JP6436887B2 - Semiconductor device manufacturing method, substrate processing apparatus, gas supply system, and program - Google Patents

Description

  The present invention relates to a semiconductor device manufacturing method, a substrate processing apparatus, a gas supply system, and a program.

  In recent years, with higher integration and higher performance of semiconductor devices such as MOSFETs (Metal-Oxide-Semiconductor Field Effect Transistors), device shapes have become finer and more complex, and finer processing techniques have been demanded. (See Patent Document 1).

JP 2011-6783 A

  With the miniaturization and complexity of device shapes in recent LSI manufacturing processes, when forming thin films, the width of the space that can be deposited has become smaller, requiring higher step coverage and higher embedding characteristics. Has been.

  An object of the present invention is to provide a technique for forming a thin film having good step coverage and embedding characteristics.

According to one aspect of the invention,
Supplying a halogen-based source gas to the substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate under a first process condition;
Repeating a predetermined number of cycles in a time-sharing manner,
Supplying a halogen-based source gas to the substrate;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate under a second process condition different from the first process condition;
Repeating a predetermined number of cycles in a time-sharing manner,
And a technique for forming a film in the trench is provided.

  According to the present invention, it is possible to provide a technique for forming a thin film having good step coverage and embedding characteristics.

It is a longitudinal cross-sectional view of the substrate processing apparatus used suitably by embodiment of this invention. It is a figure for demonstrating the gas supply system of the substrate processing apparatus used suitably by embodiment of this invention. It is a block diagram which shows the structure of the controller which the substrate processing apparatus shown in FIG. 1 has. It is a figure which shows the sequence in the 1st Embodiment of this invention. It is a figure which shows the sequence in the 2nd Embodiment of this invention. It is a figure which shows the sequence in the 3rd Embodiment of this invention. It is a figure which shows the sequence in the 4th Embodiment of this invention. In embodiment of this invention, it is a figure which shows the case where the quantity of the gas below the quantity of the film-forming inhibition gas required in order to cover all the surfaces of a board | substrate is supplied to the board | substrate surface. It is a figure which shows the case where source gas is supplied after the reaction inhibition gas in FIG. 8 is supplied. It is a figure which shows the case where the reaction gas is supplied after supplying the source gas in FIG. (A) is a figure which shows the case where little reaction inhibition gas is supplied. (B) is a figure which shows the case where reaction inhibition gas is supplied moderately. (C) is a figure which shows the case where many reaction inhibition gas is supplied. (A) is a figure which shows the film-forming at the time of supplying reaction reaction gas little, (b) is a figure which shows the film-forming at the time of supplying reaction-inhibiting gas moderately, (c), It is a figure which shows the film-forming at the time of supplying many reaction inhibition gas. FIG. 3 is a diagram illustrating a mechanism assumed for the first embodiment. It is a figure which shows the mechanism assumed with respect to the modification 6 of 1st Embodiment.

As a technique for obtaining a film having a good step coverage, the inventors have intensively studied and as a result, as shown in FIG. 8, a gas (film formation inhibiting gas) is formed on the upper portion 301 of the trench 300. ) And a gas that inhibits the reaction between the source gas and the reaction gas (reaction inhibition gas), and a method for reducing the film formation rate mainly for the upper portion 301 of the trench has been established. For example, let A be the amount of reaction-inhibiting gas required to react with the entire surface of the substrate (or cover the entire surface of the substrate). When an amount of gas equal to or greater than A is supplied to the substrate surface shown in FIG. 8, the number of collisions with the gas in the upper portion of the trench 301 is greater than that in the lower portion 302 of the trench 300. Can be reacted (or adsorbed).

The source gas may be supplied before supplying the reaction-inhibiting gas, or the source gas may be supplied after supplying the reaction-inhibiting gas. An example of supply will be described. When the source gas is supplied after supplying the reaction-inhibiting gas, the trench upper portion 301 reacts (has adsorbed) with the reaction-inhibiting gas, so that the adsorption of the source gas is hindered. Adsorb (FIG. 9). Next, when the reaction gas is supplied, since the upper film portion 301 has a small amount of source gas adsorbed, the film thickness to be formed is reduced, but the lower trench portion 302 is sufficiently adsorbed with the source gas. The film thickness to be formed is larger than that of the trench upper part 301 (FIG. 10). From these results, a film 303 having better step coverage can be obtained.

By changing the supply amount of the reaction inhibiting gas, as shown in FIG. 11, the adsorption place of the reaction inhibiting gas can be controlled. 11A shows a case where a small amount of reaction inhibiting gas is supplied, FIG. 11B shows a case where a moderate amount of reaction inhibiting gas is supplied, and FIG. 11C shows an amount of reaction inhibiting gas. This shows the case where a large amount is supplied. By gradually reducing the supply amount of the reaction-inhibiting gas, it is possible to control the location where the film is formed in the trench 300 as shown in FIG. For example, the film formation is performed under the first process condition where the supply amount of the reaction inhibiting gas is large at the initial stage of film formation, and the film formation is performed under the second process condition where the supply amount of the reaction inhibiting gas is small at the final stage of the film formation. To do. By doing so, embedding of Voice Free can be achieved. Further, it is preferable to increase the supply amount of the reaction-inhibiting gas at the initial stage of film formation, and to form a film with priority over the lower part of the trench (FIG. 12A). Thereafter, the supply amount of the reaction-inhibiting gas is made smaller than in the initial stage of film formation, so that the film is also formed on the upper part of the trench than in the initial stage of film formation (FIG. 12B). By doing so, the adsorption place of the reaction inhibiting gas can be controlled. Preferably, as the deposition process cycle progresses, the film is gradually deposited on the upper portion of the trench by gradually reducing the supply amount of the reaction inhibiting gas (FIGS. 12B and 12C). Thereby, embedding of Voice Free can be achieved. Details will be described below.

<First Embodiment of the Present Invention>
Hereinafter, a preferred first embodiment of the present invention will be described with reference to FIGS. The substrate processing apparatus 10 is configured as an example of an apparatus used in a substrate processing process, which is a process of manufacturing a semiconductor device (device).

  First, the substrate processing apparatus used in this embodiment will be described. This substrate processing apparatus is specifically a semiconductor device manufacturing apparatus, and is used in one step of a semiconductor device manufacturing process.

  In the following description, as an example of the substrate processing apparatus, a case where a single-wafer type substrate processing apparatus that performs film formation processing or the like on one substrate at a time will be described.

(1) Configuration of Substrate Processing Apparatus First, a schematic configuration diagram of a substrate processing apparatus 10 that is preferably used in the present embodiment.

<Processing chamber>
As shown in FIG. 1, the substrate processing apparatus according to this embodiment includes a processing container 102. The processing container 102 is configured as, for example, a flat sealed container having a circular top view. The processing container 102 is made of, for example, a metal material such as aluminum (Al) or stainless steel (SUS), or quartz (SiO ₂ ). A processing chamber 101 is formed in the processing container 102. In the processing chamber 101, a wafer 100 such as a silicon wafer as a substrate is processed.

<Support stand>
A support base 103 that supports the wafer 100 is provided in the processing container 102. The support base 103 is made of, for example, quartz (SiO ₂ ), carbon, ceramics, silicon carbide (SiC), aluminum oxide (Al ₂ O ₃ ), or aluminum nitride (AlN). On the upper surface of the support base 103, for example, a susceptor as a support plate made of quartz (SiO ₂ ), carbon, ceramics, silicon carbide (SiC), aluminum oxide (Al ₂ O ₃ ), or aluminum nitride (AlN). 117 is provided, and the wafer 100 is placed on the susceptor 117. The support base 103 incorporates a heater 106 as a heating means (heating source) for heating the wafer 100. In addition, the lower end (support) of the support base 103 penetrates the bottom of the processing container 102.

<Elevating mechanism>
An elevating mechanism 107 b connected to the lower end of the support base 103 is provided outside the processing container 102. By operating the lifting mechanism 107b, the support base 103 is raised and lowered, and the wafer 100 supported on the susceptor 117 is raised and lowered. The support table 103 (susceptor 117) is lowered to the height of a wafer transfer port 150 (to be described later) when the wafer 100 is transferred, and is raised to a wafer processing position (shown position) when the wafer 100 is processed. Note that the periphery of the lower end portion of the support base 103 is covered with a bellows 103a, and the inside of the processing container 102 is kept airtight.

<Lift pin>
A plurality of, for example, three lift pins 108b are provided on the bottom surface (floor surface) of the processing container 102. Further, the support base 103 (including the susceptor 117) is provided with through holes 108a through which the lift pins 108b pass, at positions corresponding to the lift pins 108b. When the support base 103 is lowered to the wafer transfer position, the upper end of the lift pin 108b protrudes from the upper surface of the susceptor 117 through the through hole 108a, and the lift pin 108b supports the wafer 100 from below. When the support base 103 is raised to the wafer processing position, the lift pins 108b are buried from the upper surface of the susceptor 117, and the susceptor 117 supports the wafer 100 from below. Note that the lift pins 108b are preferably made of a material such as quartz or alumina, for example, in order to directly contact the wafer 100.

<Wafer transfer port>
A wafer transfer port 150 for transferring the wafer 100 into and out of the processing container 102 is provided on the side surface of the inner wall of the processing container 102. The wafer transfer port 150 is provided with a gate valve 151. By opening the gate valve 151, the inside of the processing chamber 102 and the transfer chamber (preliminary chamber) 171 communicate with each other. The transfer chamber 171 is formed in a transfer container (sealed container) 172, and a transfer robot 173 for transferring the wafer 100 is provided in the transfer chamber 171. The transfer robot 173 includes a transfer arm 173 a that supports the wafer 100 when the wafer 100 is transferred. By opening the gate valve 151 with the support base 103 lowered to the wafer transfer position, the transfer robot 173 can transfer the wafer 100 between the processing chamber 101 and the transfer chamber 171. . The wafer 100 transferred into the processing chamber 101 is temporarily placed on the lift pins 108b as described above. A load lock chamber (not shown) is provided on the opposite side of the transfer container 172 to the side where the wafer transfer port 150 is provided, and the wafer 100 is transferred between the load lock chamber and the transfer chamber 171 by the transfer robot 173. Can be transported. The load lock chamber functions as a spare chamber for temporarily storing unprocessed or processed wafers 100.

