JP2015195410A - Manufacturing method of semiconductor device, substrate processing apparatus, program, and record medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a thin film having excellent ashing resistance while maintaining high etching resistance.SOLUTION: A manufacturing method of a semiconductor device comprises a process of performing the predetermined number of cycles each including: a step of supplying to a substrate, material gas which serves as a silicon source and a carbide source or material gas which serves as a silicon source but does not serve as a carbon source, and catalyst gas; a step of supplying oxide gas and catalyst gas to the substrate; and a step of supplying to the substrate, reformed gas including at least either of carbide or nitride, thereby to form, on the substrate, a thin film containing silicon, oxide and carbon, or a thin film containing silicon, oxide, carbon, and nitrogen.

Description

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

As a process of manufacturing the semiconductor device, a process of forming a thin film such as a silicon oxide film on the substrate by supplying, for example, a source gas containing silicon, an oxidizing gas, or the like to the substrate may be performed. At that time, for example, by using a catalyst gas, it is possible to form a film at a relatively low temperature, and it is possible to improve a thermal history received by the semiconductor device.

When forming the thin film as described above on the substrate, for example, by adding carbon or the like to the thin film, resistance to wet etching by hydrofluoric acid (HF aqueous solution) or the like can be improved.

However, under a relatively low temperature condition, a sufficient amount of carbon is not taken into the film, and it may be difficult to obtain a thin film having high etching resistance. In addition, a thin film to which carbon is added may be inferior in ashing resistance.

An object of the present invention is to form a thin film having high etching resistance and high ashing resistance.

According to one aspect of the invention,
Supplying a source gas that is a silicon source and a carbon source to the substrate or a source gas that is a silicon source but not a carbon source, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate;
Supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A semiconductor device manufacturing method including a step of forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including Is done.

According to another aspect of the invention,
A processing chamber for accommodating the substrate;
A raw material gas supply system for supplying a raw material gas that becomes a silicon source and a carbon source or a silicon source but does not become a carbon source into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber;
A catalyst gas supply system for supplying a catalyst gas into the processing chamber;
A reformed gas supply system for supplying a reformed gas containing at least one of carbon and nitrogen into the processing chamber;
A process for supplying the source gas and the catalyst gas to the substrate in the process chamber; a process for supplying the oxidizing gas and the catalyst gas to the substrate in the process chamber; and the substrate in the process chamber. A thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate A control unit for controlling the raw material gas supply system, the oxidizing gas supply system, the catalyst gas supply system, and the reformed gas supply system so as to perform the forming process;
A substrate processing apparatus is provided.

According to yet another aspect of the invention,
A procedure for supplying a source gas that is a silicon source and a carbon source or a silicon source but not a carbon source to the substrate in the processing chamber, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate in the processing chamber;
Supplying a reformed gas containing at least one of carbon and nitrogen to the substrate in the processing chamber;
A program for causing a computer to execute a procedure for forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a predetermined number of cycles including The

According to the present invention, a thin film having high etching resistance and high ashing resistance can be formed.

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus used suitably by 1st 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 the vertical processing furnace of the substrate processing apparatus used suitably by 1st Embodiment of this invention, and is a figure which shows a processing furnace part with the sectional view on the AA line of FIG. It is a schematic block diagram of the controller of the substrate processing apparatus used suitably by 1st 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 flow in the film-forming sequence of 1st Embodiment of this invention. (A) is a figure which shows the timing of the gas supply in the film-forming sequence of 1st Embodiment of this invention, (b) is a figure which shows the modification. It is a figure which shows the film-forming flow in the film-forming sequence of the other modification of 1st Embodiment of this invention, Comprising: (a) is a figure which shows a SiOC film formation process, (b) is a SiOC film modification process FIG. It is a figure which shows the film-forming flow in the film-forming sequence of 2nd Embodiment of this invention. (A) is a figure which shows the timing of gas supply and RF electric power supply in the film-forming sequence of 2nd Embodiment of this invention, (b) is a figure which shows the modification. It is a figure which shows the film-forming flow in the film-forming sequence of 3rd Embodiment of this invention. (A) is a figure which shows the timing of the gas supply in the film-forming sequence of 3rd Embodiment of this invention, (b) is a figure which shows the modification. It is a figure which shows the film-forming flow in the film-forming sequence of the other modification of 3rd Embodiment of this invention. (A) is a figure which shows the timing of the gas supply and RF electric power supply in the film-forming sequence of the other modification of 3rd Embodiment of this invention, (b) is a figure which shows another modification. It is explanatory drawing of the catalytic reaction of the thin film formation process of 1st Embodiment of this invention, Comprising: (a) is explanatory drawing in step 1a, (b) is explanatory drawing in step 2a. It is a figure which shows the name of various amines used as catalyst gas, a chemical composition formula, a chemical structural formula, and an acid dissociation constant. (A)-(e) is a figure which shows the chemical structural formula of various silane used as source gas, Comprising: It is a figure which shows the chemical structural formula of BTCSM, BTCSE, TCMDDS, DCTMDS, and MCPMDS, respectively. It is a graph which shows the wet etching rate of the thin film formed into a film under the various conditions of the Example and comparative example of this invention.

<First Embodiment>
Hereinafter, a first embodiment of the present invention will be described with reference to the drawings.

(1) Overall 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 heater base (not shown) as a holding plate. The heater 207 activates (excites) the gas with heat.
It also functions as an activation mechanism (excitation unit).

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 (inlet flange) 209 is disposed below the reaction tube 203 concentrically with the reaction tube 203. The manifold 209 is made of, for example, a metal such as stainless steel, 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. Manifold 2
An O-ring 220a as a seal member is provided between 09 and the reaction tube 203. As the manifold 209 is supported by the heater base, the reaction tube 203 is installed vertically. Mainly, a processing vessel (by a reaction tube 203 and a manifold 209)
Reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing container, and is configured so that wafers 200 as substrates can be accommodated in a state of being aligned in multiple stages in a horizontal posture and in a vertical direction by a boat 217 described later.

In the processing chamber 201, nozzles 249a to 249d are provided so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249d have gas supply pipes 232a to 232a.
2d are connected to each other. A gas supply pipe 232e is connected to the gas supply pipe 232a. A gas supply pipe 232f is connected to the gas supply pipe 232c. Thus, the reaction tube 203 includes four nozzles 249a to 249d and a plurality of gas supply tubes 232.
a to 232f, and a plurality of types of gases can be supplied into the processing chamber 201.

The upstream end of the gas supply pipe 232a has, for example, (SiCl ₃ ) ₂ C as a source gas supply source.
An H ₂ (BTCSM) gas supply source 242a is connected. For example, a Si ₂ Cl ₆ (HCDS) gas supply source 242e as a source gas supply source is connected to the upstream end of the gas supply pipe 232e. At the upstream end of the gas supply pipe 232b, for example, H ₂ O as an oxidizing gas supply source is provided.
A gas supply source 242b is connected. For example, a C ₅ H ₅ N (pyridine) gas supply source 242c as a catalyst gas supply source is connected to the upstream end of the gas supply pipe 232c. A C ₃ H ₆ gas supply source 242f as a reformed gas supply source containing, for example, carbon (C) is connected to the upstream end of the gas supply pipe 232f. At the upstream end of the gas supply pipe 232d, for example, nitrogen (N
) Including an NH ₃ gas supply source 242d as a reformed gas supply source. For example, N ₂ gas supply sources 242g to 242j as inert gas supply sources are connected to upstream ends of the gas supply tubes 232g to 232j connected to the gas supply tubes 232a to 232d, respectively. A mass flow controller (MFC) 2 that is a flow rate controller (flow rate control unit) is sequentially connected to the gas supply pipes 232a to 232j in the upstream direction to which the gas supply sources 242a to 242j are connected.
41a to 241j and valves 243a to 243j which are on-off valves are provided, respectively. The downstream ends of the gas supply pipes 232g to 232j are connected to the downstream sides of the valves 243a to 243d of the gas supply pipes 232a to 232d, respectively. Gas supply pipes 232a, 23
The downstream ends of the gas supply pipes 232e and 232f are also connected to the downstream side of the 2c valves 243a and 243c, respectively.

The nozzles 249a to 249c described above are connected to the distal ends of the gas supply pipes 232a to 232c, respectively. As shown in FIG. 2, the nozzles 249 a to 249 c are arranged in an annular space 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. It is provided to stand up towards each. 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 nozzles 249a to 249c are each configured as an L-shaped long nozzle, and each horizontal portion thereof is provided so as to penetrate the side wall of the manifold 209, and each vertical portion thereof is at least one end of the wafer arrangement region. It is provided so as to rise from the side toward the other end side. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. As shown in FIG. 2, the gas supply holes 250 a to 250 c are opened so as to face the center of the reaction tube 203, and gas can be supplied toward the wafer 200. These gas supply holes 250a-250c
Are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided at the same opening pitch.

The nozzle 249d is connected to the tip of the gas supply pipe 232d. Nozzle 2
49d is provided in the buffer chamber 237 which is a gas dispersion space. Buffer room 237
2 is provided in the annular space between the inner wall of the reaction tube 203 and the wafer 200 as shown in FIG. It has been. That is, the buffer chamber 237 is provided on the side of the wafer arrangement area, in a region that horizontally surrounds the wafer arrangement area, along the wafer arrangement area. A gas supply hole 250 for supplying a gas is provided at the end of the buffer chamber 237 adjacent to the wafer 200.
e is provided. The gas supply hole 250 e is opened so as to face the center of the reaction tube 203, and gas can be supplied toward the wafer 200. This gas supply hole 25
A plurality of 0e are provided from the lower part to the upper part of the reaction tube 203, each having the same opening area, and further provided at the same opening pitch.

As shown in FIG. 2, the nozzle 249 d is provided at the end of the buffer chamber 237 opposite to the end where the gas supply hole 250 e is provided, along the upper portion from the lower portion of the inner wall of the reaction tube 203.
It is provided so as to rise upward in the stacking direction of 0. That is, the nozzle 249
d is provided along the wafer arrangement region in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged. The nozzle 249d is configured as an L-shaped long nozzle, and its horizontal portion is provided so as to penetrate the side wall of the manifold 209, and its vertical portion is at least from one end side to the other end side of the wafer arrangement region. It is provided to stand up. A gas supply hole 250d for supplying a gas is provided on a side surface of the nozzle 249d. As shown in FIG. 2, the gas supply hole 250 d is opened to face the center of the buffer chamber 237. The gas supply hole 250d is provided in the buffer chamber 237.
Similarly to the gas supply hole 250e, a plurality of reaction tubes 203 are provided from the bottom to the top. Each of the gas supply holes 250d has the same opening area from the upstream side (lower part) to the downstream side (upper part) when the differential pressure between the buffer chamber 237 and the processing chamber 201 is small. However, when the differential pressure is large, the opening area may be increased from the upstream side to the downstream side, or the opening pitch may be decreased.

In the present embodiment, by adjusting the opening area and opening pitch of each gas supply hole 250d from the upstream side to the downstream side as described above, first, there is a difference in flow velocity from each of the gas supply holes 250d. However, the gas with the same flow rate is ejected. The gas ejected from each of the gas supply holes 250d is once introduced into the buffer chamber 237, and the difference in gas flow velocity is made uniform in the buffer chamber 237. That is,
The gas ejected into the buffer chamber 237 from each of the gas supply holes 250d is transferred to the buffer chamber 23.
7, after the particle velocity of each gas is relaxed, the gas is ejected into the processing chamber 201 from the gas supply hole 250e. Thus, the gas ejected into the buffer chamber 237 from each of the gas supply holes 250d becomes a gas having a uniform flow rate and flow velocity when ejected into the processing chamber 201 from each of the gas supply holes 250e.

Thus, in the gas supply method using the long nozzle in the present embodiment, the reaction tube 2
The nozzles 249a to 249d and the buffer chamber 237 are arranged in an annular vertically long space defined by the inner wall of 03 and the ends of a plurality of stacked wafers 200, that is, in a cylindrical space. Gas is transferred via the nozzles 249a to 249d and the buffer chamber 237.
The gas is first ejected into the reaction tube 203 from the gas supply holes 250a to 250e respectively opened in the vicinity of the wafer 200, and the main flow of the gas in the reaction tube 203 is in a direction parallel to the surface of the wafer 200, that is, The horizontal direction. With such a configuration, it is possible to supply gas uniformly to each wafer 200, and there is an effect of improving the uniformity of the film thickness formed on the surface of each wafer 200. The gas flowing on the surface of the wafer 200, that is, the residual gas after the reaction flows toward the exhaust port, that is, the direction of the exhaust pipe 231 described later. The direction of the flow of the residual gas depends on the position of the exhaust port. And is not limited to the vertical direction.

From the gas supply pipe 232a, as a source gas containing Si (C) and carbon (C) and a halogen element (fluorine (F), chlorine (Cl), bromine (Br), etc.) and having a Si-C bond, for example, A chlorosilane-based source gas containing a methylene group, which is a source gas containing Si, a methylene group as an alkylene group, and a chloro group as a halogen group, is supplied into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a. . The chlorosilane-based source gas containing a methylene group is a silane-based source gas containing a methylene group and a chloro group, and is a source gas containing at least Si, a methylene group containing C, and Cl as a halogen element. That is. As the chlorosilane-based source gas containing a methylene group supplied from the gas supply pipe 232a, for example, methylene bis (trichlorosilane) gas, that is,
Bis (trichlorosilyl) methane ((SiCl ₃ ) ₂ CH ₂ , abbreviation: BTCSM) gas can be used.

As shown in FIG. 15A, BTCSM includes a methylene group as an alkylene group in its chemical structural formula (in one molecule). In the methylene group contained in BTCSM, two bonds are respectively bonded to Si to form a Si—C—Si bond. The Si—C bond included in the source gas is, for example, a part of the Si—C—Si bond included in BTCSM, and the methylene group included in BTCSM includes C constituting the Si—C bond.

The source gas containing Si, C and a halogen element and having a Si—C bond includes, for example, Si, ethylene group as an alkylene group, and chlorosilane containing an ethylene group which is a source gas containing a chloro group as a halogen group. System material gas is included. As the chlorosilane-based source gas containing an ethylene group, for example, ethylene bis (trichlorosilane) gas, that is, 1,2-bis (trichlorosilyl) ethane ((SiCl ₃ ) ₂ C ₂ H ₄ , abbreviation: B
TCSE) gas or the like can be used.

As shown in FIG. 15B, BTCSE includes an ethylene group as an alkylene group in its chemical structural formula (in one molecule). In the ethylene group contained in BTCSE, two bonds are bonded to Si, respectively, to form a Si—C—C—Si bond. The Si—C bond included in the source gas is, for example, a part of the Si—C—C—Si bond included in BTCSE, and the ethylene group included in BTCSE contains C constituting the Si—C bond.

The alkylene group is a functional group obtained by removing two hydrogen (H) atoms from a chain saturated hydrocarbon (alkane) represented by the general formula C _n H _{2n + 2} , and represented by the general formula C _n H _2n. Is an assembly of atoms. The alkylene group includes a propylene group and a butylene group in addition to the methylene group and ethylene group mentioned above. Thus, the source gas containing Si, C and a halogen element and having a Si—C bond includes an alkylenehalosilane-based source gas containing Si, an alkylene group and a halogen element. The alkylene halosilane-based source gas is a halosilane-based source gas containing an alkylene group, and, for example, an alkylene between Si-Si bonds is maintained while maintaining a state in which many halogen elements are bonded to Si bonds in the halosilane-based source gas. It can be said that the gas has a structure in which a group is introduced. BTCSM gas, BTCSE gas, and the like are included in the alkylenehalosilane-based source gas.

The source gas containing Si, C and a halogen element and having a Si—C bond includes, for example, Si, a methyl group as an alkyl group, and a chlorosilane containing a methyl group that is a source gas containing a chloro group as a halogen group. System material gas is included. The chlorosilane-based source gas containing a methyl group is a silane-based source gas containing a methyl group and a chloro group, and is a source gas containing at least Si, a methyl group containing C, and Cl as a halogen element. That is. Examples of the chlorosilane-based source gas containing a methyl group include 1,1,2,2-
Tetrachloro-1,2-dimethyldisilane ((CH ₃ ) ₂ Si ₂ Cl ₄ , abbreviation: TCDM
DS) gas, 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH ₃ ) ₄
Si ₂ Cl ₂ (abbreviation: DCTMDS) gas, and 1-monochloro-1,1,2,2,2-
Pentamethyldisilane ((CH ₃ ) ₅ Si ₂ Cl, abbreviation: MCPMDS) gas or the like can be used.

As shown in FIG. 15 (c), TCDMDS contains two methyl groups as alkyl groups in its chemical structural formula (in one molecule). In the two methyl groups contained in TCDMDS, each bond is bonded to Si to form a Si—C bond. The Si—C bond of the source gas is
For example, it is a Si—C bond included in TCMDDS, and two methyl groups included in TCMDDS each include C constituting such a Si—C bond.

As shown in FIG. 15D, DCTMDS includes four methyl groups as alkyl groups in its chemical structural formula (in one molecule). Each of the four methyl groups contained in DCTMDS is bonded to Si to form a Si—C bond. The Si—C bond of the source gas is
For example, it is a Si—C bond included in DCTMDS, and four methyl groups included in DCTMDS each include C constituting such a Si—C bond.

As shown in FIG. 15 (e), MCPMDS contains five methyl groups as alkyl groups in its chemical structural formula (in one molecule). Each of the five methyl groups contained in MCPMDS is bonded to Si to form a Si—C bond. The Si—C bond of the source gas is
For example, it is a part of the Si—C bond contained in MCPMDS, and the five methyl groups contained in MCPMDS each contain C constituting the Si—C bond that the source gas has. BT mentioned above
Unlike source gases such as CSM gas, BTCSE gas, TCMDDS gas, DCTMDS gas, etc., MCPMDS gas is untargeted due to the arrangement of methyl and chloro groups surrounding Si in the MCPMDS molecule (in the chemical structure) It has an asymmetry structure. As described above, in this embodiment, not only the source gas whose chemical structural formula is as shown in FIGS. 15A to 15D but also the source gas whose chemical structural formula is asymmetry may be used. it can.

The alkyl group is a functional group obtained by removing one H atom from a chain saturated hydrocarbon (alkane) represented by the general formula C _n H _{2n + 2} , and includes an atom represented by the general formula C _n H _{2n + 1.} It is an aggregate. The alkyl group includes an ethyl group, a propyl group, a butyl group and the like in addition to the methyl group listed above. As described above, the source gas containing Si, C and a halogen element and having a Si—C bond includes an alkylhalosilane-based source gas containing Si, an alkyl group, and a halogen element. The alkylhalosilane-based source gas is a halosilane-based source gas containing an alkyl group, and can be said to be a gas having a structure in which some halogen groups of the halosilane-based source gas are replaced with alkyl groups. TCMDDS gas, DCTMDS gas, MCPMDS gas, and the like are included in the alkylhalosilane-based source gas.

