CN111243994A - Gas supply nozzle, substrate processing apparatus, and method for manufacturing semiconductor device - Google Patents

Abstract

The present invention relates to a gas supply nozzle, a substrate processing apparatus, and a method for manufacturing a semiconductor device. The present invention provides a technique capable of improving the uniformity of film thickness between substrates. The present invention provides a technique comprising: a nozzle base end portion extending in the vertical direction in a processing chamber for processing a substrate and into which a processing gas for processing the substrate is introduced; a nozzle a front end portion having a U-shaped configuration and provided with a gas supply hole for supplying the process gas into the process chamber on a side surface on the substrate side; and a gas retention suppressing hole provided in the nozzle The downstream end of the front end portion has a larger diameter than the gas supply hole.

Description

Gas supply nozzle, substrate processing apparatus, and manufacturing method of semiconductor device

This application is a divisional application of Chinese Invention Patent Application No. 201610526212.2 with an application date of July 5, 2016, and the invention title is "Gas Supply Nozzle, Substrate Processing Apparatus, and Manufacturing Method of Semiconductor Device".

technical field

The present invention relates to a gas supply nozzle, a substrate processing apparatus, and a method for manufacturing a semiconductor device.

Background technique

As one of the manufacturing steps of a semiconductor device (device), a process of forming a film on a substrate by asynchronously supplying a raw material gas and a reaction gas to a substrate arranged in multiple layers in a processing chamber may be performed.

Japanese Patent Laid-Open No. 2009-295729

SUMMARY OF THE INVENTION

However, in recent years, such semiconductor devices have tended to be highly integrated, and the pattern size has been remarkably reduced, so that it has become difficult to form a film uniformly on a substrate. An object of the present invention is to provide a technique capable of improving the uniformity of film thickness between substrates.

Through a scheme of the present invention, a kind of technology is provided, and it has:

a base end portion of the nozzle, which is arranged to extend in the vertical direction in a processing chamber for processing the substrate, and is introduced into the processing gas for processing the substrate;

a front end portion of the nozzle, which has a U-shaped configuration, and is provided with a gas supply hole for supplying the process gas into the process chamber on the side surface on the substrate side; and

The gas retention suppressing hole is provided at the downstream end of the nozzle tip portion and has a larger diameter than the gas supply hole.

This application relates to the following:

Item 1. A gas supply nozzle having:

a base end portion of the nozzle, which is arranged to extend in the vertical direction in a processing chamber for processing the substrate, and is introduced into the processing gas for processing the substrate;

a front end portion of the nozzle, which has a U-shaped configuration, and is provided with a gas supply hole for supplying the process gas into the process chamber on the side surface on the substrate side; and

The gas retention suppressing hole is provided at the downstream end of the nozzle tip portion and has a larger diameter than the gas supply hole.

Item 2. The gas supply nozzle according to Item 1, wherein the gas retention suppressing hole is provided at a position lower than a position where the substrate is arranged.

Item 3. The gas supply nozzle according to Item 1, wherein a hole diameter of the gas retention suppressing hole is formed so as to be 1.1 to 25 times the hole diameter of the gas supply hole.

Item 4. The gas supply nozzle of Item 1, wherein the nozzle front end has:

an upstream line connected to the base end of the nozzle;

a turn-back portion that changes the direction of airflow through the upstream-side pipeline; and

A downstream pipeline that is connected to the folded portion and extends vertically downward,

The hole diameter of the gas retention suppression hole is configured so that the flow velocity of the gas in the upstream end of the upstream line and the downstream end of the downstream line are equal.

Item 5. The gas supply nozzle according to Item 4, wherein the gas supply hole is provided only on the downstream side line.

Item 6. The gas supply nozzle according to Item 4, wherein the gas supply hole is provided only on the upstream side line.

Item 7. The gas supply nozzle according to Item 4, wherein the gas supply holes are provided at different heights on the upstream line and the downstream line.

Item 8. A substrate processing apparatus having:

a processing chamber for processing the substrate; and

a gas supply unit for supplying the process gas through the first gas supply nozzle,

The first gas supply nozzle includes:

a nozzle base end portion, which is arranged in the processing chamber to extend in the vertical direction, and is introduced into the processing gas for processing the substrate;

a front end portion of the nozzle, which has a U-shaped configuration, and is provided with a gas supply hole for supplying the process gas into the process chamber on the side surface on the substrate side; and

The gas retention suppressing hole is provided at the downstream end of the nozzle tip portion and has a larger diameter than the gas supply hole.

Item 9. The substrate processing apparatus according to Item 8, wherein the gas retention suppressing hole is provided at a position lower than a position where the substrate is arranged.

Item 10. The substrate processing apparatus according to Item 8, wherein the hole diameter of the gas retention suppression hole is formed so as to be 1.1 to 25 times the diameter of the gas supply hole.

Item 11. The substrate processing apparatus of Item 8, wherein the nozzle front end has:

an upstream line connected to the base end of the nozzle;

a turn-back portion that changes the direction of airflow through the upstream-side pipeline; and

A downstream pipeline that is connected to the folded portion and extends vertically downward,

The hole diameter of the gas retention suppression hole is configured so that the flow velocity of the gas in the upstream end of the upstream line and the downstream end of the downstream line are equal.

Item 12. The substrate processing apparatus according to Item 8, wherein the processing gas supplied from the gas supply unit is at least a raw material gas, a reactive gas, and an inert gas.

Item 13. The substrate processing apparatus according to Item 11, wherein the raw material gas supplied from the gas supply unit is supplied into the processing chamber through at least the first gas supply nozzle.

Item 14. A method of manufacturing a semiconductor device, comprising the following steps:

a process of preparing a substrate processing apparatus; and

The step of processing the substrate by supplying a processing gas from a gas supply unit,

The substrate processing apparatus has:

a processing chamber for processing the substrate; and

the gas supply unit that supplies the process gas through a first gas supply nozzle,

The first gas supply nozzle includes:

a nozzle base end portion, which is arranged in the processing chamber to extend in the vertical direction, and is introduced into the processing gas for processing the substrate;

a front end portion of the nozzle, which has a U-shaped configuration, and is provided with a gas supply hole for supplying the process gas into the process chamber on the side surface on the substrate side; and

The gas retention suppressing hole is provided at the downstream end of the nozzle tip portion and has a larger diameter than the gas supply hole.

According to the present invention, the uniformity of film thickness between substrates can be improved.

Description of drawings

1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus to which an embodiment of the present invention is applied, and is a diagram showing a portion of the processing furnace in a vertical cross-sectional view.

2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus to which an embodiment of the present invention is applied, and is a diagram showing a portion of the processing furnace by a cross-sectional view taken along the line A-A in FIG. 1 .

[ Fig. 3] Fig. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus to which an embodiment of the present invention is applied, and is a block diagram showing a control system of the controller.

[ Fig. 4] Fig. 4 is a diagram showing an installation example of a processing container and a nozzle of a substrate processing apparatus to which an embodiment of the present invention is applied.

[ Fig. 5] Fig. 5 is a diagram showing a perspective view of a nozzle of a substrate processing apparatus to which an embodiment of the present invention is applied.

[ Fig. 6] (a) is a view obtained by enlarging a broken line region A in the nozzle of Fig. 5 , and (b) is a view obtained by enlarging a broken line region B in the nozzle of Fig. 5 .

7A] (a) is a diagram showing the relationship between the height direction of the nozzle of the straight pipe type nozzle shape and the reaction ratio of the gas, and (b) is a diagram showing the gas retention suppressing hole at the tip of the nozzle in the nozzle shape of FIG. 5 A graph showing the relationship between the height direction of the nozzle and the reaction ratio of the gas when the pore diameter of 1.1 is medium.

7B] (c) is a diagram showing the relationship between the height direction of the nozzle and the reaction ratio of the gas when the nozzle shape of FIG. 5 is used and the diameter of the gas retention suppressing hole at the tip of the nozzle is medium 4, and (d) is A diagram showing the relationship between the height direction of the nozzle and the reaction ratio of the gas when the nozzle shape is the nozzle shape of FIG. 5 and the diameter of the gas retention suppressing hole at the tip of the nozzle is φ8.

[Fig. 8] (a) is a diagram showing an image of the gas reaction ratio distribution of the nozzle shape of the straight pipe type, (b) is a diagram showing the nozzle shape of Fig. 5 and the hole diameter of the gas retention suppressing hole at the tip of the nozzle is φ1. 1 is a diagram showing an image of the gas reaction ratio distribution, and (c) is a diagram showing an image of the gas reaction ratio distribution when the nozzle shape is the nozzle shape of FIG.

[ Fig. 9] Fig. 9 is a diagram showing a film formation sequence applied to an embodiment of the present invention.

[ Fig. 10A ] (a) is a diagram showing the nozzle shape of FIG. 5 and the diameter of the gas retention suppressing hole at the nozzle tip is medium 4, (b) is the nozzle shape shown in FIG. 5 and the gas retention at the nozzle tip (c) is a diagram showing the case where the diameter of the suppression hole is φ1.1, and (c) is a view showing the nozzle shape of FIG. 5 and the diameter of the gas retention suppression hole at the tip of the nozzle is φ8.

[ Fig. 10B ] (d) is a view showing the nozzle shape of Fig. 5 , the diameter of the gas retention suppressing hole at the tip of the nozzle is medium 4, and the gas supply hole is provided in the nozzle portion on the downstream side of the turning portion of the nozzle. , (e) is a diagram showing the nozzle shape of FIG. 5 , the diameter of the gas retention suppressing hole at the tip of the nozzle is φ4, and the gas supply hole is provided in the nozzle portion on the upstream side of the turning portion of the nozzle, and (f) is The nozzle shape shown in FIG. 5 has a diameter of φ4 of the gas retention suppressing hole at the tip of the nozzle, and a gas supply hole is provided between the center of the nozzle and the base end of the nozzle on the nozzle portion on the upstream side of the turning portion of the nozzle, and a gas supply hole is provided at the nozzle base. Figure 5 shows a case where a gas supply hole is provided between the center of the nozzle and the folded part of the nozzle on the nozzle part on the downstream side of the folded part of the nozzle, (g) shows the nozzle shape of FIG. 5 and the gas retention suppression hole at the tip of the nozzle The hole diameter is medium 4. A gas supply hole is provided between the center of the nozzle on the nozzle part on the upstream side of the turn-back part and the turn-back part of the nozzle, and the center of the nozzle on the nozzle part on the downstream side of the turn-back part of the nozzle is the same as that of the nozzle. A diagram showing a state in which a gas supply hole is provided between the tip ends of the nozzles.

[FIG. 10C] (h) shows the nozzle shape of FIG. 5 and the diameter of the gas retention suppressing hole at the tip of the nozzle is φ4, so as to extend the length of the nozzle portion on the downstream side of the turn-back portion of the nozzle and make the turn-back portion of the nozzle The figure of the case where the installation position of the gas supply hole on the part of the downstream side is located in the lower part of the reaction tube, (i) is the nozzle shape shown in FIG. The figure of the case where the length of the nozzle part on the downstream side of the folded-back part of the nozzle is extended, and the installation position of the gas supply hole is made the same height upstream and downstream of the folded-back part of the nozzle, (j) is the nozzle shown in FIG. 5 . In the case where the diameter of the gas retention suppression hole at the tip of the nozzle is φ4, the length of the nozzle portion on the downstream side of the turning portion of the nozzle is extended, and the gas supply hole is provided only on the upstream side of the turning portion of the nozzle. Fig. 5, (k) is the nozzle shape shown in Fig. 5 and the diameter of the gas retention suppressing hole at the tip of the nozzle is φ4, the length of the nozzle portion on the downstream side of the turn-back portion of the nozzle is extended, and the length of the nozzle portion is only longer than the nozzle. A diagram showing a case where a gas supply hole is provided at a position on the downstream side of the folded portion.