<Exhaust system>
An exhaust port 160 that exhausts the atmosphere in the processing container 102 is provided on the inner wall side surface of the processing container 102 and on the opposite side of the wafer transfer port 150. An exhaust pipe 161 is connected to the exhaust port 160 via an exhaust chamber 160a. The exhaust pipe 161 has a pressure adjustment such as an APC (Auto Pressure Controller) as a pressure control device for controlling the inside of the processing chamber 101 to a predetermined pressure. A vessel 162, a raw material recovery trap 163, and a vacuum pump 164 are connected in series in this order. An exhaust system (exhaust line) is mainly configured by the exhaust port 160, the exhaust pipe 161, and the pressure regulator 162. The material recovery trap 163 and the vacuum pump 164 may be included in the exhaust system.

<Gas inlet>
A gas inlet 110 for supplying various gases into the processing container 102 is provided at the upper part of the processing container 102 (the upper surface (ceiling wall) of a shower head 140 described later). A gas supply system (described later) is connected to the gas inlet 110.

<Shower head>
A shower head 140 as a gas dispersion mechanism is provided between the gas inlet 110 and the processing chamber 101 in the processing container 202. The shower head 140 is a dispersion plate 140 a that disperses the gas introduced from the gas introduction port 110, and a shower plate that further uniformly disperses the gas that has passed through the dispersion plate 140 a and supplies the gas to the surface of the wafer 100 on the support base 103. 140b. The dispersion plate 140a and the shower plate 140b are provided with a plurality of vent holes. The dispersion plate 140 a is disposed so as to face the upper surface of the shower head 140 and the shower plate 140 b, and the shower plate 140 b is disposed so as to face the wafer 100 on the support base 103. In addition, spaces are provided between the upper surface of the shower head 140 and the dispersion plate 140a, and between the dispersion plate 140a and the shower plate 140b, respectively, and these spaces are supplied from the gas inlet 110. Respectively, and a second buffer space 140d for diffusing the gas that has passed through the dispersion plate 140a.

<Exhaust duct>
A stepped portion 101 a is provided on the inner wall side surface of the processing chamber 101. The step portion 101 a holds the conductance plate 104. The conductance plate 104 is configured as a ring-shaped plate member provided with a hole for accommodating the wafer 100 in the inner periphery. A plurality of discharge ports 104 a arranged in the circumferential direction at predetermined intervals are provided on the outer periphery of the conductance plate 104.

  A lower plate 105 is locked to the outer peripheral portion of the support base 103 in the processing container 102. The lower plate 105 includes a ring-shaped concave portion 105b and a flange portion 105a provided integrally on the inner peripheral upper side of the concave portion 105b. The recessed portion 105 b is provided so as to close a gap between the outer peripheral portion of the support base 103 and the inner wall side surface of the processing chamber 101. A part of the bottom of the recess 105b near the exhaust port 160 is provided with a plate exhaust port 105c that discharges (circulates) gas from the recess 105b to the exhaust port 160 side. The flange portion 105 a functions as a locking portion that locks on the upper outer periphery of the support base 103. When the flange portion 105 a is locked on the upper outer periphery of the support base 103, the lower plate 105 is lifted and lowered together with the support base 103 as the support base 103 is raised and lowered.

  When the support base 103 is raised to the wafer processing position, the conductance plate 104 closes the upper opening surface of the recess 105b of the lower plate 105, and an exhaust duct 159 is formed with the interior of the recess 105b as the gas flow path region. The conductance plate 104 and the lower plate 105 are made of a material that can be kept at a high temperature, for example, a high temperature resistant and high load in consideration of the case where the reaction product deposited on the inner wall of the exhaust duct 159 is etched (self cleaning). Preferably, it is made of quartz for use.

  Here, the flow of gas in the processing chamber 101 during wafer processing will be described. First, the gas supplied from the gas inlet 110 to the shower head 140 enters the second buffer space 140d from the hole of the dispersion plate 140a through the first buffer space 140c, and further passes through the hole of the shower plate 140b for processing. It is supplied into the chamber 101 and uniformly supplied onto the wafer 100. The gas supplied onto the wafer 100 flows radially outward of the wafer 100 in the radial direction. The surplus gas after contacting the wafer 100 flows radially on the exhaust duct 159 located on the outer periphery of the wafer 100, that is, on the conductance plate 104, radially outward of the wafer 100. Is discharged into the gas flow path region (in the recess 105b) in the exhaust duct 159. Thereafter, the gas flows in the exhaust duct 159 and is exhausted to the exhaust port 160 via the plate exhaust port 105c. By flowing the gas in this way, gas wraparound to the lower portion of the processing chamber, that is, the back surface of the support base 103 or the bottom surface of the processing chamber 101 is suppressed.

<Gas supply system>
Next, the configuration of the gas supply system that configures the gas supply system and is connected to the gas inlet 110 described above will be described with reference to FIG. FIG. 2 is a configuration diagram of a gas supply system of the substrate processing apparatus according to the embodiment of the present invention.

(Gas supply system)
The gas supply pipes 310, 320, and 330 are provided with mass flow controllers (MFCs) 312, 322, 332 that are flow rate controllers (flow rate control units), and valves 314, 324, and 334 that are on-off valves in order from the upstream side. ing. Gas supply pipes 510, 520, and 530 for supplying an inert gas are connected to downstream sides of the valves 314, 324, and 334 of the gas supply pipes 310, 320, and 330, respectively. The gas supply pipes 510, 520, and 530 are provided with MFCs 512, 522, and 532 that are flow rate controllers (flow rate control units) and valves 514, 524, and 534 that are on-off valves, in order from the upstream side.

  As an example of the above configuration, a reaction-inhibiting gas is supplied from the gas supply pipe 310 as a processing gas into the processing chamber 101 via the MFC 312 and the valve 314. As the reaction inhibition gas, for example, a halide (halogen-based gas), for example, a hydrogen halide gas (hydrogen halide) can be used. As the hydrogen halide, for example, hydrogen chloride (HCl) gas composed of chlorine (Cl) and hydrogen (H) can be used.

From the gas supply pipe 320, a raw material gas is supplied into the processing chamber 101 through the MFC 322 and the valve 324 as a processing gas. As the source gas, a halogen-based source gas (halogen compound, halide), for example, a gas containing a metal element (metal-containing gas) can be used. The metal-containing gas is, for example, a gas containing titanium (Ti), which is a transition metal element, as a metal element (a titanium (Ti) -containing raw material, a Ti-containing raw material gas, a Ti-containing gas, a Ti source), and a halogen element containing chlorine. Titanium tetrachloride (TiCl ₄ ) containing (Cl) is used. When the term “raw material” is used in the present specification, it means “a liquid raw material in a liquid state”, “a raw material gas in a gaseous state”, or both of them. There is.

From the gas supply pipe 330, a reactive gas is supplied as a processing gas into the processing chamber 101 through the MFC 332 and the valve 334. The reaction gas is a nitrogen (N) -containing gas (nitriding gas, nitriding agent), and for example, ammonia (NH ₃ ) gas can be used.

From the gas supply pipes 510, 520, and 530, nitrogen (N ₂ ) gas as an inert gas is supplied to the gas inlet 110 through the MFCs 512, 522, 532, valves 514, 524, and 534, respectively.

  When the processing gas as described above is allowed to flow from the gas supply pipes 310, 320, and 330, a processing gas supply system is mainly configured by the gas supply pipes 310, 320, 330, MFCs 312, 322, 332, and valves 314, 324, and 334. Is done. The gas inlet 110 may be included in the processing gas supply system. The processing gas supply system can be simply referred to as a gas supply system.

  When a reaction inhibiting gas is allowed to flow as a processing gas from the gas supply pipe, a reaction inhibiting gas supply system is mainly configured by the gas supply pipe 310, the MFC 312 and the valve 314. When flowing a hydrogen halide gas, which is a halide (halogen-based gas), as a reaction-inhibiting gas from the gas supply pipe 310, the reaction-inhibiting gas supply system can also be referred to as a hydrogen halide gas supply system (hydrogen halide supply system). . When supplying HCl gas as the hydrogen halide gas, the hydrogen halide gas supply system may be referred to as an HCl gas supply system. The HCl gas supply system can also be referred to as an HCl supply system.

When the raw material gas is flowed as the processing gas from the gas supply pipe 320, the raw material gas supply system is mainly configured by the gas supply pipe 320, the MFC 322, and the valve 324. When a halogen-based source gas is allowed to flow as a source gas from the gas supply pipe 320, the source gas supply system can also be referred to as a halogen-based source gas supply system. When a metal-containing gas is allowed to flow from the gas supply pipe 320 as the halogen-based source gas, the halogen-based source gas supply system can also be referred to as a metal-containing gas supply system. When flowing a Ti-containing gas as a metal-containing gas from the gas supply pipe 320, the metal-containing gas supply system can also be referred to as a Ti-containing gas supply system. When flowing TiCl ₄ gas as the Ti-containing gas, the Ti-containing gas supply system can also be referred to as a TiCl ₄ gas supply system. The TiCl ₄ gas supply system can also be referred to as a TiCl ₄ supply system.

When a reaction gas is allowed to flow as a processing gas from the gas supply pipe 330, a reaction gas supply system is mainly configured by the gas supply pipe 330, the MFC 332, and the valve 334. When an N-containing gas is allowed to flow as a reaction gas from the gas supply pipe 330, the N-containing gas supply system can also be referred to as an NH ₃ gas supply system. The NH ₃ gas supply system can also be referred to as an NH ₃ supply system.

