JP2021036602A - Semiconductor device manufacturing method, substrate processing device and program - Google Patents

Abstract

To provide a semiconductor device manufacturing method and a substrate processing device that suppress occurrence of a film thickness drop phenomenon when a film is formed on a substrate.SOLUTION: A method performs, at a predetermined frequency, a cycle of executing, in a non-simultaneous manner, a step of supplying a raw material containing a main element and a halogen element constituting a film to be formed to a substrate having an uneven structure formed on the surface thereof to form a first layer containing the main element and the halogen element, a step of supplying a first reactant consisting of three elements of carbon, nitrogen and hydrogen to the substrate to form a second layer containing the main elements, carbon and nitrogen, and a step of supplying a second reactant containing oxygen to the substrate to oxidize the second layer and form a third layer containing the main elements, oxygen, carbon and nitrogen, thereby forming a film containing the main elements, oxygen, carbon and nitrogen. A supply time of the first reactant per cycle is set to twice or more of the supply time of the raw material per cycle and 1.5 times or more of the supply time of the second reactant per cycle.SELECTED DRAWING: Figure 4

Description

The present invention relates to a method for manufacturing a semiconductor device, a substrate processing device, and a program.

As one step in the manufacturing process of a semiconductor device, a process of supplying a raw material and a reactant to a substrate non-simultaneously to form a film on the substrate may be performed (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-140944

When a film is formed on a substrate having a pattern formed on the surface, the film thickness of the formed film becomes thinner than when the film is formed on a substrate having no pattern formed on the surface (hereinafter referred to as). , This phenomenon is also referred to as a film thickness drop phenomenon). An object of the present invention is to provide a technique capable of suppressing the occurrence of a film thickness drop phenomenon when forming a film on a substrate having a pattern formed on the surface.

According to one aspect of the invention
(A) A step of forming a first layer containing the main element by supplying a raw material containing a main element constituting a film to be formed to a substrate having a pattern formed on the surface.
(B) By supplying the first reactant containing carbon and nitrogen to the substrate, a substance in which a part of the first reactant is decomposed is adsorbed on the first layer, and the main element, The process of forming the second layer containing carbon and nitrogen,
A step of forming a film containing the main element, carbon, and nitrogen on the pattern is performed by performing the cycle of performing the above non-simultaneously a predetermined number of times.
In (b), a technique for supplying the first reactant is provided until the densities of the adsorption layers of the substance formed on at least the upper surface, the side surface and the lower surface of the pattern are equal to each other.

According to the present invention, it is possible to suppress the occurrence of the film thickness drop phenomenon when forming a film on a substrate.

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus preferably used in embodiment of this invention, and is the figure which shows the processing furnace part in the vertical sectional view. It is a schematic block diagram of a part of the vertical processing furnace of the substrate processing apparatus preferably used in embodiment of this invention, and is the figure which shows the part of the processing furnace by the cross-sectional view taken along line AA of FIG. It is a schematic block diagram of the controller of the substrate processing apparatus preferably used in embodiment of this invention, and is the figure which shows the control system of the controller by the block diagram. (A) is a diagram showing a film forming sequence of one embodiment of the present invention, and (b) is a diagram showing a modified example of the film forming sequence of one embodiment of the present invention. (A) is an enlarged cross-sectional view of a substrate having a pattern formed on the surface, and (b) is a schematic view showing a state after supplying a raw material to the substrate having a pattern formed on the surface, (c). ) (D) are schematic views showing a state after the raw material and the reactant are sequentially supplied to the substrate on which the pattern is formed on the surface, respectively. (A) to (c) are diagrams showing the evaluation results of the film thickness of the film formed on the substrate, respectively.

<One Embodiment of the present invention>
Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 to 5.

(1) Configuration of Substrate Processing Device As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating means (heating mechanism). The heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation portion) for activating (exciting) the gas with heat.

Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made _{of a heat-resistant material such as quartz (SiO 2} ) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end open. A processing chamber 201 is formed in the hollow portion of the reaction tube 203. The processing chamber 201 is configured to accommodate the wafer 200 as a substrate.

Nozzles 249a and 249b are provided in the processing chamber 201 so as to penetrate the lower side wall of the reaction tube 203. Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively.

The gas supply pipes 232a and 232b are provided with mass flow controllers (MFCs) 241a and 241b which are flow rate controllers (flow control units) and valves 243a and 243b which are on-off valves, respectively, in this order from the upstream side. Gas supply pipes 232c and 232d for supplying the inert gas are connected to the downstream side of the valves 243a and 243b of the gas supply pipes 232a and 232b, respectively. The gas supply pipes 232c and 232d are provided with MFC 241c and 241d and valves 243c and 243d, respectively, in this order from the upstream side.

As shown in FIG. 2, the nozzles 249a and 249b are arranged in an annular space in a plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper part of the inner wall of the reaction tube 203 from the lower part of the wafer 200. Each is provided so as to stand upward in the arrangement direction. That is, the nozzles 249a and 249b are provided along the wafer arrangement region in the region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafer 200 is arranged. Gas supply holes 250a and 250b for supplying gas are provided on the side surfaces of the nozzles 249a and 249b, respectively. The gas supply holes 250a and 250b are opened so as to face the center of the reaction tube 203, respectively, so that gas can be supplied toward the wafer 200. A plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.

From the gas supply pipe 232a, a halosilane-based gas containing silicon (Si) as a main element constituting the film to be formed and a halogen element as a raw material (raw material gas) passes through the MFC 241a, the valve 243a, and the nozzle 249a. It is supplied into the processing chamber 201. The raw material gas is a raw material in a gaseous state, for example, a gas obtained by vaporizing a raw material in a liquid state under normal temperature and pressure, a raw material in a gaseous state under normal temperature and pressure, and the like. Halogen elements include chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and the like. As the halosilane gas, for example, a chlorosilane gas containing Cl can be used. As the chlorosilane-based gas, for example, hexachlorodisilane (Si ₂ Cl ₆ , abbreviation: HCDS) gas can be used.

From the gas supply pipe 232b, as the first reactant (first reaction gas), an amine-based gas containing carbon (C) and nitrogen (N) is introduced into the processing chamber via the MFC 241b, the valve 243b, and the nozzle 249b. It is supplied into 201. The amine-based gas is a gas composed of three elements, N, C and H. As the amine-based gas, for example, triethylamine ((C ₂ H ₅ ) ₃ N, abbreviation: TEA) gas can be used.

From the gas supply pipe 232b, an oxidizing gas (oxidizing agent), which is a gas containing oxygen (O), is introduced into the processing chamber 201 as a second reactant (second reaction gas) via the MFC 241b, the valve 243b, and the nozzle 249b. Is supplied to. As the oxidation gas, for example, oxygen (O ₂ ) gas can be used.

From the gas supply pipes 232c and 232d, the inert gas is supplied into the processing chamber 201 via the MFC 241c and 241d, the valves 243c and 243d, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b, respectively. As the inert gas, for example, nitrogen (N ₂ ) gas can be used.

The raw material supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. Mainly, the gas supply pipe 232b, the MFC 241b, and the valve 243b constitute the first and second reactor supply systems, respectively. Mainly, the gas supply pipes 232c, 232d, MFC241c, 241d, and valves 243c, 243d constitute an inert gas supply system.

Of the various supply systems described above, any or all of the supply systems may be configured as an integrated supply system 248 in which valves 243a to 243d, MFC 241a to 241d, and the like are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232d, and supplies various gases into the gas supply pipes 232a to 232d, that is, the opening / closing operation of the valves 243a to 243d and the MFC 241a to 241d. The flow rate adjustment operation and the like are configured to be controlled by the controller 121 described later. The integrated supply system 248 is configured as an integrated or divided integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232d in units of the integrated unit. It is configured so that maintenance, replacement, expansion, etc. can be performed on an integrated unit basis.

