JP6731527B2 - Semiconductor device manufacturing method, substrate processing apparatus, and program - Google Patents

Description

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

As one of the steps of manufacturing a semiconductor device, a process of forming a film on a substrate may be performed (see, for example, Patent Document 1).

JP, 2010-118462, A

An object of the present invention is to provide a technique capable of controlling the in-plane film thickness distribution of a film formed on a substrate.

According to one aspect of the invention,
Supplying the raw material to the substrate from the first nozzle and exhausting it from an exhaust port;
Supplying a first reactant from a second nozzle located farther from the exhaust port than the first nozzle with respect to the substrate and exhausting the exhaust gas from the exhaust port;
Supplying a second reactant from a third nozzle arranged closer to the exhaust port than the second nozzle to the substrate and exhausting the second reactant from the exhaust port;
A step of forming a film on the substrate by performing a predetermined number of cycles of non-simultaneously,
When the raw material is supplied, the flow rate of the inert gas supplied from the second nozzle, the flow rate of the inert gas supplied from the third nozzle, and the flow rate of the inert gas supplied from the first nozzle are balanced. Controlling provides a technique for controlling the in-plane film thickness distribution of the film formed on the substrate.

According to the present invention, it is possible to control the in-plane film thickness distribution of a film formed on a substrate.

FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in an embodiment of the present invention, showing a processing furnace portion in a vertical sectional view. It is a schematic block diagram of a part of vertical processing furnace of the substrate processing apparatus suitably used in the embodiment of the present invention, and is a view showing a part of the processing furnace in a sectional view taken along the line AA of FIG. 1. It is a schematic block diagram of the controller of the substrate processing apparatus suitably used in the embodiment of the present invention, and is a block diagram of the control system of the controller. It is a figure which shows the film-forming sequence of one Embodiment of this invention. It is a figure which shows the modification 1 of the film-forming sequence of one Embodiment of this invention. It is a figure which shows the modification 2 of the film-forming sequence of one Embodiment of this invention. It is a figure which shows the modification 3 of the film-forming sequence of one Embodiment of this invention. It is a figure which shows the evaluation result of the film thickness distribution in board|substrate surface of the film formed on the board|substrate. (A)-(c) is a figure which shows the evaluation result of the film thickness distribution in board|substrate surface of the film|membrane formed on the board|substrate, respectively.

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

(1) Configuration of Substrate Processing Apparatus As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjusting unit). 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 unit) that activates (excites) gas by 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 has a cylindrical shape with an upper end closed and a lower end opened. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), and has a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a as a seal member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is vertically installed like the heater 207. A processing container (reaction container) is mainly configured by the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to be capable of accommodating a plurality of wafers 200 as substrates.

A nozzle 249a serving as a first nozzle, a nozzle 249b serving as a second nozzle, and a nozzle 249c serving as a third nozzle are provided in the processing chamber 201 so as to penetrate a sidewall of the manifold 209. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively.

The gas supply pipes 232a to 232c are provided with mass flow controllers (MFCs) 241a to 241c that are flow rate controllers (flow rate control units) and valves 243a to 243c that are open/close valves in this order from the upstream side. Gas supply pipes 232d to 232f for supplying an inert gas are respectively connected to the gas supply pipes 232a to 232c on the downstream side of the valves 243a to 243c. The gas supply pipes 232d to 232f are provided with MFCs 241d to 241f and valves 243d to 243f in this order from the upstream side.

As shown in FIG. 2, the nozzles 249a to 249c are arranged in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, along the upper portion of the inner wall of the reaction tube 203 and the upper portion of the wafer 200. They are provided so as to rise upward in the loading direction. That is, the nozzles 249a to 249c are provided on the sides of the wafer arranging region where the wafers 200 are arranged, in regions horizontally surrounding the wafer arranging region and along the wafer arranging region. The nozzle 249b is arranged farther from the exhaust port 231a described later than the nozzle 249a, and the nozzle 249c is arranged closer to the exhaust port 231a than the nozzle 249b. Further, in this embodiment, the nozzles 249a and 249b are arranged so as to face each other in a straight line with the center of the wafer 200 loaded into the processing chamber 201 interposed therebetween. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are respectively opened so as to face the center of the reaction tube 203, and it is possible to supply gas toward the wafer 200. From these facts, the gas supply holes 250a and 250b face each other in a straight line across the center of the wafer 200 described above. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

From the gas supply pipe 232a, as a raw material (raw material gas), for example, a halosilane-based gas containing Si as a predetermined element (main element) and a halogen element is introduced into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a. Supplied. 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 normal pressure, a raw material in a gaseous state under normal temperature and normal pressure, and the like. Halosilane is a silane having a halogen group. The halogen group includes a chloro group, a fluoro group, a bromo group, an iodo group and the like. That is, the halogen group includes halogen elements such as chlorine (Cl), fluorine (F), bromine (Br) and iodine (I). As the halosilane-based gas, for example, a raw material gas containing Si and Cl, that is, a chlorosilane-based gas can be used. The chlorosilane-based gas acts as a Si source. 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 a first reactant (reactant) having a chemical structure (molecular structure) different from that of the raw material, for example, an amine gas containing C and N is processed through the MFC 241b, the valve 243b, and the nozzle 249b. It is supplied into the chamber 201. The amine-based gas acts as a C source and also acts as an N source. As the amine-based gas, for example, triethylamine ((C ₂ H ₅ ) ₃ N, abbreviation: TEA) gas can be used.

As the second reactant (reactant) having a chemical structure (molecular structure) different from that of the raw material, for example, an O-containing gas is supplied from the gas supply pipe 232c into the processing chamber 201 through the MFC 241c, the valve 243c, and the nozzle 249c. To be done. The O-containing gas acts as an oxidizing gas, that is, an O source. As the O-containing gas, for example, oxygen (O ₂ ) gas can be used.

From the gas supply pipes 232d to 232f, as an inert gas, for example, nitrogen (N ₂ ) gas is passed through the MFCs 241d to 241f, the valves 243d to 243f, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c, respectively. It is supplied into 201. The N ₂ gas acts as a purge gas and a carrier gas, and further acts as a film thickness distribution control gas for controlling the in-plane film thickness distribution of the film formed on the wafer 200.

A raw material supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a. The first reactant supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. Further, the second reactant supply system is mainly configured by the gas supply pipe 232c, the MFC 241c, and the valve 243c. An inert gas supply system is mainly configured by the gas supply pipes 232d to 232f, the MFCs 241d to 241f, and the valves 243d to 243f.

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

An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. An exhaust pipe 231 is connected to the exhaust port 231a. Through the exhaust pipe 231, a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator) are provided. A vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 can perform vacuum evacuation and vacuum evacuation in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, with the vacuum pump 246 operating The pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening degree based on the pressure information detected by the pressure sensor 245. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

Below the manifold 209, a seal cap 219 is provided as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal such as SUS and has a disk shape. On the upper surface of the seal cap 219, an O-ring 220b as a seal member that comes into contact with the lower end of the manifold 209 is provided. Below the seal cap 219, a rotation mechanism 267 for rotating the boat 217 described later is installed. The rotating shaft 255 of the rotating 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 moved up and down by a boat elevator 115 as an elevating mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that moves the boat 217, that is, the wafer 200 in and out of the processing chamber 201 by moving the seal cap 219 up and down. Further, below the manifold 209, there is provided a shutter 219s as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209 while the seal cap 219 is being lowered by the boat elevator 115. The shutter 219s is made of a metal such as SUS and has a disk shape. On the upper surface of the shutter 219s, an O-ring 220c as a sealing member that comes into contact with the lower end of the manifold 209 is provided. The opening/closing operation (elevating operation, rotating operation, etc.) of the shutter 219s is controlled by the shutter opening/closing mechanism 115s.

The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200 in a horizontal posture and in a vertical direction with the centers thereof aligned with each other in a vertical direction, that is, It is configured to be arranged at intervals. The boat 217 is made of a heat resistant material such as quartz or SiC. Below the boat 217, a plurality of heat insulating plates 218 made of a heat resistant material such as quartz or SiC are supported in multiple stages.