  In addition, an inert gas supply system is mainly configured by the gas supply pipes 510, 520, 530, the MFCs 512, 522, 532, and the valves 514, 524, 534. Since the inert gas acts as a purge gas, a dilution gas, a carrier gas, or the like, the inert gas supply system can also be called a purge gas supply system, a dilution gas supply system, or a carrier gas supply system. Wafers such as film thickness uniformity within the surface of the wafer 100 placed on the susceptor 117 by diluting the reaction inhibition gas, source gas, and reaction gas supplied from the gas supply pipes 310, 320, and 330 with a carrier gas, respectively. The uniformity of processing of the wafer 100 in 100 can be adjusted.

(Control part)
As shown in FIG. 1, the substrate processing apparatus includes a controller 300 as a control unit. FIG. 3 shows a connection example between the control unit and each component according to the present embodiment. The controller 300 which is a control unit (control means) is configured as a computer including a CPU (Central Processing Unit) 380a, a RAM (Random Access Memory) 380b, a storage device 380c, and an I / O port 380d. The RAM 380b, the storage device 380c, and the I / O port 380d are configured to exchange data with the CPU 380a via the internal bus 380e. The controller 300 is connected with an input device 382 configured as, for example, a touch panel or a display device (display) 372 as a man-machine interface.

  The storage device 380c is configured by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 380c, a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the procedure and conditions of the substrate processing described later, and the like are stored in a readable manner. The process recipe is a combination of instructions so that the controller 300 can execute each procedure in a substrate processing step to be described later to obtain a predetermined result, and functions as a program. Hereinafter, process recipes, control programs, and the like are collectively referred to simply as programs. The process recipe is also simply called a recipe. When the term “program” is used in this specification, it may include only a process recipe alone, only a control program alone, or both. The RAM 380b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 380a are temporarily stored.

  The I / O port 380d includes a heater 106, an elevating mechanism 107b, a gate valve 151, a transfer robot 173, a pressure regulator 162, a vacuum pump 164, MFC 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534 and the like.

  The CPU 380a reads and executes a control program from the storage device 380c, and reads a process recipe from the storage device 380c in response to an operation command input from the input / output device 382 or the like. The CPU 380a adjusts the flow rates of various gases by the MFCs 312, 322, 332, 512, 522, 532 and opens / closes the valves 314, 324, 334, 514, 524, 534 in accordance with the contents of the read control program and process recipe. It is configured to control the operation, the pressure adjustment operation of the pressure regulator 162, the temperature adjustment operation of the heater 106, the start and stop of the vacuum pump 164, the elevation operation of the support base 103 by the elevation mechanism 107b, and the like.

  The controller 300 is an external storage device (for example, a magnetic tape, a magnetic disk such as a flexible disk or a hard disk, an optical disk such as a CD or a DVD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory (USB Flash Drive) or a memory card). ) The above program stored in 383 can be installed in a computer. The storage device 380c and the external storage device 383 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as a recording medium. When the term “recording medium” is used in this specification, it may include only the storage device 380c alone, may include only the external storage device 383 alone, or may include both of them. The provision of the program to the computer may be performed using communication means such as the Internet or a dedicated line without using the external storage device 383.

(2) Substrate processing process (film formation process)
As an example of a manufacturing process of a semiconductor device (device), an example of a process of forming a metal film on a substrate having a trench (groove) formed on the surface will be described with reference to FIG. The step of forming the metal film is performed in the processing chamber 101 of the substrate processing apparatus 10 described above. In the following description, the operation of each part constituting the substrate processing apparatus 10 is controlled by the controller 300.

<First Embodiment of the Present Invention>
In a preferred film forming sequence (also simply referred to as a sequence) of the present embodiment, a halogen-based source gas (for example, TiCl ₄ gas) containing a metal element (for example, titanium (Ti)) as the first element is applied to the wafer 100. Supplying the wafer 100 with a reaction inhibiting gas (for example, HCl gas) that inhibits the reaction between the first halogen-based source gas and a reaction gas to be described later. On the other hand, a step of supplying a reaction gas (for example, NH ₃ gas) containing a second element (for example, nitrogen (N)) and reacting with the first element is time-shared (asynchronous, intermittent, A thin film (for example, titanium nitride) formed on the wafer 100 by controlling the supply flow rate of the reaction inhibition gas in the step of supplying the reaction inhibition gas in a predetermined number of times. It is possible to improve the higher step coverage of the film (TiN film)).

  In this specification, “processing (or process, cycle, step, etc.) is performed a predetermined number of times” means that this processing or the like is performed once or a plurality of times. That is, it means that the process is performed once or more. FIG. 4 shows an example in which each process (cycle) is repeated n cycles. The value of n is appropriately selected according to the film thickness required for the finally formed TiN film. That is, the number of times each of the above-described processes is performed is determined according to the target film thickness.

  In this specification, “time division” means that time division (separation) is performed. For example, in the present specification, performing each process in a time-sharing manner means that each process is performed asynchronously, that is, without being synchronized. In other words, it means that each process is performed intermittently (pulsed). That is, it means that the processing gases supplied in each process are supplied so as not to mix with each other. When each process is performed a plurality of times in a time-sharing manner, the process gases supplied in each process are alternately supplied so as not to mix with each other.

  In this specification, when the term “wafer” is used, it means “wafer itself” or “a laminate (aggregate) of a wafer and a predetermined layer or film formed on the surface”. In some cases (that is, a wafer including a predetermined layer or film formed on the surface is referred to as a wafer). In addition, when the term “wafer surface” is used in this specification, it means “the surface of the wafer itself (exposed surface)” or “the surface of a predetermined layer or film formed on the wafer”. That is, it may mean “the outermost surface of the wafer as a laminated body”.

  Therefore, in the present specification, the phrase “supplying a predetermined gas to the wafer” means “supplying a predetermined gas directly to the surface (exposed surface) of the wafer itself”. , It may mean that “a predetermined gas is supplied to a layer, a film, or the like formed on the wafer, that is, to the outermost surface of the wafer as a laminated body”. Further, in this specification, when “describe a predetermined layer (or film) on the wafer” is described, “determine a predetermined layer (or film) directly on the surface (exposed surface) of the wafer itself”. This means that a predetermined layer (or film) is formed on a layer or film formed on the wafer, that is, on the outermost surface of the wafer as a laminate. There is a case.

  In this specification, the term “substrate” is used in the same manner as the term “wafer”.

  In this specification, the term “metal film” means a film composed of a conductive substance containing metal atoms, and includes a conductive metal nitride film (metal nitride film), a conductive metal oxide film. (Metal oxide film), conductive metal oxynitride film (metal oxynitride film), conductive metal composite film, conductive metal alloy film, conductive metal silicide film (metal silicide film), conductive A metal carbide film (metal carbide film), a conductive metal carbonitride film (metal carbonitride film) and the like are included. The TiN film is a conductive metal nitride film.

(Board preparation step)
First, the gate valve 151 provided at the wafer transfer port 150 is opened, and the transfer robot 173 transfers the wafer 100 having a trench (groove) formed on the surface thereof from the transfer chamber 171 into the processing container 102.

(Substrate placement step)
The wafer 100 transferred into the processing container 102 is placed on the lift pins 108b. Then, the wafer 100 is placed on the susceptor 117 by raising the support base 103 to the wafer processing position.

(Pressure / temperature adjustment step)
When the wafer 100 is placed on the susceptor 117, the gate valve 151 is closed, and the processing chamber 101 is evacuated by the vacuum pump 164 so that a desired pressure (degree of vacuum) is obtained. At this time, the pressure in the processing chamber 101 is measured by a pressure sensor (not shown) and feedback controlled by the APC valve 162. Further, the wafer 100 placed on the susceptor 117 is heated to a predetermined temperature by the heater 106 built in the support base 103. At this time, the energization amount to the heater 106 is feedback-controlled based on temperature information detected by a temperature sensor (not shown) so that the wafer 100 has a predetermined temperature distribution.

  The pressure adjustment and temperature adjustment described above are always executed until the film forming process described later is completed.

(TiN film formation step)
Subsequently, a step of forming a TiN film is performed. The TiN film formation step includes a halogen-based source gas supply step, a reaction inhibition gas supply step, a residual gas removal step, an N-containing gas supply step, and a residual gas removal step, which will be described below.

Specifically, as in the sequence shown in FIG. 4, a titanium nitride film (TiN film) is formed by performing a predetermined number of times (n times) of flowing a TiCl ₄ gas, an HCl gas, and an NH ₃ gas in a time-sharing manner. To do. For the sake of convenience, the sequence shown in FIG. 4 is represented as the following equation (1). P / V indicates a gas removal step described later. In the following description, the same notation is used for convenience.

(TiCl ₄ → HCl → P / V → NH ₃ → P / V) × n => TiN (1)

(Halogen source gas supply step)
First, the valve 324 is opened, and a TiCl ₄ gas that is a halogen-based material is caused to flow into the gas supply pipe 320. The flow rate of the TiCl ₄ gas that has flowed through the gas supply pipe 320 is adjusted by the MFC 322. The flow-adjusted TiCl ₄ gas is supplied from the gas inlet 110 into the processing chamber 101 and exhausted from the exhaust pipe 161. At this time, TiCl ₄ gas is supplied to the wafer 100. That is, the surface of the wafer 100 (including the trench) is exposed to TiCl ₄ gas. At the same time, the valve 524 is opened, and an inert gas such as N ₂ gas is allowed to flow into the gas supply pipe 520. The flow rate of the N ₂ gas flowing through the gas supply pipe 520 is adjusted by the MFC 522. The N ₂ gas whose flow rate has been adjusted is supplied into the processing chamber 101 together with the TiCl ₄ gas, and is exhausted from the exhaust port 160.

