WO2018163250A1

WO2018163250A1 - Semiconductor device manufacturing method, substrate processing device, and recording medium

Info

Publication number: WO2018163250A1
Application number: PCT/JP2017/008796
Authority: WO
Inventors: 中谷　公彦; 隆史佐々木; 司鎌倉; 花島　建夫
Original assignee: 株式会社ＫｏｋｕｓａｉＥｌｅｃｔｒｉｃ
Priority date: 2017-03-06
Filing date: 2017-03-06
Publication date: 2018-09-13
Also published as: JPWO2018163250A1; JP6778318B2

Abstract

A film is formed on a substrate by performing (a) a step of supplying, from a first supply section, raw materials including a main element constituting the film to a substrate, and exhausting the raw materials via an exhaust section, and (b) a step of supplying, from a pair of second supply sections disposed adjacent to the first supply section so as to sandwich a straight line passing through the first supply section and the exhaust section, a reactant not containing the main element to the substrate, and exhausting the reactant via the exhaust section. The steps are performed under a condition such that the raw materials, when present independently, are not thermally decomposed, and simultaneously for at least a certain period.

Description

Semiconductor device manufacturing method, substrate processing apparatus, and recording medium

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

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 2014-99427 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,
(A) supplying the raw material containing the main element constituting the film from the first supply unit to the substrate and exhausting it from the exhaust unit;
(B) From the pair of second supply parts disposed adjacent to the first supply part so as to sandwich a straight line passing through the first supply part and the exhaust part, the main element-free reactant is obtained. Supplying to the substrate and exhausting from the exhaust unit;
When the raw material is present alone, the technique for forming the film on the substrate is provided by simultaneously performing at least a certain period under the condition that the raw material is not thermally decomposed.

According to the present invention, it is possible to control the in-plane film thickness distribution of the film formed on the 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. FIG. 2 is a schematic configuration 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 as 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. (A) is a schematic diagram which shows a mode that a reactant is supplied only from either one of a pair of 2nd supply parts, when supplying a raw material from a 1st supply part, (b) It is a schematic diagram which shows a mode that a reactant is supplied using both of a pair of 2nd supply part when supplying a raw material from a 1st supply part. (A) is a figure which shows the evaluation result of the film thickness distribution in the substrate surface of the film | membrane formed on the board | substrate, (b) is a figure which extracts and shows a part of process conditions at the time of forming a film | membrane. is there. (A), (b) is a cross-sectional view which respectively shows the modification of a vertical processing furnace, and is a figure which extracts and shows a reaction tube, a buffer chamber, a nozzle, etc. partially.

<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 heating means (heating mechanism). The heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation 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 material such as stainless steel (SUS), for example, and has 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 hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate.

In the processing chamber 201, a nozzle 249 a as a first supply unit and

nozzles

249 b and 249 c as a pair of second supply units 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, which are flow rate controllers (flow rate control units), and valves 243a to 243c, which are on-off valves, in order from the upstream side of the gas flow. . 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 of the gas flow.

As shown in FIG. 2, the nozzles 249a to 249c are arranged in an annular space in a plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper part from the lower part of the inner wall of the reaction tube 203. Each is provided so as to rise upward in the arrangement direction. That is, the nozzles 249a to 249c are 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 249a is arranged so as to face an exhaust portion 231a (described later) on a straight line (straight line 201b) across the center of the wafer 200 carried into the processing chamber 201 in plan view. Precisely, the center of the nozzle 249a and the exhaust part 231a are opposed to each other across the center of the wafer 200, and the respective centers are positioned on a straight line 201b passing through the center of the wafer 200. Has been placed. The

nozzles

249b and 249c are disposed adjacent to the nozzle 249a so as to sandwich a straight line 201b passing through the nozzle 249a and the exhaust part 231a. In other words, the

nozzles

249b and 249c are disposed on both sides of the nozzle 249a, that is, along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200) so as to sandwich the nozzle 249a from both sides. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c is opened so as to face the exhaust part 231a in plan view, and can supply gas toward the wafer 200. The gas supply holes 250 a to 250 c may be opened so as to face the center of the wafer 200. In any case, the center of the gas supply hole 250a is located on a straight line 201b passing through the center of the wafer 200 and the center of the exhaust part 231a in plan view. 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, a silicon hydride gas containing silicon (Si) as a main element constituting a film to be formed is supplied from the gas supply pipe 232a through the MFC 241a, the valve 243a, and the nozzle 249a. Supplied into 201. 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. Silicon hydride is a silane raw material containing a chemical bond (Si—H bond) between Si and hydrogen (H) and containing no carbon (C) and nitrogen (N). Silicon hydride is also a silane raw material containing no halogen element such as chlorine (Cl), fluorine (F), bromine (Br), iodine (I) and the like. As the silicon hydride gas, for example, disilane (Si ₂ H ₆ , abbreviation: DS) gas can be used.