BTCSM gas, BTCSE gas, TCDMDS gas, DCTMDS gas, MCPMD
S gas contains C, halogen element (Cl) and at least two Si atoms in one molecule.
It can be said that the source gas has a -C bond. These can also be referred to as source gases to be a silicon (Si) source and a carbon (C) source. By using this type of source gas,
As will be described later, C can be taken into the thin film to be formed at a high concentration. On the other hand, as will be described later, HCDS gas, which is a chlorosilane-based source gas that does not contain C in gas molecules, or BTB, which is an aminosilane-based source gas that contains C in gas molecules but has no Si—C bond.
AS gas or the like is a raw material gas that becomes a Si source but does not become a C source. Even when this type of source gas is used, C is hardly taken into the thin film to be formed, as will be described later.

From the gas supply pipe 232e, a source gas containing silicon (Si) and a halogen element, that is, a halosilane-based source gas not containing C in gas molecules, for example, containing chloro groups as Si and halogen groups, and gas molecules A chlorosilane-based source gas not containing C is supplied into the processing chamber 201 via the MFC 241e, the valve 243e, the gas supply pipe 232a, and the nozzle 249a. As described above, the chlorosilane-based source gas that does not contain C in the gas molecules is a source gas that becomes a Si source but does not become a C source. For example, hexachlorodisilane (Si ₂ Cl ₆ , abbreviation: HCDS) gas can be used as the chlorosilane-based source gas that does not contain C in the gas molecules and is supplied from the gas supply pipe 232e.

Here, the raw material gas is a raw material in a gaseous state, 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. In the present specification, when the term “raw material” is used, it means “a liquid raw material in a liquid state”, “a raw material gas in a gaseous state”, or both. is there. Therefore, when the term “halosilane-based material (chlorosilane-based material)” is used in the present specification, the term “halosilane-based material in a liquid state (chlorosilane-based material)” means “halosilane-based material in a gas state”. It may mean "source gas (chlorosilane-based source gas)" or both. BTCSM, BTCSE, TCD
When using a liquid raw material that is in a liquid state at normal temperature and pressure, such as MDS, DCTMDS, MCPMDS, and HCDS, the liquid raw material is vaporized by a vaporization system such as a vaporizer or a bubbler, and the raw material gas (BTCSM gas, BTCSE gas, TCMDDS gas, DCTMDS gas, MC
(PMDS gas, HCDS gas).

From the gas supply pipe 232b, as an oxidizing gas, for example, a gas containing oxygen (O) (oxygen-containing gas) is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b. Examples of the oxidizing gas supplied from the gas supply pipe 232b include water vapor (
H ₂ O gas) can be used. When supplying the H ₂ O gas, an oxygen (O ₂ ) gas and a hydrogen (H ₂ ) gas may be supplied to an external combustion apparatus (not shown) to generate and supply the H ₂ O gas.

From the gas supply pipe 232c, as a catalyst gas having an acid dissociation constant (hereinafter also referred to as pKa) of about 1 to 11, preferably about 5 to 11, more preferably 5 to 7, for example, nitrogen having a lone pair of electrons. Gas containing (N) (nitrogen-based gas) is MFC 241c, valve 243c,
It is supplied into the processing chamber 201 through the nozzle 249c. Here, the acid dissociation constant (pKa) is one of the indices quantitatively representing the strength of the acid, and the equilibrium constant Ka in the dissociation reaction in which hydrogen ions are released from the acid is represented by a negative common logarithm. Is. The catalyst gas contains N having a lone pair of electrons, so that its catalytic action weakens the bonding force of the O—H bond of the surface of the wafer 200 or an oxidizing gas such as H ₂ O gas, and the like, Promotes decomposition and also H ₂
Promotes oxidation reaction with O gas. As a nitrogen-based gas containing N having a lone electron pair,
For example, an amine-based gas containing an amine in which at least one hydrogen atom of ammonia (NH ₃ ) is substituted with a hydrocarbon group such as an alkyl group can be given. As the catalyst gas supplied from the gas supply pipe 232c, for example, pyridine (C ₅ H ₅ N) gas which is an amine-based gas can be used.

As shown in FIG. 14, various amines used as the catalyst gas include, for example, pyridine (C ₅
Aminopyridine (C ₅ H ₆ N ₂ , pKa = 6.89) in addition to H ₅ N, pKa = 5.67)
, Picoline (C ₆ H ₇ N, pKa = 6.07), lutidine (C ₇ H ₉ N, pKa = 6.9)
6), pyrimidine _{(C 4 H 4 N 2,} pKa = 1.30), quinoline _{(C 9} H 7 N, pKa
= 4.97), piperazine _{(C 4 H 10 N 2,} pKa = 9.80), and piperidine (
C ₅ H ₁₁ N, pKa = 11.12) and the like. The various amines shown in FIG. 14 are also cyclic amines in which the hydrocarbon group is cyclic. It can be said that these cyclic amines are heterocyclic compounds having a cyclic structure composed of a plurality of kinds of elements of C and N, that is, nitrogen-containing heterocyclic compounds. These amine-based gases as catalyst gases can be said to be amine-based catalyst gases.

Here, the amine-based gas refers to a gas containing an amine in a gaseous state, for example, a gas obtained by vaporizing an amine that is in a liquid state at normal temperature and normal pressure, or a gas that is in a gaseous state at normal temperature and normal pressure. It is. When the term “amine” is used herein, it may mean “amine in liquid state”, “amine-based gas in gas state”, or both. is there. When using amines that are in a liquid state at normal temperature and pressure, such as pyridine, aminopyridine, picoline, lutidine, pyrimidine, quinoline, piperazine, and piperidine, the liquid amine is vaporized by a vaporizer such as a vaporizer or bubbler. Thus, it is supplied as an amine-based gas (pyridine gas, aminopyridine gas, picoline gas, lutidine gas, pyrimidine gas, quinoline gas, piperazine gas, and piperidine gas). In contrast, trimethylamine ((CH ₃ ) ₃ N, abbreviated as T, which will be described later.
In the case of using an amine that is in a gaseous state under normal temperature and pressure as in MA), the amine can be supplied as an amine-based gas (TMA gas) without being vaporized by a vaporization system such as a vaporizer or a bubbler.

From the gas supply pipe 232f, as a reformed gas containing at least one of carbon (C) and nitrogen (N), for example, a carbon-containing gas (C-containing gas) as a reformed gas containing C is MFC241f, The gas is supplied into the processing chamber 201 through the valve 243f, the gas supply pipe 232c, and the nozzle 249c. The C-containing gas includes a hydrocarbon-based gas. The hydrocarbon may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may be a chain hydrocarbon or a cyclic hydrocarbon. As the C-containing gas supplied from the gas supply pipe 232f, for example, propylene (which is a hydrocarbon-based gas containing a chain unsaturated hydrocarbon having one double bond)
C ₃ H ₆ ) gas can be used.

From the gas supply pipe 232d, as a reformed gas containing at least one of C and N, for example, a nitrogen-containing gas (N-containing gas) as a reformed gas containing N is MFC241d.
, And supplied to the processing chamber 201 through the valve 243d, the nozzle 249d, and the buffer chamber 237. The N-containing gas includes a non-amine gas. As the N-containing gas supplied from the gas supply pipe 232d, for example, NH ₃ gas which is a non-amine gas can be used.

From the gas supply pipes 232g to 232j, as an inert gas, for example, nitrogen (N ₂ ) gas includes MFCs 241g to 241j, valves 243g to 243j, and gas supply pipe 232, respectively.
a to 232d, nozzles 249a to 249d, and the buffer chamber 237 are supplied into the processing chamber 201. N ₂ gas as an inert gas also acts as a purge gas. The N ₂ gas supplied from the gas supply pipe 232j may also act as an assist gas (ignition gas) that assists plasma ignition.

When the gas as described above is caused to flow from each gas supply pipe, the gas supply pipe 232a,
232e, MFCs 241a and 241e, and valves 243a and 243e constitute a source gas supply system that supplies source gas. Nozzle 249a, BTCSM gas supply source 242a,
The HCDS gas supply source 242e may be included in the source gas supply system. The source gas supply system can also be referred to as a source supply system. The source gas supply system is regarded as an assembly of a plurality of supply lines (supply systems) that supply a plurality of types of source gases that are element sources of different elements and a plurality of types of source gases that have different molecular structures. You can also. That is, the raw material gas supply system includes a BTCSM gas supply line mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a, and mainly the gas supply pipe 232e, the MFC 241e, and the valve 243.
It can be said that it is an aggregate of the HCDS gas supply line constituted by e. You may consider including the nozzle 249a and each corresponding source gas supply source 242a, 242e in each supply line.

In addition, an oxidizing gas supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. The nozzle 249b and the H ₂ O gas supply source 242b may be included in the oxidizing gas supply system.

Further, a catalyst gas supply system is mainly configured by the gas supply pipe 232c, the MFC 241c, and the valve 243c. The nozzle 249c and the pyridine gas supply source 242c may be included in the catalyst gas supply system. The catalyst gas supply system can also be referred to as an amine-based catalyst gas supply system.

In addition, the gas supply pipes 232d and 232f, the MFCs 241d and 241f, and the valve 24 are mainly used.
3d and 243f constitute a reformed gas supply system for supplying a reformed gas containing at least one of C and N. Nozzle 249d, buffer chamber 237, NH ₃ gas supply source 2
The 42d, C ₃ H ₆ gas supply source 242f may be included in the reformed gas supply system. Further, the reformed gas supply system is regarded as an aggregate of a plurality of supply lines (supply systems) that respectively supply a plurality of types of reformed gases containing different elements and a plurality of types of reformed gases having different molecular structures. You can also. That is, the reformed gas supply system mainly includes the gas supply pipe 232d and the MFC 241d.
, NH ₃ gas supply line constituted by the valve 243d, mainly gas supply pipe 232f,
It can be said that this is an assembly of the MFC 241f and the C ₃ H ₆ gas supply line constituted by the valve 243f. The individual supply lines may include the corresponding nozzles 249d and 249c, the reformed gas supply sources 242d and 242f, and the buffer chamber 237.

Further, mainly, gas supply pipes 232g to 232j, MFCs 241g to 241j, a valve 24
An inert gas supply system is configured by 3g to 243j. The gas supply pipes 232a-2
The nozzles 249a to the downstream side of the connecting portions with the gas supply pipes 232g to 232j in 32d
249d, buffer chamber 237, and N ₂ gas supply sources 242g to 242j may be included in the inert gas supply system. The inert gas supply system also functions as a purge gas supply system. Gas supply pipe 232j for supplying N ₂ gas as assist gas, MFC 241j, valve 243j
Can also be referred to as an assist gas supply system. Nozzle 249d, buffer chamber 237, N ₂
The gas supply source 242j may be included in the assist gas supply system.

For supply systems other than the source gas supply system and the reformed gas supply system, such as an oxidizing gas supply system and a catalyst gas supply system, supply lines (supply systems) that supply a plurality of types of gases having different molecular structures, etc. ) May be provided.

In the buffer chamber 237, as shown in FIG.
The rod-shaped electrodes 269 and 270 are arranged along the stacking direction of the wafer 200 from the lower part to the upper part of the reaction tube 203. Each of the rod-shaped electrodes 269 and 270 has a nozzle 249d.
Are provided in parallel. Each of the rod-shaped electrodes 269 and 270 is protected by being covered with an electrode protection tube 275 from the upper part to the lower part. One of the rod-shaped electrodes 269 and 270 is connected to the high-frequency power source 273 via the matching unit 272, and the other is connected to the ground that is the reference potential. The rod-shaped electrode 26 is supplied from the high-frequency power source 273 via the matching unit 272.
By applying radio frequency (RF) power between the electrodes 9 and 270, plasma is generated in the plasma generation region 224 between the rod-shaped electrodes 269 and 270. The rod-shaped electrodes 269 and 270 and the electrode protection tube 275 mainly constitute a plasma source as a plasma generator (plasma generator). The matching device 272 and the high-frequency power source 273 may be included in the plasma source. The plasma source functions as an activation mechanism (excitation unit) that activates (excites) gas into a plasma state.

The electrode protection tube 275 has a structure in which each of the rod-shaped electrodes 269 and 270 can be inserted into the buffer chamber 237 while being isolated from the atmosphere in the buffer chamber 237. Here, when the oxygen concentration inside the electrode protection tube 275 is approximately the same as the oxygen concentration in the outside air (atmosphere), the electrode protection tube 2
The rod-shaped electrodes 269 and 270 respectively inserted into the 75 are oxidized by heat from the heater 207. Therefore, the inside of the electrode protection tube 275 is filled with an inert gas such as N ₂ gas, or the inside of the electrode protection tube 275 is purged with an inert gas such as N ₂ gas using an inert gas purge mechanism. Thus, the oxygen concentration inside the electrode protective tube 275 is reduced, and the rod-shaped electrode 269 is reduced.
, 270 can be prevented from being oxidized.

The reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 includes a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure in the processing chamber 201 and an APC (Auto Pre) as a pressure regulator (pressure adjustment unit).
A vacuum pump 246 as an evacuation device is connected via a s sure controller) valve 244. The APC valve 244 can open and close the valve while the vacuum pump 246 is operated, thereby evacuating and stopping the evacuation in the processing chamber 201. Further, with the vacuum pump 246 operated, The valve is configured such that 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. The exhaust pipe 231 is not limited to being provided in the reaction pipe 203, and the nozzles 249 a to 249 are provided.
It may be provided in the manifold 209 in the same manner as d.

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 configured to contact the lower end of the manifold 209 from the lower side in the vertical direction. The seal cap 219 is made of a metal such as stainless steel and has a disk shape. On the upper surface of the seal cap 219, an O-ring 2 serving as a seal member that comes into contact with the lower end of the manifold 209 is provided.
20b is provided. On the opposite side of the seal cap 219 from the processing chamber 201, a rotation mechanism 267 for rotating a boat 217 described later is installed. Rotation shaft 2 of the rotation mechanism 267
55 is connected to the boat 217 through the seal cap 219. Rotating mechanism 267
Is configured to rotate the wafer 200 by rotating the boat 217.
The seal cap 219 is configured to be lifted and lowered in the vertical direction by a boat elevator 115 as a lifting mechanism vertically installed outside the reaction tube 203. The boat elevator 115 raises and lowers the seal cap 219 to move the boat 217 into the processing chamber 201.
It is configured to be able to carry in and out. That is, the boat elevator 115 transfers the wafer 217 and the wafer 200 supported by the boat 217 to the processing chamber 2.
It is configured as a transport device (transport mechanism) for transporting in and out of 01.

The boat 217 as a substrate support is made of a heat-resistant material such as quartz or silicon carbide, and supports a plurality of wafers 200 in a horizontal posture and aligned in a state where the centers are aligned with each other in multiple stages. It is configured. Under the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or silicon carbide are supported in multiple stages in a horizontal posture, and the heater 20
7 is configured such that the heat from 7 is not easily transmitted to the seal cap 219 side. However, a heat insulating cylinder configured as a cylindrical member made of a heat resistant material such as quartz or silicon carbide may be provided without providing the heat insulating plate 218 under the boat 217.

A temperature sensor 263 as a temperature detector is installed in the reaction tube 203, and the temperature in the processing chamber 201 is adjusted by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. It is configured to have a desired temperature distribution. Temperature sensor 26
3 is configured in an L shape similarly to the nozzles 249 a to 249 d, and 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), has a CPU (Cen
tral Processing Unit) 121a, RAM (Random Acc)
ess Memory) 121b, a storage device 121c, and an I / O port 121d. RAM 121b, storage device 121c, I / O port 1
21d is configured to be able 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, for example, a flash memory, a HDD (Hard Disk Dri).
ve) 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 substrate processing such as thin film formation 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 substrate processing process such as a thin film forming process to be described later. Hereinafter, the process recipe, the control program, and the like are collectively referred to simply as a program. When the term “program” is used in this specification, it may include only a process recipe alone, only a control program alone, or both. The RAM 121b
It is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily stored.

The I / O port 121d includes the above-described MFCs 241a to 241j and valves 243a to 243.
j, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, matching unit 272, high frequency power supply 273, rotating mechanism 267, boat elevator 11
Connected to 5 mag.

The CPU 121a is configured to read out and execute a control program from the storage device 121c, and to read out a process recipe from the storage device 121c in response to an operation command input from the input / output device 122 or the like. Then, the CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241j, the opening and closing operations of the valves 243a to 243j, the opening and closing operations of the APC valve 244, and the APC valve 244 based on the pressure sensor 245 so as to follow the contents of the read process recipe. Pressure adjustment operation by the motor, activation 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, boat 217 by the boat elevator 115
And the like, the impedance adjustment operation by the matching device 272, the power supply of the high frequency power supply 273, and the like are controlled.

The controller 121 is not limited to being configured as a dedicated computer, and may be configured as a general-purpose computer. For example, an external storage device storing the above-described program (for example, magnetic tape, magnetic disk such as a flexible disk or hard disk, optical disk such as CD or DVD, magneto-optical disk such as MO, semiconductor memory such as USB memory or memory card) 123 is prepared and the controller 12 according to the present embodiment is installed by installing a program on a general-purpose computer using the external storage device 123.
1 can be configured. However, means for supplying the program to the computer are:
It is not limited to the case of supplying via the external storage device 123. For example, the program may be supplied without using the external storage device 123 by using communication means such as the Internet or a dedicated line. 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.

(2) Thin Film Formation Step Next, a sequence example in which a thin film is formed (film formation) on a substrate as one step of a semiconductor device (semiconductor device) manufacturing process using the processing furnace 202 of the substrate processing apparatus described above. explain. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

In this embodiment,
Supplying a source gas serving as a silicon (Si) source and a carbon (C) source or a source gas serving as a silicon source but not a carbon source to the wafer 200 as a substrate, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the wafer 200;
Supplying a modified gas containing at least one of carbon (C) and nitrogen (N) to the wafer 200;
Is performed a predetermined number of times, a thin film containing silicon (Si), oxygen (O), carbon (C), or silicon (Si), oxygen (O), carbon (C),
And a thin film containing nitrogen (N) is formed.

Here, the cycle includes each step of “a step of supplying a source gas and a catalyst gas”, “a step of supplying an oxidizing gas and a catalyst gas”, and “a step of supplying a reformed gas”. It means that each step is included once or more in the cycle. Accordingly, each step may be performed once in one cycle, or at least one of the steps may be performed a plurality of times. 1
In the cycle, each step may be performed the same number of times or a different number of times. The execution order of each step in the cycle can be arbitrarily determined. In this way, the number of times each process is performed,
By appropriately changing the order, combination, etc., thin films having different film quality, film composition, component ratio, and the like can be formed. “Performing a cycle a predetermined number of times” means performing this cycle one or more times, that is, performing this cycle once or repeating it a plurality of times.

