.

[0084] Figure 4 It is a system diagram schematically showing the structure of a third embodiment of the mixed gas supply device of the present invention.

[0085] Figure 5 It is a system diagram schematically showing the structure of a fourth embodiment of the mixed gas supply device of the present invention.

[0086] Figure 6 It is a system diagram schematically showing the structure of a fifth embodiment of the mixed gas supply device of the present invention.

[0087] Figure 7 It is a system diagram schematically showing the structure of a sixth embodiment of the mixed gas supply device of the present invention.

[0088] Figure 8 It is a system diagram schematically showing the structure of a seventh embodiment of the mixed gas supply device of the present invention.

[0089] Fig. 9 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0090] Fig.10 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0091] Fig.11 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0092] Fig.12This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0093] Fig.13 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0094] Fig.14 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention. DETAILED DESCRIPTION

[0095] The following terms in this specification have the following meanings.

[0096] "Nitrogen-containing compound raw material" refers to a substance containing nitrogen-containing compounds having one or more nitrogen atoms as a main component. In addition, the nitrogen-containing compound raw material may contain two or more nitrogen-containing compounds within an appropriate range. In addition, the nitrogen-containing compound raw material may contain original raw materials before purification, by-products generated when synthesizing nitrogen-containing compounds, and by-products generated during storage as impurities within an appropriate range.

[0097] "Metal nitride film" refers to a film containing metal elements and N atoms as main components. In addition, the metal nitride film may also contain O atoms and C atoms in the film within an appropriate range. Specifically, the metal nitride film may contain 0 to 30 atomic % of O atoms and 0 to 30 atomic % of C atoms in the film.

[0098] The term “to” indicating a numerical range means that the numerical values ​​described before and after the “to” are included as the lower limit and the upper limit.

[0099] <Metal Nitride Film Manufacturing Apparatus>

[0100] First, the metal nitride film manufacturing apparatus of the present invention will be described in detail with reference to the drawings. Figure 1 It is a system diagram schematically showing the structure of one embodiment of the metal nitride film manufacturing apparatus of the present invention.

[0101] like Figure 1 As shown, the metal nitride film manufacturing device (hereinafter, also referred to as "film forming device") 1 of the present embodiment includes: a processing chamber (chamber) 2 as a reaction field; a temperature control device 3 for controlling the surface temperature of the substrate P to be processed in the processing chamber 2; a purge gas supply path L1 for supplying a purge gas to the processing chamber 2; an exhaust path L2 for exhausting the atmosphere in the processing chamber 2; a raw gas supply path L3 for supplying a metal compound raw material as a raw material gas; and a reaction gas supply path L4 for supplying a nitrogen-containing compound raw material as a reaction gas.

[0102] The film forming apparatus 1 of this embodiment is a film forming apparatus that forms a metal nitride film on at least a portion of the surface of the substrate P to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material. The film forming apparatus 1 is not particularly limited as long as it can be applied to the chemical vapor growth method. As the film forming apparatus 1, a CVD (chemical vapor deposition) apparatus or an ALD (atomic layer deposition) apparatus can be used.

[0103] The substrate P to be processed is not particularly limited as long as a metal nitride film can be formed on at least a portion of the surface. The substrate P to be processed is not particularly limited, and examples thereof include semiconductor wafers, resins, and glass. Specifically, crystalline silicon (Si <100> or Si <111> The invention can be applied to metals such as silicon nitride, silicon carbide, silicon carbonitride, silicon oxynitride, silicon oxycarbide, silicon oxynitride, metals such as Cu, Al, Ru, Ta, W, Ti, Co, Zr, and Hf, metal nitrides such as TiN, TaN, and WN, metal oxides such as ZrO, HfO, TiO, TaO, and WO, patterned or unpatterned wafers, semiconductor wafers including at least one of the above, etc. In addition, resins such as polyethylene, polypropylene, polyolefin resins, polyvinyl chloride resins, fluorine resins, and polyester resins can be used.

[0104] The metal nitride film is not particularly limited as long as it contains one or more metal elements selected from the group consisting of silicon (Si), titanium (Ti), tantalum (Ta), aluminum (Al), gallium (Ga), vanadium (V), iron (Fe), zirconium (Zr), niobium (Nb), tungsten (W), molybdenum (Mo), indium (In) and hafnium (Hf). Among them, it is preferred to contain one or more of silicon, titanium and tantalum.

[0105] Specifically, examples of the silicon-containing metal nitride film include silicon nitride film (SiN), silicon carbonitride film (SiCN), silicon oxynitride film (SiON), and silicon oxycarbonitride film (SiOCN). Among them, silicon nitride film and silicon carbonitride film are preferred, and silicon nitride film is more preferred.

[0106] Examples of the titanium-containing nitride film include titanium nitride film (TiN), titanium carbonitride film (TiCN), titanium oxynitride film (TiON), and titanium oxycarbonitride film (TiOCN). Among them, titanium nitride film and titanium carbonitride film are preferred, and titanium nitride film is more preferred.

[0107] The temperature control device 3 is not particularly limited as long as it can control the surface temperature of the substrate P in the processing chamber 2 to a desired temperature. As the temperature control device 3, a heater and a control device thereof can be used.

[0108] The temperature control device 3 can heat the surface temperature of the substrate P to be processed in the processing chamber 2 to any temperature. Specifically, the temperature can be controlled to be above 500°C or below 500°C. When film formation at a lower temperature is required, the surface temperature of the substrate P to be processed can be controlled to be below 450°C.

[0109] The purge gas supply path L1 supplies a purge gas into the processing chamber 2 .

[0110] The purge gas is not particularly limited, and examples thereof include rare gases such as helium (He) and argon (Ar), nitrogen (N 2 ), hydrogen (H 2 ), etc. The purge gas may be any one of these or a mixture of two or more thereof.

[0111] The exhaust path L2 decompresses the processing chamber 2 by exhausting the atmosphere gas including the purge gas, the source gas, the reaction gas, etc. in the processing chamber 2 from the processing chamber 2. A decompression device 4 such as a decompression pump is arranged on the exhaust path L2.

[0112] The source gas supply path L3 merges with the purge gas supply path L1, and supplies a metal compound source as a source gas through the purge gas supply path L1 into the processing chamber 2. The source gas supply path L3 is connected to a source of supply of the metal compound source (not shown).

[0113] The metal compound raw material is not particularly limited, and examples thereof include metal halogen compounds and organic metal compounds.

[0114] Specifically, the metal halogen compound includes TiCl4, Si2Cl6 (HCDS: hexachlorodisilane), SiCl4, SiHCl3, SiH2Cl2, SiH3Cl, SiI4, SiHI3, SiH2I2, SiH3I, TaCl5, AlCl3, GaCl3, ZrCl4, HfCl4, MoCl5, WF6, WCl6, and WCl5. It is preferred to use any one or two or more of them as the metal compound raw material.

[0115] In addition, examples of the organometallic compound include TDMAT (tetrakis(dimethylamino)titanium), 3DMAS (tris(dimethylamino)silane), BDEAS (bis(diethylamino)silane), BTBAS (bis(tert-butylamino)silane), PDMAT (penta(dimethylamino)tantalum), TMA (trimethylaluminum), and TMG (trimethylgallium). It is preferred to use any one or two or more of them as the metal compound raw material.

[0116] In addition, the metal compound raw material may be supplied into the processing chamber 2 together with a carrier gas such as an inert gas.

[0117] The carrier gas is not particularly limited, and examples thereof include rare gases such as helium (He) and argon (Ar), nitrogen (N 2 ), and hydrogen (H 2 ). The carrier gas may be any one of these or a mixture of two or more thereof.

[0118] The reaction gas supply path L4 merges with the purge gas supply path L1, and supplies the nitrogen-containing compound raw material as the reaction gas into the processing chamber 2 via the purge gas supply path L1. The mixed gas supply device 10 is located in the reaction gas supply path L4. That is, the film forming apparatus 1 of the present embodiment includes any one of the mixed gas supply devices 10 to 70 of the first to seventh modes described later as a supply source of the nitrogen-containing compound raw material, and supplies the mixed gas supplied by the mixed gas supply device into the processing chamber 2 as the reaction gas.

[0119] <Mixed gas supply device>

[0120] Next, the mixed gas supply device of the present invention will be described with reference to the drawings.

[0121] The mixed gas supply device of the present invention is a device for supplying a mixed gas containing a hydrazine compound and ammonia as a nitrogen-containing compound raw material.

[0122] (First method)

[0123] Figure 2 It is a system diagram schematically showing the structure of a first embodiment of the mixed gas supply device of the present invention.

[0124] like Figure 2 As shown, the mixed gas supply device 10 of the first mode includes: a raw material container 11 for accommodating a hydrazine compound; a heater 12 for heating the raw material container 11; a heater adjustment device 13 for adjusting the output power of the heater 12; an inlet path L11 and an outlet path L12 connected to the raw material container 11; a dilution gas supply path L13 for supplying a dilution gas; an ammonia supply path L14 for supplying ammonia; a mixed gas outlet path L15 connected to the outlet path L12; a bypass path L16 located between the inlet path L11 and the outlet path L12; a dilution gas flow control device 14; an ammonia flow control device 15; a mixed gas flow meter 16; and a computing device 17.

[0125] The raw material container 11 is a container (supply source) that accommodates a hydrazine compound as a nitrogen-containing compound.

[0126] The hydrazine compound is not particularly limited, and examples thereof include hydrazine (N2H4), monomethylhydrazine, dimethylhydrazine, tert-butylhydrazine, phenylhydrazine, propylhydrazine, and the like. As the hydrazine compound, any one of the hydrazine compounds can be selected from the group thereof, or two or more thereof can be mixed and used. In addition, in the manufacturing device and manufacturing method of the metal nitride film of the present invention, hydrazine is preferably used alone as the hydrazine compound. Since only hydrazine is used, carbon from the hydrazine compound will not be mixed into the metal nitride film, and significant degradation of electrical properties can be prevented.

[0127] In general, it is known that hydrazine compounds can produce explosive reactions so that they can be used as propellants for spacecraft or fuel for rocket engines. In addition, hydrazine and monomethylhydrazine are highly toxic, and their allowable concentration (TLV-TWA) is 0.01ppm, which is much lower than ammonia (allowable concentration: 25ppm), phosphine (allowable concentration: 0.3ppm), and monosilane (allowable concentration: 5ppm) used in semiconductor manufacturing processes. In the NFPA (National Fire Protection Association), which is a standard for indicating the danger of chemicals, hydrazine is 4-4-4 (Health-Flammability-Instability) and monomethylhydrazine is 4-3-2. It can be seen that these properties are also obvious, and full consideration of safety is required in handling. Therefore, the raw material container 11 is preferably a sealed container.

[0128] The heater 12 is located around the raw material container 11 and heats the raw material container 11 so that the hydrazine compound in the raw material container 11 is within a predetermined temperature range.

[0129] The heater 12 is not particularly limited as long as it can heat the raw material container 11. Examples of the heater 12 include a breeze heater, a mantle heater, a water bath, and an oil bath. Among them, when heating the hydrazine compound in the container, a water bath or an oil bath is preferably used from the viewpoint of heat uniformity and safety.

[0130] The heater adjustment device 13 is not particularly limited as long as it can adjust (control) the output of the heater 12. The heater adjustment device 13 only needs to have a function of adjusting (controlling) the output of the heater 12, and may be integrated with the heater 12.