[ Fig. 11] Fig. 11 is a diagram showing an installation example of a processing container and a nozzle of a substrate processing apparatus to which another embodiment of the present invention is applied.

12 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus to which another embodiment of the present invention is applied, and is a diagram showing a portion of the processing furnace by a cross-sectional view taken along the line A-A in FIG. 1 .

Description of reference numerals

121 Controller (control unit)

200 wafers (substrate)

201 Processing Room

202 Processing Furnace

203 reaction tube

249a, 249b nozzles (first nozzle, second nozzle)

Detailed ways

<First Embodiment>

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 to 3 .

(1) Configuration of substrate processing apparatus (heating apparatus)

As shown in FIG. 1 , the processing furnace 202 has a heater 207 as a heating means (heating mechanism). The heater 207 has a cylindrical shape, and is vertically mounted by being supported on a heater base (not shown) serving as a holding plate. As will be described later, the heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas with heat.

Inside the heater 207 , a reaction tube 203 constituting a reaction vessel (processing vessel) is provided concentrically with the heater 207 . The reaction tube 203 is made of, for example, a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and is formed in a cylindrical shape with an upper end closed and a lower end open. A processing chamber 201 is formed in the cylindrical hollow portion of the reaction tube 203 . The processing chamber 201 is configured such that the wafers 200 serving as substrates can be accommodated in a horizontal posture in a state in which multiple layers are aligned in the vertical direction by the wafer boat 217 , which will be described later.

(Gas Supply Section)

In the processing chamber 201 , a nozzle 249 a serving as a first gas supply nozzle and a nozzle 249 b serving as a second gas supply nozzle, which will be described later, are respectively assembled so as to penetrate the lower side wall of the reaction tube 203 . The nozzles 249a and 249b are each made of quartz. The gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively. As described above, the two nozzles 249a and 249b and the two gas supply pipes 232a and 232b are provided in the reaction tube 203 , and several kinds of gases can be supplied into the processing chamber 201 .

However, the processing furnace 202 of this embodiment is not limited to the above-mentioned form. For example, a metal header supporting the reaction tubes 203 may be provided below the reaction tubes 203, and each nozzle may be provided so as to penetrate through the side walls of the header. In this case, an exhaust pipe 231 which will be described later may be further provided in the header. In this case, the exhaust pipe 231 may not be provided at the header, but may be provided at the lower part of the reaction tube 203 . As described above, the furnace mouth portion of the processing furnace 202 may be made of metal, and a nozzle or the like may be attached to the metal furnace mouth portion.

Mass flow controllers (MFC) 241a and 241b serving as flow controllers (flow rate controllers) and valves 243a and 243b serving as on-off valves are respectively provided in the gas supply pipes 232a and 232b in this order from the upstream direction. The gas supply pipes 232c and 232d for supplying the inert gas are connected to the positions closer to the downstream side than the valves 243a and 243b of the gas supply pipes 232a and 232b, respectively. The gas supply pipes 232c and 232d are respectively provided with MFCs 241c and 41d as flow controllers (flow rate controllers) and valves 243c and 243d as on-off valves in this order from the upstream direction.

Nozzles 249a and 249b, which will be described in detail later, are connected to the tip portions of the gas supply pipes 232a and 232b, respectively. In addition, the nozzles 249a and 249b are also collectively abbreviated as the nozzle 249. As shown in FIG. 2 , the nozzles 249 a and 249 b are respectively disposed in a circular ring between the inner wall of the reaction tube 203 and the wafer 200 so as to stand up from the lower part to the upper part along the inner wall of the reaction tube 203 and toward the upper direction of the arrangement direction of the wafers 200 . shape space. That is, the nozzles 249a and 249b are respectively provided in the areas lateral to the wafer array area and horizontally surrounding the wafer array area so as to follow the wafer array area in which the wafers 200 are arrayed. That is, the nozzles 249a and 249b are respectively provided on the side of the end (peripheral edge) of each wafer 200 so as to be perpendicular to the surface (flat surface) of the wafer 200 carried into the processing chamber 201 . The nozzles 249a and 249b are respectively constituted as L-shaped long-diameter nozzles, and their respective horizontal portions are provided so as to penetrate the lower side wall of the reaction tube 203, and their respective vertical portions are directed toward at least one end side of the wafer array region. Set up with the other end side upright. On the side surfaces of the nozzles 249a and 249b, gas supply holes 250a and 250c, 250b and 250d for supplying gas are provided, respectively. It should be noted that the gas supply holes 250a and 250c provided at the nozzle 249a are also abbreviated as gas supply holes 250a ( 250c ), or the gas supply holes 250b and 250d provided at the nozzle 249a are also abbreviated as gas supply holes 250b ( 250d ). ). Furthermore, the gas supply holes 250 a , 250 b , 250 c , and 250 d are also collectively referred to simply as the gas supply holes 250 . The gas supply hole 250 a ( 250 c ) and the gas supply hole 250 b ( 250 d ) are respectively opened so as to face the center of the reaction tube 203 , and can supply gas toward the wafer 200 . A plurality of gas supply holes 250a (250c) and gas supply holes 250b (250d) are respectively provided in the range from the lower part to the upper part of the reaction tube 203, and they have the same opening area and are provided with the same opening pitch.

As described above, in the present embodiment, the gas is fed through the nozzles 249a and 249b arranged at the inner wall of the side wall of the reaction tube 203 and the end (peripheral portion) of the stacked wafers 200 . ) in the annular longitudinally long space, that is, in the cylindrical space. Then, gas is ejected into the reaction tube 203 from the gas supply holes 250a ( 250c ) and 250b ( 250d ) opened to the nozzles 249a and 249b , respectively, in the vicinity of the wafer 200 . In addition, the main flow direction of the gas in the reaction tube 203 is the direction parallel to the surface of the wafer 200 , that is, the horizontal direction. With such a configuration, the gas can be supplied to each wafer 200 uniformly, and the uniformity of the film thickness of the thin film formed on each wafer 200 can be improved. 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, in the direction of the exhaust pipe 231 to be described later. However, the flow direction of the residual gas can be appropriately determined according to the position of the exhaust port, and is not limited to the vertical direction.

As the raw material gas, for example, a halosilane raw material gas containing Si as a predetermined element and a halogen element is supplied into the processing chamber 201 from the gas supply pipe 232a through the MFC 241a, the valve 243a, and the nozzle 249a.

The halosilane raw material gas refers to a gaseous halosilane raw material, for example, a gas obtained by vaporizing a liquid halosilane raw material at normal temperature and pressure, a gaseous halosilane raw material at normal temperature and normal pressure, and the like. The term "halosilane raw material" refers to a silane raw material having a halogen group. Halo groups include chloro, fluoro, bromo, iodo, and the like. That is, the halogen group includes halogens such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). The halosilane starting material can also be considered to be a type of halide. When the term "raw material" is used in this specification, it may refer to "liquid liquid raw material", sometimes "gaseous raw material gas", or sometimes both.

As the halosilane raw material gas, for example, a raw material gas containing Si and Cl and not containing C, that is, an inorganic chlorosilane raw material gas can be used. As the inorganic chlorosilane source gas, for example, hexachlorodisilane (Si ₂ Cl ₆ , abbreviated: HCDS) gas, octachlorotrisilane (Si ₃ Cl ₈ , abbreviated: OCTS) gas, and the like can be used. These gases can also be considered to be source gases that contain at least two Si in one molecule, and also contain Cl, and have Si—Si bonds. These gases function as Si sources in the film formation process to be described later.

In addition, as the halosilane raw material gas, for example, a raw material gas containing Si, Cl and an alkylene group and having a Si—C bond, that is, an alkylene chlorosilane raw material gas which is an organic chlorosilane raw material gas can also be used. Alkylene groups include methylene, ethylene, propylene, butylene, and the like. The alkylene chlorosilane raw material gas may also be referred to as an alkylene halosilane raw material gas. As the alkylene chlorosilane raw material gas, for example, bis(trichlorosilyl)methane ((SiCl ₃ ) ₂ CH ₂ , abbreviated as BTCSM) gas, ethylene bis(trichlorosilane) gas, that is, 1, 2-bis(trichlorosilyl)ethane ((SiCl ₃ ) ₂ C ₂ H ₄ , abbreviation: BTCSE) gas, etc. These gases can also be considered to be source gases that contain at least two Si in one molecule, and also contain C and Cl, and have Si—C bonds. These gases function as both a Si source and a C source in the film formation process to be described later.

In addition, as the halosilane raw material gas, for example, a raw material gas containing Si, Cl and an alkyl group and having a Si—C bond, that is, an alkyl chlorosilane raw material gas which is an organic chlorosilane raw material gas can also be used. Alkyl groups include methyl, ethyl, propyl, butyl, and the like. The alkylchlorosilane raw material gas may also be referred to as an alkylhalosilane raw material gas. As the alkylchlorosilane raw material gas, for example, 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH ₃ ) ₂ Si ₂ Cl ₄ , abbreviated as TCDMDS) gas, 1, 2-Dichloro-1,1,2,2-tetramethyldisilane ((CH ₃ ) ₄ Si ₂ Cl ₂ , abbreviation: DCTMDS) gas, 1-monochloro-1,1,2,2,2- Pentamethyldisilane ((CH ₃ ) ₅ Si ₂ Cl, abbreviation: MCPMDS) gas and the like. These gases can also be considered to be source gases that contain at least two Si in one molecule, and also contain C and Cl, and have Si—C bonds. In addition, these gases also have Si-Si bonds. These gases function as both a Si source and a C source in the film formation process to be described later.

When using a liquid raw material that is liquid at normal temperature and pressure such as HCDS, BTCSM, TCDMDS, etc., the liquid raw material is vaporized by a gasification system such as a vaporizer and a bubbler, and the raw material gas (HCDS gas, BTCSM gas, TCDMDS gas, etc.) are supplied.

Further, as a reaction gas having a chemical structure (molecular structure) different from that of the source gas, for example, a gas containing carbon (C) is supplied into the processing chamber 201 from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a. As the C-containing gas, for example, a hydrocarbon-based gas can be used. It is also considered that the hydrocarbon-based gas is composed of only two elements, C and H, and functions as a C source in the film-forming process to be described later. As the hydrocarbon-based gas, for example, propylene (C ₃ H ₆ ) gas can be used.

Further, as a reaction gas having a chemical structure different from that of the source gas, for example, an oxygen (O)-containing gas is supplied into the processing chamber 201 from the gas supply pipe 232b via the MFC 241b, the valve 243b, and the nozzle 249b. The O-containing gas functions as an oxidizing gas, that is, an O source in the film formation process described later. As the O-containing gas, for example, oxygen gas (O ₂ ) can be used.

Further, as a reaction gas having a chemical structure different from that of the source gas, for example, a hydrogen (H)-containing gas is supplied into the processing chamber 201 from the gas supply pipe 232b and the MFC 241b via the valve 243b and the nozzle 249b.

As the H-containing gas, for example, a hydrogen nitride-based gas, which is a gas containing nitrogen (N) and hydrogen (H), can be used. The hydrogen nitride-based gas may be considered to be composed of only two elements, N and H, and may also be referred to as nitrogen (N)-containing gas. The N-containing gas functions as a nitriding gas, that is, an N source in the film formation process described later. As the hydrogen nitride-based gas, for example, ammonia gas (NH ₃ ) can be used.

In addition, as the H-containing gas, for example, a gas containing N, C, and H, that is, an amine-based gas can also be used. The amine gas can also be considered to be a substance composed of only three elements of C, N, and H, and can also be referred to as a gas containing N and C. The amine-based gas functions as both an N source and a C source in the film-forming process to be described later. As the amine gas, for example, triethylamine ((C ₂ H ₅ ) ₃ N, abbreviated: TEA) gas can be used. When using a liquid amine such as TEA at normal temperature and normal pressure, the liquid amine is vaporized by a vaporization system such as a vaporizer and a bubbler, and is supplied as an amine gas (TEA gas).