At this time, the vacuum pump 164 is appropriately adjusted so that the pressure in the processing chamber 101 is, for example, a (predetermined) pressure within a range of 1 to 70000 Pa, preferably a (predetermined) pressure within a range of 1 to 1333 Pa. The pressure is preferably (predetermined) within a range of 20 to 50 Pa. If the pressure in the processing chamber 101 is higher than 70,000 Pa, residual gas removal described later may not be performed sufficiently. If the pressure in the processing chamber 101 is lower than 0.01 Pa, the reaction rate of TiCl ₄ gas may not be sufficiently obtained. In addition, in this specification, when it describes as 1-70000 Pa as a range of a numerical value, it means 1 Pa or more and 70000 Pa or less. That is, 1 Pa and 70000 Pa are included in the numerical range. The same applies not only to pressure but also to all numerical values described in this specification, such as flow rate, time, temperature, and the like.

The supply flow rate of the TiCl ₄ gas controlled by the MFC 322 is a sufficient amount to cover the entire surface of the wafer 100 (including the inner surface of the trench 300), for example, a (predetermined) flow rate within a range of 1 to 10,000 sccm, preferably Is a (predetermined) flow rate in the range of 0 to 2000 sccm, more preferably a (predetermined) flow rate in the range of 10 to 600 sccm. If the supply flow rate of TiCl ₄ gas is more than 10,000 sccm, a large amount of impurities such as Cl may be taken in, and residual gas removal described later may not be sufficiently performed. When the supply flow rate of TiCl ₄ gas is less than 1 sccm, there is a possibility that the reaction rate of TiCl ₄ gas cannot be obtained sufficiently.

The supply flow rate of N ₂ gas controlled by the MFC 512 is, for example, a (predetermined) flow rate in the range of 1 to 20000 sccm, preferably a (predetermined) flow rate in the range of 500 to 15000 sccm, more preferably in the range of 600 to 800 sccm. (Predetermined) flow rate. When the supply flow rate of N ₂ gas is more than 20000 sccm, there is a possibility that the reaction rate of TiCl ₄ gas cannot be sufficiently obtained. If the supply flow rate of N ₂ gas is less than 1 sccm, residual gas removal described later may not be sufficiently performed.

The time for supplying the TiCl ₄ gas to the wafer 100, that is, the gas supply time (irradiation time) is, for example, in the range of 0.1 to 120 seconds (predetermined), preferably in the range of 1 to 30 seconds ( (Predetermined), and more preferably (predetermined) time within a range of 2 to 6 seconds. If the gas supply time is longer than 120 seconds, a large amount of impurities such as Cl may be taken in. If the gas supply time is less than 0.1 seconds, the film formation rate may be lowered.

As for the temperature of the heater 106, the temperature of the wafer 100 is, for example, a (predetermined) temperature within a range of 200 to 600 ° C., preferably a (predetermined) temperature within a range of 200 to 550 ° C., more preferably 200 to 400 ° C. The temperature is set to a (predetermined) temperature within the range. When the temperature of the heater 106 is higher than 600 ° C., the thermal decomposition of the TiCl ₄ gas is promoted, so that the film formation rate becomes too high and the controllability of the film thickness is deteriorated and the uniformity is deteriorated. In some cases, a large amount of impurities such as those causes the resistivity to increase. On the other hand, when the temperature of the heater 106 is lower than 200 ° C., the reactivity becomes low and film formation may be difficult. The gases flowing into the processing chamber 101 are only TiCl ₄ gas and N ₂ gas, and a Ti-containing layer is formed on the wafer 100 (surface underlayer film) by supplying the TiCl ₄ gas.

The Ti-containing layer may be a Ti layer composed of Ti, a Ti layer containing Cl, or a TiCl ₄ adsorption layer (hereinafter also referred to simply as an adsorption layer of raw material molecules). Or all of them may be included. The Ti layer containing Cl is a general term including a continuous layer made of Ti and containing Cl, a discontinuous layer, and a Ti thin film containing Cl formed by overlapping these layers. A continuous layer made of Ti and containing Cl may be referred to as a Ti thin film containing Cl. Ti constituting the Ti layer containing Cl includes not only the bond with Cl not completely broken but also the one with bond completely broken with Cl.

The adsorption layer of raw material molecules includes a discontinuous adsorption layer as well as a continuous adsorption layer composed of TiCl ₄ molecules. That is, the adsorption layer of raw material molecules includes an adsorption layer having a thickness of less than one molecular layer or less than one molecular layer composed of TiCl ₄ molecules. The TiCl ₄ molecules constituting the raw material molecule adsorption layer include those in which the bond between Ti and Cl is partially broken. That is, the adsorption layer of source molecules may be a physical adsorption layer of TiCl _4, may be a chemical adsorption layer of TiCl4 _4, may include both of them.

  Here, a layer having a thickness of less than one atomic layer means an atomic layer formed discontinuously, and a layer having a thickness of one atomic layer means an atomic layer formed continuously. Means. A layer having a thickness of less than one molecular layer means a molecular layer formed discontinuously, and a layer having a thickness of one molecular layer means a molecular layer formed continuously. ing. The Ti-containing layer containing Cl can include both a Ti layer containing Cl and an adsorption layer of source molecules. However, as described above, the Ti-containing layer containing Cl is expressed using expressions such as “one atomic layer” and “several atomic layer”.

Under conditions where the TiCl ₄ gas is self-decomposed (thermally decomposed), Ti is deposited on the wafer 100 to form a Ti layer. Under conditions where the TiCl ₄ gas is not self-decomposed (thermally decomposed), an adsorption layer of raw material molecules is formed by the adsorption of TiCl ₄ on the wafer 100. It is preferable to form a Ti layer on the wafer 100 in that the film formation rate can be increased, rather than forming an adsorption layer of raw material molecules on the wafer 100.

  When the thickness of the Ti-containing layer (hereinafter sometimes referred to as the first layer) formed in one halogen-based source gas supply step exceeds several atomic layers, the reforming in the N-containing gas supply step described later Will not reach the entire first layer. The minimum thickness of the first layer is less than one atomic layer. Therefore, it is preferable that the thickness of the first layer be less than one atomic layer to several atomic layers. By setting the thickness of the first layer to 1 atomic layer or less, that is, 1 atomic layer or less than 1 atomic layer, it is possible to relatively increase the effect of reforming in the N-containing gas supply step described later, The time required for reforming in the contained gas supply step can be shortened. The time required for forming the first layer in the halogen-based source gas supply step can also be shortened. As a result, the processing time per cycle can be shortened, and the total processing time can be shortened. That is, the film forming rate can be increased. Moreover, the controllability of the film thickness uniformity can be improved by setting the thickness of the first layer to 1 atomic layer or less.

(Reaction inhibiting gas supply step)
After the Ti-containing film is formed, the valve 324 is closed and the supply of TiCl ₄ gas is stopped. Next, the valve 314 is opened, and HCl gas, which is a reaction inhibition gas, is caused to flow into the gas supply pipe 310. The flow rate of the HCl gas flowing through the gas supply pipe 310 is adjusted by the MFC 312. The flow-adjusted HCl gas is supplied from the gas inlet 110 into the processing chamber 101 and exhausted from the exhaust pipe 161. At this time, HCl gas is supplied to the wafer 100. That is, the surface of the wafer 100 is exposed to HCl gas. At the same time, the valve 514 is opened and N ₂ gas is allowed to flow into the gas supply pipe 510. The flow rate of the N ₂ gas flowing through the gas supply pipe 510 is adjusted by the MFC 512. The N ₂ gas whose flow rate has been adjusted is supplied into the processing chamber 101 together with the HCl gas, and is exhausted from the exhaust pipe 161.

At this time, the pressure regulator 162 is appropriately adjusted so that the pressure in the processing chamber 101 is, for example, a (predetermined) pressure within a range of 1 to 13300 Pa, preferably a (predetermined) pressure within a range of 1 to 1330 Pa, More preferably, the pressure is a (predetermined) pressure within a range of 1 to 133 Pa. If the pressure in the processing chamber 101 is higher than 13300 Pa, the HCl gas may excessively react (or adsorb) with the wafer 100, which may hinder the reaction between the Ti-containing layer and the NH ₃ gas beyond a predetermined amount. . If the pressure in the processing chamber 101 is lower than 1 Pa, the reaction rate of HCl gas may not be sufficiently obtained.

The supply flow rate of the HCl gas controlled by the MFC 312 is a flow rate equal to or less than an amount necessary to cover the entire surface of the wafer 100, and is, for example, a (predetermined) flow rate in the range of 1 to 3000 sccm, preferably in the range of 10 to 1000 sccm. (Predetermined) flow rate, more preferably (predetermined) flow rate in the range of 10-100 sccm. If the supply flow rate of the HCl gas is greater than 3000 sccm, the HCl gas may significantly enter the trench lower portion 302, which may affect the formation of the TiN film in the trench lower portion 302. If the supply flow rate of HCl gas is less than 1 sccm, the reaction inhibition effect between the Ti-containing layer and NH ₃ gas by HCl gas may not be sufficiently obtained.

  Note that the HCl gas supply flow rate may be changed between the initial stage and the final stage of the TiN film formation. For example, at the initial stage of film formation, the supply amount of the reaction inhibiting gas is increased as the first process condition, and the TiN film is formed in preference to the lower part of the trench. Thereafter, a TiN film is formed also on the trench by reducing the supply amount of the reaction inhibiting gas as a second process condition at the final stage of film formation. By such bottom-up film formation, film formation with a reduced void is possible, and the embedding characteristic of void free can be achieved.

  Furthermore, it is preferable to gradually decrease the supply flow rate of HCl gas as the number of processing cycles increases (that is, as the number of n in n cycles increases) from the initial stage to the middle stage to the final stage of TiN film formation. For example, the supply amount of the reaction inhibiting gas is increased in the initial stage of film formation, and a TiN film is formed in preference to the lower part of the trench (FIG. 12A). Thereafter, as the film forming process cycle proceeds, a TiN film is gradually formed on the upper part of the trench by gradually decreasing the supply amount of the reaction inhibiting gas (FIGS. 12B and 12C). . Thus, the supply amount of HCl, which is a reaction inhibiting gas, is adjusted according to the depth of the trench. By such bottom-up film formation, as shown in FIGS. 12A, 12B, and 12C, by gradually reducing the supply flow rate of HCl gas, it becomes possible to form a film with a reduced void. Free embedding characteristics can be achieved.