For example, one cycle of this embodiment is
Supplying a source gas and a catalyst gas to the wafer 200;
Supplying an oxidizing gas and a catalyst gas to the wafer 200;
By performing a set including a predetermined number of times on the wafer 200, at least Si and O
Forming a first thin film comprising:
By performing the process of supplying the reformed gas to the wafer 200, the first thin film is further converted into a second thin film further including C, the second thin film including C and further including N, or C and N. Modifying the second thin film to include.

  In the present embodiment, each process is performed in a non-plasma atmosphere.

In the present embodiment, the composition ratio of the thin film to be formed includes a plurality of elements constituting the thin film to be formed in order to make the composition ratio be a stoichiometric composition or a predetermined composition different from the stoichiometric composition. Control the supply conditions of multiple types of gases. For example, the supply conditions are controlled in order to make at least one element out of a plurality of elements constituting the thin film to be formed more excessive than the other elements with respect to the stoichiometric composition. Hereinafter, a sequence example in which film formation is performed while controlling the ratio of a plurality of elements constituting the thin film to be formed, that is, the composition ratio of the thin film will be described.

  Hereinafter, the film forming sequence of the present embodiment will be described with reference to FIGS. 4 and 5A.

here,
BTCSM gas as a source gas containing silicon (Si), carbon (C), and a halogen element and having a Si—C bond as a source gas serving as a silicon (Si) source and a carbon (C) source with respect to the wafer 200 A step of supplying pyridine gas as a catalyst gas (step 1a),
A step of supplying H ₂ O gas as an oxidizing gas and pyridine gas as a catalyst gas to the wafer 200 (step 2a);
Forming a silicon oxycarbide film (SiOC film) as a first thin film containing Si, O, and C on the wafer 200 by performing a set including n a predetermined number of times (n times);
As a reformed gas containing at least one of C and N with respect to the wafer 200, N
By performing a process of supplying NH ₃ gas as an N-containing gas that is a reformed gas containing
A silicon oxycarbonitride film (SiOC) as a second thin film containing SiO and further containing N
N film),
A description will be given of an example in which a cycle including is performed a predetermined number of times, for example, once.

By this film forming sequence, a SiOCN film, that is, a SiOC film doped with N (added) is formed on the wafer 200 as a thin film containing Si, O, C, and N. In addition, this SiOCN film is made of C-doped silicon oxynitride film (SiON film), C and N
It can also be referred to as a silicon oxide film doped with (SiO ₂ film, hereinafter also referred to as SiO film).

In this specification, when the term “wafer” is used, it means “wafer itself” or “a laminate (aggregate) of a wafer and a predetermined layer or film formed on the surface”. In other words, it may be called a wafer including a predetermined layer or film formed on the surface. In addition, when the term “wafer surface” is used in this specification, it means “the surface of the wafer itself (exposed surface)” or “the surface of a predetermined layer or film formed on the wafer”. That is, it may mean “the outermost surface of the wafer as a laminated body”.

In the present specification, the phrase “supplying a predetermined gas to the wafer” means “supplying a predetermined gas directly to the surface (exposed surface) of the wafer itself” or “ It may mean that a predetermined gas is supplied to a layer, a film, or the like formed on the wafer, that is, to the outermost surface of the wafer as a laminated body. Further, in this specification, when “describe a predetermined layer (or film) on the wafer” is described, “determine a predetermined layer (or film) directly on the surface (exposed surface) of the wafer itself”. This means that a predetermined layer (or film) is formed on a layer or film formed on the wafer, that is, on the outermost surface of the wafer as a laminate. There is a case.

The use of the term “substrate” in this specification is the same as the case where the term “wafer” is used. In that case, “wafer” may be replaced with “substrate” in the above description.

(Wafer charge and boat load)
When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), 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 processing chamber 201 is evacuated by a vacuum pump 246 so that a desired pressure (degree of vacuum) is obtained. 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 (pressure adjustment). The vacuum pump 246 maintains a state in which it is always operated until at least the processing on the wafer 200 is completed. 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 (temperature adjustment). Heating of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed. However, as will be described later, when processing the wafer 200 at room temperature, the processing chamber 201 by the heater 207 is used.
The inside heating may not be performed. Subsequently, the boat 217 and the wafer 2 by the rotation mechanism 267
00 rotation starts. The rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is as follows.
The process is continuously performed at least until the process on the wafer 200 is completed.

(SiOC film formation process)
Thereafter, the next two steps, that is, steps 1a and 2a are sequentially executed.

[Step 1a]
(BTCSM gas + pyridine gas supply)
The valve 243a is opened and BTCSM gas is allowed to flow into the gas supply pipe 232a. The flow rate of the BTCSM gas is adjusted by the MFC 241a, supplied into the processing chamber 201 through the gas supply hole 250a, and exhausted from the exhaust pipe 231. At this time, the BTCSM gas is supplied to the wafer 200 (BTCSM gas supply). At the same time, the valve 243g is opened, and an inert gas such as N ₂ gas is allowed to flow into the gas supply pipe 232g. N ₂ gas is MFC241g
The flow rate of the exhaust pipe 231 is adjusted by the flow rate and supplied into the processing chamber 201 together with the BTCSM gas.
Exhausted from.

Further, the valve 243c is opened, and pyridine gas is caused to flow into the gas supply pipe 232c. The flow rate of the pyridine gas is adjusted by the MFC 241c, supplied into the processing chamber 201 through the gas supply hole 250c, and exhausted from the exhaust pipe 231. At this time, pyridine gas is supplied to the wafer 200 (pyridine gas supply). At the same time, the valve 243i is opened,
An inert gas such as N ₂ gas is allowed to flow through the gas supply pipe 232i. The flow rate of the N ₂ gas is adjusted by the MFC 241 i, supplied into the processing chamber 201 together with the pyridine gas, and exhausted from the exhaust pipe 231.

Further, in order to prevent BTCSM gas and pyridine gas from entering the nozzles 249 b and 249 d and the buffer chamber 237, the valves 243 h and 243 j are opened and the gas supply pipe 232 is opened.
h, N ₂ gas is allowed to flow in 232j. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 232b and 232d, the nozzles 249b and 249d, and the buffer chamber 237, and the exhaust pipe 23
1 is exhausted.

At this time, the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 1
The pressure is in the range of ˜13330 Pa, preferably 133 to 2666 Pa. MFC24
The supply flow rate of the BTCSM gas controlled by 1a is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. The supply flow rate of the pyridine gas controlled by the MFC 241c is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. The supply flow rate of the N ₂ gas controlled by the MFCs 241g to 241j is, for example, a flow rate in the range of 100 to 10000 sccm. The time for supplying the BTCSM gas and pyridine gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, 1 to 100 seconds, preferably 5 to 60 seconds.

At this time, the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 is, for example, room temperature to 150 ° C., preferably room temperature to 100 ° C., more preferably 50 ° C. to 100 ° C. To do. When the catalyst gas is not supplied at the time of supplying the BTCSM gas, when the temperature of the wafer 200 is less than 250 ° C., the BTCSM is difficult to be chemically adsorbed on the wafer 200, and a practical film formation rate may not be obtained. By supplying pyridine gas as the catalyst gas as in this embodiment, this can be eliminated even if the temperature of the wafer 200 is less than 250 ° C. Wafer 2 in the presence of pyridine gas
By setting the temperature of 00 to 150 ° C. or lower, and further to 100 ° C. or lower, the amount of heat applied to the wafer 200 can be reduced, and the thermal history received by the wafer 200 can be favorably controlled. In the presence of pyridine gas, if the temperature of the wafer 200 is room temperature or higher, BTCSM can be sufficiently adsorbed on the wafer 200, and a sufficient film formation rate can be obtained. Therefore, the temperature of the wafer 200 is from room temperature to 150 ° C., preferably from room temperature to 10 ° C.
The temperature may be 0 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower.

By supplying BTCSM gas to the wafer 200 under the above-described conditions, the wafer 2
A silicon-containing layer (Si-containing layer) containing C and Cl having a thickness of, for example, less than one atomic layer to several atomic layers is formed as a first layer on 00 (surface underlayer film). The Si-containing layer containing C and Cl may be a silicon layer (Si layer) containing C and Cl, or BTCS.
It may be an adsorption layer of M gas or both of them.

The Si layer containing C and Cl includes not only a continuous layer made of Si and containing C and Cl, but also a discontinuous layer and a silicon thin film containing Si and C (Cl thin film) containing these layers. It is a generic name including. A continuous layer made of Si and containing C and Cl may be referred to as a Si thin film containing C and Cl. Si constituting the Si layer containing C and Cl is C
In addition to those in which the bond with C and Cl is not completely broken, the bonds with C and Cl are completely broken.

The BTCSM gas adsorption layer includes a discontinuous adsorption layer as well as a continuous adsorption layer of gas molecules of the BTCSM gas. That is, the BTCSM gas adsorbing layer includes an adsorbing layer having a thickness of less than one molecular layer composed of BTCSM molecules or less than one molecular layer. The BTCSM ((SiCl ₃ ) ₂ CH ₂ ) molecules constituting the BTCSM gas adsorption layer are not only those having the chemical structural formula shown in FIG. 15 (a) but also those in which the bond between Si and C is partially broken. , Including those in which the bond between Si and Cl is partially broken. That is, the BTCSM gas adsorption layer is a BTCSM molecule chemical adsorption layer or BTCS
Includes a physical adsorption layer of CSM molecules.

Here, a layer having a thickness of less than one atomic layer means an atomic layer formed discontinuously, and a layer having a thickness of one atomic layer means an atomic layer formed continuously. Means. In addition, a layer having a thickness less than one molecular layer means a molecular layer formed discontinuously, and a layer having a thickness of one molecular layer means a molecular layer formed continuously. I mean. The Si-containing layer containing C and Cl can include both an Si layer containing C and Cl and an adsorption layer of BTCSM gas. However, as described above, for the Si-containing layer containing C and Cl, “1 atom Layer "," several atomic layer "
The following expressions are used.

When the thickness of the Si-containing layer containing C and Cl as the first layer formed on the wafer 200 exceeds several atomic layers, the action of oxidation in step 2a described later reaches the entire first layer. Disappear. The minimum thickness of the first layer that can be formed on the wafer 200 is less than one atomic layer. Accordingly, 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, the action of the oxidation reaction in Step 2a described later can be relatively enhanced, and in Step 2a The time required for the oxidation reaction can be reduced. The time required for forming the first layer in step 1a can also be shortened. As a result, the processing time per set can be shortened, and the total processing time can be shortened. That is, the film forming rate can be increased. Further, by controlling the thickness of the first layer to 1 atomic layer or less, it becomes possible to improve the controllability of film thickness uniformity.

Under conditions where the BTCSM gas undergoes self-decomposition (pyrolysis), that is, under conditions where a thermal decomposition reaction of BTCSM occurs, Si is deposited on the wafer 200 to form a Si layer containing C and Cl. Under conditions where BTCSM gas does not self-decompose (thermally decompose), that is, BTCS
Under the condition that the thermal decomposition reaction of M does not occur, the BTCSM gas adsorption layer is formed by adsorbing the BTCSM gas on the wafer 200. It is preferable to form a Si layer containing C and Cl on the wafer 200 rather than forming an adsorption layer of BTCSM gas on the wafer 200 because the deposition rate can be increased. However, in this embodiment, since the temperature of the wafer 200 is set to a low temperature of, for example, 150 ° C. or lower, a BTCSM gas adsorption layer is formed on the wafer 200 rather than the Si layer containing C and Cl formed on the wafer 200. There is a possibility that the formation will be superior. Further, when the catalyst gas is not supplied, in the BTCSM gas adsorption layer, the physical adsorption state in which the bond to the base such as the surface of the wafer 200 or the bond between the BTCSM molecules is weaker than the chemical adsorption is dominant. there is a possibility. That is, when the catalyst gas is not supplied, the BTCSM gas adsorption layer may be mostly composed of the BTCSM gas physical adsorption layer.

The pyridine gas as the catalyst gas weakens the bonding force of the O—H bond existing on the surface of the wafer 200, promotes the decomposition of the BTCSM gas, and promotes the formation of the first layer by the chemical adsorption of the BTCSM molecules. That is, as shown in FIG. 13A, for example, pyridine gas as a catalyst gas acts on O—H bonds existing on the surface of the wafer 200 to weaken the O—H bond strength. The hydrogen chloride (HCl) gas is generated and desorbed by the reaction between H having weak bonding force and Cl of the BTCSM gas, and BTCSM molecules (halides) that have lost Cl are chemically adsorbed on the surface of the wafer 200. That is, a BTCSM gas chemical adsorption layer is formed on the surface of the wafer 200. The reason why the pyridine gas weakens the bonding force between O and H is that an N atom having a lone electron pair in the pyridine molecule has an action of attracting H. The magnitude of the action of a predetermined compound containing an N atom or the like to attract H can be determined, for example, using the above-described acid dissociation constant (pKa) as one index.

As described above, pKa is an equilibrium constant Ka in a dissociation reaction in which hydrogen ions are released from an acid.
Is a constant represented by a negative common logarithm, and a compound having a large pKa has a strong ability to attract H.
For example, by using a compound having a pKa of 5 or more as the catalyst gas, it is possible to promote the formation of the first layer by promoting the decomposition of the BTCSM gas. On the other hand, when the pKa of the catalyst gas is excessively large, Cl extracted from the BTCSM molecule is combined with the catalyst gas, thereby producing a salt (Salt: ionic compound) such as ammonium chloride (NH ₄ Cl), It may be a particle source. In order to suppress this, it is desirable that the pKa of the catalyst gas is about 11 or less, preferably 7 or less. Pyridine gas has a relatively large pKa of about 5.67, and H
Strong attraction. Further, since pKa is 7 or less, particles are hardly generated.

As described above, by supplying the pyridine gas as the catalyst gas together with the BTCSM gas, for example, the decomposition of the BTCSM gas is promoted even under a low temperature condition of 150 ° C. or less.
The first layer can be formed so that the formation of the chemisorption layer rather than the formation of the SM gas physical adsorption layer is dominant.

In addition, as described above, by using BTCSM gas as a source gas containing Si, C and a halogen element and having a Si—C bond, the first C can be incorporated into the layer. The first layer containing C is oxidized in the subsequent step 2a. For example, a silicon oxycarbide layer (Si
OC layer) and such a SiOC layer are laminated, and a SiOC film containing C at a high concentration can be formed. In addition, the C concentration in the SiOC layer and the SiOC film can be controlled with high accuracy.

(Residual gas removal)
After the Si-containing layer containing C and Cl as the first layer is formed on the wafer 200, the valve 243a is closed and the supply of the BTCSM gas is stopped. Also, close the valve 243c,
Stop the supply of pyridine gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the unreacted remaining in the processing chamber 201 or after contributing to the formation of the first layer BTCSM gas and pyridine gas are excluded from the processing chamber 201 (residual gas removal). Further, the valves 243g to 243j are kept open and the supply of N ₂ gas as an inert gas into the processing chamber 201 is maintained. N ₂
The gas acts as a purge gas, which can enhance the effect of removing the unreacted BTCSM gas and pyridine gas remaining in the processing chamber 201 or contributing to the formation of the first layer from the processing chamber 201. .

At this time, the gas remaining in the processing chamber 201 may not be completely removed.
It is not necessary to completely purge the inside. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effects will occur in the subsequent step 2a. The flow rate of the N ₂ gas supplied into the processing chamber 201 does not need to be a large flow rate. For example, by supplying an amount similar to the volume of the reaction tube 203 (processing chamber 201), an adverse effect occurs in step 2a. There can be no purging. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. The consumption of N ₂ gas can be suppressed to the minimum necessary.

As a source gas containing Si, C and a halogen element and having a Si—C bond, BTCS
In addition to M gas, BTCSE gas, TCDMDS gas, DCTMDS gas, and MCPMD
S gas or the like may be used. As catalyst gas, in addition to pyridine gas, aminopyridine gas,
Amine-based catalyst gases such as picoline gas, lutidine gas, pyrimidine gas, quinoline gas, piperazine gas, and piperidine gas may be used. As the inert gas, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas may be used in addition to N ₂ gas.

[Step 2a]
(H ₂ O gas + pyridine gas supply)
After step 1a is completed and residual gas in the processing chamber 201 is removed, the valve 243b is opened, and H ₂ O gas is allowed to flow into the gas supply pipe 232b. The flow rate of the H ₂ O gas is adjusted by the MFC 241b, supplied into the processing chamber 201 from the gas supply hole 250b, and exhausted from the exhaust pipe 231. At this time, H ₂ O gas is supplied to the wafer 200 in a non-plasma atmosphere (H ₂ O gas supply). At the same time, the valve 243h is opened, and N ₂ gas as an inert gas is caused to flow into the gas supply pipe 232h. The flow rate of the N ₂ gas is adjusted by the MFC 241h, supplied into the processing chamber 201 together with the H ₂ O gas, and exhausted from the exhaust pipe 231.

Further, pyridine gas is supplied to the wafer 200 (pyridine gas supply) in the same manner as the supply of pyridine gas in step 1a.

Further, in order to prevent invasion of H ₂ O gas and pyridine gas into the nozzles 249a and 249d and the buffer chamber 237, the valves 243g and 243j are opened, and the gas supply pipes 232g,
N ₂ gas is allowed to flow into 232j. The N ₂ gas is supplied from the gas supply pipes 232a and 232d and the nozzle 24.
9a, 249d and the buffer chamber 237 are supplied into the processing chamber 201 and exhausted from the exhaust pipe 231.

At this time, the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, 1
The pressure is in the range of ˜13330 Pa, preferably 133 to 2666 Pa. MFC24
The supply flow rate of the H ₂ O gas controlled by 1b is, for example, 1000 to 10000 sccm, preferably 10 to 1000 sccm. The supply flow rate of the pyridine gas controlled by the MFC 241c is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. The supply flow rate of the N ₂ gas controlled by the MFCs 241g to 241j is, for example, a flow rate in the range of 100 to 10000 sccm. The time for supplying H ₂ O gas and pyridine gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, 1 to 100 seconds, preferably 5 to 60 seconds. The temperature of the heater 207 is such that the temperature of the wafer 200 is similar to the temperature of the wafer 200 in step 1a, that is, for example, room temperature to 150 ° C., preferably room temperature to 100 ° C., more preferably 5
It sets so that it may become the temperature within the range of 0 degreeC or more and 100 degrees C or less.

The H ₂ O gas supplied into the processing chamber 201 is activated by heat and exhausted from the exhaust pipe 231. At this time, H ₂ O gas activated by heat is supplied to the wafer 200. That is, the gas flowing in the processing chamber 201 is a thermally activated H ₂ O gas, and no BTCSM gas is flowing in the processing chamber 201. Therefore, the H ₂ O gas does not cause a gas phase reaction, and is supplied to the wafer 200 in an activated state.
a reacts with at least a portion of the first layer (the Si-containing layer containing C and Cl) formed on the wafer 200. As a result, the first layer is thermally oxidized by non-plasma, and Si,
It is changed to a second layer containing O and C, that is, a SiOC layer.