In addition, as the H-containing gas, for example, a gas containing N, C, and H, that is, an organic hydrazine-based gas can also be used. The organic hydrazine-based gas can also be considered to be a substance composed of only three elements of N, C, and H, and can also be referred to as a gas containing N and C. The organic hydrazine-based gas functions not only as an N source but also as a C source in the film-forming process to be described later. As the organic hydrazine gas, for example, trimethylhydrazine ((CH ₃ ) ₂ N ₂ (CH ₃ )H, abbreviated: TMH) gas can be used. When using liquid hydrazine at room temperature and pressure like TMH, the liquid hydrazine is vaporized by a vaporization system such as a vaporizer and a bubbler, and supplied as an organic hydrazine gas (TMH gas). .

In addition, as the H-containing gas, for example, a gas that does not contain N and C, such as hydrogen gas (H ₂ ) and deuterium gas (D ₂ ), can also be used.

As an inert gas, for example, nitrogen gas (N ₂ ) is supplied from the gas supply pipes 232c and 232d to the processing chamber 201 via the MFCs 241c and 241d, the valves 243c and 243d, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b, respectively. Inside.

When the source gas is supplied from the gas supply pipe 232a, the source gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A nozzle 249a may also be included in the raw gas supply system. The raw material gas supply system may also be referred to as a raw material supply system. When the halosilane raw material gas is supplied from the gas supply pipe 232a, the raw material gas supply system may be referred to as a halosilane raw material gas supply system or a halosilane raw material supply system.

When the C-containing gas is supplied from the gas supply system 232a, the C-containing gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A nozzle 249a may also be included in the C-containing gas supply system. When the hydrocarbon-based gas is supplied from the gas supply pipe 232a, the C-containing gas supply system may also be referred to as a hydrocarbon-based gas supply system or a hydrocarbon-based gas supply system.

When supplying the O-containing gas from the gas supply system 232b, the O-containing gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. A nozzle 249b may also be included in the O-containing gas supply system. The O-containing gas supply system may also be referred to as an oxidizing gas supply system or an oxidant supply system.

When the H-containing gas is supplied from the gas supply pipe 232b, the H-containing gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. A nozzle 249b may also be included in the H-containing gas supply system. When the gas containing N and H is supplied from the gas supply pipe 232b, the H-containing gas supply system may also be referred to as an N-containing gas supply system, a gas supply system containing N and H, or the like. In addition, when the gas containing N, C, and H is supplied from the gas supply pipe 232b, the H-containing gas supply system may also be referred to as an N-containing gas supply system, a C-containing gas supply system, a N- and C-containing gas supply system, or the like. . The N-containing gas supply system may also be referred to as a nitriding gas supply system or a nitriding agent supply system. When supplying a hydrogen nitride-based gas, an amine-based gas, or an organic hydrazine-based gas as the H-containing gas, the H-containing gas supply system may also be referred to as a hydrogen nitride-based gas supply system, an amine-based gas supply system, or an organic hydrazine-based gas. supply system, etc.

Any one or all of the above-mentioned C-containing gas supply system, O-containing gas supply system, and H-containing gas supply system or all of the gas supply systems may be referred to as a reaction gas supply system or a reactant supply system.

In addition, the inert gas supply system is mainly composed of gas supply pipes 232c and 232d, MFCs 241c and 241d, and valves 243c and 243d. The inert gas supply system may also be referred to as a purge gas supply system, a dilution gas supply system, or a carrier gas supply system.

In addition, all gases, such as a raw material gas, a reaction gas, and an inert gas, supplied into the processing chamber 201 via the nozzles 249a and 249b are collectively called processing gas.

(exhaust part)

The reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 . The exhaust pipe 231 is passed through a pressure sensor 245 as a pressure detector (pressure detector) that detects the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator) On the other hand, a vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 is a valve configured such that the inside of the processing chamber 201 can be evacuated and stopped by opening and closing the valve while the vacuum pump 246 is operating, and further, by operating the vacuum pump 246 In the state, the valve opening degree is adjusted based on the pressure information detected by the pressure sensor 245, and the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of an exhaust pipe 231 , an APC valve 244 , and a pressure sensor 245 . A vacuum pump 246 may also be included in the exhaust system.

(peripheral institutions)

Below the reaction tube 203 is provided a sealing cover 219 serving as a furnace mouth cover capable of airtightly closing the lower end opening of the reaction tube 203 . The sealing cap 219 is configured to be in contact with the lower end of the reaction tube 203 from the lower side in the vertical direction. The sealing cover 219 is made of metal such as SUS, for example, and is formed in a disk shape. An O-ring 220 serving as a sealing member is provided on the upper surface of the sealing cover 219 , which is in contact with the lower end of the reaction tube 203 . On the side opposite to the processing chamber 201 of the sealing cover 219, a rotation mechanism 267 that rotates the wafer boat 217 described later is provided. The rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 and is connected to the wafer boat 217 . The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217 . The sealing cover 219 is configured so as to be moved up and down in the vertical direction by the boat lift 115 as a lift mechanism provided vertically outside the reaction tube 203 . The boat lift 115 is configured so that the wafer boat 217 can be carried into and out of the processing chamber 201 by raising and lowering the sealing cover 219 . That is, the boat lift 115 is configured as a transport device (transport mechanism) that transports the wafer boat 217 (ie, the wafers 200 ) inside and outside the processing chamber 201 .

(substrate support)

The wafer boat 217 serving as a substrate supporter is configured by arranging several wafers 200, for example, 25 to 200 wafers 200 in a horizontal posture and aligned with each other in the vertical direction, and supporting them in multiple layers. That is, the wafers 200 are arranged at intervals. The wafer boat 217 is made of, for example, a heat-resistant material such as quartz or SiC. In the lower part of the wafer boat 217, a heat insulating plate 218 made of, for example, a heat-resistant material such as quartz and SiC is supported in a horizontal position in multiple layers. With such a configuration, the heat from the heater 207 is less likely to be transferred to the sealing cover 219 side. However, this embodiment is not limited to the above-mentioned form. For example, instead of providing the heat insulating plate 218 in the lower part of the wafer boat 217, a heat insulating cylinder made of a heat-resistant material such as quartz or SiC and configured as a cylindrical member may be provided.

(Temperature Sensor)

A temperature sensor 263 serving as a temperature detector is provided in the reaction tube 203 . By adjusting the energization state of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 can be set to a desired temperature distribution. The temperature sensor 263 is configured in an L-shape similarly to the nozzles 249 a and 249 b and is provided along the inner wall of the reaction tube 203 .

(control unit)

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

The storage device 121c is constituted by, for example, a flash memory, an HDD (Hard Disk Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, an etching process describing the steps and conditions of the etching process of the nozzle and the film forming process, and the like described later, are stored in a readable manner. process, etc. The etching process and the process process are combined so that the controller 121 executes each step in the substrate processing process to be described later, and a predetermined result can be obtained, and functions as a program. Hereinafter, the process process, the control program, and the like are also collectively referred to as a program. In addition, the etching process and the process process are also referred to as processes for short. In this specification, when the term "program" is used, sometimes only the process is included alone, sometimes only the control program is included alone, or sometimes both of the above are included. The RAM 121b is configured in the form of a storage area (work area) that temporarily holds programs, data, and the like read by the CPU 121a.

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

The CPU 121a is configured to read and execute the control program from the storage device 121c, and to read the process recipe from the storage device 121c in accordance with the input of an operation command from the input/output device 122 or the like. The CPU 121a is configured to control the flow rate of various gases by the MFCs 241a to 241d, open and close the valves 243a to 243d, open and close the APC valve 244, and a pressure sensor according to the content of the read process. 245 and the pressure adjustment operation by the APC valve 244, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 by the temperature sensor 263, the rotation of the boat 217 by the rotation mechanism 267 and the rotation speed adjustment operation, use The lifting and lowering operation of the boat 217 by the boat lift 115 and the like are controlled.

The controller 121 can install the above-mentioned program stored in the external storage device (for example, magnetic tapes, floppy disks, hard disks, etc.; CDs, DVDs, etc.; optical disks such as MOs; constitute. The storage device 121c and the external storage device 123 are constituted in the form of a computer-readable recording medium. Hereinafter, these are also collectively referred to simply as recording media. When the term "recording medium" is used in this specification, only the storage device 121c may be included alone, only the external storage device 123 may be included alone, or both of the above may be included in some cases. It should be noted that, for providing a program to a computer, communication means such as the Internet and a dedicated line may be used instead of the external storage device 123 .

(gas supply nozzle)

Next, the nozzle 249 for supplying the processing gas will be described with reference to FIGS. 4 to 8 . As shown in FIG. 4 , in the reaction tube 203, nozzles 249a and 249b for supplying gas extend in the vertical direction. As shown in FIG. 5 , the nozzle 249 includes an L-shaped nozzle base end portion 270 and a U-shaped nozzle distal end portion 271 . In addition, as shown in FIGS. 5 , 6( a ), and 6 ( b ), the nozzle distal end portion 271 is connected by a folded portion 273 , an upstream line 271 - 1 connecting the nozzle base end portion 270 and the folded portion 273 , and A downstream line 271 - 2 is formed at the downstream end of the turn-back portion 273 . The gas supply ports 250 for supplying the processing gas into the processing chamber 201 are provided on the side surfaces of the upstream line 271-1 and the downstream line 271-2 in a direction different from the turning direction of the turning portion 273, respectively. At the downstream end of the downstream line 271-2, a gas retention suppressing hole 280 for suppressing the retention of the processing gas in the nozzle is provided.

Here, the folded portion 273 refers to the gas supply nozzle 249 on the upper side in the vertical direction of the gas supply nozzle 250 located at the uppermost position, and refers to a portion where the gas flow direction is changed. It should be noted that, when the term "turned-back portion 273" is used in this specification, it may mean "nozzle 249 that exists on the upper side in the vertical direction than gas supply hole 250 located at the top" and "change nozzle tip portion 271." "The part in the direction of gas flow" either one, or may refer to both of the above.

As shown in FIG. 6( b ), in order to prevent the processing gas supplied into the nozzle 249 from stagnant inside the nozzle, the gas stagnation suppression hole 280 is formed so as to have a diameter larger than that of the gas supply hole 250 , and the hole 280 is formed to have a diameter larger than that of the downstream gas supply hole 250 . The side pipeline 271-2 is formed in the form of a small hole diameter of the pipeline. By configuring as described above, it is possible to prevent the supplied process gas from remaining at the downstream end of the downstream line 271-2. In addition, it is possible to suppress the formation of a bottleneck formed by the gas retention suppressing hole 280 , and to uniformly supply the activated process gas to the wafer 200 from the gas supply hole 250 with high efficiency.

If the diameter of the gas retention suppressing hole 280 is made smaller than that of the gas supply hole 250, the gas supplied into the nozzle 249 cannot easily pass through, and the gas stays at the downstream end of the downstream line 271-2. Therefore, the activated process gas heated by the heating device is likely to be supplied in large quantities mainly from the vicinity of the downstream end of the downstream line 271-2, and the film thickness uniformity between the surfaces of the wafers 200 arranged in a horizontal multi-layered manner cannot be obtained. In addition, the activated process gas may form a deposition film on the inner wall near the downstream end of the downstream side line 271-2, and the gas supply hole 250 may be blocked in some cases. Conversely, if the hole diameter of the gas stagnation suppression hole 280 is formed to have a constant diameter, for example, the same diameter as the line diameter of the downstream line 271-2, the supplied process gas will be discharged from the gas stagnation suppression hole 280. The gas exhaust bottleneck makes it difficult to supply gas from the gas supply hole 250 .