An exhaust pipe 231 that exhausts the atmosphere in the processing chamber 201 is connected to the reaction pipe 203. The exhaust pipe 231 is provided via a pressure sensor 245 as a pressure detector (pressure detector) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator). , A vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 can perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve with the vacuum pump 246 operating, and further, with the vacuum pump 246 operating, the APC valve 244 can perform vacuum exhaust and vacuum exhaust stop. By adjusting the valve opening degree based on the pressure information detected by the pressure sensor 245, the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of an exhaust pipe 231, an APC valve 244, and a pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

Below the reaction tube 203, a seal cap 219 is provided as a furnace palate body capable of airtightly closing the lower end opening of the reaction tube 203. The seal cap 219 is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220 as a sealing member that comes into contact with the lower end of the reaction tube 203 is provided on the upper surface of the seal cap 219. Below the seal cap 219, a rotation mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotation shaft 255 of the rotation mechanism 267 penetrates the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically lifted and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transport device (convey mechanism) for loading and unloading (conveying) the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

The boat 217 as a substrate support supports a plurality of wafers, for example 25 to 200 wafers, in a horizontal position and vertically aligned with each other, that is, in multiple stages. It is configured to be arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. In the lower part of the boat 217, a heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages.

A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. By adjusting the degree of energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. Has been done. The RAM 121b, the storage device 121c, and the I / O port 121d are configured so that data can be exchanged with the CPU 121a via the internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121.

The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing device, a process recipe in which the procedures and conditions for substrate processing described later are described, and the like are readablely stored. The process recipes are combined so that the controller 121 can execute each procedure in the substrate processing described later and obtain a predetermined result, and functions as a program. Hereinafter, process recipes, control programs, etc. are collectively referred to simply as programs. In addition, a process recipe is also simply referred to as a recipe. When the term program is used in the present specification, it may include only a recipe alone, a control program alone, or both of them. The RAM 121b is configured as a memory area (work area) in which programs, data, and the like read by the CPU 121a are temporarily held.

The I / O port 121d is connected to the above-mentioned MFC 241a to 241d, valves 243a to 243d, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115 and the like. ..

The CPU 121a is configured to read and execute a control program from the storage device 121c and read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a adjusts the flow rate of various gases by the MFCs 241a to 241d, opens and closes the valves 243a to 243d, opens and closes the APC valve 244, and adjusts the pressure by the APC valve 244 based on the pressure sensor 245 so as to follow the contents of the read recipe. Control operation, start and stop of vacuum pump 246, temperature adjustment operation of heater 207 based on temperature sensor 263, rotation and rotation speed adjustment operation of boat 217 by rotation mechanism 267, lifting operation of boat 217 by boat elevator 115, etc. It is configured in.

The controller 121 installs the above-mentioned program stored in an external storage device (for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, or a semiconductor memory such as a USB memory) 123 in a computer. Can be configured by. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, these are collectively referred to simply as a recording medium. When the term recording medium is used in the present specification, it may include only the storage device 121c alone, it may include only the external storage device 123 alone, or it may include both of them. The program may be provided to the computer by using a communication means such as the Internet or a dedicated line without using the external storage device 123.

(2) Film formation processing FIG. 4 (FIG. 4) shows an example of a sequence in which a silicon oxycarbonate film (SiOCN film) is formed on a wafer 200 as a substrate as one step of a manufacturing process of a semiconductor device using the above-mentioned substrate processing apparatus. This will be described using a). Here, an example in which a pattern wafer having a pattern (concave and convex structure) formed on the surface is used as the wafer 200 will be described. FIG. 5A is an enlarged cross-sectional view of only a part of the concave-convex structure of the wafer 200 in which a pattern including the upper surface 200a, the side surface 200b, and the lower surface (bottom surface) 200c is formed on the surface. The pattern wafer has a large surface area as compared with a bare wafer in which a pattern is not formed on the surface. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

In the film formation sequence shown in FIG. 4 (a),
Step A of forming the first layer containing Si by supplying HCDS gas (raw material) to the wafer 200 having the pattern formed on the surface, and
By supplying TEA gas (first reactant) to the wafer 200, a substance in which a part of TEA gas is decomposed is adsorbed on the first layer to form a second layer containing Si, C and N. Step B to do and
_{By supplying O 2} gas (second reactant) to the wafer 200, the second layer is oxidized to form the third layer containing Si, O, C and N, and step C.
A SiOCN film is formed on the pattern by performing a cycle of performing the above non-simultaneously a predetermined number of times.

In step B, the TEA gas is supplied until the densities of the adsorption layers of the substances in which a part of the TEA gas formed on at least the upper surface 200a, the side surface 200b, and the lower surface 200c of the pattern are decomposed become equal. ..

In the present specification, the film formation sequence shown in FIG. 4A may be shown as follows for convenience. The same notation is used in the following description of the modified examples and the like.

(HCDS → TEA → O ₂ ) × n ⇒ SiOCN

When the term "wafer" is used in the present specification, it may mean the wafer itself or a laminate of a wafer and a predetermined layer or film formed on the surface thereof. When the term "wafer surface" is used in the present specification, it may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. In the present specification, when it is described that "a predetermined layer is formed on a wafer", it means that a predetermined layer is directly formed on the surface of the wafer itself, or a layer formed on the wafer or the like. It may mean forming a predetermined layer on top of it. The use of the term "board" in the present specification is also synonymous with the use of the term "wafer".

(Wafer charge and boat load)
A plurality of wafers 200 are loaded into the boat 217 (wafer charge). After that, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 is in a state of sealing the lower end of the reaction tube 203 via the O-ring 220.

(Pressure adjustment and temperature adjustment)
The inside of the processing chamber 201 is evacuated (decompressed exhaust) by the vacuum pump 246 so that the inside of the processing chamber 201, that is, the space where the wafer 200 exists has a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the state of energization of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Further, the rotation mechanism 267 starts the rotation of the wafer 200. Exhaust in the processing chamber 201, heating and rotation of the wafer 200 are all continuously performed at least until the processing of the wafer 200 is completed.

(Film formation step)
After that, steps A to C are sequentially executed.

[Step A]
In this step, HCDS gas is supplied to the wafer 200 in the processing chamber 201.

Specifically, the valve 243a is opened to allow HCDS gas to flow into the gas supply pipe 232a. The flow rate of the HCDS gas is adjusted by the MFC 241a, is supplied into the processing chamber 201 via the nozzle 249a, and is exhausted from the exhaust pipe 231. At this time, HCDS gas is supplied to the wafer 200. At this time, the valve 243 c, open the 243 d, the gas supply pipe 232c, may be supplied with _{N 2} gas into the 232 d.

The processing conditions in this step are
HCDS gas supply flow rate: 1 to 2000 sccm, preferably 10 to 1000 sccm
HCDS gas supply time _T A: 1 to 120 seconds, preferably 60 seconds N ₂ gas supply flow rate: 0～10000Sccm
Treatment temperature: 250-800 ° C, preferably 400-750 ° C, more preferably 550-700 ° C
Processing pressure: 1-2666 Pa, preferably 67-1333 Pa
Is exemplified.

If the processing temperature is less than 250 ° C., it becomes difficult for HCDS to be chemically adsorbed on the wafer 200, and a practical film forming rate may not be obtained. This can be solved by setting the treatment temperature to 250 ° C. or higher. By setting the treatment temperature to 400 ° C. or higher, further 550 ° C. or higher, HCDS can be more sufficiently adsorbed on the wafer 200, and a more sufficient film forming rate can be obtained.

