Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and program product

Abstract

This invention relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a process product. A technique is provided capable of forming a homogeneous layer (or film) on a substrate. It comprises: (a) a step of forming a layer containing a first element on a substrate by performing (a1), (a2), and (a3) ​​as described below; (a1) a step of supplying a barrier gas to the substrate and forming barrier groups on the substrate, wherein the barrier groups barrier the adsorption of a first gas containing atoms of the first element onto the substrate; (a2) a step of supplying a promoting gas to the substrate after (a1) and forming promoting groups on the substrate, wherein the promoting groups promote the adsorption of the first gas onto the substrate; and (a3) ​​a step of supplying the first gas to the substrate after (a2).

Description

Technical Field

[0001] This invention relates to substrate processing methods, semiconductor device manufacturing methods, substrate processing apparatus, and process products. Background Technology

[0002] As a step in the manufacturing process of semiconductor devices or the substrate processing process, a layer with trace amounts of a specified element is sometimes formed on the substrate (see, for example, Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2011 / 093203 Summary of the Invention

[0004] The problem that the invention aims to solve This invention provides a technique for forming a homogeneous layer (or film) on a substrate.

[0005] Methods for solving problems According to one aspect of the present invention, a technique is provided comprising: (a) performing the following steps (a1), (a2), and (a3) ​​to form a layer comprising a first element on a substrate. (a1) A step of supplying a barrier gas to the substrate and forming a barrier group on the substrate, wherein the barrier group prevents the adsorption of a first gas containing atoms of the first element onto the substrate; (a2) A step of supplying a promoting gas to the substrate and forming a promoting group on the substrate, which is later than the start of (a1), wherein the promoting group promotes the adsorption of the first gas onto the substrate; (a3) is the process of supplying the first gas to the substrate after (a2).

[0006] Invention Effects According to the present invention, a homogeneous layer (or film) can be formed on a substrate. Attached Figure Description

[0007] Figure 1 This is a schematic diagram of the vertical processing furnace of the substrate processing apparatus, showing the processing furnace 202 section in a longitudinal cross-section.

[0008] Figure 2 This is a schematic diagram of the controller 121 of the substrate processing apparatus, and a block diagram showing the control system of the controller 121.

[0009] Figure 3 (A) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the second gas is supplied; Figure 3(B) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the reactive gas is supplied; Figure 3 (C-1) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the gas supply is blocked; Figure 3 (C-2) is viewed from above. Figure 3 A schematic diagram of (C-1) in the diagram; Figure 3 (D-1) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the gas supply has been facilitated; Figure 3 (D-2) is viewed from above. Figure 3 A schematic diagram of (D-1) in the diagram; Figure 3 (E) in the figure is a partially enlarged cross-sectional view of the surface of the wafer 200 after the first gas is supplied; Figure 3 (F) in the figure is a partially enlarged cross-sectional view of the surface of the wafer 200 after the gas supply has been removed; Figure 3 (G) in the figure is a partially enlarged cross-sectional view of the surface of the wafer 200 after the second gas is supplied; Figure 3 (H) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the reactive gas is supplied.

[0010] Figure 4 (A) is a partially enlarged cross-sectional view of the recess of the wafer 200 after the supply of barrier gas and promoter gas; Figure 4 (B) is a partially enlarged cross-sectional view of the recess of the wafer 200 after the first gas is supplied; Figure 4 (C) is a partially enlarged cross-sectional view of the recess of the wafer 200 after the gas supply / second gas supply and reaction gas supply have been removed.

[0011] Explanation of reference numerals in the attached figures 200 wafers (substrates) Detailed Implementation

[0012] <One aspect of the invention> The following is mainly based on Figures 1-4 One aspect of the present invention will be described below. It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements may not be consistent between different drawings.

[0013] (1) Composition of substrate processing device like Figure 1As shown, the processing furnace 202 has a heater 207 that serves as a temperature control unit (heating unit). The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gases by heat. A reaction tube 203 is disposed inside the heater 207. A manifold 209 is disposed below the reaction tube 203, and an O-ring 220a, serving as a sealing component, is provided between the manifold 209 and the reaction tube 203. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed inside the processing container.

[0014] Inside the processing chamber 201, nozzles 249a to 249c are respectively provided as the first to third supply units. These nozzles are also referred to as the first to the third nozzles. Gas supply pipes 232a to 232c are connected to each of the nozzles 249a to 249c. Each of the nozzles 249a to 249c has a gas supply hole 250a to 250c for supplying gas to the wafer 200. Multiple gas supply holes 250a to 250c are provided from the lower part to the upper part of each of the nozzles 249a to 249c.

[0015] On gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c, serving as flow controllers (flow control units), and valves 243a to 243c, serving as on / off valves, are sequentially installed from the upstream side of the airflow. Gas supply pipes 232d and 232g are connected downstream of valve 243a on gas supply pipe 232a. Gas supply pipes 232e and 232h are connected downstream of valve 243b on gas supply pipe 232b. Gas supply pipes 232f and 232i are connected downstream of valve 243c on gas supply pipe 232c. On gas supply pipes 232d to 232i, MFCs 241d to 241i and valves 243d to 243i are sequentially installed from the upstream side of the airflow.