From the gas supply pipe 232b, Si-free alkylborane gas is supplied as a reactant (reaction gas) into the processing chamber 201 through the

MFCs

241b and 241c,

valves

243b and 243c, and

nozzles

249b and 249c. Alkylborane is a halogen-free gas containing boron (B), containing an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. As the alkylborane-based gas, for example, triethylborane ((CH ₃ CH ₂ ) ₃ B, abbreviation: TEB) gas can be used.

The DS gas is a gas that satisfies the octet rule, and the TEB gas is a gas that does not satisfy the octet rule. The octet rule is an empirical rule that a compound or ion exists stably when the number of outermost electrons of an atom is 8, that is, an empirical rule that the reactivity of a compound or ion is stabilized by having a closed shell structure. That is.

Since DS gas satisfying the octet rule is stable, when supplied into the processing chamber 201, the adsorption force on the surface of the wafer 200 tends to be weak, that is, the DS gas tends not to be adsorbed on the surface of the wafer 200. is there. Further, since the pyrolysis temperature of the DS gas is higher than the pyrolysis temperature of the TEB gas, the DS gas tends to be harder to decompose than the TEB gas. Further, since the TEB gas that does not satisfy the octet law has a strong reaction force to satisfy the octet law and is unstable, when it is supplied into the processing chamber 201, the adsorption force to the surface of the wafer 200 is increased. There is a tendency to become stronger, that is, to be easily adsorbed to the surface of the wafer 200. Moreover, since the thermal decomposition temperature of TEB gas is lower than the thermal decomposition temperature of DS gas, TEB gas tends to be more thermally decomposed than DS gas.

From the gas supply pipes 232d to 232f, for example, nitrogen (N ₂ ) gas as an inert gas passes 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.

Mainly, the raw material supply system is configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a. In addition, a reactant supply system is mainly configured by the

gas supply pipes

232b and 232c, the MFCs 241b and 241c, and the

valves

243b and 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 divided type integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232f in units of integrated units. Maintenance, replacement, expansion, etc. can be performed in units of integrated units.

The reaction tube 203 is provided with an exhaust part (exhaust port) 231a for exhausting the atmosphere in the processing chamber 201. As shown in FIG. 2, the exhaust unit 231a is provided at a position facing (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in plan view. An exhaust pipe 231 is connected to the exhaust part 231a. The exhaust pipe 231 is connected to 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 part 231a, 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 opening lid capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material 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 carries the wafer 200 in and out of the processing chamber 201 by moving the seal cap 219 up and down. Below the manifold 209, a shutter 219s is provided as a furnace opening lid capable of airtightly closing the lower end opening of the manifold 209 with the seal cap 219 lowered and the boat 217 carried out of the processing chamber 201. Yes. The shutter 219s is made of a metal material 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 multi-stage manner by aligning them vertically in a horizontal posture and 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.

In the reaction tube 203, a temperature sensor 263 is installed 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 having 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 includes, for example, a flash memory, a HDD (Hard Disk Drive), and the like. In the storage device 121c, a control program that controls the operation of the substrate processing apparatus, a process recipe that describes the procedure and conditions of the substrate processing described later, and the like are stored in a readable manner. The process recipe is a combination of processes so that a predetermined result can be obtained by causing the controller 121 to execute each procedure in substrate processing 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 out 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 A in which DS gas is supplied from the nozzle 249a to the wafer 200 and exhausted from the exhaust unit 231a;
Step B in which TEB gas is supplied to the wafer 200 from the

nozzles

249b and 249c and exhausted from the exhaust unit 231a;
When a DS gas is present alone, a film containing Si (Si film) is formed on the wafer 200 by simultaneously performing at least a certain period of time under the condition that the DS gas is not thermally decomposed. Note that B or C may be added to the Si film formed at this time. A Si film to which B and C are added, that is, a film containing Si, B, and C can also be referred to as a SiBC film. The SiBC film is also a film containing Si as a main element. However, in this specification, a Si film to which B or C is added may be simply referred to as a Si film for convenience.

In this specification, the film forming sequence shown in FIG. 4 may be shown as follows for convenience.

DS + TEB ⇒ Si

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 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 adjustment and temperature adjustment)
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 wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired 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 in the processing chamber 201 and the heating and rotation of the wafer 200 are all continuously performed at least until the processing on the wafer 200 is completed.

(Deposition step)
Thereafter, the above steps A and B are performed simultaneously. That is, DS gas and TEB gas are simultaneously supplied to the wafer in the processing chamber 201 and exhausted from the exhaust unit 231a.

Specifically, the valves 243a to 243c are opened, and DS gas is allowed to flow into the gas supply pipe 232a, and TEB gas is allowed to flow into the

gas supply pipes

232b and 232c. The DS gas and the TEB gas are adjusted in flow rates by the MFCs 241a to 241c, supplied into the processing chamber 201 through the nozzles 249a to 249c, mixed in the processing chamber 201, and exhausted from the exhaust unit 231a. At this time, the DS gas and the TEB gas are supplied to the wafer 200 together, that is, simultaneously. At this 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 N ₂ gas is supplied into the processing chamber 201 together with the DS gas and the TEB gas, and is exhausted from the exhaust unit 231a.