If the treatment temperature exceeds 800 ° C., an excessive gas phase reaction occurs, and the film thickness uniformity tends to deteriorate, which may be difficult to control. By setting the treatment temperature to 800 ° C. or lower, an appropriate gas phase reaction can be generated, deterioration of film thickness uniformity can be suppressed, and its control becomes possible. In particular, when the treatment temperature is set to 750 ° C. or lower, further 700 ° C. or lower, the surface reaction becomes predominant over the gas phase reaction, the film thickness uniformity can be easily ensured, and the control thereof becomes easy.

By supplying HCDS gas to the wafer 200 under the above conditions, the first is applied to the surface of the wafer 200, that is, the surface 200a, the side surface 200b, and the lower surface 200c of the pattern formed on the surface of the wafer 200. As the layer (initial layer), for example, a Si-containing layer containing Cl having a thickness of less than one atomic layer (one molecular layer) to several atomic layers (several molecular layers) is formed. The first layer is formed by physically adsorbing HCDS on the surface of the wafer 200, chemically adsorbing a substance in which a part of HCDS is decomposed, thermally decomposing HCDS, and the like. Herein, a material constituting the Si-containing layer containing Cl, _convenience, also referred to as _{Si x Cl y (1 ≦ x} ≦ 2,0 ≦ y ≦ 6). Further, the Si-containing layer containing Cl is also simply referred to as a Si-containing layer for convenience.

The HCDS gas containing Cl is more active (easily decomposed) than the TEA gas composed of only N, C and H, and has a high adsorption efficiency on the surface of the wafer 200. Therefore, by the supplying time _{T A} of the HCDS gas and time within the above range, i.e., without a long time as _{T B} to be described later, the surface 200a of the patterns, are formed on each side 200b and bottom surface 200c The densities of the first layers can be made equal to each other. FIG. 5B shows a state in which the first layer is continuously formed at a high density (equivalent density) on each of the front surface 200a, the side surface 200b, and the lower surface 200c of the pattern by carrying out step A. It is a schematic diagram which shows. In FIG. 5 (b), .smallcircle represents the _Si x Cl _y. This point is the same in FIGS. 5 (c) and 5 (d).

After the first layer is formed, the valve 243a is closed to stop the supply of HCDS gas to the wafer 200. Then, the inside of the processing chamber 201 is evacuated, and the gas or the like remaining in the processing chamber 201 is removed from the inside of the processing chamber 201. At this time, the valve 243 c, open the 243 d, and supplies a _{N 2} gas into the processing chamber 201. The N ₂ gas acts as a purge gas, whereby the inside of the processing chamber 201 is purged.

As raw materials, in addition to HCDS gas, for example, monochlorosilane (SiH ₃ Cl, abbreviation: MCS) gas, dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS) gas, trichlorosilane (SiHCl ₃ , abbreviation: TCS) gas, Chlorosilane-based gases such as tetrachlorosilane (SiCl ₄ , abbreviation: STC) gas and octachlorotrisilane (Si ₃ Cl ₈ , abbreviation: OCTS) gas can be used. Further, as the raw material gas, tetrafluorosilane (SiF ₄ ) gas, tetrabromosilane (SiBr ₄ ) gas, tetraiodosilane (SiI ₄ ) gas and the like can be used. That is, as the raw material gas, a halosilane gas other than the chlorosilane gas such as a fluorosilane gas, a bromosilane gas, and an iodosilane gas can be used.

As raw materials, 1,2-bis (trichlorosilyl) ethane ((SiCl ₃ ) ₂ C ₂ H ₄ , abbreviation: BTCSE) gas, bis (trichlorosilyl) methane ((SiCl ₃ ) ₂ CH ₂ , abbreviation: BTCSM) alkylene halosilane gas such as gas, 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH ₃ ) ₂ Si ₂ Cl ₄ , abbreviated as TCDMDS) gas, 1,2- Dichloro-1,1,2,2-tetramethyldisilane ((CH _{3 ) 4} Si ₂ Cl ₂ , abbreviation: DCTMDS) gas, 1-monochromelo-1,1,2,2,2-pentamethyldisilane ((CH 3)) ₃ ) An _{alkylhalosilane-based gas such as 5} Si ₂ Cl, abbreviated as MCPMDS) gas can be used. Since all of these gases contain Si—C bonds, it is possible to increase the C concentration of the SiOCN film finally formed.

Further, as a raw material _{, silicon hydride gas such as monosilane (SiH 4} , abbreviation: MS) gas, disilane (Si ₂ H ₆ , abbreviation: DS) gas, trisilane (Si ₃ H ₈ , abbreviation: TS) gas is used. be able to.

Further, as the raw material, tetrakis (dimethylamino) silane _{(Si [N (CH 3)} 2] 4, abbreviation: 4DMAS) Gas, trisdimethylaminosilane _{(Si [N (CH 3)} 2] 3 H, abbreviation: 3DMAS) Gas, bis Diethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , abbreviation: BDEAS) gas, Vista Charlie Butylaminosilane (SiH ₂ [NH (C ₄ H ₉ )] ₂ , abbreviation: BTBAS) gas, diisopropylaminosilane Aminosilane-based gas such as (SiH ₃ N [CH (CH ₃ ) ₂ ] ₂ , abbreviation: DIPAS) gas can be used. Since all of these contain Si—N bonds, it is possible to increase the N concentration of the SiOCN film finally formed.

As the inert gas, in addition to the N ₂ gas, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used. This point is the same in steps B and C.

[Step B]
After the step A is completed, TEA gas is supplied to the wafer 200 in the processing chamber 201, that is, the first layer formed on the wafer 200.

In this step, the opening / closing control of the valves 243b to 243d is performed in the same procedure as the opening / closing control of the valves 243a, 243c, 243d in step A. The flow rate of the TEA gas is adjusted by the MFC 241b, is supplied into the processing chamber 201 via the nozzle 249b, and is exhausted from the exhaust pipe 231. At this time, TEA gas is supplied to the wafer 200.

The processing conditions in this step are
TEA gas supply flow rate: 1 to 2000 sccm, preferably 10 to 1000 sccm
TEA gas supply time _{T B:} a longer time than the above-mentioned _{T A,} preferably 2 times or more _{T A} is more preferably _{T A} 4-fold or more, more preferably _{T A} of 10 times or more, more preferably 15 times longer treatment pressure of _{T a: 1~4000Pa,} preferably 1~3000Pa
Is exemplified. Other processing conditions are the same as the processing conditions in step A.

By supplying TEA gas to the wafer 200 under the above-mentioned conditions, the first layer formed on the wafer 200 in step A can be reacted with the TEA gas. That is, Cl contained in the first layer can be reacted with the ethyl group contained in TEA gas. As a result, at least a part of Cl contained in the first layer is extracted (separated) from the first layer, and at least a part of the ethyl groups contained in the TEA gas is extracted from the TEA gas. Can be separated. Then, the N of the TEA gas from which at least a part of the ethyl groups have been separated and the Si contained in the first layer can be bonded to form a Si—N bond. At this time, it is also possible to form a Si-C bond by binding C contained in the ethyl group (-CH ₂ CH _{3) separated from the TEA gas and Si contained in the first layer.} .. As a result, Cl is desorbed from the first layer, and an adsorption layer of a substance in which a part of TEA is decomposed is formed on the first layer. In the present specification, the substance in which a part of TEA is decomposed is also referred to as N (C _{x Hy} ) _z (0 ≦ x ≦ 2, 0 ≦ y ≦ 5, 0 ≦ z ≦ 3) for convenience. The wafer 200 contains, as the second layer, a layer _{containing a first layer and an N (C x Hy} ) _z adsorption layer formed on the first layer, that is, Si, C, and N. A silicon carbonitriding layer (SiCN layer), which is a layer, is formed.