[0016] The first gas is supplied to the processing chamber 201 via gas supply pipe 232a, MFC 241a, valve 243a, and nozzle 249a. The first gas is a gas containing atoms of the first element. The second gas is supplied to the processing chamber 201 via gas supply pipe 232b, MFC 241b, valve 243b, and nozzle 249b. The second gas is a gas containing atoms of a second element different from the first element. The reaction gas is supplied to the processing chamber 201 via gas supply pipe 232c, MFC 241c, valve 243c, and nozzle 249c. The barrier gas is supplied to the processing chamber 201 via gas supply pipe 232d, MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a. The barrier gas is a gas that forms barrier groups on the wafer 200 to prevent the adsorption of the first gas on the wafer 200. The promoting gas is supplied into the processing chamber 201 via gas supply pipe 232e, MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b. The promoting gas is a gas that forms promoting groups on the wafer 200 to promote the adsorption of the first gas on the wafer 200. The removing gas is supplied into the processing chamber 201 via gas supply pipe 232f, MFC 241f, valve 243f, gas supply pipe 232c, and nozzle 249c. The removing gas is a gas that removes at least a portion of the hindering groups on the wafer 200.

[0017] Inactive gases are supplied to the treatment chamber 201 via gas supply pipes 232g-232i, MFC 241g-241i, valves 243g-243i, gas supply pipes 232a-232c, and nozzles 249a-249c. These inactive gases function as purge gases, carrier gases, and dilution gases.

[0018] The first gas supply system mainly consists of gas supply pipe 232a, MFC 241a, and valve 243a. The second gas supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The reaction gas supply system mainly consists of gas supply pipe 232c, MFC 241c, and valve 243c. The obstruction gas supply system mainly consists of gas supply pipe 232d, MFC 241d, and valve 243d. The promoting gas supply system mainly consists of gas supply pipe 232e, MFC 241e, and valve 243e. The removal gas supply system mainly consists of gas supply pipe 232f, MFC 241f, and valve 243f. The inactive gas supply system mainly consists of gas supply pipes 232g-232i, MFC 241g-241i, and valves 243g-243i. The gas supply system is composed of all or at least any of the above-mentioned supply systems. The nozzles connected to the gas supply pipes constituting the above-mentioned supply systems may also be included in the supply system.

[0019] An exhaust pipe 231 is connected to the lower side wall of the reaction tube 203, and an exhaust port 231a is provided for exhausting the atmosphere inside the processing chamber 201. A vacuum pump 246, serving as a vacuum exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245 (pressure detector) that detects the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 (pressure regulator). The APC valve 244 can perform vacuum exhaust and stop vacuum exhaust within the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. The APC valve 244 is also configured to adjust the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating, thereby regulating the pressure inside the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also possible to include the vacuum pump 246 in the exhaust system.

[0020] A sealing cap 219 is provided below the manifold 209 to airtightly seal the lower opening of the manifold 209. An O-ring 220b, which contacts the lower end of the manifold 209, is provided on the upper surface of the sealing cap 219 as a sealing component. A rotating mechanism 267 is provided below the sealing cap 219, which is connected to the crystal boat 217 via a rotating shaft 255 to rotate the crystal boat 217 and the wafer 200. The crystal boat lift 115 (lifting mechanism) is configured as a conveying device (transfer mechanism) that moves the wafer 200 in and out of the processing chamber 201 by raising and lowering the sealing cap 219.

[0021] Below the manifold 209, a gate 219s is provided, capable of airtightly sealing the lower opening of the manifold 209 when the sealing cover 219 is lowered and the crystal boat 217 is removed from the processing chamber 201. An O-ring 220c, serving as a sealing component, is provided on the upper surface of the gate 219s, abutting against the lower end of the manifold 209. The opening and closing actions (lifting, rotating, etc.) of the gate 219s are controlled by the gate opening and closing mechanism 115s.

[0022] The crystal boat 217, serving as a substrate support, is configured to support, for example, 25 to 200 wafers 200 in a horizontal, multi-layered manner. It should be noted that the numerical range "25 to 200 wafers" in this specification refers to the inclusion of both the lower and upper limits within that range. Therefore, "25 to 200 wafers" means "more than 25 wafers and less than 200 wafers." The same applies to other numerical ranges. At the lower part of the crystal boat 217, a heat-insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple layers.

[0023] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. By adjusting the power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 or the wafer 200 can be adjusted to achieve the desired temperature distribution. The temperature sensor 263 is disposed along the inner wall of the reaction tube 203.

[0024] like Figure 2 As shown, the controller 121, serving as the control unit (control unit), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. Furthermore, the controller 121 is configured to connect to an external storage device 123. It should be noted that the substrate processing apparatus may be configured to have one control unit or multiple control units. That is, one control unit can be used to control the processing sequence described later, or multiple control units can be used to control the processing sequence described later. Furthermore, multiple control units may be configured as a control system interconnected via a wired or wireless communication network, or the entire control system may be used to control the processing sequence described later. When the term "control unit" is used in this specification, in addition to the case of having one control unit, there are also cases of having multiple control units, and cases of having a control system composed of multiple control units.