[0131] The temperature at which the raw material container 11 is heated by the heater 12 and the heater adjustment device 13 can be appropriately set according to the supply flow rate of the hydrazine compound raw material. In addition, in order to safely handle the hydrazine compound, the heating temperature of the raw material container 11 is set below the decomposition temperature of the hydrazine compound. Specifically, it is preferably set in the range of room temperature (20°C) to 100°C, and more preferably in the range of 30 to 60°C.

[0132] The introduction path L11 is a line for introducing a carrier gas into the raw material container 11. The front end of the introduction path L11 in the gas flow direction is connected to the raw material container 11. That is, the flow path in the introduction path L11 communicates with the space in the raw material container 11.

[0133] The outlet path L12 is a line for outlet gas containing hydrazine compound from the raw material container 11. The base end of the outlet path L12 in the gas flow direction is connected to the raw material container 11. That is, the flow path in the outlet path L12 communicates with the space in the raw material container 11.

[0134] In the mixed gas supply device 10 of this embodiment, an introduction path L11 and an outlet path L12 are connected to the raw material container 11, so that ammonia and a diluent gas described later can be introduced into the raw material container 11 from the introduction path L11 as a carrier gas, and the hydrazine compound with the carrier gas can be discharged into the outlet path L12 in the form of gas. In addition, when the carrier gas is introduced into the raw material container 11, it can be supplied by bubbling, or it can be supplied to the gas phase (that is, the vapor of the hydrazine compound) in the container.

[0135] The mixed gas outlet path L15 is a path for supplying a mixed gas containing a hydrazine compound and ammonia to the outside of the mixed gas supply device 10. The base end of the mixed gas outlet path L15 is connected to the outlet path L12 at the front end Q of the outlet path L12. In addition, the front end of the mixed gas outlet path L15 is connected to the reaction gas supply path L4 of the above-mentioned film forming apparatus 1.

[0136] In addition, a pipe heater 18 is provided in the outlet path L12 and the mixed gas outlet path L15 so as to cover the surface of these pipes. By providing the pipe heater 18 in the path where the gas (gas) containing the hydrazine compound flows, it is possible to maintain a temperature higher than that of the raw material container 11. Thus, the hydrazine compound can be prevented from being liquefied again in the outlet path L12 and the mixed gas outlet path L15, and the mixed gas containing the hydrazine compound can be safely and stably supplied to the reaction gas supply path L4.

[0137] The bypass path L16 branches from the introduction path L11 and merges with the outlet path L12 without passing through the raw material container 11. By selecting the bypass path L16 as the flow path, the carrier gas supplied to the introduction path L11 can be supplied to the outlet path L12 on the secondary side of the raw material container 11 without being introduced into the raw material container 11. In addition, when removing the gas containing the hydrazine compound remaining in the outlet path L12, the dilution gas is supplied through the bypass path L16, thereby effectively purging and removing the residual gas.

[0138] The dilution gas supply path L13 is a path for supplying dilution gas. In the present embodiment, the dilution gas supply path L13 is connected to the inlet path L11, the outlet path L12, and the mixed gas outlet path L15 at the base end P of the inlet path L11 and the front end Q of the outlet path L12 (i.e., the base end Q of the mixed gas outlet path L15). Since the dilution gas supply path L13 is connected to the inlet path L11, the dilution gas can be supplied to the inlet path L11 as a carrier gas. In addition, since the dilution gas supply path L13 is connected to the outlet path L12 and the mixed gas outlet path L15, the dilution gas supplied from the dilution gas supply path L13 is mixed with the gas containing the hydrazine compound supplied from the outlet path L12 to adjust the concentration, and then can be supplied to the mixed gas outlet path L15.

[0139] The diluent gas is not particularly limited, and includes rare gases such as helium (He), argon (Ar), nitrogen (N2), hydrogen (H2), etc. The diluent gas may be any one of them, or two or more may be mixed and used. In addition, in the mixed gas supply device 10 of this embodiment, the diluent gas is an arbitrary component, so the diluent gas may not be used.

[0140] The ammonia supply path L14 is a path for supplying ammonia as a nitrogen-containing compound in the form of gas. In the present embodiment, the ammonia supply path L14 is connected to the inlet path L11 at the base end P of the inlet path L11. Since the ammonia supply path L14 is connected to the inlet path L11, ammonia can be supplied to the inlet path L11 as a carrier gas. In addition, by selecting the bypass path L16 as the flow path, ammonia can be supplied to the outlet path L12 on the secondary side of the raw material container 11 without passing through the raw material container 11. Furthermore, since the ammonia supply path L14 is connected to the dilution gas supply path L13, the ammonia supplied from the dilution gas supply path L13 is mixed with the gas containing the hydrazine compound supplied from the outlet path L12 to adjust the concentration, and then can be supplied to the mixed gas outlet path L15. In addition, when supplying ammonia, the dilution gas may not be included.

[0141] In the mixed gas supply device 10 of this embodiment, one or more on-off valves are provided on each path, and by appropriately selecting the on-off state of the on-off valve, any flow path can be formed according to the purpose.

[0142] The dilution gas flow control device 14 is located in the dilution gas supply path L13. The dilution gas flow control device 14 controls the flow rate of the dilution gas supplied to the dilution gas supply path L13. The dilution gas flow control device 14 is not particularly limited as long as it can control the flow rate. As the dilution gas flow control device 14, for example, a mass flow controller (MFC) or a pressure regulator with a controllable opening can be cited.

[0143] The ammonia flow control device 15 is located on the ammonia supply path L14. The ammonia flow control device 15 controls the flow rate of ammonia supplied to the ammonia supply path L14. The ammonia flow control device 15 is not particularly limited as long as it can control the flow rate. As the ammonia flow control device 15, for example, a mass flow controller (MFC) or a pressure regulator with a controllable opening can be cited.

[0144] The flow rate of ammonia supplied to the ammonia supply path L14 is not particularly limited and can be appropriately selected. The control range of the ammonia flow rate by the ammonia flow rate control device 15 is preferably in the range of 10 to 10,000 sccm.

[0145] The mixed gas flow meter 16 is located in the mixed gas outlet path L15. The mixed gas flow meter 16 measures the flow rate of the mixed gas outlet to the mixed gas outlet path L15. The mixed gas flow meter 16 is not particularly limited as long as it can measure the flow rate. As the mixed gas flow meter 16, for example, a mass flow meter (MFM) can be cited.

[0146] The computing device 17 calculates the flow rate of the hydrazine compound contained in the mixed gas. The computing device 17 can transmit and receive electrical signals with the dilution gas flow control device 14, the ammonia flow control device 15, and the mixed gas flow meter 16 by wire or wireless. Thus, the computing device 17 receives the values ​​of the dilution gas flow rate, the ammonia flow rate, and the mixed gas flow rate in the form of electrical signals, and can calculate the flow rate of the hydrazine compound contained in the mixed gas and the content ratio of the hydrazine compound contained in the mixed gas based on these values.

[0147] According to the mixed gas supply device 10 of this embodiment, by introducing ammonia as a carrier gas from the introduction path L11 into the raw material container 11, the mixed gas containing the hydrazine compound and ammonia can be safely and stably discharged to the mixed gas discharge path L15. This can effectively carry along a large amount of vapor of the hydrazine compound contained in the raw material container 11, which is more preferable.

[0148] Furthermore, according to the mixed gas supply device 10 , a diluent gas may be used as the carrier gas, or a mixed gas of ammonia and the diluent gas may be used.

[0149] In addition, according to the mixed gas supply device 10, when ammonia is not used as a carrier gas, ammonia is supplied to the mixed gas outlet path L15 via the dilution gas supply path L13, or ammonia is supplied to the outlet path L12 via the ammonia supply path L14, the introduction path L11, and the bypass path L16. Thus, the mixed gas containing the hydrazine compound and ammonia can be discharged to the mixed gas outlet path L15.

[0150] In addition, according to the mixed gas supply device 10, without using the dilution gas as the carrier gas, the dilution gas is supplied from the dilution gas supply path L13 to the mixed gas outlet path L15, or the dilution gas is supplied to the outlet path L12 via the dilution gas supply path L13, the introduction path L11 and the bypass path L16, thereby enabling the mixed gas diluted to any concentration to be outlet to the mixed gas outlet path L15.

[0151] Furthermore, according to the mixed gas supply device 10, the calculation device 17 monitors the dilution gas flow rate, ammonia flow rate and mixed gas flow rate, so that the flow rate and content ratio of the hydrazine compound contained in the mixed gas can be grasped regardless of the presence or absence of the dilution gas.

[0152] (Second method)

[0153] Figure 3 It is a system diagram schematically showing the structure of a second embodiment of the mixed gas supply device of the present invention.

[0154] like Figure 3 As shown, the difference between the mixed gas supply device 20 of the second embodiment and the mixed gas supply device 10 is that an ammonia supply path L24 is provided to replace the ammonia supply path L14 constituting the mixed gas supply device 10, and the other structures are the same. Therefore, in the mixed gas supply device 20 of this embodiment, the same reference numerals are attached to the same structures as those of the mixed gas supply device 10, and their descriptions are omitted.

[0155] The ammonia supply path L24 is a path for supplying ammonia as a nitrogen-containing compound in the form of gas. In this embodiment, the ammonia supply path L24 is branched into a path L24A and a path L24B on the secondary side of the ammonia flow control device 15. In addition, switch valves are respectively provided on the path L24A and the path L24B, and the path can be appropriately selected by combining the switch states of these switch valves.

[0156] The path L24A is connected to the mixed gas lead-out path L15 at the base end Q of the mixed gas lead-out path L15.

[0157] When the path L24A is selected, the path L24A is connected to the mixed gas outlet path L15, so after ammonia is supplied to the gas containing the hydrazine compound supplied from the outlet path L12, it can be supplied to the mixed gas outlet path L15 as a mixed gas. In addition, the dilution gas flow rate, the ammonia flow rate, and the mixed gas flow rate are monitored in the computing device 17, so the flow rate of the hydrazine compound contained in the mixed gas and the content ratio of the hydrazine compound contained in the mixed gas can be grasped regardless of the presence or absence of the dilution gas.

[0158] The path L24B is connected to the mixed gas lead-out path L15 on the secondary side of the mixed gas flow meter 16 of the mixed gas lead-out path L15.

[0159] When the path L24B is selected, the path L24B is connected to the mixed gas outlet path L15, so that the gas containing the hydrazine compound and ammonia can be mixed in the mixed gas outlet path L15. In addition, the dilution gas flow rate and the mixed gas flow rate are monitored in the computing device 17, so the hydrazine compound flow rate can be calculated regardless of the presence or absence of the dilution gas. Furthermore, the content ratio of the hydrazine compound in the mixed gas on the secondary side of the mixed gas flowmeter 16 can be grasped based on the value of the ammonia flow rate.

[0160] According to the mixed gas supply device 20 of this embodiment, similarly to the mixed gas supply device 10 described above, the mixed gas containing the hydrazine compound and ammonia can be safely and stably discharged to the mixed gas discharge path L15 .

[0161] (Third Method)

[0162] Figure 4 It is a system diagram schematically showing the structure of a third embodiment of the mixed gas supply device of the present invention.

[0163] like Figure 4 As shown, the difference between the mixed gas supply device 30 of the third embodiment and the mixed gas supply device 10 is that, on the basis of the structure of the mixed gas supply device 10, a first pressure gauge 31, a switch valve 32 and a pressure regulating device 33 are further provided, while the other structures are the same. Therefore, in the mixed gas supply device 30 of this embodiment, the same reference numerals are attached to the same structures as those of the mixed gas supply device 10, and their descriptions are omitted.

[0164] The first pressure gauge 31 is located in the lead-out path L12 and measures the pressure in the raw material container 11 .

