Method of processing substrate, method of manufacturing semiconductor device, program, and substrate processing apparatus

Abstract

The present invention can improve the film quality of a film formed on a substrate. The invention comprises: (a) a process of supplying a first treatment gas containing a first element and a halogen to a substrate; (b) a process of supplying a second treatment gas having NN bonds and NH bonds to a substrate; and (c) a process of forming a first film containing a first element by performing (a) and (b) X times (X is a natural number) while the substrate is heated to a temperature of 250°C or lower.

Description

Technology Field

[0001] The present disclosure relates to a substrate processing method, a method for manufacturing a semiconductor device, a program, and a substrate processing device. Background Technology

[0002] For example, a low-resistance metal film is used as a word line of a 3D NAND-type flash memory or DRAM having a three-dimensional structure. In addition, a barrier film is formed between this metal film and an insulating film (see, for example, Patent Documents 1 and 2). Prior art literature

[0003] Japanese Patent Publication No. 2011-252221 and Japanese Patent Publication No. 2017-069407 The problem to be solved

[0004] The present disclosure provides a technology capable of improving the film quality of a film formed on a substrate. means of solving the problem

[0005] According to one aspect of the present disclosure,

[0006] A technology is provided having the following steps: (a) supplying a first treatment gas containing a first element and a halogen to a substrate; (b) supplying a second treatment gas having NN bonds and NH bonds to a substrate; and (c) performing (a) and (b) X times (X is a natural number) while the substrate is heated to a temperature of 250°C or lower to form a first film containing a first element. Effects of the invention

[0007] According to the present disclosure, the film quality of a film formed on a substrate can be improved. Brief explanation of the drawing

[0008] FIG. 1 is a cross-sectional view illustrating a schematic diagram of a substrate processing apparatus in one embodiment of the present disclosure. Figure 2 is a schematic cross-sectional view of line AA in Figure 1. FIG. 3 is a schematic diagram of a controller of a substrate processing device in one embodiment of the present disclosure, and is a diagram showing the control system of the controller as a block diagram. FIG. 4 is a drawing illustrating a substrate processing sequence in one embodiment of the present disclosure. FIG. 5 is a drawing illustrating a substrate processing sequence in one embodiment of the present disclosure. FIG. 6 is a drawing illustrating a substrate processing sequence in one embodiment of the present disclosure. Specific details for implementing the invention

[0009] The following description will be explained with reference to FIGS. 1 to 6. Furthermore, all drawings used in the following description are schematic, and the dimensional relationships of each element and the ratios of each element shown in the drawings do not necessarily correspond to reality. Also, the dimensional relationships of each element and the ratios of each element do not necessarily correspond to each other among multiple drawings.

[0010] (1) Configuration of the substrate processing device

[0011] The substrate processing device (10) is provided with a processing furnace (202) that has a heater (207) as a heating means (heating mechanism, heating system). The heater (207) is cylindrical in shape and is mounted vertically by being supported on a heater base (not shown) as a holding support plate.

[0012] Inside the heater (207), an outer tube (203) concentric with the heater (207) is arranged to form a processing vessel. The outer tube (203) is made of a heat-resistant material, such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed top and an open bottom. Below the outer tube (203), a manifold (inlet flange) (209) is arranged concentric with the outer tube (203). The manifold (209) is made of a metal, such as stainless steel (SUS), and is formed in a cylindrical shape with an open top and bottom. An O-ring (220a) serving as a sealing member is provided between the upper part of the manifold (209) and the outer tube (203). As the manifold (209) is supported on the heater base, the outer tube (203) is mounted vertically.

[0013] An inner tube (204) constituting a processing vessel is disposed on the inner side of the outer tube (203). The inner tube (204) is composed of a heat-resistant material such as, for example, quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with the top closed and the bottom open. The processing vessel is mainly composed of the outer tube (203), the inner tube (204), and the manifold (209). A processing chamber (201) is formed in the hollow portion of the processing vessel (inside the inner tube (204)).

[0014] The processing room (201) is configured to accommodate wafers (200) as substrates arranged in multiple stages in a horizontal position in a vertical direction by boats (217) described later.

[0015] In the processing chamber (201), nozzles (410, 420, 430, 440) are provided to penetrate the side wall of the manifold (209) and the inner tube (204). Gas supply pipes (310, 320, 330, 340) are each connected to the nozzles (410, 420, 430, 440). However, the processing furnace (202) of the present embodiment is not limited to the form described above.

[0016] In the gas supply pipes (310, 320, 330, 340), a mass flow controller (MFC) (312, 322, 332, 342), which is a flow controller (flow control unit), is provided in order from the upstream side. In addition, in the gas supply pipes (310, 320, 330, 340), a valve (314, 324, 334, 344), which is an opening and closing valve, is provided in each of the gas supply pipes (310, 320, 330, 340). A gas supply pipe (510, 520, 530, 540) that supplies inert gas is connected to the downstream side of the valve (314, 324, 334, 344) of the gas supply pipes (310, 320, 330, 340). In the gas supply pipes (510, 520, 530, 540), MFCs (512, 522, 532, 542), which are flow controllers (flow control units), and valves (514, 524, 534, 544), which are opening and closing valves, are respectively provided in order from the upstream side.

[0017] A nozzle (410, 420, 430, 440) is connected to the tip of each gas supply pipe (310, 320, 330, 340). The nozzle (410, 420, 430, 440) is configured as an L-shaped nozzle, and its horizontal portion is provided to penetrate the side wall of the manifold (209) and the inner tube (204). The vertical portion of the nozzle (410, 420, 430, 440) is provided inside a channel-shaped (groove-shaped) pre-chamber (201a) that is formed to protrude outward in the diameter direction of the inner tube (204) and also extend in the vertical direction, and is provided upward along the inner wall of the inner tube (204) within the pre-chamber (201a) (upward in the arrangement direction of the wafer (200)).

[0018] The nozzles (410, 420, 430, 440) are provided to extend from the lower region of the processing chamber (201) to the upper region of the processing chamber (201), and each has a plurality of gas supply holes (410a, 420a, 430a, 440a) provided at a position facing the wafer (200). By doing so, processing gas is supplied to the wafer (200) from each of the gas supply holes (410a, 420a, 430a, 440a) of the nozzles (410, 420, 430, 440). These gas supply holes (410a, 420a, 430a, 440a) are provided in plurality from the lower to the upper part of the inner tube (204), each having the same opening area and also provided with the same opening pitch. However, the gas supply holes (410a, 420a, 430a, 440a) are not limited to the shape described above. For example, the opening area may be gradually increased from the bottom to the top of the inner tube (204). By doing so, it becomes possible to make the flow rate of the gas supplied from the gas supply holes (410a, 420a, 430a, 440a) more uniform.