[0025] The storage device 121c is configured such as flash memory, HDD (Hard Disk Drive), or SSD (Solid State Drive). The storage device 121c contains, in a readable manner, a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the substrate processing steps and conditions, as described later. The process flow functions as a program, combining elements such as the process flow, the control program, etc., to enable the substrate processing apparatus to execute the steps of the substrate processing described later and obtain a predetermined result. Hereinafter, the process flow, control program, etc., will be collectively referred to as a program (program product). The process flow will also be referred to simply as a process. In this specification, the term "program" may refer only to the process flow, only to the control program, or both. RAM 121b is configured as a memory area (working area) that temporarily holds the program, data, etc., read from the CPU 121a.

[0026] I / O port 121d is connected to the aforementioned MFC241a~241i, valves 243a~243i, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, crystal boat elevator 115, gate opening and closing mechanism 115s, etc.

[0027] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on inputs such as operation commands from input / output device 122. CPU 121a is configured to control the following according to the content of the read processes: flow regulation of various substances (various gases) based on MFC 241a to 241i, opening and closing of valves 243a to 243i, opening and closing of APC valve 244 and pressure regulation of APC valve 244 based on pressure sensor 245, starting and stopping of vacuum pump 246, temperature regulation of heater 207 based on temperature sensor 263, rotation and rotation speed regulation of crystal boat 217 based on rotation mechanism 267, lifting and lowering of crystal boat 217 based on crystal boat elevator 115, opening and closing of gate 219s based on gate opening and closing mechanism 115s, etc.

[0028] The controller 121 can be configured to install the aforementioned program, recorded and stored in the external storage device 123, into the computer. The external storage device 123 includes, for example, a hard disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a USB memory, and a semiconductor memory such as an SSD. The storage device 121c and the external storage device 123 constitute a computer-readable recording medium. Hereinafter, they will be collectively referred to as recording media. When the term "recording medium" is used in this specification, it may include only the storage device 121c, only the external storage device 123, or both. It should be noted that the external storage device 123 may also be omitted, and the program may be provided to the computer using a communication unit such as the Internet or a dedicated line.

[0029] (2) Substrate processing process Main use Figure 3 (A) ~ Figure 3 In section (H), an example of a process sequence for forming a layer containing a first element and a second element, which is doped with a trace amount of a first element, on wafer 200 will be described. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by controller 121.

[0030] In the processing sequence of this method, step a includes: performing... (a1) The step of supplying a barrier gas to the wafer 200 and forming a barrier group on the wafer 200, wherein the barrier group prevents the adsorption of the first gas containing atoms of the first element onto the wafer 200; and (a2) A step of supplying a promoting gas to the wafer 200 and forming a promoting group on the wafer 200, which is performed after the start of (a1), wherein the promoting group promotes the adsorption of the first gas onto the wafer 200; and (a3) is the step of supplying the first gas to the wafer 200, which begins later than (a2). The step of forming a layer containing the first element on wafer 200.

[0031] Furthermore, as step a, there is a step of supplying a removal gas to the wafer 200 after the start of (a3) ​​to remove at least a portion of the barrier groups on the wafer 200.

[0032] Additionally, step b includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error.] (b1) The step of supplying a second gas containing atoms of a second element different from the first element to the wafer 200; and (b2) Step of supplying reactant gas to wafer 200 The process involves repeating the loop a specified number of times to form a layer containing the first and second elements.

[0033] Furthermore, in this method, the case where step b and step a are performed a specified number of times (p times, where p is an integer of 1 or 2 or more) is explained, wherein step b is the step of performing the first loop containing (b1) and (b2) a specified number of times (m times, where m is an integer of 1 or 2 or more), and step a is the step of performing the second loop containing (a1) and (a2) and (a3) ​​and (a4) a specified number of times (n times, where n is an integer of 1 or 2 or more).

[0034] For convenience, the above processing order is sometimes represented as follows in this specification.

[0035] [(Second gas → Reacting gas →) × m → (Obstructing gas → Promoting gas → First gas → Removing gas →) × n] × p In this specification, the above "→" indicates that a purging process is performed to purge the treatment chamber 201.

[0036] The term "wafer" as used in this specification can refer to the wafer itself, or to a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" as used in this specification can refer to the surface of the wafer itself, or to the surface of a specified layer, etc., formed on the wafer. When described as "forming a specified layer on the wafer," this can mean forming the specified layer directly on the surface of the wafer itself, or forming the specified layer on top of a layer, etc., formed on the wafer. In this specification, the term "substrate" is synonymous with the term "wafer."

[0037] As used in this specification, the term "layer" includes at least one of continuous and discontinuous layers. For example, a deposited layer may include a continuous layer, a discontinuous layer, or both.

[0038] In this specification, when describing the adsorption and reaction of each gas on the surface of the wafer 200, it includes not only the way in which they adsorb and react on the surface of the wafer 200 in their undecomposed state, but also the way in which they decompose and the intermediates generated by the detachment of their ligands adsorb and react on the surface of the wafer 200.

[0039] (Wafer filling and crystal boat loading) Multiple wafers 200 are loaded (wafer filling) into the wafer boat 217. The gate 219s is moved by the gate opening / closing mechanism 115s, opening the lower end of the manifold 209 (gate opening). Then, the wafer boat 217, supporting multiple wafers 200, is lifted by the wafer boat elevator 115 and moved into the processing chamber 201 (wafer boat loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 via the O-ring 220b. Thus, as... Figure 1 As shown, the chip 200 is prepared (provided) in the processing chamber 201.