The TEA gas is a gas having a smaller degree of activity (difficult to decompose) and a lower adsorption efficiency on the surface of the wafer 200 than the HCDS gas containing Cl. Therefore, if the supply time of the HCDS gas supply time _{T B} of the TEA gas _{T A} following time _{(T B} ≦ _{T A),} the surface 200a of the patterns, N that are formed in the respective side surfaces 200b and the lower surface 200c _{(C x} The densities of the adsorption layers of _Hy ) _{z may differ from each other.} FIG. 5 (c), _T in the case where the _B ≦ _{T A,} on the surface of the wafer 200 _N formed (on the surface of the first _{layer) (C x} H y) schematically showing the density of the adsorption layer of the _z It is a figure. In FIG. 5 (c), the ◎ mark indicates N (C _{x Hy} ) _z . This point is the same in FIG. 5 (d).

As shown in FIG. 5 (c), when the _{T B} ≦ _{T A,} in the surface 200a of the _patterns, there is a case where the adsorption layer of the N _{(C x} H _{y) z} is formed at a relatively high density. However, on the side surface 200b of the pattern, _{the adsorption amount of N (C x Hy} ) _z is greatly reduced, and _{the adsorption layer of N (C x Hy} ) _z may become a discontinuous layer. Further, on the lower surface 200c of the pattern, N (C _{x Hy} ) _z is hardly adsorbed, and _{an adsorption layer of N (C x Hy} ) _z may not be formed. N If the density of the adsorption layer of _{(C x} H _{y) z} is uneven as shown in FIG. 5 (c), the thickness of the SiOCN film to be finally formed, the surface 200a of the patterns, side 200b and bottom surface Each of the 200c will be very different. As a result, the film thickness (average film thickness) of the SiOCN film formed on the wafer 200 is higher than the film thickness (average film thickness) of the SiOCN film formed on the bare wafer according to the same treatment procedure and treatment conditions as in this case. The phenomenon of thinning, that is, the film thickness drop phenomenon is likely to occur. _Further, N _{(C x} H _y) the density of the adsorption layer of _z becomes uneven as illustrated in FIG. 5 (c), the surface 200a of the patterns, N that are formed in the respective side surfaces 200b and the lower surface 200c _{(C x} At least one of the N concentration and the C concentration in the adsorption layer of _Hy ) _{z is different from each other.} As a result, the composition of the SiOCN film finally formed is significantly different on each of the front surface 200a, the side surface 200b, and the bottom surface 200c of the pattern.

In contrast, as in this embodiment, the supply time _{T B} of the TEA gas longer than the supply time _{T A} of the HCDS gas _(T B> _{T A)} that is, the surface 200a of the patterns, side 200b and bottom surface 200c It is possible to make the densities of the _{N (C x Hy} ) _z adsorption layers formed in each of the above the same. 5 (d) _is by the _{T B> T A, N (} C x H y) adsorption layer of _z is, the surface 200a of the patterns, on each side 200b and the lower surface 200c, a high density (equivalent density It is a schematic diagram which shows the state which was formed continuously by). N _{(C x} H _y) of the density distribution of the adsorption layer of _z by aligning in the plane as shown in FIG. 5 (d), the thickness of the SiOCN film finally formed, the surface 200a of the patterns, side surface 200b It is possible to make the same on each of the lower surface 200c and the lower surface 200c. As a result, according to the present embodiment, even when a pattern wafer is used as the wafer 200, it is possible to avoid a decrease in the film thickness (average film thickness) of the SiOCN film, that is, to suppress the occurrence of the film thickness drop phenomenon. It becomes possible to do. Further, by aligning the density distribution of the adsorption layer of N (C _{x Hy} ) _z in the plane as shown in FIG. 5 (d), N (N () formed on each of the surface 200a, the side surface 200b and the bottom surface 200c of the pattern. At least one of the N concentration and the C concentration in the adsorption layer of _{C x Hy} ) _{z can be made equivalent.} As a result, the composition of the SiOCN film finally formed can be made equal on each of the front surface 200a, the side surface 200b, and the bottom surface 200c of the pattern. Incidentally, by setting the _{T B} 2 times or more the time _{T A (T B ≧ 2T A} ), is as the above effect can be sufficiently obtained, _{T B} and _{T A} 4 times the time (T with _B ≧ 4T _a), so that the above effect can be obtained more sufficiently. In addition, by setting _{T B} to _{T A} 10 times or more the time _{(T B} ≧ 10T _A), now the above-described effects can be reliably obtained, _{T B} and _{T A} 15 times or more the time (T with _B ≧ 15T _a), so that the above effect can be obtained more reliably. For example, when the _{T A} and timed in the range of 10 to 13 seconds, look like the above-described effects can be reliably obtained by making the 100-130 seconds or more _{T B,} the _{T B} from 150 to 195 seconds or more and By doing so, the above-mentioned effect can be obtained more reliably. However, considering the productivity, preferably in the the _{T B T A} 20 times the time _{(T B} ≦ 20T _A).

Incidentally, to obtain the effects described above, not only to increase the supply time T _B of the TEA gas, it is effective to increase the supply flow rate of the TEA gas. However, TEA gas is a gas obtained by vaporizing a liquid raw material that is in a liquid state under normal temperature and pressure, and it is often difficult to increase the flow rate thereof. Therefore, in the case of using a liquid raw material and the obtained by vaporizing gas such as TEA gas as a first reactant, as in the present embodiment, a technique for adjusting the supply time T _B of the TEA gas, i.e., T _B > _{T a,} preferably _{T B} ≧ 2T _a, more preferably _{T B} ≧ 4T _a, more preferably _{T B} ≧ 10T _a, more preferably a technique for the _{T B} ≧ 15T _a particularly effective.

After the second layer is formed, the valve 243b is closed to stop the supply of TEA gas to the wafer 200. Then, by the same processing procedure as in step A, the gas or the like remaining in the processing chamber 201 is removed from the processing chamber 201.

Examples of the amine-based gas as the first reactant include TEA gas, diethylamine ((C ₂ H ₅ ) ₂ NH, abbreviation: DEA) gas, monoethylamine (C ₂ H ₅ NH ₂ , abbreviation: MEA) gas and the like. Ethylamine-based 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 Methylamine-based gas such as, 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 , propylamine gas such as MPA gas, triisopropylamine ([(CH ₃ ) ₂ CH] ₃ N, abbreviation: TIPA) gas, diisopropylamine ([(CH ₃ ) _{2) 2 CH]} 2 NH, abbreviated DIPA) gas, monoisopropylamine _{((CH 3) 2 CHNH 2} , abbreviation: MIPA) and isopropyl amine-based gas such as a gas, tributylamine _{((C 4 H 9) 3} N, abbreviation: Butylamine-based gas such as TBA) gas, dibutylamine ((C ₄ H ₉ ) ₂ NH, abbreviation: DBA) gas, monobutylamine (C ₄ H ₉ NH ₂ , abbreviation: MBA) gas, triisobutylamine ([( 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 and other isobutylamine-based gases can be used.

Further, as the first reactant, an organic hydrazine-based gas can be used in addition to the amine-based gas. Examples of the organic hydrazine-based gas include monomethylhydrazine ((CH ₃ ) HN ₂ H ₂ , abbreviation: MMH) gas, dimethylhydrazine ((CH ₃ ) ₂ N ₂ H ₂ , abbreviation: DMH) gas, and trimethylhydrazine ((CH _3)). ) ₂ N ₂ (CH ₃ ) H, abbreviation: TMH) gas or the like methylhydrazine gas or ethylhydrazine ((C ₂ H ₅ ) HN ₂ H ₂ , abbreviation: EH) gas or the like is used. be able to.