A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. The temperature inside the processing chamber 201 has a desired temperature distribution by adjusting the degree of energization to the heater 207 based on the temperature information detected by the temperature sensor 263. 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 to be able to exchange data with the CPU 121a via the internal bus 121e. An input/output device 122 configured as a touch panel or the like 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 apparatus, a process recipe in which a procedure and conditions of a film forming process, which will be described later, and the like are readablely stored. The process recipe is a combination that causes the controller 121 to execute each procedure in the film forming process described below and obtains a predetermined result, and functions as a program. Hereinafter, process recipes, control programs, and the like are collectively referred to simply as programs. In addition, the process recipe is also simply referred to as a recipe. When the word program is used in this specification, it may include only the recipe alone, the control program alone, or both of them. The RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily stored.

The I/O port 121d includes the MFCs 241a to 241f, the valves 243a to 243f, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the temperature sensor 263, the heater 207, the rotating mechanism 267, the boat elevator 115, the shutter opening/closing mechanism 115s, and the like. It is connected to the.

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. The CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241f, opens and closes the valves 243a to 243f, 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. Operation, start and stop of the vacuum pump 246, temperature adjustment operation of the heater 207 based on the temperature sensor 263, rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, up/down operation of the boat 217 by the boat elevator 115, shutter opening/closing mechanism 115s. Is configured to control the opening/closing operation of the shutter 219s.

The controller 121 installs the above program stored in an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory) 123 into a computer. It 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 this specification, it may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both of them. The program may be provided to the computer using communication means such as the Internet or a dedicated line without using the external storage device 123.

(2) Film Forming Process As an example of a semiconductor device manufacturing process using the substrate processing apparatus described above, a sequence example of forming a film on a wafer 200 as a substrate will be described with reference to FIG. In the following description, the operation of each part of the substrate processing apparatus is controlled by the controller 121.

The film forming sequence shown in FIG.
Step 1 of supplying the HCDS gas to the wafer 200 from the nozzle 249a and exhausting the HCDS gas from the exhaust port 231a;
Step 2 of supplying the TEA gas from the nozzle 249b arranged farther from the exhaust port 231a than the nozzle 249a to the wafer 200 and exhausting the TEA gas from the exhaust port 231a.
Step 3 of supplying O ₂ gas from the nozzle 249c arranged closer to the exhaust port 231a than the nozzle 249b with respect to the wafer 200 and exhausting it from the exhaust port 231a;
A film containing Si, O, C, and N, that is, a silicon oxycarbonitride film (SiOCN film) is formed on the wafer 200 by performing a cycle in which is not performed at a predetermined number of times.

Further, in the film-forming sequence shown in FIG. 4, when HCDS gas supply, and the flow rate of _{N 2} gas supplied from the nozzle 249 b, and the flow rate of _{N 2} gas supplied from the nozzle 249 c, the flow rate of _{N 2} gas supplied from the nozzle 249a By controlling the balance between and, the in-wafer film thickness distribution of the SiOCN film formed on the wafer 200 (hereinafter, also simply referred to as in-plane film thickness distribution) is controlled.

Here, as an example, when HCDS gas supply, the flow rate of _{N 2} gas supplied from the nozzle 249 b, is made larger than the flow rate of _{N 2} gas supplied from the nozzle 249a, the in-plane film thickness distribution of the SiOCN film, FIG. An example will be described in which the distribution is thickest at the central portion of the wafer 200 and gradually becomes thinner toward the peripheral portion (hereinafter, also referred to as central convex distribution), as shown on the right side of FIG. In addition, if a film with a central convex distribution can be formed on a bare wafer with a small surface area where no uneven structure is formed on the surface, it is possible to form a central pattern on a patterned wafer with a large surface area where a fine uneven structure is formed on the surface. It is possible to form a film having a flat film thickness distribution (hereinafter, also referred to as flat distribution) with a small film thickness change from the periphery to the periphery.

In this specification, the film formation sequence shown in FIG. 4 may be referred to as follows for convenience. The same notation will be used in the description of the modified examples below.

(HCDS→TEA→O ₂ )×n ⇒ SiOCN

When the film forming sequence shown in FIG. 4 is performed, a N-free film containing Si, O and C, that is, a silicon oxycarbide film (SiOC film) may be formed on the wafer 200 depending on the processing conditions. Can also Hereinafter, an example in which a bare wafer is used as the wafer 200 and a SiOCN film is formed thereon will be described, but the present invention is not limited to this example.

When the term “wafer” is used in this specification, it may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on the surface thereof. When the term "wafer surface" is used herein, 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, the description of “forming a predetermined layer on a wafer” means forming a predetermined layer directly on the surface of the wafer itself, a layer formed on the wafer, etc. It may mean that a predetermined layer is formed on. In this specification, the term “substrate” is also synonymous with the term “wafer”.

(Wafer charge and boat load)
When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter opening/closing mechanism 115s moves the shutter 219s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

(Pressure/temperature adjustment step)
The processing chamber 201 is evacuated (decompressed) by the vacuum pump 246 so that the inside of the processing chamber 201, that is, the space where the wafer 200 is present has a desired pressure (vacuum degree). At this time, the pressure inside 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 inside of the processing chamber 201 is heated by the heater 207 so that the wafer 200 in the processing chamber 201 has a desired processing temperature. At this time, the power supply to 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 of the wafer 200 by the rotation mechanism 267 is started. The exhaust of the processing chamber 201, the heating, and the rotation of the wafer 200 are all continuously performed at least until the processing on the wafer 200 is completed.

(Film forming step)
Then, the following steps 1 to 3 are sequentially executed.

[Step 1]
In this step, the HCDS gas is supplied to the wafer 200 in the processing chamber 201 and exhausted through the exhaust port 231a.

Specifically, the valve 243a is opened to flow the HCDS gas 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 port 231a. At this time, the HCDS gas is supplied to the wafer 200. At this time, the valves 243d to 243f are simultaneously opened, and the N ₂ gas is caused to flow into the gas supply pipes 232d to 232f. The flow rate of the N ₂ gas is adjusted by the MFCs 241d to 241f, is supplied into the processing chamber 201 via the nozzles 249a to 249c, and is exhausted from the exhaust port 231a.

At this time, the supply flow rate of the HCDS gas supplied from the nozzle 249a is, for example, a predetermined flow rate within the range of 1 to 2000 sccm, preferably 10 to 1000 sccm. The supply flow rate of the N ₂ gas supplied from the nozzle 249a is, for example, a predetermined flow rate within the range of 500 to 2000 sccm. The supply time of the HCDS gas is, for example, 1 to 120 seconds, and preferably a predetermined time within the range of 1 to 60 seconds. The pressure in the processing chamber 201 is, for example, a predetermined pressure within the range of 1 to 2666 Pa, preferably 67 to 1333 Pa. The temperature of the wafer 200 (film forming temperature) is, for example, a predetermined temperature in the range of 250 to 800° C., preferably 400 to 750° C., and more preferably 550 to 700° C.

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

When the film forming temperature exceeds 800° C., an excessive gas phase reaction occurs, the film thickness uniformity is likely to deteriorate, and the control thereof becomes difficult. By setting the film forming temperature to 800° C. or lower, an appropriate gas phase reaction is caused, the deterioration of the film thickness uniformity can be suppressed, and the control thereof can be performed. In particular, by setting the film forming temperature to 750° C. or lower, and further 700° C. or lower, the surface reaction becomes more dominant than the gas phase reaction, the film thickness uniformity can be easily ensured, and the control thereof can be facilitated.

By supplying the HCDS gas to the wafer 200 under the above-mentioned conditions, the first layer (initial layer), for example, from less than 1 atomic layer to several atomic layers (from less than 1 molecular layer) is provided on the outermost surface of the wafer 200. A Si-containing layer containing Cl having a thickness of several molecular layers) is formed. The Si-containing layer containing Cl may be a Si layer containing Cl, may be an HCDS adsorption layer, or may include both of them.

The Si layer containing Cl is a general term including a continuous layer formed of Si and containing Cl, a discontinuous layer, and a Si thin film containing Cl formed by overlapping these layers. Si that constitutes the Si layer containing Cl includes not only those whose bond with Cl is not completely broken but also those whose bond with Cl is completely broken.