[0019] The gas supply holes (410a, 420a, 430a, 440a) of the nozzles (410, 420, 430, 440) are provided in multiple locations at a height from the bottom to the top of the boat (217) described later. Accordingly, the processing gas supplied into the processing chamber (201) from the gas supply holes (410a, 420a, 430a, 440a) of the nozzles (410, 420, 430, 440) is supplied to the entire area of ​​the wafer (200) accommodated from the bottom to the top of the boat (217). The nozzles (410, 420, 430, 440) may be provided to extend from the lower area to the upper area of ​​the processing chamber (201), but it is preferable that they be provided to extend to the vicinity of the ceiling of the boat (217).

[0020] From the gas supply pipe (310), a first treatment gas is supplied into the treatment chamber (201) through the MFC (312), valve (314), and nozzle (410). In this disclosure, the first treatment gas is also referred to as a gas containing a first element (gas containing a first element).

[0021] From the gas supply pipe (320), a second treatment gas is supplied into the treatment chamber (201) through the MFC (322), valve (324), and nozzle (420). In this disclosure, the second treatment gas is also referred to as the first reforming gas or the first reducing gas.

[0022] From the gas supply pipe (330), a third treatment gas is supplied into the treatment chamber (201) through the MFC (332), valve (334), and nozzle (430). In the present disclosure, the second reducing gas is used as a reaction gas to react with the raw material gas. In the present disclosure, the third treatment gas is also referred to as the second reforming gas or the second reducing gas.

[0023] From the gas supply pipe (340), a fourth treatment gas is supplied into the treatment chamber (201) through the MFC (342), valve (344), and nozzle (440). In this disclosure, the fourth treatment gas is also referred to as a gas containing a second element (a gas containing a second element).

[0024] Additionally, the fifth treatment gas may be configured to be supplied into the treatment chamber (201) from the gas supply pipe (340) through the MFC (342), valve (344), and nozzle (440). In this disclosure, the fifth treatment gas is also referred to as a gas containing a third element (gas containing a third element). Additionally, the fourth treatment gas and the fifth treatment gas may be the same gas.

[0025] From the gas supply pipes (510, 520, 530, 540), nitrogen (N2) gas, for example, as an inert gas is supplied into the processing chamber (201) through the MFC (512, 522, 532, 542), valve (514, 524, 534, 544), and nozzle (410, 420, 430, 440), respectively. Below, an example of using N2 gas as an inert gas will be described, but as an inert gas, in addition to N2 gas, noble gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas may be used.

[0026] The treatment gas supply system is mainly composed of a gas supply pipe (310, 320, 330, 340), an MFC (312, 322, 332, 342), a valve (314, 324, 334, 344), and a nozzle (410, 420, 430, 440), but the nozzle (410, 420, 430, 440) may be considered as the treatment gas supply system. The treatment gas supply system may simply be referred to as the gas supply system. When the first treatment gas is flowed from the gas supply pipe (310), the first treatment gas supply system is mainly composed of the gas supply pipe (310), an MFC (312), and a valve (314), but the nozzle (410) may be considered as included in the first treatment gas supply system. Additionally, when a second treatment gas is flowed from the gas supply pipe (320), the second treatment gas supply system is mainly formed by the gas supply pipe (320), MFC (322), and valve (324), but the nozzle (420) may also be included in the second treatment gas supply system. Additionally, when a third treatment gas is flowed from the gas supply pipe (330), the third treatment gas supply system is mainly formed by the gas supply pipe (330), MFC (332), and valve (334), but the nozzle (430) may also be included in the third treatment gas supply system. Additionally, when a fourth treatment gas is flowed from the gas supply pipe (340), the fourth treatment gas supply system is mainly formed by the gas supply pipe (340), MFC (342), and valve (344), but the nozzle (440) may also be included in the fourth treatment gas supply system. In addition, the inert gas supply system is mainly composed of gas supply pipes (510, 520, 530, 540), MFCs (512, 522, 532, 542), and valves (514, 524, 534, 544).

[0027] In the present embodiment, the method of gas supply involves conveying gas through nozzles (410, 420, 430, 440) placed in a pre-chamber (201a) within a circular, vertically elongated space defined by the inner wall of the inner tube (204) and the end of a plurality of wafers (200). Then, gas is ejected into the inner tube (204) from a plurality of gas supply holes (410a, 420a, 430a, 440a) provided at positions facing the wafers of the nozzles (410, 420, 430, 440). More specifically, through the gas supply hole (410a) of the nozzle (410), the gas supply hole (420a) of the nozzle (420), the gas supply hole (430a) of the nozzle (430), and the gas supply hole (440a) of the nozzle (440), processing gas, etc., is ejected in a direction parallel to the surface of the wafer (200).

[0028] The exhaust hole (exhaust port) (204a) is a through hole formed in a position opposite to the nozzle (410, 420, 430, 440) on the side wall of the inner tube (204), and is, for example, a through hole in the shape of a slit that is thin and long in the vertical direction. Gas supplied into the processing chamber (201) from the gas supply holes (410a, 420a, 430a, 440a) of the nozzle (410, 420, 430, 440) and flowing over the surface of the wafer (200) flows through the exhaust hole (204a) into the exhaust passage (206) which is composed of a gap formed between the inner tube (204) and the outer tube (203). Then, the gas flowing into the exhaust passage (206) flows into the exhaust pipe (231) and is discharged out of the processing chamber (202).

[0029] The exhaust hole (204a) is provided in a position facing the plurality of wafers (200), and the gas supplied from the gas supply holes (410a, 420a, 430a, 440a) to the vicinity of the wafers (200) in the processing room (201) flows in a horizontal direction and then flows into the exhaust passage (206) through the exhaust hole (204a). The exhaust hole (204a) is not limited to being configured as a slit-shaped through hole, but may be configured by a plurality of holes.

[0030] The manifold (209) is provided with an exhaust pipe (231) for exhausting the atmosphere inside the processing room (201). The exhaust pipe (231) is connected in order from the upstream side to the pressure sensor (245) as a pressure detector (pressure detection unit) for detecting the pressure inside the processing room (201), an APC (Auto Pressure Controller) valve (243), and a vacuum pump (246) as a vacuum exhaust device. The APC valve (243) can perform vacuum exhaust and vacuum exhaust stoppage inside the processing room (201) by opening and closing the valve while the vacuum pump (246) is operating, and can also adjust the pressure inside the processing room (201) by adjusting the degree of valve opening while the vacuum pump (246) is operating. The exhaust system is mainly composed of an exhaust hole (204a), an exhaust passage (206), an exhaust pipe (231), an APC valve (243), and a pressure sensor (245). The vacuum pump (246) can be considered to be included in the exhaust system.