[0040] (Pressure and temperature regulation) After the crystal boat loading is completed, vacuum exhaust (pressure reduction exhaust) is performed by vacuum pump 246 to bring the pressure (vacuum level) inside processing chamber 201, i.e., the space where wafer 200 exists, to the desired pressure. At this time, the pressure inside processing chamber 201 is measured by pressure sensor 245, and APC valve 244 is controlled based on the measured pressure information. In addition, wafer 200 inside processing chamber 201 is heated by heater 207 to reach the desired processing temperature. At this time, the power supplied to heater 207 is controlled based on the temperature information detected by temperature sensor 263 to achieve the desired temperature distribution inside processing chamber 201. In addition, the rotation of wafer 200 is started based on rotation mechanism 267. The exhaust in processing chamber 201, the heating of wafer 200, and the rotation are all carried out continuously until the processing of wafer 200 is completed.

[0041] (Film-forming treatment) (Step b) First, perform the following steps b1 and b2 sequentially on the chip 200.

[0042] [Step b1] In this step, a second gas is supplied to the wafer 200 within the processing chamber 201. Specifically, valve 243b is opened, allowing the second gas to flow into the gas supply pipe 232b. The flow rate of the second gas is regulated using MFC 241b, and it is supplied to the processing chamber 201 and the wafer 200 via nozzle 249b, and exhausted from exhaust port 231a (second gas supply). At this time, valves 243g to 243i can also be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0043] Examples of processing conditions for supplying the second gas in this step include: Processing temperature: 350–900℃, preferably 500–800℃ Processing pressure: 1–10000 Pa, preferably 10–1333 Pa The second gas supply flow rate is 0.01–3 slm, preferably 0.1–2 slm. Second gas supply time: 10-120 seconds, preferably 20-60 seconds Inactive gas supply flow rate (per gas supply pipe): 0-10 slm.

[0044] It should be noted that in the following description, the processing temperature and inactive gas supply flow rate in each step of the film formation process are set in the same way as in this step.

[0045] It should be noted that the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure refers to the pressure inside the processing chamber 201. Furthermore, the processing time refers to the duration of the processing. Additionally, the supply flow rate refers to the flow rate of gas supplied to the processing chamber 201. Furthermore, if the supply flow rate includes 0 slm, 0 slm means that the substance (gas) is not supplied to the processing chamber 201. These same principles apply to the following descriptions.

[0046] Through this step, at least a portion of the second gas can be physically or chemically adsorbed onto the surface of the wafer 200 to form the first layer 11 (see [link]). Figure 3 (A)). Specifically, this allows at least a portion of the second gas to be physically or chemically adsorbed onto at least a portion of the surface of the wafer 200 to form the first layer 11 discontinuously. More specifically, this allows at least a portion of the second gas to be physically or chemically adsorbed onto the surface of the wafer 200 to form the first layer 11 entirely.

[0047] As the second gas, a silane-based gas containing silicon (Si) as the second element can be used, for example. As a silane-based gas, a gas containing Si and a halogen can be used, i.e., a halosilane-based gas. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. That is, a halosilane-based gas has at least one of the halogen groups such as chlorine (Cl), fluorine (F), bromine (Br), and iodine (I) as a functional group.

[0048] As a second gas, for example, the following chlorosilane gases may also be used: monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachlorodisilazane (Si2Cl6), octachlorotrisilane (Si3Cl8), etc.; fluorosilane gases such as tetrafluorosilane (SiF4), trifluorosilane (SiHF3), difluorosilane (SiH2F2), etc.; bromosilane gases such as tetrabromosilane (SiBr4), tribromosilane (SiHBr3), dibromosilane (SiH2Br2), etc.; and iodosilane gases such as tetraiodosilane (SiI4), triiodosilane (SiHI3), diiodosilane (SiH2I2), etc. One or more of these may be used as the second gas.

[0049] Additionally, as a second gas, a gas containing Si as a second element and an organic ligand can be used, for example. Examples of gases containing Si and an organic ligand include: tetra(dimethylamino)silane (Si[N(CH3)2]4), tri(dimethylamino)silane (Si[N(CH3)2]3H), bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tert-butylamino)silane (SiH2[NH(C4H9)]2), and (diisopropylamino)silane (SiH3[N(C3H7)2]), etc., which are aminosilane-based gases. Furthermore, as a second gas, a gas containing Si as a second element and a hydrogen (H) group can be used. Examples of gases containing Si and H groups include silane (SiH4) and disilane (Si2H6), and one or more of these can be used as the second gas.

[0050] In addition to the above, as a second gas, gases containing Si and alkyl groups as organic ligands, i.e., alkylsilane gases, can also be used. The alkyl group can be linear or branched. Examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc. One or more of these can be used as the second gas.

[0051] In addition, as a second element, one or more of the following can be used: tungsten (W), titanium (Ti), molybdenum (Mo), tantalum (Ta), cobalt (Co), yttrium (Y), ruthenium (Ru), hafnium (Hf), zirconium (Zr), aluminum (Al), boron (B), gallium (Ga), indium (In), phosphorus (P), and carbon (C).