As processing conditions for this step,
DS gas supply flow rate: 1 to 2000 sccm
TEB gas supply flow rate: 1 ~ 1000sccm
N ₂ gas supply flow rate (each gas supply pipe): 100 to 10000 sccm
Gas supply time: 10 to 60 minutes Processing temperature: 200 to 400 ° C, preferably 300 to 400 ° C
Processing pressure: 1 to 1000 Pa, preferably 20 to 100 Pa
Is exemplified.

When the processing temperature is less than 200 ° C. or the processing pressure is less than 1 Pa, the film formation reaction on the wafer 200 is difficult to proceed, and a practical film formation rate may not be obtained. By setting the processing temperature to a temperature of 200 ° C. or higher, or the processing pressure to a pressure of 1 Pa or higher, the film forming reaction on the wafer 200 is advanced, and a practical film forming rate can be obtained. By setting the processing temperature to 300 ° C. or higher or the processing pressure to 20 Pa or higher, the film forming reaction on the wafer 200 can be promoted, and the film forming rate can be further increased.

When the processing temperature exceeds 400 ° C. or the processing pressure exceeds 1000 Pa, the DS gas is thermally decomposed without supplying the TEB gas together with the DS gas (simultaneously), and the TEB gas is supplied. May lose its significance. Also, when DS gas and TEB gas are supplied together under such processing conditions, the film thickness uniformity is likely to deteriorate due to excessive gas phase reaction, making it difficult to control it. There is. By setting the processing temperature to 400 ° C. or lower or the processing pressure to 1000 Pa or lower, it becomes possible to effectively use the catalytic action of TEB gas when decomposing DS gas. The technical significance of supplying the TEB gas together can be obtained. Further, when supplying the DS gas and the TEB gas together, an appropriate gas phase reaction can be caused, deterioration of the film thickness uniformity can be suppressed, and the control thereof can be performed. This effect can be further enhanced by setting the processing pressure to 100 Pa or less.

By supplying the DS gas and the TEB gas together (simultaneously) to the wafer 200 under the above-described conditions, these gases can be appropriately mixed and reacted in the processing chamber 201. Then, it becomes possible to decompose the DS gas and cut at least part of the Si—H bonds in the DS gas. The DS gas Si that has dangling bonds due to the extraction of H is quickly adsorbed and deposited on the wafer 200. As a result, the formation of the Si film on the wafer 200 proceeds at a practical rate. Depending on the processing conditions, it is possible to add a B component or a C component contained in the TEB gas into the Si film.

Note that the thermal decomposition temperature of the DS gas varies depending on the pressure conditions in the processing chamber 201, but exceeds 400 ° C. under the pressure conditions described above, for example, a temperature in the range of 440 to 460 ° C. That is, the above-described processing temperature is a temperature lower than the thermal decomposition temperature of the DS gas, and is a temperature at which the DS gas does not thermally decompose when the DS gas exists alone in the processing chamber 201. In addition, the temperature within the range of 200 to 325 ° C. (200 ° C. or more and 325 ° C. or less) among the above processing temperatures is a temperature lower than the thermal decomposition temperature of the TEB gas, and the TEB gas is alone in the processing chamber 201. The temperature at which the TEB gas does not thermally decompose when present.

It is considered that the film forming process can proceed at a practical rate even under such a low temperature condition because of the catalytic action of the TEB gas. The TEB gas acts to promote the decomposition of the DS gas supplied into the processing chamber 201 and promote the film forming process. It is considered that the TEB gas acts as a catalyst due to the polarity of the TEB molecule. Here, the polarity means an electric bias existing in a molecule (or chemical bond). The state where polarity exists means that the distribution of positive and negative charges in the molecule is uneven, for example, the charge distribution on one side in the molecule is positive and the charge distribution on the other side is negative. In other words, a state where the centroid of positive charge and the centroid of negative charge in the molecule are inconsistent. By using a TEB gas having a polarity equivalent to or higher than that of the DS gas as the reactant, it is possible to cause this gas to act as a catalyst and to proceed the film forming process at a practical rate. Note that the TEB gas in this embodiment is decomposed by reacting with the DS gas and changes itself before and after the reaction. Therefore, although the TEB gas in the reaction system of the present embodiment has a catalytic action, strictly speaking, it can be considered as a pseudo catalyst different from the catalyst.

As a raw material, general formula Si _n H _{2n + 2} (n is 1 or more) such as DS gas, monosilane (SiH ₄ , abbreviation: MS) gas, trisilane (Si ₃ H ₈ ) gas, tetrasilane (Si ₄ H ₁₀ ) gas, etc. Or a silicon hydride gas can be used.