[0031] Below the manifold (209), a seal cap (219) is provided as a cover capable of hermetically sealing the lower opening of the manifold (209). The seal cap (219) is configured to be in contact with the lower end of the manifold (209) from the vertical lower side. The seal cap (219) is made of a metal such as SUS, for example, and is formed in a disc shape. On the upper surface of the seal cap (219), an O-ring (220b) is provided as a sealing member that contacts the lower end of the manifold (209). On the side opposite the processing chamber (201) at the seal cap (219), a rotating mechanism (267) is installed to rotate a boat (217) that accommodates a wafer (200). The rotation axis (255) of the rotating mechanism (267) passes through the seal cap (219) and is connected to the boat (217). The rotating mechanism (267) is configured to rotate the wafer (200) by rotating the boat (217). The seal cap (219) is configured to be raised vertically by a boat elevator (115) which is a lifting mechanism installed vertically on the outside of the outer tube (203). The boat elevator (115) is configured to enable the boat (217) to be brought in and out of the processing room (201) by raising and lowering the seal cap (219). The boat elevator (115) is configured as a conveying device (conveying system) that conveys the boat (217) and the wafer (200) contained in the boat (217) to and from the processing room (201).

[0032] The boat (217) serving as a substrate support is configured to allow multiple wafers (200), for example 25 to 200 wafers, to be arranged in a horizontal position and spaced apart in the vertical direction while centered relative to each other. The boat (217) is composed of a heat-resistant material, for example, quartz or SiC. At the bottom of the boat (217), an insulating plate (218), composed of a heat-resistant material, for example, quartz or SiC, is supported in a horizontal position in multiple stages (not shown). With this configuration, heat from the heater (207) is made difficult to transfer to the seal cap (219). However, this embodiment is not limited to the form described above. For example, an insulating tube composed of a tube-shaped member made of a heat-resistant material, such as quartz or SiC, may be provided without providing an insulating plate (218) at the bottom of the boat (217).

[0033] As shown in FIG. 2, a temperature sensor (263) as a temperature detector is installed inside the inner tube (204), and the amount of current supplied to the heater (207) is adjusted based on the temperature information detected by the temperature sensor (263), thereby configuring the temperature inside the processing room (201) to have a desired temperature distribution. The temperature sensor (263) is configured in an L-shape, similar to the nozzles (410, 420, 430, 440), and is provided along the inner wall of the inner tube (204).

[0034] As illustrated in FIG. 3, the controller (121), which is a control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) (121a), RAM (Random Access Memory) (121b), a memory device (121c), and an I / O port (121d). The RAM (121b), the memory device (121c), and the I / O port (121d) are configured to exchange data with the CPU (121a) through an internal bus. An input / output device (122), configured as, for example, a touch panel, is connected to the controller (121).

[0035] The memory device (121c) is composed of, for example, flash memory, HDD (Hard Disk Drive), etc. Within the memory device (121c), a control program that controls the operation of the substrate processing device, and a process recipe containing the steps or conditions of the semiconductor device manufacturing method described later are stored in a readable manner. The process recipe is a combination that allows each process (each step) of the semiconductor device manufacturing method described later to be executed by the controller (121) to obtain a predetermined result, and functions as a program. Hereinafter, this process recipe, control program, etc. are collectively referred to simply as a program. In this specification, when the term "program" is used, it may include only the process recipe, only the control program, or a combination of the process recipe and the control program. The RAM (121b) is configured as a memory area (work area) in which programs or data read by the CPU (121a) are temporarily stored.

[0036] The I / O port (121d) is connected to the above-described MFC (312, 322, 332, 342, 512, 522, 532, 542), valve (314, 324, 334, 344, 514, 524, 534, 544), pressure sensor (245), APC valve (243), vacuum pump (246), heater (207), temperature sensor (263), rotating mechanism (267), boat elevator (115), etc.

[0037] The CPU (121a) is configured to read and execute a control program from a memory device (121c), and also to read a recipe, etc. from the memory device (121c) in accordance with the input of an operation command from an input / output device (122). The CPU (121a) performs the following operations to follow the contents of the read recipe: flow rate adjustment of various gases by the MFC (312, 322, 332, 342, 512, 522, 532, 542), opening and closing operation of the valve (314, 324, 334, 344, 514, 524, 534, 544), opening and closing operation of the APC valve (243) and pressure adjustment operation based on the pressure sensor (245) by the APC valve (243), temperature adjustment operation of the heater (207) based on the temperature sensor (263), starting and stopping of the vacuum pump (246), rotation and rotation speed adjustment operation of the boat (217) by the rotating mechanism (267), lifting operation of the boat (217) by the boat elevator (115), receiving operation of the wafer (200) into the boat (217), etc. It is configured to be controllable.

[0038] The controller (121) can be configured by installing the above-described program stored in an external storage device (e.g., magnetic tape, magnetic disk such as a flexible disk or hard disk, optical disk such as a CD or DVD, magneto-optical disk such as an MO, semiconductor memory such as a USB memory or memory card) (123) on a computer. The storage device (121c) and the external storage device (123) are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. In this specification, the recording media may include only the storage device (121c), only the external storage device (123), or both. Providing the program to the computer may be done by using communication means such as the internet or a dedicated line, without using the external storage device (123).

[0039] (2) Substrate processing process (substrate processing method)

[0040] As a process of manufacturing a semiconductor device, an example of a process of forming a first element-containing film containing a first element on a wafer (200) is described using FIG. 4. This process is carried out using the processing furnace (202) of the substrate processing device (10) described above. In the following description, the operation of each part constituting the substrate processing device (10) is controlled by a controller (121).

[0041] In the substrate processing process (semiconductor device manufacturing process) according to the present embodiment,

[0042] (a) a process of supplying a first treatment gas containing a first element and a halogen to a wafer (200), and

[0043] (b) a process of supplying a second treatment gas having NN bonds and NH bonds to a wafer (200), and

[0044] (c) A process of forming a first film containing the first element by performing (a) and (b) a predetermined number of times while the wafer (200) is heated to a temperature of 250°C or lower.

[0045] has

[0046] In this specification, the term "wafer" may refer to "the wafer itself" or "a laminate of a wafer and a predetermined layer or film formed on its surface." In this specification, the term "surface of the wafer" may refer to "the surface of the wafer itself" or "the surface of a predetermined layer or film formed on the wafer." In this specification, the term "substrate" is also synonymous with the use of the term "wafer."

[0047] (Wafer import)

[0048] When multiple wafers (200) are loaded (wafer charged) into the boat (217), as shown in FIG. 1, the boat (217) supporting the multiple wafers (200) is lifted by the boat elevator (115) and brought into the processing chamber (201) of the processing container (boat loaded) and accommodated in the processing container. In this state, the seal cap (219) closes the lower opening of the outer tube (203) through the O-ring (220).

