JP2019195106A - Method of manufacturing semiconductor device, substrate processing device, and program - Google Patents

Abstract

To control in-plane film thickness distribution of a film formed on a substrate.SOLUTION: A method of manufacturing a semiconductor device includes a steps of forming a film on a substrate by performing a cycle predetermined times non-simultaneously, the cycle including the steps of: supplying a material from a first nozzle to the substrate and exhausting the material from an exhaust port; supplying a first reactant to the substrate from a second nozzle arranged at a more distant side from the exhaust port than the first nozzle and exhausting the first reactant from the exhaust port; and supplying a second reactant to the substrate from a third nozzle arranged at a closer side to the exhaust port than the second nozzle and exhausting the second reactant from the exhaust port. At supplying the material, a balance of a flow rate of an inactive gas supplied from the second nozzle, a flow rate of an inactive gas supplied from the third nozzle, and a flow rate of an inactive gas supplied from the first nozzle, is controlled to control substrate in-plane film thickness distribution of the film formed on the substrate.SELECTED DRAWING: Figure 4

Description

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

  As a process 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 from the exhaust port;
Supplying the first reactant from a second nozzle disposed on the substrate farther from the exhaust port than the first nozzle and exhausting the substrate from the exhaust port;
Supplying a second reactant from a third nozzle disposed closer to the exhaust port than the second nozzle to the substrate and exhausting from the exhaust port;
A step of forming a film on the substrate by performing a non-simultaneous cycle a predetermined number of times,
A balance between 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 when the raw material is supplied. By controlling, a technique for controlling the in-plane film thickness distribution of the film formed on the substrate is provided.

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

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus used suitably by embodiment of this invention, and is a figure which shows a processing furnace part with a longitudinal cross-sectional view. It is a schematic block diagram of a part of a vertical processing furnace of a substrate processing apparatus suitably used in an embodiment of the present invention, and is a diagram showing a part of the processing furnace in a cross-sectional view taken along line AA of FIG. It is a schematic block diagram of the controller of the substrate processing apparatus used suitably by embodiment of this invention, and is a figure which shows the control system of a controller with a block diagram. 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 the board | substrate surface of the film | membrane formed on the board | substrate. (A)-(c) is a figure which shows the evaluation result of the film thickness distribution in the 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 adjustment 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 with heat.

A reaction tube 203 is disposed inside the heater 207 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 opened. A manifold 209 is disposed below the reaction tube 203 concentrically with the reaction tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), for example, and is formed in a cylindrical shape with an upper end and a lower end opened. The upper end portion of the manifold 209 is engaged with the lower end portion 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 installed vertically like the heater 207. The reaction vessel 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to accommodate a plurality of wafers 200 as substrates.

  In the processing chamber 201, a nozzle 249a as a first nozzle, a nozzle 249b as a second nozzle, and a nozzle 249c as a third nozzle are provided so as to penetrate the side wall 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 (MFC) 241a to 241c as flow rate controllers (flow rate control units) and valves 243a to 243c as opening / closing valves, respectively, in order from the upstream side. Gas supply pipes 232d to 232f for supplying an inert gas are connected to the gas supply pipes 232a to 232c on the downstream side of the valves 243a to 243c, respectively. The gas supply pipes 232d to 232f are respectively provided with MFCs 241d to 241f and valves 243d to 243f in order from the upstream side.

  As shown in FIG. 2, the nozzles 249 a to 249 c 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 portion from the lower portion of the inner wall of the reaction tube 203. Each is provided so as to rise upward in the stacking direction. That is, the nozzles 249a to 249c are respectively provided along the wafer arrangement area in the area horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged. The nozzle 249b is disposed on a side farther from an exhaust port 231a described later than the nozzle 249a, and the nozzle 249c is disposed on a side closer to the exhaust port 231a than the nozzle 249b. In the present embodiment, the nozzles 249a and 249b are arranged so as to face each other on a straight line across the center of the wafer 200 carried into the processing chamber 201. 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 250 a to 250 c are each opened so as to face the center of the reaction tube 203, and gas can be supplied toward the wafer 200. For these reasons, 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 250 a to 250 c 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 and a halogen element as predetermined elements (main elements) enters the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a. Supplied. The raw material gas is a gaseous raw material, for example, a gas obtained by vaporizing a raw material that is in a liquid state under normal temperature and normal pressure, or a raw material that is in a gaseous state under normal temperature and normal pressure. A halosilane is a silane having a halogen group. The halogen group includes chloro group, fluoro group, bromo group, iodo group and the like. That is, the halogen group includes halogen elements such as chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and the like. As the halosilane-based gas, for example, a source 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-based 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.

From the gas supply pipe 232c, for example, an O-containing gas is supplied into the processing chamber 201 through the MFC 241c, the valve 243c, and the nozzle 249c as a second reactant (reactant) having a chemical structure (molecular structure) different from that of the raw material. Is done. The O-containing gas acts as an oxidizing gas, that is, an O source. The O-containing gas, for example, may be used oxygen gas (O _2).