[0052] As the second gas, for example, a gas containing a second element and a halogen element can be used. Examples of such gases include tungsten hexachloride (WCl6), tungsten hexafluoride (WF6), titanium tetrachloride (TiCl4), titanium tetrafluoride (TiF4), molybdenum pentachloride (MoCl5), molybdenum pentafluoride (MoF5), molybdenum dichlorodioxide (MoO2Cl2), molybdenum tetrachloride (MoOCl4), tantalum pentachloride (TaCl5), tantalum pentafluoride (TaF5), cobalt difluoride (CoF2), cobalt dichloride (CoCl2), yttrium trifluoride (YF3), yttrium trichloride (YCl3), ruthenium trichloride (RuCl3), ruthenium trifluoride (RuF3), hafnium tetrachloride (HfCl4), zirconium tetrachloride (ZrCl4), zirconium tetrafluoride (ZrF4), aluminum trichloride (AlCl3), and aluminum trifluoride (AlF3). Additionally, as a second gas, examples such as boron trifluoride (BF3), boron trichloride (BCl3), gallium trifluoride (GaF3), gallium trichloride (GaCl3), indium trifluoride (InF3), indium trichloride (InCl3), phosphorus trifluoride (PF3), phosphorus pentafluoride (PF5), phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), carbon tetrafluoride (CF4), carbon tetrachloride (CCl4), trifluoromethane (CHF3), fluoromethane (CH3F), chloroform (CHCl3), and chloromethane (CH3Cl) can also be used. For example, gases having a second element and a Br group, or gases having a second element and an I group, can also be used as the second gas. One or more of these can be used as the second gas.

[0053] Furthermore, as the second gas, for example, a gas having a second element and an organic ligand, or a gas having a second element and a hydrogen group, can be used. As the organic ligand, for example, alkyl, cycloalkyl, alkoxide, phenyl, or cyclopentadienyl groups can be used. As the second gas, for example, hexadimethylaminoditungsten (W2[N(CH3)2]6), bis-tert-butylimide bis(dimethylamide tungsten) ((t-C4H9NH)2W=(Nt-C4H9)2), tetraethylmethylaminotitanium (Ti[N(C2H5)(CH3)]4), bis(ethylcyclopentadienyl ruthenium) (Ru(CH2CH3)Cp)2), bis(cyclopentadienyl ruthenium) (Ru(Cp)2), tetraethylmethylaminohafnium (Hf[N(CH3)(CH2CH3)]4), tetraethylaminohafnium (Hf[N(CH2CH3)2]4), tetraethylaminohafnium (Hf[... Hafnium tridimethylaminocyclopentadienyl ((Cp)Hf[N(CH3)2]3), tetraethylmethylaminozirconium (Zr[N(CH3)Cp]4), tetraethylaminozirconium (Zr[N(CH2CH3)2]4), tetraethylaminozirconium (Zr[N(CH3)2]4), trimethylaminocyclopentadienylzirconium ((Cp)Zr[N(CH3)2]3), trimethylaluminum (Al(CH3)3), borane (BH3), trimethylgallium (Ga(CH3)3), trimethylindium (In(CH3)3), phosphine (PH3), methane (CH4), etc. One or more of these can be used as the second gas.

[0054] As inert gases, rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. One or more of these can be used as inert gases. This also applies to the steps described later.

[0055] After the first layer 11 is formed on the surface of the wafer 200, valve 243b is closed to stop the supply of the second gas to the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances and other substances remaining in the processing chamber 201. At this time, valves 243g to 243i are opened to supply inactive gas into the processing chamber 201 through nozzles 249a to 249c. The inactive gas supplied from nozzles 249a to 249c acts as a purging gas, thereby purging the space where the wafer 200 exists, i.e., the processing chamber 201.

[0056] [Step b2] Following step b1, reactive gas is supplied to the wafer 200, where the first layer 11 has been formed on its surface, within the processing chamber 201. Specifically, valve 243c is opened, allowing reactive gas to flow into the gas supply pipe 232c. The flow rate of the reactive gas is regulated using MFC 241c, and it is supplied to the processing chamber 201 and the wafer 200 via nozzle 249c, and exhausted from exhaust port 231a (reactive gas supply). At this time, valves 243g to 243i can also be opened to supply inactive gas into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0057] Examples of processing conditions for supplying the reactant gas in this step include: Processing pressure: 1–10000 Pa, preferably 10–1333 Pa Reactant gas supply flow rate: 1–30 slm, preferably 2–20 slm Reaction gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0058] Through this step, at least a portion of the first layer 11 formed on the surface of the wafer 200 reacts with and is modified by the reactive gas. As a result, a modified layer (hereinafter sometimes referred to as the second layer 12) forming the first layer 11 is formed on the surface of the wafer 200 (see [link to documentation]). Figure 3 (B) In the formation of the second layer 12, the reactive gas preferably removes (detaches) at least a portion of the functional groups formed on the wafer 200 in step b1 from the first layer 11 through a chemical reaction. The removed functional groups are discharged from the processing chamber 201. Thus, the second layer 12 becomes a layer with fewer impurities than the first layer 11 formed in step b1.

[0059] For example, gases including reducing gases, oxidizing gases, nitriding gases, sulfiding gases, selenizing gases, and tellurizing gases can be used as reacting gases. One or more of these can be used as reacting gases.