[0049] (Pressure adjustment and temperature adjustment)

[0050] The space within the processing room (201), that is, the space where the wafer (200) exists, is vacuumed by a vacuum pump (246) so that the pressure (vacuum level) is reached. At this time, the pressure within the processing room (201) is measured by a pressure sensor (245), and based on this measured pressure information, the APC valve (243) is feedback controlled (pressure adjustment). The vacuum pump (246) is kept in a constantly operating state for at least until the processing of the wafer (200) is completed. Additionally, the processing room (201) is heated by a heater (207) so that the temperature within the processing room (201) is reached. At this time, the amount of current supplied to the heater (207) is feedback controlled (temperature adjustment) based on temperature information detected by a temperature sensor (263) so that the temperature distribution within the processing room (201) is reached. The heating of the processing room (201) by the heater (207) is continued for at least until the processing of the wafer (200) is completed.

[0051] (1st treatment gas supply, Step A)

[0052] The valve (314) is opened to flow the first treatment gas into the gas supply pipe (310). The first treatment gas, whose flow rate is adjusted by the MFC (312), is supplied into the treatment chamber (201) from the gas supply hole (410a) of the nozzle (410) and exhausted from the exhaust pipe (231).

[0053] At this time, the APC valve (243) is adjusted to set the pressure inside the processing chamber (201) to a pressure within, for example, a range of 1 to 3990 Pa. The supply flow rate of the first processing gas controlled by the MFC (312) is set to a flow rate within, for example, a range of 0.01 to 3 slm. Hereinafter, the temperature of the heater (207) is set to a temperature such that the temperature of the wafer (200) is, for example, within a range of 100 to 400°C. Preferably, the temperature of the wafer (200) is set to 250°C or lower. More preferably, the temperature is set to 180°C or higher and 220°C or lower. This temperature is maintained at least during the formation of the first film. Furthermore, the notation of a numerical range such as "1 to 3990 Pa" in this disclosure means that the lower limit value and the upper limit value are included within that range. Therefore, for example, “1 to 3990 Pa” means “1 Pa or more and 3990 Pa or less.” The same applies to other numerical ranges.

[0054] At this time, a first treatment gas is supplied to the wafer (200). As the first treatment gas, titanium tetrachloride (TiCl4) gas, which is a gas containing a first element and a halogen element, for example, a gas containing titanium (Ti) and chlorine (Cl), may be used. When TiCl4 gas is used as the gas containing the first element, by supplying TiCl4 gas, TiCl4 is formed on the wafer (200) (the underlayer on the surface). x (X is an integer less than or equal to 4) is adsorbed, and a Ti-containing layer is formed.

[0055] (Fuzzy, Step A)

[0056] After the supply of the first treatment gas is started, the valve (314) is closed after a predetermined time has elapsed, for example, 0.1 to 10 seconds, to stop the supply of the first treatment gas. At this time, the APC valve (243) of the exhaust pipe (231) is left open, and the inside of the treatment chamber (201) is vacuum-exhausted by the vacuum pump (246) to remove residual gas from the wafer (200) and to exclude unreacted first treatment gas or reaction by-products remaining in the treatment chamber (201) from the treatment chamber (201). At this time, the valves (514, 524, 534, 542) are opened to supply an inert gas as a purge gas into the treatment chamber (201). The inert gas acts as a purge gas to remove residual gas from the wafer (200), thereby enhancing the effect of excluding unreacted first treatment gas or reaction by-products remaining in the treatment chamber (201) from the treatment chamber (201). The supply flow rate of the inert gas controlled by the MFC (512, 522, 532, 542) is, for example, 0.1 to 30 slm.

[0057] (2nd treatment gas supply, Step C)

[0058] After a predetermined amount of time has elapsed since the start of purging, for example, after 0.1 to 10 seconds, the valves (514, 524, 534, 544) are closed to stop the supply of inert gas into the processing chamber (201). At this time, the valve (324) is opened to flow a second processing gas into the gas supply pipe (320). The second processing gas is flow-regulated by the MFC (322), supplied into the processing chamber (201) from the gas supply hole (420a) of the nozzle (420), and exhausted from the exhaust pipe (231). At this time, the second processing gas is supplied to the wafer (200). Also, at this time, the valve (524) may be opened to flow an inert gas into the gas supply pipe (520). In addition, to prevent the intrusion of reaction gas into the nozzle (410, 430, 440), the valve (514, 534, 544) may be opened to allow inert gas to flow into the gas supply pipe (510, 530, 540).

[0059] At this time, the APC valve (243) is adjusted to set the pressure inside the processing chamber (201) to a pressure within the range of, for example, 1 to 3990 Pa. The supply flow rate of the reaction gas controlled by the MFC (322) is set to a flow rate within the range of, for example, 0.1 to 30 slm. The time for supplying the reaction gas to the wafer (200) is set to a time within the range of, for example, 0.01 to 30 seconds.

[0060] At this time, a second treatment gas is supplied to the wafer. Here, as the second treatment gas, a gas having, for example, NN bonds and NH bonds can be used. An example of such a gas is hydrazine (N2H4) gas. The N2H4 gas used as the second treatment gas has NN bonds and NH bonds. Among these bonds, the NN bond is more easily dissociated compared to the NH bond, so NH from N2H4 x is generated. Here, x is 1, 2. This NH xIt undergoes a substitution reaction with at least a portion of the Ti-containing layer formed on the wafer (200). During the substitution reaction, the Ti contained in the Ti-containing layer combines with the N contained in the N2H4 gas to form a TiN layer on the wafer (200). Specifically, TiCl adsorbed on the wafer (200) x and N2H4 or NH x By reacting, a TiN film is formed on a wafer (200) on which an oxide film is formed on the surface, thereby improving the coverage rate of the TiN film. Additionally, during the substitution reaction, reaction by-products such as HCl, ammonium chloride (NH4Cl), and H2 are generated.

[0061] (Fuzzy, Step D)

[0062] After the supply of the second treatment gas is started, the valve (324) is closed after a predetermined time has elapsed, for example, 0.01 to 60 seconds, to stop the supply of the second treatment gas. At this time, the APC valve (243) of the exhaust pipe (231) is left open, and the inside of the treatment chamber (201) is vacuum-exhausted by the vacuum pump (246) to remove residual gas from the wafer (200) and to exclude unreacted or second treatment gas or reaction by-products that contributed to the formation of the film remaining in the treatment chamber (201) from the treatment chamber (201). At this time, the valves (514, 524, 534, 544) are opened to supply an inert gas as a purge gas into the treatment chamber (201). The inert gas acts as a purge gas to remove residual gas from the wafer (200), thereby enhancing the effect of excluding unreacted second processing gas or the above-described reaction by-products remaining in the processing chamber (201) from the processing chamber (201). The supply flow rate of the inert gas controlled by the MFC (512, 522, 532, 542) is, for example, 0.1 to 30 slm.

[0063] That is, unreacted gas remaining in the treatment chamber (201) or the second treatment gas after contributing to the formation of the film, or the above-described reaction by-products, are excluded from the treatment chamber (201). The inert gas acts as a purge gas.