From the gas supply pipes 232d to 232f, for example, nitrogen (N ₂ ) gas is supplied as an inert gas through the MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. 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. In addition, a first reactant supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. In addition, a second reactant supply system is mainly configured by the gas supply pipe 232c, the MFC 241c, and the valve 243c. Further, 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, MFCs 241a to 241f, and the like 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, opens and closes the valves 243a to 243f and MFCs 241a to 241f. The flow rate adjusting operation and the like are configured to be controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated or split-type integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232f and the like in units of integrated units. Maintenance, replacement, expansion, etc. can be performed in units of integrated units.

  Below the side wall of the reaction tube 203, an exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided. An exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is connected via 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 adjustment unit). A vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 can perform vacuum evacuation and vacuum evacuation stop in the processing chamber 201 by opening and closing the valve with the vacuum pump 246 activated, and further, with the vacuum pump 246 activated, The pressure in the processing chamber 201 can be adjusted by adjusting the valve opening 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 lid that can airtightly close the lower end opening of the manifold 209. The seal cap 219 is made of a metal such as SUS and is formed in a disk shape. On the upper surface of the seal cap 219, an O-ring 220b is provided as a seal member that comes into contact with the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 for rotating a boat 217 described later is installed. A rotation shaft 255 of the rotation mechanism 267 passes through 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 raised and lowered in the vertical direction 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 loads and unloads the boat 217, that is, the wafer 200 into and out of the processing chamber 201 by moving the seal cap 219 up and down. A shutter 219s is provided below the manifold 209 as a furnace port lid that can airtightly close the lower end opening of the manifold 209 while the seal cap 219 is lowered by the boat elevator 115. The shutter 219s is made of a metal such as SUS and is formed in a disk shape. On the upper surface of the shutter 219s, an O-ring 220c as a seal 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, for example, 25 to 200 wafers 200 in a horizontal posture and in a multi-stage by aligning them in the vertical direction with their centers aligned. It is configured to arrange at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. Under the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

  A temperature sensor 263 is installed in the reaction tube 203 as a temperature detector. By adjusting the power supply to 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. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via the internal bus 121e. For example, an input / output device 122 configured as a touch panel or the like is connected to the controller 121.

  The storage device 121c is configured by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program that controls the operation of the substrate processing apparatus, a process recipe that describes a film forming process procedure and conditions that will be described later, and the like are stored in a readable manner. The process recipe is a combination of functions so that a predetermined result can be obtained by causing the controller 121 to execute each procedure in a film forming process to be described later, and functions as a program. Hereinafter, process recipes, control programs, and the like are collectively referred to simply as programs. The process recipe is also simply called a recipe. When the term “program” is used in this specification, it may include only a recipe, only a control program, or both. 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 stored.

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

  The CPU 121a is configured to read and execute a control program from the storage device 121c and to read a recipe from the storage device 121c in response to an operation command input from the input / output device 122 or the like. The CPU 121a adjusts the flow rate of various gases by the MFCs 241a to 241f, the opening / closing operation of the valves 243a to 243f, the opening / closing operation of the APC valve 244, and the pressure adjustment 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, raising / lowering operation of the boat 217 by the boat elevator 115, shutter opening / closing mechanism 115s Is configured to control the opening / closing operation and the like of the shutter 219s.

  The controller 121 installs the above-described 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, or a semiconductor memory such as a USB memory) 123 in a computer. Can be configured. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as 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 a communication means such as the Internet or a dedicated line without using the external storage device 123.

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

The film forming sequence shown in FIG.
Step 1 of supplying HCDS gas to the wafer 200 from the nozzle 249a and exhausting it from the exhaust port 231a;
Step 2 of supplying TEA gas from a nozzle 249b disposed on the side farther from the exhaust port 231a than the nozzle 249a to the wafer 200 and exhausting it from the exhaust port 231a;
Step 3 of supplying O ₂ gas from a nozzle 249c arranged on the side closer to the exhaust port 231a than the nozzle 249b with respect to the wafer 200 and exhausting it from the exhaust port 231a;
By performing a non-simultaneous cycle for a predetermined number of times, a film containing Si, O, C, and N, that is, a silicon oxycarbonitride film (SiOCN film) is formed on the wafer 200.

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, the wafer in-plane film thickness distribution (hereinafter also simply referred to as the in-plane film thickness distribution) of the SiOCN film formed on the wafer 200 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. As shown on the right side of FIG. 4, an example in which the distribution is the thickest at the central portion of the wafer 200 and gradually becomes thinner as the peripheral portion is approached (hereinafter also referred to as a central convex distribution) will be described. If a film with a central convex distribution can be formed on a bare wafer with a small surface area that does not have an uneven structure on the surface, the center of the pattern wafer with a large surface area that has a fine uneven structure on the surface can be formed. Thus, it is possible to form a film having a flat film thickness distribution (hereinafter also referred to as flat distribution) with little film thickness change from the edge to the periphery.

  In this specification, the film forming sequence shown in FIG. 4 may be shown as follows for convenience. The same notation is used in the following description of the modified examples.