[0060] As a reducing gas, one or more of the following gases can be used: hydrogen (H2), deuterium (D2), borane (BH3), diborane (B2H6), carbon monoxide (CO), ammonia (NH3), silane (SiH4), disilane (Si2H6), propane (Si3H8), germanane (GeH4), and digerane (Ge2H6). As a reacting gas, an oxidizing gas containing oxygen (O) can be used. As an oxidizing gas, one or more of the following gases can be used: oxygen (O2), ozone (O3), water vapor (H2O), a mixture of H2 and O2, hydrogen peroxide (H2O2), and nitrous oxide (N2O). As a nitriding gas, one or more of the following hydrogen nitriding gases can be used: ammonia (NH3), diazepines (N2H2), hydrazine (N2H4), and N3H8. For example, gases containing thioalkylene (H₂S), dithioalkylene (H₂S₂), diammonium sulfide ((NH₄)₂S), dimethyl sulfide ((CH₃)₂S), etc., can be used as sulfide gases. One or more of these can be used as sulfide gases. For example, gases containing hydrogen selenide (H₂Se), hydrogen diselenide (H₂Se₂), dimethylselenide ((CH₃)₂Se), etc., can be used as selenide gases. One or more of these can be used as selenide gases. For example, gases containing hydrogen telluride (H₂Te), hydrogen ditelluride (H₂Te₂), dimethyl telluride ((CH₃)₂Te), etc., can be used as telluride gases. One or more of these can be used as telluride gases.

[0061] After the second layer 12 is formed on the surface of the wafer 200, valve 243c is closed to stop the supply of reaction gas to the processing chamber 201. Then, vacuum exhaust and purging of the processing chamber 201 are performed in the same manner as in step b1.

[0062] [Number of times stipulated for implementation] By performing the first cycle, which includes the above steps b1 and b2, a predetermined number of times (m times, where m is an integer of 1 or 2 or more), a second layer 12 can be stacked on the surface of the wafer 200 to form a second layer 12 containing a second element with a desired film thickness.

[0063] For example, when the reactant gas is a reducing gas, a layer mainly composed of the second element can be formed on the wafer 200. For example, when any of the following reactant gases—oxidizing gas, nitriding gas, sulfiding gas, selenizing gas, and tellurizing gas—is used, an oxide layer containing the second element, a nitriding layer containing the second element, a sulfiding layer containing the second element, a selenizing layer containing the second element, and a tellurizing layer containing the second element can be formed on the wafer 200. For example, when using a gas containing Hf as the second gas and an oxidizing gas as the reactant gas, an oxide layer containing hafnium (HfO layer) can be formed on the wafer 200.

[0064] (Step a) Next, the following steps a1, a2, a3, and a4 are performed sequentially on the chip 200.

[0065] [Step a1] Next, a barrier gas (inhibitor) is supplied to the wafer 200 within the processing chamber 201 after a layer containing the second element (also referred to as the second layer 12 of the desired film thickness) is formed on its surface. Specifically, valve 243d is opened to allow the barrier gas to flow into the gas supply pipe 232d. The flow rate of the barrier gas is regulated using MFC 241d, and it is supplied to the processing chamber 201 and the wafer 200 via nozzle 249a, and exhausted from the exhaust port 231a (barrier gas supply). At this time, valves 243g to 243i may also be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0066] Examples of processing conditions for supplying the barrier gas in this step include: Processing pressure: 1–10000 Pa, preferably 10–1333 Pa Impeding gas supply flow rate: 0.001–2 slm, preferably 0.01–1 slm Gas supply obstruction time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0067] Through this step, the hindering group 13, which prevents the adsorption of the first gas to the wafer 200, can be adsorbed onto adsorption sites present on the surface of the wafer 200 where a layer containing the second element is formed (see [link to relevant documentation]). Figure 3 (C-1) Figure 3(C-2) Specifically, this allows the barrier group 13 to be discontinuously adsorbed onto at least a portion of the surface of the wafer 200. In this case, the barrier group 13 preferentially adsorbs onto regions where gas supply is easy, compared to regions where gas supply is difficult. Specifically, for example, the barrier group 13 preferentially adsorbs onto the ends of the wafer 200 closer to the gas supply hole 250a, compared to the central portion of the wafer 200 farther from the gas supply hole 250a. Here, the barrier group 13 is formed by adsorbing at least a portion of its gas-blocking molecular structure onto the wafer 200.

[0068] As a barrier gas, a halogen-containing gas containing at least one of Cl, F, Br, and I can be used. The halogen-containing gas has at least one of the halogen groups, such as Cl, F, Br, or I, as a functional group. Examples of barrier gases that can be used include: elemental gases of halogens such as fluorine (F₂), chlorine (Cl₂), bromine (Br₂), and iodine (I₂); interhalogen compound gases such as chlorine fluoride (ClF₃), bromine chloride (BrCl), iodine chloride (ICl), iodine fluoride (IF₅), bromine fluoride (BrF₃), and iodine bromide (IBr); hydrogen halide compound gases such as hydrogen chloride (HCl), hydrogen fluoride (HF), hydrogen bromide (HBr), and hydrogen iodide (HI); or gases composed of combinations of these gases.