[Step C]
_{After the step B is completed, the O 2} gas is supplied to the wafer 200 in the processing chamber 201, that is, the second layer formed on the wafer 200.

In this step, the opening / closing control of the valves 243b to 243d is performed in the same procedure as the opening / closing control of the valves 243a, 243c, 243d in step A. The _{flow rate of the O 2} gas is adjusted by the MFC 241b, is supplied into the processing chamber 201 via the nozzle 249b, and is exhausted from the exhaust pipe 231. At this time, O ₂ gas is supplied to the wafer 200.

The processing conditions in this step are
O ₂ gas supply flow rate: 100 to 10,000 sccm
O ₂ gas supply time _T C: 1 to 120 seconds, preferably 60 seconds treatment pressure: 1～4000Pa, preferably 1~3000Pa
Is exemplified. Other processing conditions are the same as the processing conditions in step A.

_{By supplying O 2} gas to the wafer 200 under the above conditions, at least a part of the second layer formed on the wafer 200 can be modified (oxidized) by carrying out step B. .. That is, _{at least a part of the O component contained in the O 2} gas can be added to the second layer to form a Si—O bond in the second layer. By modifying the second layer, a silicon nitriding layer (SiOCN layer), which is a layer containing Si, O, C, and N, is formed as the third layer on the wafer 200. When the third layer is formed, at least a part of the C component and the N component contained in the second layer is maintained (retained) in the second layer without being desorbed from the second layer. When the third layer is formed, the Cl contained in the second layer constitutes a gaseous substance containing at least Cl in the process of the reforming reaction with the _{O 2 gas, and is discharged from the treatment chamber 201.} That is, impurities such as Cl in the second layer are separated from the second layer by being extracted or removed from the second layer. As a result, the third layer becomes a layer having less impurities such as Cl as compared with the second layer.

After the third layer is formed, the valve 243b is closed to stop the supply _{of O 2 gas to the wafer 200.} Then, by the same processing procedure as in step A, the gas or the like remaining in the processing chamber 201 is removed from the processing chamber 201.

As the oxidation gas as the second reactant _{, in addition to O 2} gas, water vapor (H ₂ O gas), nitrogen monoxide (NO) gas, nitrogen sulfite (N ₂ O) gas, nitrogen dioxide (NO ₂ ) gas. , Carbon monoxide (CO) gas, carbon dioxide (CO ₂ ) gas, ozone (O ₃ ) gas, hydrogen (H ₂ ) gas + O ₂ gas, H ₂ gas + O ₃ gas and other O-containing gases can be used. ..

[Implemented a predetermined number of times]
By performing the cycles in which steps A to C are performed non-simultaneously, that is, without synchronization, one or more times (n times), a SiOCN film having a desired composition and a desired film thickness can be formed on the wafer 200. The above cycle is preferably repeated a plurality of times. That is, until the thickness of the third layer formed per cycle is made thinner than the desired film thickness and the film thickness of the SiOCN film formed by laminating the third layer reaches the desired film thickness. It is preferable to repeat the above cycle a plurality of times.

(After purging-return to atmospheric pressure)
Desired composition on the wafer 200, when SiOCN film having a desired thickness is formed, the nozzle 249a, the _{N 2} gas is supplied into the process chamber 201 from each 249 b, it is exhausted from the exhaust pipe 231. As a result, the inside of the treatment chamber 201 is purged, and the gas and reaction by-products remaining in the treatment chamber 201 are removed from the inside of the treatment chamber 201 (after-purge). After that, the atmosphere in the treatment chamber 201 is replaced with the inert gas (replacement of the inert gas), and the pressure in the treatment chamber 201 is restored to the normal pressure (return to atmospheric pressure).

(Boat unloading and wafer discharge)
The seal cap 219 is lowered by the boat elevator 115 to open the lower end of the reaction tube 203. Then, the processed wafer 200 is carried out (boat unloading) from the lower end of the reaction tube 203 to the outside of the reaction tube 203 while being supported by the boat 217. The processed wafer 200 is carried out of the reaction tube 203 and then taken out from the boat 217 (wafer discharge).

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

In (a) step _B, by a T B> _{T A,} the surface 200a of the patterns, the density of the adsorption layer of _{N (C x} H _{y) z} which is formed on each side 200b and the lower surface 200c, each equivalent It becomes possible to. As a result, the film thickness of the SiOCN film finally formed can be made equal on each of the front surface 200a, the side surface 200b, and the bottom surface 200c of the pattern, and as a result, the occurrence of the film thickness drop phenomenon can be suppressed. It will be possible.

(B) In step _B, by a _T B> T _A, N concentration and C concentration in the adsorption layer of _{N (C x} H _{y) z} which is formed on each surface 200a, side surfaces 200b and the bottom surface 200c of the pattern At least one of them can be equal to each other. As a result, the composition of the SiOCN film finally formed can be made equal on each of the front surface 200a, the side surface 200b, and the bottom surface 200c of the pattern.

(C) In step _B, or the T B> _{T A,} by or with T B> _{T C,} increasing the thickness of the SiOCN layer formed per cycle, i.e., to increase the cycle rate Is possible.

In step (d) _B, or a _T B> T _A, by or with _T B> T _C, the composition of the SiOCN film finally formed can be finely adjusted. Specifically, the longer the T _B, in a direction increasing the C concentration of the SiOCN film, also in the direction of reducing the N concentration, it is possible to control respectively.

(E) the T _A rather, since longer only T _B, wafer in-plane film thickness uniformity of the SiOCN film finally formed, while avoiding the respective deterioration of step coverage, the thickness drop phenomenon It is possible to suppress the occurrence. In contrast, not only T _B, when like the T _B also T _A long, even possible if suppress the occurrence of thickness drop phenomenon, the decomposition of HCDS on the wafer 200 becomes excessive, The uniformity of the film thickness inside the wafer surface and the step coverage of the finally formed SiOCN film are likely to decrease.

(F) The above-mentioned effects can be obtained when the above-mentioned raw materials other than HCDS gas are used, when the above-mentioned first reactant other than TEA gas is used, or when the above-mentioned second reactant other than _{O 2 gas is used.} The same can be obtained when the above-mentioned inert gas other than the _{N 2 gas is used.}

(4) Modification example This embodiment can be modified as the following modification example. Moreover, these modified examples can be arbitrarily combined.

(Modification example 1)
The deposition sequence described above, has been mainly described a technique for the T _B> T _A, even if the T _B> T _C, the same effect as film-forming sequence shown in FIGS. 4 (a) can get. In addition, by setting the _{T B T C} 1.5 times or more the time _{(T B} ≧ 1.5T _C), is as the above effect can be sufficiently obtained, _{T B} 3 times from _{T C} to by the time (T _B ≧ 3T _C), so that the above effect can be obtained more sufficiently. In addition, by setting the _{T B T C} 5 times the time _{(T B} ≧ 5T _C), is as the above-described effects can be reliably obtained, _{T B} and _{T C} of 10 times or more of the time (T with _B ≧ 10T _C), so that the above effect can be obtained more reliably. However, considering the productivity, preferably in the the _{T B T C} 20 times the time _{(T B} ≦ 20T _C). Other treatment procedures and treatment conditions can be the same as the treatment procedures and treatment conditions of the film formation sequence described above.

(Modification 2)
As in FIG. 4B and the film formation sequence shown below, TEA gas may be supplied in a divided manner (pulse, intermittently) in step B in one cycle. That is, in step B in one cycle, the supply of TEA gas to the wafer 200 and the purging in the processing chamber 201 may be alternately repeated a plurality of times (m times).