(HCDS → TEA → O ₂ ) × n ⇒ SiOCN

  When the film forming sequence shown in FIG. 4 is performed, an 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 processing conditions. You 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 the present 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 in this specification, it may mean the surface of the wafer itself, or may mean the surface of a predetermined layer or the like formed on the wafer. In this specification, the phrase “form a predetermined layer on the wafer” means that the predetermined layer is directly formed on the surface of the wafer itself, a layer formed on the wafer, etc. It may mean that a predetermined layer is formed on the substrate. 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 219s is moved by the shutter opening / closing mechanism 115s, and the lower end opening of the manifold 209 is opened (shutter open). Thereafter, as shown in FIG. 1, the boat 217 that supports 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 inside of the processing chamber 201 is evacuated (reduced pressure) by the vacuum pump 246 so that the space in which the wafer 200 exists is at a desired pressure (degree of vacuum). 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 interior 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, heating, and rotation of the wafer 200 in the processing chamber 201 are all continuously performed at least until the processing on the wafer 200 is completed.

(Deposition step)
Thereafter, the following steps 1 to 3 are sequentially executed.

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

Specifically, the valve 243a is opened and HCDS gas is allowed to flow into the gas supply pipe 232a. The flow rate of the HCDS gas is adjusted by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust port 231a. At this time, HCDS gas is supplied to the wafer 200. At the same time, the valves 243d to 243f are opened, and N ₂ gas is allowed 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, supplied into the processing chamber 201 through the nozzles 249a to 249c, and 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 in 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 set to a predetermined flow rate in the range of 500 to 2000 sccm, for example. The supply time of the HCDS gas is, for example, a predetermined time in the range of 1 to 120 seconds, preferably 1 to 60 seconds. The pressure in the processing chamber 201 is, for example, a predetermined pressure in the range of 1 to 2666 Pa, preferably 67 to 1333 Pa. The temperature (film formation temperature) of the wafer 200 is set to a predetermined temperature within a range of 250 to 800 ° C., preferably 400 to 750 ° C., and more preferably 550 to 700 ° C., for example.

  When the film formation temperature is less than 250 ° C., it is difficult for HCDS to be chemically adsorbed on the wafer 200, and a practical film formation 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 sufficient film forming speed can be obtained.

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

  By supplying HCDS gas to the wafer 200 under the above-described conditions, the first layer (initial layer) is formed on the outermost surface of the wafer 200, for example, from less than one atomic layer to several atomic layers (from less than one molecular layer). 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, an adsorption layer of HCDS, or both of them.

  The Si layer containing Cl is a generic name including a continuous layer made of Si and containing Cl, a discontinuous layer, and a Si thin film containing Cl formed by overlapping these layers. Si constituting the Si layer containing Cl includes not only those that are not completely disconnected from Cl but also those that are completely disconnected from Cl.

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

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

  Under the condition that the HCDS gas is self-decomposed (thermally decomposed), Si is deposited on the wafer 200 to form a Si layer containing Cl. Under the condition that the HCDS gas does not self-decompose (thermally decompose), the adsorption layer of HCDS is formed by the adsorption of HCDS on the wafer 200. It is more preferable to form a Si layer containing Cl on the wafer 200 than to form an HCDS adsorption layer on the wafer 200 in that the film formation rate can be increased. Hereinafter, the Si-containing layer containing Cl is also simply referred to as a Si-containing layer for convenience.

  When the thickness of the first layer exceeds several atomic layers, the modification effect in Steps 2 and 3 described later does not reach the entire first layer. The minimum thickness of the first layer is less than one atomic layer. Therefore, it is preferable that the thickness of the first layer be less than one atomic layer to several atomic layers. By setting the thickness of the first layer to 1 atomic layer or less, that is, 1 atomic layer or less than 1 atomic layer, it is possible to relatively increase the action of the modification in Steps 2 and 3 described later. , 3 can reduce the time required for reforming. The time required for forming 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 be shortened. That is, the film forming rate can be increased. Moreover, the controllability of the film thickness uniformity can be improved by setting the thickness of the first layer to 1 atomic layer or less.

In the present embodiment, when the HCDS gas supply, the flow rate of _{N 2} gas supplied from the nozzle 249 b, is greater than the flow rate of _{N 2} gas supplied from the nozzle 249a.

By setting the flow rate balance of the N ₂ gas supplied from the nozzles 249b and 249a in this way, an annular space (hereinafter simply referred to as “annular space” in a plan view between the inner wall of the reaction tube 203 and the wafer 200 is set. The pressure in the wafer arrangement region, that is, the pressure in the space between the wafers 200 can be made larger. As a result, it is possible to suppress the outflow of HCDS gas to the annular space, promote the supply of HCDS gas to the space between the wafers 200, and increase the supply amount of HCDS gas to the center of the wafer 200. It becomes possible. In addition, the partial pressure (concentration) of the HCDS gas in the annular space can be reduced, and the supply amount of the HCDS gas to the peripheral portion of the wafer 200 can be reduced. As a result, the thickness distribution of the first layer in the plane of the wafer 200, and hence the in-plane thickness distribution of the SiOCN film formed on the wafer 200, can be the above-described central convex distribution. Hereinafter, such film thickness distribution control is also referred to as central convex distribution control.