Therefore, the gas retention suppressing hole 280 must be configured to be larger than the hole diameter of the gas supply hole 250 . It is desirable that the gas retention suppressing holes 280 be configured to be in the range of 1.1 times to 25 times the diameter of the gas supply holes 250 , and it is more desirable that the gas retention suppressing holes 280 be configured to have the diameter of the gas supply holes 250 . It is ideal to constitute in the range of 5 times to 15 times. In addition, it is preferable that the hole diameter of the gas retention suppressing hole 280 is constituted in such a manner that the horizontal cross section S1 of the upstream line 271-1 flows through the upstream line 271-1 (the ratio of the upstream line 271-1 is the highest The ratio of the flow velocity of the gas in the lower gas supply hole 250a (250b) to the horizontal cross section S2 (the downstream side line 271-2 of the gas supply hole 250c (250d) at the lowermost position) flowing through the downstream line 271-2 ), the flow velocity of the gas in the lower position) is the same level.

Moreover, the gas retention suppression hole 280 is located in the vicinity of the exhaust port as shown in FIG. 1, FIG. By configuring as described above, it is possible to suppress supply of excessive gas to the wafer 200 , and in addition to this, by-products such as particles generated in the nozzle 249 can be easily discharged without adhering to the wafer 200 .

Next, the gas reaction ratio (decomposition ratio) in the nozzle when gas is supplied using a straight nozzle (for example, the nozzle 251 of FIG. 11 described later) shown in FIG. 7A will be described using FIG. 7A . (b) of FIG. 7B , (c) to (d) of FIG. 7B , and FIG. 8 describe the gas reaction ratio (decomposition ratio) in the nozzle 249 that supplies gas using the nozzle 249 shown in FIG. 5 . For the evaluation conditions in FIGS. 7A and 7B , the substrate processing temperature was heated to 600° C., 0.3 slm of HCDS gas was supplied as the processing gas, 0.5 slm of N ₂ gas was supplied, and the substrate processing pressure was set to 50 Pa, The hole diameter and the number of the gas supply holes were φ1 mm×143, and the interval (pitch) of the gas supply holes was about 8 mm. In addition, in (a) to (d) shown in FIGS. 7A and 7B , numbers are attached to the gas supply holes from the lower side toward the upper side in the vertical direction of the nozzle 249 so that the numbers corresponding to the numbers of the gas supply holes are indicated. The numerical value of the height is on the vertical axis, and the calculation is performed using the pressure, temperature, density, and gas flow rate in the nozzle, and the obtained reaction ratio (PTρ/V ^a ) in the nozzle 249 is shown on the horizontal axis. That is, the vertical axis represents the height of the nozzle 249 in the vertical direction, and the horizontal axis represents the amount of gas reacted (decomposed) in the nozzle 249 .

In (a) shown in FIG. 7A , it is found that the process gas reacts (decomposes) in the nozzle as it approaches the upper part of the pattern. That is, when the process gas reacts at the part farthest from the upstream part of the nozzle into which the process gas is introduced, and when compared with the predetermined film formed on the wafer 200, it can be determined that the wafer 200 is vertically upward. As the film thickness becomes larger, the uniformity between the surfaces cannot be obtained. In this case, if a schematic diagram of a nozzle shape is used and the amount of disintegration is expressed in shades of color, as shown in (a) of FIG. The reason for this is considered to be that the heating time and distance of the processing gas above the nozzle are longer than those of the processing gas below the nozzle. In other words, this is considered to be because the flow velocity of the supplied processing gas becomes slower to approach 0 m/s as it goes toward the upper end of the nozzle, and the slower the flow velocity, the easier the processing gas is to be heated and the more easily the reaction proceeds.

On the other hand, in (b) shown in FIG. 7A , it is found that, contrary to (a) shown in FIG. 7A , the process gas reacts in the nozzle 249 as it approaches the lower part of the graph. The reason for this is that the process gas reacts at the position farthest from the nozzle base end portion 270 into which the process gas is introduced, as in (a) shown in FIG. 7A , but the gas front end portion 271 of the nozzle 249 has a U-shape, The part farthest from the upstream part of the nozzle into which the processing gas is introduced, that is, the tip of the nozzle 249 is located vertically downward. Therefore, the thickness of the predetermined film formed on the wafer 200 increases as it goes downward in the vertical direction, and it is difficult to obtain the inter-plane uniformity of the wafer 200 .

However, in (b) shown in FIG. 7A , the gas retention suppressing hole 280 having a diameter of φ1.1 mm is provided at the tip of the nozzle 249, and the process gas is discharged from the gas retention suppressing hole 280, so it can be determined that the As compared with (a) shown in FIG. 7A , the faster the flow rate of the processing gas at the tip of the nozzle, the higher the interplane uniformity of the film thickness in the wafer 200 is improved accordingly.

Furthermore, in (c) shown in FIG. 7B , as in (b) shown in FIG. 7A , it is found that the gas reacts in the nozzle 249 as it approaches the lower part of the pattern. This is because, as in (b) shown in FIG. 7A , the gas front end 271 of the nozzle 249 has a U-shape, and the front end of the nozzle 249 , which is the part farthest from the upstream part of the nozzle into which the processing gas is introduced, is located vertically downward. , therefore, the activated gas is easily supplied to the lower side. In this case, if a schematic diagram of the nozzle shape is used and the amount of disintegration is represented by the shade of color, as shown in (b) of FIG. 8 , the upstream line 271-1 is substantially uniform. The density of the color, however, at the downstream side line 271-2, shows that the color becomes thicker as it goes below the nozzle.

Here, in (c) shown in FIG. 7B , it is found that the deviation between the reaction ratio below the nozzle and the reaction ratio above the nozzle is suppressed as compared with (b) shown in FIG. 7A . This is because the gas retention suppressing hole 280 has a diameter of φ4 mm, which is larger than (b) shown in FIG. 7A , so that the flow velocity of the processing gas in the tip portion of the nozzle 249 is further increased, and the retention of the processing gas in the tip portion of the nozzle 249 is reduced. Therefore, it can be judged that the interplane uniformity of the film thickness in the wafer 200 is remarkably improved.

In (d) shown in FIG. 7B , it was found that there was almost no inclination of the pattern in the vertical direction, and the reaction ratio in the nozzle was substantially uniform in the upper and lower ranges. That is, it was found that the inter-plane uniformity of the wafer 200 can be obtained. The reason for this is considered to be that, as shown in (c) of FIG. 8 , since the gas retention suppressing hole 280 has a diameter of 8 mm in diameter, the flow rate of the processing gas at the tip of the nozzle 249 is faster than that shown in FIG. 7B . In the case of (c), it is close to the flow rate of the processing gas introduced into the nozzle tip portion 271 . It can be determined that the process gas supplied to the gas supply nozzle 249 does not become an exhaust bottleneck of the exhaust gas from the gas retention suppression hole 280 by configuring the gas retention suppression hole 280 as described above, and it can be determined that the gas retention at the tip of the nozzle 249 can be suppressed. The process gas is retained, and the heated process gas is uniformly supplied into the process chamber 201 from the gas supply hole.

From this, it can be seen that it is desirable to configure the hole diameter of the gas retention suppressing hole 280 to be in the range of 1/90 times or more and less than 1 times the nozzle diameter of the nozzle 249 . It is desirable that the hole diameter of the gas retention suppressing hole 280 is configured to be 0.3 times or more and 0.7 times or less the diameter of the nozzle of the nozzle 249 .

In addition, it is desirable that the hole diameter of the gas retention suppressing hole 280 be configured to be in the range of 0.05 times or more and less than 1 time with respect to the front end area of the nozzle 249 . It is desirable that the hole diameter of the gas retention suppressing hole 280 is configured to be 0.1 times or more and 0.5 times or less with respect to the front end area of the nozzle 249 .

In addition, the gas retention suppressing hole 280 may be provided not only in the center of the front end portion of the nozzle 249, but also in any position or in a plurality as long as it is provided on the front end surface of the nozzle 249. By configuring as described above, the accumulation of gas at the tip of the nozzle 249 can be suppressed more effectively.

(2) Film formation treatment

A sequence example of a process for forming a film on a substrate (hereinafter also referred to as a film forming process) using the substrate processing apparatus described above will be described with reference to FIG. 9 as one of the steps of manufacturing a semiconductor device (device). In the following description, the controller 121 controls the operation of each part constituting the substrate processing apparatus.

In the film formation process of the present embodiment, a film is formed on the wafer 200 by performing a cycle of non-simultaneously performing the following steps through a nozzle serving as a first nozzle for a predetermined number of times (one or more). 249a, the step of supplying the raw material gas to the wafer 200 serving as the substrate in the processing chamber 201; and supplying the O-containing gas to the wafer 200 in the processing chamber 201 through the nozzle 249b which is made of quartz and is the second nozzle different from the nozzle 249a and the step of supplying the H-containing gas to the wafer 200 in the processing chamber 201 via the nozzle 249b.

It should be noted that, in the film formation sequence shown in FIG. 9 , as an example, by performing a predetermined number of cycles (n times) in which the following steps are performed asynchronously, that is, asynchronously, the wafer 200 containing Si is formed on the wafer 200 . , O, C, and N films, that is, a silicon oxycarbonitride film (SiOCN film), the steps are: step 1 of supplying HCDS gas to the wafer 200 in the processing chamber 201 through the nozzle 249a; Step 2 of supplying C ₃ H ₆ gas to the wafer 200 in the chamber; Step ₃ of supplying O ₂ gas to the wafer 200 in the processing chamber 201 via the nozzle 249b ; Step 4. It should be noted that the SiOCN film may also be referred to as a C-containing silicon oxynitride film (SiON film), a C-added (doped) SiON film, or a C-containing SiON film.

In this specification, for convenience of explanation, the film-forming sequence shown in FIG. 9 is sometimes shown as follows. In addition, in the description of the following modification and other embodiment, the same representation is used.

When the term "wafer" is used in this specification, it may refer to "wafer itself" or "laminate (aggregate) obtained from a wafer and a predetermined layer, film, etc. formed on the surface", that is, sometimes The predetermined layer, film, etc. formed on the surface is referred to as a wafer here. In addition, when the term "wafer surface" is used in this specification, it may refer to "the surface (exposed surface) of the wafer itself", or it may refer to "the surface of a predetermined layer, film, etc. formed on the wafer, that is, the wafer as a laminate. the outermost surface". .

Therefore, when it is stated in this specification that "the predetermined gas is supplied to the wafer", it may mean "the predetermined gas is directly supplied to the surface (exposed surface) of the wafer itself", and sometimes it means "the layer or film formed on the wafer is supplied with the predetermined gas". etc., that is, a predetermined gas is supplied to the outermost surface of the wafer which is a laminate". In addition, when it is described in this specification that "a predetermined layer (or film) is formed on a wafer", it may mean "a predetermined layer (or film) is directly formed on the surface (exposed surface) of the wafer itself", and sometimes it means "A predetermined layer (or film) is formed on the layer, film, etc. formed on the wafer, that is, on the outermost surface of the wafer as a laminate".

In addition, the case where the term "substrate" is used in this specification also has the same meaning as the case where the term "wafer" is used, and in this case, in the above description, "wafer" may be replaced by "substrate".

(Wafer filling and boat loading)

Several wafers 200 are loaded (wafer filled) in the wafer boat 217 . Then, as shown in FIG. 1 , the boat lift 115 lifts up the boat 217 supporting the wafers 200 of several wafers, and carries it into the processing chamber 201 (boat loading). In this state, the sealing cap 219 closes the lower end of the reaction tube 203 via the O-ring 220 .

(pressure regulation and temperature regulation)

Vacuum evacuation (decompression evacuation) is performed by the vacuum pump 246 so that the inside of the processing chamber 201 , that is, the space where the wafer 200 exists, becomes a desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. The vacuum pump 246 maintains a state in which it operates at least until the processing of the wafer 200 is completed. In addition, the wafer 200 in the processing chamber 201 is heated to a desired temperature by the heater 207 . At this time, based on the temperature information detected by the temperature sensor 263 , the energization of the heater 207 is feedback-controlled so that the inside of the processing chamber 201 has a desired temperature distribution. The heating of the inside of the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed. In addition, the rotation of the boat 217 and the wafer 200 is started by the rotation mechanism 267 . The rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is continued at least until the processing of the wafer 200 is completed.