The pyridine gas as the catalyst gas weakens the bonding force of the O—H bond of the H ₂ O gas,
Promote degradation of _{2 O} gas, thereby promoting the reaction between the H 2 _O gas and the first layer. That is, FIG.
As shown in (b), pyridine gas as a catalyst acts on the O—H bond of the H ₂ O gas to weaken the bonding force between O—H. The H having weakened the bonding force reacts with Cl in the first layer formed on the wafer 200, so that HCl gas is generated and desorbed, and H is lost.
O of ₂ O gas is bonded to Si of the first layer in which Cl is desorbed and at least a part of C remains.

In the step of supplying H ₂ O gas and pyridine gas, the supply amount of pyridine gas to be supplied can be appropriately adjusted according to the desired film composition and the like. When the supply amount of pyridine gas is increased, the action of pyridine gas is enhanced, the oxidizing power of H ₂ O gas is improved, the Si—C bond is broken, and C is easily desorbed. As a result, the C concentration in the SiOC layer Decreases. When the supply amount of pyridine gas is lowered, the action of pyridine gas is weakened and the oxidizing power of H ₂ O gas is lowered, and Si
The -C bond is easily maintained, and as a result, the C concentration in the SiOC layer is increased. Accordingly, by appropriately adjusting the supply amount of pyridine gas, the C concentration, the silicon concentration (Si concentration), and the oxygen concentration (O concentration) in the SiOC layer, and thus in the SiOC film formed by laminating the SiOC layer, are adjusted.
Etc. can be changed relatively.

The adjustment of the supply amount of the catalyst gas supplied in the step of supplying the oxidizing gas and the catalyst gas is independent from the adjustment of the supply amount of the catalyst gas supplied in the step of supplying the raw material gas and the catalyst gas. Can be done. That is, the supply amount of the catalyst gas in both steps may be adjusted to be the same, or may be adjusted to be different.

At this time, the process recipe (with the catalyst gas supply amount and flow rate set to different values)
A plurality of programs in which processing procedures and processing conditions are described can be prepared in advance.

For example, under a low temperature condition of 150 ° C. or lower, Si containing a relatively large amount of moisture (H ₂ O).
An OC layer is easily formed. Therefore, the SiOC film formed by laminating such SiOC layers may contain a lot of moisture and the like. The moisture contained in the SiOC layer or the SiOC film is derived from, for example, H ₂ O gas used as the oxidizing gas.

(Residual gas removal)
Thereafter, the valve 243b is closed and the supply of H ₂ O gas is stopped. Also, the valve 243c
Is closed and the supply of pyridine gas is stopped. At this time, the APC valve 244 of the exhaust pipe 231
Is kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246, and the processing chamber 20
The H ₂ O gas, the pyridine gas, and the reaction by-product remaining in the reactor 1 after being unreacted or contributing to the reaction are removed from the processing chamber 201 (residual gas removal). Also, the valves 243g to 243j
Is kept open and the supply of N ₂ gas as an inert gas into the processing chamber 201 is maintained. The N ₂ gas acts as a purge gas, and thereby, H ₂ O gas, pyridine gas, and reaction byproducts remaining in the processing chamber 201 and contribute to the formation of the second layer are transferred into the processing chamber 201. The effect which excludes from can be heightened.

At this time, the gas remaining in the processing chamber 201 may not be completely removed.
It is not necessary to completely purge the inside. If the amount of gas remaining in the processing chamber 201 is very small, no adverse effect will occur in the subsequent step 1a. The flow rate of the N ₂ gas supplied into the processing chamber 201 does not need to be a large flow rate. For example, by supplying an amount similar to the volume of the reaction tube 203 (processing chamber 201), an adverse effect occurs in step 1a. There can be no purging. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. The consumption of N ₂ gas can be suppressed to the minimum necessary.

As the oxidizing gas, other the _{H 2} O gas, using hydrogen peroxide _(H 2 _{O 2)} gas, hydrogen _{(H 2)} gas and oxygen gas _{(O 2), H 2} gas + ozone _{(O 3)} gas or the like May be. As the catalyst gas, in addition to pyridine gas, various amine-based catalyst gases listed above may be used. As the inert gas, various rare gases listed above may be used in addition to N ₂ gas.

(Performed times)
The above-described steps 1a and 2a are set as one set, and this set is performed at least once, that is, a predetermined number of times (n times), whereby a SiOC film having a predetermined composition and a predetermined thickness is formed on the wafer 200 as a first thin film. Can be formed. The above set is preferably repeated multiple times. That is, it is preferable that the thickness of the SiOC layer formed per set is made smaller than the desired film thickness and the above set is repeated a plurality of times until the desired film thickness is obtained.

At this time, by controlling the processing conditions such as the pressure in the processing chamber 201 and the gas supply time in each step, the ratio of each element component in the SiOC layer, that is, Si component, O component and C component, that is, Si concentration , O concentration and C concentration can be finely adjusted, SiOC
The composition ratio of the film can be controlled more precisely.

In the case where the set is performed a plurality of times, at least in each step after the second set, the portion described as “supplying a predetermined gas to the wafer 200” is “to the layer formed on the wafer 200, That is, a predetermined gas is supplied to the outermost surface of the wafer 200 as a laminate. In addition, a portion described as “form a predetermined layer on the wafer 200” means “a predetermined layer on the layer formed on the wafer 200, that is, on the outermost surface of the wafer 200 as a stacked body. Is meant to form. This point is as described above. This also applies to the case where a set or cycle is performed a plurality of times in a later-described modification or other embodiments.

(SiOC film modification process)
Although the SiOC film formed as described above is a film formed under a low temperature condition of, for example, 150 ° C. or less, it has excellent etching resistance and a low dielectric constant. However, the SiOC film may be inferior in ashing resistance. Therefore, in the present embodiment, a process of modifying the SiOC film into a SiOCN film with NH ₃ gas as a reforming gas is performed to form a thin film having high etching resistance and high ashing resistance.

(Pressure adjustment and temperature adjustment)
The inside of the processing chamber 201 is evacuated (pressure adjustment) by the vacuum pump 246 while feedback controlling the APC valve 244 so that the inside of the processing chamber 201 has a desired pressure (degree of vacuum). 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 temperature sensor 26 is set so that the inside of the processing chamber 201 has a desired temperature distribution.
3 is feedback-controlled based on the temperature information detected by the heater 207.
Temperature adjustment). Also in this process, the boat 217 and the wafer 200 by the rotation mechanism 267 are used.
Keep rotating.

(NH ₃ gas supply)
The valve 243d is opened and NH ₃ gas is allowed to flow into the gas supply pipe 232d. NH ₃ gas is M
The flow rate is adjusted by the FC 241d, supplied into the buffer chamber 237 through the gas supply hole 250d, further supplied into the processing chamber 201 through the gas supply hole 250e, and exhausted from the exhaust pipe 231. At this time, NH ₃ gas is supplied to the wafer 200 (NH ₃ gas supply). At the same time, the valve 243j is opened, and an inert gas such as N ₂ gas is allowed to flow into the gas supply pipe 232j. The flow rate of the N ₂ gas is adjusted by the MFC 241j, supplied to the processing chamber 201 together with the NH ₃ gas, and exhausted from the exhaust pipe 231.

Further, in order to prevent the NH ₃ gas from entering the nozzles 249a to 249c, the valve 24
3g to 243i are opened, and N ₂ gas is allowed to flow through the gas supply pipes 232g to 232i. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipes 232a to 232c and the nozzles 249a to 249c, and is exhausted from the exhaust pipe 231.

At this time, the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, a pressure lower than atmospheric pressure, preferably 1 to 13330 Pa (0.0075 to 100 Torr), more preferably 133 to 2666 Pa (1 to The pressure is within the range of 20 Torr). MFC
The supply flow rate of NH ₃ gas controlled by 241d is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. N controlled by MFC 241g-241j
The supply flow rates of the _two gases are, for example, flow rates in the range of 100 to 10,000 sccm, respectively. The time for supplying the NH ₃ gas to the wafer 200 is, for example, 1 to 120 minutes, preferably 10 to 120 minutes.

At this time, the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 is higher than the temperature of the wafer 200 in the above-described step of forming the SiOC film, for example. Specifically, the temperature of the wafer 200 is 200 ° C. or higher and 900 ° C. or lower, preferably 200 ° C. or higher and 7 ° C.
The temperature is set to 00 ° C. or lower, more preferably 200 ° C. or higher and 600 ° C. or lower. Such a temperature range is determined in consideration of, for example, the thermal load and thermal history that the wafer 200 receives. That is, when the temperature of the wafer 200 exceeds 900 ° C., the thermal load becomes too large, which may affect the electrical characteristics of the semiconductor device formed on the wafer 200. Wafer 2
By setting the temperature of 00 to at least 900 ° C. or less, it is possible to suppress the influence on the electrical characteristics and the like due to this heat load. Specifically, when the wafer 200 on which the heat-treated SiOC film is formed is for a memory device, it can withstand heat of about 900 ° C. Even if such a wafer 200 is for a logic device, it can withstand heat of about 700 ° C. If the temperature of the wafer 200 is further set to 600 ° C. or less, it becomes easier to avoid thermal damage to the device structure and the like more reliably. On the other hand, the temperature of the wafer 200 is 2
When the temperature is less than 00 ° C., the effect of modifying the SiOC film is reduced, and the supply time of the NH ₃ gas, that is, the time for the modification treatment is prolonged, and the productivity is lowered. By setting the temperature of the wafer 200 to 200 ° C. or higher, the modification of the SiOC film is moderately promoted, and the modification process time can be kept within a practical processing time. Therefore, the temperature of the wafer 200 is 200 ° C. or higher and 900 ° C. or lower, preferably 200 ° C. or higher and 700 ° C. or lower, more preferably 200 ° C. or higher and 60 ° C. or lower.
The temperature is preferably within a range of 0 ° C. or lower.

The NH ₃ gas supplied into the processing chamber 201 is activated by heat and exhausted from the exhaust pipe 231. At this time, NH ₃ gas activated by heat is supplied to the wafer 200. That is, the gas flowing in the processing chamber 201 is a thermally activated NH ₃ gas, and no BTCSM gas, H ₂ O gas, or pyridine gas is flowing in the processing chamber 201. Therefore, the NH ₃ gas does not cause a gas phase reaction, is supplied to the wafer 200 in an activated state, and the first thin film formed on the wafer 200 by performing steps 1a and 2a a predetermined number of times. Reacts with at least part of (SiOC film). As a result, the SiOC film is thermally modified by non-plasma to form a second thin film containing Si, O, C, and N, that is, S
It is changed to an iOCN film.

At this time, as described above, the temperature of the wafer 200 is set to a relatively high temperature.
The reaction between the _three gases and the SiOC film is promoted, and the N component can penetrate into the SiOC film. Further, since the temperature of the wafer 200 is higher than the temperature of the wafer 200 in the step of forming the above-described SiOC film, as described above, when the SiOC film contains a large amount of moisture, the moisture from the film is absorbed. It becomes easy to detach. A minute hole (pore), that is, a minute space is formed in the portion where the moisture is removed from the SiOC film, and the SiOC film becomes a porous film. When N enters such a hole from which moisture has been removed, the N component is more easily taken into the SiOC film, and the modification of the SiOC film reaches almost the entire film. At this time, SiOC
At least a part of N taken into the film may form a Si—N bond or the like with a component in the film, such as Si.

In the SiOC film modification process, for example, after the temperature of the wafer 200 is raised to a desired temperature by the above-described temperature adjustment, the temperature of the wafer 200 is stably maintained at the desired temperature. Done. That is, the step of modifying the SiOC film refers to a period in which, for example, NH ₃ gas is supplied to the wafer 200 while the temperature of the wafer 200 is maintained at a predetermined temperature. However, when the temperature of the wafer 200 is raised in the step of adjusting the temperature of the wafer 200 described above, supply of NH ₃ gas to the wafer 200 is started at an arbitrary timing, and Si
The OC film modification step may be started. Alternatively, the temperature reduction of the wafer 200 performed in the process of purging the inside of the processing chamber 201 described later may be started while the NH ₃ gas is supplied, and the SiOC film modification process may be continued while the temperature of the wafer 200 is decreased. As described above, during at least a part of the process of adjusting (heating) the temperature of the wafer 200 and the process of lowering the temperature of the wafer 200, NH
_By supplying _three gases, these periods may be included in the step of modifying the SiOC film. However, the desired temperature adjusted as described above is a temperature suitable for incorporating N into the SiOC film. Therefore, for example, when the temperature of the wafer 200 is lower than that during temperature increase or decrease, the incorporation of N into the SiOC film is limited or does not occur at all, and the modification process may hardly proceed. Therefore, the reforming process is more preferably performed at a constant temperature while maintaining the wafer 200 at the desired temperature. As a result, the incorporation rate and the incorporation amount of N into the SiOC film are stabilized, and a thin film having higher quality and stable characteristics can be obtained.

(Residual gas removal and purging)
Thereafter, the valve 243d is closed, and the supply of NH ₃ gas is stopped. At this time, the exhaust pipe 23
1, the APC valve 244 is kept open, and the processing chamber 201 is evacuated by the vacuum pump 246 to process the NH ₃ gas and reaction by-products remaining in the processing chamber 201 or contributed to the reaction. Exclude from the chamber 201 (residual gas removal). Also, the valve 243g ~
243j is kept open and the supply of N ₂ gas as an inert gas into the processing chamber 201 is maintained. The N ₂ gas acts as a purge gas, whereby NH ₃ gas and reaction by-products remaining in the processing chamber 201 and contribute to reforming the SiOC film are removed from the processing chamber 20.
It is possible to enhance the effect of exclusion from the inside (purge).

As the reformed gas containing at least one of C and N, as N-containing gas which is a reformed gas containing N, in addition to NH ₃ gas, diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H
₄ ) A non-amine-based gas composed of two elements of N and H, such as a gas and N ₃ H ₈ gas, may be used. As the inert gas, various rare gases listed above may be used in addition to N ₂ gas.

(Return to atmospheric pressure)
Even after the inside of the processing chamber 201 is purged with an inert gas, the valves 243g to 243j are kept open, and N ₂ gas as an inert gas is continuously supplied into the processing chamber 201 from each of the gas supply pipes 232g to 232j. Thus, 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).

Further, the temperature of the wafer 200 is lowered so that the temperature of the wafer 200 is, for example, less than 200 ° C., preferably about room temperature (temperature lowering step). That is, the temperature of the wafer 200 is lowered by adjusting the power supply to the heater 207 or by stopping the power supply to the heater 207. By lowering the temperature of the wafer 200 in parallel with the purge and the return to atmospheric pressure, the temperature of the wafer 200 can be lowered to a predetermined temperature in a shorter time due to the cooling effect of the purge gas such as N ₂ gas. it can. However, as described above, the temperature lowering process for lowering the temperature of the wafer 200 may be started during the NH ₃ gas supply process. Also in this case, the temperature of the wafer 200 can be lowered to a predetermined temperature in a shorter time due to the cooling effect of the NH ₃ gas.

(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). Thereafter, the processed wafer 200 is taken out from the boat 217 (wafer discharge).

(3) Effects according to the present embodiment According to the present embodiment, the following one or more effects are achieved.

(A) According to the film forming sequence of this embodiment, BTCSM gas is supplied to the wafer 200 as a source gas in step 1a of the SiOC film forming process. Thus, Si, C,
A film containing C at a high concentration by using a source gas having Cl and containing Si—C bonds, in particular, a source gas containing C, Cl and at least two Si in one molecule and having Si—C bonds. That is, an SiOC film having a high C concentration can be formed. S
The C concentration in the iOC film can be accurately controlled. Therefore, for example, a SiOC film having high etching resistance and low dielectric constant can be obtained.

When a thin film such as a SiO film is formed using a catalyst gas under a low temperature condition, for example, a wet etching rate (hereinafter also referred to as WER) using 1% concentration hydrofluoric acid (1% HF aqueous solution).
A film having a high thickness, that is, a film having a low etching resistance is easily formed. If C is contained in the film,
Although the etching resistance of the film can be enhanced, for example, when film formation is performed at a low temperature of 150 ° C. or less, C is hardly taken into the SiO film.

Therefore, in the present embodiment, a source gas containing Si, C, Cl, such as BTCSM gas, and having a Si—C bond is used. Thus, C can be taken into the first layer when the first layer is formed as an initial layer on the wafer 200, and a SiOC film having a sufficient C concentration can be formed. In addition, the C concentration in the SiOC film can be controlled with high accuracy.
Therefore, for example, a SiOC film having high etching resistance and low dielectric constant can be obtained.

(B) According to the film forming sequence of this embodiment, in the SiOC film modifying step, NH ₃ gas is supplied to the wafer 200 to modify the SiOC film into a SiOCN film. Thereby, a thin film having high etching resistance and high ashing resistance can be obtained.

An SiOC film containing C in the film may have low ashing resistance or dry etching resistance. For this reason, etching resistance to HF of the SiOC film may be lowered by ashing using O ₂ plasma or the like, dry etching, or the like. This is because the oxidation of the SiOC film further proceeds due to the strong oxidizing power of O ₂ plasma or the like, and a large amount of C in the film.
This is probably because a —O bond is formed. C combined with O is easily desorbed from the SiOC film as CO gas or CO ₂ gas. Therefore, it is considered that the C concentration in the SiOC film is lowered by ashing or the like, and the film becomes low in etching resistance.

Therefore, in the present embodiment, NH ₃ gas is used as a reformed gas, and N is introduced into the SiOC film. Thus, by introducing a new element such as N into the SiOC film, Si, O,
Each bonding state of C changes from the SiOC film before modification. As a result, when ashing using O ₂ plasma or the like is performed, a C—O bond is formed in the film, or C—
Can be prevented from being detached. Thus, for example, SiO before modification
Compared with the C film, the ashing resistance of the thin film, that is, the oxidation resistance can be improved. That is, it is possible to suppress deterioration of etching resistance of the thin film to HF due to ashing or the like. As a result, a thin film having high etching resistance and high ashing resistance can be obtained.

(C) Further, according to the film forming sequence of the present embodiment, a thin film having high etching resistance and high ashing resistance can be obtained. Accordingly, when such a thin film is applied to, for example, various semiconductor devices, it is possible to realize a highly integrated semiconductor device that hardly causes a signal delay and operates at high speed.