This effect becomes stronger as the flow rate of the N ₂ gas supplied from the nozzle 249b is increased. For example, the flow rate of N ₂ gas supplied from the nozzle 249 b, 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, to reliably achieve a central convex distribution described above It becomes possible. In addition, this effect becomes stronger as the position of the nozzle 249b is further away from the position of the exhaust port 231a, and is maximized when the nozzle 249b and the exhaust port 231a face each other on a straight line across the center of the wafer 200. This effect is obtained more effectively as the position of the nozzle 249b is further away from the position of the nozzle 249a. For example, as shown in FIG. 2, the nozzle 249b is positioned opposite to the nozzle 249a with the center of the wafer 200 interposed therebetween. In this case, it can be obtained more effectively.

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. Thereby, the pressure of the above-mentioned annular space can be further increased. 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, the pressure in the annular space can be increased more uniformly in the circumferential direction. Become. As a result, the above-described central convex distribution can be more easily realized. 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 disposed 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 the N ₂ gas 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 the 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 Therefore, it can be realized at a low cost. When the HCDS gas is supplied, N ₂ gas supply from the nozzle 249b is not performed, and the flow rate of the N ₂ gas supplied from the nozzle 249c is set to a very large flow rate, thereby realizing the above-described central convex distribution control. In theory, it is also possible. However, considering that most of the N ₂ gas supplied from the nozzle 249c is exhausted from the exhaust port 231a soon before contributing to the above-described in-plane film thickness distribution control, this alternative method has a central convex distribution. An attempt to increase the degree (to increase the film thickness difference between the central part and the peripheral part) is very expensive as compared with the method of the present embodiment, and it can be said that it is not realistic.

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 N ₂ gas supplied from the nozzle 249b at the time of HCDS supply is larger than the flow rate of N ₂ gas supplied from the nozzle 249b at the time of TEA gas supply at step 2, and the nozzle at the time of O ₂ gas supply at 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, a purge step of exhausting HCDS gas, TEA gas, and O ₂ gas from the inside of the processing chamber 201 and supplying N ₂ gas as purge gas into the processing chamber 201. 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 It becomes larger than the flow rate of N ₂ gas.

The flow rate of the N ₂ gas supplied from the nozzles 249b and 249c satisfies the above-described flow rate balance, and is set to a predetermined flow rate within a range of 3000 to 6000 sccm, for example.

After the first layer is formed, the valve 243a is closed and the supply of HCDS gas is stopped. At this time, while the APC valve 244 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the HCDS gas remaining in the processing chamber 201 or contributing to the formation of the first layer is removed. 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 N ₂ gas supplied from each gas supply pipe is set to a flow rate in the range of 500 to 2000 sccm, for example.

[Step 2]
After step 1 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, and exhausted from the exhaust port 231a.

  In this step, the opening / closing control of the valves 243b, 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 TEA gas is adjusted by the MFC 241b, supplied into the processing chamber 201 through the nozzle 249b, and 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 set to a predetermined flow rate within a range of 200 to 10,000 sccm, for example. The supply time of the TEA 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 N ₂ gas supplied from each gas supply pipe is set to a predetermined flow rate in the range of 500 to 2000 sccm, for example. The pressure in the processing chamber 201 is, for example, a predetermined pressure in the range of 1 to 5000 Pa, preferably 1 to 4000 Pa. By setting the pressure in the processing chamber 201 to such a relatively high pressure zone, the TEA gas can be thermally activated by non-plasma. 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 easier. 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. This extracts (separates) at least a portion of the plurality of Cl contained in the first layer from the first layer, and at least removes some of the ethyl groups contained in the TEA gas from the TEA. It can be separated from the gas. Then, it becomes possible to form a Si—N bond by bonding N of TEA gas from which at least a part of ethyl groups is separated and Si contained in the first layer. In addition, it is possible to form a Si—C bond by bonding 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 a C component and an 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 on the wafer 200 as the second layer.

  When forming the second layer, Cl contained in the first layer and H contained in the TEA gas are at least one of Cl and H in the course 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 from or desorbed from the first layer. As a result, the second layer is a layer having less impurities such as Cl than the first layer.

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

[Step 3]
After step 2 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, and is 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, supplied into the processing chamber 201 through the nozzle 249c, and 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 set to a predetermined flow rate within a range of 100 to 10,000 sccm, for example. The O ₂ gas supply time is, for example, a predetermined time in the range of 1 to 120 seconds, preferably 1 to 60 seconds. The supply flow rate of N ₂ gas supplied from each gas supply pipe is set to a predetermined flow rate in the range of 500 to 2000 sccm, for example. The pressure in the processing chamber 201 is, for example, a predetermined pressure in 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 zone, the O ₂ gas can be thermally activated by non-plasma. When the O ₂ gas is activated and supplied with heat, a relatively soft reaction can be caused, and the formation of a third layer to be described later becomes easier. 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, and Si—O bonds can be formed 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 on the wafer 200 as the third layer. When forming the third layer, at least a part of the C component and N component contained in the second layer is maintained in the second layer without detachment 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 course of the reforming reaction with O ₂ gas, and is discharged from 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. Thereby, the third layer is a layer having 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, O ₂ gas and reaction by-products remaining in the processing chamber 201 or contributed to the formation of the third layer are removed in the processing chamber 201 by the same processing procedure and processing conditions as the purge step in Step 1. To eliminate.