As raw materials, monomethylsilane (SiH ₃ CH ₃ , abbreviation: MMS) gas, dimethylsilane (SiH ₂ (CH ₃ ) ₂ , abbreviation: DMS) gas, monoethylsilane (SiH ₃ C ₂ H ₅ , abbreviation: MES) gas, vinylsilane (SiH ₃ C ₂ H ₃ , abbreviation: VS) gas, monomethyldisilane (SiH ₃ SiH ₂ CH ₃ , abbreviation: MMDS) gas, hexamethyldisilane ((CH ₃ ) ₃ —Si—Si— ( CH ₃ ) ₃ , abbreviation: HMDS) gas, 1,4-disilabutane (SiH ₃ CH ₂ CH ₂ SiH ₃ , abbreviation: 1,4-DSB) gas, 1,3-disilabutane (SiH ₃ CH ₂ SiH ₂ CH ₃ , abbreviation: 1, 3-DSB) gas, 1,3,5-sila-pentane _{_{_{_{(SiH 3 CH 2 SiH 2 CH}}}} 2 SiH 3, abbreviation: 1 3, 5-TSP) can also be used alkyl silane gas such as a gas. In this case, C can be added to the Si film formed on the wafer 200.

In addition, as raw materials, Bistally butylaminosilane (SiH ₂ [NH (C ₄ H ₉ )] ₂ , abbreviation: BTBAS) gas, trisdimethylaminosilane (SiH [N (CH ₃ ) ₂ ] ₃ , abbreviation: 3DMAS) gas An aminosilane-based gas such as trisilylamine ((SiH ₃ ) ₃ N, abbreviation: TSA) gas can be used. In this case, N can be added to the Si film formed on the wafer 200.

As the reactant, in addition to TEB gas, trimethylborane (B (CH ₃ ) ₃ , abbreviation: TMB) gas, tripropylborane (B (C ₃ H ₇ ) ₃ , abbreviation: TPB) gas, tributylborane (B ( An alkylborane-based gas represented by a general formula BR ₃ (R is an alkyl group) such as C ₄ H ₉ ) ₃ , abbreviation: TBB) gas, can be used. In this case, B or C can be added to the Si film formed on the wafer 200.

As reactants, trisdimethylaminoborane (B (N (CH ₃ ) ₂ ) ₃ , abbreviation: TDMAB) gas, trisdiethylaminoborane (B (N (C ₂ H ₅ ) ₂ ) ₃ , abbreviation: TDAB) Gas, trisdipropylaminoborane (B (N (C ₃ H ₇ ) ₂ ) ₃ , abbreviation: TDPAB) gas, trisdibutylaminoborane (B (N (C ₄ H ₉ ) ₂ ) ₃ , abbreviation: TDAB) gas A gas represented by the general formula B (NR ₂ ) ₃ such as an aminoborane-based gas can also be used. In this case, B, N, or C can be added to the Si film formed on the wafer 200. The Si film to which B, N, and C are added can also be referred to as a SiBCN film. The SiBCN film is also a film containing Si as a main element.

As reactants, trimethyl borate (B (OCH ₃ ) ₃ , abbreviation: TMOB) gas, triethyl borate (B (OC ₂ H ₅ ) ₃ , abbreviation: EOB) gas, tripropyl borate (B ( OC ₃ H ₇ ) ₃ , abbreviation: TPOB) gas, tributyl borate (B (OC ₄ H ₉ ) ₃ , abbreviation: TBOB) gas, etc., gas represented by the general formula B (OR) ₃ , that is, alkoxyborane A system gas can also be used. In this case, B, O, or C can be added to the Si film formed on the wafer 200. A Si film to which B, O, and C are added can also be referred to as a SiBOC film. The SiBOC film is also a film containing Si as a main element.

These reactants all contain B and do not satisfy the octet rule, and act catalytically on the above-described raw materials.

As the inert gas, for example, 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 to return to atmospheric pressure)
After the Si film having a desired film thickness is formed on the wafer 200, N ₂ gas as a purge gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249c and exhausted from the exhaust unit 231a. 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)
The seal cap 219 is lowered by the boat elevator 115 and the lower end of the manifold 209 is opened. Then, 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 unloading). 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 taken out of 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) In the film forming step, the DS gas is supplied from the nozzle 249a, and the TEB gas is supplied from the

nozzles

249b and 249c provided adjacent to the nozzle 249a so as to sandwich the straight line 201b. It is possible to control the in-plane film thickness distribution (hereinafter also simply referred to as “in-plane film thickness distribution”) of the Si film formed on the substrate.

FIG. 5A shows a case where the DS gas is supplied from the nozzle 249a, the TEB gas is supplied from the nozzle 249b, and the TEB gas is not supplied from the nozzle 249c. It is a figure which shows density distribution typically. When each gas is supplied in this way, the gas concentration distribution on the surface of the wafer 200 may become nonuniform (biased). For example, as shown in FIG. 5A, the concentration of the DS gas is locally high (part of the TEB gas) in a partial region A (region closer to the nozzle 249c than the nozzle 249a) on the surface of the wafer 200. The concentration of the TEB gas is locally high (the concentration of the DS gas) in the region B (region closer to the nozzle 249b than the nozzle 249a) on the surface of the wafer 200, which is different from the region A. May be locally low). As a result, the in-plane film thickness distribution of the Si film formed on the wafer 200 is, for example, the thickest at the peripheral portion of the wafer 200 and gradually decreasing as it approaches the central portion (hereinafter also referred to as a central concave distribution). It may become. In addition, when the inventors supply the DS gas and the TEB gas from the