(Formation process of SiOCN film)

After that, the following four steps, that is, steps 1 to 4, are sequentially executed.

[step 1]

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

The valve 243a is opened, and the HCDS gas flows through the gas supply pipe 232a. The flow rate of the HCDS gas is adjusted by the MFC 241 a , is supplied into the processing chamber 201 via the nozzle 249 a , and is discharged from the exhaust pipe 231 . At this time, the HCDS gas is supplied to the wafer 200 . At this time, the valve 243c is opened at the same time, and N ₂ gas flows through the gas supply pipe 232c. The flow rate of the N ₂ gas is adjusted by the MFC 241 c , and is supplied into the processing chamber 201 together with the HCDS gas, and is discharged from the exhaust pipe 231 .

In addition, in order to prevent the HCDS gas from intruding into the nozzle 249b, the valve 243d is opened, and the N ₂ gas flows through the gas supply pipe 232d. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipe 232 b and the nozzle 249 b and is discharged from the exhaust pipe 231 .

The supply flow rate of the HCDS gas controlled by the MFC 241a is, for example, a flow rate within a range of 1 to 2000 sccm, or preferably 10 to 1000 sccm. The supply flow rate of the N ₂ gas controlled by the MFCs 241c and 241d is, for example, a flow rate within a range of 100 to 10000 sccm, respectively. The pressure in the processing chamber 201 is, for example, 1 to 2666 Pa, or preferably a pressure in the range of 67 to 1333 Pa. The time for supplying the HCDS gas to the wafer 200 , that is, the gas supply time (irradiation time) is, for example, a time in the range of 1 to 120 seconds, or preferably 1 to 60 seconds. The temperature of the heater 207 is set so that the temperature of the wafer 200 may be in the range of, for example, 250 to 700°C, preferably 300 to 650°C, and more preferably 350 to 600°C.

When the temperature of the wafer 200 is lower than 250° C., HCDS is not easily chemically adsorbed on the wafer 200 , and a practical film formation rate may not be obtained. This problem can be solved by setting the temperature of the wafer 200 to be 250° C. or higher. By setting the temperature of the wafer 200 to be 300° C. or higher, and further to 350° C. or higher, HCDS can be more sufficiently adsorbed on the wafer 200 , and a more sufficient film-forming rate can be obtained.

When the temperature of the wafer 200 is higher than 700° C., the CVD reaction is too intense (excessive gas phase reaction occurs), and thus the uniformity of the film thickness tends to deteriorate, making it difficult to control. By setting the temperature of the wafer 200 to be 700° C. or lower, an appropriate gas-phase reaction can occur, whereby the deterioration of the uniformity of the film thickness can be suppressed and control can be performed. In particular, by setting the temperature of the wafer 200 to be 650° C. or lower, and further 600° C. or lower, the surface reaction is more dominant than the gas-phase reaction, and the uniformity of the film thickness can be easily ensured and controlled.

Therefore, the temperature of the wafer 200 is preferably set to a temperature within the range of 250 to 700°C, preferably 300 to 650°C, and more preferably 350 to 600°C.

By supplying the HCDS gas to the wafer 200 under the above-described conditions, a Si-containing layer containing Cl having a thickness of, for example, less than 1 atomic layer to several atomic layers is formed on the outermost surface of the wafer 200 as a first layer. The Si-containing layer containing Cl may be a Si layer containing Cl, an adsorption layer of HCDS, or both.

The Si layer containing Cl is a general term that includes not only a continuous layer composed of Si and containing Cl, but also a discontinuous layer, and a Si thin film containing Cl in which they are superimposed. A continuous layer composed of Si and containing Cl is sometimes referred to as a Si thin film containing Cl. The Si constituting the Si layer containing Cl includes not only Si whose bond with Cl is not completely cut, but also Si whose bond with Cl is completely cut.

The adsorption layer of HCDS includes not only the continuous adsorption layer composed of HCDS molecules, but also the discontinuous adsorption layer. That is, the adsorption layer of HCDS includes 1 molecular layer or an adsorption layer having a thickness of less than 1 molecular layer composed of HCDS molecules. The HCDS molecules constituting the adsorption layer of HCDS also include molecules in which the bond between Si and Cl is partially cleaved. That is, the adsorption layer of HCDS may be a physical adsorption layer of HCDS or a chemical adsorption layer of HCDS, or may include both of the above.

Here, a layer with a thickness of less than 1 atomic layer refers to an atomic layer formed discontinuously, and a layer with a thickness of 1 atomic layer refers to an atomic layer formed continuously. A layer with a thickness of less than one molecular layer refers to a molecular layer formed discontinuously, and a layer with a thickness of one molecular layer refers to a molecular layer formed continuously. The Si-containing layer containing Cl may include both: a Si layer containing Cl and an adsorption layer of HCDS. However, as described above, the Si-containing layer containing Cl is represented by expressions such as “one atomic layer” and “several atomic layers”.

The Si layer containing Cl is formed by depositing Si on the wafer 200 under the conditions of self-decomposition (thermal decomposition) of the HCDS gas, that is, under conditions in which the thermal decomposition reaction of the HCDS gas occurs. The adsorption layer of HCDS is formed by adsorbing HCDS on the wafer 200 under the condition that the HCDS gas does not undergo self-decomposition (thermal decomposition), that is, under the condition that the thermal decomposition reaction of the HCDS gas does not occur. Forming the Si layer containing Cl on the wafer 200 can improve the film formation rate compared to forming the adsorption layer of HCDS on the wafer 200 . From this viewpoint, it is preferable to form the Si layer containing Cl on the wafer 200 .

If the thickness of the first layer is larger than several atomic layers, the reforming action in steps 3 and 4 described later will not reach the entirety of the first layer. In addition, the minimum value of the thickness of the first layer is less than 1 atomic layer. Therefore, the thickness of the first layer is preferably less than 1 atomic layer to several atomic layers. By setting the thickness of the first layer to be 1 atomic layer or less, that is, 1 atomic layer or less, the effect of the modification reactions in steps 3 and 4 to be described later can be relatively enhanced, and the modification in steps 3 and 4 can be shortened. time required for the qualitative reaction. The time required for the formation of the first layer in Step 1 can also be shortened. As a result, the processing time per cycle can be shortened, and the overall processing time can also be shortened. That is, the film formation rate can also be improved. In addition, by setting the thickness of the first layer to be 1 atomic layer or less, the controllability of the uniformity of the film thickness can also be improved.

After the first layer is formed, the valve 243a is closed, and the supply of the HCDS gas is stopped. At this time, the APC valve 244 is kept open, the processing chamber 201 is evacuated by the vacuum pump 246 , and the unreacted HCDS gas remaining in the processing chamber 201 or the HCDS gas after the formation of the first layer is discharged from the processing chamber 201 . At this time, the valves 243c and 243d are kept open, and the N ₂ gas is continuously supplied into the processing chamber 201 . The N ₂ gas acts as a purge gas, whereby the effect of exhausting the gas remaining in the processing chamber 201 from the processing chamber 201 can be enhanced.

At this time, the gas remaining in the processing chamber 201 may not be completely exhausted, and the processing chamber 201 may not be completely purged. If the gas remaining in the processing chamber 201 is in a small amount, there will be no adverse effect in Step 2 to be performed later. 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 the N ₂ gas in the same amount as the volume of the reaction tube 203 (processing chamber 201 ), it is possible to use the N 2 gas in step 2. Purge to such an extent that there is no adverse effect. As described above, by incompletely purging the inside of the processing chamber 201, the purging time can be shortened and the throughput can be improved. It is also possible to suppress the consumption of N ₂ gas to the necessary minimum.

As the raw material gas, in addition to HCDS gas, for example, OCTS gas, dichlorosilane (SiH ₂ Cl ₂ , abbreviated: DCS) gas, monochlorosilane (SiH ₃ Cl, abbreviated: MCS) gas, tetrachlorosilane or tetrachlorosilane can be used. Inorganic halosilane raw material gas such as silicon chloride (SiCl ₄ , abbreviated: STC) gas, trichlorosilane (SiHCl ₃ , abbreviated: TCS) gas.

In addition, as the raw material gas, organic halosilane raw material gas such as BTCSE gas, BTCSM gas, TCDMDS gas, DCTMDS gas, and MCPMDS gas can be used.

In addition, as the raw material gas, for example, monosilane (SiH ₄ , abbreviated: MS) gas, disilane (Si ₂ H ₆ , abbreviated: DS) gas, trisilane (Si ₃ H ₈ , abbreviated: TS) gas, etc. can be used. Halogen-containing inorganic silane raw material gas.

In addition, as the raw material gas, for example, dimethylsilane (SiC ₂ H ₈ , abbreviated: DMS) gas, trimethylsilane (SiC ₃ H ₁₀ , abbreviated: TMS) gas, diethylsilane (SiC ₄ H ) gas can also be used. ₁₂ , abbreviation: DES) gas, 1,4-disilabutane (Si ₂ C ₂ H ₁₀ , abbreviation: DSB) gas and other organic silane raw material gases that do not contain halogen groups.

In addition, as the raw material gas, for example, tris(dimethylamino)silane (Si[N(CH ₃ ) ₂ ] ₃ H, abbreviated as 3DMAS) gas, tetrakis(dimethylamino) silane (Si[N( CH ₃ ) ₂ ] ₄ , abbreviation: 4DMAS) gas, bis(diethylamino) silane (Si[N(C ₂ H ₅ ) ₂ ] ₂ H ₂ , abbreviation: BDEAS) gas, bis(tert-butylamino) Silane (SiH ₂ [NH(C ₄ H ₉ )] ₂ , abbreviated as BTBAS) gas and the like are ammonia-based (amine-based) silane raw material gases that do not contain halogen groups.

In addition, when using the organohalosilane raw material gas and organosilane raw material gas which also functions as a C source as a raw material gas, C can be contained in a 1st layer. As a result, the C concentration in the SiOCN film finally formed on the wafer 200 can be increased compared to the case of using the inorganic-based halosilane source gas or the inorganic-based silane source gas as the source gas. In addition, when an amino-based silane source gas that also functions as a C source and an N source is used as the source gas, C and N can be contained in the first layer, respectively. As a result, the C concentration and the N concentration in the SiOCN film finally formed on the wafer 200 can be increased, respectively, compared with the case of using the inorganic silane source gas as the source gas.

As the inert gas, other than N ₂ gas, for example, rare gas such as Ar gas, He gas, Ne gas, and Xe gas can be used.

[Step 2]

After step 1 is completed, the C ₃ H ₆ gas activated by heat is supplied to the wafer 200 in the processing chamber 201 , that is, the first layer formed on the wafer 200 .

In this step, the opening and closing of the valves 243a, 243c, and 243d are controlled in the same procedure as the opening and closing control of the valves 243a, 243c, and 243d in Step 1. The flow rate of the C ₃ H ₆ gas is adjusted by the MFC 241 a , is supplied into the processing chamber 201 via the nozzle 249 a , and is discharged from the exhaust pipe 231 . At this time, C ₃ H ₆ gas is supplied to the wafer 200 .

The supply flow rate of the C ₃ H ₆ gas controlled by the MFC 241a is, for example, a flow rate within the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure within a range of 1 to 5000 Pa, or preferably 1 to 4000 Pa. The partial pressure of the C ₃ H ₆ gas in the processing chamber 201 is, for example, a pressure within a range of 0.01 to 4950 Pa. By setting the pressure in the processing chamber 201 in such a high pressure range, the C ₃ H ₆ gas can be heated by non-plasma. By activating the C ₃ H ₆ gas with heat and then supplying it, a relatively mild reaction can occur, and the C-containing layer described later can be easily formed. The time for supplying the C ₃ H ₆ gas to the wafer 200 , that is, the gas supply time (irradiation time) is, for example, 1 to 200 seconds, preferably 1 to 120 seconds, and more preferably a time in the range of 1 to 60 seconds. Other processing conditions are, for example, the same processing conditions as in Step 1.