[Performed times]
A SiOCN film having a predetermined composition and a predetermined film thickness can be formed on the wafer 200 by performing the steps 1 to 3 non-simultaneously, that is, by performing a cycle in which the steps 1 to 3 are performed without being synchronized one or more times (n times). The above cycle is preferably repeated multiple times. That is, until the thickness of the third layer formed per cycle is made thinner than the desired thickness and the thickness of the SiOCN film formed by stacking the third layers becomes the desired thickness, The above cycle is preferably repeated a plurality of times.

As raw materials, 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 (abbreviation: STC) gas or octachlorotrisilane (Si ₃ Cl ₈ , abbreviation: OCTS) gas can be used.

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

As the second reactant, in addition to O ₂ gas, water vapor (H ₂ O gas), nitrogen monoxide (NO) gas, nitrous oxide (N ₂ O) gas, nitrogen dioxide (NO ₂ ) gas, carbon monoxide O-containing, 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, 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.

(After purge and return to atmospheric pressure)
When a film having a desired composition and a desired film thickness is formed on the wafer 200, the valves 243a to 243c are closed, and the supply of the raw materials and reactants 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 232 d to 232 f and exhausted from the exhaust pipe 231. As a result, the inside of the processing chamber 201 is purged, and the gas and reaction byproducts remaining in the processing chamber 201 are removed from the processing chamber 201 (after purge). Thereafter, 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 unloaded 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 unloading, 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 unloaded from the reaction tube 203 and then taken out from the boat 217 (wafer discharge).

(3) Effects According to the Present Embodiment According to the present embodiment, one or more effects shown below 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 The in-plane film thickness distribution of the film can be a central convex distribution. As a result, when a pattern wafer is used as the wafer 200, a SiOCN film having a flat distribution can be formed on the wafer 200. Incidentally, the flow rate of N ₂ gas supplied from the nozzle 249 b, 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, reliably realize the central convex distribution described above become able to.

  The in-plane film thickness distribution of the film formed on the wafer 200 depends on the surface area of the wafer 200 because of a so-called loading effect. As the surface area of the wafer 200 to be deposited increases, a larger amount of raw material such as HCDS gas is consumed at the peripheral edge of the wafer 200, and it becomes difficult to reach the center. In this case, the film thickness distribution of the film formed on the wafer 200 is a distribution (hereinafter also referred to as a central concave distribution) in which the peripheral portion of the wafer 200 is the thickest and gradually decreases as it approaches the central portion.

According to the present embodiment, even when a pattern wafer having a large surface area is used as the wafer 200, the flow rate balance of the N ₂ gas supplied from the nozzles 249b and 249a is set as described above, so that the wafer 200 is placed on the wafer 200. The in-plane film thickness distribution of the film to be formed can be freely controlled by correcting from a central concave distribution to a flat distribution, and further correcting to a central convex distribution.

(B) When the flow rate of N ₂ gas supplied from the nozzle 249c is larger than the flow rate of N ₂ gas supplied from the nozzle 249a at the time of HCDS gas supply, the above-described central convex distribution 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 by the amount of gas consumption. As described above, this is because the nozzle 249b is disposed at a position 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 used, an increase in manufacturing cost and maintenance cost of the substrate processing apparatus can be avoided.

(E) The above-described effects are obtained when a raw material gas other than HCDS gas is used, when a gas containing C and N other than TEA gas is used, when an oxidizing gas other than O ₂ gas is used, or other than N ₂ gas The same can be obtained when using an inert gas.

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

(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 equal to or lower than the flow rate of N ₂ gas supplied from the nozzle 249a. FIG. 5 shows an example in which the flow rate of N ₂ gas supplied from the nozzle 249c is equal to the flow rate of 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 more moderate 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 the direction closer to the flat distribution. When a pattern wafer having a relatively small surface area (however, a surface area is larger than that of a bare wafer) is used as the wafer 200, the film 200 has a flat distribution on the wafer 200 by adopting the film forming sequence of this modification. It becomes possible to form a SiOCN film. In order to suppress the intrusion of the HCDS gas into the nozzle 249c, for example, the N ₂ gas supplied from the nozzle 249a can be supplied without suspending the supply of the N ₂ gas from the nozzle 249c when supplying the HCDS gas. It is preferable to carry out under a flow rate condition equivalent to the flow rate.