[0064] (Perform X number of times)

[0065] By performing the cycle of performing steps A through D described above in order at least once (X times), a first film of a predetermined thickness is formed on a wafer (200). Here, the first film is a film containing Ti as a first element, and specifically, a TiN film is formed.

[0066] (After purge and return to atmospheric pressure)

[0067] Inert gas is supplied into the treatment chamber (201) from each of the gas supply pipes (510 to 530) and exhausted through the exhaust pipe (231). The inert gas acts as a purge gas, thereby purging the treatment chamber (201) with inert gas, and removing any remaining gas or reaction by-products from the treatment chamber (201) (after purge). Afterward, the atmosphere inside the treatment chamber (201) is replaced with inert gas (inert gas replacement), and the pressure inside the treatment chamber (201) is returned to normal pressure (atmospheric pressure return).

[0068] (Wafer Export)

[0069] After that, the seal cap (219) is lowered by the boat elevator (115), and the bottom of the outer tube (203) is opened. Then, the processed wafer (200) is unloaded from the bottom of the outer tube (203) to the outside of the outer tube (203) while being supported by the boat (217). After that, the processed wafer (200) is discharged from the boat (217).

[0070] (3) Effects of this embodiment

[0071] According to the present embodiment, one or more of the effects shown below can be obtained.

[0072] (a) By using a gas having NN bonds and NH bonds as the second treatment gas, the reduction (nitridation) of the layer formed on the wafer (200) can be promoted. In a gas having NN bonds and NH bonds, the NN bonds are easily dissociated, and as the NN bonds dissociate, NH-ligands are generated. Due to the NH-ligands, TiCl4 adsorbed on the wafer (200) is generated, for example, when a gas containing a halogen, specifically TiCl4, is used as the first treatment gas. x It can remove nitrogen (N) while removing Cl. TiCl x As Cl is removed, TiCl x It can suppress the inhibition of adsorption caused by steric hindrance.

[0073] (b) By using a gas having NN bonds and NH bonds as the second treatment gas, it becomes possible to reduce (nitride) the layer formed on the wafer (200) even at low temperatures, such as 100°C to 400°C. In particular, even at low temperatures such as 250°C or lower, it becomes possible to suppress the reduction of the formation rate of the first film formed on the wafer (200) compared to the formation rate when the first film is formed at the same temperature using a gas that does not have NN bonds and NH bonds. Additionally, by keeping the temperature at 250°C or lower, the amount of the second treatment gas that decomposes before being supplied to the wafer (200) can be reduced. If the second treatment gas decomposes before being supplied to the wafer (200), the NH generated by the decomposition of the second treatment gas x a. is exhausted without being supplied to the wafer (200), and thus the amount of reduction (nitridation) of the layer containing the first element formed on the wafer (200) is reduced. In addition, NH generated by the decomposition of the second treatment gas xThere is also a possibility that reactions such as decomposition may occur, resulting in the formation of N2 or H2 with low reactivity. By keeping the temperature at 250°C or lower, the amount of decomposition of the second treatment gas before it is supplied to the wafer (200) can be reduced.

[0074] (c) By making the temperature of the wafer (200) at 180°C or higher when forming the first film, the generation of by-products such as NH4Cl can be suppressed. The amount of NH4Cl generated increases at temperatures below 180°C. As by-products such as NH4Cl are generated, they hinder the adsorption of molecules of the first treatment gas onto the wafer (200). Consequently, the formation rate of the first film is reduced. Additionally, the problem arises that NH4Cl is introduced into the first film, causing the characteristics of the first film to deteriorate.

[0075] (d) By keeping the temperature of the wafer (200) at 220°C or lower when forming the first film, the decomposition of the second treatment gas having NN bonds and NH bonds before reaching the wafer (200) can be suppressed. In other words, if the temperature of the wafer (200) is higher than 220°C, the second treatment gas decomposes before reaching the wafer (200), and NH x The amount supplied to the wafer (200) decreases. As a result, the formation speed of the first film decreases.

[0076] (e) By using a second treatment gas having NN bonds and NH bonds, the rate of formation of the first film can be suppressed even if the surface of the wafer (200) is an oxide film. If such a second treatment gas is not used, when the surface of the wafer (200) is an oxide film, the amount of adsorption of the first treatment gas is not obtained in a predetermined amount, and the rate of formation of the first film is reduced. When the surface of the wafer (200) is an oxide film and the first treatment gas contains a halogen element, there are cases where molecules of the first treatment gas are not adsorbed on the surface of the oxide film. As a result, the amount of molecules of the first treatment gas adsorbed on the oxide film when the predetermined number of times X=1 is reduced, and the second treatment gas when the predetermined number of times X=1 is supplied to the oxide film. At this time, the surface of the oxide film is terminated by NH- groups by the second treatment gas. When the predetermined number of times X≥2 is an oxide film in this state, the first treatment gas is supplied to the termination of the NH- groups. Since the NH-group termination and the halogen have a tendency to combine easily, the amount of molecules of the first treatment gas adsorbed on the oxide film at a predetermined number of times X≥2 can be increased. In other words, the formation rate of the first film can be increased.

[0077] (f) Decomposition product of the second treatment gas (NH x By supplying ) to the wafer (200) (especially the oxide film), the amount of NH-group terminations formed on the surface of the wafer (200) can be increased.

[0078] (4) Other embodiments

[0079] The embodiments of the present disclosure have been described in detail above. However, the present disclosure is not limited to the embodiments described above, but can be modified in various ways without departing from the gist thereof.

[0080] (Variation Example 1)

[0081] FIG. 5 shows a variation 1 of a substrate processing sequence in one embodiment of the present disclosure. Variation 1 is a substrate processing sequence in which steps E to H are performed Y times after a process in which steps A to D are performed X times. Here, steps A to D are the same as described above. Steps E, F, and H are omitted from description as they are the same as steps A, B, and D described above. Step G will be described.

[0082] (Supply of 3rd treatment gas, Step G)

[0083] In Step G, after a predetermined time has elapsed since the start of the purging in Step F, for example, after 0.1 to 10 seconds, the valves (514, 524, 534, 544) are closed to stop the supply of inert gas into the processing chamber (201). At this time, the valve (334) is opened to flow a third processing gas into the gas supply pipe (330). The flow rate of the third processing gas is controlled by the MFC (332), supplied into the processing chamber (201) from the gas supply hole (430a) of the nozzle (430), and exhausted from the exhaust pipe (231). At this time, the third processing gas is supplied to the wafer (200). Also, at this time, the valve (534) may be opened to flow an inert gas into the gas supply pipe (520). In addition, to prevent the intrusion of the third treatment gas into the nozzle (410, 420, 440), the valve (514, 524, 544) may be opened to allow inert gas to flow into the gas supply pipe (510, 520, 540).