The supply flow rate of N ₂ gas controlled by the MFC 512 is, for example, a (predetermined) flow rate in the range of 1 to 20000 sccm, preferably a (predetermined) flow rate in the range of 500 to 15000 sccm, more preferably in the range of 600 to 800 sccm. (Predetermined) flow rate. If the supply flow rate of N ₂ gas is more than 20000 sccm, the reaction rate of HCl gas may not be sufficiently obtained. If the supply flow rate of N ₂ gas is less than 1 sccm, residual gas removal described later may not be sufficiently performed.

The time for supplying HCl gas to the wafer 100, that is, the gas supply time (irradiation time) is, for example, a (predetermined) time within a range of 0.01 to 120 seconds, preferably within a range of 0.1 to 60 seconds. (Predetermined) time, more preferably (predetermined) time within a range of 1 to 10 seconds. When the gas supply time is longer than 120 seconds, the HCl gas excessively reacts (adsorbs) with the wafer 100, and the reaction between the Ti-containing layer and the NH ₃ gas may be inhibited more than a predetermined amount. If the gas supply time is shorter than 1 second, the film formation rate may be lowered.

  The temperature of the heater 106 is the same as that in the halogen-based source gas supply step. The supply of HCl gas causes the Ti-containing layer and the HCl gas to react.

(Residual gas removal step)
Thereafter, the valve 314 is closed and the supply of HCl gas is stopped. At this time, the pressure regulator 162 of the exhaust pipe 161 is kept open, the processing chamber 101 is evacuated by the vacuum pump 164, and HCl that has served as an unreacted or reaction-inhibiting gas remaining in the processing chamber 101 is obtained. Gases and reaction by-products are removed from the processing chamber 101. At this time, the point that the gas remaining in the processing chamber 101 does not have to be completely removed is the same as in the halogen-based source gas supply step.

(N-containing gas supply step)
After the residual gas in the processing chamber 101 is removed, the valve 334 is opened, and NH ₃ gas that is N-containing gas is caused to flow into the gas supply pipe 330. The flow rate of NH ₃ gas that has flowed through the gas supply pipe 330 is adjusted by the MFC 332. The NH ₃ gas whose flow rate has been adjusted is supplied from the gas inlet 110 into the processing chamber 101 and exhausted from the exhaust pipe 161. At the same time, the valve 534 is opened to allow N ₂ gas to flow into the gas supply pipe 530. The flow rate of the N ₂ gas flowing through the gas supply pipe 530 is adjusted by the MFC 532. N ₂ gas is supplied into the processing chamber 101 together with NH ₃ gas, and is exhausted from the exhaust pipe 161.

When flowing NH ₃ gas, the pressure regulator 162 is appropriately adjusted, and the pressure in the processing chamber 101 is, for example, a (predetermined) pressure within a range of 0.01 to 13300 Pa, preferably within a range of 1 to 1330 Pa. (Predetermined) pressure, more preferably (predetermined) pressure within the range of 10 to 133 Pa. If the pressure in the processing chamber 101 is higher than 13300 Pa, residual gas removal described later may not be performed sufficiently. If the pressure in the processing chamber 101 is lower than 0.01 Pa, a sufficient film formation rate may not be obtained.

The supply flow rate of NH ₃ gas controlled by the MFC 332 is an amount sufficient to cover the entire surface of the wafer 100, and is, for example, a (predetermined) flow rate in the range of 10 to 50000 sccm, preferably in the range of 300 to 10000 sccm. A (predetermined) flow rate, more preferably a (predetermined) flow rate in the range of 1000 to 8000 sccm. The larger the NH ₃ gas supply flow rate, the more preferable it is because the incorporation of impurities derived from the source gas into the TiN film can be reduced. However, when the NH ₃ gas supply flow rate is more than 50000 sccm, the residual gas is sufficiently removed in the residual gas removal step described later. It may not be possible. When the supply flow rate of NH ₃ gas is less than 10 sccm, there is a possibility that the reaction cannot be sufficiently performed.

The supply flow rate of N ₂ gas controlled by the MFC 532 is, for example, a (predetermined) flow rate in the range of 10 to 20000 sccm, preferably a (predetermined) flow rate in the range of 400 to 15000 sccm, more preferably in the range of 400 to 7500 sccm. (Predetermined) flow rate. If the supply flow rate of N ₂ gas is more than 20000 sccm, the film formation rate may be too low. If the supply flow rate of the N ₂ gas is less than 10 sccm, the NH ₃ gas may not be sufficiently supplied to the wafer 100.

The time for supplying the NH ₃ gas to the wafer 100, that is, the gas supply time (irradiation time) is, for example, a (predetermined) time in the range of 0.001 to 300 seconds, preferably in the range of 0.1 to 60 seconds. (Predetermined) time, more preferably (predetermined) time within a range of 10 to 25 seconds. A longer gas supply time is preferable because the incorporation of impurities derived from the source gas into the TiN film can be reduced. However, if the gas supply time is longer than 300 seconds, the throughput may deteriorate. If the gas supply time is shorter than 0.001 seconds, the reaction rate may not be sufficiently obtained.

  The temperature of the heater 106 is set to the same temperature as in the halogen-based source gas supply step.

At this time, the gases flowing into the processing chamber 101 are only NH ₃ gas and N ₂ gas. The NH ₃ gas undergoes a substitution reaction with at least a portion of the Ti-containing layer formed on the wafer 100 in the halogen-based source gas supply step that did not react with the HCl gas in the reaction inhibition gas supply step. By the substitution reaction, a TiN layer containing Ti and N is formed on the wafer 100. The TiN layer is mainly composed of Ti and N, but the TiN layer contains a Ti-containing layer that has not undergone a substitution reaction, and Cl and H that are other elements derived from the respective raw materials contained in the Ti-containing layer. There is.

(Residual gas removal step)
After forming the TiN layer, the valve 334 is closed and the supply of NH ₃ gas is stopped. Then, the unreacted NH ₃ gas remaining in the processing chamber 101, that is, the space where the wafer 100 on which the TiN layer is formed, is reacted by the same processing procedure as the residual gas removal step after the halogen-based source gas supply step. By-products, NH ₃ gas after contributing to the formation of the TiN layer, and the like are removed from the processing chamber 101. At this time, the point that it is not necessary to completely eliminate the gas remaining in the processing chamber 101 is the same as the residual gas removal step after the halogen-based source gas supply step.

(Performed times)
By performing one or more (predetermined number of times) cycles in which the halogen-based source gas supply step, the reaction inhibition gas supply step, the residual gas removal step, the N-containing gas supply step, and the residual gas supply step are sequentially performed in a time-sharing manner. That is, the halogen-based source gas supply step, the residual gas removal step, the reaction inhibition gas supply step, the residual gas removal step, the N-containing gas supply step, and the residual gas supply step are set as one cycle, and these processes are performed for n cycles (n Is performed on the wafer 100 to form a TiN film as a metal nitride film having a predetermined thickness (for example, 0.1 to 10 nm). The above cycle is preferably repeated multiple times. Note that the supply flow rate of the reaction inhibiting gas is preferably gradually reduced according to the number of cycles. The supply amount of the reaction inhibiting gas is preferably adjusted (changed or controlled) according to the depth of the trench formed on the surface of the wafer 100.

  When the cycle is performed a plurality of times, at least in each step after the second cycle, the portion described as “supplying gas to the wafer 100” is “to the layer formed on the wafer 100, that is, This means that a predetermined gas is supplied to the outermost surface of the wafer 100 as a laminated body, and a portion described as “form a predetermined layer on the wafer 100” is “formed on the wafer 100. It means that a predetermined layer is formed on a certain layer, that is, on the outermost surface of the wafer 100 as a laminate. This also applies to the examples described later.

(After purge step and atmospheric pressure recovery step)
The valves 514, 524 and 534 are opened, N ₂ gas is supplied into the processing chamber 101 from the gas supply pipes 510, 520 and 530, and exhausted from the exhaust pipe 231. The N ₂ gas acts as a purge gas, whereby the inside of the processing chamber 101 is purged with an inert gas, and the gas and by-products remaining in the processing chamber 101 are removed from the inside of the processing chamber 101 (after purge). Thereafter, the atmosphere in the processing chamber 101 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 101 is returned to normal pressure (return to atmospheric pressure).

  Thereafter, the support base 103 is lowered, the gate valve 151 is opened, and the processed wafer 100 is carried out of the processing container 102 by the transfer robot 173.

An example of a mechanism assumed for the first embodiment will be described with reference to FIG. When TiCl ₄ gas is supplied to a substrate having a trench on the surface and NH bonded thereto, NH and TiCl ₄ gas are combined (TiCl ₄ molecules are adsorbed by NH), and Ti and Cl are formed on the substrate. A Ti-containing layer containing is formed. When HCl gas is supplied to the substrate on which the Ti-containing layer has been formed by adjusting the process conditions, the Ti-containing layer formed on the upper portion of the trench is etched (NH and Ti bonds are broken, and instead NH is used. H is substituted), and TiCl ₄ is desorbed from the substrate. That is, the intermediate of TiCl ₄ molecules adsorbed on the adsorption site existing above the trench on the substrate surface is separated from the adsorption site and H is adsorbed instead. Next, even if NH ₃ gas is supplied to the substrate having NH—H bonds at the top of the trench, there are many places where Ti has already been desorbed, so that it is difficult to form a TiN layer at the top of the trench. On the other hand, since the NH—Ti bond remains in the lower part of the trench, the NH ₃ gas and the NH—Ti bond undergo a substitution reaction, and a TiN layer is easily formed.

(3) Effects according to this embodiment According to this embodiment, one or more of the following effects can be obtained.