[0165] The on-off valve 32 is located in the outlet path L12 or the mixed gas outlet path L15. The on-off valve 32 can freely adjust the opening degree between fully closed (opening degree 0%) and fully open (opening degree 100%).

[0166] The pressure regulating device 33 can transmit and receive electric signals with the first pressure gauge 31 and the switch valve 32 by wire or wirelessly. Specifically, the pressure regulating device 33 sends a control signal for adjusting the opening of the switch valve 32 to the switch valve 32 based on the measured value of the pressure in the raw material container 11 received from the first pressure gauge 31.

[0167] According to the mixed gas supply device 30 of this embodiment, similarly to the mixed gas supply device 10 described above, the mixed gas containing the hydrazine compound and ammonia can be safely and stably discharged to the mixed gas discharge path L15 .

[0168] Furthermore, according to the mixed gas supply device 30 of this embodiment, the first pressure gauge 31 and the on-off valve 32 are linked via the pressure regulator 33 , thereby freely controlling the pressures of the raw material container 11 , the outlet path L12 , and the mixed gas outlet path L15 .

[0169] Furthermore, according to the mixed gas supply device 30 of the present embodiment, when the carrier gas is not supplied into the raw material container 11 , the vapor pressure of the hydrazine compound can be measured by the first pressure gauge 31 .

[0170] (Fourth Method)

[0171] Figure 5 It is a system diagram schematically showing the structure of a fourth embodiment of the mixed gas supply device of the present invention.

[0172] like Figure 5 As shown, the difference between the mixed gas supply device 40 of the fourth embodiment and the mixed gas supply device 30 is that the mixed gas supply device 40 is further provided with a setting device 41 on the basis of the structure of the mixed gas supply device 30, and the other structures are the same. Therefore, in the mixed gas supply device 40 of this embodiment, the same reference numerals are attached to the same structures as those of the mixed gas supply device 30, and their descriptions are omitted.

[0173] The setting device 41 is a device that inputs the flow rate of the hydrazine compound in the mixed gas and the content ratio of ammonia and the hydrazine compound in the mixed gas as setting values.

[0174] The computing device 17 can transmit and receive electrical signals with the setting device 41 and the heater adjustment device 13 by wire or wireless in addition to the above functions. Specifically, the computing device 17 has the following functions: calculating the difference between the calculated value of the hydrazine compound flow rate and the set value referenced from the setting device 41, and updating (correcting, changing) the set value of the heater adjustment device 13 based on the difference.

[0175] According to the mixed gas supply device 40 of this embodiment, similarly to the mixed gas supply device 30 described above, the mixed gas containing the hydrazine compound and ammonia can be safely and stably discharged to the mixed gas discharge path L15 .

[0176] Furthermore, according to the mixed gas supply device 40 of the present embodiment, the set value of the heating temperature of the raw material container 11 can be automatically updated so that the flow rate and content ratio of the hydrazine compound calculated by the operation device 17 become the set flow rate and content ratio. That is, when the calculated value of the hydrazine compound flow rate is less than the set value, or when the flow rate of the hydrazine compound is reduced as the mixed gas is continuously supplied, the vapor pressure of the hydrazine compound in the raw material container 11 becomes insufficient. Therefore, by automatically adjusting the heating temperature of the raw material container 11 (that is, the set value of the heater adjustment device 13) to match the set value, the mixed gas can be supplied more stably.

[0177] On the other hand, when the calculated value of the hydrazine compound flow rate is greater than the set value, the vapor pressure of the hydrazine compound in the raw material container 11 is excessive, and therefore the temperature in the raw material container 11 can be lowered by temporarily stopping the output power of the heater 12 for heating the raw material container 11. Therefore, according to the mixed gas supply device 40 of this embodiment, the mixed gas can be supplied more safely.

[0178] Furthermore, the mixed gas supply device 40 of the present embodiment may include an interlock mechanism (interlock) for forcibly closing an on-off valve in a path near the raw material container 11. This can reliably stop the flow rate of the hydrazine compound.

[0179] In addition, the supply of ammonia and dilution gas may be forcibly stopped in accordance with the stop of the supply of the hydrazine compound, or only the dilution gas may be automatically supplied so that no ammonia and hydrazine compound remain in the path. Furthermore, all the on-off valves in the mixed gas supply device 40 may be forcibly closed. By providing these interlock mechanisms, it is possible to prevent excessive supply of the hydrazine compound in advance, so that the mixed gas can be supplied more safely.

[0180] (Fifth Method)

[0181] Figure 6 It is a system diagram schematically showing the structure of a fifth embodiment of the mixed gas supply device of the present invention.

[0182] like Figure 6 As shown, the mixed gas supply device 50 of the fifth embodiment is different from the mixed gas supply device 40 in that the function of the computing device 17 constituting the mixed gas supply device 40 is different, while the other structures are the same. Therefore, in the mixed gas supply device 50 of this embodiment, the same reference numerals are attached to the same structures as those of the mixed gas supply device 40, and the description thereof is omitted.

[0183] The operation device 17 can transmit and receive electrical signals with the setting device 41, the dilution gas flow control device 14, and the ammonia flow control device 15 by wire or wireless in addition to the above functions. Specifically, the operation device 17 has the following functions: calculating the difference between the calculated value of the hydrazine compound flow rate and the set value referenced from the setting device 41, and updating (correcting, changing) the set values ​​of the dilution gas flow control device 14 and the ammonia flow control device 15 based on the difference.

[0184] According to the mixed gas supply device 50 of this embodiment, similarly to the mixed gas supply device 40 described above, the mixed gas containing the hydrazine compound and ammonia can be safely and stably discharged to the mixed gas discharge path L15 .

[0185] Furthermore, according to the mixed gas supply device 50 of this embodiment, the set values ​​of the dilution gas flow rate control device 14 and the ammonia flow rate control device 15 can be automatically updated so that the flow rate and content ratio of the hydrazine compound calculated by the calculation device 17 become the set flow rate and content ratio.

[0186] (Sixth Method)

[0187] Figure 7 It is a system diagram schematically showing the structure of a sixth embodiment of the mixed gas supply device of the present invention.

[0188] like Figure 7 As shown, the difference between the mixed gas supply device 60 of the sixth embodiment and the mixed gas supply devices 40 and 50 is that the function of the computing device 17 constituting the mixed gas supply devices 40 and 50 is different, while the other structures are the same. Therefore, in the mixed gas supply device 60 of this embodiment, the same reference numerals are attached to the same structures as those of the mixed gas supply devices 40 and 50, and their descriptions are omitted.

[0189] The computing device 17 can transmit and receive electrical signals with the setting device 41 and the pressure regulating device 33 by wire or wireless in addition to the above functions. Specifically, the computing device 17 has the following functions: calculating the difference between the calculated value of the hydrazine compound flow rate and the set value referenced from the setting device 41, and updating (correcting, changing) the set value of the pressure regulating device 33 based on the difference.

[0190] According to the mixed gas supply device 60 of this embodiment, similarly to the mixed gas supply devices 40 and 50 described above, the mixed gas containing the hydrazine compound and ammonia can be safely and stably discharged to the mixed gas discharge path L15 .

[0191] In addition, according to the mixed gas supply device 60 of the present embodiment, the set value of the pressure regulating device 33 can be automatically updated so that the flow rate and content ratio of the hydrazine compound calculated by the operation device 17 become the set flow rate and content ratio. That is, when the calculated value of the hydrazine compound flow rate is less than the set value, or when the flow rate of the hydrazine compound is reduced as the mixed gas is continuously supplied, since the vapor pressure of the hydrazine compound in the raw material container 11 is insufficient, the opening of the on-off valve 32 is adjusted in the opening direction to match the set value, and the mixed gas of the set value can be supplied with good responsiveness. By automatically adjusting the opening of the on-off valve 32 (that is, the set value of the pressure regulating device 33), the mixed gas can be supplied more stably.

[0192] (Seventh Method)

[0193] Figure 8 It is a system diagram schematically showing the structure of a seventh embodiment of the mixed gas supply device of the present invention.

[0194] like Figure 8 As shown, the mixed gas supply device 70 of the seventh embodiment is different from the mixed gas supply device 60 in that it is provided with a buffer tank (storage tank) 34, a second pressure gauge 35 and a flow path selection device, and the function of the computing device 17 constituting the mixed gas supply device 60 is different, while the other structures are the same. Therefore, in the mixed gas supply device 70 of this embodiment, the same reference numerals are attached to the same structures as the mixed gas supply device 60, and their descriptions are omitted.

[0195] The buffer tank 34 is located in the mixed gas outlet path L15 and is a container for storing the mixed gas. Specifically, the mixed gas branch path L17 and the mixed gas confluence path L18 are connected to the buffer tank 34, and the mixed gas outlet path L15 is communicated through these paths L17 and L18. In other words, the buffer tank 34 is located between the mixed gas branch path L17 and the mixed gas confluence path L18, and the mixed gas branch path L17 branches from the mixed gas outlet path L15 on the primary side of the switch valve 32, and the mixed gas confluence path L18 merges with the mixed gas outlet path L15 on the secondary side of the switch valve 32.

[0196] The structure of the buffer tank 34 is not particularly limited, and a circular buffer tank or a cylindrical buffer tank is preferably used. Among them, a circular buffer tank is preferred because of its excellent pressure resistance.

[0197] The material of the buffer tank 34 is not particularly limited, and can be selected from stainless steel such as SUS316L, SUS316, and SUS304, alloys such as Hastelloy, Inconel, and brass, metals such as nickel (Ni), chromium (Cr), molybdenum (Mo), titanium (Ti), aluminum (Al), tantalum (Ta), zirconium (Zr), magnesium (Mg), zinc (Zn), copper (Cu), and iron (Fe), quartz glass (SiO2), silicon carbide (SiC), tungsten carbide (WC), aluminum oxide (Al2O3), carbon (C), and silicon (Si). Among them, stainless steel, Inconel, aluminum oxide, and quartz glass are preferably used because of their good corrosion resistance to hydrazine compounds and ammonia, and stainless steel is more preferably used.

[0198] The capacity of the buffer tank 34 is not particularly limited, and a capacity of 1 to 100 L can be used. From the perspective of ensuring the supply amount in a short filling time, a capacity of 1 to 50 L is preferred, and from the perspective of accurately managing the concentration of the mixed gas, a capacity of 10 to 40 L is preferred.

[0199] The second pressure gauge 35 is located in the mixed gas branch path L17 and measures the pressure in the buffer tank 34 .

[0200] The flow path selection device includes first to fourth on-off valves V1 to V4 and an on-off valve control device 36 .

[0201] The first on-off valve V1 is located in the mixed gas merging path L18.

[0202] The second on-off valve V2 is located in the mixed gas branch path L17.

[0203] The third switching valve V3 is located in the outlet path L12.

[0204] The fourth on-off valve V4 is located in the ammonia supply path L14.

[0205] The first to fourth on-off valves V1 to V4 can freely adjust the opening degrees between fully closed (opening degree 0%) and fully open (opening degree 100%).

[0206] The switch valve control device 36 can transmit and receive electrical signals with the first to fourth switch valves V1 to V4 by wire or wirelessly. Specifically, the switch valve control device 36 sends control signals for adjusting the openings of the first to fourth switch valves V1 to V4 to the first to fourth switch valves V1 to V4, respectively, based on the measured values ​​of the pressure in the raw material container 11 and the measured values ​​of the pressure in the buffer tank 34 received from the first pressure gauge 31 and the second pressure gauge 35 via the pressure measuring device 33 and the computing device 17.