nozzles

249a and 249b, the surface of the Si film formed on the wafer 200 is supplied by simultaneously supplying the N ₂ gas from the nozzle 249c. We tried to control the inner film thickness distribution. However, it is difficult to control the in-plane film thickness distribution of the Si film formed on the wafer 200 even if the N ₂ gas is supplied from the nozzle 249c or the supply flow rate is changed. I found out. That is, the film thickness distribution of the Si film formed on the wafer 200 is a flat film thickness distribution (hereinafter also referred to as flat distribution) with little film thickness change from the center to the periphery, or the thickest at the center of the wafer 200. It has been found that it is difficult to obtain a distribution that is gradually thinner as it approaches the periphery (hereinafter also referred to as a central convex distribution).

FIG. 5B schematically shows the gas concentration distribution on the surface of the wafer 200 when the DS gas is supplied from the nozzle 249a and the TEB gas is supplied from both the nozzles 249b and 249c. is there. When each gas is supplied in this manner, mixing of the DS gas and the TEB gas in the processing chamber 201 can be promoted, and the gas concentration distribution on the surface of the wafer 200 can be made uniform. For example, as shown in FIG. 5B, the generation of a region A in which the concentration of DS gas is locally increased over almost the entire surface of the wafer 200, or the region B in which the concentration of TEB gas is locally increased. Each generation can be prevented, and as a result, substantially the entire surface of the wafer 200 can be covered with the region C in which the DS gas and the TEB gas are substantially uniformly mixed. As a result, the in-plane film thickness distribution of the Si film formed on the wafer 200 can be controlled. For example, the degree of central concave distribution of the in-plane film thickness distribution of the Si film formed on the wafer 200 can be weakened. Further, for example, the in-plane film thickness distribution of the Si film formed on the wafer 200 can be changed from the central concave distribution to the flat distribution, or further changed to the central convex distribution.

(B) In Step B, the in-plane film thickness distribution of the Si film formed on the wafer 200 can be controlled by supplying N ₂ gas together with the TEB gas from the

nozzles

249b and 249c. .

For example, in Step B, TEB gas and N ₂ gas are supplied together from the

nozzles

249b and 249c, and at this time, the flow rate of the N ₂ gas supplied from the

nozzles

249b and 249c is changed to the TEB gas supplied from the

nozzles

249b and 249c. By making each larger than the flow rate, it becomes possible to weaken the degree of the central concave distribution of the in-plane film thickness distribution of the Si film formed on the wafer 200. Such a control of the flow rate balance between the N ₂ gas and the TEB gas may be realized by adjusting the flow rate of the N ₂ gas supplied from the

nozzles

249b and 249c, or may be supplied from the

nozzles

249b and 249c. This may be realized by adjusting the flow rate of the TEB gas, or may be realized by adjusting the flow rates of both the N ₂ gas and the TEB gas supplied from the

nozzles

249b and 249c.

As described above, in Step B, by adjusting at least one of the supply flow rate of N ₂ gas and the supply flow rate of TEB gas supplied from the

nozzles

249b and 249c, the in-plane of the Si film formed on the wafer 200 is adjusted. It is possible to control the film thickness distribution.

(C) In step A, the in-plane film thickness distribution of the Si film formed on the wafer 200 can be controlled by supplying N ₂ gas together with the DS gas from the nozzle 249a.

For example, in step A, DS gas and N ₂ gas are supplied together from the nozzle 249a, and at this time, the flow rate of N ₂ gas supplied from the nozzle 249a is made larger than the flow rate of DS gas supplied from the nozzle 249a. Thus, the film thickness on the outer periphery of the Si film formed on the wafer 200 can be reduced. Further, for example, in step A, DS gas and N ₂ gas are supplied together from the nozzle 249a, and at this time, the flow rate of the DS gas supplied from the nozzle 249a is made larger than the flow rate of the N ₂ gas supplied from the nozzle 249a. As a result, it is possible to increase the film thickness on the outer periphery of the Si film formed on the wafer 200. Such control of the flow rate balance between the N ₂ gas and the DS gas may be realized by adjusting the flow rate of the N ₂ gas supplied from the nozzle 249a, or the flow rate of the DS gas supplied from the nozzle 249a. May be realized by adjusting the flow rate, or may be realized by adjusting the flow rates of both the N ₂ gas and the DS gas supplied from the nozzle 249a.

As described above, in Step A, the in-plane film thickness of the Si film formed on the wafer 200 is adjusted by adjusting at least one of the supply flow rate of N ₂ gas and the supply flow rate of DS gas supplied from the nozzle 249a. The distribution can be controlled. The supply of N ₂ gas from the nozzle 249a and the flow control of the DS gas and N ₂ gas supplied from the nozzle 249a are particularly effective for fine adjustment of the film thickness on the outer periphery of the Si film formed on the wafer 200.