[0084] At this time, the APC valve (243) is adjusted to set the pressure inside the processing chamber (201) to a pressure within the range of, for example, 1 to 3990 Pa. The supply flow rate of the third processing gas controlled by the MFC (322) is set to a flow rate within the range of, for example, 0.1 to 30 slm. The time for supplying the reaction gas to the wafer (200) is set to a time within the range of, for example, 0.01 to 30 seconds.

[0085] At this time, a third treatment gas is supplied to the wafer (200). Here, as the third treatment gas, for example, a gas having an NH bond may be used. Examples of such gases include NH3, diazene (N2H2), triazene (N3H3), hydrazine (N2H4), and other gases containing amine groups, at least one of which is included. Additionally, the third treatment gas may be the same as the second treatment gas, but it is preferable to use a different type of gas for the third treatment gas than for the second treatment gas. If N2H4 gas is used as the second treatment gas, NH3 gas is used as the third treatment gas. Although significant effects as described above can be obtained by using N2H4 gas, the problem arises that the cost of forming the film increases when N2H4 gas is used because the gas is expensive. Here, it is preferable to use a relatively inexpensive NH3 gas as the third treatment gas.

[0086] (Fuzzy, Step H)

[0087] After the supply of the third treatment gas is started, the valve (334) is closed after a predetermined time has elapsed, for example, 0.01 to 60 seconds, to stop the supply of the third treatment gas. After the third treatment gas is stopped, a purge similar to that of Step D described above is performed.

[0088] (Perform a predetermined number of times Y)

[0089] By performing the cycle of carrying out steps E to H described above in order at least once (Y times), a second film of a predetermined thickness is formed on the first film. Here, the second film is a film containing Ti as the first element, and specifically, a TiN film is formed.

[0090] According to Variation Example 1, in addition to the effects described above, at least one of the following effects can be obtained.

[0091] (g) A film containing the first element can be formed while reducing the amount of the second treatment gas used.

[0092] (h) When the first film is formed, the second film is formed using the third treatment gas, so that the first treatment gas used when forming the second film is supplied to the first film, and thus the amount of the first treatment gas adsorbed on the first film can be increased. That is, when forming the second film, the influence of the surface condition of the wafer (200) (e.g., the presence or absence of an oxide film) can be suppressed, and thus the decrease in the formation speed of the second film can be suppressed.

[0093] (Variation Example 2)

[0094] FIG. 6 shows a variation 2 of a substrate processing sequence in one embodiment of the present disclosure. Variation 2 is a substrate processing sequence in which a fourth processing gas is supplied in parallel with Step A (Step E). Furthermore, as indicated by the dashed line in FIG. 6, the supply of the fourth processing gas is not essential and is performed in parallel with at least any one of Step A, Step B, Step E, and Step F. Hereinafter, as an example, the case in which the fourth processing gas is supplied in Step A and Step B will be described. The details regarding the supply of the fourth processing gas in Step E and Step F are omitted because they are the same as those in Step A and Step B.

[0095] (At Step A of the 4th treatment gas supply)

[0096] After the supply of the first treatment gas has begun and a predetermined amount of time has elapsed, the valve (344) is opened to flow the fourth treatment gas into the gas supply pipe (340). The fourth treatment gas, whose flow rate is adjusted by the MFC (342), is supplied into the treatment chamber (201) from the gas supply hole (440a) of the nozzle (440) and exhausted from the exhaust pipe (231).

[0097] At this time, the APC valve (243) is adjusted to set the pressure inside the processing chamber (201) to a pressure within the range of, for example, 1 to 3990 Pa. The supply flow rate of the fourth processing gas controlled by the MFC (342) is set to a flow rate within the range of, for example, 0.1 to 5 slm. The time for supplying the first processing gas and the fourth processing gas to the wafer (200) simultaneously is set to a time within the range of, for example, 0.01 to 70 seconds.

[0098] At this time, the first processing gas and the fourth processing gas are supplied to the wafer (200). That is, at least the first processing gas and the fourth processing gas have a timing in which they are supplied simultaneously. The fourth processing gas is a gas containing a second element different from the first element. Here, the second element is, for example, at least one of silicon (Si), boron (B), phosphorus (P), etc. The gas containing the second element is, for example, a gas containing this second element and hydrogen. Specifically, silane-based gases such as silane (SiH4), disilane (Si2H6), and trisilane (Si3H8), boran-based gases such as monoborane (BH3) and diborane (B2H6), and phosphane-based gases such as phosphine (PH3) gas may be used. As for the gas containing the second element, it is preferable to use a gas that is difficult to introduce into the first film (second film). For example, SiH4 gas is a gas that is difficult to introduce into the first film (second film).

[0099] By supplying the fourth treatment gas in this way, reaction by-products and adsorption inhibiting gases that hinder film formation, such as hydrogen chloride (HCl), are removed. Then, the adsorption sites where reaction by-products such as HCl were adsorbed are emptied, and TiCl is formed on the surface of the wafer (200). x Adsorption sites capable of adsorbing a first element such as can be formed. By increasing the number of adsorption sites, it becomes possible to improve the formation rate of the first film (second film).

[0100] (At Step B of the 4th treatment gas supply)

[0101] After the supply of the first treatment gas is started and a predetermined time has elapsed, the valve (314) is closed to stop the supply of the first treatment gas. In other words, after the supply of the fourth treatment gas is started and a predetermined time has elapsed, the fourth treatment gas is being supplied, and the supply of the first treatment gas is stopped during the supply of the fourth treatment gas. The fourth treatment gas is flow-regulated by the MFC (342), supplied into the treatment chamber (201) from the gas supply hole (440a) of the nozzle (440), and exhausted through the exhaust pipe (231). At the same time, the valve (544) is opened to flow an inert gas into the gas supply pipe (540). In addition, to prevent the fourth treatment gas from entering the nozzle (410, 420, 430), the valve (514, 524, 534) may be opened to allow inert gas to flow into the gas supply pipe (510, 520, 530).

[0102] At this time, the APC valve (243) is adjusted to set the pressure inside the processing chamber (201) to, for example, a pressure within the range of 1 to 3990 Pa. The time for supplying only the fourth processing gas to the wafer (200) is, for example, a time within the range of 0.01 to 60 seconds.

[0103] At this time, only the fourth treatment gas and the inert gas are supplied to the wafer (200). By supplying the fourth treatment gas, reaction by-products and adsorption inhibiting gases, such as hydrogen chloride (HCl), are removed, and the adsorption sites where HCl was adsorbed are emptied, so that TiCl on the surface of the wafer (200) x It can form adsorption sites capable of adsorption.

[0104] Here, the time from the end of the first treatment gas supply to the end of the fourth treatment gas supply is made longer than the time from the start of the fourth treatment gas supply to the end of the first treatment gas supply. By doing so, on the surface of the wafer (200), TiCl x It can form many adsorption sites capable of adsorption.