[0207] According to the mixed gas supply device 70 of the seventh embodiment, since the buffer tank 34 is provided in the mixed gas outlet path L15, the mixed gas containing the hydrazine compound and ammonia after the concentration is adjusted can be temporarily stored. In addition, according to the mixed gas supply device 70, the mixed gas of the desired concentration can be prepared in the buffer tank 34 by supplying the hydrazine compound and ammonia to the buffer tank 34 respectively.

[0208] That is, according to the mixed gas supply device 70 of the seventh method, in the step of supplying a nitrogen-containing compound raw material into the processing chamber 2 in the metal nitride film manufacturing method described later, the mixed gas adjusted to a desired concentration can be stored in the buffer tank 34, and the mixed gas discharged from the buffer tank 34 can be used as the nitrogen-containing compound raw material.

[0209] Next, a method of preparing a mixed gas having a desired concentration in the buffer tank 34 using the mixed gas supply device 70 according to the seventh embodiment will be described.

[0210] First, the concentration of the mixed gas containing ammonia and a hydrazine compound is set using the setting device 41 (mixed gas concentration setting step).

[0211] Next, vacuuming is performed using an exhaust mechanism (not shown) to exhaust the residual gas in the buffer tank 34 (vacuuming step). At this time, vacuuming may be performed simultaneously in the mixed gas outlet path L15 or other paths (pipes).

[0212] Next, the fourth on-off valve V4 and the first on-off valve V1 are closed and the third on-off valve V3 and the second on-off valve V2 are opened using the on-off valve control device 36. Thus, the hydrazine compound gas with low vapor pressure is filled into the buffer tank 34 (hydrazine compound filling step).

[0213] Next, when the pressure value in the raw material container 11 and the pressure value in the buffer tank 34 become the same value using the first pressure gauge 31 and the second pressure gauge 35 (that is, it means that the equivalent vapor pressure of the hydrazine compound is filled in the buffer tank 34), the third on-off valve V3 is closed and the fourth on-off valve V4 is opened using the on-off valve control device 36. Thus, ammonia is filled into the buffer tank 34 (ammonia filling) until the pressure reaches the set ammonia / hydrazine compound mixed concentration.

[0214] Next, the switch valve control device 36 is used to close the fourth switch valve V4 and open the first switch valve V1, thereby supplying the mixed gas of ammonia / hydrazine compound modulated (manufactured) to the required concentration into the processing chamber (chamber) 2 (ammonia / hydrazine compound mixed gas supply step).

[0215] According to the mixed gas supply device 70 of the seventh embodiment, through these steps, the mixed gas of ammonia / hydrazine compound controlled to a desired concentration can be stably supplied to the processing room (chamber) 2 using the buffer tank 34 .

[0216] Here, the filling pressure of ammonia (ammonia partial pressure) is calculated by the following formula (I) for the set mixed gas concentration of ammonia / hydrazine compound.

[0217] C=B×(100-A) / A (I)

[0218] A: Hydrazine concentration in the mixed gas of ammonia / hydrazine compound (%)

[0219] B: Pressure in the raw material container (vapor pressure of the hydrazine compound)

[0220] C: Required ammonia filling pressure (ammonia partial pressure in the buffer tank 34)

[0221] B+C: Total pressure in the buffer tank 34 (filling pressure of the mixed gas)

[0222] In addition, the above formula (I) is a formula calculated from B / (B+C)=A / 100.

[0223] Next, a method for preparing a mixed gas having a desired concentration in the buffer tank 34 using the mixed gas supply device 70 of the seventh embodiment will be specifically described using an example.

[0224] (Example 1)

[0225] Ammonia / hydrazine compound: 90% / 10% is set using the setting device 41. Here, when the pressure in the raw material container 11 (i.e., the vapor pressure of the hydrazine compound) is 4 kPa, the filling pressure of ammonia gas is 36 kPa, and a mixed gas with a total pressure of 40 kPa is produced in the buffer tank 34.

[0226] Alternatively, the mixed gas can be produced by setting the total pressure of the mixed gas (filling pressure in the buffer tank 34) to a predetermined value. In this case, the filling pressure of ammonia (ammonia partial pressure) is calculated by the following formula (II) for the set mixed gas concentration of ammonia / hydrazine compound.

[0227] A / 100×D=B (II)

[0228] DB=C

[0229] A: Hydrazine concentration in the mixed gas of ammonia / hydrazine compound (%)

[0230] B: Pressure in the raw material container (vapor pressure of the hydrazine compound)

[0231] C: Required ammonia filling pressure (ammonia partial pressure in the buffer tank 34)

[0232] D: B+C = total pressure in the buffer tank 34 (filling pressure of the mixed gas)

[0233] (Example 2)

[0234] Ammonia / hydrazine compound: 90% / 10% is set using the setting device 41. Here, when the pressure in the buffer tank 34 (i.e., the pressure of the mixed gas) is set to 100 kPa, the filling pressure of the hydrazine compound is 10 kPa, and the filling pressure of ammonia is 90 kPa, and a mixed gas of 100 kPa is produced in the buffer tank 34.

[0235] As described above, according to the method of Example 2, since the filling pressure of the mixed gas to the buffer tank 34 can be set in advance, a large flow rate of the mixed gas can be stably supplied to the processing room (chamber) 2 .

[0236] In addition, according to the method of Example 2, in the hydrazine compound filling step, after the desired filling pressure of the hydrazine compound is reached in the buffer tank 34, the ammonia filling step is entered. When the vapor pressure of the hydrazine compound does not reach the desired filling pressure from the measured value of the first pressure gauge 31, the vapor pressure of the hydrazine compound can be increased by heating the raw material container 11 of the hydrazine compound by the heater 12. At this time, the raw material container 11 can also be automatically heated by the heater adjustment device 13.

[0237] The filling pressure of the mixed gas to the buffer tank 34 is not particularly limited, and may be in the range of 1 to 1000 kPa. In the above range, it is preferred to produce the mixed gas in a short time and in the range of 1 to 200 kPa so that the filling amount of the mixed gas can be increased. From the viewpoint of concentration accuracy, it is more preferred to produce the mixed gas in the range of 1 to 100 kPa.

[0238] According to the mixed gas supply device 70 of the seventh aspect, since the concentration of the mixed gas containing ammonia and the hydrazine compound can be adjusted by the pressure value, the mixed gas having the concentration adjusted with high accuracy can be stably supplied to the processing chamber 2 .

[0239] Furthermore, according to the mixed gas supply device 70 , the mixed gas of adjusted concentration can be stored in the buffer tank 34 . Therefore, even when the consumption of the mixed gas in the processing chamber 2 increases, the mixed gas can be stably supplied to the processing chamber 2 .

[0240] Furthermore, according to the mixed gas supply device 70, since the buffer tank 34 is provided in the mixed gas outlet path L15, even when the pressure of the raw material container 11 increases sharply, the pressure of the raw material container 11 can be reduced to a safe range by outlet the hydrazine compound to the buffer tank 34. Thus, the mixed gas supply device 70 can be operated more safely.

[0241] As described above, according to the mixed gas supply devices 10 to 70 of the first to seventh aspects of the present invention, it is possible to safely and stably deliver the mixed gas containing the hydrazine compound and ammonia to the mixed gas delivery path L15.

[0242] In addition, according to the mixed gas supply devices 10 to 70 of the first to seventh embodiments, by controlling the temperature of the raw material container 11 or the pressure in the raw material container 11, the hydrazine compound can be supplied at a flow rate range of 1 to 5000 sccm, and the mixed gas containing ammonia and the hydrazine compound can be supplied at a flow rate range of 1 to 10,000 sccm.

[0243] In addition, in the film forming apparatus 1 of the above-mentioned embodiment, when the mixed gas supply devices 10 to 70 of the first to seventh embodiments are used as the supply source of the reaction gas, from the viewpoint of the quality of the metal nitride film, the concentration of H2O contained in the nitrogen-containing compound raw material is preferably 0.1 ppm or less. Similarly, from the viewpoint of the quality of the metal nitride film, the concentration of H2O contained in the hydrazine compound is preferably 10 ppm or less, and more preferably 1 ppm or less.

[0244] When the water concentration in the nitrogen-containing compound raw material or the hydrazine compound is high, the mixed gas supply devices 10 to 60 may be configured to include a purifier including an adsorbent, a separation membrane, or the like.

[0245] Regarding the mixed gas supply device 40 of the fourth embodiment described above, since it takes time to heat the raw material container 11 and stabilize the vapor pressure of the hydrazine compound, the responsiveness is worrying, but the vapor pressure of the hydrazine compound can be controlled according to the set values ​​of the flow rate and content ratio of the hydrazine compound, so the mixed gas of ammonia and the hydrazine compound can be efficiently supplied.

[0246] In contrast, in the mixed gas supply devices 50 and 60 of the fifth and sixth embodiments, since the temperature of the raw material container 11 is constant, when the vapor pressure of the hydrazine compound is insufficient, the calculated values ​​of the flow rate and content ratio of the hydrazine compound may not reach the set values. However, even when the pressure of the subsequent processing chamber 2 changes, the adjustment of the dilution gas flow rate and the ammonia flow rate can be controlled with good responsiveness, or the pressure value in the raw material container 11 can be controlled with good responsiveness by adjusting the opening of the switch valve 32.

[0247] In addition, the structures of the mixed gas supply devices 10 to 70 of the first to seventh embodiments described above are merely examples and are not limited thereto. For example, the dilution gas supply path L13 of the mixed gas supply device 10 may also be a structure connected to any one of the base end P of the introduction path L11 and the front end Q of the outlet path L12 (i.e., the base end Q of the mixed gas outlet path L15).

[0248] In addition, the mixed gas supply device 20 of the second embodiment may be configured to include the first pressure gauge 31 , the on-off valve 32 , and the pressure regulating device 33 , similarly to the third embodiment described above.

[0249] In addition, the mixed gas supply devices 40 to 60 of the fourth to sixth embodiments described above are described as an example in which the computing device 17 has a different function. However, the present invention is not limited thereto and may have any two functions or all functions.

[0250] The interlock mechanism included in the mixed gas supply device 40 of the fourth embodiment described above may be a structure included in other mixed gas supply devices.

[0251] In addition, for the mixed gas supply device 70 of the seventh embodiment described above, a structure having one buffer tank 34 is described as an example, but it is not limited to this, and it may also be a structure having two or more buffer tanks 34 in parallel. If it is a structure having two or more buffer tanks 34, it is possible to modulate (manufacture) a mixed gas of a desired concentration in another buffer tank while a mixed gas is supplied from any buffer tank to the processing chamber 2. In this way, by using two or more buffer tanks 34 to alternately supply and manufacture the mixed gas, the mixed gas of ammonia / hydrazine compounds can be continuously supplied to the processing chamber 2.

[0252] In addition, in the mixed gas supply device 70 of the seventh embodiment described above, a gas concentration measuring device for measuring the gas concentration in the buffer tank 34 may be used instead of the mixed gas flow meter 16 .

[0253] In addition, the mixed gas supply devices 10 to 70 of the first to seventh aspects described above may also be configured such that the mixed gas containing the hydrazine compound and ammonia contains one or more of inert gases such as helium (He), nitrogen (N2), argon (Ar), and hydrogen (H2).

[0254] <Method for Manufacturing Metal Nitride Film>

[0255] The method for producing a metal nitride film of the present invention is a method for forming a metal nitride film on at least a portion of the surface of a substrate to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material.

[0256] The chemical vapor growth method is not particularly limited, and examples thereof include CVD, plasma CVD, MOCVD, ALD, and plasma ALD. Among them, CVD and ALD are preferred, and ALD is more preferred.

[0257] The method for producing a metal nitride film of the present invention can be performed using the above-mentioned film forming apparatus 1 .