(A) After supplying a halogen-based source gas to a substrate having a trench formed on the surface, a reaction-inhibiting gas that inhibits the reaction between the halogen-based source gas and the reactive gas is supplied. By reducing the deposition rate and then supplying the reaction gas, a thin film can be formed mainly under the trench, and the supply of the halogen-based source gas, the supply of the reaction inhibiting gas, and the supply of the reaction gas are repeated. As a result, a thin film having good step coverage and embedding can be formed in the trench. This is particularly effective when a thin film is formed in a trench having a high (rough) aspect ratio.
(B) In the initial stage of TiN film deposition, the supply amount of reaction inhibiting gas is increased as the first process condition, the TiN film is deposited in preference to the lower part of the trench, and then the final stage of TiN film deposition Then, as a second process condition, by forming a TiN film on the upper portion of the trench by reducing the supply amount of reaction inhibiting gas, bottom-up film formation can be performed, and film formation with reduced voids becomes possible. Free embedding characteristics can be achieved.
(C) By gradually changing the supply amount of the reaction inhibiting gas according to the number of cycles (with gradation added to the supply amount of the reaction inhibiting gas), a film is formed in the trench, and according to the depth of the trench. A supply amount of reaction inhibiting gas can be supplied to the substrate, and the reaction inhibiting gas can be reacted to a desired location in the trench. For example, by increasing the supply amount of the reaction inhibiting gas at the initial stage of film formation, film formation is performed with priority over the lower part of the trench, and the supply amount of the reaction inhibiting gas is gradually decreased as the film forming process cycle proceeds. By going, it becomes possible to gradually form a film on the upper part of the trench, and it becomes possible to achieve good embedding characteristics of Void Free.
(D) By using a gas containing Cl, which is a halogen element contained in a halogen-based source gas, as a reaction inhibiting gas, the types of impurity elements that are unintentionally incorporated into the thin film during processing are reduced. Is possible.
(E) After supplying the halogen-based source gas to the substrate having a trench formed on the surface, the substrate is adsorbed on the substrate by supplying a reaction inhibiting gas that inhibits the reaction between the halogen-based source gas and the reactive gas. The etching action acts on the source molecules of the halogen-based source gas, the amount of Cl remaining in the thin film is reduced, and the resistance value of the thin film can be lowered.
(F) By supplying the halogen-based source gas and the reaction-inhibiting gas in a time-sharing manner, it is possible to prevent reaction by-products such as NH ₄ Cl from being taken into the film and increasing the resistivity of the thin film. It becomes possible.

<Modification 1>
As shown in FIG. 5, a residual gas removal step similar to the residual gas removal step after the reaction inhibition gas supply step may be performed between the halogen-based source gas supply step and the reaction inhibition gas supply step. For convenience, this sequence is shown as the following formula (2). Also in the first modification, in addition to obtaining the same effect as the film forming sequence shown in FIG. 4, there is an effect of suppressing the incorporation of halogen atoms or the like contained in the halogen-based source gas into the film as impurities. can get.

(TiCl ₄ → P / V → HCl → P / V → NH ₃ → P / V) × n => TiN (2)

<Modification 2>
Further, the halogen source gas (TiCl ₄ ) supply step, the reaction inhibiting gas supply step, the residual gas removal step, the N-containing gas supply step, and the residual gas supply step are set as one cycle, and these processes are performed in n cycles (n is In the first few cycles, for example, m cycles (m is an integer greater than or equal to 1 and less than n), the reaction inhibition gas supply step is not performed, and the reaction inhibition gas supply step is performed after the mth cycle. You may make it perform. For convenience, this sequence is represented as the following formula (3).

(TiCl ₄ → P / V → NH ₃ → P / V) × m → (TiCl ₄ → HCl → P / V → NH ₃ → P / V) × (nm) => TiN (3)

Also in the second modification, the same effect as the film forming sequence shown in FIG. 4 can be obtained. In addition, during the initial cycle (up to the m-th cycle), even if the TiCl ₄ gas is supplied to the wafer 100, the Ti-containing layer may not be formed uniformly without unevenness. Therefore, after forming the Ti-containing layer (and the TiN layer) without supplying the reaction-inhibiting gas until the underlying film of the resulting TiN film is not exposed, the cycle including the reaction-inhibiting gas supply step is an nm cycle. By performing, it is possible to suppress the influence of the reaction inhibiting gas directly on the base film. For example, when an HCl gas containing a halogen element is used as the reaction inhibiting gas, etching of the base film can be suppressed.

<Modification 3>
Furthermore, the halogen-based source gas (TiCl ₄ ) supply step, the reaction inhibition gas (HCl) supply step, the residual gas removal step, the N-containing gas (NH ₃ ) supply step, and the residual gas supply step are processed as one cycle. When processing is performed for n cycles (n is an integer of 1 or more), the first few cycles, for example, p cycle (p is an integer of 1 or more and less than n) is a halogen-based source gas of reaction inhibition gas in the reaction inhibition gas supply step. The exposure ratio with respect to the halogen-based source gas in the reaction inhibiting gas supply step may be increased after the p-th cycle. The exposure ratio of the reaction inhibiting gas to the halogen-based source gas in the reaction inhibiting gas supply step can be controlled by adjusting the supply time or the supply amount of the reaction inhibiting gas or the halogen-based source gas. For convenience, this sequence is shown as the following formula (4).

(TiCl ₄ → HCl → P / V → NH ₃ → P / V) × p → (TiCl ₄ → HCl → P / V → NH ₃ → P / V) × (n−p) => TiN (4)

Also in the third modification, the same effect as the film forming sequence shown in FIG. 4 can be obtained. Further, during the initial cycle (up to the p-th cycle), even if the TiCl ₄ gas is supplied to the wafer 100, the Ti-containing layer may not be formed uniformly without unevenness. Therefore, after forming a Ti-containing layer (and a TiN layer) in a state where the exposure ratio of the reaction inhibiting gas to the halogen-based source gas is lowered until the underlying film of the obtained TiN film is not exposed, the reaction inhibiting gas By performing the np cycle by increasing the exposure ratio with respect to the halogen-based source gas, it is possible to suppress the influence of the reaction inhibiting gas directly on the underlying film. For example, when an HCl gas containing a halogen element is used as the reaction inhibiting gas, etching of the base film can be suppressed.

<Modification 4>
The exposure amount of the N-containing gas in the N-containing gas supply step may be increased according to the place (target region) where it is desired to form a film in the trench. In order to increase the exposure amount of the N-containing gas, it is preferable to increase the time for supplying the N-containing gas to the wafer 100 or increase the partial pressure of the N-containing gas. Also in the fourth modification, the same effect as the film forming sequence shown in FIG. 4 can be obtained. In addition, by increasing the exposure amount of the N-containing gas, even if the constituent molecules of the reaction-inhibiting gas are adsorbed on the Ti-containing layer, the constituent molecules of the reaction-inhibiting gas are caused by the reaction with the N-containing gas. This makes it possible to eliminate the constituent molecules of the reaction-inhibiting gas from remaining as impurities in the film.

<Modification 5>
The exposure amount of the halogen-based source gas in the halogen-based source gas supply step may be increased according to the target region in the trench. In order to increase the exposure amount of the halogen-based source gas, the time for supplying the halogen-based source gas to the wafer 100 is lengthened, or at least one of the partial pressure of the halogen-based source gas is increased. Good. Also in this modification 5, the same effect as the film-forming sequence shown in FIG. 4 is acquired. In addition, by increasing the exposure amount of the halogen-based source gas, it is possible to increase the film forming speed that is reduced by the supply of the reaction inhibiting gas.

<Modification 6>
In this embodiment, as shown in FIG. 6, a halogen-based source gas (TiCl ₄ ) supply step, a residual gas removal step, an N-containing gas supply step (NH ₃ ), a reaction inhibition gas (HCl) supply step, and a residual gas removal A TiN film is formed on the wafer 100 by repeating time cycles in which the step cycle is one cycle and repeating n cycles (n is an integer of 1 or more). For the sake of convenience, the sequence shown in FIG. 6 is represented as the following equation (5).

(TiCl ₄ → P / V → NH ₃ → HCl → P / V) × n => TiN (5)

Also in the sixth modification, the same effect as the film forming sequence shown in FIG. 4 can be obtained. Further, as shown in FIG. 14, HCl molecules of the HCl gas supplied in the reaction inhibiting gas supply step are adsorbed to NH 2 of Ti—NH 2 bonds formed on the wafer 100, and a halogen-based source gas ( TiCl ₄ ) TiCl ₄ molecules of the TiCl ₄ gas supplied in the supply step can be inhibited from adsorbing on the wafer 100 (adsorption sites for adsorbing TiCl ₄ molecules are reduced). Note that the reaction-inhibiting gas supply step may not be performed in the nth cycle, thereby obtaining an effect that the amount of impurities such as Cl remaining in the TiN film can be reduced.

<Modification 7>
As shown in FIG. 7, a residual gas removal step similar to the residual gas removal step after the N-containing gas supply step may be performed between the N-containing gas supply step and the reaction inhibiting gas supply step. For convenience, this sequence is shown as the following formula (6). Also in this modified example 7, in addition to obtaining the same effect as the film forming sequence shown in FIG. 4, the N-containing gas after contributing to the formation of the unreacted N-containing gas, the reaction by-product, and the TiN layer Etc. can be effectively removed.

(TiCl ₄ → P / V → NH ₃ → P / V → HCl → P / V) × n => TiN (6)

<Other Embodiments of the Present Invention>
The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the invention.

  For example, in the first embodiment, the sequences of the formulas (1) to (6) have been described. However, the present invention is not limited to this, and can be applied to the following sequences, for example. The above-described embodiments and modifications such as the following sequences can be variously combined without departing from the scope of the invention.

(TiCl ₄ → P / V → NH ₃ / HCl → P / V) × n => TiN (7)
(TiCl ₄ / HCl → P / V → NH ₃ → PV) × n => TiN (8)
(TiCl ₄ / HCl → P / V → NH ₃ / HCl → P / V) × n => TiN (9)
(TiCl ₄ → P / V → NH ₃ → P / V → P / V) × n → HCl => TiN (10)
In the above formula, NH ₃ / HCl indicates that NH ₃ and HCl are supplied simultaneously, and TiCl ₄ / HCl indicates that TiCl ₄ and HCl are supplied simultaneously.