At this time, the gas flowing into the processing chamber 201 is thermally activated C ₃ H ₆ gas, and the HCDS gas does not flow into the processing chamber 201 . Therefore, the C ₃ H ₆ gas does not cause a gas phase reaction, but is supplied to the wafer 200 in an activated state. As a result, a carbon-containing layer (C-containing layer) is formed on the surface of the first layer formed on the wafer 200 in Step 1, that is, the Si-containing layer containing Cl. The C-containing layer may be either a C layer or a C ₃ H ₆ adsorption layer, or may contain both of the above. The C-containing layer is a layer with a thickness of less than 1 molecular layer or less than 1 atomic layer, that is, a discontinuous layer. For example, when an adsorption layer of C ₃ H ₆ is formed as the C-containing layer, the chemical adsorption layer of molecules constituting C ₃ H ₆ is formed in an unsaturated state. Thereby, the second layer including Si, Cl, and C is formed on the outermost surface of the wafer 200 . The second layer includes a Si-containing layer containing Cl, and a C-containing layer. Note that, depending on the conditions, a part of the first layer may react with C ₃ H ₆ gas to reform (carbonize) the first layer, and the second layer may contain a SiC layer.

The C-containing layer must be a discontinuous layer. When the C-containing layer is a continuous layer, the entire surface of the Si-containing layer containing Cl is covered by the C-containing layer. In this case, Si does not exist on the surface of the second layer, and as a result, the oxidation reaction of the second layer in Step 3 to be described later and the nitridation reaction of the third layer in Step 4 to be described later may be difficult in some cases. . This is because, under the above-mentioned processing conditions, although O and N are bonded to C, O and N are not easily bonded to Si. In order to cause the desired reaction in Step 3 and Step 4 to be described later, it is necessary to make the adsorption state of the C-containing layer, for example, a chemical adsorption layer of C ₃ H ₆ on the Si-containing layer containing Cl unsaturated, A state in which Si is exposed on the surface of the second layer. In addition, the C-containing layer can be made into a discontinuous layer by making the processing conditions in step 2 the processing conditions in the said processing condition range.

After the formation of the second layer, the valve 243a was closed, and the supply of the C ₃ H ₆ gas was stopped. Then, the unreacted C ₃ H ₆ gas and reaction by-products remaining in the processing chamber 201 are discharged from the processing chamber 201 according to the same processing steps and processing conditions as in Step 1. At this time, it is the same as step 1 in that the gas remaining in the processing chamber 201 can be partially exhausted and the like.

As the C-containing gas, in addition to C ₃ H ₆ gas, hydrocarbon-based gas such as acetylene (C ₂ H ₂ ) gas and ethylene (C ₂ H ₄ ) gas can be used.

As the inert gas, in addition to N ₂ gas, for example, various rare gases exemplified in Step 1 can be used.

[Step 3]

After step 2 is completed, the O ₂ gas activated by heat is supplied to the wafer 200 in the processing chamber 201 , that is, the second layer formed on the wafer 200 .

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

The supply flow rate of the O ₂ gas controlled by the MFC241b is, for example, a flow rate within the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, 1 to 4000 Pa, or preferably a pressure in the range of 1 to 3000 Pa. The partial pressure of the O ₂ gas in the processing chamber 201 is, for example, a pressure within a range of 0.01 to 3960 Pa. By setting the pressure in the processing chamber 201 in such a high pressure range, it is possible to activate the O ₂ gas by heating using non-plasma. By activating the O ₂ gas with heat and then supplying it, a relatively mild reaction can occur, and the below-described oxidation can be mildly performed. The time for supplying the O ₂ gas to the wafer 200 , that is, the gas supply time (irradiation time) is, for example, a time in the range of 1 to 120 seconds, preferably 1 to 60 seconds. Other processing conditions are, for example, the same processing conditions as in Step 1.

At this time, the gas flowing into the processing chamber 201 is the thermally activated O ₂ gas, and neither the HCDS gas nor the C ₃ H ₆ gas flows into the processing chamber 201 . Therefore, the O ₂ gas is supplied to the wafer 200 in an activated state without causing a gas phase reaction. The O ₂ gas supplied to the wafer 200 reacts with at least a part of the second layer including Si, Cl, and C (which includes: a Si-containing layer including Cl, and a C-containing layer) formed on the wafer 200 in step 2 . Thereby, the second layer is oxidized by heating by non-plasma, and is transformed (modified) into a third layer including Si, O, and C, that is, a silicic acid carbide layer (SiOC layer). It should be noted that, when the third layer is formed, impurities such as Cl contained in the second layer constitute a gaseous substance containing at least Cl during the reforming reaction using O ₂ gas, and are discharged from the processing chamber 201 . That is, impurities such as Cl in the second layer are pulled out or detached from the second layer, and are separated from the second layer. Thereby, the third layer becomes a layer with less impurities such as Cl than that of the second layer.

At this time, the oxidation reaction of the second layer is unsaturated. For example, in the case where a Si-containing layer with a thickness of several atomic layers is formed containing Cl in Step 1, and a C-containing layer with a thickness of less than 1 atomic layer is formed in Step 2, the surface layer (one atomic layer on the surface) is at least partially oxidized. In this case, the oxidation of the second layer is carried out under the condition that the oxidation reaction of the second layer is unsaturated so as not to oxidize the whole of the second layer. It should be noted that although several layers below the surface layer of the second layer can be oxidized depending on the conditions, the controllability of the composition ratio of the SiOCN film finally formed on the wafer 200 can be improved by oxidizing only the surface layer. , so it is preferred. In addition, for example, in the case where a Si-containing layer containing Cl having a thickness of 1 atomic layer or less is formed in Step 1, and a C-containing layer having a thickness of less than 1 atomic layer is formed in Step 2, the surface layer is similarly formed. part of the oxidation. Even in this case, the oxidation of the second layer is carried out under the condition that the oxidation reaction of the second layer is unsaturated so as not to oxidize the whole of the second layer. In addition, the oxidation reaction of a 2nd layer can be unsaturated by making the process conditions in step 3 into the process conditions of the said process condition range.

In this case, in particular, the above-mentioned processing conditions can be adjusted so as to increase the dilution rate of the O ₂ gas (reduce the concentration), to shorten the supply time of the O ₂ gas, or to reduce the partial pressure of the O ₂ gas. For example, compared with steps 2 and 4, the dilution rate of the reaction gas may be increased, the supply time of the reaction gas may be shortened, or the partial pressure of the reaction gas may be reduced. Thereby, the oxidizability in step 3 can be moderately reduced, and the oxidation reaction of the second layer can be more easily unsaturated.

By reducing the oxidizability in step 3, it is possible to suppress desorption of C from the second layer during the oxidation process. Compared with the Si-C bond, the bond energy of the Si-O bond is larger, and therefore, if the Si-O bond is formed, the Si-C bond tends to be broken. On the other hand, by appropriately reducing the oxidizing property in step 3, it is possible to suppress the breakage of the Si-C bond when the Si-O bond is formed in the second layer, and it is possible to suppress the breakage of the bond with Si from C from the second layer. break away.

In addition, by reducing the oxidizability in step 3, it is possible to maintain a state in which Si is exposed on the outermost surface of the second layer after the oxidation treatment, that is, the third layer. By maintaining the state in which Si is exposed on the outermost surface of the third layer, it becomes easy to nitride the outermost surface of the third layer in step 4 described later. In a state in which Si-O bonds and Si-C bonds are formed over the entire outermost surface of the third layer, and Si is not exposed on the outermost surface, under the conditions of step 4 described later Tendency to be difficult to form Si-N bonds. However, by maintaining the state in which Si is exposed on the outermost surface of the third layer, that is, by pre-existing Si capable of bonding with N on the outermost surface of the third layer under the conditions of Step 4 described later, Thus, Si-N bonds are easily formed.

After the third layer was formed, the valve 243b was closed, and the supply of the O ₂ gas was stopped. Then, the unreacted O ₂ gas and reaction by-products remaining in the processing chamber 201 after helping to form the third layer are discharged from the processing chamber 201 according to the same processing steps and processing conditions as in Step 1. At this time, it is the same as step 1 in that the gas remaining in the processing chamber 201 can be partially exhausted and the like.

As the oxidizing gas, in addition to O ₂ gas, water vapor (H ₂ O gas), nitric oxide (NO) gas, nitrous oxide (N ₂ O) gas, nitrogen dioxide (NO ₂ ) gas, O-containing gas such as carbon monoxide (CO) gas, carbon dioxide (CO ₂ ) gas, and ozone (O ₃ ) gas.

As the inert gas, in addition to N ₂ gas, for example, various rare gases exemplified in Step 1 can be used.

[Step 4]

After step 3 is completed, the NH ₃ gas activated by heat is supplied to the wafer 200 in the processing chamber 201 , that is, the third layer formed on the wafer 200 .

In this step, the opening and closing of the valves 243b to 243d is controlled in the same procedure as the opening and closing control of the valves 243a, 243c, and 243d in Step 1. The flow rate of the NH ₃ gas is adjusted by the MFC 241 b , is supplied into the processing chamber 201 via the nozzle 249 b , and is discharged from the exhaust pipe 231 . At this time, NH ₃ gas is supplied to the wafer 200 .

The supply flow rate of the NH ₃ gas controlled by the MFC 241b is, for example, a flow rate within a range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, 1 to 4000 Pa, or preferably a pressure in the range of 1 to 3000 Pa. The partial pressure of the NH ₃ gas in the processing chamber 201 is, for example, a pressure within a range of 0.01 to 3960 Pa. By setting the pressure in the processing chamber 201 within such a high pressure range, it is possible to activate the NH ₃ gas by heating using non-plasma. By activating the NH ₃ gas with heat and then supplying it, a relatively mild reaction can occur, and nitridation described later can be performed mildly. The time for supplying the NH ₃ gas to the wafer 200 , that is, the gas supply time (irradiation time) is, for example, a time in the range of 1 to 120 seconds, preferably 1 to 60 seconds. Other processing conditions are, for example, the same processing conditions as in Step 1.

At this time, the gas flowing into the processing chamber 201 is thermally activated NH ₃ gas, and HCDS gas, C ₃ H ₆ gas or O ₂ gas is not flowing into the processing chamber 201 . Therefore, the NH ₃ gas does not cause a gas phase reaction, but is supplied to the wafer 200 in an activated state. The NH ₃ gas supplied to the wafer 200 reacts with at least a part of the third layer (SiOC layer) formed on the wafer 200 in step 3 . Thereby, the third layer is thermally nitrided by non-plasma, and transformed (modified) into a silicon oxycarbonitride layer (SiOCN layer) as the fourth layer including Si, O, C, and N. It should be noted that when the fourth layer is formed, impurities such as Cl contained in the third layer constitute a gaseous substance containing at least Cl during the reforming reaction using NH ₃ gas, and are discharged from the processing chamber 201 . That is, impurities such as Cl in the third layer are pulled out or detached from the third layer, and are separated from the third layer. Thereby, the fourth layer becomes a layer with less impurities such as Cl than that of the third layer.

In addition, by supplying the activated NH ₃ gas to the wafer 200 , the outermost surface of the third layer is modified during the process of nitriding the third layer. During the nitriding process, the outermost surface of the third layer, that is, the outermost surface of the fourth layer, which has been subjected to surface modification treatment during the nitriding process, is performed in the next cycle. In step 1, HCDS is easily adsorbed and Si is easily deposited. surface state. That is, the NH ₃ gas used in Step 4 also functions as an adsorption and deposition promoting gas (promoting adsorption and deposition of HCDS and Si on the outermost surface of the fourth layer (the outermost surface of the wafer 200 )).