[0258] Furthermore, the method for producing a metal nitride film of the present invention uses any one of the mixed gas supply devices 10 to 70 of the first to seventh aspects described above, and uses a mixed gas containing hydrazine and ammonia as a nitrogen-containing compound raw material.

[0259] In addition, the content ratio of hydrazine and ammonia in the mixed gas is 1:99 to 50:50 in terms of volume flow ratio, and preferably 1:99 to 10:90 from the viewpoint of further reducing the amount of hydrazine used. If the content ratio of hydrazine is 1 volume % or more in the total 100 volume % of hydrazine and ammonia, the effect of lowering the film forming temperature of the metal nitride film can be obtained. In addition, if the content ratio of hydrazine is 50% or less, the use of expensive hydrazine can be relatively reduced, which can reduce costs, thereby improving productivity.

[0260] As a method for forming a silicon-containing thin film using the above-described film forming apparatus 1 , the following methods 1 to 7 will be specifically described with reference to the drawings.

[0261] (Method 1)

[0262] First, as a preparatory step, a substrate (base material to be processed) P is placed in the processing chamber 2, and the surface temperature of the substrate P is controlled to a desired temperature.

[0263] Next, a film forming process including the following steps is performed.

[0264] Step 1A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0265] Step 1B: A reaction gas containing a nitrogen-containing compound raw material is supplied to the substrate P in the processing chamber 2 .

[0266] In step 1A, any one or two or more of the group consisting of the above-mentioned metal compound raw materials are used.

[0267] The raw material gas may contain the above-mentioned carrier gas as a coexistent gas in addition to the metal compound raw material.

[0268] In step 1B, a mixed gas containing hydrazine and ammonia is used as a nitrogen-containing compound raw material (a step of supplying a nitrogen-containing compound raw material).

[0269] The mixed gas is supplied using any of the mixed gas supply devices 10 to 70 of the first to seventh aspects described above. In addition, the reaction gas may contain the above-described carrier gas as a coexistent gas in addition to the mixed gas.

[0270] In method 1, step 1A and step 1B are performed until the thin film on the substrate P reaches a desired film thickness.

[0271] Step 1A and step 1B may be performed simultaneously (CVD method) or alternately (ALD method).

[0272] (Method 2)

[0273] Method 2 is a method for manufacturing a metal nitride film (film forming method) using the ALD method. Fig. 9 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0274] First, similarly to method 1, as a preparatory step, the surface temperature of the substrate P transported into the processing chamber 2 is controlled to a desired temperature.

[0275] Next, a film forming process including the following steps is performed (see Fig. 9 ).

[0276] Step 2A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0277] Step 2B: Stop the supply of raw material gas.

[0278] Step 2C: A reaction gas containing a nitrogen-containing compound raw material is supplied to the substrate P in the processing chamber 2 (a step of supplying a nitrogen-containing compound raw material).

[0279] Step 2D: Stop the supply of the reaction gas.

[0280] In step 2A, a raw material gas is supplied to the substrate P in the processing chamber 2 under vacuum. The raw material gas may be the raw material gas described in step 1A of the above method 1. As a result, a chemical adsorption reaction occurs between the surface of the substrate P and the metal compound raw material.

[0281] In step 2B, the supply of the raw material gas is stopped after the above-mentioned chemical adsorption reaction.

[0282] In step 2C, a reaction gas is supplied to the substrate P in the processing chamber 2 under vacuum. The reaction gas may be the reaction gas described in step 1B of the above method 1. Thus, the metal compound raw material adsorbed on the surface of the substrate P in step 2A is nitrided.

[0283] In step 2D, the supply of the reaction gas is stopped after the nitridation reaction of the metal compound raw material.

[0284] In the film forming process, one or both of step 2B of stopping the supply of the metal compound source and step 2D of stopping the supply of the nitrogen-containing compound source may include a step of supplying only the inert gas into the processing chamber 2 .

[0285] In addition, the process may include a step of vacuum exhausting the processing chamber 2 without supplying the inert gas.

[0286] Alternatively, the method may include a step of continuously performing the step of supplying only the inert gas and the step of vacuum exhausting.

[0287] Furthermore, the configuration may further include a step of supplying ammonia or ammonia diluted with an inert gas into the processing chamber 2 .

[0288] In method 2, by repeating the above-mentioned cycle a plurality of times (for example, 500 cycles), a metal nitride film having a desired film thickness can be manufactured (formed) on the substrate P.

[0289] In addition, in method 2, steps 2A to 2D are performed sequentially in the above cycle, but the next step may be started after the previous step is completed, or before the previous step is completed, and steps 2B and 2D may be omitted. In this way, by skipping or omitting some steps, the time of each cycle can be shortened. Furthermore, the film forming speed can be controlled so as to be a desired speed.

[0290] (Method 3)

[0291] Fig.10 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0292] First, similarly to method 1, as a preparatory step, the surface temperature of the substrate P transported into the processing chamber 2 is controlled to a desired temperature.

[0293] Next, as a film forming process, a cycle including the following steps is repeated multiple times (refer to Fig.10 ).

[0294] Step 3A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0295] Step 3B: Stop supplying the source gas, and supply an inert gas into the processing chamber 2 .

[0296] Step 3C: The supply of the inert gas is stopped, and a reaction gas containing a nitrogen-containing compound raw material is supplied to the substrate P in the processing chamber 2 (a step of supplying a nitrogen-containing compound raw material).

[0297] Step 3D: Stop supplying the reaction gas, and supply an inert gas into the processing chamber 2 .

[0298] Step 3E: Stop the supply of the inert gas.

[0299] In step 3A, a raw material gas is supplied to the substrate P in the processing chamber 2 under vacuum. The raw material gas may be the metal compound raw material described in step 1A of the above method 1. Thus, a chemical adsorption reaction occurs between the surface of the substrate P and the metal compound raw material.

[0300] In step 3B, the supply of the raw material gas is stopped after the chemical adsorption reaction, and an inert gas is supplied to remove unreacted metal compound raw materials remaining in the processing chamber 2 , thereby purging the processing chamber 2 .

[0301] In step 3C, the supply of the inert gas is stopped, and a reaction gas is supplied to the substrate P in the processing chamber 2 under vacuum. As the reaction gas, a mixed gas containing hydrazine and ammonia as shown in step 1B of the above method 1 can be applied. Thus, the metal compound raw material adsorbed on the surface of the substrate P in step 3A is nitrided.

[0302] In step 3D, after the nitridation reaction of the metal compound raw material, the supply of the reaction gas is stopped, and inert gas is supplied to remove unreacted nitrogen-containing compound raw material remaining in the processing chamber 2 , and the processing chamber 2 is purged.

[0303] In step 3E, the supply of the inert gas is stopped.

[0304] Method 3 may include a step of vacuum exhausting the processing chamber 2 without supplying an inert gas, or may continuously perform a step of supplying only an inert gas and a step of vacuum exhausting the processing chamber 2, or may include a step of supplying ammonia or ammonia diluted with an inert gas.

[0305] (Method 4)

[0306] Fig.11 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0307] First, similarly to method 1, as a preparatory step, the surface temperature of the substrate P transported into the processing chamber 2 is controlled to a desired temperature.

[0308] Next, as a film forming process, a cycle including the following steps is repeated multiple times (refer to Fig.11 ).

[0309] Step 4A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0310] Step 4B: Stop the supply of the raw material gas and evacuate the processing chamber 2.

[0311] Step 4C: The vacuum exhaust in the processing chamber 2 is stopped, and a reaction gas containing a nitrogen-containing compound raw material is supplied to the substrate P in the processing chamber 2 (a step of supplying a nitrogen-containing compound raw material).

[0312] Step 4D: Stop supplying the reaction gas and evacuate the processing chamber.

[0313] Step 4E: Stop the vacuum exhaust in the processing chamber 2.

[0314] In step 4A, a raw material gas is supplied to the substrate P in the processing chamber 2 under vacuum. The raw material gas may be the metal compound raw material described in step 1A of the above method 1. Thus, a chemical adsorption reaction occurs between the surface of the substrate P and the metal compound raw material.

[0315] In step 4B, the supply of the raw material gas is stopped after the chemical adsorption reaction, and the processing chamber 2 is evacuated to remove the unreacted metal compound raw material remaining in the processing chamber 2 .

[0316] In step 4C, the vacuum exhaust in the processing chamber 2 is stopped, and a reaction gas is supplied to the substrate P in the processing chamber 2 under vacuum. As the reaction gas, a mixed gas containing hydrazine and ammonia as shown in step 1B of the above method 1 can be applied. In this way, the metal compound raw material adsorbed on the surface of the substrate in step 4A is nitrided.

[0317] In step 4D, after the nitridation reaction of the metal compound raw material, the supply of the reaction gas is stopped, and the processing chamber 2 is evacuated to remove the unreacted nitrogen-containing compound remaining in the processing chamber 2 .

[0318] In step 4E, vacuum exhaust in the processing chamber 2 is stopped.

[0319] The method 4 may include a step of supplying only the inert gas, or may continuously perform the step of supplying only the inert gas and the step of performing vacuum exhaust, or may include a step of supplying ammonia or ammonia diluted with the inert gas.

[0320] (Method 5)

[0321] Fig.12 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0322] First, similarly to method 1, as a preparatory step, the surface temperature of the substrate P transported into the processing chamber 2 is controlled to a desired temperature.

[0323] Next, as a film forming process, a cycle including the following steps is repeated multiple times (refer to Fig.12 ).

[0324] Step 5A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0325] Step 5B: Stop the supply of the raw material gas and evacuate the processing chamber 2.

[0326] Step 5C: The vacuum exhaust in the processing chamber 2 is stopped, and an inert gas is supplied into the processing chamber 2 .

[0327] Step 5D: Stop the supply of the inert gas and evacuate the processing chamber 2 .

[0328] Step 5E: The vacuum exhaust in the processing chamber 2 is stopped, and a reaction gas containing a nitrogen-containing compound raw material is supplied to the substrate in the processing chamber 2 (a step of supplying a nitrogen-containing compound raw material).

[0329] Step 5F: Stop the supply of the reaction gas and evacuate the processing chamber 2.

[0330] Step 5G: The vacuum exhaust in the processing chamber 2 is stopped, and an inert gas is supplied into the processing chamber 2 .

[0331] Step 5H: The supply of the inert gas is stopped, and the processing chamber 2 is evacuated to a vacuum state.

[0332] Step 5I: Stop the vacuum exhaust in the processing chamber 2.

[0333] In step 5A, a raw material gas is supplied to the substrate P in the processing chamber 2 under vacuum. The raw material gas may be the metal compound raw material described in step 1A of the above method 1. Thus, a chemical adsorption reaction occurs between the surface of the substrate and the metal compound raw material.

[0334] In step 5B, the supply of the raw material gas is stopped after the chemical adsorption reaction, and the processing chamber 2 is evacuated to remove the unreacted metal compound raw material remaining in the processing chamber 2 .

[0335] In step 5C, vacuum exhaust in the processing chamber 2 is stopped, and an inert gas is supplied into the processing chamber 2 to purge the processing chamber 2 .

[0336] In step 5D, the supply of the inert gas is stopped, and the processing chamber 2 is evacuated to remove the inert gas remaining in the processing chamber 2 .

[0337] In step 5E, the vacuum exhaust in the processing chamber 2 is stopped, and a reaction gas is supplied to the substrate P in the processing chamber 2 under vacuum. As the reaction gas, a mixed gas containing hydrazine and ammonia can be used. Thus, the metal compound raw material adsorbed on the surface of the substrate P in step 5A is nitrided.