(D) The catalytic action of the TEB gas makes it possible to form the Si film under low temperature conditions, for example, in the range of 200 to 400 ° C., preferably 300 to 400 ° C. As a result, the thermal history of the wafer 200 can be favorably controlled. This technique is particularly effective in a process (for example, middle end) in which a process temperature is required to be lowered among semiconductor device manufacturing processes.

(E) Suppressing the decomposition of the DS gas in the nozzle 249a by performing the film forming step under the above-described temperature condition in which the DS gas is not thermally decomposed when the DS gas is present alone in the processing chamber 201. Is possible. Thereby, Si deposition in the nozzle 249a can be suppressed, and the maintenance frequency of the substrate processing apparatus can be reduced.

(F) The film forming step is performed in a temperature condition in which the TEB gas is not thermally decomposed when the TEB gas is present alone in the processing chamber 201 among the above-described temperature conditions, whereby in the

nozzles

249b and 249c. It becomes possible to suppress decomposition of the TEB gas. Thereby, accumulation of B or the like in the

nozzles

249b and 249c can be suppressed, and the maintenance frequency of the substrate processing apparatus can be reduced.

(G) Since DS gas and TEB gas are separately supplied into the processing chamber 201 using different nozzles, and these gases are mixed (Post-Mix) for the first time in the processing chamber 201, the inside of the nozzles 249a to 249c It is possible to avoid the reaction between these gases. Thereby, the deposition of the Si film in the nozzles 249a to 249c can be suppressed, and the maintenance frequency of the substrate processing apparatus can be reduced.

Note that when the DS gas and the TEB gas are mixed (Pre-Mix) outside the processing chamber 201 in advance and then supplied into the processing chamber 201, the gas state between the upstream portion and the downstream portion in the processing chamber 201 (For example, the degree of mixing and decomposition, concentration, etc.) may change, and the inter-wafer film quality uniformity and inter-wafer film thickness uniformity of the Si film formed on the wafer 200 may be reduced. According to the present embodiment that employs the Post-Mix method, such a problem can be solved.

(H) B and C can be added to the Si film formed on the wafer 200 by appropriately selecting and adjusting (controlling) the processing conditions in the film forming step. Thereby, this film can be made into a film excellent in processing resistance such as etching resistance.

(I) The above-mentioned effect is the same when using the above-mentioned raw material other than DS gas, when using the above-mentioned reactant other than TEB gas, or when using the above-mentioned inert gas other than N ₂ gas. Can get to.

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

In the film forming step, one of the DS gas and the TEB gas may be continuously supplied, and the other gas may be intermittently supplied a plurality of times. For example, the TEB gas may be intermittently supplied several times during a period in which the DS gas is continuously supplied, and the DS gas is intermittently supplied several times during the period in which the TEB gas is continuously supplied. You may make it supply.

Further, in the film forming step, both the DS gas and the TEB gas may be intermittently supplied a plurality of times. At this time, the DS gas supply period and the TEB gas supply period may be the same or different. When the DS gas supply period and the TEB gas supply period are different, for example, the TEB gas may be supplied during the DS gas supply period, or the DS gas is supplied during the TEB gas supply period. You may make it do.

In addition, when both the DS gas and the TEB gas are intermittently supplied a plurality of times in the film forming step, the DS gas supply period and the TEB gas supply period are partially overlapped with each other. Also good. For example, in the film forming step, a cycle including a step of supplying only TEB gas, a step of supplying DS gas and TEB gas at the same time, and a step of supplying only DS gas may be performed a plurality of times.

Also in these modified examples, the processing conditions can be the same as the film forming sequence shown in FIG. Also in these modified examples, the same effect as the film forming sequence shown in FIG. 4 can be obtained. Furthermore, according to these modified examples, the film thickness can be controlled by changing the number of intermittent supply repetitions, and the controllability of the film thickness can be improved. Further, according to these modified examples, reaction by-products generated during the film forming step can be efficiently removed from the processing chamber 201, and the quality of the film forming process can be improved.

<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.

For example, in the above-described embodiment, the case where one kind of silane raw material is used as the raw material has been described.

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-described recipe is not limited to a case of newly creating, but may be prepared by changing an existing recipe that has already been installed in the substrate processing apparatus, for example. 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, the example in which the first and second supply units are provided in the processing chamber so as to follow the inner wall of the reaction tube has been described. However, the present invention is not limited to the above-described embodiment. For example, as shown in FIG. 7A, the vertical processing furnace has a cross-sectional structure. A buffer chamber is provided on the side wall of the reaction tube, and the first and second supply units having the same configuration as that of the above-described embodiment are provided in the buffer chamber. May be provided in the same arrangement as in the above-described embodiment. FIG. 7A shows an example in which a supply buffer chamber and an exhaust buffer chamber are provided on the side wall of the reaction tube, and they are arranged at positions facing each other across the wafer. FIG. 7A shows an example in which the supply buffer chamber is partitioned into a plurality of (three) spaces and each nozzle is arranged in each space. The arrangement of the three spaces in the buffer chamber is the same as the arrangement of the first and second supply units. Also, for example, as shown in FIG. 7B, the vertical processing furnace has a sectional structure, a buffer chamber is provided in the same arrangement as in FIG. 7A, a first supply unit is provided in the buffer chamber, You may make it provide a 2nd supply part so that a communication part with a process chamber may be pinched | interposed from both sides, and it may follow an inner wall of a reaction tube. The configuration other than the reaction tube described in FIGS. 7A and 7B is the same as the configuration of each part of the processing furnace shown in FIG. Even when these processing furnaces are used, the same effects as those of the above-described embodiment can be obtained.