Flash memory, DRAM (Dynamic Random Access Mem
ory) and SRAM (Static Random Access Memory), and semiconductor devices such as logic devices have recently been required to be highly integrated. In order to realize this, there is a method of reducing the size of each semiconductor device by miniaturizing the pattern by reducing the pitch which is the sum of the pattern width and the pattern interval.
Thus, for example, in order to cope with the miniaturization of transistors, it has been studied to use a thin film having a low dielectric constant for a sidewall spacer (SWS) which is a peripheral structure of the gate electrode. Further, the semiconductor device can be highly integrated by increasing the number of wiring layers. In this case, a thin film having a low dielectric constant is increasingly used as an interlayer insulating film for separating patterns in a fine pattern, elements in a three-dimensional structure such as a multilayer wiring layer, and wiring layers. As described above, the SWS or the interlayer insulating film is a low dielectric constant thin film, that is, a thin film having a low-k film characteristic, so that it is possible to suppress a signal propagation delay (signal delay) due to electrostatic induction or the like. Become.

In the present embodiment, after the SiOC film is formed, the SiOC film is further modified to perform S
The iOC film is modified to a SiOCN film. Therefore, a thin film having high etching resistance and high ashing resistance can be obtained, and a highly integrated semiconductor device can be obtained that operates at high speed.

(D) The substrate processing apparatus of the present embodiment may include a plurality of gas supply lines for each gas such as a source gas, a catalyst gas, an oxidizing gas, and a reformed gas, and a plurality of types of gases having different molecular structures. A specific gas may be selected from the gas and supplied. By adopting such an apparatus configuration, it is easy to select and supply a specific source gas, catalyst gas, oxidizing gas, or reformed gas from a plurality of types of gases according to a desired film composition or the like. Become. Therefore, 1
Thin films having various composition ratios and film quality can be formed for general purpose and with good reproducibility by using a single substrate processing apparatus. In addition, it is possible to ensure the degree of freedom of apparatus operation when adding or replacing gas types.

(E) In the substrate processing apparatus of the present embodiment, a plurality of process recipes (programs describing processing procedures and processing conditions) used for forming a thin film are previously stored for each gas type, that is, for each different gas system. Can be prepared. Further, in the substrate processing apparatus of the present embodiment, a plurality of process recipes can be prepared for different processing conditions such as different supply amounts and flow rates of the respective gases such as the catalyst gas. From these, depending on the desired film composition, film quality, film thickness, etc., select a specific source gas, catalyst gas, oxidizing gas, or reformed gas from multiple types of gases, and select their flow rates, etc. It becomes easy to supply. The operator may select an appropriate process recipe from a plurality of process recipes according to a desired film composition and the like, and execute a film forming process. Therefore, thin films with various composition ratios, film qualities, and film thicknesses can be formed for general use with good reproducibility using a single substrate processing apparatus. Further, it is possible to reduce an operator's operation burden (such as an input burden of a processing procedure and a processing condition), and to quickly start substrate processing while avoiding an operation error.

(4) Modification of this Embodiment Next, the modification of this embodiment is demonstrated using FIG.5 (b) and FIG.

(Modification)
In the above-described SiOC film reforming step, by selecting the type of reformed gas to be supplied, for example, an element other than N can be selected as an element to be added to the SiOC film.

That is, in the SiOC film reforming step, C is selected from among a plurality of types of reformed gases containing different elements, that is, a plurality of types of reformed gases containing at least one of C and N as reformed gases. A specific reformed gas is selectively supplied from a carbon-containing gas (C-containing gas) that is a reformed gas, an N-containing gas that is a reformed gas containing N, or a reformed gas containing C and N Thus, an element to be contained in the SiOC film can be selected.

To select and supply a specific reformed gas from multiple types of reformed gases, supply multiple types of reformed gases containing different elements or multiple types of reformed gases with different molecular structures. A specific reformed gas can be supplied by selecting a specific supply line from a plurality of supply lines. As described above, in the example of the film forming sequence shown in FIGS. 4 and 5A, by selecting the NH ₃ gas supply line from among the NH ₃ gas supply line and the C ₃ H ₆ gas supply line, NH ₃ gas is supplied as a specific reformed gas. In addition, FIG.
), In the example of the film forming sequence of the modified example of the present embodiment, the NH ₃ gas supply line,
C ₃ H ₆ by selecting the _C 3 _{H 6} gas supply line from the gas supply line, the _C 3 _{H 6} gas supplying as certain of the reformed gas. In this way, by using C ₃ H ₆ gas instead of NH ₃ gas as the reformed gas, unlike the SiOCN film obtained in the above-described embodiment, the SiOC film further containing C, that is, before the reforming, Si with higher C concentration than SiOC film
An OC film is obtained. Here, the SiOC film further containing C can also be referred to as an SiOC film further doped (added) with C, or an SiOC film further containing C.

In this modification, instead of the above NH ₃ gas supply process, C is applied to the wafer 200.
A SiOC film modification step including a step of supplying ₃ H ₆ gas is performed. C ₃ for wafer 200
The procedure for supplying H ₆ gas will be described below.

(C ₃ H ₆ gas supply)
Steps similar to Steps 1a and 2a described above are performed a predetermined number of times to form SiO2 on the wafer 200.
After forming the C film and adjusting the pressure and temperature, the valve 243f is opened, and the C ₃ H ₆ gas is allowed to flow into the gas supply pipe 232f. The flow rate of the C ₃ H ₆ gas is adjusted by the MFC 241f, supplied to the processing chamber 201 from the gas supply hole 250c through the gas supply pipe 232c, and exhausted from the exhaust pipe 231. At this time, C ₃ H ₆ gas is supplied to the wafer 200 (C ₃ H ₆ gas supply). At the same time, the valve 243i is opened and the gas supply pipe 23 is opened.
An inert gas such as N ₂ gas is allowed to flow through 2i. The flow rate of the N ₂ gas is adjusted by the MFC 241i, supplied into the processing chamber 201 together with the C ₃ H ₆ gas, and exhausted from the exhaust pipe 231.

The C ₃ H ₆ gas supplied into the processing chamber 201 is activated by heat and exhausted from the exhaust pipe 231. At this time, C ₃ H ₆ gas activated by heat is supplied to the wafer 200. That is, the gas flowing in the processing chamber 201 is a thermally activated C ₃ H ₆ gas, and no BTCSM gas, H ₂ O gas, or pyridine gas is flowing in the processing chamber 201. Therefore, the C ₃ H ₆ gas does not cause a gas phase reaction, is supplied to the wafer 200 in an activated state, and is formed on the wafer 200 by performing the same steps as Steps 1a and 2a a predetermined number of times. It reacts with at least a part of the formed SiOC film. As a result, SiO
The C film is thermally modified by non-plasma and changed into a thin film containing Si, O, and C, that is, a SiOC film further containing C.

At this time, by setting the temperature of the wafer 200 to a relatively high temperature, the C ₃ H ₆ gas and the SiO 2
The reaction with the C film is promoted, and the C component of the C ₃ H ₆ gas can penetrate into the SiOC film. Further, the temperature of the wafer 200 is changed to the wafer 20 in the step of forming the SiOC film.
By setting the temperature higher than 0, when the SiOC film contains a lot of moisture, the moisture is easily desorbed from the film. A minute hole (pore) is formed in the portion where the moisture is removed from the SiOC film.
The iOC film is a porous film. When C enters such a hole from which moisture has been removed,
The components are more easily incorporated into the SiOC film, and the modification of the SiOC film reaches almost the entire film. At this time, at least a part of C taken into the SiOC film may form a Si—C bond or the like with a component in the film, such as Si.

Thus, by modifying the SiOC film after film formation into a SiOC film further containing C, a thin film having high ashing resistance can be obtained. This is because the SiOC film after modification contains a higher concentration of C than the SiOC film before modification, so that even if a predetermined amount of C is desorbed from the film by ashing, for example, This is because the C concentration can be kept high. By using a SiOC film further containing C instead of N, the wet etching rate for hot phosphoric acid is also improved. By using a SiOC film further containing C instead of N, the dielectric constant can also be reduced as compared with the SiOC film before modification.

After the deposited SiOC film is modified to a SiOC film further containing C, the valve 243f is closed and the supply of the C ₃ H ₆ gas is stopped.

Note that the pressure in the processing chamber 201 at this time, the supply flow rate of each gas such as a reformed gas and N ₂ gas,
Regarding the processing conditions such as the supply time and the temperature of the wafer 200, for example, FIG. 4 and FIG.
The processing conditions can be set within the same range as the processing conditions in this sequence. C ₃ H ₆
When the gas is supplied, the nozzles 249a and 24 that are not used are the same as in the above-described embodiment.
N ₂ gas is supplied to prevent C ₃ H ₆ gas from entering 9b and 249d and the buffer chamber 237.

As a reformed gas containing at least one of C and N, as a C-containing gas that is a reformed gas containing C, in addition to C ₃ H ₆ gas, ethylene (C ₂ H ₄ ) gas, methane (CH ₄ )
A hydrocarbon gas such as a gas, monomethylsilane (CH ₃ SiH ₃ ) gas, or the like may be used. As the inert gas, various rare gases listed above may be used in addition to N ₂ gas.

As the reformed gas, a reformed gas containing C and N can also be used. In this case,
A SiOCN film further containing C and N can be formed. The reformed gas containing C and N may be a gas containing a C-containing gas such as C ₃ H ₆ gas and an N-containing gas such as NH ₃ gas. The reformed gas containing C and N may contain a gas containing C and N in one molecule (C and N-containing gas), for example, an amine-based gas. As the amine-based gas, triethylamine ((C ₂ H ₅ ) ₃ N, abbreviation: TEA) gas, diethylamine ((C ₂ H ₅
) ₂ NH, abbreviation: DEA) gas, monoethylamine ((C ₂ H ₅ ) NH ₂ , abbreviation: MEA
) Gas, trimethylamine ((CH ₃ ) ₃ N, abbreviation: TMA) gas, and monomethylamine ((CH ₃ ) NH ₂ , abbreviation: MMA) gas.

In this way, by using the reformed gas containing C and N and forming the SiOCN film further containing C and N, the C concentration can be increased as compared with the SiOC film before the reforming and newly introduced. The bonding state of each element in the film is changed by N, so that a film with higher ashing resistance can be obtained.

As described above, the method of changing the composition in the film by changing the type of gas supplied to the wafer 200 can be applied to, for example, the SiOC film forming process.

That is, in the step of supplying the source gas and the catalyst gas, the type of source gas to be supplied is appropriately selected from, for example, BTCSM gas, BTCSE gas, TCMDDS gas, DCTMDS gas, and MCPMDS gas, In the SiOC layer,
The C concentration in the SiOC film formed by laminating the SiOC layer can be controlled. That is,
In the step of supplying the source gas and the catalyst gas, by selecting and supplying a specific source gas from a plurality of types of source gases having different molecular structures as the source gas, the C in the SiOC layer or the SiOC film is supplied. The concentration can be controlled.

As one factor that makes it possible to control the C concentration in the SiOC film depending on the type of the source gas selected, for example, a difference in the arrangement of C in the molecular structure of each source gas can be considered. BTCSM gas, BTCSE gas, and the like, which are alkylenehalosilane-based source gases having a Si—C—Si bond or Si—C—C—Si bond in one molecule, have a molecular structure in which C is sandwiched between Si. Therefore, a state in which a large amount of Cl is bonded to the surplus Si bonds is maintained. For example, in both BTCSM gas and BTCSE gas, Cl is bonded to three of the four bonds of Si. A large amount of Cl contained in the molecule is considered to improve the reactivity of BTCSM gas, BTCSE gas, and the like. Thereby, for example, the deposition rate of the SiOC film is improved by using BTCSM gas, BTCSE gas, or the like. By improving the film forming rate, the usable condition range (process window) of the film forming process using BTCSM gas, BTCSE gas, or the like is expanded. As described above, for example, a film forming condition for obtaining a desired C concentration can be selected from a wide range of process windows. As a result, it is easy to increase the C concentration in the SiOC film. Controllability of the C concentration in the SiOC film can also be improved. Although the number of C contained in the BTCSM gas is smaller than that of the TCMDDS gas, for example, it is considered that this point does not adversely affect the improvement of the C concentration in the SiOC film. According to the present inventors, for example, it has been confirmed that the use of BTCSM gas is relatively easy to improve the C concentration compared to the case of using TCMDDS gas.

TCD, which is an alkylhalosilane-based source gas in which an alkyl group such as a methyl group is bonded to Si
MDS gas, DCTMDS gas, MCPMDS gas, and the like have a molecular structure in which some chloro groups of chlorosilane-based source gas are replaced with methyl groups. As the number of Cl in the gas molecules decreases, the reaction proceeds relatively slowly in these TCMDDS gas, DCTMDS gas, MCPMDS gas, etc., and a denser SiOC film is easily obtained. For this reason, it is easy to maintain high etching resistance, for example even if it is a SiOC film | membrane which suppressed C density | concentration appropriately. TC
In comparison between DMDS gas and DCTMDS gas, it has been confirmed that DCTMDS gas containing a large number of methyl groups, that is, C, in the molecule favors the amount of C incorporated into the film.

Similarly, in the step of supplying the oxidizing gas and the catalyst gas, the type of the catalyst gas to be supplied can be appropriately selected according to the desired film composition and the like. For example, it is considered that catalyst gases having different molecular structures have different catalytic effects, for example. Such a difference in the strength of the catalytic action is considered as one factor that makes it possible to control the film composition and the like of the SiOC film by selecting the type of the catalyst gas. For example, by selecting a catalyst gas having a large pKa value that serves as an indicator of catalytic action, the oxidizing power of the oxidizing gas is improved, the Si—C bond is broken, and the C concentration tends to decrease. In addition, for example, by selecting a catalyst gas having a small pKa, the oxidizing power of the oxidizing gas may decrease, the Si—C bond may be maintained, and the C concentration may increase. Other factors that make it possible to control the composition of the SiOC film include differences in the vapor pressure of various substances involved in catalytic reactions such as various catalyst gases and generated salts, or differences in these pKa values and vapor pressures. A combination of factors such as these can be considered. Thus, by selecting and supplying a specific catalyst gas from a plurality of types of catalyst gases having different molecular structures, for example, S
The C concentration in the iOC layer or the SiOC film can be controlled.

The type of catalyst gas supplied in the step of supplying the oxidizing gas and the catalyst gas may be the same as or different from the type of catalyst gas supplied in the step of supplying the raw material gas and the catalyst gas.

When selecting the type of the source gas or the catalyst gas, the Si concentration and the O concentration may be relatively changed by controlling the C concentration in the SiOC film. That is, the composition of the SiOC film may be changed as a whole, and the type of the source gas or catalyst gas may be selected for the purpose of overall control of the composition of the SiOC film.

In the case where the above-described setting of 1a and 2a is performed a plurality of times, the type of the raw material gas and the catalyst gas may be changed in the middle. When the setting of 1a and 2a is performed a plurality of times, the supply amount of the catalyst gas may be changed during the setting. Thereby, the C concentration in the SiOC film can be changed in the film thickness direction.

(Other variations)
In the above-described embodiment, the example in which the SiOC film forming process and the SiOC film modifying process are performed in a state where the wafer 200 for processing is accommodated in the same processing chamber 201 has been described. In this modification, the SiOC film forming step and the SiOC film modifying step are performed by accommodating the wafers 200 for processing in different processing chambers.

That is, as shown in FIG. 6, for example, the SiOC film forming process is performed similarly to the above-described embodiment.
A processing chamber 201 provided in the substrate processing apparatus (hereinafter also referred to as a first substrate processing unit) shown in FIGS.
(Hereinafter also referred to as the first treatment chamber). The operation of each part constituting the first substrate processing unit is controlled by a controller 121 (hereinafter also referred to as a first control unit). And after performing the set including step 1b, 2b similar to the above-mentioned step 1a, 2a a predetermined number of times, processing chamber 20
1 purge, return to atmospheric pressure, boat unload, and wafer discharge are sequentially executed.

Subsequently, a process of modifying the SiOC film formed on the wafer 200 taken out from the boat 217 is performed in a processing chamber different from the processing chamber 201. As such a processing chamber, for example, a substrate processing apparatus similar to that of the above-described embodiment, which is provided in a substrate processing apparatus (hereinafter also referred to as a second substrate processing unit) different from the apparatus that performed the SiOC film forming process. A chamber (hereinafter also referred to as a second treatment chamber) can be used. The operation of each part constituting the second substrate processing unit is controlled by the second control unit. In the second substrate processing unit, wafer charging and boat loading are sequentially executed in the first substrate processing unit as in the above-described embodiment. Further, the pressure adjustment, temperature adjustment, NH ₃ gas supply, and residual gas removal are performed as in the case of performing the SiOC film modification process of the above-described embodiment. Thereafter, similarly to the above-described embodiment, purge, atmospheric pressure return, boat unloading, and wafer discharge are sequentially executed.

In the above case, the substrate processing system is mainly configured by the first substrate processing unit that forms the SiOC film and the second substrate processing unit that modifies the SiOC film.

As described above, the SiOC film formation step and the SiOC film modification step can be performed in the same processing chamber 201 (in-situ), and each has a different processing chamber (first processing chamber and second processing chamber). It can also be performed in the room) (ex-situ). If both processes are performed in In-situ, the wafer 200 can be consistently processed while being left under vacuum without being exposed to the air on the way. Therefore, a more stable film forming process can be performed. If both steps are performed in Ex-Situ, the temperature in each processing chamber can be set in advance to, for example, the processing temperature in each step or a temperature close thereto, and the time required for temperature adjustment can be shortened. Therefore, production efficiency can be further increased.

The processing chamber for modifying the SiOC film is an apparatus different from the substrate processing apparatus of the above-described embodiment,
For example, a processing chamber provided in a heat treatment furnace used for heat treatment or a diffusion furnace for performing diffusion may be used. In the substrate processing system, the first substrate processing unit and the second substrate processing unit may be configured as a group of independent devices (stand-alone devices) as described above. One device (cluster type device) on which the substrate processing unit is mounted on the same platform
It may be configured as. Even in such a substrate processing system, for example, FIG.
The thin film can be formed under the processing conditions within the same range as the processing conditions in the sequence of FIG.

Second Embodiment
Next, a second embodiment of the present invention will be described.

(1) Thin Film Forming Process In the above-described embodiment, the example in which the SiOC film is formed by performing the set including the steps 1a and 2a a predetermined number of times and the SiOC film is modified with the modifying gas has been described. In the present embodiment, Si formed by steps 1c and 2c performed in the same manner as steps 1a and 2a described above.
A cycle of modifying the OC layer into a SiOCN layer further containing N is performed a predetermined number of times, and SiOCN
A film is formed. Also in the present embodiment, the substrate processing apparatus shown in FIGS. 1 and 2 is used as in the above-described embodiment. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

As shown in FIGS. 7 and 8A, in this embodiment,
Supplying a BTCSM gas as a raw material gas and a pyridine gas as a catalyst gas to the wafer 200 (step 1c);
A step of supplying H ₂ O gas as an oxidizing gas and pyridine gas as a catalyst gas to the wafer 200 (step 2c);
As a reformed gas containing at least one of C and N with respect to the wafer 200, N
Supplying NH ₃ gas as a reformed gas containing (step 3c),
Are performed in this order in a predetermined number of times, so that Si, O, C are formed on the wafer 200.
An example of forming a SiOCN film as a thin film containing N and N will be described.