[0338] In step 5F, after the nitridation reaction of the metal compound raw material, the supply of the reaction gas is stopped, and the processing chamber 2 is evacuated to remove the unreacted nitrogen-containing compound remaining in the processing chamber 2 .

[0339] In step 5G, vacuum exhaust in the processing chamber 2 is stopped, and an inert gas is supplied into the processing chamber 2 to purge the processing chamber 2 .

[0340] In step 5H, the supply of the inert gas is stopped, and the processing chamber 2 is evacuated to remove the unreacted inert gas remaining in the processing chamber 2 .

[0341] In step 5I, vacuum exhaust in the processing chamber 2 is stopped.

[0342] The method 5 may include a step of supplying ammonia or ammonia diluted with an inert gas.

[0343] (Method 6)

[0344] Fig.13 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0345] First, similarly to method 1, as a preparatory step, the surface temperature of the substrate P transported into the processing chamber 2 is controlled to a desired temperature.

[0346] Next, as a film forming process, a cycle including the following steps is repeated multiple times (refer to Fig.13 ).

[0347] Step 6A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0348] Step 6B: Stop supplying the source gas, and supply an inert gas into the processing chamber 2 .

[0349] Step 6C: The supply of the inert gas is stopped, and the first reaction gas containing the nitrogen-containing compound raw material is supplied to the substrate in the processing chamber 2 (a step of supplying the nitrogen-containing compound raw material).

[0350] Step 6D: Stop supplying the first reaction gas, and supply an inert gas into the processing chamber 2 .

[0351] Step 6E: The supply of the inert gas is stopped, and the second reaction gas containing ammonia is supplied to the substrate in the processing chamber 2 .

[0352] Step 6F: Stop supplying the second reaction gas, and supply an inert gas into the processing chamber 2 .

[0353] Step 6G: Stop the supply of the inert gas.

[0354] In step 6A, a raw material gas is supplied to the substrate P in the processing chamber 2 under vacuum. As the raw material gas, the metal compound raw material described in step 1A of the above-mentioned method 1 can be used.

[0355] In step 6B, the supply of the raw material gas is stopped, and an inert gas is supplied into the processing chamber 2 for purging in order to remove unreacted metal compound raw materials remaining in the processing chamber 2 .

[0356] In step 6C, the supply of the inert gas is stopped, and the first reaction gas is supplied under vacuum to the substrate in the processing chamber 2. As the first reaction gas, a mixed gas containing hydrazine and ammonia can be used.

[0357] In step 6D, the supply of the first reaction gas is stopped, and an inert gas is supplied into the process chamber 2 to perform a purge in order to remove unreacted first reaction gas remaining in the process chamber 2 .

[0358] In step 6E, the supply of the inert gas is stopped, and the second reaction gas containing ammonia is supplied.

[0359] In step 6F, the supply of the second reaction gas is stopped, and an inert gas is supplied into the process chamber 2 to perform a purge in order to remove unreacted second reaction gas remaining in the process chamber 2 .

[0360] In step 6G, the supply of the inert gas is stopped.

[0361] As the second reaction gas, ammonia or ammonia diluted with one or more inert gases can be used.

[0362] The method 6 may include a step of vacuum exhausting the processing chamber 2 without supplying a gas, or a step of supplying only an inert gas and a step of vacuum exhausting may be performed continuously.

[0363] (Method 7)

[0364] Fig.14 This is a timing chart showing an example of a film forming step in the method for producing a metal nitride film of the present invention.

[0365] First, similarly to method 1, as a preparatory step, the surface temperature of the substrate P transported into the processing chamber 2 is controlled to a desired temperature.

[0366] Next, as a film forming process, a cycle including the following steps is repeated multiple times (refer to Fig.14 ).

[0367] Step 7A: A raw material gas including a metal compound raw material is supplied to the substrate P in the processing chamber 2 .

[0368] Step 7B: Stop supplying the source gas, and supply an inert gas into the processing chamber 2 .

[0369] Step 7C: The supply of the inert gas is stopped, and the first reaction gas containing ammonia is supplied to the substrate P in the processing chamber 2 .

[0370] Step 7D: Stop supplying the first reaction gas, and supply an inert gas into the processing chamber 2 .

[0371] Step 7E: The supply of the inert gas is stopped, and the second reaction gas containing the nitrogen-containing compound raw material is supplied to the substrate P in the processing chamber 2 (a step of supplying the nitrogen-containing compound raw material).

[0372] Step 7F: Stop supplying the second reaction gas, and supply an inert gas into the processing chamber 2 .

[0373] Step 7G: Stop the supply of the inert gas.

[0374] In step 7A, a raw material gas is supplied to the substrate P in the processing chamber 2 under vacuum. As the raw material gas, the metal compound raw material described in step 1A of the above-mentioned method 1 can be used.

[0375] In step 7B, the supply of the raw material gas is stopped, and an inert gas is supplied into the processing chamber 2 for purging in order to remove the unreacted metal compound raw material remaining in the processing chamber 2 .

[0376] In step 7C, the supply of the inert gas is stopped, and the first reaction gas is supplied to the substrate P in the processing chamber 2 under vacuum. As the reaction gas, the first reaction gas containing ammonia is supplied.

[0377] In step 7D, the supply of the first reaction gas is stopped, and an inert gas is supplied into the process chamber 2 to perform a purge in order to remove unreacted first reaction gas remaining in the process chamber 2 .

[0378] In step 7E, the supply of the inert gas is stopped, and the second reaction gas is supplied under vacuum. The second reaction gas containing ammonia is supplied. A mixed gas containing hydrazine and ammonia can be used as the second reaction gas.

[0379] In step 7F, the supply of the second reaction gas is stopped, and an inert gas is supplied into the process chamber 2 to perform a purge in order to remove unreacted second reaction gas remaining in the process chamber 2 .

[0380] In step 7G, the supply of the inert gas is stopped.

[0381] As the first reaction gas, ammonia or ammonia diluted with one or more inert gases can be used.

[0382] The method 7 may include a step of vacuum exhausting the processing chamber 2 without supplying the inert gas, or a step of supplying only the inert gas and a step of vacuum exhausting may be performed continuously.

[0383] According to the method for producing a metal nitride film of the present invention, since a mixed gas containing hydrazine and ammonia is used as a reaction gas instead of ammonia alone and hydrazine alone, the following effects can be obtained.

[0384] (1) Since hydrazine is more reactive than ammonia, the metal nitride film formation temperature can be lowered when the hydrazine content in the mixed gas is 1 volume % or more in the total of 100 volume % of hydrazine and ammonia.

[0385] (2) Since hydrazine has a higher reducing property than ammonia, the content of chlorine in the film as an impurity can be reduced. In addition, chlorine in the film is not only a major factor in resistance degradation, but also hydrogen chloride (HCl) generated by reaction with hydrogen (H) in the film can damage the substrate. In particular, when the film formation temperature is lowered, there is a tendency for the chlorine content in the film to increase.

[0386] (3) Since hydrazine is more reactive than ammonia, the film formation rate of the metal nitride film can be increased and productivity can be improved as long as the hydrazine content in the mixed gas is 1 volume % or more in the total 100 volume % of hydrazine and ammonia.

[0387] In addition, according to the method for manufacturing a metal nitride film of the present invention, since the cycle constituting the film forming process includes a vacuum exhaust step, residual gases in the processing chamber such as raw material gas, reaction gas, and inert gas can be effectively removed. In the above method 4, by introducing the vacuum exhaust step in the film forming cycle, the residual gas can be effectively removed, so that a metal nitride film with good coverage characteristics can be formed. In addition, in the above method 5, since the vacuum exhaust step is provided before and after the supply of the raw material gas, the reaction gas, and the inert gas, respectively, the purge efficiency is higher than the purge efficiency of method 4.

[0388] In addition, according to the method for manufacturing a metal nitride film of the present invention, as shown in methods 6 and 7, a film is formed by a reaction of more than three steps, and a thin film is formed while improving the surface structure of the substrate, so that a metal nitride film with better quality can be formed than a general film formed by a reaction of two steps. Specifically, in an ammonia nitrided surface structure formed by supplying ammonia, a mixed gas containing hydrazine and ammonia is supplied to the unnitrided surface side of the substrate to achieve nitridation, forming a dense metal nitride film. In particular, when the ammonia nitrided surface structure is adjacent to the hydrazine nitrided surface structure, in the subsequent chemical adsorption reaction of the metal compound raw material (for example, TiCl4), the reaction is carried out with less steric hindrance, so that the effect of reducing the activation energy can be obtained.

[0389] According to the method for manufacturing a metal nitride film of the present invention, since the mixed gas supply devices 10 to 70 of the first to seventh aspects described above are used, a mixed gas having a H2O concentration of 0.1 ppm or less contained in the nitrogen-containing compound raw material can be supplied as a reaction gas. As a result, since impurities (oxygen components) derived from H2O are not easily mixed into the metal nitride film, a metal nitride film having excellent electrical characteristics, hydrofluoric acid resistance, etc., and film quality can be obtained.

[0390] According to the method for manufacturing a metal nitride film of the present invention, since hydrazine is used as the nitrogen-containing compound, carbon atoms (C), halogen atoms such as chlorine (Cl), and oxygen (O) atoms from the nitrogen-containing compound are not easily mixed into the metal nitride film, and a metal nitride film with excellent film quality can be obtained.

[0391] The above-mentioned methods 1 to 7 are merely examples of the method for producing the metal nitride film of the present invention and are not limited thereto. For example, in addition to methods 1 to 7, the metal compound raw material and the nitrogen-containing compound raw material may be supplied by various methods.

[0392] <Method for evaluating metal nitride film>

[0393] The film quality, film formation amount, and film density of the metal nitride film obtained by the method for producing a metal nitride film of the present invention can be evaluated by the following method.

[0394] (Evaluation of film quality)

[0395] The film quality of the thin film can be evaluated based on the measured values ​​of the film thickness and the refractive index using a commercially available spectroscopic ellipsometer (for example, a spectroscopic ellipsometer manufactured by SOPRA).

[0396] For example, when the metal nitride film is a titanium nitride film, a refractive index of less than 1.80 can generally be evaluated as a titanium nitride film of good quality. In addition, the smaller the refractive index, the less impurities there are, which means that the titanium nitride film is dense.

[0397] On the other hand, when the refractive index is 1.80 or more, and particularly when the refractive index is greater than 1.9, it means that 30% or more of oxygen components are mixed in the film, which indicates the properties of a titanium oxide film or a titanium oxynitride film.

[0398] Furthermore, when the metal nitride film is a silicon nitride film, when the refractive index is within a range of 1.8 to 2.1, it can be generally evaluated as a silicon nitride film of good quality.

[0399] On the other hand, when the refractive index is less than 1.80, it can be evaluated that the silicon nitride film has a rough film structure. In addition, the smaller the numerical value of the refractive index is, the more oxygen components are mixed in the film.

[0400] In addition, when the refractive index is 1.6 or less, it generally represents the properties of a silicon oxide film or a silicon oxynitride film.

[0401] When the refractive index is larger than 1.8, a carbon component may be contained in the film, and the refractive index tends to increase as the content of the carbon component increases.

[0402] (Film formation amount)

[0403] GPC (Growth per cycle), which is the amount of film formed per cycle, can be calculated from the obtained film thickness.

[0404] (Resistivity)

[0405] The resistivity of the thin film is measured by a four-probe method at room temperature using a commercially available low resistivity meter (eg, Loresta-GP manufactured by Mitsubishi Chemical Analytech Co., Ltd.) A TFP probe (probe interval: 1 mm) can be used as the electrode probe.