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 as these can be obtained.

Also, 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.

Hereinafter, examples will be described.

As the sample 1, using the substrate processing apparatus shown in FIG. 1, a step of supplying DS gas and N ₂ gas from a first supply unit (hereinafter referred to as nozzle A), and one of the pair of second supply units ( The Si film was formed on the wafer (bare wafer) by simultaneously performing the step of independently supplying the TEB gas from the nozzle B). Gas supply from the other supply part (hereinafter, nozzle C) different from the one supply part in the pair of second supply parts was not performed. The supply flow rates of the gases from the nozzles A and B were set to predetermined flow rates within the range shown in the column of the sample 1 in FIG. The other processing conditions are set to predetermined values within the processing condition range described in the above embodiment.

As the samples 2 to 4, the substrate processing apparatus shown in FIG. 1 is used, and the step of supplying the DS gas independently from the nozzle A and the step of supplying the TEB gas and N ₂ gas from the nozzles B and C are performed simultaneously. Thus, an Si film was formed on the wafer (bare wafer). The gas supply flow rates from the nozzles A to C were set to predetermined flow rates within the ranges shown in the rows of samples 2 to 4 in FIG. The other processing conditions are set to predetermined values within the processing condition range described in the above embodiment.

Using the substrate processing apparatus shown in FIG. 1 as the sample 5, the step of supplying the DS gas and the N ₂ gas from the nozzle A and the step of supplying the TEB gas and the N ₂ gas from the nozzles B and C are performed simultaneously. Thus, a Si film was formed on the wafer (bare wafer). The gas supply flow rates from the nozzles A to C were set to predetermined flow rates within the range shown in the column of the sample 5 in FIG. The other processing conditions are set to predetermined values within the processing condition range described in the above embodiment.

Then, the in-plane film thickness distributions of the Si films of Samples 1 to 5 were measured. FIG. 6A shows the measurement result. The vertical axis in FIG. 6A represents the difference from the average film thickness / average film thickness [a. u. The horizontal axis indicates the distance [mm] from the center of the wafer at the measurement position. In FIG. 6 (a), ■, □, ◇, ▲, and ○ indicate samples 1 to 5, respectively.

FIG. 6A shows that the in-plane film thickness distribution of the Si film of sample 1 is a central concave distribution, and the degree thereof is strong. That is, when the DS gas is supplied from the nozzle A, when the TEB gas is supplied from the nozzle B and the TEB gas is not supplied from the nozzle C, the central concave portion having a strong in-plane film thickness distribution of the Si film is used. It can be seen that there may be a distribution.

Further, according to FIG. 6A, it can be seen that the in-plane film thickness distribution of the Si film of Sample 2 has a lower degree of central concave distribution than that of the Si film of Sample 1. That is, when supplying the DS gas from the nozzle A, when supplying the TEB gas from both the nozzles B and C, the degree of the central concave distribution of the in-plane film thickness distribution of the Si film is reduced. It can be seen that the in-plane film thickness distribution can be controlled.

Further, according to FIG. 6A, the in-plane film thickness distribution of the sample 3 Si film has a lower degree of central concave distribution than that of the sample 2 Si film, and is close to a flat distribution. That is, when the DS gas is supplied from the nozzle A, not only the TEB gas is supplied from both the nozzles B and C, but also the flow rate of the N ₂ gas supplied from the nozzles B and C is increased, so that the surface of the Si film It can be seen that the in-plane film thickness distribution of the Si film can be controlled over a wide range, for example, by bringing the inner film thickness distribution closer to a flat distribution.

Further, according to FIG. 6A, it can be seen that the in-plane film thickness distribution of the sample 4 Si film has a higher degree of central convex distribution than that of the sample 3 Si film. That is, when the DS gas is supplied from the nozzle A, not only the TEB gas is supplied from both the nozzles B and C, but also the flow rate of the TEB gas supplied from the nozzles B and C is increased to increase the in-plane of the Si film. It can be seen that the in-plane film thickness distribution of the Si film can be controlled over a wide range, such as by central convex differentiation of the film thickness distribution.

Further, according to FIG. 6A, the in-plane film thickness distribution of the Si film of Sample 5 shows a clear central convex distribution as compared with that of the Si film of Sample 4, and the degree thereof is strong. I understand. That is, when the DS gas is supplied from the nozzle A, not only the TEB gas is supplied from both the nozzles B and C, but also the flow rate of the N ₂ gas supplied from the nozzle A is increased, so that the film on the outer periphery of the Si film is increased. It can be seen that the in-plane film thickness distribution of the Si film can be controlled over a wide range, for example, by making the thickness thinner than the film thickness in other regions and making the in-plane film thickness distribution of the Si film a strong central convex distribution. And, if a central convex distribution Si film can be formed on a bare wafer with a small surface area where no uneven structure is formed on the surface, on a pattern wafer with a large surface area where a fine uneven structure is formed on the surface, It is possible to form a flat distribution Si film.