At this time, the nitridation reaction of the third layer is unsaturated. For example, when the third layer having a thickness of several atomic layers is formed in steps 1 to 3, at least a part of the surface layer (one atomic layer on the surface) is nitrided. In this case, the nitridation is performed under the condition that the nitridation reaction of the third layer is unsaturated so as not to nitride the whole of the third layer. It should be noted that although several layers below the surface layer of the third layer can be nitrided depending on the conditions, only the surface layer of the third layer can be nitrided to increase the composition ratio of the SiOCN film finally formed on the wafer 200 . controllability is therefore preferred. In addition, when forming a third layer having a thickness of 1 atomic layer or less in steps 1 to 3, for example, a part of the surface layer is similarly nitrided. Also in this case, the nitridation is performed under the condition that the nitridation reaction of the third layer is unsaturated so that the whole of the third layer is not nitrided. In addition, the nitridation reaction of the third layer can be unsaturated by making the processing conditions in step 4 the processing conditions within the range of the above-mentioned processing conditions.

After the formation of the fourth layer, the valve 243b was closed, and the supply of the NH ₃ gas was stopped. Then, the unreacted NH ₃ gas and reaction by-products remaining in the processing chamber 201 after the unreacted or assisting formation of the fourth layer are discharged from the processing chamber 201 according to the same processing steps and processing conditions as in Step 1. At this time, it is the same as step 1 in that the gas remaining in the processing chamber 201 can be partially exhausted and the like.

As the nitriding gas, in addition to NH ₃ gas, hydrogen nitride-based gas such as diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, and N ₃ H ₈ gas, including these Compound gases, etc.

As the inert gas, in addition to N ₂ gas, for example, various rare gases exemplified in Step 1 can be used.

(implemented the specified number of times)

A SiOCN film of a predetermined composition and a predetermined film thickness can be formed on the wafer 200 by performing the cycle of performing the above-mentioned four steps asynchronously, ie, asynchronously, a predetermined number of times (n times). In addition, it is preferable to repeat the said cycle several times. That is, it is preferable that the thickness of the fourth layer (SiOCN layer) formed when the above cycle is performed once is smaller than a desired film thickness, and the above cycle is repeated several times until the fourth layer (SiOCN layer) is laminated. On the other hand, the film thickness of the formed SiOCN film becomes a desired film thickness.

(Purge and restore atmospheric pressure)

After the formation of the SiOCN film is completed, the valves 243 c and 243 d are opened, and N ₂ gas is supplied into the processing chamber 201 from the gas supply pipes 232 c and 232 d, respectively, and discharged from the exhaust pipe 231 . N ₂ gas acts as a purge gas. Thereby, the inside of the processing chamber 201 is purged, and the gas and reaction by-products remaining in the processing chamber 201 are removed (purged) from the inside of the processing chamber 201 . After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

(boat unloading and wafer removal)

The sealing cover 219 is lowered by the boat lift 115 to open the lower end of the reaction tube 203 . Then, the processed wafer 200 is carried out from the lower end of the reaction tube 203 to the outside of the reaction tube 203 in a state supported by the wafer boat 217 (boat unloading). The processed wafer 200 is removed from the wafer boat 217 (wafer removal).

(3) Effects of the present embodiment

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

(a) By making the nozzle tip portion 271 U-shaped, the time and distance during which the processing gas introduced into the gas supply nozzle is heated can be extended, and the activated processing gas can be uniformly supplied to the wafer.

(b) By providing the gas retention suppressing hole 280 at the tip of the nozzle 249, it is possible to suppress the retention of the processing gas in the tip of the nozzle.

(c) By providing the gas retention suppressing hole 280 at the tip of the nozzle 249, the gas flow rate of the processing gas can be suppressed from decreasing as it flows toward the tip of the nozzle, and the processing gas can be uniformly supplied to the wafer from the gas supply hole.

(d) By providing the gas retention suppressing hole 280 at the tip of the nozzle 249 , by-products such as particles generated in the nozzle 249 can be suppressed from adhering to the wafer 200 .

(e) By providing the diameter of the gas retention suppressing hole 280 to be larger than that of the gas supply hole 250 , it is possible to effectively suppress the retention of gas at the tip of the nozzle.

(f) By setting the hole diameter of the gas retention suppressing hole 280 to be the flow velocity at which the supplied gas flows through the most upstream of the upstream line 271-1 and the flow velocity at which the supplied gas flows through the most downstream of the downstream line 271-2 With the same size, the supplied process gas can be prevented from becoming an exhaust bottleneck for exhausting from the gas retention suppression hole 280 , and the gas can be uniformly supplied to the wafer from the gas supply hole 250 .

(Variation)

Next, a modification of the present invention will be described with reference to FIGS. 10A to 10C .

Not only are the gas supply holes 250 provided in both the upstream line 271-1 and the downstream line 271-2 of the nozzle 249 as shown in (a), (b), and (c) of FIG. 10A , but also As shown in (d) of 10B, only the gas supply hole 250 is provided in the downstream side line 271-2, whereby the process gas activated by heating can be easily supplied to the wafer 200, and the surface uniformity of the wafer can be improved. Effect.

In addition, by providing the gas supply hole 250 only in the upstream line 271-1 as shown in FIG. 10B (e), even if by-products such as particles are generated in the nozzle, it is not provided on the downstream line 271-2 side. Because of the gas supply hole 250, the effect of easily discharging by-products such as particles in the exhaust direction can also be obtained.

In addition, as shown in FIG. 10B (f) and FIG. 10B (g), the arrangement heights of the gas supply holes 250 provided in the upstream line 271-1 and the downstream line 271-2 are different. By forming the gas supply holes 250 in such a way, the effect that the activated process gas can be uniformly supplied to the wafer 200 can be obtained. That is, by providing the gas supply hole 250 as in (f), the activated process gas can be easily supplied to the height direction center portion of the upstream line 271-1 and the height direction center portion of the downstream line 271-2, so that it is possible to Supplying a large amount of processing gas to the vicinity of the center of the wafer array area can be effectively used when the reaction of the process gas is poor in the vicinity of the center of the wafer array area. Furthermore, by providing the gas supply holes 250 as in (g), the activated process gas can be easily supplied to the uppermost or the lowermost vicinity of the wafer arrangement region, so that it can be effectively used for the uppermost or lowermost of the wafer arrangement region. When the reaction of the nearby process gas is poor.

In addition, by extending the length of the downstream side line 271-2 as shown in (h) to (k) of FIG. 10C , the gas retention suppressing hole 280 can be provided as much as possible in the downward direction in the vertical direction, and secondary particles such as particles can be suppressed. The product is attached to the wafer 200 . In this case, it is preferable to form the gas retention suppressing hole 280 so as to be provided at a position lower than the region supporting the wafer 200 . That is, by extending the length of the downstream side line 271 - 2 to form the gas retention suppressing hole 280 so as to be located in an insulating region below the region supporting the wafer 200 , the gas retention suppressing hole 280 can be arranged at the exhaust port. In the vicinity, the gas containing by-products such as particles can be discharged to the vicinity of the exhaust port. Therefore, even if by-products such as particles are generated in the nozzle 249 due to the peeling of the deposition film or the like, the gas discharged from the gas retention suppressing hole 280 can be immediately discharged from the exhaust port of the exhaust pipe 231, and the adhesion of by-products such as particles can be suppressed. on wafer 200 .

Furthermore, as shown in (h) of FIG. 10C , if the gas supply holes 250 are also arranged in the insulating region, the etching gas can be directly supplied to the insulating region when the etching gas is supplied to clean the processing chamber. Therefore, the deposited film deposited in the heat insulating region can be efficiently removed.

<Second Embodiment>

Next, a second embodiment of the present invention will be described with reference to FIGS. 11 and 12 . The substrate processing apparatus in the second embodiment is different from the first embodiment in that, as shown in FIG. 11 , the nozzles 249 a for supplying the source gas are arranged in the form of U-shaped nozzles instead of FIGS. 1 and 2 . As for the nozzle 249b shown, the nozzle which supplies a reaction gas and an inert gas is arrange|positioned in the form of the straight pipe type nozzle 251. The other configuration is the same as that of the first embodiment.

Moreover, as shown in FIG. 12, by arranging only the nozzle 249a which supplies the raw material gas which needs to be activated by heating in the form of a U-shaped nozzle, it becomes possible to perform maintenance easily, or to reduce apparatus cost.

By configuring as in the second embodiment, the following effects can be obtained.

(g) Maintenance of the apparatus can be easily performed by reducing the number of U-shaped nozzles having a complicated structure.

(h) The device cost can be reduced by reducing the number of U-shaped nozzles having a complicated structure.

<Other Embodiments>

The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the above-described embodiments, and various changes can be made without departing from the gist thereof, and the above-described effects can be obtained.

For example, in the first embodiment of the present invention, the case where the same nozzle is used for the nozzles 249a and 249b has been described, but the present invention is not limited to this. In (e) and the like shown in 10B, the installation positions of the gas supply holes are set differently on the nozzles 249a and 249b.

In addition, for example, in the film formation sequence in the present embodiment, the film to be formed can be changed by changing the type and timing of the gas to be supplied, as described below.

As shown in the above modification example, the composition, composition ratio, film quality, etc. of the formed film can be changed by arbitrarily selecting and using the reactant gas, or arbitrarily changing the supply timing of the source gas and the reactant gas. In addition, it is also possible to use several kinds of reaction gases in any combination. For example, C ₃ H ₆ gas may be added (mixed) to NH ₃ gas, TEA gas, and HCDS gas and used. Thereby, the composition, composition ratio, film quality, etc. of the formed film can be changed.

By using the silicon-based insulating film formed in accordance with the film formation sequence shown in FIG. 9 and each modification as a sidewall spacer, a device formation technique with low leakage current and excellent workability can be provided. In addition, by using the above-mentioned silicon-based insulating film as an etch stopper, it is possible to provide a device formation technique excellent in workability. In addition, according to the film-forming sequence shown in FIG. 9 and each modification example, a silicon-based insulating film having an ideal theoretical mixing ratio can be formed without using plasma. Since the silicon-based insulating film can be formed without using plasma, it can also be applied to processes in which plasma damage is concerned, such as the SADP film of DPT.

In the above modification, in the step of supplying the thermally activated TEA gas to the wafer 200, the supply flow rate of the TEA gas controlled by the MFC 241b is, for example, a flow rate in the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure within a range of 1 to 5000 Pa, or preferably 1 to 4000 Pa. In addition, the partial pressure of the TEA gas in the processing chamber 201 is, for example, a pressure within a range of 0.01 to 4950 Pa. The time for supplying the TEA gas to the wafer 200 , that is, the gas supply time (irradiation time) is, for example, 1 to 200 seconds, preferably 1 to 120 seconds, and more preferably a time in the range of 1 to 60 seconds. Other processing conditions are, for example, the same processing conditions as in Step 4 of the film formation sequence shown in FIG. 9 . As the gas containing N, C, and H, in addition to TEA gas, for example, diethylamine ((C ₂ H ₅ ) ₂ NH, abbreviated: DEA) gas, monoethylamine (C ₂ H ₅ NH ₂ , abbreviated as: DEA) gas can be used. : Ethylamine gas such as MEA gas, trimethylamine ((CH ₃ ) ₃ N, abbreviation: TMA) gas, dimethylamine ((CH ₃ ) ₂ NH, abbreviation: DMA) gas, monomethylamine (CH ₃ NH) gas ₂ Abbreviation: MMA) gas and other methylamine gases, etc.

The processing steps and processing conditions in the other steps may be the same as, for example, the processing steps and processing conditions of the respective steps in the film formation sequence shown in FIG. 9 .