In this case, the process of supplying NH ₃ gas to the wafer 200 is supplied with NH ₃ gas excited in a plasma state to the wafer 200.

Note that this sequence is different from the film forming sequence of the above-described embodiment only in the step 3c in which NH ₃ gas is excited and supplied to a plasma state and the order of execution of each step including the step 3c. Steps 1c and 2c are the same as in the above-described embodiment. Hereinafter, step 3c of this embodiment and the execution order of each step including this will be described.

[Step 3c]
(NH ₃ gas supply)
After step 2c is completed and residual gas in the processing chamber 201 is removed, the valve 243d is opened, and NH ₃ gas is allowed to flow into the gas supply pipe 232d. The flow rate of the NH ₃ gas is adjusted by the MFC 241d and is supplied into the buffer chamber 237 from the gas supply hole 250d. At this time, by applying radio frequency (RF) power from the high frequency power supply 273 via the matching unit 272 between the rod-shaped electrodes 269 and 270, the NH ₃ gas supplied into the buffer chamber 237 is plasma-excited and becomes active species. The gas is supplied from the gas supply hole 250 e into the processing chamber 201 and is exhausted from the exhaust pipe 231. At this time, NH ₃ gas activated (excited) in a plasma state is supplied to the wafer 200 (NH ₃ gas supply). At the same time, the valve 243j is opened and N ₂ gas is allowed to flow into the gas supply pipe 232j. The flow rate of N ₂ gas is adjusted by the MFC 241j,
The NH ₃ gas is supplied into the processing chamber 201 together with the NH ₃ gas, and is exhausted from the exhaust pipe 231. When supplying each gas, the nozzles 249a to 249a that are not used at that time are the same as in the above-described embodiment.
N ₂ gas supply for preventing intrusion of NH ₃ gas into 49c and the like is appropriately performed.

At this time, the APC valve 244 is appropriately adjusted so that the pressure in the processing chamber 201 is, for example, a pressure lower than atmospheric pressure, preferably 1 to 13330 Pa (0.0075 to 100 Torr), more preferably 133 to 2666 Pa (1 to The pressure is within the range of 20 Torr). MFC
The supply flow rate of NH ₃ gas controlled by 241d is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. N controlled by MFC 241g-241j
The supply flow rates of the _two gases are, for example, flow rates in the range of 100 to 10,000 sccm, respectively. The time for supplying the NH ₃ gas to the wafer 200 is, for example, 1-100 seconds, preferably 5-60 seconds.

The temperature of the heater 207 is the same as that of the wafer 200 in steps 1c and 2c.
A temperature range similar to the above temperature, that is, for example, room temperature to 150 ° C., preferably room temperature to 1
The temperature is set to be 00 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. The high frequency power applied between the rod-shaped electrodes 269 and 270 from the high frequency power supply 273 is, for example, 5
It sets so that it may become electric power within the range of 0-1000W.

At this time, the gas flowing into the processing chamber 201 is NH ₃ gas excited into a plasma state, and includes active species such as N radical (N ^* ). Further, B in the processing chamber 201
TCSM gas, H ₂ O gas and pyridine gas are not flowing. Therefore, the NH ₃ gas does not cause a gas phase reaction and is supplied to the wafer 200 in an activated state. The reforming process is performed on the SiOC layer as the second layer formed on the wafer 200 in Steps 1c and 2c mainly by the active species. The energy possessed by the active species is higher than the energy possessed by the thermally activated NH ₃ gas, for example, as in the above-described embodiment. For this reason, by giving the energy of the active species to the SiOC layer, Si—O contained in the SiOC layer is obtained.
At least a part of the bond, Si—C bond, etc. is cut off. N ^* , which is an active species, is combined with an excess bond of Si that has been disconnected from O or C. Thus, it is considered that at least a part of N taken into the SiOC layer forms a Si—N bond. Further, a part of N may be combined with an extra bond of O or C to form an N—O bond or an N—C bond.
Thus, the SiOC layer as the second layer is a third layer containing N, that is, SiO
It is changed (modified) into a CN layer.

(Residual gas removal)
After the SiOCN layer as the third layer is formed on the wafer 200, the application of the high frequency power from the high frequency power supply 273 to the rod-shaped electrodes 269 and 270 is stopped. Further, the valve 243d is closed, and the supply of NH ₃ gas is stopped. At this time, the residual gas is removed from the processing chamber 201 in the same procedure as in the above-described embodiment.

As the reformed gas containing at least one of C and N, the N-containing gas mentioned above may be used in addition to the NH ₃ gas as the reformed gas containing N. As an inert gas, N ₂
In addition to gas, various rare gases listed above may be used.

(Performed times)
Steps 1c, 2c, and 3c are defined as one cycle, and this cycle is performed once or more, that is, a predetermined number of times (n times), whereby a SiOCN having a predetermined composition and a predetermined film thickness is formed on the wafer 200.
A film can be formed. The above cycle is preferably repeated multiple times. That is, it is preferable that the thickness of the SiOCN layer formed per cycle is made smaller than the desired film thickness and the above-described cycle is repeated a plurality of times until the desired film thickness is obtained.

Thereafter, purging, returning to atmospheric pressure, boat unloading, and wafer discharging are performed in the same procedure as in the above-described embodiment, and the film forming process of this embodiment is completed.

(2) Effects according to this embodiment According to this embodiment, in addition to the same effects as those of the first embodiment described above, the following one or more effects are achieved.

(A) According to the film forming sequence of the present embodiment, NH ₃ gas excited to a plasma state is supplied to the wafer 200 in step 3c. As a result, the NH ₃ gas becomes more activated than the thermally activated state, and the modification action of the NH ₃ gas on the SiOC layer can be remarkably enhanced. The active species N ^* is not only taken into the SiOC layer, but many of them are combined with Si and the like and contained in the SiOC layer in a stronger and stable state. That is, the SiOCN layer obtained by the modification treatment is changed to S
A stronger and more stable layer containing many i-N bonds and the like can be obtained. Therefore, the finally obtained SiOCN film can be made a much better thin film.

(B) Further, according to the film forming sequence of the present embodiment, in step 3c, the NH ₃ gas excited in a plasma state, it can significantly enhance the reforming action on SiOC layer.
Thereby, even under a low temperature condition of, for example, 150 ° C. or less, the SiOC layer can be sufficiently modified. Therefore, the thermal history received by the wafer 200 can be further improved.

For example, the use of a low melting point metal material around the gate of a transistor has increased.
For this reason, when forming a thin film or the like that is used for SWS, an interlayer insulating film, or the like and has a low-k film characteristic, film formation at a low temperature of, for example, 150 ° C. or less, sometimes 100 ° C. or less is required.

In the present embodiment, both the SiOC film forming process and the SiOC film modifying process are performed at a low temperature of, for example, 150 ° C. or less to form the SiOCN film. Accordingly, a thin film having high etching resistance and high ashing resistance can be obtained, and a highly integrated semiconductor device can be obtained with high speed operation.

(C) Also, according to the film forming sequence of the present embodiment, the wafer 200 in step 3c.
Is set equal to the temperature of the wafer 200 in steps 1c and 2c. Thereby, for example, when a cycle in which steps 1c, 2c, and 3c are performed in this order is performed a predetermined number of times, each step can be performed without performing temperature adjustment in the middle. Therefore, it is possible to reduce the processing time per cycle by omitting the time required to raise or lower the temperature of the wafer 200, and it is possible to reduce the total processing time.

(3) Modification of this embodiment Next, a modification of this embodiment will be described.

As shown in FIG. 8B, in the modification, a reformed gas containing C and N may be used in place of the reformed gas containing N in the reforming process of the SiOC layer. As the reformed gas containing C and N, a gas containing a C-containing gas and an N-containing gas may be used. For example, both the C ₃ H ₆ gas and the NH ₃ gas are excited into a plasma state to the wafer 200. May be supplied. In this case, it is preferable that the C ₃ H ₆ gas is indirectly excited in the processing chamber 201 by plasma of NH ₃ gas supplied into the processing chamber 201. Alternatively, as a reformed gas containing C and N, for example, an amine-based gas may be excited into a plasma state and supplied to the wafer 200. In this case, the amine-based gas, for example, supplied from a nozzle provided in the buffer chamber 237 outside the process chamber 201, the N ₂ gas or the like supplied to the excited into a plasma state processing chamber 201 at the buffer chamber 237 Indirect excitation is preferably performed in the processing chamber 201 with the assist gas. Thereby, a SiOCN film further containing C and N is obtained.

In another modification, a reformed gas containing C may be used instead of the reformed gas containing N in the modification process of the SiOC layer. As the reformed gas containing C, for example, C ₃ H ₆ gas may be supplied to the wafer 200 after being excited into a plasma state, preferably by indirect excitation with an assist gas. Thereby, a SiOC film further containing C is obtained.

In yet another modification, in the modification process of the SiOC layer, C as a reformed gas containing C
Rather than exciting ₃ H ₆ gas into a plasma state and supplying it to the wafer 200, C ₃ H
₆ gas may be supplied to the wafer 200 with the pyridine gas as a catalyst gas. C
Also by supplying ₃ H ₆ gas together with pyridine gas, for example, C ₃ H ₆ gas can be activated under low temperature conditions of 150 ° C. or lower, and the SiO ₃ layer of C ₃ H ₆ gas can be modified. . Further, the temperature of the wafer 200 in the modification process of the SiOC layer can be made equal to the temperature of the wafer 200 at the time of forming the SiOC layer, and the processing time per cycle can be shortened.

Regarding the processing conditions such as the pressure in the processing chamber 201, the supply flow rate of each gas such as a reformed gas and N ₂ gas, the supply time, the temperature of the wafer 200 in these modified examples, for example, FIG. 7 and FIG.
The processing conditions can be set within the same range as the processing conditions in this sequence. The supply flow rate of the catalyst gas when using the catalyst gas can be set to a flow rate in the range of 1 to 2000 sccm, preferably 10 to 1000 sccm, for example. When supplying each gas, the nozzles 249a to 249d and the buffer chamber 2 which are not used are used as in the above-described embodiment.
N ₂ gas is supplied to prevent each gas from entering 37 and the like.

In the above-described second embodiment and its modification, the cycle of sequentially supplying each gas to the wafer 200 is performed a predetermined number of times. However, as in the first embodiment described above, by performing a set including a step performed in the same manner as steps 1a and 2a a predetermined number of times,
First, a SiOC film may be formed on the wafer 200. In addition, the reformed gas may be excited to a plasma state, or C ₃ H ₆ gas as the reformed gas may be supplied to the wafer 200 together with the pyridine gas. As a result, the SiOC film is modified and C
Alternatively, a SiOC film or a SiOCN film further containing N or N may be used. In this case as well, for example, the processing conditions can be set within the same range as the processing conditions in the sequences of FIGS.

However, SiO 3 can be obtained by supplying C ₃ H ₆ gas together with pyridine gas to the wafer 200.
When modifying the C film, the temperature of the wafer 200 is set to the wafer 2 when the SiOC film is formed.
Preferably, the temperature is higher than 00. Specifically, it is preferable to set the temperature of the wafer 200 to a temperature similar to the temperature of the wafer 200 in the SiOC film modification process of the first embodiment described above, for example. When the temperature of the wafer 200 when modifying the SiOC film is substantially the same as the temperature of the wafer 200 in the SiOC film forming process in the sequence shown in FIGS. 4 and 5A, for example, at least the surface layer portion of the SiOC film Although the effect of reforming is obtained,
There is a possibility that the reforming action by the C ₃ H ₆ gas does not reach the entire film. By making the temperature of the wafer 200 when modifying the SiOC film higher than the temperature of the wafer 200 when forming the SiOC film, the modification action by the C ₃ H ₆ gas is applied to almost the entire SiOC film. And a more uniform thin film can be obtained. Further, moisture is easily desorbed from the SiOC film, and C is easily taken into holes from which moisture has been removed.

When the SiOC film is modified by exciting the reformed gas into a plasma state and supplying it to the wafer 200, the temperature of the wafer 200 is set to the temperature of the wafer 200 in the same step as in steps 1a and 2a, for example. The temperature can be equal. The reformed gas excited to the plasma state is in a more active state, so even under such low temperature conditions,
The reforming action of the reformed gas can be spread over almost the entire SiOC film. However, even in the case of using plasma, the temperature of the wafer 200 may be made higher than the temperature of the wafer 200 in the step performed in the same manner as in steps 1a and 2a.
The temperature can be lower than or equal to ° C. If the temperature of the wafer 200 is up to 500 ° C., the higher the temperature, the easier the moisture is desorbed from the SiOC film, and the more easily C, N, etc. are taken into the holes from which moisture has been removed. If the temperature of the wafer 200 exceeds 500 ° C., the effects of moisture desorption and incorporation of C, N, etc. may not be further enhanced. Therefore, the temperature of the wafer 200 is set to 5
By setting the temperature to 00 ° C. or lower, the thermal history of the wafer 200 is not unnecessarily deteriorated, and SiO 2
The effect of desorption of moisture from the C film and incorporation of C, N, etc. into the SiOC film can be enhanced. In particular, the temperature of the wafer 200 is 300 ° C. or more and 500 ° C. or less, preferably 300 ° C.
By setting the temperature to 400 ° C. or lower, these effects can be further enhanced.
<Third Embodiment>
Next, a third embodiment of the present invention will be described.

(1) Thin film formation process In the above-mentioned embodiment, it is S using raw material gas used as Si source and C source, such as BTCSM gas.
An example in which an iOC film is formed and the SiOC film is modified with a modifying gas has been described. In the present embodiment, a SiO film is formed using a source gas that becomes a Si source but not a C source, and the SiO film is modified by a reforming gas. Also in the present embodiment, the substrate processing apparatus shown in FIGS. 1 and 2 is used as in the above-described embodiment. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

As shown in FIGS. 9 and 10A, in this embodiment,
HCDS gas as a raw material gas containing Si and a halogen element, a pyridine gas as a catalyst gas, as a raw material gas that becomes a Si source but not a C source for the wafer 200,
(Step 1d),
A step of supplying H ₂ O gas as an oxidizing gas and pyridine gas as a catalyst gas to the wafer 200 (step 2d);
Forming a SiO film as a first thin film containing Si and O on the wafer 200 by performing a set including a predetermined number of times (n times);
By performing a step of supplying C ₃ H ₆ gas and NH ₃ gas as a reformed gas containing C and N as a reformed gas containing at least C of C and N to wafer 200, the SiO film is formed. An example of modifying to a SiOCN film as a second thin film further containing C, N will be described.

(SiO film formation process)
Similar to the above-described embodiment, after performing wafer charging, boat loading, pressure adjustment, and temperature adjustment, the following two steps, that is, steps 1d and 2d are sequentially executed.

[Step 1d]
(HCDS gas + pyridine gas supply)
The valve 243e is opened and HCDS gas is allowed to flow into the gas supply pipe 232e. The flow rate of the HCDS gas is adjusted by the MFC 241e, supplied into the processing chamber 201 through the gas supply hole 250a, and exhausted from the exhaust pipe 231. At this time, HCDS gas is supplied to the wafer 200 (HCDS gas supply). At the same time, the valve 243g is opened, and an inert gas such as N ₂ gas is allowed to flow into the gas supply pipe 232g. The flow rate of the N ₂ gas is adjusted by the MFC 241 g, supplied into the processing chamber 201 together with the BTCSM gas, and exhausted from the exhaust pipe 231.

Further, pyridine gas is supplied to the wafer 200 in the same manner as the above-described supply of pyridine gas. When each gas is supplied, the nozzle 2 is not used as in the above-described embodiment.
N ₂ gas is supplied to prevent the intrusion of each gas into 49b and 249d and into the buffer chamber 237.

Thus, by supplying the HCDS gas to the wafer 200, the wafer 200
On the (surface undercoat film), as the first layer, for example, a Si-containing layer containing Cl having a thickness of less than one atomic layer to several atomic layers is formed. The Si-containing layer containing Cl may be a Si layer containing Cl, an adsorption layer of HCDS gas, 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. A continuous layer made of Si and containing Cl may be referred to as a Si thin film containing Cl. 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 gas includes a discontinuous adsorption layer as well as a continuous adsorption layer of gas molecules of HCDS gas. That is, the adsorption layer of the HCDS gas includes an adsorption layer having a thickness of less than one molecular layer composed of HCDS molecules or less than one molecular layer. HCDS constituting the adsorption layer of HCDS gas
The (Si ₂ Cl ₆ ) molecule includes those in which the bond between Si and Cl is partially broken. That is, HC
The DS gas adsorption layer includes a chemical adsorption layer of HCDS molecules and a physical adsorption layer of HCDS molecules.

The pyridine gas as the catalyst gas weakens the bonding force of the O—H bond existing on the surface of the wafer 200, promotes the decomposition of the HCDS gas, and promotes the formation of the first layer by chemical adsorption of HCDS molecules. That is, for example, pyridine gas as a catalyst gas acts on O—H bonds existing on the surface of the wafer 200 to weaken the bonding force between O—H. H and HCDS with weak binding
By reacting with the gas Cl, hydrogen chloride (HCl) gas is generated and desorbed, and HCDS molecules (halides) that have lost Cl are chemically adsorbed on the surface of the wafer 200. That is, an HCDS gas chemical adsorption layer is formed on the surface of the wafer 200. Thus, the pyridine gas as the catalyst gas also exhibits the same catalytic action as the catalyst gas for the HCDS gas as in the case of the raw material gas serving as the Si source and the C source such as the BTCSM gas described above.

Note that the processing conditions such as the pressure in the processing chamber 201 at this time, the supply flow rate of each gas such as a raw material gas, a catalyst gas, and N ₂ gas, the supply time, the temperature of the wafer 200, etc.
The processing conditions within the same range as the processing conditions in the sequence of FIG.

(Residual gas removal)
After the Si-containing layer containing Cl as the first layer is formed on the wafer 200, the valve 24
3e is closed and supply of HCDS gas is stopped. In the same procedure as the above embodiment,
The supply of pyridine gas is stopped, and residual gas is removed from the processing chamber 201.

As a source gas which becomes a Si source but does not become a C source, as a source gas containing Si and a halogen element, in addition to HCDS gas, silicon tetrachloride (SiCl ₄ , abbreviation: ST)
C) gas, trichlorosilane (SiHCl ₃ , abbreviation: TCS) gas, dichlorosilane (S
iH ₂ Cl ₂ , abbreviation: DCS) gas, and monochlorosilane (SiH ₃ Cl, abbreviation: M)
A chlorosilane-based source gas that does not contain C in gas molecules, such as CS) gas, may be used.
As the catalyst gas, in addition to pyridine gas, various amine-based catalyst gases listed above may be used. As the inert gas, various rare gases listed above may be used in addition to N ₂ gas.