200 wafer (substrate)
249a Nozzle (first supply unit)
249b Nozzle (second supply unit)
249c Nozzle (second supply unit)

Claims

(A) supplying the raw material containing the main element constituting the film from the first supply unit to the substrate and exhausting it from the exhaust unit;
(B) From the pair of second supply parts disposed adjacent to the first supply part so as to sandwich a straight line passing through the first supply part and the exhaust part, the main element-free reactant is obtained. Supplying to the substrate and exhausting from the exhaust unit;
A method of manufacturing a semiconductor device, comprising: forming the film on the substrate by simultaneously performing at least a certain period of time under the condition that the raw material is not thermally decomposed when the raw material is present alone.
2. The step of forming the film, wherein (a) and (b) are performed simultaneously for at least a certain period under a condition that each of the raw material and the reactant does not thermally decompose when each of the raw material and the reactant exists alone. Semiconductor device manufacturing method.
2. The method of manufacturing a semiconductor device according to claim 1, wherein the raw material has a thermal decomposition temperature higher than a thermal decomposition temperature of the reactant.
2. The method of manufacturing a semiconductor device according to claim 1, wherein the raw material satisfies an octet rule, and the reactant does not satisfy an octet rule.
The method for manufacturing a semiconductor device according to claim 1, wherein the reactant acts catalytically on the raw material.
2. The method of manufacturing a semiconductor device according to claim 1, wherein the raw material includes Si—H bonds, and the reactant includes boron.
The method of manufacturing a semiconductor device according to claim 6, wherein the reactant does not contain chlorine.
The method of manufacturing a semiconductor device according to claim 7, wherein the raw material includes silicon hydride, and the reactant includes alkylborane.
2. The method of manufacturing a semiconductor device according to claim 1, wherein in (b), an inert gas is supplied together with the reactant from the second supply unit.
The film thickness distribution of the film to be formed is controlled by adjusting at least one of a supply flow rate of an inert gas supplied from the second supply unit and a supply flow rate of the reactant. A method for manufacturing a semiconductor device.
10. The method of manufacturing a semiconductor device according to claim 9, wherein a film thickness distribution of the film to be formed is controlled by adjusting a supply flow rate of an inert gas supplied from the second supply unit.
2. The method of manufacturing a semiconductor device according to claim 1, wherein in (a), an inert gas is supplied together with the raw material from the first supply unit.
The semiconductor according to claim 12, wherein the film thickness distribution of the film to be formed is controlled by adjusting at least one of a supply flow rate of an inert gas supplied from the first supply unit and a supply flow rate of the raw material. Device manufacturing method.
13. The method of manufacturing a semiconductor device according to claim 12, wherein the film thickness distribution of the formed film is controlled by adjusting a supply flow rate of the inert gas supplied from the first supply unit.
2. The method of manufacturing a semiconductor device according to claim 1, wherein the pair of second supply units are arranged adjacent to the first supply unit so as to sandwich the first supply unit.
2. The method of manufacturing a semiconductor device according to claim 1, wherein the exhaust unit is disposed at a position facing the first supply unit across the substrate in plan view.
A processing chamber in which processing is performed on the substrate;
An exhaust system for exhausting the atmosphere in the processing chamber from an exhaust unit;
A raw material supply system for supplying a raw material containing a main element constituting the film to the substrate in the processing chamber from the first supply unit;
From the pair of second supply parts arranged adjacent to the first supply part so as to sandwich a straight line passing through the first supply part and the exhaust part, the reactant containing no main element is transferred to the substrate. A reactant supply system to be supplied to
A heater for heating the substrate in the processing chamber;
In the processing chamber, (a) a process of supplying the raw material from the first supply unit to the substrate and exhausting from the exhaust unit, and (b) the reactant from the second supply unit to the substrate. A process of forming the film on the substrate by simultaneously performing at least a certain period of time under the condition that the raw material is not thermally decomposed when the raw material is present alone. A controller configured to control the raw material supply system, the reactant supply system, the exhaust system, and the heater,
A substrate processing apparatus.
In the processing chamber of the substrate processing apparatus,
(A) A procedure for supplying a raw material containing a main element constituting the film from the first supply unit to the substrate and exhausting it from the exhaust unit;
(B) From the pair of second supply parts disposed adjacent to the first supply part so as to sandwich a straight line passing through the first supply part and the exhaust part, the main element-free reactant is obtained. A procedure for supplying to the substrate and exhausting from the exhaust unit;
A program for causing the substrate processing apparatus to execute a procedure for forming the film on the substrate by a computer by simultaneously performing at least a certain period of time under the condition that the raw material is not thermally decomposed when the raw material is present alone. A recorded computer-readable recording medium.