(Modification 2)
When HCDS gas supply, the flow rate of _{N 2} gas supplied from the nozzle 249c, while greater than the flow rate of _{N 2} gas supplied from the nozzle 249a, the flow rate of _{N 2} gas supplied from the nozzle 249 b, supplied by nozzle 249c it may be smaller than the flow rate of the N ₂ gas. In this case, the degree of central convex distribution of the SiOCN film formed on the wafer 200 is reduced in a direction that is softer than that in the first modification, that is, in the direction in which the in-plane film thickness distribution of the SiOCN film is made closer to a 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 approaching. When a patterned wafer having a surface area that is the same as or slightly larger than that of the bare wafer is used as the wafer 200, a flat distribution can be obtained on the wafer 200 by employing the film forming sequence of this modification. It is possible to form a SiOCN film having the same. In order to suppress the intrusion of the HCDS gas into the nozzle 249b, for example, the N ₂ gas supplied from the nozzle 249a can be prevented without supplying the N ₂ gas from the nozzle 249b when supplying the HCDS gas. It is preferable to carry out under a flow rate condition equivalent to 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 reliably set to a flat distribution rather than a 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 N ₂ gas supplied from the nozzle 249c when supplying HCDS is larger than the flow rate of N ₂ gas supplied from the nozzle 249c when supplying TEA gas in step 2, and the nozzle when supplying O ₂ gas in step 3 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, at the time of supplying HCDS gas, the flow rate of N ₂ gas supplied from each of the nozzle 249b and the nozzle 249c may be equal to the flow rate of N ₂ gas supplied from the nozzle 249a. In this case, the 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 , abbreviation: TCMDDS) gas, or trisdimethyl Aminosilane raw materials such as aminosilane (Si [N (CH ₃ ) ₂ ] ₃ H, abbreviation: 3DMAS) gas and bis (diethylamino) silane (SiH ₂ [N (C ₂ H ₅ ) ₂ ] ₂ , abbreviation: BDEAS) gas Gas may be used. Alternatively, a silane source gas such as monosilane (SiH ₄ ) gas or disilane (Si ₂ H ₆ ) gas may be used.

Further, 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 as the reactant. Furthermore, as the oxidizing agent, it may be used the _{O 3} gas and _O ^{2 *} gas.

  Then, for example, by the following film forming sequence, on the wafer 200, 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 (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
(TCMDDS → NH ₃ → O ₂ ) × n ⇒ SiOCN
(HCDS → NH ₃ → O ₂ ) × n ⇒ SiON
(HCDS → C ₃ H ₆ → NH ₃ ) × n ⇒ SiCN
(TCMDDS → 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 the film forming sequence shown in FIG. The same effect can be obtained. 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 processing conditions for supplying the raw materials and reactants can be the same as those in the film forming sequence shown in FIG.

<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 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, HCDS gas, O ₂ gas, and TEA gas may be supplied from nozzles 249a to 249c, respectively, TEA gas, O ₂ gas, and HCDS gas may be supplied, respectively, O ₂ gas, TEA gas, and HCDS. Each gas may be supplied. Even in these cases, when the HCDS gas supply, the control of the flow rate balance of _{N 2} gas supplied from the nozzle 249A～249c, by performing in the same manner as the film-forming sequence and third modifications shown in FIG. 4, The same effects as these can be obtained.

In the above-described embodiment, the 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 N ₂ gas flow rate balance control may be performed not when the HCDS gas is supplied but when the TEA gas is supplied. In this case, it is possible to control the N concentration distribution and the C concentration distribution in the wafer 200 plane of the film formed on the wafer 200. Further, for example, the flow rate balance of the N ₂ gas may be controlled when the O ₂ gas is supplied. In this case, it becomes possible to control the distribution of O concentration in the wafer 200 surface of the film formed on the wafer 200. Control of the flow rate balance of N ₂ gas at the time of TEA gas supply or O ₂ gas supply can be performed by the same film formation sequence as shown in FIG.

  In the above-described embodiment, the example in which the film containing Si as the main element is formed on the substrate has been described. However, the present invention is not limited to such a mode. That is, the present invention can be suitably applied to the case where a film containing a metal element such as germanium (Ge) or boron (B) as a main element in addition to Si is formed on a substrate. The present invention also provides titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), yttrium (Y), and lanthanum (La). The present invention 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 , abbreviation: TMA) gas is used as a raw material, and a titanium titanate carbonitride film ( TiOCN film), titanium titanate carbon 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 also be suitably used 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

  The recipe used for the substrate processing is preferably prepared individually according to the processing content and stored in the storage device 121c via the telecommunication line or the external storage device 123. And when starting a process, it is preferable that CPU121a selects a suitable recipe suitably from the some recipe stored in the memory | storage device 121c according to the content of the board | substrate process. Accordingly, it is possible to form films having various film types, composition ratios, film qualities, and film thicknesses with a single substrate processing apparatus with good reproducibility. Further, the burden on the operator can be reduced, and the processing can be started quickly while avoiding an operation error.

  The above-mentioned recipe is not limited to a case of newly creating, and for example, it may be prepared by changing an existing recipe that has already been installed in the substrate processing apparatus. When changing the recipe, the changed recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe is recorded. Further, an existing recipe that has already been installed in the substrate processing apparatus may be directly changed by operating the input / output device 122 provided in the existing 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 one time has been described. The present invention is not limited to the above-described embodiment, and can be suitably applied to a case where a film is formed using, for example, a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In the above-described embodiment, an example in which a film is formed 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 a 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 with the same sequence and processing conditions as those of the above-described embodiments and modifications, and the same effects can be obtained.