[0105] (Variation Example 3)

[0106] In the above description, the formation of a first film (second film) containing a first element was described, but the present disclosure is not limited thereto. For example, heat treatment may be performed after the formation of the first film (second film). Here, the heat treatment is performed at a temperature higher than the temperature at which the first film (second film) is formed, for example, by raising the temperature to 450°C to 550°C and performing heat treatment for a predetermined time. By performing heat treatment at such a temperature, the amount of impurities contained in the first film (second film) can be reduced. Here, impurities are by-products as described above, such as Cl, HCl, NH4Cl, etc. Additionally, by supplying a second treatment gas or a third treatment gas to the wafer (200) during heat treatment, it is possible to supply elements contained in the third treatment gas into the first film (second film) while removing impurities in the first film (second film). Here, if the second treatment gas or the third treatment gas is the gas described above, nitrogen (N) can be supplied to the first film (second film). As the gas used here, at least one of the second treatment gas and the third treatment gas is used. By using the second treatment gas, the nitriding efficiency of the first film (second film) can be improved, and by using the third treatment gas, the cost of film formation can be reduced.

[0107] In addition, while increasing the temperature to the temperature of this heat treatment, at least one of the second treatment gas and the third treatment gas may be supplied. By supplying at least one of the second treatment gas and the third treatment gas while increasing the temperature, nitrogen can be bonded to the empty sites from which impurities have been detached from the first film (second film) while increasing the temperature, thereby improving the coverage rate of the first film (second film).

[0108] (Variation Example 4)

[0109] The first film (second film) described above has the characteristic of being prone to oxidation by reacting with oxygen in the atmosphere even at room temperature. When the first film (second film) oxidizes, there is a problem in that the characteristics of the film deteriorate. For example, if the first film (second film) is a conductive film, the conductivity changes due to oxidation, which affects the characteristics of the semiconductor device. To solve this problem, it is desirable to form a third film on the first film (second film). Here, the third film is a film containing, for example, an element different from the first element. For example, it is a film containing a second element. The second element here is, for example, an element of Group 13 or Group 14 of the periodic table. Specifically, silicon (Si) and aluminum (Al) are examples. The formation of a film containing such an element can be carried out by supplying a gas containing the aforementioned silicon and hydrogen at, for example, 450°C to 550°C. Specifically, this is done by opening the valve (344) while the wafer (200) is at a temperature of 450°C to 550°C and flowing the fourth treatment gas into the gas supply pipe (340).

[0110] At this time, the APC valve (243) is adjusted to set the pressure inside the processing chamber (201) to a pressure within the range of, for example, 1 to 3990 Pa. The supply flow rate of the fourth processing gas controlled by the MFC (342) is set to a flow rate within the range of, for example, 0.1 to 5 slm. The time for supplying the fourth processing gas to the wafer (200) is set to a time within the range of, for example, 0.01 to 70 seconds.

[0111] Under these conditions, by supplying, for example, SiH4 gas as the fourth processing gas, a decomposition reaction of SiH4 occurs on the wafer (200), thereby forming a film containing Si on the first film (second film). By forming a film containing Si on the first film (second film) in this way, oxidation of the first film (second film) can be suppressed even if it is exposed to the atmosphere. Furthermore, if the first film (second film) is a TiN film as described above, the fluorine (F) in the tungsten fluoride (WF6) gas supplied during the formation of the tungsten film formed after the TiN film in the semiconductor device manufacturing process can be suppressed from diffusing into the first film (second film). That is, barrier properties can be improved. In addition, if the third film is formed as a Si film, it is possible to sublimate the Si film with the WF6 gas during the formation of the tungsten film, thereby reducing the possibility of affecting the characteristics of the semiconductor device.

[0112] In addition, by performing the third film formation at a temperature similar to the heat treatment temperature described above, the temperature adjustment time from heat treatment to the formation of the third film can be shortened, so even if a series of substrate processing steps of formation of the first film (second film) → heat treatment → formation of the third film is performed, the film formation time can be suppressed from increasing significantly.

[0113] In addition, although a fourth treatment gas was used here as the gas forming the third film, if the second element is a third element different from the element contained in the fourth treatment gas, a fifth treatment gas containing the third element may be used. Also, the fourth treatment gas may equal the fifth treatment gas.

[0114] (Variation Example 5)

[0115] Before forming the first film described above, a second treatment gas may be supplied. As described above, in a gas containing NN bonds and NH bonds, the NN bonds are prone to dissociation, and NH xIt is easy to generate. Utilizing this characteristic, by supplying a second treatment gas before forming the first film, NH x By supplying it to the wafer (200), NH-group terminals can be formed on the surface of the wafer (200). Since the first treatment gas is supplied to the NH-group terminals, the molecules of the first treatment gas (e.g., TiCl x The amount of adsorption onto the wafer (200) can be increased. That is, it becomes possible to improve the formation speed of the first film. In addition, the amount of adsorption of molecules of the first treatment gas within the surface of the wafer (200) can be increased, thereby improving the flatness of the first film or the continuity of the film. Furthermore, the amount of Cl detached from TiCl4 can be reduced by the reaction between the NH-group termination and TiCl4. That is, TiCl x By reducing the number of x of, TiCl x The size of the three-dimensional obstruction can be reduced.

[0116] (Variation Example 6)

[0117] In Step C, which forms the first film described above, an example was shown in which only the second treatment gas is supplied, but this is not limited thereto, and the third treatment gas may also be supplied in Step C. Here, in Step C, the second treatment gas and the third treatment gas may be supplied simultaneously, supplied separately in sequence, or supplied with their supply timings partially overlapping. By using both the second treatment gas and the third treatment gas in Step C, it becomes possible to reduce the supply amount of the second treatment gas while maintaining the nitriding amount.

[0118] In addition, in the above embodiment, the case in which TiCl4 gas containing Ti and Cl is used as the first treatment gas has been described, but the present disclosure is not limited thereto. As the first element-containing gas, a gas containing a first element and a halogen may be used. Here, the first element may be, for example, at least one element such as zirconium (Zr), hafnium (Hf), molybdenum (Mo), ruthenium (Ru), aluminum (Al), gallium (Ga), Si, and germanium (Ge). The halogen may be, for example, at least one of chlorine (Cl), fluorine (F), and bromine (Br). Furthermore, a gas containing a first element in which the halogen is chlorine is referred to as a gas containing a first element and chlorine. It can be suitably applied even when such a gas is used.

[0119] In addition, in the above modified example 2, an example (Fig. 6) in which the supply of the fourth treatment gas is continued after the supply of the first treatment gas was described, but the present disclosure is not limited to this. For example, the timing of the end of the supply of the first treatment gas may be matched with the timing of the end of the supply of the fourth treatment gas. Even in such cases, at least one of the effects of the present disclosure can be obtained.