  In the above-described embodiment, an example in which Ti is used as the metal element has been described. The present invention is not limited to the above-described embodiment, and as elements other than Ti, tantalum (Ta), tungsten (W), cobalt (Co), yttrium (Y), ruthenium (Ru), aluminum (Al), hafnium (Hf) ), Zirconium (Zr), molybdenum (Mo), niobium (Nb), manganese (Mn), nickel (Ni), silicon (Si) and other nitride films, oxide films, carbonized films, and boride films Such a film or a composite film thereof can also be suitably applied.

  When forming a film containing the above-described element, in addition to a titanium (Ti) -containing gas as a source gas, a tantalum (Ta) -containing gas, a tungsten (W) -containing gas, a cobalt (Co) -containing gas, and yttrium (Y) Containing gas, ruthenium (Ru) containing gas, aluminum (Al) containing gas, hafnium (Hf) containing gas, zirconium (Zr) containing gas, molybdenum (Mo) containing gas, niobium (Nb) containing gas, manganese (Mn) containing Gas, nickel (Ni), silicon (Si) -containing gas, or the like can be used.

When forming a film containing the above-described element, examples of the halogen-based source gas include, in addition to TiCl ₄ , titanium tetrafluoride (TiF ₄ ), tantalum pentachloride (TaCl ₅ ), and tantalum pentafluoride (TaF _5). ), Tungsten hexachloride (WCl ₆ ), tungsten hexafluoride (WF ₆ ), cobalt dichloride (CoCl ₂ ), cobalt dichloride (CoF ₂ ), yttrium trichloride (YCl ₃ ), yttrium trifluoride (YF ₃₎ ), Ruthenium trichloride (RuCl ₃ ), ruthenium trifluoride (RuF ₃ ), aluminum trichloride (AlCl ₃ ), aluminum trifluoride (AlF ₃ ), hafnium tetrachloride (HfCl ₄ ), hafnium tetrafluoride (HfF) ₄ ), zirconium tetrachloride (ZrCl ₄ ), zirconium tetrafluoride (ZrF ₄ )), molybdenum pentafluoride (MoF ₅ ), five Molybdenum chloride (MoCl ₅ ), niobium trifluoride (NbF ₃ ), niobium trichloride (NbCl ₃ ), manganese difluoride (MnF ₂ ), manganese dichloride (MnCl ₂ ), nickel difluoride (NiF ₂ ), Nickel dichloride (NiCl ₂ ), tetrachlorosilane, that is, silicon tetrachloride or silicon tetrachloride (SiCl ₄ , abbreviation: STC), dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS), monochlorosilane (SiH ₃ Cl, abbreviation: MCS) ), Hexachlorodisilane, that is, disilicon hexachloride (Si ₂ Cl ₆ , abbreviation: HCDS), or the like can also be used.

In the case of forming a film containing the above elements, examples of the reaction gas include nitrogen (N ₂ ), nitrous oxide (N ₂ O), diazene (N ₂ H ₂ ) gas, hydrazine in addition to NH _3. A gas containing an N—H bond such as (N ₂ H ₄ ) gas or N ₃ H ₈ gas can be used. In addition to the above-described gases, the gas containing an N—H bond may be an organic hydrazine-based gas such as monomethylhydrazine ((CH ₃ ) HN ₂ H ₂ , abbreviation: MMH) gas, dimethylhydrazine ((CH _{3) 2} N ₂ H _2, abbreviation: DMH) gas, trimethyl hydrazine _{((CH 3) 2 N 2} (CH 3) H, abbreviation: TMH) and methylhydrazine-based gas such as a gas, ethyl hydrazine ((C ₂ H ₅ ) Ethylhydrazine-based gas such as HN ₂ H ₂ , abbreviation: EH) gas, can be used. In addition, triethylamine ((C ₂ H ₅ ) ₃ N, abbreviation: TEA) gas, diethylamine ((C ₂ H ₅ ) ₂ NH, abbreviation: DEA) gas, monoethylamine (C ₂ H ₅ NH ₂ , abbreviation: MEA) Gas such as ethylamine gas, trimethylamine ((CH ₃ ) ₃ N, abbreviation: TMA) gas, dimethylamine ((CH ₃ ) ₂ NH, abbreviation: DMA) gas, monomethylamine (CH ₃ NH ₂ , abbreviation: MMA) Gas such as methylamine gas, tripropylamine ((C ₃ H ₇ ) ₃ N, abbreviation: TPA) gas, dipropylamine ((C ₃ H ₇ ) ₂ NH, abbreviation: DPA) gas, monopropylamine ( C ₃ H ₇ NH _2, abbreviation: MPA) propylamine-based gas such as a gas, triisopropylamine _{([(CH 3) 2 CH} ] 3 N, abbreviation: TIPA) gas, diisopropylamine ( _{(CH 3) 2 CH] 2} NH, abbreviation: DIPA) Gas, monoisopropylamine _{((CH 3) 2 CHNH 2} , abbreviation: MIPA) isopropyl amine-based gas such as a gas, tributylamine ((C ₄ H _{9) 3} N, abbreviation: TBA) gas, dibutylamine ((C ₄ H ₉ ) ₂ NH, abbreviation: DBA) gas, butylamine gas such as monobutylamine (C ₄ H ₉ NH ₂ , abbreviation: MBA) gas, or tri Isobutylamine ([(CH ₃ ) ₂ CHCH ₂ ] ₃ N, abbreviation: TIBA) gas, diisobutylamine ([(CH ₃ ) ₂ CHCH ₂ ] ₂ NH, abbreviation: DIBA) gas, monoisobutylamine ((CH ₃ ) ₂ CHCH ₂ NH ₂ (abbreviation: MIBA) gas or other isobutylamine-based gas can be used. That is, the amine-based gas, for _{example, (C 2 H 5) x} NH 3-x, (CH 3) x NH 3-x, (C 3 H 7) x NH 3-x, [(CH 3) 2 _{CH] x NH 3-x,} (C 4 H 9) x NH 3-x, by a composition formula of _{[(CH 3) 2 CHCH 2} ] x NH 3-x ( wherein, x is an integer of 1 to 3) Of the gases represented, at least one gas can be used. When an organic hydrazine-based gas or an amine-based gas is used, the reactivity can be increased and C can be taken into the film, so that the work function of the film can be adjusted by controlling the C concentration.

  In the above-described embodiment, an example in which HCl gas is used as the reaction-inhibiting gas has been described. However, the present invention is not limited to this, and other gases can be used as long as they are hydrogen halides. For example, hydrogen fluoride (HF), Hydrogen bromide (HBr), hydrogen iodide (HI), or the like may be used.

In the above-described embodiment, an example in which N ₂ gas is used as the inert gas has been described. However, the present invention is not limited to this, and argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas are used. A noble gas such as may be used.

  In the above-described embodiment, the case where film formation is performed using a single-wafer type substrate processing apparatus that processes one substrate at a time has been described. However, when film formation is performed using a processing furnace having another structure. The present invention is also applicable. For example, a substrate processing apparatus that is a batch-type vertical apparatus that processes a plurality of substrates at a time, and a nozzle for supplying a processing gas is erected in one reaction tube (single tube), and the reaction tube The present invention can also be applied to the case where a film is formed using a processing furnace having a structure in which an exhaust port is provided in the lower part of the substrate. In addition, an inner tube and an outer tube, which are two reaction tubes (double tubes), may be provided, and the processing gas may be supplied from a gas supply port that opens to the side wall of the inner tube. At this time, the exhaust port opened to the outer tube may be opened according to the height at which there are a plurality of substrates stacked and accommodated in the processing chamber. Further, the shape of the exhaust port may be a hole shape or a slit shape. Even in these cases, the processing conditions can be the same processing conditions as in the above-described embodiment, for example.

  The process recipes (programs describing processing procedures and processing conditions) used to form these various thin films are the contents of the substrate processing (film type, composition ratio, film quality, film thickness, processing procedure, processing of the thin film to be formed) It is preferable to prepare individually (multiple preparations) according to the conditions. And when starting a substrate processing, it is preferable to select a suitable process recipe suitably from several process recipes according to the content of a substrate processing. Specifically, the substrate processing apparatus includes a plurality of process recipes individually prepared according to the contents of the substrate processing via an electric communication line or a recording medium (external storage device 123) on which the process recipe is recorded. It is preferable to store (install) in the storage device 121c in advance. When starting the substrate processing, the CPU 121a included in the substrate processing apparatus appropriately selects an appropriate process recipe from a plurality of process recipes stored in the storage device 121c according to the content of the substrate processing. Is preferred. With this configuration, thin films with various film types, composition ratios, film qualities, and film thicknesses can be formed for general use with good reproducibility using a single substrate processing apparatus. In addition, it is possible to reduce the operation burden on the operator (such as an input burden on the processing procedure and processing conditions), and to quickly start the substrate processing while avoiding an operation error.

  The present invention can also be realized by changing a process recipe of an existing substrate processing apparatus, for example. When changing a process recipe, the process recipe according to the present invention is installed in an existing substrate processing apparatus via a telecommunication line or a recording medium recording the process recipe, or input / output of the existing substrate processing apparatus It is also possible to operate the apparatus and change the process recipe itself to the process recipe according to the present invention.

  Hereinafter, desirable aspects of the present invention will be additionally described.

[Appendix 1]
According to one aspect of the invention,
Supplying a halogen-based source gas to the substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate under a first process condition;
Repeating a cycle that performs time-sharing (asynchronously, intermittently, and pulsed) a predetermined number of times,
Supplying the halogen-based source gas to the substrate;
Supplying the reaction gas to the substrate;
Supplying the reaction-inhibiting gas to the substrate under a second process condition different from the first process condition;
Repeating a predetermined number of cycles in a time-sharing manner,
And a method for manufacturing a semiconductor device or a substrate processing method for forming a film in the trench.