(HCDS → TEA × m → O ₂ ) × n ⇒ SiOCN

Also in this modification, in step B, the TEA gas is formed until the densities of the _{N (C x Hy} ) _z adsorption layers formed on at least the upper surface 200a, the side surface 200b, and the lower surface 200c of the pattern are equal to each other. Continue the split supply of. For example, the total supply time of TEA gas in step B per cycle (total supply time of each pulse), or longer than the supply time T _A of the HCDS gas in step A per cycle, step per cycle This can be achieved by making the supply time of O _{2 gas in C longer than TC.}

Incidentally, in this modification, the supply time of the TEA gas per pulse in step B in one cycle, shorter than the supply time T _A of the HCDS gas in step A per cycle, divided supply of the TEA gas It is preferable to carry out this a plurality of times. Further, it is preferable that the TEA gas supply time per pulse in step B in one cycle _{is shorter than the O 2} gas supply time in step C per cycle, and the TEA gas is dividedly supplied a plurality of times. .. Other processing procedures and processing conditions can be the same as the processing procedures and processing conditions for the film formation sequence shown in FIG. 4 (a).

Also in this modified example, the same effect as the film forming sequence shown in FIG. 4A can be obtained.

Further, according to this modification, by separately supplying the TEA gas in step B, the _{adsorption efficiency of N (C x Hy} ) _z on the surface of the wafer 200 can be increased. This is because some of the TEA gas supplied to the wafer 200 stays on the surface of the first layer without causing a reaction with the first layer, and N on the first layer. (C _{x Hy} ) _z may inhibit the formation of an adsorption layer. In addition, _{the reaction by-products generated when forming the N (C x Hy} ) _z adsorption layer stays on the surface of the first layer, and the N (C _{x Hy} ) _z adsorption layer is placed on the first layer. May inhibit the formation of. On the other hand, as in this modification, in step B, the supply of TEA gas to the wafer 200 and the purging in the processing chamber 201 are alternately performed a plurality of times, so that N (C) on the first layer is performed. factors which inhibit the formation of the adsorption layer of the _x H _{y) z} and (fail adsorbed reacted TEA gas and reaction by-products), it is possible to rapidly remove from the surface of the first layer. As a result, it is possible to improve the adsorption efficiency for N (C _x H _{y) z} surface of the wafer 200, further it is possible to suppress the generation of the final film thickness drop phenomenon in SiOCN film formed. Further, the thickness of the SiOCN layer formed per cycle can be further increased, that is, the cycle rate can be further increased.

(Modification example 3)
As in the film formation sequence shown below, step C may be omitted and a silicon carbon nitride film (SiCN film) containing Si, C and N may be formed on the wafer 200. The processing procedures and processing conditions of steps A and B of this modification can be the same as the processing procedures and processing conditions of steps A and B of the film formation sequence shown in FIG. 4 (a).

(HCDS → TEA) × n ⇒ SiCN
(HCDS → TEA × m) × n ⇒ SiCN

Also in this modified example, the same effect as the film forming sequence shown in FIG. 4A can be obtained.

<Other Embodiments>
The embodiment of the present invention has been specifically described above. However, the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the gist thereof.

For example, the present invention can be suitably applied to the case of forming a metal-based thin film such as a titanium oxynitride film (TiOCN film) and a titanium carbon dioxide film (TiCN film). These films can be formed by the following film-forming sequence using, for example, _{a raw material such as titanium tetrachloride (TiCl 4} ) gas or a reactant such as the above-mentioned amine gas or oxidation gas. Even when these film formation sequences are performed, the film formation can be performed under the same treatment procedure and treatment conditions as those in the above-described embodiment, and the same effects as those in the above-described embodiment can be obtained.

(TiCl ₄ → TEA → O ₂ ) × n ⇒ TiOCN
(TiCl ₄ → TEA × m → O ₂ ) × n ⇒ TIOCN
(TiCl ₄ → TEA) × n ⇒ TiCN
(TiCl ₄ → TEA × m) × n ⇒ TiCN

It is preferable that the recipes used for the substrate processing are individually prepared according to the processing content and stored in the storage device 121c via a telecommunication line or an external storage device 123. Then, when starting the processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from the plurality of recipes stored in the storage device 121c according to the content of the substrate processing. As a result, it becomes possible to form films having various film types, composition ratios, film qualities, and film thicknesses with good reproducibility with one substrate processing device. In addition, the burden on the operator can be reduced, and the process can be started quickly while avoiding operation mistakes.

The above-mentioned recipe is not limited to the case of newly creating, and may be prepared, for example, by modifying an existing recipe already installed in the substrate processing apparatus. When changing the recipe, the changed recipe may be installed on the substrate processing apparatus via a telecommunication line or a recording medium on which the recipe is recorded. Further, the input / output device 122 included in the existing board processing device may be operated to directly change the existing recipe already installed in the board processing device.

In the above-described embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at one time has been described. The present invention is not limited to the above-described embodiment, and can be suitably applied to, for example, a case where a film is formed by using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. Further, in the above-described embodiment, an example of forming a film by using a substrate processing apparatus having a hot wall type processing furnace has been described. The present invention is not limited to the above-described embodiment, and can be suitably applied to the case where a film is formed by using a substrate processing apparatus having a cold wall type processing furnace.

Even when these substrate processing devices are used, the film can be formed under the same sequence and processing conditions as those in the above-described embodiment and modification, and the same effects as these can be obtained.

In addition, the above-described embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions at this time can be, for example, the same as the processing procedure and processing conditions of the above-described embodiment.

Various films formed by the methods of the above-described embodiments and modifications can be widely used as an insulating film, a spacer film, a mask film, a charge storage film, a stress control film and the like. In recent years, with the miniaturization of semiconductor devices, it has been required to realize more accurate film thickness control for a film formed on a wafer. The present invention, which can accurately control the film thickness of the film formed on the pattern wafer in which the high-density pattern is formed on the surface, is very useful as a technique for meeting this demand.

Hereinafter, examples will be described.

As Example 1, using the substrate processing apparatus shown in FIG. 1, the process of forming a SiOCN film on a plurality of wafers was carried out twice by the film forming sequence shown in FIG. 4 (a). In the first film forming process, all of the 100 wafers loaded on the boat were made into bare wafers. In the second film forming process, of the wafers loaded on the boat, 25 wafers on the upper side were made into pattern wafers having a surface area 10 times that of the bare wafers, and the other 75 wafers were made into bare wafers. In any film forming process, the supply time _{T B} of the TEA gas in step B per cycle, and 2-4 times the supply time _{T A} of the HCDS gas in step A per cycle, also 1 cycle and 1 to 5 times the feed time _{T C} of the _{O 2} gas per. The other processing conditions were predetermined conditions within the processing condition range described in the above-described embodiment.

As Example 2, using the substrate processing apparatus shown in FIG. 1, the process of forming a SiOCN film on a plurality of wafers was carried out twice by the film forming sequence shown in FIG. 4 (a). In the first film forming process, all of the 100 wafers loaded on the boat were made into bare wafers. In the second film forming process, of the wafers loaded on the boat, 25 wafers on the upper side were made into pattern wafers having a surface area 10 times that of the bare wafers, and the other 75 wafers were made into bare wafers. In any film forming process, the supply time of the TEA gas _{T B} in step B per cycle, and 10 to 15 times the supply time _{T A} of the HCDS gas in step A per cycle, also 1 cycle was 10-20 times the supply time _{T C} of the _{O 2} gas per. Other processing conditions were the same as those of Example 1.

As Example 3, using the substrate processing apparatus shown in FIG. 1, the process of forming a SiOCN film on a plurality of wafers was carried out twice by the film forming sequence shown in FIG. 4 (b). In the first film forming process, all of the 100 wafers loaded on the boat were made into bare wafers. In the second film forming process, of the wafers loaded on the boat, 25 wafers on the upper side were made into pattern wafers having a surface area 10 times that of the bare wafers, and the other 75 wafers were made into bare wafers. In any film forming process, a total supply time of TEA gas in step B per cycle (total feed time of each pulse), and the supply time T _B of the TEA gas in step B per cycle in Example 1 Equivalent. Other processing conditions were the same as those of Example 1.