[0406] The resistivity is calculated based on the resistance value obtained and the film thickness of the test sample. For example, if it is a titanium nitride film, the lower the resistivity, the better the film quality. On the other hand, the higher the resistivity, the more impurities such as oxygen, chlorine, and carbon are in the film, which can be evaluated as poor film quality.

[0407] (Impurities of the membrane)

[0408] The amount of impurities in the thin film can be evaluated by secondary ion mass spectrometry (SIMS) to determine the contents of chlorine, oxygen, and carbon in the film. For example, "PHI ADEPT-1010" manufactured by ULVAC-PHI can be used as the device.

[0409] (Hydrofluoric acid resistance)

[0410] The hydrofluoric acid resistance of the silicon nitride film can be evaluated based on the hydrofluoric acid etching rate.

[0411] The hydrofluoric acid etching rate is calculated by the following method: a sample containing a silicon film is immersed in a hydrofluoric acid solution diluted in a ratio of hydrogen fluoride (HF): water = 1:100, and after a predetermined time, it is quickly washed with pure water and dried by blowing nitrogen gas, etc., and then the hydrofluoric acid etching rate per unit time is calculated from the change in film thickness before and after immersion in hydrofluoric acid.

[0412] As described above, according to the mixed gas supply device of the present invention, since the mixed gas contains a hydrazine compound and ammonia and does not use a large amount of hydrazine compound, it is possible to safely and stably supply a mixed gas containing a nitrogen-containing compound raw material useful as a reaction gas when forming a nitride film.

[0413] Furthermore, according to the mixed gas supply device of the present invention, since the flow rate of the hydrazine compound and the mixing ratio with ammonia in the mixed gas can be controlled safely and stably, the mixed gas can be easily handled.

[0414] In addition, in the metal nitride film manufacturing apparatus and the metal nitride film manufacturing method of the present invention, since a mixed gas containing hydrazine and ammonia is used as the reaction gas, a metal nitride film with good film quality can be obtained compared to the case where ammonia alone is used as the reaction gas, and the film formation speed, that is, the productivity can also be improved.

[0415] Furthermore, according to the metal nitride film manufacturing apparatus and metal nitride film manufacturing method of the present invention, since a mixed gas containing hydrazine and ammonia is used as a reaction gas, the material cost can be significantly reduced compared to the case of using hydrazine alone as the reaction gas.

[0416] In addition, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention. For example, in the film forming apparatus 1 of the above-described embodiment, a structure in which each has one raw material gas supply path L3 and one reaction gas supply path L4 is taken as an example, but it is not limited thereto. Since the raw material gas supply path L3 supplies a plurality of metal compound raw materials into the processing chamber 2, it can be a plurality of paths or a structure having a branch path. In addition, since the reaction gas supply path L4 supplies a plurality of nitrogen-containing compound raw materials into the processing chamber 2, it can be a plurality of paths or a structure having a branch path.

[0417] Examples

[0418] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

[0419] Regarding the metal nitride films of Examples 1 to 7 and Comparative Examples 1 to 8, film formation was performed using the Figure 1 film forming apparatus 1 shown below under the following conditions.

[0420] · Film formation method: ALD

[0421] · Raw material gas: titanium tetrachloride (TiCl4), hexachlorodisilane (HCDS)

[0422] · Reaction gas: hydrazine (N2H4), monomethylhydrazine (MMH), ammonia (NH3)

[0423] · Volume flow rate ratio of reaction gas (mixed gas): described in Tables 1, 2, and 3

[0424] · Partial pressure of raw material gas: 0.004 (Torr)

[0425] · Partial pressure of reaction gas: 0.04 (Torr)

[0426] · Film formation temperature: respectively described in Tables 1, 2, and 3

[0427] · Regarding the three steps: described in detail in Table 2

[0428] <ALD cycle>

[0429] In Examples 1 to 3, 5 to 7 and Comparative Examples 1 to 5, film formation was performed by the above method 3.

[0430] · Step 3A: Supply the raw material gas containing the metal compound raw material to the substrate in the processing chamber for 2 seconds.

[0431] · Step 3B: Stop the supply of the raw material gas and supply an inert gas to the processing chamber for 10 seconds.

[0432] Step 3C: The supply of the inert gas is stopped, and a reaction gas containing a nitrogen-containing compound raw material is supplied to the substrate in the processing chamber for 2 seconds.

[0433] Step 3D: The supply of the reaction gas is stopped, and an inert gas is supplied into the processing chamber for 10 seconds.

[0434] Step 3E: Stop the supply of the inert gas.

[0435] Cycle repetition times: 1000 times

[0436] Furthermore, in order to confirm the incubation time for Comparative Example 1 and Example 2 (film formation temperature: 400° C.), the dependence of the film thickness on the number of cycles (100, 300, 500, and 1000 cycles) was investigated.

[0437] Example 4 Film formation was performed by the above-mentioned method 7.

[0438] Step 7A: A raw material gas containing a metal compound raw material is supplied to the substrate in the processing chamber for 2 seconds.

[0439] Step 7B: The supply of the source gas is stopped, and an inert gas is supplied into the processing chamber for 10 seconds.

[0440] Step 7C: The supply of the inert gas is stopped, and the first reaction gas containing ammonia is supplied to the substrate in the processing chamber for 2 seconds.

[0441] Step 7D: The supply of the first reaction gas is stopped, and an inert gas is supplied into the processing chamber for 10 seconds.

[0442] Step 7E: The supply of the inert gas is stopped, and the second reaction gas containing the nitrogen-containing compound raw material is supplied to the substrate in the processing chamber for 2 seconds.

[0443] Step 7F: The supply of the second reaction gas is stopped, and an inert gas is supplied into the processing chamber for 10 seconds.

[0444] Step 7G: Stop the supply of the inert gas.

[0445] Cycle repetition times: 1000 times

[0446] <Evaluation Results>

[0447] In addition, the evaluation results of the films are shown in Tables 1 to 4, respectively.

[0448] [Titanium nitride film]

[0449] (1) GPC and membrane quality

[0450] As shown in Table 1, among Comparative Examples 1 and 2, in Comparative Example 2 using hydrazine as the reaction gas, the GPC was generally increased at each film formation temperature, and a titanium nitride film (TiN) of excellent quality was formed.

[0451] In particular, as shown in Comparative Example 1, when ammonia is used as the reaction gas, the GPC decreases as the film formation temperature decreases, and the refractive index tends to be greater than 1.8.

[0452] On the other hand, as shown in Comparative Example 2, when hydrazine was used as the reaction gas, the GPC tended to be improved and there was no difference in the refractive index.

[0453] This is probably because hydrazine (N2H4) is more reactive than ammonia (NH3) and the nitridation reaction proceeds even in a low film formation temperature region.

[0454] Examples 1 to 3 used a mixed gas of hydrazine and ammonia as the reaction gas, and although the volume flow rate ratio of hydrazine was reduced compared with Comparative Example 2, they had GPC and membrane quality equal to or better than that of Comparative Example 2.

[0455] As shown in Example 1, when a mixed gas having a volume flow ratio (N2H4:NH3) of 50:50 is used as the reaction gas, the film formation characteristics (GPC improvement and refractive index reduction) are better than those of Comparative Example 2 using hydrazine monomer as the reaction gas.

[0456] As shown in Example 3, when a mixed gas with a volume flow ratio reduced to 1:99 is used as the reaction gas, the film forming characteristics (GPC) are improved and the refractive index is reduced compared to Comparative Example 1 using ammonia monomer as the reaction gas, and almost the same results as those of Comparative Example 2 using hydrazine monomer as the reaction gas are obtained.

[0457] According to the above results, Examples 1 to 3 use a mixed gas of hydrazine and ammonia as a reaction gas, thereby reducing the supply flow rate of hydrazine (N2H4), and obtain film formation results that are almost equivalent to those of Comparative Example 2 using hydrazine monomer as a reaction gas. In addition, it can be seen that Examples 1 to 3 can reduce costs by more than 50% compared to Comparative Example 2 using hydrazine monomer as a reaction gas.

[0458] (2) Impurities in the membrane

[0459] As shown in Table 1, among Comparative Examples 1 and 2, Comparative Example 2 using hydrazine as the reaction gas tends to have less impurities such as chlorine and oxygen in the film as a whole at each film formation temperature.

[0460] In particular, as shown in Comparative Example 1, when ammonia is used as the reaction gas, the amount of chlorine and oxygen in the film increases sharply when the film forming temperature is lower than 350°C. The increase in the amount of nitrogen in the film is because the lower the film forming temperature, the less nitridation energy is for the TiCl4 structure adsorbed on the surface of the substrate, and the nitridation reaction does not proceed (that is, because a large amount of Ti-Cl bonds remain in the film).

[0461] In addition, the increase in the amount of oxygen in the film is because the nitridation reaction does not proceed, resulting in a rough film and the mixing of oxygen and moisture in the atmosphere into the film.

[0462] In contrast, as shown in Comparative Example 2, when hydrazine is used as the reaction gas, since hydrazine has high nitriding properties, even when the film formation temperature is lower than 350° C., the impurities in the film are less than those in Comparative Example 1, and a titanium nitride film of excellent quality is formed.

[0463] Examples 1 to 3 used a mixed gas of hydrazine and ammonia as the reaction gas, and had the same amount of impurities in the film as that of Comparative Example 2, although the volume flow rate ratio of hydrazine was lower than that of Comparative Example 2.

[0464] As shown in Example 3, when the mixed gas with the volume flow ratio reduced to 1:99 was used as the reaction gas, the impurities in the film were reduced compared with Comparative Example 1 in which ammonia alone was used as the reaction gas.

[0465] From the above results, it is understood that a titanium nitride film with less impurities in the film can be obtained by using a mixed gas containing a small amount of hydrazine in ammonia as a reaction gas.

[0466] In contrast, in Comparative Examples 3 and 4 using monomethylhydrazine (MMH) as the hydrazine compound, although the amount of chlorine in the film is equivalent to the case of using hydrazine (N2H4), carbon derived from hydrocarbons contained in monomethylhydrazine is mixed into the film.

[0467] (3) Electrical characteristics

[0468] As shown in Table 1, among Comparative Examples 1 and 2, Comparative Example 2 using hydrazine as the reaction gas tends to have a lower resistivity overall at each film formation temperature.

[0469] In particular, as shown in Comparative Example 1, when ammonia is used as the reaction gas, it is confirmed that the resistivity tends to increase significantly while the film formation temperature is 350° C. or lower.

[0470] On the other hand, as shown in Comparative Example 2, when hydrazine is used as the reaction gas, it is confirmed that the resistivity difference with respect to the film formation temperature is small and a favorable resistivity tends to be exhibited.

[0471] When ammonia monomer is used as the reaction gas, the resistivity increases. This is presumably because the lower the film formation temperature, the more impurities remain in the film, which significantly deteriorates the film quality.

[0472] Examples 1 to 3 use a mixed gas of hydrazine and ammonia as a reaction gas, and have resistivities equal to or higher than that of Comparative Example 2, although the volume flow rate ratio of hydrazine is reduced compared to Comparative Example 2.

[0473] As shown in Example 1, when a mixed gas having a volume flow ratio (N2H4:NH3) of 50:50 is used as the reaction gas, the resistivity is lower than that of Comparative Example 2.

[0474] As shown in Example 3, when a mixed gas with a volume flow ratio (N2H4:NH3) reduced to 1:99 is used as the reaction gas, the resistivity is also lower than that of Comparative Example 1, and the result is equivalent to that of Comparative Example 2.