[0069] In addition, as a blocking gas, a gas containing organic functional groups or a gas containing organic compounds can be used. As a gas containing organic compounds, a gas comprising at least any one of the group consisting of ether compounds, ketone compounds, amine compounds, organohydrazine compounds, and compounds having a cyclic structure in their molecular structure can be used. As a gas containing ether compounds, a gas comprising at least any one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, pyran, tetrahydropyran, etc. can be used. As a gas containing ketone compounds, a gas comprising at least any one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, etc. can be used. As a gas containing amine compounds, a gas comprising at least any one of methylamine compounds such as monomethylamine, dimethylamine, and trimethylamine, ethylamine compounds such as monoethylamine, diethylamine, and triethylamine, and methylethylamine compounds such as dimethylethylamine and methyldiethylamine can be used. As a gas containing organohydrazine compounds, a gas comprising at least any one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used. As a gas containing a compound with a cyclic structure, gases such as methoxycyclopentane, anisole, and propylene oxide, which have a cyclic structure containing at least one of cycloalkyl, benzene ring, or carbon in their molecular structure, can be used. One or more of these can be used as a barrier gas. Alkyl-containing gases containing alkyl groups can also be used. Methane (CH4), ethane (C2H6), and propane (C3H8) can be used as barrier gases.

[0070] As the barrier gas, it is preferable to use a gas that does not contain atoms of the first element contained in the first gas. This further reduces the concentration rise of the first element at locations where the gas is readily supplied, thus allowing for the formation of a layer with a uniform amount of the first element.

[0071] After the barrier group 13 is adsorbed onto the surface of the wafer 200, valve 243d is closed to stop the supply of barrier gas to the processing chamber 201. Then, vacuum degassing and purging of the processing chamber 201 are performed in the same manner as in step b1.

[0072] [Step a2] Following step a1, a promoting gas is supplied to the wafer 200 within the processing chamber 201 after the adsorption of the barrier groups 13 on its surface. Specifically, valve 243e is opened to allow the promoting gas to flow into the gas supply pipe 232b. The promoting gas flow rate is regulated using MFC 241e, and it is supplied to the processing chamber 201 and the wafer 200 via nozzle 249b, and exhausted from exhaust port 231a (promoting gas supply). At this time, valves 243g to 243i can also be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0073] Examples of processing conditions for supplying the promoting gas in this step include: Processing pressure: 1–10000 Pa, preferably 10–1333 Pa Promote gas supply flow rate: 1-30 slm, preferably 2-20 slm Gas supply time: 1 to 120 seconds, preferably 1 to 30 seconds.

[0074] Through this step, the promoting group 14 can be adsorbed onto at least a portion of the surface of the wafer 200. At this time, the formation of the promoting group 14 based on the promoting gas is hindered by the hindering group 13. Therefore, the promoting group 14 that promotes the adsorption of the first gas onto the wafer 200 can be adsorbed onto the adsorption sites of the unadsorbed hindering groups 13 on the surface of the wafer 200. That is, the promoting group 14 can be adsorbed in the gaps between the hindering groups 13 (see...). Figure 3 (D-1) Figure 3 (D-2)). Thus, it is possible to suppress the increase in the amount of the first gas adsorbed at the site where the gas is easily supplied.

[0075] Furthermore, in this step, by supplying a sufficient amount of promoting gas relative to the surface area of ​​the wafer 200, more promoting groups 14 can be formed in areas where it is difficult to form barrier groups 13 or where gas supply is difficult. Specifically, for example, compared to the end of the wafer 200 closer to the gas supply hole 250b, the promoting groups 14 are preferentially adsorbed in the central portion of the wafer 200 farther from the gas supply hole 250b. Therefore, it is preferable that the supply of promoting gas continues until the reaction with the surface of the wafer 200 is saturated, so that promoting groups are sufficiently formed even in areas where gas supply is difficult.

[0076] The promoting group 14 is preferably formed by adsorbing at least a portion of the molecular structure of the promoting gas onto a region on the wafer 200 where the hindering group 13 is not formed. In this case, the first gas can be easily adsorbed in the region between the hindering groups 13.

[0077] It should be noted that the gases used as both the promoting and hindering gases are preferably configured such that the molecular size of the promoting gas is smaller than that of the hindering gas. That is, the molecular radius of the promoting gas is preferably smaller than that of the hindering gas. This makes it easier for the promoting group 14 to adsorb the first gas in the region between the hindering groups 13.

[0078] As a promoting gas, for example, a gas containing two or more OH bonds in its molecular structure, or a gas containing two or more NH bonds in its molecular structure, can be used. For example, a gas containing H₂O, H₂O₂, etc., can be used. For example, a gas containing NH₃, etc., can be used as a promoting gas.

[0079] After the promoting groups are formed on the surface of the wafer 200, valve 243e is closed to stop the supply of promoting gas to the processing chamber 201. Then, vacuum exhaust and purging of the processing chamber 201 are performed in the same manner as in step b1.