The HCDS adsorption layer includes a discontinuous adsorption layer as well as a continuous adsorption layer composed of HCDS molecules. The HCDS molecules forming the HCDS adsorption layer include those in which the bond between Si and Cl is partially broken. That is, the adsorption layer of HCDS may be a physical adsorption layer of HCDS, a chemical adsorption layer of HCDS, or both of them.

Here, a layer having a thickness less than one atomic layer (molecular layer) means an atomic layer (molecular layer) formed discontinuously, and a layer having a thickness of one atomic layer (molecular layer). Means an atomic layer (molecular layer) formed continuously. The Si-containing layer containing Cl may include both a Si layer containing Cl and an adsorption layer of HCDS. However, for convenience, the Si-containing layer containing Cl will be expressed by using expressions such as “one atomic layer” and “several atomic layers”, and “atomic layer” may be used synonymously with “molecular layer”.

Under the condition that the HCDS gas self-decomposes (thermally decomposes), Si is deposited on the wafer 200 to form a Si layer containing Cl. Under the condition that the HCDS gas does not undergo self-decomposition (thermal decomposition), HCDS is adsorbed on the wafer 200 to form an HCDS adsorption layer. It is preferable to form the Si layer containing Cl on the wafer 200 rather than forming the HCDS adsorption layer on the wafer 200 because the film formation rate can be increased. Hereinafter, the Si-containing layer containing Cl is simply referred to as a Si-containing layer for convenience.

When the thickness of the first layer exceeds several atomic layers, the modification action in steps 2 and 3 described later cannot reach the entire first layer. Moreover, the minimum value of the thickness of the first layer is less than one atomic layer. Therefore, the thickness of the first layer is preferably less than one atomic layer to several atomic layers. By setting the thickness of the first layer to be 1 atomic layer or less, that is, 1 atomic layer or less than 1 atomic layer, the action of modification in steps 2 and 3 described later can be relatively enhanced. , 3 can be shortened. The time required to form the first layer in step 1 can also be shortened. As a result, the processing time per cycle can be shortened, and the total processing time can also be shortened. That is, it is possible to increase the film forming rate. Further, by controlling the thickness of the first layer to be one atomic layer or less, it becomes possible to enhance the controllability of the film thickness uniformity.

In the present embodiment, the flow rate of the N ₂ gas supplied from the nozzle 249b is made higher than the flow rate of the N ₂ gas supplied from the nozzle 249a when the HCDS gas is supplied.

By setting the flow rate balance of the N ₂ gas supplied from the nozzles 249b and 249a in this way, an annular space between the inner wall of the reaction tube 203 and the wafer 200 (hereinafter, simply referred to as “an annular space”). (Also referred to as “”) can be greater than the pressure in the wafer array region, that is, the pressure in the space between the wafers 200. As a result, it is possible to suppress the outflow of the HCDS gas into the annular space, promote the supply of the HCDS gas to the space between the wafers 200, and increase the supply amount of the HCDS gas to the central portion of the wafers 200. It will be possible. It is also possible to reduce the partial pressure (concentration) of the HCDS gas in the annular space and reduce the supply amount of the HCDS gas to the peripheral portion of the wafer 200. As a result, the thickness distribution of the first layer in the plane of the wafer 200, and further, the in-plane thickness distribution of the SiOCN film formed on the wafer 200, can be the central convex distribution described above. Hereinafter, such film thickness distribution control is also referred to as central convex distribution control.

Note that this effect becomes stronger as the flow rate of the N ₂ gas supplied from the nozzle 249b is increased. For example, by setting the flow rate of the N ₂ gas supplied from the nozzle 249b to be greater than the total flow rate of the HCDS gas supplied from the nozzle 249a and the flow rate of the N ₂ gas, the central convex distribution described above is reliably realized. It becomes possible. Further, this effect becomes stronger as the position of the nozzle 249b is moved away from the position of the exhaust port 231a, and becomes maximum when the nozzle 249b and the exhaust port 231a face each other across the center of the wafer 200 in a straight line. Note that this effect is more effectively obtained as the position of the nozzle 249b is farther from the position of the nozzle 249a. For example, as shown in FIG. 2, the nozzle 249b faces the nozzle 249a with the center of the wafer 200 interposed therebetween. It is possible to obtain it more effectively when arranging in.

In the film formation sequence shown in FIG. 4, when HCDS gas supply, not only from the nozzle 249 b, from the nozzles 249 c, supplying a _{N 2} gas at high flow rate than the flow rate of _{N 2} gas supplied from the nozzle 249a. This can further increase the pressure in the annular space. Further, by supplying N ₂ gas at a large flow rate from a plurality of different locations in the circumferential direction using a plurality of nozzles, it is possible to more uniformly increase the pressure in the annular space described above in the circumferential direction. Become. As a result, it becomes easier to realize the above-described central convex distribution. Figure 4 is a flow rate of _{N 2} gas supplied from the nozzle 249 b, and the flow rate of _{N 2} gas supplied from the nozzle 249 c, a shows an example of equivalent.

However, as described above, the nozzle 249c is arranged closer to the exhaust port 231a than the nozzle 249b. The N ₂ gas supplied from the nozzle 249c has a shorter residence time in the processing chamber 201 than the N ₂ gas supplied from the nozzle 249b, and most of it is exhausted from the exhaust port 231a in a short time. _{N 2} gas supplied from the nozzle 249c is compared with the _{N 2} gas supplied from the nozzle 249 b, influence on the in-plane film thickness distribution of the film formed on the wafer 200 can be said to be weak. In other words, better to the flow rate of N ₂ gas and N ₂ gas at a flow rate or flow rate supplied from the nozzle 249c for supplying the nozzle 249b is than to reverse these flow magnitude relationship between the central convex distribution described above It also means that control can be realized efficiently. The flow rate of N ₂ gas supplied from the nozzle 249 b, or N ₂ equivalent to the flow rate of the gas supplied from the nozzle 249 c, or to be at increased, the same central convex distribution control, in the consumption of less N ₂ gas It is possible to realize at low cost. When the HCDS gas is supplied, the N ₂ gas is not supplied from the nozzle 249b, and the flow rate of the N ₂ gas supplied from the nozzle 249c is set to a very large flow rate, so that the above central convex distribution control cannot be realized. , Theoretically possible. However, considering that most of the N ₂ gas supplied from the nozzle 249c is exhausted from the exhaust port 231a immediately before it contributes to the above-described in-plane film thickness distribution control, the central convex distribution of this alternative method is used. It can be said that trying to increase the degree (increasing the film thickness difference between the central portion and the peripheral portion) is extremely expensive as compared with the method of the present embodiment, and lacks in reality.

When setting the flow balance of N ₂ gas as in this embodiment, the flow rate of _{N 2} gas supplied from the nozzle 249b at HCDS supply is larger than the flow rate of _{N 2} gas supplied from the nozzle 249b at HCDS not supplied .. For example, the flow rate of the N ₂ gas supplied from the nozzle 249b at the time of supplying the HCDS is higher than the flow rate of the N ₂ gas supplied from the nozzle 249b at the time of supplying the TEA gas in step 2, and the nozzle is supplied at the time of supplying the O ₂ gas in step 3. It becomes larger than the flow rate of N ₂ gas supplied from 249b. As will be described later, in each of Steps 1 to 3, the HCDS gas, the TEA gas, and the O ₂ gas are exhausted from the inside of the processing chamber 201, and the purge step of supplying N ₂ gas as the purge gas into the processing chamber 201 is performed. I do. When setting the flow balance of N ₂ gas as described above, the flow rate of _{N 2} gas supplied from the nozzle 249b at HCDS supplied, _{N 2} gas supplied from the nozzle 249b during purging of the process chamber 201, i.e., as a purge gas Is larger than the flow rate of N ₂ gas.

The flow rates of the N ₂ gas supplied from the nozzles 249b and 249c satisfy the above-mentioned flow rate balance, and are predetermined flow rates in the range of 3000 to 6000 sccm, respectively.