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

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

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

Example 1
A sample in which a SiOCN film is formed on a wafer by a film forming sequence in which a cycle for supplying HCDS gas, TEA gas, and O ₂ gas to the wafer in this order non-simultaneously is performed a predetermined number of times using the substrate processing apparatus shown in FIG. 1-3 were produced. As the wafer, a bare wafer having no uneven structure on the surface was used. When producing Sample 1, the supply flow rates of N ₂ gas from the second and third nozzles during the supply of HCDS gas were each set to a flow rate in the range of 2500 to 3500 sccm. When producing Sample 2, the supply flow rates of N ₂ gas from the second and third nozzles during the supply of HCDS gas were set to flow rates in the range of 1000 to 2000 sccm, respectively. When preparing Sample 3, the supply flow rates of N ₂ gas from the second and third nozzles during the supply of 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 when supplying the HCDS gas was set to a flow rate in the range of 400 to 600 sccm. Other processing conditions are the same as the processing conditions in the above-described embodiment.

And the in-plane film thickness distribution of the SiOCN film | membrane of samples 1-3 was measured, respectively. FIG. 8 shows the measurement results. The vertical axis in FIG. 8 indicates the film thickness [Å], and the horizontal axis indicates 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 indicate the evaluation results of samples 1 to 3, respectively. According to FIG. 8, the in-plane film thickness distribution of the SiOCN film approaches the central convex distribution from the flat distribution as the N ₂ gas supply flow rate from the second and third nozzles at the time of HCDS gas supply increases. It turns out that becomes large.

(Example 2)
Using the substrate processing apparatus shown in FIG. 1, a film forming sequence is performed on a wafer by a predetermined number of cycles in which HCDS gas, C ₃ H ₆ gas, NH ₃ gas, and O ₂ gas are supplied in this order non-simultaneously to the wafer. Samples 4 to 6 on which a SiOCN film was formed were produced. As the wafer, a bare wafer having no uneven structure on the surface was used. When preparing the sample 4, the supply flow rate of N ₂ gas from the second nozzle when supplying the HCDS gas is set to a flow rate in the range of 5000 to 7000 sccm, and the supply flow rate of N ₂ gas from the third nozzle is 400 to 600 sccm. The flow rate was within the range. When preparing the sample 5, the supply flow rate of N ₂ gas from the second nozzle when supplying the HCDS gas is set to a flow rate in the range of 400 to 600 sccm, and the supply flow rate of N ₂ gas from the third nozzle is 5000 to 7000 sccm. The flow rate was within the range. When the sample 6 was produced, the supply flow rate of N ₂ gas from the second and third nozzles when supplying the HCDS gas was set to a flow rate in the range of 400 to 600 sccm. In any case, the supply flow rate of N ₂ gas from the first nozzle during the supply of HCDS gas was set to a flow rate in the range of 400 to 600 sccm. Other processing conditions are the same as the processing conditions in the above-described embodiment.

  And the in-plane film thickness distribution of the SiOCN film | membrane of the samples 4-6 was measured, respectively. FIGS. 9A to 9C show the measurement results of Samples 4 to 6, respectively. In these drawings, the vertical axis indicates the film thickness [Å], and the horizontal axis indicates the distance [mm] from the center of the wafer at the measurement position.

According to FIG. 9A, when supplying HCDS gas, the flow rate of N ₂ gas supplied from the second nozzle is made larger than the flow rate of N ₂ gas supplied from the first nozzle, and N supplied from the third nozzle. _It can be seen that in the sample 4 produced by making the flow rate of the _two gases 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 produced by making the gas flow rate larger 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 supplying the HCDS gas, 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. In the produced sample 6, it can be seen that the in-plane film thickness distribution of the SiOCN film has a central concave distribution.

<Preferred embodiment of the present invention>
Hereinafter, 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 from the exhaust port;
Supplying the first reactant from a second nozzle disposed on the substrate farther from the exhaust port than the first nozzle and exhausting the substrate from the exhaust port;
Supplying a second reactant from a third nozzle disposed closer to the exhaust port than the second nozzle to the substrate and exhausting from the exhaust port;
A step of forming a film on the substrate by performing a non-simultaneous cycle a predetermined number of times,
A balance between 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 when the raw material is supplied. By controlling, a method for manufacturing a semiconductor device or a substrate processing method for controlling the in-plane film thickness distribution of the film formed on the substrate is provided.

(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 larger 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 set 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,
At the time of supplying the raw material, the flow rate of the inert gas supplied from the third nozzle is made larger 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 lower 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 equal to the flow rate of the inert gas supplied from the first nozzle.

(Appendix 7)
The method according to appendix 1, preferably,
When the raw material is supplied, 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 larger 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 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 9)
The method according to appendix 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 for processing the substrate;
An exhaust system for exhausting the processing chamber from an exhaust port;
A raw material supply system for supplying the raw material from the first nozzle into the processing chamber;
A first reactant supply system for supplying a first reactant from a second nozzle disposed on the side farther from the exhaust port than the first nozzle into the processing chamber;
A second reactant supply system for supplying a second reactant from a third nozzle disposed closer to the exhaust port than the second nozzle into the processing chamber;
An inert gas supply system that supplies an inert gas from the first nozzle, the second nozzle, and the third nozzle into the processing chamber;
In the processing chamber, the raw material is supplied to the substrate from the first nozzle and exhausted from the exhaust port, and the first reactant is supplied to the substrate from the second nozzle and from the exhaust port. A film is formed on the substrate by performing a predetermined number of cycles of 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, 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 The raw material supply system, the first reactant supply system, and the second reactant are controlled so as to control the in-plane film thickness distribution of the film formed on the substrate by controlling the balance with the flow rate. Supply system, inactive When configured controller to control the scan supply system, and the exhaust system,
A substrate processing apparatus is provided.