[Step 2d]
(H ₂ O gas + pyridine gas supply)
After step 1d is completed and residual gas in the processing chamber 201 is removed, H ₂ O gas and pyridine gas are supplied to the wafer 200 in the same procedure as in the above-described embodiment. H ₂
When supplying O gas or pyridine gas, as in the above-described embodiment, N ₂ gas is supplied to prevent the entry of each gas into the nozzles 249a and 249d and the buffer chamber 237 which are not used.

By supplying heat activated H ₂ O gas to the wafer 200, step 1 is performed.
It reacts with at least a part of the first layer (Si-containing layer containing Cl) formed on the wafer 200 in d, and the first layer is thermally oxidized by non-plasma and contains Si and O. The second layer,
That is, it is changed to the SiO layer.

The pyridine gas as the catalyst gas acts on the O—H bond of the H ₂ O gas and weakens the bonding force between O—H. A weakened cohesive H, by a Cl having the first layer formed on the wafer 200 is reacted, HCl gas is generated desorbed, of the H _{2 O} gas lost H O
Bonds to Si in the first layer from which Cl is eliminated. As described above, the pyridine gas as the catalyst gas is used for the above-described S containing C and Cl even when the Si-containing layer containing Cl is modified.
The same catalytic action as when the i-containing layer is modified is shown.

Note that the processing conditions such as the pressure in the processing chamber 201 at this time, the supply flow rate of each gas such as the oxidizing gas, the catalyst gas, and the N ₂ gas, the supply time, the temperature of the wafer 200, and the like are illustrated in FIG.
The processing conditions within the same range as the processing conditions in the sequence of FIG.

For example, under a low temperature condition of 150 ° C. or lower, an SiO layer containing a relatively large amount of moisture (H ₂ O) and an SiO film formed by laminating such an SiO layer are easily formed. The moisture contained in the SiO layer and the SiO film is derived from, for example, H ₂ O gas used as an oxidizing gas.

(Residual gas removal)
After the second layer is formed on the wafer 200, the HCD is performed in the same procedure as in the above-described embodiment.
The supply of S gas and pyridine gas is stopped, and residual gas is removed from the processing chamber 201.

As the oxidizing gas, in addition to H ₂ O gas, various gases mentioned above may be used. As the catalyst gas, in addition to pyridine gas, various amine-based catalyst gases listed above may be used.
As the inert gas, various rare gases listed above may be used in addition to N ₂ gas.

(Performed times)
The above-described steps 1d and 2d are set as one set, and this set is performed at least once, that is, a predetermined number of times (n times), whereby a SiO film having a predetermined composition and a predetermined film thickness is formed on the wafer 200 as a first thin film. Can be formed. The above set is preferably repeated multiple times. That is, the thickness of the SiO layer formed per set is made smaller than the desired film thickness,
It is preferable to repeat the above set a plurality of times until a desired film thickness is obtained.

At this time, by controlling the processing conditions such as the pressure in the processing chamber 201 and the gas supply time in each step, each element component in the SiO layer, that is, the ratio of the Si component and the O component,
That is, the Si concentration and the O concentration can be adjusted, and the composition ratio of the SiO film can be controlled.

(SiO film modification process)
As described above, by using the HCDS gas that does not contain C in the gas molecules as the source gas, at least C derived from the source gas is not included in the film, and the SiO film as described above is formed. In the SiO film reforming step, for example, the SiO film is reformed using C ₃ H ₆ gas as a C-containing gas and NH ₃ gas as an N-containing gas as a reformed gas containing C and N.

(C ₃ H ₆ gas + NH ₃ gas supply)
After performing pressure adjustment and temperature adjustment in the same procedure as the above-mentioned first embodiment, the above-mentioned C ₃ H
_The C ₃ H ₆ is supplied to the wafer 200 in the same procedure as the supply of the ₆ gas and the supply of the NH ₃ gas.
Gas and NH ₃ gas are supplied.

By supplying heat activated C ₃ H ₆ gas and NH ₃ gas to the wafer 200, the first thin film (SiO film) formed on the wafer 200 by performing steps 1d and 2d a predetermined number of times. ) React with C ₃ H ₆ gas and NH ₃ gas. As a result, the SiO film is thermally modified by non-plasma and changed into a second thin film containing Si, O, C, and N, that is, a SiOCN film.

At this time, by setting the temperature of the wafer 200 to a relatively high temperature, C ₃ H ₆ gas and NH
The reaction between the _three gases and the SiO film is promoted, and the C component and the N component can penetrate into the SiO film. Further, by setting the temperature of the wafer 200 to be higher than the temperature of the wafer 200 in the step of forming the above-described SiO film, as described above, when the SiO film contains a lot of moisture, the moisture from the film is Is easily detached. A minute hole (pore), that is, a minute space is generated in a portion where the moisture of the SiO film is removed, and the SiO film becomes a porous film. When C or N enters such a hole from which moisture has been removed, the C component and the N component are further improved.
It becomes easy to be taken into the O film, and the modification of the SiO film reaches almost the entire film. At this time, at least a part of C and N taken into the SiO film is made up of components in the film such as Si and S.
An i-C bond, Si-N bond, or the like may be formed.

Note that the pressure in the processing chamber 201 at this time, the supply flow rate of each gas such as a reformed gas and N ₂ gas,
The processing conditions such as the supply time and the temperature of the wafer 200 can be set within the same ranges as the processing conditions in the above-described sequences of FIGS. In addition, C ₃ H ₆
When supplying the gas and NH ₃ gas, as in the above-described embodiment, N ₂ gas is supplied to prevent the intrusion of each gas into the nozzles 249a and 249b that are not used.

(Residual gas removal and purging)
After the SiOCN film as the second thin film is formed on the wafer 200, the above-described FIGS.
The supply of the C ₃ H ₆ gas and the NH ₃ gas is stopped in the same procedure as in the above sequence. At this time, the residual gas is removed from the processing chamber 201 and the processing chamber 201 is purged in the same procedure as in the above-described embodiment.

Thereafter, atmospheric pressure return, boat unloading, and wafer discharge are performed in the same procedure as the sequence of FIGS. 4 and 5A described above, and the film forming process of this embodiment is completed.

As the reformed gas containing C and N, various C-containing gases and N-containing gases mentioned above may be used in addition to the C ₃ H ₆ gas and the NH ₃ gas. As a reformed gas containing C and N,
Various amine-based gases listed above may be used.

In the above description, the SiOCN film is formed using the reformed gas containing C and N. For example, instead of the reformed gas containing C and N as in the modification shown in FIG. A reformed gas containing C, such as C ₃ H ₆ gas, may be used after being thermally activated. As a result, S
The iO film can be modified to form a SiOC film as a thin film containing Si, O, and C. Alternatively, instead of the reformed gas containing C and N, a reformed gas containing N such as NH ₃ gas may be thermally activated and used. In this way, the SiON film can be formed as a thin film containing Si, O, and N by modifying the SiO film with a reforming gas containing N. The SiON film can also be referred to as an SiO film containing N, an SiO film doped with (added to) N, or the like. Even in these cases, for example, the processing conditions within the same range as the processing conditions in the sequences of FIGS. 9 and 10A can be set.

(2) Effects according to the present embodiment According to the present embodiment, in addition to the same effects as those of the above-described embodiments, the following one or more effects are achieved.

(A) According to the film forming sequence of the present embodiment, after the SiO film is formed in steps 1d and 2d, the SiO film is modified with a modifying gas containing C and N to form the SiOCN film. As a result, the SiOCN film can be obtained even using a chlorosilane-based source gas that does not contain C in the gas molecules. That is, it is possible to obtain a thin film having high etching resistance and high ashing resistance by a simpler and cheaper gas system.

(B) According to the film forming sequence of the present embodiment, after the SiO film is formed in steps 1d and 2d, the SiO film is modified with a modifying gas containing C to form the SiOC film. At this time, for example, by increasing the time of the SiO film modification step, it is possible to obtain a SiOC film having a C concentration higher than that of the SiOC film formed using the above-described source gas serving as the Si source and the C source. Is possible. Thus, by increasing the C concentration in the film, for example, the C concentration in the film can be maintained high even after ashing, and a thin film having high ashing resistance can be obtained. Therefore, it is possible to obtain a thin film having high etching resistance and high ashing resistance by a simpler and cheaper gas system.

(3) Modification of this embodiment Next, a modification of this embodiment will be described.

In addition to the modification shown in FIG. 10 (b), as shown in FIGS. 11 and 12 (a), in another modification of the present embodiment, C ₃ H ₆ gas and NH ₃ gas are excited to a plasma state. Then, the SiO layer is modified.

That is,
A step of supplying an HCDS gas as a raw material gas and a pyridine gas as a catalyst gas to the wafer 200 (step 1e);
A step of supplying H ₂ O gas as an oxidizing gas and pyridine gas as a catalyst gas to the wafer 200 (step 2e);
A step of exciting and supplying a C ₃ H ₆ gas and an NH ₃ gas as a reformed gas containing C and N to the wafer 200 in a plasma state (step 3e);
Are performed in this order in a predetermined number of times, so that Si, O, C are formed on the wafer 200.
Alternatively, a SiOCN film as a thin film containing N and N may be formed.

The NH ₃ gas itself is easily plasma-excited and becomes a plasma state and is activated. The C ₃ H ₆ gas is a gas that is hardly plasma-excited by itself, but the processing chamber 20
By being indirectly excited in the processing chamber 201 by the NH ₃ gas plasma supplied into the plasma 1, the plasma state is activated. Thus, activated C ₃
By using H ₆ gas and NH ₃ gas, the SiO layer formed on the wafer 200 in steps 1e and 2e can be modified to form a SiOCN layer.

As the reformed gas containing C and N, various C-containing gases and N-containing gases mentioned above may be used in addition to the C ₃ H ₆ gas and the NH ₃ gas. As a reformed gas containing C and N,
Various amine-based gases listed above may be used. When the selected amine-based gas is a gas that is hardly plasma-excited by itself, the amine-based gas may be excited to a plasma state by a method using an assist gas.

In addition, as shown in FIG. 12B, in still another modification of the present embodiment, instead of C ₃ H ₆ gas and NH ₃ gas, C ₃ H ₆ gas is excited into a plasma state to generate a SiO layer. May be modified into a SiOC layer. At this time, as described below, an assist gas can be used. As still another modification of the present embodiment, instead of C ₃ H ₆ gas and NH ₃ gas,
NH ₃ gas may be excited to a plasma state to modify the SiO layer into a SiON layer. Thus, by using a reformed gas containing N, a thin film containing Si, O and N is used as SiON.
A film can also be formed.

As described above, C ₃ H ₆ gas is a gas that is difficult to be plasma-excited by itself. On the other hand,
For example, N ₂ gas has a relatively low ionization energy, and is itself a gas that is easily plasma-excited. This N ₂ gas is used as an assist gas for assisting plasma ignition. That is, at the same time as the supply of the C ₃ H ₆ gas is started, the valve 243j is opened and the gas supply pipe 232 is opened.
N ₂ gas is allowed to flow into j. The flow rate of N ₂ gas is adjusted by the MFC 241j, and the gas supply hole 2
50d is supplied into the buffer chamber 237, and high frequency (RF) power is supplied to the rod-shaped electrodes 269, 27.
By being applied to 0, the N ₂ gas enters a plasma state. N ₂ supplied into the processing chamber 201
The C ₃ H ₆ gas supplied into the processing chamber 201 is indirectly excited by the gas plasma,
C ₃ H ₆ gas is also in a plasma state and activated. At this time, for example, the supply of N ₂ gas may be started before the supply of C ₃ H ₆ gas. That is, first, the N ₂ gas in a plasma state may be supplied alone into the processing chamber 201, and the C ₃ H ₆ gas may be supplied thereto. As a result, the C ₃ H ₆ gas is supplied into the N ₂ gas atmosphere in the plasma state, and the C ₃ H ₆ gas is more easily excited by the plasma. Note that the N ₂ gas may act as an assist gas that assists the dissociation of the C ₃ H ₆ gas in the plasma.

With the activated C ₃ H ₆ gas, the SiO layer can be modified to form the SiOC layer. By modifying the SiO layer with the C ₃ H ₆ gas activated in the plasma state, for example, the C concentration is higher than that of the SiOC film obtained by the above-described thermally activated C ₃ H ₆ gas. A high SiOC layer or SiOC film can be obtained.

As assist gas for assisting the ignition of plasma, in addition to N ₂ gas, Ar gas, He
A rare gas such as gas, Ne gas, or Xe gas may be used.

As still another modification of the present embodiment, the SiO layer may be modified by supplying C ₃ H ₆ gas to the wafer 200 together with pyridine gas as a catalyst gas. The SiO layer can be modified with a C ₃ H ₆ gas activated by pyridine gas to form a SiOC layer.

Regarding the processing conditions such as the pressure in the processing chamber 201, the supply flow rate of each gas such as a reformed gas and N ₂ gas, the supply time, the temperature of the wafer 200 in these modifications, for example, in the sequence of FIGS. The processing conditions can be set within the same range as the processing conditions. The supply flow rate of N ₂ gas as the assist gas can be set to a flow rate in the range of 100 to 10,000 sccm, for example. When supplying each gas, as in the above-described embodiment, N ₂ gas is supplied to prevent the intrusion of each gas into the nozzles 249a to 249d and the buffer chamber 237 that are not used.

In these modified examples, a cycle for sequentially supplying each gas to the wafer 200 is performed a predetermined number of times. However, similar to the sequence shown in FIG. 9 and FIG. 10A described above, a SiO film is first formed on the wafer 200 by performing a set including steps performed in the same manner as steps 1d and 2d. Also good. In addition, the reformed gas may be excited to a plasma state, or C ₃ H ₆ gas as the reformed gas may be supplied to the wafer 200 together with the pyridine gas. As a result, the SiO film is modified so that C, N
It is good also as the SiOC film | membrane and SiOCN film | membrane which further contain etc. When the SiO film is modified by the reformed gas excited to the plasma state, the temperature condition can be made equal to the temperature condition in the above steps 1d and 2d, and the temperature of the wafer 200 is set to a temperature of 500 ° C. or less, for example. can do. When modifying the SiO film with C ₃ H ₆ gas activated with a catalyst gas,
The temperature condition can be made equal to the temperature condition in the reforming step of the sequence shown in FIGS.

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

For example, in the above-described first embodiment, the example in which the steps 1a and 2a are performed a predetermined number of times and the cycle for performing the SiOC film modification process is performed only once has been described, but the cycle may be repeated a plurality of times. In the second embodiment described above, steps 1c, 2c, and 3c are set to 1 in this order.
Although an example in which the cycle of performing each time is performed a predetermined number of times has been described, for example, steps 1c and 2c may be repeated a plurality of times, and the cycle of performing step 3c may be performed a predetermined number of times. This is because the steps 1d and 2d are performed a predetermined number of times in the above-described third embodiment, and the cycle of performing the SiOC film modification process is performed only once, and in the modified example, the steps 1e, 2e, and 3e are 1 in this order. The present invention is also applicable to an example in which a cycle that is performed once is performed a predetermined number of times.

In the above-described embodiment and the like, the example in which the step of supplying the reformed gas is performed separately from the step of supplying the raw material gas and the oxidizing gas has been described. However, the step of supplying the reformed gas may be performed during the step of supplying the raw material gas and the catalyst gas or during the step of supplying the oxidizing gas and the catalyst gas. Further, a step of supplying the reformed gas may be inserted between the step of supplying the source gas and the catalyst gas and the step of supplying the oxidizing gas and the catalyst gas. In this case, for example, FIG.
The processing conditions within the same range as the processing conditions in the sequence of FIG.

In the above embodiment, C ₃ H ₆ gas is supplied to the nozzle 249 provided outside the buffer chamber 237.
The example in which the process chamber 201 is supplied into the processing chamber 201 without passing through the buffer chamber 237 has been described. However, the C ₃ H ₆ gas is supplied from the nozzle provided in the buffer chamber 237 to the buffer chamber 237.
May be supplied into the processing chamber 201 via Even in this case, the C ₃ H ₆ gas supplied into the buffer chamber 237 may be indirectly excited by N ₂ gas plasma with the assistance of N ₂ gas or the like.

In the above-described embodiments and the like, a chlorosilane-based source gas that does not contain C in gas molecules, such as HCDS gas that is a source gas containing Si and a halogen element, is used as a source gas that becomes a Si source but not a C source. An example was described. However, the source gas that becomes the Si source but not the C source is not limited thereto. For example, an aminosilane-based source gas that is a source gas containing Si and an amino group (amine group) may be used as a source gas containing Si, C, and N and having a Si—N bond. The aminosilane-based source gas is a silane-based source gas containing an amino group, and is an organic source gas containing at least Si and an amino group containing C and N. The aminosilane-based source gas contains C in the gas molecules but does not have a Si-C bond, and even if this type of source gas is used, C derived from the source gas constitutes the thin film in the thin film to be formed. Is rarely captured as As the aminosilane-based source gas, for example, bistally butylaminosilane (SiH ₂ [NH (C ₄ H ₉ )] ₂
, Abbreviation: BTBAS) gas, tetrakisdimethylaminosilane (Si [N (CH ₃ ) ₂ ])
₄ , abbreviation: 4DMAS) gas, trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃
H, abbreviation: 3DMAS) gas, bisethylmethylaminosilane (Si [N (C ₂ H ₅ ) (
CH ₃ )] ₂ H ₂ , abbreviation: BEMAS) gas, and bisdiethylaminosilane (Si [
N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , abbreviation: BDEAS) gas, or the like can be used.

By using such an aminosilane-based source gas as a source gas, an SiO layer or S
An iO film is formed, and then a modification process is performed, so that an SiOC film further containing C or N or Si
An OCN film can be formed. The aminosilane-based source gas is supplied to the wafer 200 without supplying a catalyst gas such as pyridine gas. This allows S as the first layer.
An i-containing layer is formed. Thereafter, the first layer is oxidized using an oxygen-containing gas (O-containing gas) such as O ₂ gas excited to a plasma state as an oxidizing gas to obtain a SiO layer as the second layer. As described above, the method of exciting and using an O-containing gas or the like as an oxidizing gas in a plasma state uses the above-described alkylene halosilane-based source gas, alkylhalosilane-based source gas, or halosilane-based source gas (chlorosilane-based gas) as a source gas. It can be applied to the case of using as. However, when an alkylenehalosilane-based source gas or an alkylhalosilane-based source gas is used as a source gas, attention must be paid to setting the high-frequency power at the time of supplying an oxidizing gas, for example. This is because the oxidation reaction is allowed to proceed relatively gently and C is prevented from desorbing from the SiOC layer or the SiOC film. Even when these aminosilane-based source gases are used, for example, the processing conditions can be set within the same range as the processing conditions in any of the sequences of the above-described embodiments.