Furthermore, the film-forming sequence described in the above-described embodiment can also be suitably applied to the formation of materials containing titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum ( In the case of an oxide film of metal elements such as Al), molybdenum (Mo), and tungsten (W), that is, a metal-based oxide film. That is, the above-described film formation sequence can also be suitably applied to the formation of a TiOCN film, a TiOC film, a TiON film, a TiO film, a ZrOCN film, a ZrOC film, a ZrON film, a ZrO film, a HfOCN film, a HfOC film, a HfON film, a HfO film, TaOCN film, TaOC film, TaON film, TaO film, NbOCN film, NbOC film, NbON film, NbO film, AlOCN film, AlOC film, AlON film, AlO film, MoOCN film, MoOC film, MoON film, MoO film , WOCN film, WOC film, WON film, WO film.

When forming the metal-based oxide film, as the source gas, for example, titanium tetrachloride (TiCl ₄ ) gas, titanium tetrafluoride (TiF ₄ ) gas, zirconium tetrachloride (ZrCl ₄ ) gas, zirconium tetrafluoride (TiCl 4 ) gas, ZrF ₄ ) gas, hafnium tetrachloride (HfCl ₄ ) gas, hafnium tetrafluoride (HfF ₄ ) gas, tantalum pentachloride (TaCl ₅ ) gas, tantalum pentafluoride (TaF ₅ ) gas, niobium pentachloride ( NbCl ₅ ) gas, niobium pentafluoride (NbF ₅ ) gas, aluminum trichloride (AlCl ₃ ) gas, aluminum trifluoride (AlF ₃ ) gas, molybdenum pentachloride (MoCl ₅ ) gas, molybdenum pentafluoride ( Inorganic metal source gas containing metal elements and halogen elements, such as MoF ₅ ) gas, tungsten hexachloride (WCl ₆ ) gas, and tungsten hexafluoride (WF ₆ ) gas. Moreover, as a raw material gas, the organometallic raw material gas containing a metal element and carbon, such as trimethylaluminum (Al( _CH3 ) ₃ , abbreviation: TMA) gas, can also be used, for example. As the reactive gas, the same gas as in the above-described embodiment was used.

For example, a TiON film and a TiO film can be formed on the wafer 200 according to the film formation sequence shown below.

That is, the present invention can be suitably applied to the case of forming a film containing a predetermined element such as a semiconductor element and a metal element. Even in the case of performing these film formations, the film formation can be performed under the same processing conditions as those of the above-described embodiment, and the same effects as those of the above-described embodiment can be obtained.

For a process for substrate processing (a program in which processing steps, processing conditions, etc. are described), it is preferable that the processing content (film type, composition ratio, film quality, film thickness, processing step of the film formed on the substrate) , processing conditions, etc.) are separately prepared and stored in the storage device 121 c in advance via the electrical communication line and the external storage device 123 . When starting various processes, it is preferable that the CPU 121a appropriately selects an appropriate process from among a plurality of processes stored in the storage device 121c according to the content of the process. As a result, it is possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility by one substrate processing apparatus. In addition, the operator's burden (input burden of processing steps, processing conditions, etc., etc.) can be reduced, operational errors can be avoided, and substrate processing can be started quickly.

The above-mentioned process is not limited to the case of new fabrication, for example, it can be prepared by changing an existing process already installed in a substrate processing apparatus. When the process is changed, the changed process can be installed in the substrate processing apparatus via an electrical communication line or a recording medium on which the process is recorded. In addition, the input/output device 122 of the existing substrate processing apparatus can also be operated, and the existing process already installed in the substrate processing apparatus can be directly changed.

An example in which a film is formed using a substrate processing apparatus having a hot-wall processing furnace has been described. The present invention is not limited to the above-described embodiments, and can be suitably applied to a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

Even when the above-described substrate processing apparatus is used, film formation can be performed at the same timing and processing conditions as those of the above-described embodiment and modification, and the same effects as those of the above-described embodiment and modification can be obtained.

In addition, the above-described embodiments and modifications may be appropriately combined. In addition, the processing conditions at this time may be, for example, the same processing conditions as those of the above-described embodiment and modification.

Claims (20)

1. A gas supply nozzle having: The upstream side pipeline, which is used to introduce gas; a turn-back part, which is connected to the downstream end of the upstream-side pipeline and changes the flow direction of the gas; a downstream side line connected to the turn-back portion; and a plurality of gas supply holes provided on the side surfaces of the upstream-side pipeline and the downstream-side pipeline and oriented in a direction intersecting with the folded portion, A pair of gas supply holes in the plurality of gas supply holes is configured as follows: Each of the gas supply holes arranged on the side surface of the upstream-side pipeline has the same distance from the turn-back portion as the gas supply holes arranged on the side surface of the downstream-side pipeline. Each is comprised so that the said gas can be supplied. 2. The gas supply nozzle of claim 1, wherein: The distance from the turn-back portion to the gas supply hole provided on the lowermost side among the plurality of gas supply holes provided on the side surface of the upstream line is configured to be the same as the distance from the turn-back portion to the gas supply hole provided downstream from the turn-back portion Among the plurality of gas supply holes on the side surface of the side line, the distance between the gas supply holes provided on the lowermost side is different. 3. The gas supply nozzle of claim 1, wherein: Gas supply holes are provided on the side surface of any one of the upstream line and the downstream line at a predetermined pitch over the entire line, and gas supply holes are provided on a part of the side surface of the other line . 4. The gas supply nozzle of claim 1, wherein: The distance from the turn-back portion to the gas supply hole provided in any one of the upstream-side line and the downstream-side line is configured to be the same as the distance from the turn-back portion to all the gas supply holes provided in the other one. The distance between any one of the gas supply holes is the same. 5. The gas supply nozzle of claim 4, wherein: The distance from the turn-back portion to all the gas supply holes arranged on the side surface of the upstream line is configured to be the same as the distance from the turn portion to all the gas supply holes arranged on the side surface of the downstream line . 6. The gas supply nozzle of claim 1, wherein: The turn-back portion is positioned above the gas supply hole in the uppermost position of the upstream line and the downstream line in the vertical direction. 7 . The gas supply nozzle according to claim 1 , further comprising a connecting portion that connects the upstream line and the downstream line. 8 . 8. The gas supply nozzle of claim 7, wherein: The connection portion is provided so as to connect the upstream side of the upstream line and the downstream side of the downstream line. 9. The gas supply nozzle according to claim 1, further comprising a gas introduction portion for introducing the gas into the upstream line, The center of the gas introduction portion is configured to be located in the middle of a straight line connecting the center of the upstream line and the center of the downstream line. 10. The gas supply nozzle of claim 1, Further, the gas supply hole arranged at the position closest to the turn-back portion is configured to be provided at the upstream end of the turn-back portion and the downstream end of the upstream-side pipeline, or the downstream end of the turn-back portion and the downstream end of the turn-back portion. the upstream end of the downstream pipeline. 11. A substrate processing apparatus having: a reaction tube formed with a processing chamber for processing the substrate; a first gas supply system; and a control unit that controls the first gas supply system so as to process the surfaces of the plurality of substrates, Wherein, the first gas supply system has a first nozzle front end, and the first nozzle front end includes: a first upstream side pipeline for introducing gas; a downstream side connected to the first upstream side pipeline, changing a first folded portion of the flow direction of the gas; a first downstream-side pipeline connected to the folded-back portion; and a plurality of gas supply holes respectively provided on the side surfaces of the upstream-side pipeline and the downstream-side pipeline, and, A pair of gas supply holes among the plurality of gas supply holes facing in a direction intersecting with the folded portion is configured such that each of the gas supply holes arranged on the side surface of the first upstream line is separated from the folded-back portion. The distances of the parts are the same as the distances from the folded-back parts in the gas supply holes arranged on the side surfaces of the first downstream-side pipelines, and are configured to be able to supply the gas, respectively. 12. The substrate processing apparatus according to claim 11, further comprising a second gas supply system, the second gas supply system further having a second nozzle front end, The front end portion of the second nozzle includes: a second upstream line for introducing a second gas; a second turn-back portion connected to a downstream end of the second upstream-side line; and a downstream portion connected to the second turn-back portion end of the second downstream side pipeline, The plurality of second gas supply holes arranged on the side surfaces of the second upstream line and the second downstream line are configured to face the center of the reaction tube. 13 . The substrate processing apparatus according to claim 12 , wherein a pair of gas supply holes among the plurality of gas supply holes facing in a direction intersecting with the second turn-back portion is configured to be arranged in the first The distance from each of the gas supply holes on the side surfaces of the two upstream pipelines from the second folded portion and the respective distances from the second folded portion in the gas supply holes arranged on the side surface of the second downstream pipeline The distances are the same, and each is configured to be able to supply the gas. 14. The substrate processing apparatus according to claim 11, further comprising a second gas supply system, the second gas supply system further having a second nozzle front end, The front end portion of the second nozzle includes: a second upstream line for introducing a second gas; a second turn-back portion connected to a downstream end of the second upstream-side line; and a downstream portion connected to the second turn-back portion end of the second downstream side pipeline, The plurality of second gas supply holes arranged on the side surface of the second downstream line are configured to face the center of the reaction tube. 15. The substrate processing apparatus according to claim 12 or 14, wherein the control section is configured such that: supplying raw material gas via the first gas supply system, The reactive gas is supplied via the second gas supply system. 16. The substrate processing apparatus of claim 11, further comprising a third gas supply system, The third gas supply system has a third nozzle base end including: a third gas supply pipe for introducing the third gas; and a third extension pipe, which is provided in the third gas supply The downstream end of the tube is vertically erected in the reaction tube, The straight-pipe type nozzle connected to the downstream end of the said 3rd extension pipe is comprised so that the 3rd gas supply hole may be arrange|positioned in the side surface of the said straight-pipe-type nozzle. 17. The substrate processing apparatus of claim 16, which is composed of: supplying raw material gas via the first gas supply system, The reactive gas is supplied via the third gas supply system. 18. The substrate processing apparatus of claim 16, which is composed of: An inert gas is supplied via the third gas supply system. 19. A method of manufacturing a semiconductor device, comprising a step of supplying a gas via a gas supply nozzle to process a substrate, the gas supply nozzle having: an upstream-side pipeline for introducing a process gas; a turn-back part connected to the downstream side of the upstream-side pipeline to change the flow direction of the process gas; a downstream-side pipeline connected to the turn-back part; and a plurality of gases supply holes provided on the sides of the upstream-side pipeline and the downstream-side pipeline, A pair of gas supply holes of the plurality of gas supply holes facing in a direction intersecting with the folded portion is configured such that each of the gas supply holes arranged on the side surface of the upstream pipeline is separated from the folded portion. The distances are the same as the distances from the turn-back portions in the gas supply holes arranged on the side surfaces of the downstream-side pipelines, and are configured to be able to supply the gas, respectively. 20. A computer-readable recording medium storing a program for causing a substrate processing apparatus to perform the following steps by a control section, the steps being: the step of receiving the substrate in a processing chamber of the substrate processing apparatus; and the step of processing the substrate by supplying a process gas from a first gas supply system, Wherein, the substrate processing apparatus has: a reaction tube formed with a processing chamber for processing the substrate; a first gas supply system; and a control unit that controls the first gas supply system to process the substrate, Wherein, the first gas supply system has: a first upstream side pipeline for introducing gas; a first turn-back part connected to the downstream side of the first upstream side pipeline and changing the flow direction of the gas; connected to the the first downstream side line of the turn-back portion; and a plurality of gas supply holes provided on the side surfaces of the first upstream side line and the first downstream side line, and facing all the directions intersecting with the turn-back portion A pair of gas supply holes among the plurality of gas supply holes is configured such that a distance from the turn-back portion of each of the gas supply holes arranged on the side surface of the first upstream side pipeline and the gas supply holes arranged on the first downstream side Each of the gas supply holes on the side surfaces of the side line has the same distance from the turn-back portion, and is configured to be able to supply the gas.

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