[Appendix 2]
According to another aspect of the invention,
Supplying a halogen-based source gas to the substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate;
A cycle of performing time division (asynchronously, intermittently, and pulsed) is repeated a predetermined number of times, and the supply amount of the reaction inhibiting gas is gradually changed according to the number of cycles to form a film in the trench. A semiconductor device manufacturing method or substrate processing method is provided.

[Appendix 3]
The method according to appendix 2, preferably,
The cycle includes evacuating a processing chamber in which the substrate is accommodated,
In the cycle, a step of supplying the halogen-based source gas, a step of supplying the reaction inhibiting gas, a step of exhausting the processing chamber, a step of supplying the reactive gas, and a step of exhausting the processing chamber are sequentially performed.

[Appendix 4]
The method according to appendix 2 or appendix 3, preferably,
The reaction gas supply time and / or pressure is gradually increased according to the number of cycles.

[Appendix 5]
The method according to appendix 3, preferably,
A step of supplying the halogen-based source gas, a step of exhausting the processing chamber, a step of supplying the reaction gas, a step of supplying the reaction inhibiting gas, and a step of exhausting the processing chamber are sequentially performed.

[Appendix 6]
The method according to appendix 5, preferably,
The supply time and / or pressure of the halogen-based source gas is gradually increased according to the number of cycles.

[Appendix 7]
The method according to appendix 2, preferably,
The step of supplying the halogen-based source gas and the step of supplying the reaction inhibiting gas are performed at different timings.

[Appendix 8]
The method according to appendix 2, preferably,
The step of supplying the reaction gas is performed continuously (always) during the cycle.

[Appendix 9]
The method according to any one of appendices 2 to 8, preferably,
The reaction inhibiting gas contains the same halogen element as the halogen-based material.

[Appendix 10]
The method according to any one of appendices 2 to 9, preferably,
The halogen-based source gas contains a metal element, and the film formed in the trench is a metal-containing film and is a conductive film.

[Appendix 11]
The method according to any one of appendices 2 to 10, preferably,
The supply amount of the reaction inhibiting gas is adjusted (adjusted or tuned) according to the depth of the trench.

[Appendix 12]
The method according to any one of appendices 2 to 11, preferably
As the number of cycles increases, the supply amount of the reaction inhibiting gas is gradually decreased.

[Appendix 13]
The method according to any one of appendices 2 to 12, preferably:
The reaction gas is a nitrogen-containing gas.

[Appendix 14]
The method according to appendix 13, preferably,
The film is a metal nitride film.

[Appendix 15]
According to another aspect of the invention,
A processing chamber for accommodating the substrate;
A gas supply system for supplying a halogen-based source gas, a reaction gas, and a reaction inhibition gas to the processing chamber;
A process of controlling the gas supply system to supply the halogen-based source gas to a substrate housed in the processing chamber and having a trench formed on the surface thereof, and a process of supplying the reaction gas to the substrate And a process of supplying a reaction inhibiting gas to the substrate under the first process condition in a time-division manner (asynchronous, intermittent, pulsed), a process of repeating a predetermined number of times, On the other hand, the reaction inhibition is performed in a process for supplying the halogen-based source gas, a process for supplying the reaction gas to the substrate, and a second process condition different from the first process condition for the substrate. A control unit configured to form a film in the trench by performing a process of supplying a gas and a process of repeating a predetermined number of cycles in a time-sharing manner (asynchronously, intermittently, and pulsed) ,
A substrate processing apparatus is provided.

[Appendix 16]
According to another aspect of the invention,
A processing chamber for accommodating the substrate;
A gas supply system for supplying a halogen-based source gas, a reaction gas, and a reaction inhibition gas to the processing chamber;
Controlling the gas supply system to supply the halogen-based source gas to the substrate housed in the processing chamber and having a trench formed on the surface thereof, and supplying the reaction gas to the substrate A cycle of performing processing and supplying the reaction inhibiting gas to the substrate in a time-sharing manner (asynchronously, intermittently, pulsed) is repeated a predetermined number of times, and the supply amount of the reaction inhibiting gas is increased. A controller configured to gradually change according to the number of cycles to form a film in the trench;
A substrate processing apparatus is provided.

[Appendix 17]
According to another aspect of the invention,
A first supply system (part) for supplying a halogen-based source gas to a substrate having a trench formed on the surface;
A second supply system (part) for supplying a reactive gas to the substrate;
A third supply system (part) for supplying a reaction-inhibiting gas to the substrate;
Have
The process of supplying the halogen-based source gas to the substrate from the first supply system, the process of supplying the reaction gas to the substrate, and the substrate under the first process conditions A process of supplying a reaction inhibiting gas, a process including a process of performing time division (asynchronously, intermittently, and pulsed), a process of repeating a predetermined number of times, and the first supply system to the substrate. The reaction-inhibiting gas under a second process condition different from the first process condition for the process of supplying the halogen-based source gas, the process of supplying the reaction gas to the substrate, and the first process condition And a process of repeating a predetermined number of cycles including a process of performing time division (asynchronously, intermittently, and pulsed), and forming a film in the trench. To do Gas supply system for control is provided.

[Appendix 18]
According to another aspect of the invention,
A first supply system (part) for supplying a halogen-based source gas to a substrate having a trench formed on the surface;
A second supply system (part) for supplying a reactive gas to the substrate;
A third supply system (part) for supplying a reaction-inhibiting gas to the substrate;
Have
From the first supply system, a process of supplying the halogen-based source gas to the substrate, a process of supplying the reaction gas to the substrate, and supplying the reaction-inhibiting gas to the substrate And a process including time-division processing (asynchronous, intermittent, pulsed) is repeated a predetermined number of times, and the supply amount of the reaction-inhibiting gas is gradually changed according to the number of cycles, And a gas supply system that is controlled to perform the process of forming the film.

[Appendix 19]
According to another aspect of the invention,
A procedure for supplying a halogen-based source gas to a substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate under a first process condition;
A procedure for repeating a predetermined number of cycles in a time-sharing manner (asynchronous, intermittent, pulse-like),
Supplying the halogen-based source gas to the substrate;
Supplying the reaction gas to the substrate;
Supplying the reaction inhibiting gas to the substrate under a second process condition different from the first process condition;
A procedure for repeating a predetermined number of cycles in a time-sharing manner (asynchronous, intermittent, pulse-like),
And a program for causing a computer to execute a procedure for forming a film in the trench, or a computer-readable recording medium on which the program is recorded is provided.

[Appendix 20]
According to another aspect of the invention,
A procedure for supplying a halogen-based source gas to a substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate;
A cycle including a procedure for performing time division (asynchronous, intermittent, and pulse) is repeated a predetermined number of times, and the amount of the reaction inhibiting gas supplied is gradually changed according to the number of cycles to form a film in the trench. There is provided a program for causing a computer to execute the procedure, or a computer-readable recording medium on which the program is recorded.

  As described above, the present invention can be used for, for example, a semiconductor device manufacturing method, a substrate processing apparatus for processing a substrate such as a semiconductor wafer or a glass substrate, and the like.

DESCRIPTION OF SYMBOLS 10 ... Substrate processing apparatus 100 ... Wafer 101 ... Processing chamber

Claims (5)

Supplying a halogen-based source gas to the substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate under a first process condition;
Repeating a predetermined number of cycles in a time-sharing manner,
Supplying the halogen-based source gas to the substrate;
Supplying the reaction gas to the substrate;
Supplying the reaction-inhibiting gas to the substrate under a second process condition different from the first process condition;
Repeating a predetermined number of cycles in a time-sharing manner,
And a method of manufacturing a semiconductor device, wherein a film is formed in the trench. Supplying a halogen-based source gas to the substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate;
A method for manufacturing a semiconductor device in which a cycle in which time division is performed is repeated a predetermined number of times, and a supply amount of the reaction inhibiting gas is gradually changed according to the number of cycles to form a film in the trench. A processing chamber for accommodating the substrate;
A gas supply system for supplying a halogen-based source gas, a reaction gas, and a reaction inhibition gas to the processing chamber;
A process of controlling the gas supply system to supply the halogen-based source gas to a substrate housed in the processing chamber and having a trench formed on the surface thereof, and a process of supplying the reaction gas to the substrate And a process of supplying a reaction inhibiting gas to the substrate under the first process condition in a time-sharing manner, a process of repeating a predetermined number of times, and supplying the halogen-based source gas to the substrate Processing, supplying the reaction gas to the substrate, and supplying the reaction-inhibiting gas to the substrate under a second process condition different from the first process condition. And a controller configured to repeat a predetermined number of cycles, and to form a film in the trench;
A substrate processing apparatus. A first supply system (part) for supplying a halogen-based source gas to a substrate having a trench formed on the surface;
A second supply system (part) for supplying a reactive gas to the substrate;
A third supply system (part) for supplying a reaction-inhibiting gas to the substrate;
Have
The process of supplying the halogen-based source gas to the substrate from the first supply system, the process of supplying the reaction gas to the substrate, and the substrate under the first process conditions A process of supplying a reaction-inhibiting gas, a process including a process including time-division processing, a process of repeating a predetermined number of times, a process of supplying the halogen-based source gas to the substrate from the first supply system, A process of supplying the reaction gas to the substrate and a process of supplying the reaction-inhibiting gas to the substrate under a second process condition different from the first process condition are performed in a time-sharing manner. A gas supply system controlled to perform a process of repeating a cycle including the process a predetermined number of times and to form a film in the trench. A procedure for supplying a halogen-based source gas to a substrate having a trench formed on the surface;
Supplying a reactive gas to the substrate;
Supplying a reaction inhibiting gas to the substrate under a first process condition;
A procedure for repeating a predetermined number of cycles in a time-sharing manner,
Supplying the halogen-based source gas to the substrate;
Supplying the reaction gas to the substrate;
Supplying the reaction inhibiting gas to the substrate under a second process condition different from the first process condition;
A procedure for repeating a predetermined number of cycles in a time-sharing manner,
And a program for causing a computer to execute a procedure for forming a film in the trench.