After the first layer is formed, the valve 243a is closed and the supply of HCDS gas is stopped. At this time, with the APC valve 244 kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the unreacted HCDS gas remaining in the processing chamber 201 or contributing to the formation of the first layer is treated with HCDS gas. Eliminate from within 201. At this time, the valves 243d to 243f are kept open and N ₂ gas as a purge gas is supplied into the processing chamber 201 (purge step). The supply flow rate of the N ₂ gas supplied from each gas supply pipe is, for example, within a range of 500 to 2000 sccm.

[Step 2]
After step 1 is completed, the TEA gas is supplied to the wafer 200 in the processing chamber 201, that is, the first layer formed on the wafer 200, and is exhausted from the exhaust port 231a.

In this step, the opening/closing control of the valves 243b and 243d to 243f is performed in the same procedure as the opening/closing control of the valves 243a and 243d to 243f in step 1. The flow rate of the TEA gas is adjusted by the MFC 241b, is supplied into the processing chamber 201 through the nozzle 249b, and is exhausted from the exhaust pipe 231. At this time, the TEA gas is supplied to the wafer 200.

The supply flow rate of the TEA gas is, for example, a predetermined flow rate within the range of 200 to 10,000 sccm. The supply time of the TEA gas is, for example, 1 to 120 seconds, and preferably a predetermined time within the range of 1 to 60 seconds. The supply flow rate of the N ₂ gas supplied from each gas supply pipe is, for example, a predetermined flow rate within the range of 500 to 2000 sccm. The pressure in the processing chamber 201 is set to a predetermined pressure within the range of, for example, 1 to 5000 Pa, preferably 1 to 4000 Pa. By setting the pressure in the processing chamber 201 to such a relatively high pressure band, it becomes possible to thermally activate the TEA gas in a non-plasma manner. When the TEA gas is activated by heat and supplied, a relatively soft reaction can be caused and the formation of the second layer described later becomes easy. The other processing conditions are the same as those in step 1.

By supplying the TEA gas to the wafer 200 under the above-described conditions, the first layer formed on the wafer 200 in step 1 can be reacted with the TEA gas. As a result, at least a part of the 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 converted to TEA. It can be separated from the gas. Then, N of TEA gas in which at least a part of ethyl groups are separated and Si contained in the first layer can be bonded to each other to form a Si—N bond. It is also possible to form a Si—C bond by combining C contained in the ethyl group separated from the TEA gas and Si contained in the first layer. As a result, Cl is desorbed from the first layer, and C component and N component are newly taken into the first layer. In this way, by modifying the first layer, a layer containing Si, C, and N, that is, a silicon carbonitride layer (SiCN layer) is formed as the second layer on the wafer 200.

When the second layer is formed, Cl contained in the first layer and H contained in the TEA gas are at least one of Cl and H in the process of the reforming reaction of the first layer by the TEA gas. And is discharged from the processing chamber 201 through the exhaust pipe 231. That is, impurities such as Cl in the first layer are separated from the first layer by being extracted or desorbed from the first layer. As a result, the second layer becomes a layer containing less impurities such as Cl than the first layer.

After the second layer is formed, the valve 243b is closed and the supply of TEA gas is stopped. Then, the TEA gas and reaction by-products remaining in the processing chamber 201 after contributing to the formation of the second layer are treated from the inside of the processing chamber 201 by the same processing procedure and processing conditions as the purging step of step 1. Exclude.

[Step 3]
After step 2 is completed, O ₂ gas is supplied to the wafer 200 in the processing chamber 201, that is, the second layer formed on the wafer 200, and exhausted from the exhaust port 231a.

In this step, the opening/closing control of the valves 243c, 243d to 243f is performed in the same procedure as the opening/closing control of the valves 243a, 243d to 243f in step 1. The flow rate of the O ₂ gas is adjusted by the MFC 241c, is supplied into the processing chamber 201 through the nozzle 249c, and is exhausted from the exhaust pipe 231. At this time, O ₂ gas is supplied to the wafer 200.

The supply flow rate of the O ₂ gas is, for example, a predetermined flow rate within the range of 100 to 10,000 sccm. The supply time of the O ₂ gas is, for example, a predetermined time within a range of 1 to 120 seconds, preferably 1 to 60 seconds. The supply flow rate of the N ₂ gas supplied from each gas supply pipe is, for example, a predetermined flow rate within the range of 500 to 2000 sccm. The pressure in the processing chamber 201 is, for example, a predetermined pressure within the range of 1 to 4000 Pa, preferably 1 to 3000 Pa. By setting the pressure in the processing chamber 201 to such a relatively high pressure band, it becomes possible to thermally activate the O ₂ gas by non-plasma. When the O ₂ gas is activated by heat and supplied, a relatively soft reaction can be caused and the formation of the third layer described later becomes easy. The other processing conditions are, for example, the same processing conditions as in step 1.

By supplying O ₂ gas to the wafer 200 under the above-described conditions, at least a part of the second layer can be modified (oxidized). 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 layer containing Si, O, C, and N, that is, a silicon oxycarbonitride layer (SiOCN layer) is formed as a third layer on the wafer 200. When forming the third layer, at least a part of the C component and the N component contained in the second layer is maintained in the second layer without being detached from the second layer.

When forming the third layer, Cl contained in the second layer constitutes a gaseous substance containing at least Cl in the process of the reforming reaction with O ₂ gas and is discharged from the inside of the processing chamber 201. That is, impurities such as Cl in the second layer are separated from the second layer by being extracted or desorbed from the second layer. As a result, the third layer becomes a layer containing less impurities such as Cl than the second layer.

After the third layer is formed, the valve 243c is closed and the supply of O ₂ gas is stopped. Then, according to the same processing procedure and processing conditions as those in the purging step of Step 1, the O ₂ gas and the reaction by-product remaining in the processing chamber 201 after contributing to the formation of the unreacted or third layer are processed in the processing chamber 201. Eliminate from.

[Performed a predetermined number of times]
By performing Steps 1 to 3 non-simultaneously, that is, performing the cycle without synchronization at least once (n times), a SiOCN film having a predetermined composition and a predetermined film thickness can be formed on the wafer 200. The above cycle is preferably repeated multiple times. That is, the thickness of the third layer formed per cycle is made smaller than the desired film thickness, and the SiOCN film formed by stacking the third layers reaches the desired film thickness until It is preferred to repeat the above cycle multiple times.

As a raw material, in addition to HCDS gas, monochlorosilane (SiH ₃ Cl, abbreviation: MCS) gas, dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS), trichlorosilane (SiHCl ₃ , abbreviation: TCS) gas, tetrachlorosilane ( A chlorosilane source gas such as SiCl ₄ , an abbreviation: STC gas, or octachlorotrisilane (Si ₃ Cl ₈ , an abbreviation: OCTS) gas can be used.

As the first reactant, in addition to TEA gas, for example, ethylamine-based gases such as diethylamine ((C ₂ H ₅ ) ₂ NH, abbreviated as DEA) gas and monoethylamine (C ₂ H ₅ NH ₂ , abbreviated as MEA) gas Methyl such as gas, trimethylamine ((CH ₃ ) ₃ N, abbreviated: TMeA) gas, dimethylamine ((CH ₃ ) ₂ NH, abbreviated: DMeA) gas, monomethylamine (CH ₃ NH ₂ , abbreviated: MMeA) gas An amine gas or the like can be used. In addition, as the first reactant, an organic hydrazine-based gas such as trimethylhydrazine ((CH ₃ ) ₂ N ₂ (CH ₃ )H, abbreviation: TMH) gas can also be used.

As the second reactant, in addition to O ₂ gas, water vapor (H ₂ O gas), nitric oxide (NO) gas, nitrous oxide (N ₂ O) gas, nitrogen dioxide (NO ₂ ) gas, carbon monoxide O-containing gas such as (CO) gas, carbon dioxide (CO ₂ ) gas, ozone (O ₃ ) gas, plasma-excited O ₂ (O ₂ ^* ) gas, H ₂ gas+O ₂ gas, and H ₂ gas+O ₃ gas Gas can be used.