[0120] In addition, in the above-described embodiment, an example of film formation using a substrate processing device that processes multiple substrates at once was described, but the present disclosure is not limited to this and can be suitably applied to cases where film formation is performed using a single-wafer substrate processing device that processes one or several substrates at once.

[0121] It is preferable to prepare (prepare multiple) process recipes (programs containing processing steps, processing conditions, etc.) used for forming these various thin films individually according to the content of the substrate processing (film type, composition ratio, film quality, film thickness, processing steps, processing conditions, etc. of the thin film to be formed). Furthermore, when starting the substrate processing, it is preferable to appropriately select a suitable process recipe from among the multiple process recipes according to the content of the substrate processing. Specifically, it is preferable to store (install) in advance the multiple process recipes prepared individually according to the content of the substrate processing in a memory device (121c) equipped by the substrate processing device via an electrical communication line or a recording medium (external memory device (123)) on which the said process recipes are recorded. Furthermore, when starting the substrate processing, it is preferable for the CPU (121a) equipped by the substrate processing device to appropriately select a suitable process recipe from among the multiple process recipes stored in the memory device (121c) according to the content of the substrate processing. By configuring it in this way, it becomes possible to form thin films of various film types, composition ratios, film qualities, and film thicknesses in a single substrate processing device in a universal and reproducible manner. In addition, the operator's operational burden (such as input burdens like processing procedures or processing conditions) can be reduced, allowing for the rapid initiation of substrate processing while avoiding operational errors.

[0122] Furthermore, the present disclosure can also be realized, for example, by changing the process recipe of an existing substrate processing device. When changing the process recipe, it is possible to install the process recipe according to the present disclosure into the existing substrate processing device via a telecommunications line or a recording medium recording said process recipe, or to change the process recipe itself to the process recipe according to the present disclosure by operating the input / output device of the existing substrate processing device.

[0123] In addition, the present disclosure can be used in the word line portion of, for example, a NAND-type flash memory or DRAM having a three-dimensional structure.

[0124] Although various typical embodiments of the present disclosure have been described above, the present disclosure is not limited to such embodiments and may be used in appropriate combinations. Explanation of the symbols

[0125] 10: Substrate processing device 121: Controller 200: Wafer (substrate) 201: Processing Room

Claims

Claim 1 A substrate treatment method comprising: (a) a process of supplying a first treatment gas containing a first element and a halogen to a substrate; (b) a process of supplying a second treatment gas having NN bonds and NH bonds to the substrate; (c) a process of supplying a fourth treatment gas containing a second element different from the first element and hydrogen to the substrate during a period overlapping with (a) and a predetermined period after (a); and (d) a process of forming a first film containing the first element by performing (a), (b), and (c) X times (X is a natural number) while the substrate is heated to a temperature of 250°C or lower. Claim 2 In claim 1, (d) is a substrate processing method performed at a temperature of 180°C or higher and 220°C or lower. Claim 3 A substrate treatment method according to claim 1, comprising: (e) a process of supplying a third treatment gas having the NH bonds to the substrate and having a composition different from the second treatment gas; and (f) a process of subsequently performing (a) and (e) Y (Y is a natural number) times to form a second film containing the first element on the first film. Claim 4 A substrate treatment method according to claim 2, comprising: (e) a process of supplying a third treatment gas having the NH bonds to the substrate and having a composition different from the second treatment gas; and (f) a process of subsequently performing (a) and (e) Y (Y is a natural number) times to form a second film containing the first element on the first film. Claim 5 A substrate treatment method according to claim 1, wherein (g) after (d), the substrate is heat-treated at a temperature higher than the temperature of (d). Claim 6 A substrate treatment method according to paragraph 2, wherein (g) after (d), the substrate is heat-treated at a temperature higher than the temperature of (d). Claim 7 A substrate treatment method according to paragraph 3, wherein (g) after (d), the substrate is heat-treated at a temperature higher than the temperature of (d). Claim 8 A substrate treatment method according to claim 1, wherein, in (g), after (d), the substrate is heat-treated at a temperature higher than the temperature of (d), and during the heating to the higher temperature, a third treatment gas having the NH bond and having a composition different from the second treatment gas is supplied to the substrate. Claim 9 delete Claim 10 delete Claim 11 A substrate treatment method according to claim 1, wherein in (b), a third treatment gas having the NH bond and having a composition different from the second treatment gas is supplied. Claim 12 A substrate treatment method according to paragraph 2, wherein in (b), a third treatment gas having the NH bond and having a composition different from the second treatment gas is supplied. Claim 13 A substrate treatment method according to claim 1, having a process of supplying the fourth treatment gas in at least one process between (h) (a) and after (a). Claim 14 A substrate treatment method according to claim 1, wherein, after (i) (d), the fourth treatment gas is supplied to form a film containing the second element on the first film. Claim 15 A substrate processing method according to claim 1, wherein (j) (b) is performed before (d). Claim 16 A method for manufacturing a semiconductor device comprising: (a) a process of supplying a first treatment gas containing a first element and a halogen to a substrate; (b) a process of supplying a second treatment gas having NN bonds and NH bonds to the substrate; (c) a process of supplying a fourth treatment gas containing a second element different from the first element and hydrogen to the substrate during a period overlapping with (a) and a predetermined period after (a); and (d) a process of performing (a), (b), and (c) X (X is a natural number) times while the substrate is heated to a temperature of 250°C or lower to form a first film containing the first element. Claim 17 A program recorded on a computer-readable recording medium, wherein the steps of: (a) supplying a first treatment gas containing a first element and a halogen to a substrate; (b) supplying a second treatment gas having NN bonds and NH bonds to the substrate; (c) supplying a fourth treatment gas containing a second element different from the first element and hydrogen to the substrate during a period overlapping with (a) and a predetermined period after (a); and (d) performing (a), (b), and (c) X (X is a natural number) times while the substrate is heated to a temperature of 250°C or lower to form a first film containing the first element, are executed by a computer on a substrate processing device. Claim 18 A substrate processing apparatus having a first processing gas supply system for supplying a first processing gas containing a first element and a halogen to a substrate, a second processing gas supply system for supplying a second processing gas having NN bonds and NH bonds to the substrate, a heating system for heating the substrate, (a) a process of supplying the first processing gas to the substrate, (b) a process of supplying the second processing gas to the substrate, (c) a process of supplying a fourth processing gas containing a second element different from the first element and hydrogen to the substrate during a period overlapping with (a) and during a predetermined period after (a), and (d) a process of forming a first film containing the first element on the substrate by performing (a), (b), and (c) X (X is a natural number) times while the substrate is heated to a temperature of 250°C or lower, and a control unit capable of controlling the first processing gas supply system, the second processing gas supply system, and the heating system.

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