In the above-described embodiment, etc., an example of forming a SiOC film, a SiOCN film, etc. as a thin film has been described. However, a laminated film in which thin films having different compositions are laminated from the thin films, the thin film,
You may form the laminated film which laminated | stacked the thin film of a composition different from the said thin film. As the laminated film, for example, a laminated film of a SiOC film and a SiOCN film, a laminated film of a SiO film and a SiOC film,
Examples include a laminated film of a SiO film and a SiOCN film. Thus, by forming a laminated film of a plurality of films having different etching resistance, dielectric constant, and ashing resistance, the controllability of these characteristics in the laminated film can be further improved.

In the above-described embodiments and the like, the example in which the modification process is performed on the silicon oxide film such as the SiO film or the SiOC film as the thin film has been described. However, the present invention is not limited thereto, and for example, SiN
The present invention may be applied to a silicon nitride film such as a film. The SiN film formed at a low temperature contains oxygen as an impurity, and the film quality can be improved by performing the modification treatment.

By using the thin film formed by the method of each of the above-described embodiments and modifications as a SWS, it is possible to provide a device forming technique with less leakage current and excellent workability.

Further, by using a thin film formed by the method of each of the above-described embodiments and modifications as an etch stopper, it is possible to provide a device forming technique with excellent workability.

According to each embodiment and each modification excluding the above-described second embodiment and its modification, and the modification of the third embodiment, a thin film having an ideal stoichiometric ratio can be formed without using plasma. In addition, since a thin film can be formed without using plasma, it is possible to adapt to a process that is concerned about plasma damage, such as a SAPT film of DPT.

The modification process of the above-described embodiment or the like is not limited to the case where a Si-based thin film such as the above-described SiOC film or SiOCN film is formed, and for example, titanium (Ti), zirconium (Zr), hafnium (
Metal-based thin films such as metal carbide films (metal carbide) and metal oxycarbide films (metal oxycarbide) containing metal elements such as Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), and C. This can also be applied to the case of forming a film.

Process recipes (programs describing processing procedures and processing conditions) used to form these various thin films depend on the contents of the substrate processing (film type, composition ratio, film quality, film thickness, etc. of the thin film to be formed). These are preferably prepared individually (preparing a plurality). And when starting a substrate processing, it is preferable to select a suitable process recipe suitably from several process recipes according to the content of a substrate processing. Specifically, a plurality of process recipes individually prepared in accordance with the contents of the substrate processing are recorded on an electric communication line or a recording medium recording the process recipe (
Stored in advance in the storage device 121c included in the substrate processing apparatus via the external storage device 123).
It is preferable to install). When starting the substrate processing, the CPU 121a included in the substrate processing apparatus appropriately selects an appropriate process recipe from a plurality of process recipes stored in the storage device 121c according to the content of the substrate processing. Is preferred.
With this configuration, thin films with various film types, composition ratios, film qualities, and film thicknesses can be formed for general use with good reproducibility using a single substrate processing apparatus. Also, the operator's operational burden (
It is possible to reduce the burden of input of processing procedures and processing conditions, etc., and to quickly start substrate processing while avoiding operation errors.

The above-described process recipe is not limited to the case of creating a new process. For example, an existing process recipe already installed in the substrate processing apparatus may be changed. When changing the process recipe, the changed process recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium recording the process recipe. The input / output device 122 provided in the existing substrate processing apparatus may be operated to directly change the existing process recipe already installed in the substrate processing apparatus.

In the film forming sequence of the above-described embodiment and the like, the example in which the formation of the SiOC film, the SiO film and the like and the modification of these films are performed at room temperature has been described. In this case, it is not necessary to heat the processing chamber 201 with the heater 207, and the substrate processing apparatus may not be provided with a heater. Thereby, the structure of the heating system of a substrate processing apparatus can be simplified, and a substrate processing apparatus can be made cheaper and a simple structure. In this case, when the modification process for the SiOC film, the SiO film, or the like is performed at a high temperature, the modification process is performed in Ex-Situ in a process chamber different from the process chamber for performing the formation process for the SiOC film, the SiO film, or the like. It will be.

Further, in the above-described embodiment and the like, an example in which a thin film is formed using a batch-type substrate processing apparatus that processes a plurality of substrates at one time has been described, but the present invention is not limited to this, and one at a time. The present invention can also be suitably applied to the case where a thin film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates. In the above-described embodiment, an example in which a thin film is formed using a substrate processing apparatus having a hot wall type processing furnace has been described. However, the present invention is not limited to this, and a cold wall type processing furnace is provided. The present invention can also be suitably applied when forming a thin film using a substrate processing apparatus. In these substrate processing apparatuses, for example, processing conditions within the same range as the processing conditions in any of the above-described embodiments and the like can be used.

  Moreover, the above-described embodiments and modifications can be used in appropriate combination.

As examples and comparative examples of the present invention, a predetermined thin film was formed on a wafer using the substrate processing apparatus in the above-described embodiment, and the ashing resistance of these thin films was evaluated. Figure 5 above
A thin film (SiOC film) formed by the film forming sequence shown in b) and thermally modified is shown in Example 1.
It was. A thin film (SiOCN film) formed by the film forming sequence shown in FIG. 4 and FIG. A thin film (SiOCN film) formed by the film forming sequence shown in FIG. 7 and FIG. A thin film (SiOC film) in which only the steps 1a and 2a of the film forming sequence shown in FIG. 4 and FIG. About these thin films, after ashing using O ₂ plasma, a wet etching rate (WE) with a 1% HF aqueous solution is used.
R) was measured. About the comparative example, WER before ashing was also measured.

FIG. 16 is a graph showing the WER of each thin film of the example and the comparative example. The vertical axis of the graph represents WER (au). The horizontal axis of the graph shows each evaluation example. From left to right, the comparative example (before ashing), the comparative example (after ashing), the example 1, the example 2, and the example 3 (all examples are ashing). After). According to FIG. 16, it can be seen that the WER is kept low even before the ashing even in the comparative example thin film not subjected to the modification treatment. However, in the thin film of the comparative example after ashing, the WER is remarkably increased and the etching resistance is remarkably deteriorated. On the other hand, about the thin film of Examples 1-3 which performed some modification | reformation processes, it turns out that WER is restrained with low and can maintain favorable etching tolerance. In Examples 1 and 2 that were thermally modified, the thin film of Example 1 that was modified to further contain C was less than the thin film of Example 2 that was further modified to further contain N.
The WER was even lower and the etching resistance was high. In Example 3 in which the modification was performed by plasma, the WER was much lower than in Examples 1 and 2 in which the modification was performed thermally, and the etching resistance was high. From the above, it has been found that when a thin film modification process is performed during or after the formation of a thin film such as a SiOC film, the thin film has high etching resistance and high ashing resistance. In particular, it has been found that a thin film having higher etching resistance and higher ashing resistance can be obtained by the modification treatment using plasma.

<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 a source gas that is a silicon source and a carbon source to the substrate or a source gas that is a silicon source but not a carbon source, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate;
Supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A semiconductor device manufacturing method including a step of forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including Is done.

(Appendix 2)
A method of manufacturing a semiconductor device according to appendix 1, preferably,
Supplying the source gas and the catalyst gas;
The step of supplying the oxidizing gas and the catalyst gas is performed in a non-plasma atmosphere.

(Appendix 3)
A method for manufacturing a semiconductor device according to appendix 1 or 2, preferably,
Supplying the source gas and the catalyst gas;
In the step of supplying the oxidizing gas and the catalyst gas,
The temperature of the substrate is set to room temperature to 150 ° C., preferably room temperature to 100 ° C., more preferably 50 ° C. to 100 ° C.

(Appendix 4)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 3, preferably,
The cycle is
Supplying the source gas and the catalyst gas;
Supplying the oxidizing gas and the catalyst gas;
The first thin film containing at least silicon and oxygen (the first thin film containing silicon, oxygen, and carbon, or the first thin film containing silicon and oxygen) is formed on the substrate by performing a set including a predetermined number of times. Forming a step;
By performing the step of supplying the reformed gas, the first thin film is changed into a second thin film further containing carbon, a second thin film further containing nitrogen, or a second thin film further containing carbon and nitrogen. And a step of reforming.

(Appendix 5)
A method for manufacturing a semiconductor device according to appendix 4, preferably,
The step of forming the first thin film and the step of modifying the first thin film are performed in a state where the substrate is accommodated in the same processing chamber.

(Appendix 6)
A method for manufacturing a semiconductor device according to appendix 4, preferably,
The step of forming the first thin film and the step of modifying the first thin film are performed in a state where the substrates are accommodated in different processing chambers.

(Appendix 7)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 3, preferably,
The cycle is
Supplying the source gas and the catalyst gas;
Supplying the oxidizing gas and the catalyst gas;
And a step of supplying the reformed gas in this order.

(Appendix 8)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 7, preferably,
In the step of supplying the reformed gas, the temperature of the substrate is
Supplying the source gas and the catalyst gas;
The temperature is set equal to the temperature of the substrate in the step of supplying the oxidizing gas and the catalyst gas.

(Appendix 9)
A method of manufacturing a semiconductor device according to any one of appendices 1 to 6, preferably,
In the step of supplying the reformed gas, the temperature of the substrate is set to a temperature of room temperature to 500 ° C.

(Appendix 10)
A method of manufacturing a semiconductor device according to any one of appendices 1 to 6, preferably,
In the step of supplying the reformed gas, the temperature of the substrate is set to 200 ° C. or higher and 900 ° C. or lower, preferably 200 ° C. or higher and 700 ° C. or lower, more preferably 200 ° C. or higher and 600 ° C. or lower.

(Appendix 11)
A method for manufacturing a semiconductor device according to appendices 1 to 6, 10, preferably,
The step of supplying the reformed gas is performed in a non-plasma atmosphere.

(Appendix 12)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 9, preferably,
In the step of supplying the reformed gas, the reformed gas excited to a plasma state is supplied to the substrate.

(Appendix 13)
According to another aspect of the invention,
Supplying a source gas containing silicon, carbon and halogen elements and having a Si-C bond to the substrate, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate;
Supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A semiconductor device manufacturing method including a step of forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including Is done.

(Appendix 14)
The method for manufacturing a semiconductor device according to appendix 13, preferably,
The source gas includes at least one of an alkyl group and an alkylene group.

(Appendix 15)
The method for manufacturing a semiconductor device according to appendix 14, preferably,
The source gas containing the alkylene group includes Si—C—Si bond and Si—C—C—S.
at least one of i-bonds.

(Appendix 16)
A method for manufacturing a semiconductor device according to any one of appendices 13 to 15, preferably,
The reformed gas includes at least one of a carbon-containing gas, a nitrogen-containing gas, and a gas containing carbon and nitrogen in one molecule.

(Appendix 17)
According to yet another aspect of the invention,
Supplying a source gas containing silicon and a halogen element to the substrate and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate;
Supplying a reformed gas containing at least carbon of carbon and nitrogen to the substrate;
A semiconductor device manufacturing method including a step of forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including Is done.

(Appendix 18)
The method for manufacturing a semiconductor device according to appendix 17, preferably,
The source gas includes a chlorosilane-based source gas containing silicon and chlorine (chloro group).

(Appendix 19)
A method for manufacturing a semiconductor device according to appendix 17 or 18, preferably,
The reformed gas includes at least one of a carbon-containing gas, a gas containing both a carbon-containing gas and a nitrogen-containing gas, and a gas containing carbon and nitrogen in one molecule.

(Appendix 20)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 19, preferably,
The reformed gas includes at least one of a hydrocarbon gas, an amine gas, and a non-amine gas.

(Appendix 21)
A method for manufacturing a semiconductor device according to any one of appendices 1 to 20, preferably,
The catalyst gas includes an amine catalyst gas.

(Appendix 22)
According to yet another aspect of the invention,
Supplying a source gas that is a silicon source and a carbon source to the substrate or a source gas that is a silicon source but not a carbon source, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate;
Supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A substrate processing method including a step of forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate is provided by performing a cycle including a predetermined number of times. .

(Appendix 23)
According to yet another aspect of the invention,
A processing chamber for accommodating the substrate;
A raw material gas supply system for supplying a raw material gas that becomes a silicon source and a carbon source or a silicon source but does not become a carbon source into the processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber;
A catalyst gas supply system for supplying a catalyst gas into the processing chamber;
A reformed gas supply system for supplying a reformed gas containing at least one of carbon and nitrogen into the processing chamber;
A process for supplying the source gas and the catalyst gas to the substrate in the process chamber; a process for supplying the oxidizing gas and the catalyst gas to the substrate in the process chamber; and the substrate in the process chamber. A thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate A control unit for controlling the raw material gas supply system, the oxidizing gas supply system, the catalyst gas supply system, and the reformed gas supply system so as to perform the forming process;
A substrate processing apparatus is provided.

(Appendix 24)
According to yet another aspect of the invention,
A substrate processing system comprising: a first substrate processing unit that forms a first thin film on a substrate; and a second substrate processing unit that modifies the first thin film,
The first substrate processing unit includes:
A first processing chamber for accommodating a substrate;
A source gas supply system that becomes a silicon source and a carbon source or a silicon source but does not become a carbon source into the first processing chamber;
An oxidizing gas supply system for supplying an oxidizing gas into the first processing chamber;
A catalyst gas supply system for supplying a catalyst gas into the first processing chamber;
A cycle including a process of supplying the source gas and the catalyst gas to the substrate in the first processing chamber, and a process of supplying the oxidizing gas and the catalyst gas to the substrate in the first processing chamber. Is performed a predetermined number of times, the source gas supply system, the oxidation so as to perform a process of forming a first thin film containing silicon, oxygen and carbon, or a first thin film containing silicon and oxygen on the substrate. A first control unit that controls the gas supply system and the catalyst gas supply system,
The second substrate processing unit includes:
A second processing chamber for accommodating a substrate on which the first thin film is formed;
A reformed gas supply system for supplying a reformed gas containing at least one of carbon and nitrogen into the second processing chamber;
By performing the process of supplying the reformed gas to the substrate in the second processing chamber,
The reformed gas supply system so as to perform a process of modifying the first thin film into a second thin film containing silicon, oxygen, and carbon, or a second thin film containing silicon, oxygen, carbon, and nitrogen. And a second control unit that controls the substrate processing system.

(Appendix 25)
According to yet another aspect of the invention,
A procedure for supplying a source gas that is a silicon source and a carbon source or a silicon source but not a carbon source to the substrate in the processing chamber, and a catalyst gas;
Supplying an oxidizing gas and a catalyst gas to the substrate in the processing chamber;
Supplying a reformed gas containing at least one of carbon and nitrogen to the substrate in the processing chamber;
A program for causing a computer to execute a procedure for forming a thin film containing silicon, oxygen, and carbon or a thin film containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including A computer-readable recording medium recording the program is provided.

121 Controller (control unit)
200 wafer (substrate)
201 processing chamber 202 processing furnace 203 reaction tube 207 heater 209 manifold 231 exhaust pipes 232a to 232j gas supply pipe 244 APC valve (pressure adjusting unit)

Claims (12)

A first step of supplying a substrate gas containing silicon, carbon and a halogen element or a source gas containing silicon and a halogen element and a catalyst gas to the substrate; and an oxidizing gas and a catalyst gas for the substrate. A step of performing a set including a second step of supplying a predetermined number of times,
A third step of supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A method of manufacturing a semiconductor device comprising a step of forming a film containing silicon, oxygen, and carbon or containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including the predetermined number of times.   The method of manufacturing a semiconductor device according to claim 1, wherein the source gas has a chemical bond between silicon and carbon and a chemical bond between silicon and a halogen element, or has a chemical bond between silicon and a halogen element. By performing a set including the first step and the second step a predetermined number of times, silicon, oxygen and carbon are included, or a first layer containing silicon and oxygen is formed,
3. The first layer is modified into a second layer further containing carbon, further containing nitrogen, or further containing carbon and nitrogen by performing the third step. The manufacturing method of the semiconductor device as described in any one of Claims 1-3.   The method of manufacturing a semiconductor device according to claim 1, wherein the setting is performed a plurality of times.   The method for manufacturing a semiconductor device according to claim 1, wherein the cycle is performed a plurality of times.   6. The method of manufacturing a semiconductor device according to claim 1, wherein the first step, the second step, and the third step are performed in a non-plasma atmosphere. The first step and the second step are performed in a non-plasma atmosphere,
6. The method of manufacturing a semiconductor device according to claim 1, wherein in the third step, the plasma-excited reformed gas is supplied to the substrate.   The method for manufacturing a semiconductor device according to claim 1, wherein, in the third step, the temperature of the substrate is equal to the temperature of the substrate in the first step and the second step.   The method for manufacturing a semiconductor device according to claim 1, wherein, in the third step, the temperature of the substrate is higher than the temperature of the substrate in the first step and the second step. A processing chamber for accommodating the substrate;
A source gas supply system that supplies silicon, carbon and a halogen element into the processing chamber or supplies a source gas containing silicon and a halogen element;
An oxidizing gas supply system for supplying an oxidizing gas into the processing chamber;
A catalyst gas supply system for supplying a catalyst gas into the processing chamber;
A reformed gas supply system for supplying a reformed gas containing at least one of carbon and nitrogen into the processing chamber;
In the processing chamber, a set including a first process for supplying the source gas and the catalyst gas to the substrate and a second process for supplying the oxidizing gas and the catalyst gas to the substrate is performed a predetermined number of times. The substrate includes silicon, oxygen, and carbon on the substrate by performing a predetermined number of cycles including a process to be performed and a third process for supplying the reformed gas to the substrate, or silicon, The raw material gas supply system, the oxidizing gas supply system, the catalyst gas supply system, and the reformed gas supply system are controlled so as to perform a process of forming a film containing oxygen, carbon, and nitrogen. A control unit,
A substrate processing apparatus. A first procedure for supplying a substrate gas containing silicon, carbon and a halogen element or a source gas containing silicon and a halogen element and a catalyst gas to the substrate, and an oxidizing gas and a catalyst gas for the substrate. A second procedure of supplying, a procedure of performing a set including a predetermined number of times,
A third procedure for supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A program that causes a computer to execute a procedure of forming a film containing silicon, oxygen, and carbon or containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including the above. A first procedure for supplying a substrate gas containing silicon, carbon and a halogen element or a source gas containing silicon and a halogen element and a catalyst gas to the substrate, and an oxidizing gas and a catalyst gas for the substrate. A second procedure of supplying, a procedure of performing a set including a predetermined number of times,
A third procedure for supplying a reformed gas containing at least one of carbon and nitrogen to the substrate;
A program that causes a computer to execute a procedure for forming a film containing silicon, oxygen, and carbon or containing silicon, oxygen, carbon, and nitrogen on the substrate by performing a cycle including Computer-readable recording medium.