As the inert gas, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas can be used in addition to N ₂ gas.

(Afterpurge and return to atmospheric pressure)
After the film having the desired composition and the desired film thickness is formed on the wafer 200, the valves 243a to 243c are closed and the supply of the raw material and the reactant into the processing chamber 201 is stopped. Further, N ₂ gas as a purge gas is supplied into the processing chamber 201 from each of the gas supply pipes 232d to 232f and exhausted from the exhaust pipe 231. As a result, the inside of the processing chamber 201 is purged, and the gas and reaction by-products remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (after-purging). After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

(Boat unload and wafer discharge)
Thereafter, the seal cap 219 is lowered by the boat elevator 115, the lower end of the manifold 209 is opened, and the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217. (Boat unload). After the boat is unloaded, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). The processed wafer 200 is carried out of the reaction tube 203 and then taken out of the boat 217 (wafer discharge).

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

(A) when HCDS gas supply, SiOCN the flow rate of _{N 2} gas supplied from the nozzle 249 b, is made larger than the flow rate of _{N 2} gas supplied from the nozzle 249a, which is formed on the wafer 200 that is configured as a bare wafer It is possible to make the in-plane film thickness distribution of the film a central convex distribution. As a result, when a patterned wafer is used as the wafer 200, it is possible to form a SiOCN film having a flat distribution on the wafer 200. In addition, by setting the flow rate of the N ₂ gas supplied from the nozzle 249b to be larger than the total flow rate of the HCDS gas and the N ₂ gas supplied from the nozzle 249a, the central convex distribution described above can be realized more reliably. become able to.

It is considered that the in-plane film thickness distribution of the film formed on the wafer 200 depends on the surface area of the wafer 200 due to the so-called loading effect. As the surface area of the wafer 200 to be formed becomes larger, the raw material such as the HCDS gas is consumed in a larger amount in the peripheral portion of the wafer 200, and it becomes difficult to reach the central portion thereof. In this case, the film thickness distribution of the film formed on the wafer 200 is a distribution in which the peripheral portion of the wafer 200 is thickest and gradually becomes thinner toward the center (hereinafter, also referred to as central concave distribution).

According to the present embodiment, even when a pattern wafer having a large surface area is used as the wafer 200, by setting the flow rate balance of the N ₂ gas supplied from the nozzles 249b and 249a as described above, It is possible to freely control the in-plane film thickness distribution of the formed film, such as correcting from the central concave distribution to the flat distribution, and further correcting the central convex distribution.

(B) When the HCDS gas is supplied, the flow rate of the N ₂ gas supplied from the nozzle 249c is made higher than the flow rate of the N ₂ gas supplied from the nozzle 249a, so that the central convex distribution described above can be realized more reliably. Become.

The flow rate of _{N 2} gas supplied from (c) a nozzle 249 b, by the _{N 2} gas flow rate or flow rate supplied from the nozzle 249 c, the film thickness distribution control described above, efficient, i.e., less _{N 2} It can be realized at low cost with gas consumption. This is because, as described above, the nozzle 249b is located farther from the exhaust port 231a than the nozzle 249c.

(D) When controlling the in-plane film thickness distribution of the SiOCN film, it is not necessary to provide a new nozzle in addition to the nozzles 249a to 249c, and the existing nozzles 249b used for supplying the TEA gas and the O ₂ gas, Since 249c can be diverted, it is possible to avoid an increase in manufacturing cost and maintenance cost of the substrate processing apparatus.

(E) The above effect is obtained when using a source gas other than HCDS gas, when using a gas containing C and N other than TEA gas, when using an oxidizing gas other than O ₂ gas, or when using a gas other than N ₂ gas. The same can be obtained when the above inert gas is used.

(4) Modified Example The film forming step in the present embodiment can be modified as in the modified example described below.

(Modification 1)
As shown in FIG. 5, when the HCDS gas supply, the flow rate of _{N 2} gas supplied from the nozzle 249 b, in a state of being larger than the flow rate of _{N 2} gas supplied from the nozzle 249a, the _{N 2} gas supplied from the nozzle 249c The flow rate may be less than or equal to the flow rate of the N ₂ gas supplied from the nozzle 249a. FIG. 5 shows an example in which the flow rate of the N ₂ gas supplied from the nozzle 249c is made equal to the flow rate of the N ₂ gas supplied from the nozzle 249a. In this case, the degree of the central convex distribution of the SiOCN film formed on the wafer 200 is reduced in a direction that is softer than that in the film forming sequence shown in FIG. 4, that is, the in-plane film thickness distribution of the SiOCN film is changed from the central convex distribution. It is possible to control in a direction that approaches a flat distribution. When a patterned wafer having a relatively small surface area (however, the surface area is larger than that of a bare wafer) is used as the wafer 200, by adopting the film forming sequence of this modification, the wafer 200 has a flat distribution. It becomes possible to form a SiOCN film. In order to suppress the invasion of the HCDS gas into the nozzle 249c, for example, the N ₂ gas supplied from the nozzle 249a may be supplied without necessitating the supply of the N ₂ gas from the nozzle 249c when the HCDS gas is supplied. It is preferable to carry out under the same flow rate condition as the flow rate.

(Modification 2)
When supplying the HCDS gas, the flow rate of the N ₂ gas supplied from the nozzle 249c is set to be higher than the flow rate of the N ₂ gas supplied from the nozzle 249a, and the flow rate of the N ₂ gas supplied from the nozzle 249b is supplied from the nozzle 249c. It may be smaller than the flow rate of N ₂ gas. In this case, the degree of the central convex distribution of the SiOCN film formed on the wafer 200 is softened in the direction in which it is softened as compared with the case of the modified example 1, that is, the in-plane film thickness distribution of the SiOCN film is made closer to the flat distribution. It becomes possible to control.

In this case, as shown in FIG. 6, the flow rate of _{N 2} gas supplied from the nozzle 249 b, by the _{N 2} gas at a flow rate less supplied from the nozzle 249a, further flat distribution in-plane film thickness distribution of the SiOCN film It becomes possible to control in the direction of approaching. When a patterned wafer having a surface area that is substantially the same as or slightly larger than that of the bare wafer is used as the wafer 200, the film formation sequence according to the present modification is adopted to obtain a flat distribution on the wafer 200. It becomes possible to form the SiOCN film which has. In order to suppress the invasion of the HCDS gas into the nozzle 249b, for example, the N ₂ gas supplied from the nozzle 249a may be supplied without supplying the N ₂ gas from the nozzle 249b when the HCDS gas is supplied. It is preferable to carry out under the same flow rate condition as the flow rate.

In this modification, when HCDS gas supply, the flow rate of _{N 2} gas supplied from the nozzle 249 c, to be larger than the total flow rate of the flow rate of the flow rate and _{N 2} gas HCDS gas supplied from the nozzle 249a, The in-plane film thickness distribution of the SiOCN film can be more surely set to a flat distribution instead of the central concave distribution.

When setting the flow balance of N ₂ gas as in this modification, the flow rate of _{N 2} gas supplied from the nozzle 249c at HCDS supply is larger than the flow rate of _{N 2} gas supplied from the nozzle 249c at HCDS not supplied .. For example, the flow rate of the N ₂ gas supplied from the nozzle 249c at the time of supplying the HCDS is higher than the flow rate of the N ₂ gas supplied from the nozzle 249c at the time of supplying the TEA gas in Step 2, and the nozzle flow rate at the time of supplying the O ₂ gas in Step 3 is increased. It becomes larger than the flow rate of N ₂ gas supplied from 249c. Also, when setting the flow rate balance of _{N 2} gas as described above, the flow rate of _{N 2} gas supplied from the nozzle 249c at HCDS supply, than the flow rate of _{N 2} gas supplied from the nozzle 249c at purging the process chamber 201 Also grows.

(Modification 3)
As shown in FIG. 7, when the HCDS gas is supplied, the flow rate of the N ₂ gas supplied from each of the nozzles 249b and 249c may be equal to the flow rate of the N ₂ gas supplied from the nozzle 249a. In this case, the film thickness distribution of the SiOCN film formed on the wafer 200 can be made closer to the central concave distribution from the flat distribution.