(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 disposed on a side farther from the exhaust port than the first nozzle to the substrate in the processing chamber and exhausting the substrate from the exhaust port;
A procedure of supplying a second reactant from a third nozzle disposed closer to the exhaust port than the second nozzle with respect to the substrate in the processing chamber and exhausting the substrate from the exhaust port;
A procedure for forming a film on the substrate by performing a non-simultaneous cycle a predetermined number of times;
A balance between 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 when the raw material is supplied. By controlling, the procedure for controlling the in-plane film thickness distribution of the film to be formed on the substrate,
Is executed by the computer, or a computer-readable recording medium on which the program is recorded is provided.

200 wafer (substrate)
249a Nozzle (first nozzle)
249b Nozzle (second nozzle)
249c Nozzle (third nozzle)
231a Exhaust port

Claims (15)

Supplying a raw material from a first nozzle disposed on the side of the substrate with respect to the substrate and exhausting it from an exhaust port;
Supplying the first reactant from a second nozzle disposed on the side of the substrate on the side farther from the exhaust port than the first nozzle and exhausting from the exhaust port;
Supplying the second reactant from a third nozzle disposed on the side of the substrate closer to the exhaust port than the second nozzle and exhausting from the exhaust port;
A step of forming a film on the substrate by performing a non-simultaneous cycle a predetermined number of times,
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 a flow rate of the inert gas supplied from the second nozzle is supplied from the third nozzle. Device for controlling the in-plane 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.   2. 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 larger than a flow rate of the inert gas supplied from the first nozzle when the raw material is supplied.   3. The semiconductor according to claim 2, wherein the flow rate of the inert gas supplied from the second nozzle is 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 when the raw material is supplied. Device manufacturing method.   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 is larger than a flow rate of the inert gas supplied from the first nozzle when the raw material is supplied.   5. The method of manufacturing a semiconductor device according to claim 4, wherein a flow rate of the inert gas supplied from the second nozzle is set to be equal to or higher than a flow rate of the inert gas supplied from the third nozzle when the raw material is supplied.   5. The method of manufacturing a semiconductor device according to claim 4, wherein a flow rate of the inert gas supplied from the second nozzle is larger than a 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 is set to be equal to or lower than a flow rate of the inert gas supplied from the first 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 is equal to a flow rate of the inert gas supplied from the first nozzle when the raw material is supplied. When the raw material is supplied, 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,
2. The method of manufacturing a semiconductor device according to claim 1, wherein a flow rate of the inert gas supplied from the third nozzle is larger than a 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 is 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 when the raw material is supplied. Device manufacturing method.   11. The method of manufacturing a semiconductor device according to claim 9, wherein a flow rate of the inert gas supplied from the second nozzle is equal to a flow rate of the inert gas supplied from the first nozzle when the raw material is supplied.   2. 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 of manufacturing a semiconductor device according to claim 1, wherein the raw material includes halosilane. A processing chamber for processing 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 a first nozzle disposed on the side of the substrate into the processing chamber;
A first reactant supply system for supplying a first reactant from a second nozzle disposed on the side of the substrate on the side farther from the exhaust port than the first nozzle into the processing chamber;
A second reactant supply system for supplying a second reactant from a third nozzle disposed on the side of the substrate closer to the exhaust port than the second nozzle into the processing chamber;
An inert gas supply system that supplies an inert gas from the first nozzle, the second nozzle, and the third nozzle into the processing chamber;
In the processing chamber, the raw material is supplied to the substrate from the first nozzle and exhausted from the exhaust port, and the first reactant is supplied to the substrate from the second nozzle and from the exhaust port. A film is formed on the substrate by performing a predetermined number of cycles of 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. 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 is set. 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 thickness of the film formed on the substrate is controlled. Distribution Gosuru way, and the raw material supply system, the first reactant supply system, said second reactant supply system, the inert gas supply system, and the like for controlling the exhaust system configured controller,
A substrate processing apparatus. A procedure of supplying a raw material from a first nozzle disposed on a side of the substrate with respect to a substrate in a processing chamber of the substrate processing apparatus and exhausting it 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 that is farther from the exhaust port than the first nozzle and exhausted from the exhaust port. Procedure and
A second reactant is supplied from a third nozzle disposed on the side of the substrate closer to the exhaust port than the second nozzle with respect to the substrate in the processing chamber and exhausted from the exhaust port. Procedure and
A procedure for forming a film on the substrate by performing a non-simultaneous cycle a predetermined number of times;
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 a flow rate of the inert gas supplied from the second nozzle is supplied from the third nozzle. Controlling the in-plane 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; ,
For causing the substrate processing apparatus to execute the program.