As a comparative example, using the substrate processing apparatus shown in FIG. 1, a plurality of film formation sequences are performed in which a cycle of supplying HCDS gas to a wafer, supplying TEA gas to a wafer, and supplying O _{2 gas to a wafer at multiple times is performed.} The process of forming a SiOCN film on one wafer was carried out twice. In the first film forming process, all of the 100 wafers loaded on the boat were made into bare wafers. In the second film forming process, of the wafers loaded on the boat, 25 wafers on the upper side were made into pattern wafers having a surface area 10 times that of the bare wafers, and the other 75 wafers were made into bare wafers. In each of the film forming treatments, the supply time of TEA gas per cycle was set to be equivalent to the supply time of HCDS gas per cycle. Other processing conditions were the same as those of Example 1.

Then, in each of Examples 1 to 3 and Comparative Example, the in-plane average film thickness (AV ₁ ) of the SiOCN film formed on the bare wafer in the first film forming process and the pattern wafer in the second film forming process. The in-plane average film thickness (AV ₂ ) of the SiOCN film formed above was measured, and the degree of occurrence of the film thickness drop phenomenon was evaluated. 6 (a) to 6 (c) are diagrams showing the film thickness measurement results of the SiOCN film in Comparative Example, Example 1, and Example 3, respectively. The horizontal axis of each figure shows the in-plane average film thickness (Å), and the vertical axis shows the position of the wafer loaded on the boat (120 is the TOP side, 0 is the BOTTOM side). In the figure, ◆ indicates the in-plane average film thickness (AV ₁ ) of the SiOCN film formed on the bare wafer in the first film forming process, and ◇ indicates the surface of the SiOCN film formed on the pattern wafer in the second film forming process. The internal average film thickness (AV ₂ ) is shown respectively.

As shown in FIG. 6A, in the comparative example, the in-plane average film thickness (AV ₂ ) of the SiOCN film formed on the pattern wafer is the in-plane average film thickness (AV 2) of the SiOCN film formed on the bare wafer. _It was found that a film thickness drop phenomenon that is thinner than _{1) has occurred, and the film thickness drop rate represented by [(AV 1} −AV ₂ ) / AV ₁ ] × 100 reaches 14.9%. ..

Further, as shown in FIG. 6B, the film thickness drop rate in Example 1 was smaller than that in Comparative Example, and was found to be about 9.2%. That is, the supply time _{T B} of the TEA gas in step B per cycle, and greater than the supply time _{T A} of the HCDS gas in step A per cycle, also of _{O 2} gas in step C per cycle to be larger than the supply time T _C, it was found to be suppressed the occurrence of film thickness drop phenomenon.

Further, although not shown, the film thickness drop rate in Example 2 was smaller than that in Comparative Example and Example 1, and was found to be about 6.0%. That is, the supply time of the TEA gas _{T B} in step B per cycle, and 10 to 15 times the supply time _{T A} of the HCDS gas in step A per cycle, also, O in step C per cycle by 10 to 20 times the feed time T _C of ₂ gas was found to be significantly suppress the occurrence of thickness drop phenomenon.

Further, as shown in FIG. 6 (c), the film thickness drop rate in Example 3 was smaller than those in Comparative Example and Example 1, and was found to be about 6.0%. That is, the divided supply of TEA gas, also by a total supply time of TEA gas in step B per cycle, larger than the supply time T _A of the HCDS gas in step A per cycle, the film thickness drops It was found that the occurrence of the phenomenon can be significantly suppressed.

<Preferable Aspect of the Present Invention>
Hereinafter, preferred embodiments of the present invention will be added.

(Appendix 1)
According to one aspect of the invention
(A) A step of forming a first layer containing the main element by supplying a raw material containing a main element constituting a film to be formed to a substrate having a pattern formed on the surface.
(B) By supplying the first reactant containing carbon and nitrogen to the substrate, a substance in which a part of the first reactant is decomposed is adsorbed on the first layer, and the main element, The process of forming the second layer containing carbon and nitrogen,
A step of forming a film containing the main element, carbon, and nitrogen on the pattern is performed by performing the cycle of performing the above non-simultaneously a predetermined number of times.
In (b), a method for manufacturing a semiconductor device that supplies the first reactant until the densities of the adsorption layers of the substance formed on at least the upper surface, the side surface, and the lower surface of the pattern are equal to each other. Alternatively, a substrate processing method is provided.

(Appendix 2)
The method according to Appendix 1, preferably.
In (b), the first reactant is obtained until at least one of the nitrogen concentration and the carbon concentration of the adsorption layer of the substance formed on at least the upper surface, the side surface and the lower surface of the pattern becomes equivalent. To supply.

(Appendix 3)
The method according to Appendix 1 or 2, preferably.
The cycle further
(C) A step of oxidizing the second layer by supplying a second reactant containing oxygen to the substrate to form a third layer containing the main elements, oxygen, carbon and nitrogen. It includes performing non-simultaneously with each of the above (a) and (b).

(Appendix 4)
The method according to any one of Supplementary notes 1 to 3, preferably.
The supply time of the first reactant in the (b) per cycle is made longer than the supply time of the raw material in the (a) per cycle.

(Appendix 5)
The method according to any one of Supplementary notes 1 to 3, preferably.
The supply time of the first reactant in the above (b) per cycle is twice or more, preferably 4 times or more, more preferably 10 times or more the supply time of the raw material in the above (a) per cycle. , More preferably 15 times or more.

(Appendix 6)
The method according to any one of Supplementary Provisions 3 to 5, preferably.
The supply time of the first reactant in the (b) per cycle is made longer than the supply time of the second reactant in the (c) per cycle.

(Appendix 7)
The method according to any one of Supplementary note 3 to 6, preferably.
The supply time of the first reactant in the (b) per cycle is 1.5 times or more, preferably 3 times or more, more than the supply time of the second reactant in the (c) per cycle. It is preferably 5 times or more, more preferably 10 times or more.

(Appendix 8)
The method according to any one of Supplementary notes 1 to 7, preferably.
The supply time of the first reactant in the (b) per cycle is 20 times or less the supply time of the raw material in the (a) per cycle, or the first in the (c) per cycle. 2 The supply time of the reactants shall be 20 times or less.

(Appendix 9)
The method according to any one of Supplementary notes 1 to 8, preferably.
In the above (b) in one cycle, the first reactant is dividedly supplied.

(Appendix 10)
The method according to any one of Supplementary notes 1 to 9, preferably.
In the above (b) in one cycle, the supply of the first reactant and the purging of the space where the substrate exists are alternately repeated a plurality of times.

(Appendix 11)
The method according to Appendix 9 or 10, preferably.
The supply time of the first reactant per pulse in the (b) in one cycle is made shorter than the supply time of the raw material in the (a) per cycle.

(Appendix 12)
The method according to any one of Supplementary Notes 9 to 11, preferably.
The supply time of the first reactant per pulse in the cycle (b) is made shorter than the supply time of the second reactant in the cycle (c).