(Modification 4)
As a raw material, for example, an alkylhalosilane raw material gas such as 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH ₃ ) ₂ Si ₂ Cl ₄ , abbreviated as TCDMDS) gas, or trisdimethyl. aminosilane _{(Si [N (CH 3)} 2] 3 H, abbreviation: 3DMAS) gas or bis (diethylamino) silane _{(SiH 2 [N (C 2} H 5) 2] 2, abbreviated: BDEAS) aminosilane material, such as a gas Gas may be used. A silane source gas such as monosilane (SiH ₄ ) gas or disilane (Si ₂ H ₆ ) gas may be used.

Further, as the reactant, for example, a C-containing gas such as propylene (C ₃ H ₆ ) gas or an N-containing gas (nitriding agent) such as ammonia (NH ₃ ) gas may be used. Further, O ₃ gas or O ₂ ^* gas may be used as the oxidizing agent.

Then, for example, by the following film formation sequence, a SiOCN film, a SiOC film, a silicon oxynitride film (SiON film), a silicon carbonitride film (SiCN film), a silicon nitride film (SiN film), a silicon oxide film is formed on the wafer 200. (SiO film) may be formed.

(HCDS→TEA→O ₂ )×n ⇒ SiOC(N)
(HCDS→C ₃ H ₆ →O ₂ →NH ₃ )×n ⇒ SiOCN
(HCDS→C ₃ H ₆ →NH ₃ →O ₂ )×n ⇒ SiOCN
(C ₃ H ₆ →HCDS→C ₃ H ₆ →O ₂ →NH ₃ )×n ⇒ SiOCN
(C ₃ H ₆ →HCDS →C ₃ H ₆ →NH ₃ →O ₂ )×n ⇒ SiOCN
(TCDMDS→NH ₃ →O ₂ )×n ⇒ SiOCN
(HCDS→NH ₃ →O ₂ )×n ⇒ SiON
(HCDS→C ₃ H ₆ →NH ₃ )×n ⇒ SiCN
(TCDMDS→NH ₃ )×n ⇒ SiCN
(HCDS→TEA)×n ⇒ SiCN
(HCDS→NH ₃ )×n ⇒ SiN
(3DMAS→O ₃ )×n ⇒ SiO
(BDEAS→O ₂ ^* )×n ⇒ SiO

Also in these film forming sequences, by controlling the flow rate balance of the N ₂ gas supplied from the nozzles 249a to 249c at the time of supplying the raw material in the same manner as in the film forming sequence shown in FIG. The same effect as can be obtained. Note that the C ₃ H ₆ gas can be supplied from, for example, the nozzle 249a, and the NH ₃ gas can be supplied from, for example, the nozzle 249b. The processing procedure and the processing conditions for supplying the raw materials and the reactants can be the same as those of the film forming sequence shown in FIG.

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

In the above-described embodiment, the example in which the HCDS gas, the TEA gas, and the O ₂ gas are supplied from the nozzles 249a to 249c has been described, but the present invention is not limited to such an aspect. For example, the nozzle 249A～249c, HCDS gas, _{O 2} gas, may be supplied TEA gas, respectively, TEA gas, _{O 2} gas may be supplied respectively HCDS gas, _{O 2} gas, TEA gas, HCDS Each gas may be supplied. Even in these cases, by controlling the flow rate balance of the N ₂ gas supplied from the nozzles 249a to 249c at the time of supplying the HCDS gas in the same manner as in the film forming sequence shown in FIG. The same effects as these can be obtained.

In the above-described embodiment, an example in which the flow rate balance of the N ₂ gas supplied from the nozzles 249a to 249c is controlled when the HCDS gas is supplied has been described, but the present invention is not limited to such an aspect. For example, the above-described flow rate balance control of the N ₂ gas may be performed when the TEA gas is supplied instead of when the HCDS gas is supplied. In this case, it is possible to control the N concentration distribution and the C concentration distribution of the film formed on the wafer 200 within the surface of the wafer 200. Further, for example, the control of the flow rate balance of the N ₂ gas may be performed when the O ₂ gas is supplied. In this case, it is possible to control the O concentration distribution of the film formed on the wafer 200 within the surface of the wafer 200. The control of the flow rate balance of the N ₂ gas at the time of supplying the TEA gas or the O ₂ gas can be performed under the same processing conditions and processing procedures as those of the film forming sequence shown in FIG.

In the above embodiment, an example of forming a film containing Si as a main element on the substrate has been described, but the present invention is not limited to such an aspect. That is, the present invention can be suitably applied to the case where a film containing a metalloid element such as germanium (Ge) or boron (B) as a main element in addition to Si is formed on the substrate. Further, the present invention provides titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), yttrium (Y), lanthanum (La). It can also be suitably applied to the case where a film containing a metal element such as strontium (Sr) or aluminum (Al) as a main element is formed on a substrate.

For example, titanium tetrachloride (TiCl ₄ ) gas or trimethylaluminum (Al(CH ₃ ) ₃ , abbreviated as TMA) gas is used as a raw material, and a titanium oxycarbonitride film ( TiOCN film), titanium oxycarbide film (TiOC film), titanium oxynitride film (TiON film), titanium aluminum carbonitride film (TiAlCN film), titanium aluminum carbide film (TiAlC film), titanium nitride film (TiN film), titanium The present invention can be preferably used also when forming an oxide film (TiO film).

(TiCl ₄ →TEA→O ₂ )×n ⇒ TiOC(N)
(TiCl ₄ →NH ₃ →O ₂ )×n ⇒ TiON
(TiCl ₄ →TMA→NH ₃ )×n ⇒ TiAlCN
(TiCl ₄ →TMA)×n ⇒ TiAlC
(TiCl ₄ →TEA)×n ⇒ TiCN
(TiCl ₄ →NH ₃ )×n ⇒ TiN
(TiCl ₄ →H ₂ O)×n ⇒ TiO

It is preferable that the recipe used for the substrate processing is individually prepared according to the processing content and stored in the storage device 121c via the telecommunication line or the external storage device 123. Then, when starting the processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from a 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 of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility with one substrate processing apparatus. Further, the burden on the operator can be reduced, and the processing can be started promptly while avoiding an operation error.

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

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

Even when these substrate processing apparatuses are used, film formation can be performed under the same sequence and processing conditions as those of the above-described embodiment and modification, and the same effects as these can be obtained.

Further, the above-described embodiments and modified examples can be appropriately combined and used. The processing procedure and processing condition at this time can be the same as the processing procedure and processing condition of the above-described embodiment, for example.

Since the SiOCN film and the like formed by the methods of the above-described embodiment and modification have both a low dielectric constant and a high etching resistance, they are replaced with an insulating film, a spacer film, a mask film, a charge film, and a conventional SiO film or a SiN film. It can be widely used as a storage film, a stress control film, and the like. In recent years, with the miniaturization of semiconductor devices, demands for in-plane film thickness uniformity on films formed on a wafer have become strict. The present invention capable of forming a film having a flat distribution on a patterned wafer having a high-density pattern formed on its surface is considered to be very useful as a technique for responding to this demand.

Hereinafter, experimental results that support the effects obtained in the above-described embodiment will be described.

(Example 1)
Using the substrate processing apparatus shown in FIG. 1, HCDS gas to the wafer, TEA gas, O ₂ gas by a deposition sequence for a predetermined number of times the cycle is supplied to the non-simultaneously in this order, SiOCN film on the wafer is formed sample 1-3 were produced. A bare wafer having no uneven structure formed on its surface was used as the wafer. When producing the sample 1, the supply flow rates of the N ₂ gas from the second and third nozzles at the time of supplying the HCDS gas were set to flow rates in the range of 2500 to 3500 sccm. When producing the sample 2, the supply flow rates of the N ₂ gas from the second and third nozzles at the time of supplying the HCDS gas were set to flow rates in the range of 1000 to 2000 sccm, respectively. When producing the sample 3, the supply flow rates of the N ₂ gas from the second and third nozzles at the time of supplying the HCDS gas were set to flow rates in the range of 400 to 600 sccm, respectively. In any case, the supply flow rate of the N ₂ gas from the first nozzle at the time of supplying the HCDS gas was set to a flow rate within the range of 400 to 600 sccm. The other processing conditions were the same as the processing conditions in the above embodiment.