[0475] In contrast, in Comparative Examples 3 and 4 using monomethylhydrazine (MMH) as the hydrazine compound, the resistivity tended to be higher than that of Examples 1 to 3 at a film forming temperature of 400°C. This is presumably because carbon derived from hydrocarbons in monomethylhydrazine was mixed into the film, deteriorating the resistivity.

[0476] (4) Others

[0477] As shown in Table 2, in Example 2, the culture time can be reduced compared with Comparative Example 1 (film formation temperature: 400° C.).

[0478] From the above results, it was confirmed that the culture time was reduced by using a mixed gas of hydrazine and ammonia.

[0479] In Comparative Example 5, hydrazine used as a reaction gas contained H2O: 100 ppm, and the oxygen in the film increased significantly, thereby significantly deteriorating the resistivity.

[0480] In summary, it was confirmed that in order to form a metal nitride film of high quality, the water content in hydrazine as a raw material of the nitrogen-containing compound needs to be 10 ppm or less, and more preferably 1 ppm or less.

[0481] In Example 4, compared with Example 2 (film formation temperature: 400° C.) in which film formation was performed in two steps, GPC, refractive index, impurities in the film, and resistivity were improved.

[0482] From the above results, the film-forming effect in the three steps was confirmed.

[0483] As shown in Table 3, Comparative Example 6 is an example in which hydrazine alone is used as the reaction gas similarly to Comparative Example 2, but the supply flow rate of hydrazine is reduced.

[0484] The supply amount of the reaction gas in Comparative Example 6 is 1 / 100 of that in Comparative Example 1, Comparative Example 2, and Example 3, and the flow rate of hydrazine contained in the mixed gas supplied in Example 3 is the same as that in Example 3.

[0485] Comparing Comparative Example 2, Example 3 and Comparative Example 6, in Comparative Example 6 where only a small amount of hydrazine was supplied as a reaction gas, a thin film was formed at a film formation temperature of 300° C., but the film quality such as resistivity and impurities in the film was poor.

[0486] In addition, as shown in Comparative Example 1, it was confirmed that when ammonia alone was used as the reaction gas, even if the supply flow rate was set to the same as that of Comparative Example 2 and Example 3, poor film quality was formed.

[0487] In summary, it was confirmed that in order to form a metal nitride film of good quality when a small amount of hydrazine is supplied as a reaction gas, the nitrogen-containing compound raw material as the reaction gas needs to contain not only hydrazine but also ammonia. In addition, as shown in Example 3, the effect of using a mixed gas in which a small amount of hydrazine is added to ammonia as the reaction gas was confirmed.

[0488]

[0489]

[0490]

[0491] [Silicon nitride film]

[0492] As shown in Table 4, among Comparative Examples 7 and 8, in Comparative Example 8 using hydrazine as the reaction gas, GPC and hydrofluoric acid resistance were generally improved at each film formation temperature, and a silicon nitride film of excellent quality was formed.

[0493] This is probably because hydrazine (N2H4) is more reactive than ammonia (NH3) and the nitridation reaction proceeds even in a low film formation temperature region.

[0494] As shown in Example 5, when a mixed gas having a volume flow ratio (N2H4:NH3) of 50:50 is used as the reaction gas, the GPC, refractive index and hydrofluoric acid resistance are equivalent to those of Comparative Example 8 using hydrazine monomer as the reaction gas.

[0495] As shown in Examples 6 and 7, when a mixed gas with a volume flow ratio reduced to 1:99 was used as the reaction gas, GPC and hydrofluoric acid resistance were also improved compared to Comparative Example 7 using ammonia monomer as the reaction gas. In addition, the amount of impurities in the film was equivalent to that of Comparative Example 8 using hydrazine monomer as the reaction gas.

[0496] According to the above results, when forming a silicon nitride film, by using a mixed gas of hydrazine and ammonia as a reaction gas, the supply flow rate of hydrazine (N2H4) was reduced, and a film formation result almost equivalent to that of Comparative Example 7 using ammonia monomer as a reaction gas was obtained. In addition, Examples 5 to 7 can reduce the cost by more than 50% compared with Comparative Example 8 using hydrazine monomer as a reaction gas.

[0497] Furthermore, when a small amount of hydrazine is supplied as a reaction gas, it was confirmed that in order to form a silicon nitride film with less impurities in the film, the nitrogen-containing compound raw material as the reaction gas needs to contain not only hydrazine but also ammonia.

[0498] The other results also showed the same tendency as the film formation evaluation results of the titanium nitride film.

[0499]

[0500] [Other nitride films]

[0501] The other nitride films also showed the same tendency as the film formation evaluation results of the titanium nitride film and the silicon nitride film.

[0502] In addition, as raw material gases when forming other nitride films, tantalum pentachloride (TaCl5) is used in the formation of tantalum nitride film (TaN), trimethylaluminum (TMA) and aluminum chloride (AlCl3) are used in the formation of aluminum nitride (AlN), and gallium chloride (GaCl3) and trimethylgallium (TMG) are used in the formation of gallium nitride (GaN).

[0503] Description of Reference Numerals

[0504] 1...Film forming device

[0505] 2...Processing room (chamber)

[0506] 3...Temperature control device

[0507] 4...Pressure Reducing Device

[0508] 10, 20, 30, 40, 50, 60, 70...Mixed gas supply device

[0509] 11...Raw material container

[0510] 12...Heater

[0511] 13...Heater adjustment device

[0512] 14...Dilution gas flow control device

[0513] 15...Ammonia flow control device

[0514] 16...Mixed gas flow meter

[0515] 17...Computing device

[0516] 18...Pipeline heater

[0517] 31...First Pressure Gauge

[0518] 32...Switch valve

[0519] 33...Pressure regulating device

[0520] 34...Buffer tank (storage tank)

[0521] 35...Second pressure gauge

[0522] 36...Switch valve control device

[0523] 41...Setting device

[0524] P: processed substrate (substrate)

[0525] L1...Purge gas supply path

[0526] L2...Exhaust path

[0527] L3...Raw material gas supply path

[0528] L4...Reaction gas supply path

[0529] L11...Import path

[0530] L12...Export path

[0531] L13...Dilution gas supply path

[0532] L14, L24...Ammonia supply path

[0533] L15...Mixed gas outlet path

[0534] L16...Bypass path

[0535] L17...Mixed gas branch path

[0536] L18...Mixed gas confluence path

[0537] V1~V4...1st switch valve~4th switch valve

Claims

1. A mixed gas supply device, the mixed gas supply device is a device for supplying a mixed gas containing a hydrazine compound and ammonia as a nitrogen-containing compound raw material, comprising: a raw material container for containing the hydrazine compound; A heater, located around the raw material container, for heating the raw material container; A heater adjustment device for adjusting the output power of the heater; An introduction path for introducing a carrier gas into the raw material container; an outlet path for outlet the gas containing the hydrazine compound from the raw material container; A dilution gas supply path for supplying dilution gas; an ammonia supply path for supplying the ammonia; A mixed gas outlet path connected to the outlet path to outlet the mixed gas; a dilution gas flow control device, located in the dilution gas supply path, for controlling the flow rate of the dilution gas supplied to the dilution gas supply path; an ammonia flow control device, located in the ammonia supply path, and controlling the flow rate of ammonia supplied to the ammonia supply path; A mixed gas flow meter, located in the mixed gas outlet path, for measuring the flow rate of the mixed gas outlet to the mixed gas outlet path; as well as a calculation device that calculates the flow rate of the hydrazine compound contained in the mixed gas based on the flow rate of the dilution gas, the flow rate of the ammonia, and the flow rate of the mixed gas, The ammonia supply path is connected to at least any one of the introduction path, the outlet path, and the mixed gas outlet path. The dilution gas supply path is connected to one or both of the introduction path and the outlet path. The carrier gas is a dilution gas supplied from the dilution gas supply path, ammonia supplied from the ammonia supply path, or a mixed gas thereof.

2. The mixed gas supply device according to claim 1, wherein: A bypass path is further provided, the bypass path branching from the introduction path and merging with the discharge path without passing through the raw material container.

3. The mixed gas supply device according to claim 1 or 2, wherein: have: A first pressure gauge, located in the outlet path, for measuring the pressure in the raw material container; A switch valve capable of adjusting the opening degree, located in the outlet path or the mixed gas outlet path; as well as The pressure regulating device adjusts the opening of the on-off valve based on the measurement value of the first pressure gauge.

4. The mixed gas supply device according to claim 3, wherein: have: A storage tank, located on the mixed gas outlet path, storing the mixed gas; a second pressure gauge for measuring the pressure in the storage tank; and A flow path selection device selects the open / closed states of the ammonia supply path and the derivation path based on the measurement values ​​of the first pressure gauge and the second pressure gauge.

5. The mixed gas supply device according to claim 1 or 2, wherein: The computing device has a function of calculating a difference between a calculated value and a set value of the flow rate of the hydrazine compound and updating a set value of the heater adjusting device based on the difference.

6. The mixed gas supply device according to claim 1 or 2, wherein: The calculation device has a function of calculating a difference between a calculated value of the content ratio of the hydrazine compound contained in the mixed gas and a set value, and updating set values ​​of the dilution gas flow rate control device and the ammonia flow rate control device based on the difference.

7. The mixed gas supply device according to claim 3, wherein: The calculation device has a function of calculating a difference between a calculated value of the content ratio of the hydrazine compound contained in the mixed gas and a set value, and updating a set value of the pressure regulating device based on the difference.

8. The mixed gas supply device according to claim 1 or 2, wherein: The concentration of H2O contained in the nitrogen-containing compound raw material is 0.1 ppm or less.

9. The mixed gas supply device according to claim 1 or 2, wherein: The concentration of H2O contained in the hydrazine compound is 10 ppm or less.

10. The mixed gas supply device according to claim 1 or 2, wherein: The hydrazine compound is hydrazine (N2H4).

11. A metal nitride film manufacturing apparatus, which forms a metal nitride film on at least a portion of a surface of a substrate to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material, wherein: A mixed gas supply device according to any one of claims 1 to 10 is provided.

12. A method for producing a metal nitride film, comprising forming a metal nitride film on at least a portion of a surface of a substrate to be processed by a chemical vapor growth method using a metal compound raw material and a nitrogen-containing compound raw material, wherein: The nitrogen-containing compound raw material comprises hydrazine and ammonia, The method for manufacturing the metal nitride film comprises: A preparation step of placing the substrate to be processed in a processing chamber and controlling the surface temperature of the substrate to be processed to a desired temperature; and The film forming process repeats the following cycle: The cycle comprises: The step of supplying the metal compound raw material into the processing chamber; a step of stopping the supply of the metal compound raw material; The step of supplying the nitrogen-containing compound raw material into the processing chamber; and the step of stopping the supply of the nitrogen-containing compound raw material, The cycle further includes a step of supplying the ammonia or the ammonia diluted with an inert gas into the processing chamber.

13. The method for producing a metal nitride film according to claim 12, wherein: In the step of supplying the nitrogen-containing compound raw material into the processing chamber, The ammonia is introduced into a raw material container which is heated to a desired temperature and contains the hydrazine, and a mixed gas of the hydrazine and the ammonia discharged from the raw material container is used as the nitrogen-containing compound raw material.

14. The method for producing a metal nitride film according to claim 13, wherein: In the step of supplying the nitrogen-containing compound raw material into the processing chamber, The adjusted mixed gas is stored in a storage tank, and the mixed gas output from the storage tank is used as the nitrogen-containing compound raw material.

15. The method for producing a metal nitride film according to claim 13, wherein: The content ratio of the hydrazine to the ammonia in the mixed gas is 1:99 to 50:50 in terms of volume flow ratio.

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