(Appendix 13)
A processing room where processing is performed on the substrate, and
A raw material supply system that supplies a raw material containing a main element constituting a film to be formed to a substrate in the processing chamber, and a raw material supply system.
A first reactant supply system that supplies a first reactant containing carbon and nitrogen to the substrate in the treatment chamber,
In the processing chamber, (a) a process of forming a first layer containing the main element by supplying the raw material to a substrate having a pattern formed on the surface, and (b) a process of forming the first layer containing the main element, and (b) the substrate. By supplying the first reactant, a substance obtained by partially decomposing the first reactant is adsorbed on the first layer to form a second layer containing the main element, carbon and nitrogen. By performing a cycle of performing the above and non-simultaneously a predetermined number of times, a process of forming a film containing the main element, carbon and nitrogen is performed on the pattern, and in the above (b), at least the upper surface and the side surface of the pattern. The raw material supply system and the first reactant supply system are controlled so as to supply the first reactant until the densities of the adsorption layers of the substance formed on the lower surface and the lower surface are equal to each other. The control unit that is configured and
A substrate processing apparatus having the above is provided.

(Appendix 14)
According to yet another aspect of the invention.
In the processing room of the substrate processing equipment
(A) A procedure for forming a first layer containing the main element by supplying a raw material containing the main element constituting the film to be formed to the substrate having a pattern formed on the surface.
(B) By supplying the first reactant containing carbon and nitrogen to the substrate, a substance in which a part of the first reactant is decomposed is adsorbed on the first layer, and the main element, The procedure for forming the second layer containing carbon and nitrogen,
A procedure for forming a film containing the main elements, carbon, and nitrogen on the pattern by performing a cycle of performing the above non-simultaneously a predetermined number of times, and
In (b), the procedure for supplying the first reactant until the densities of the adsorption layers of the substance formed on at least the upper surface, the side surface, and the lower surface of the pattern are equal to each other.
A program for causing the substrate processing apparatus to execute the program by a computer, or a computer-readable recording medium on which the program is recorded is provided.

200 wafers (board)
Top surface of 200a pattern 200b Side surface of pattern 200c Bottom surface of pattern

Claims (18)

(A) A first containing the main element and the halogen element by supplying a raw material containing the main element and the halogen element constituting the film to be formed to the substrate having the uneven structure formed on the surface. The process of forming layers and
(B) By supplying the first reactant composed of three elements of carbon, nitrogen and hydrogen to the substrate, a substance in which a part of the first reactant is decomposed is placed on the first layer. A step of adsorbing to form a second layer containing the main elements, carbon and nitrogen, and
(C) A step of oxidizing the second layer by supplying a second reactant containing oxygen to the substrate to form a third layer containing the main elements, oxygen, carbon and nitrogen. ,
A step of forming a film containing the main elements, oxygen, carbon and nitrogen on the concavo-convex structure by performing a cycle of performing the above non-simultaneously a predetermined number of times.
The supply time of the first reactant in the (b) per cycle is at least twice the supply time of the raw material in the (a) per cycle, and the supply time of the raw material (c) per cycle. ), The method for manufacturing a semiconductor device in which the supply time of the second reactant is 1.5 times or more. The method for manufacturing a semiconductor device according to claim 1, wherein the supply time of the first reactant in the (b) per cycle is four times or more the supply time of the raw material in the (a) per cycle. .. The semiconductor device according to claim 1 or 2, wherein the supply time of the first reactant in the (b) per cycle is 10 times or more the supply time of the raw material in the (a) per cycle. Production method. Any of claims 1 to 3 in which the supply time of the first reactant in the (b) per cycle is three times or more the supply time of the second reactant in the (c) per cycle. The method for manufacturing a semiconductor device according to item 1. Any of claims 1 to 4, wherein the supply time of the first reactant in the (b) per cycle is 5 times or more the supply time of the second reactant in the (c) per cycle. The method for manufacturing a semiconductor device according to item 1. The invention according to any one of claims 1 to 5, wherein the supply time of the first reactant in the (b) per cycle is 20 times or less the supply time of the raw material in the (a) per cycle. Manufacturing method of semiconductor devices. Any one of claims 1 to 6 in which the supply time of the first reactant in the (b) per cycle is 20 times or less the supply time of the second reactant in the (c) per cycle. The method for manufacturing a semiconductor device according to the item. The method for manufacturing a semiconductor device according to any one of claims 1 to 7, wherein the supply time of the first reactant in the above (b) per cycle is 100 seconds or more. The method for manufacturing a semiconductor device according to any one of claims 1 to 7, wherein the supply time of the first reactant in the above (b) per cycle is 130 seconds or more. The method for manufacturing a semiconductor device according to any one of claims 1 to 7, wherein the supply time of the first reactant in the above (b) per cycle is 150 seconds or more. The method for manufacturing a semiconductor device according to any one of claims 1 to 7, wherein the supply time of the first reactant in the above (b) per cycle is 195 seconds or more. The method for manufacturing a semiconductor device according to any one of claims 1 to 11, wherein the first reactant is dividedly supplied in the above (b) in one cycle. The semiconductor device according to any one of claims 1 to 12, wherein in (b) in one cycle, the supply of the first reactant and the purging of the space in which the substrate exists are alternately repeated a plurality of times. Production method. The semiconductor according to claim 12 or 13, wherein the supply time of the first reactant per pulse in the (b) in one cycle is shorter than the supply time of the raw material in the (a) per cycle. Manufacturing method of the device. 12.14 of claims 12 to 14, wherein the supply time of the first reactant per pulse in the (b) in one cycle is shorter than the supply time of the second reactant in the (c) per cycle. The method for manufacturing a semiconductor device according to any one of the following items. The method for manufacturing a semiconductor device according to any one of claims 1 to 15, wherein the first reactant contains an amine-based gas or an organic hydrazine-based gas. A processing room where processing is performed on the substrate, and
A raw material supply system for supplying a raw material containing a main element and a halogen element constituting a film to be formed to a substrate in the processing chamber.
A first reactant supply system that supplies a first reactant composed of three elements, carbon, nitrogen, and hydrogen, to a substrate in the treatment chamber.
A second reactant supply system that supplies a second reactant containing oxygen to the substrate in the processing chamber,
In the treatment chamber, (a) a treatment of supplying the raw material to a substrate having an uneven structure formed on the surface to form a first layer containing the main element and a halogen element, and (b). By supplying the first reactant to the substrate, a substance obtained by partially decomposing the first reactant is adsorbed on the first layer, and the second element containing the main elements, carbon and nitrogen is contained. A third layer containing the main elements, oxygen, carbon and nitrogen by oxidizing the second layer by the treatment of forming the layer and (c) supplying the second reactant to the substrate. By performing a cycle of forming the above-mentioned and non-simultaneously a predetermined number of times, a process of forming a film containing the main elements, oxygen, carbon and nitrogen is performed on the uneven structure, and the above ( The supply time of the first reactant in b) is at least twice the supply time of the raw material in the (a) per cycle, and the second reaction in the (c) per cycle. A control unit configured to control the raw material supply system, the first reactant supply system, and the second reactant supply system so as to be 1.5 times or more the supply time of the body.
Substrate processing equipment with. In the processing room of the substrate processing equipment
(A) A first containing the main element and the halogen element by supplying a raw material containing the main element and the halogen element constituting the film to be formed to the substrate having the uneven structure formed on the surface. The procedure for forming layers and
(B) By supplying the first reactant composed of three elements of carbon, nitrogen and hydrogen to the substrate, a substance in which a part of the first reactant is decomposed is placed on the first layer. A procedure for adsorbing to form a second layer containing the main elements, carbon and nitrogen, and
(C) A procedure for oxidizing the second layer by supplying a second reactant containing oxygen to the substrate to form a third layer containing the main elements, oxygen, carbon and nitrogen. ,
A procedure for forming a film containing the main elements, oxygen, carbon, and nitrogen on the uneven structure by performing a cycle of performing the above non-simultaneous times a predetermined number of times.
The supply time of the first reactant in the (b) per cycle is at least twice the supply time of the raw material in the (a) per cycle, and the supply time of the raw material (c) per cycle. ), And the procedure for increasing the supply time of the second reactant to 1.5 times or more.
A program that causes the board processing apparatus to execute the above.