Then, the in-plane film thickness distributions of the SiOCN films of Samples 1 to 3 were measured. FIG. 8 shows the measurement result. The vertical axis of FIG. 8 represents the film thickness [Å], and the horizontal axis represents the distance [mm] from the center of the wafer at the measurement position. The horizontal axis of 0 [mm] means the center of the wafer. In the figure, □, ●, and Δ marks show the evaluation results of Samples 1 to 3, respectively. According to FIG. 8, as the supply flow rate of the N ₂ gas from the second and third nozzles at the time of supplying the HCDS gas is increased, the in-plane film thickness distribution of the SiOCN film approaches from the flat distribution to the central convex distribution, and the degree thereof It can be seen that

(Example 2)
Using the substrate processing apparatus shown in FIG. 1, a cycle in which HCDS gas, C ₃ H ₆ gas, NH ₃ gas, and O ₂ gas are non-simultaneously supplied to the wafer in this order for a predetermined number of times is used to form a film formation sequence on the wafer. Samples 4 to 6 having the SiOCN film formed were prepared. A bare wafer having no uneven structure formed on its surface was used as the wafer. When producing the sample 4, the supply flow rate of the N ₂ gas from the second nozzle at the time of supplying the HCDS gas is set to a flow rate within the range of 5000 to 7000 sccm, and the supply flow rate of the N ₂ gas from the third nozzle is set to 400 to 600 sccm. The flow rate was within the range. When producing the sample 5, the supply flow rate of the N ₂ gas from the second nozzle at the time of supplying the HCDS gas is set to a flow rate within the range of 400 to 600 sccm, and the supply flow rate of the N ₂ gas from the third nozzle is set to the range of 5000 to 7000 sccm. The flow rate was within the range. When producing the sample 6, the supply flow rates of the N ₂ gas from the second and third nozzles at the time of supplying the HCDS gas were set to flow rates in the range of 400 to 600 sccm. In any case, the supply flow rate of the N ₂ gas from the first nozzle at the time of supplying the HCDS gas was set to a flow rate within the range of 400 to 600 sccm. The other processing conditions were the same as the processing conditions in the above embodiment.

Then, the in-plane film thickness distributions of the SiOCN films of Samples 4 to 6 were measured. 9A to 9C show the measurement results of Samples 4 to 6, respectively. In these figures, the vertical axis represents the film thickness [Å], and the horizontal axis represents the distance [mm] from the center of the wafer at the measurement position.

According to FIG. 9A, at the time of supplying the HCDS gas, the flow rate of the N ₂ gas supplied from the second nozzle is set to be larger than the flow rate of the N ₂ gas supplied from the first nozzle, and the N ₂ gas supplied from the third nozzle is supplied. _It can be seen that in the sample 4 produced by making the flow rate of the ₂ gas equal to the flow rate of the N ₂ gas supplied from the first nozzle, the in-plane film thickness distribution of the SiOCN film has a central convex distribution.

According to FIG. 9 (b), when HCDS gas supply, the flow rate of _{N 2} gas supplied from the second nozzle, and equal to the flow rate of _{N 2} gas supplied from the first nozzle supplies from the third nozzle _{N 2} It can be seen that in the sample 5 manufactured by making the gas flow rate higher than the N ₂ gas flow rate supplied from the first nozzle, the in-plane film thickness distribution of the SiOCN film is a flat distribution.

According to FIG. 9C, when the HCDS gas is supplied, the flow rate of the N ₂ gas supplied from each of the second nozzle and the third nozzle is made equal to the flow rate of the N ₂ gas supplied from the first nozzle. It can be seen that in the manufactured sample 6, the in-plane film thickness distribution of the SiOCN film has a central concave distribution.

<Preferred embodiment of the present invention>
Hereinafter, the preferred embodiments of the present invention will be additionally described.

(Appendix 1)
According to one aspect of the invention,
Supplying the raw material to the substrate from the first nozzle and exhausting it from an exhaust port;
Supplying a first reactant from a second nozzle located farther from the exhaust port than the first nozzle with respect to the substrate and exhausting the exhaust gas from the exhaust port;
Supplying a second reactant from a third nozzle arranged closer to the exhaust port than the second nozzle to the substrate and exhausting the second reactant from the exhaust port;
A step of forming a film on the substrate by performing a predetermined number of cycles of non-simultaneously,
When the raw material is supplied, the flow rate of the inert gas supplied from the second nozzle, the flow rate of the inert gas supplied from the third nozzle, and the flow rate of the inert gas supplied from the first nozzle are balanced. A semiconductor device manufacturing method or substrate processing method is provided which controls the film thickness distribution in the substrate surface of the film formed on the substrate by controlling.

(Appendix 2)
The method according to Appendix 1, preferably,
At the time of supplying the raw material, the flow rate of the inert gas supplied from the second nozzle is made higher than the flow rate of the inert gas supplied from the first nozzle.

(Appendix 3)
The method according to appendix 2, preferably
At the time of supplying the raw material, the flow rate of the inert gas supplied from the second nozzle is made larger than the total flow rate of the flow rate of the raw material supplied from the first nozzle and the flow rate of the inert gas.

(Appendix 4)
The method according to Appendix 2 or 3, preferably
When the raw material is supplied, the flow rate of the inert gas supplied from the third nozzle is made higher than the flow rate of the inert gas supplied from the first nozzle.

(Appendix 5)
The method according to appendix 4, preferably
At the time of supplying the raw material, the flow rate of the inert gas supplied from the second nozzle is set to be equal to or higher than the flow rate of the inert gas supplied from the third nozzle. More preferably, the flow rate of the inert gas supplied from the second nozzle is made larger than the flow rate of the inert gas supplied from the third nozzle.

(Appendix 6)
The method according to Appendix 2 or 3, preferably
At the time of supplying the raw material, the flow rate of the inert gas supplied from the third nozzle is set to be equal to or less than the flow rate of the inert gas supplied from the first nozzle. More preferably, the flow rate of the inert gas supplied from the third nozzle is made equal to the flow rate of the inert gas supplied from the first nozzle.

(Appendix 7)
The method according to Appendix 1, preferably,
When supplying the raw material, the flow rate of the inert gas supplied from the second nozzle is made smaller than the flow rate of the inert gas supplied from the third nozzle,
The flow rate of the inert gas supplied from the third nozzle is made higher than the flow rate of the inert gas supplied from the first nozzle.

(Appendix 8)
The method according to appendix 7, preferably
At the time of supplying the raw material, the flow rate of the inert gas supplied from the third nozzle is made higher than the total flow rate of the flow rate of the raw material supplied from the first nozzle and the flow rate of the inert gas.

(Appendix 9)
The method according to supplementary note 7 or 8, preferably,
At the time of supplying the raw material, the flow rate of the inert gas supplied from the second nozzle is made equal to the flow rate of the inert gas supplied from the first nozzle.

(Appendix 10)
The method according to Appendix 1, preferably,
At the time of supplying the raw material, the flow rate of the inert gas supplied from each of the second nozzle and the third nozzle is made equal to the flow rate of the inert gas supplied from the first nozzle.

(Appendix 11)
According to another aspect of the invention,
A processing chamber where processing is performed on the substrate,
An exhaust system for exhausting the processing chamber from an exhaust port,
A raw material supply system for supplying a raw material from the first nozzle into the processing chamber,
A first reactant supply system for supplying a first reactant into the processing chamber from a second nozzle located farther from the exhaust port than the first nozzle;
A second reactant supply system for supplying a second reactant into the processing chamber from a third nozzle arranged closer to the exhaust port than the second nozzle;
An inert gas supply system for supplying an inert gas from the first nozzle, the second nozzle and the third nozzle into the processing chamber;
In the processing chamber, a process of supplying the raw material to the substrate from the first nozzle and exhausting the raw material from the exhaust port, and a process of supplying the raw material to the substrate from the second nozzle and supplying the first reactant from the exhaust port. A film is formed on the substrate by performing a predetermined number of cycles of non-simultaneously performing a process of exhausting and a process of supplying the second reactant to the substrate from the third nozzle and exhausting from the exhaust port. And the flow rate of the inert gas supplied from the second nozzle, the flow rate of the inert gas supplied from the third nozzle, and the inert gas supplied from the first nozzle when the raw material is supplied. The raw material supply system, the first reactant supply system, the second reactant so that the film thickness distribution in the substrate surface of the film formed on the substrate is controlled by controlling the balance with the flow rate. A controller configured to control a supply system, the inert gas supply system, and the exhaust system;
Provided is a substrate processing apparatus.

(Appendix 12)
According to yet another aspect of the invention,
A procedure of supplying the raw material from the first nozzle to the substrate in the processing chamber of the substrate processing apparatus and exhausting it from the exhaust port;
A procedure of supplying a first reactant from a second nozzle arranged farther from the exhaust port than the first nozzle with respect to the substrate in the processing chamber and exhausting the reactant from the exhaust port;
A step of supplying a second reactant from a third nozzle arranged closer to the exhaust port than the second nozzle with respect to the substrate in the processing chamber and exhausting the second reactant from the exhaust port;
A step of forming a film on the substrate by performing a predetermined number of cycles that do not simultaneously,
When the raw material is supplied, the flow rate of the inert gas supplied from the second nozzle, the flow rate of the inert gas supplied from the third nozzle, and the flow rate of the inert gas supplied from the first nozzle are balanced. By controlling, a procedure for controlling the in-plane film thickness distribution of the film formed on the substrate,
There is provided a program for causing the substrate processing apparatus to execute the above, or a computer-readable recording medium recording the program.

200 wafers (substrates)
249a nozzle (first nozzle)
249b nozzle (second nozzle)
249c nozzle (third nozzle)
231a exhaust port

Claims (15)

Supplying a raw material to a substrate from a first nozzle arranged on the side of the substrate and exhausting the raw material from an exhaust port;
Supplying a first reactant from a second nozzle disposed on the side of the substrate farther from the exhaust port than the first nozzle with respect to the substrate and exhausting the exhaust gas from the exhaust port;
Supplying a second reactant from a third nozzle arranged on the side of the substrate closer to the exhaust port than the second nozzle with respect to the substrate and exhausting the exhaust gas from the exhaust port;
A step of forming a film on the substrate by performing a predetermined number of cycles of non-simultaneously,
At the time of supplying the raw material, an inert gas is supplied from each of the first nozzle, the second nozzle, and the third nozzle, and the flow rate of the inert gas supplied from the second nozzle and the third nozzle are supplied. A semiconductor device that controls the in-substrate film thickness distribution of the film formed on the substrate by controlling the balance between the flow rate of the inert gas and the flow rate of the inert gas supplied from the first nozzle. Manufacturing method. The method of manufacturing a semiconductor device according to claim 1, wherein a flow rate of the inert gas supplied from the second nozzle is set to be higher than a flow rate of the inert gas supplied from the first nozzle when the raw material is supplied. The semiconductor according to claim 2, wherein the flow rate of the inert gas supplied from the second nozzle at the time of supplying the raw material is made larger than the total flow rate of the flow rate of the raw material supplied from the first nozzle and the flow rate of the inert gas. Device manufacturing method. 4. The method of manufacturing a semiconductor device according to claim 2, wherein the flow rate of the inert gas supplied from the third nozzle is set higher than the flow rate of the inert gas supplied from the first nozzle when the raw material is supplied. The method of manufacturing a semiconductor device according to claim 4, wherein the flow rate of the inert gas supplied from the second nozzle at the time of supplying the raw material is equal to or higher than the flow rate of the inert gas supplied from the third nozzle. 5. The method of manufacturing a semiconductor device according to claim 4, wherein the flow rate of the inert gas supplied from the second nozzle is set higher than the flow rate of the inert gas supplied from the third nozzle when the raw material is supplied. 4. The method of manufacturing a semiconductor device according to claim 2, wherein a flow rate of the inert gas supplied from the third nozzle at the time of supplying the raw material is equal to or less than a flow rate of the inert gas supplied from the first nozzle. 4. The method of manufacturing a semiconductor device according to claim 2, wherein the flow rate of the inert gas supplied from the third nozzle at the time of supplying the raw material is equal to the flow rate of the inert gas supplied from the first nozzle. When supplying the raw material, the flow rate of the inert gas supplied from the second nozzle is made smaller than the flow rate of the inert gas supplied from the third nozzle,
The method of manufacturing a semiconductor device according to claim 1, wherein the flow rate of the inert gas supplied from the third nozzle is made higher than the flow rate of the inert gas supplied from the first nozzle. 10. The semiconductor according to claim 9, wherein the flow rate of the inert gas supplied from the third nozzle at the time of supplying the raw material is made higher than the total flow rate of the flow rate of the raw material supplied from the first nozzle and the flow rate of the inert gas. Device manufacturing method. 11. The method of manufacturing a semiconductor device according to claim 9, wherein the flow rate of the inert gas supplied from the second nozzle at the time of supplying the raw material is equal to the flow rate of the inert gas supplied from the first nozzle. The semiconductor device according to claim 1, wherein a flow rate of the inert gas supplied from each of the second nozzle and the third nozzle at the time of supplying the raw material is equal to a flow rate of the inert gas supplied from the first nozzle. Manufacturing method. The method for manufacturing a semiconductor device according to claim 1, wherein the raw material contains halosilane. A processing chamber where processing is performed on the substrate,
An exhaust system for exhausting the processing chamber from an exhaust port,
A raw material supply system for supplying a raw material into the processing chamber from a first nozzle arranged laterally of the substrate;
A first reactant supply system for supplying the first reactant into the processing chamber from a second nozzle arranged on the side of the substrate farther from the exhaust port than the first nozzle;
A second reactant supply system for supplying a second reactant into the processing chamber from a third nozzle arranged on the side of the substrate closer to the exhaust port than the second nozzle;
An inert gas supply system for supplying an inert gas from the first nozzle, the second nozzle and the third nozzle into the processing chamber;
In the processing chamber, a process of supplying the raw material to the substrate from the first nozzle and exhausting the raw material from the exhaust port, and a process of supplying the raw material to the substrate from the second nozzle and supplying the first reactant from the exhaust port. A film is formed on the substrate by performing a predetermined number of cycles of non-simultaneously performing a process of exhausting and a process of supplying the second reactant to the substrate from the third nozzle and exhausting from the exhaust port. When the raw material is supplied, an inert gas is supplied from each of the first nozzle, the second nozzle, and the third nozzle, and a flow rate of the inert gas supplied from the second nozzle, By controlling the balance between the flow rate of the inert gas supplied from the third nozzle and the flow rate of the inert gas supplied from the first nozzle, the in-plane film thickness of the film formed on the substrate is controlled. A controller configured to control the raw material supply system, the first reactant supply system, the second reactant supply system, the inert gas supply system, and the exhaust system so as to control distribution.
A substrate processing apparatus having. A procedure of supplying a raw material to a substrate in a processing chamber of the substrate processing apparatus from a first nozzle arranged on the side of the substrate and exhausting the material from an exhaust port;
The first reactant is supplied to the substrate in the processing chamber from a second nozzle disposed on the side of the substrate farther from the exhaust port than the first nozzle and is exhausted from the exhaust port. Procedure and
The second reactant is supplied to the substrate in the processing chamber from a third nozzle located on the side closer to the exhaust port than the second nozzle and lateral to the substrate and exhausted from the exhaust port. Procedure and
A step of forming a film on the substrate by performing a predetermined number of cycles that do not simultaneously,
At the time of supplying the raw material, an inert gas is supplied from each of the first nozzle, the second nozzle, and the third nozzle, and the flow rate of the inert gas supplied from the second nozzle and the third nozzle are supplied. A procedure of controlling the in-substrate film thickness distribution of the film formed on the substrate by controlling the balance between the flow rate of the inert gas and the flow rate of the inert gas supplied from the first nozzle; ,
A program that causes the substrate processing apparatus to execute the program.