[0080] [Step a3] Following step a2, a first gas (dopant) is supplied to the wafer 200 within the processing chamber 201, after which barrier groups 13 and promoter groups 14 are adsorbed onto the surface. Specifically, valve 243a is opened, allowing the first gas to flow into the gas supply pipe 232a. The first gas is regulated by MFC 241a and supplied to the processing chamber 201 and the wafer 200 via nozzle 249a, and exhausted from exhaust port 231a (first gas supply). At this time, valves 243g to 243i may also be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0081] Examples of processing conditions for supplying the first gas in this step include: Processing pressure: 1–10000 Pa, preferably 10–1333 Pa First gas supply flow rate: 0.01–3 slm, preferably 0.1–2 slm First gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0082] As the first gas, a gas containing atoms of the first element can be used. Through this step, at least a portion of the first gas can be physically or chemically adsorbed onto the surface of the wafer 200 at sites where the hindering groups 13 are not adsorbed and where the promoting groups 14 are adsorbed. That is, it becomes easier for atoms 15 of the first element to adsorb in the gaps between the hindering groups 13 (see...). Figure 3 (E) in the middle.

[0083] Here, when gas is supplied from the end side of the wafer 200, gas is easily adsorbed on the end side of the wafer 200 closer to the gas supply holes 250a-250c, while gas is not easily adsorbed on the central part side of the wafer 200 farther from the gas supply holes 250a-250c. In this method, before supplying the first gas to the wafer 200, a barrier gas that hinders the adsorption of the first gas is supplied, so that more barrier groups 13 are adsorbed on the end side of the wafer 200 where gas is easily adsorbed than on the central part side. Then, a promoting gas that promotes the adsorption of the first gas is supplied until saturation, thereby causing the promoting groups 14 to adsorb in the barrier groups 13 and the gaps. At this time, more promoting groups 14 are adsorbed on the central part side of the wafer 200 where there are fewer barrier groups 13 than on the end side. Then, by supplying the first gas thereafter, atoms 15 of the first element can be adsorbed on the central part side of the wafer 200 where there are more promoting groups 14, thereby forming the third layer 16.

[0084] As the first element, one or more of the elements exemplified as the second element may be used, for example. As the first gas, one or more of the gases exemplified as the second element may be used, for example. As described above, in the case of forming a layer containing the second element and containing a trace amount of the first element on the wafer 200, it is preferable to use a gas that does not contain the second element as the first element.

[0085] After the third layer 16 is formed on the surface of the wafer 200, valve 243a is closed to stop the supply of the first gas into the processing chamber 201. Then, vacuum exhaust and purging of the processing chamber 201 are performed in the same manner as in step b1.

[0086] [Step a4] Following step a3, a removal gas is supplied to the wafer 200, where the third layer 16 has been formed on its surface, within the processing chamber 201. Specifically, valve 243f is opened to allow the removal gas to flow into the gas supply pipe 232c. The removal gas flow rate is regulated using MFC 241f, and it is supplied to the processing chamber 201 and the wafer 200 via nozzle 249c, and exhausted from exhaust port 231a (removal gas supply). At this time, valves 243g to 243i can also be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c, respectively.

[0087] Examples of processing conditions for supplying the removed gas in this step include: Processing pressure: 1–10000 Pa, preferably 10–1333 Pa Gas supply flow rate: 1–30 slm, preferably 2–20 slm Gas supply time: 1 to 120 seconds, preferably 1 to 30 seconds.

[0088] This step removes at least a portion of the barrier groups 13 on the surface of wafer 200, and modifies the third layer 16 containing atoms 15 of the first element into a fourth layer 17 (see [link]). Figure 3 (F)). This makes it less likely that components from the hindering group 13 will be included in layer 19 containing the first and second elements. Furthermore, in the following step b1, the physical or chemical adsorption of the second gas on the wafer 200 can be promoted. This step is preferably continued until the reaction between the removed gas and the surface of the wafer 200 is saturated. Therefore, components from the hindering group 13 are less likely to be included in layer 19, and the physical or chemical adsorption of the second gas on the wafer 200 can be promoted. For example, an oxidizing gas or a nitriding gas as described above can be used as the removed gas.

[0089] As the removal gas, a gas that more easily removes the hindering group 13 from the wafer 200 compared to the promoting gas used in step a2 is used. Therefore, since the hindering group 13 becomes less easily removed by the promoting gas, the first gas can be easily adsorbed in the region between the hindering groups 13. Furthermore, since the hindering group 13 is easily removed by the removal gas, the layer 19 containing the first and second elements is less likely to contain components from the hindering group 13. Additionally, in the following step b1, the physical or chemical adsorption of the second gas can be further promoted.

[0090] For example, a first oxidizing gas can be used as a removal gas, and a second oxidizing gas, different from the first oxidizing gas, can be used as a reacting gas. For example, when O3 is used as the second oxidizing gas, a mixture of O2, H2O, H2, and O2 can be used as the first oxidizing gas. Additionally, a nitriding gas can be used as a removal gas, and an oxidizing gas can be used as a reacting gas. For example, when a mixture of O2, H2O, H2, and O2 is used as the oxidizing gas, NH3 can be used as the nitriding gas. Furthermore, a first nitriding gas can be used as a removal gas, and a second nitriding gas, different from the first nitriding gas, can be used as a reacting gas. In the case of using, for example, NH3 as the second nitriding gas, N2H4 can be used as the first nitriding gas.

[0091] By performing steps a2 and a4 under the aforementioned processing conditions, the exposure amount of the removal gas to the wafer 200 in step a4 can be greater than the exposure amount of the promoting gas to the wafer 200 in step a2. Therefore, in step a2, it becomes difficult to remove the hindering group 13 by the promoting gas, while in step a4, it becomes easier to remove the hindering group 13 by the removal gas. Consequently, the layer 19 containing the first and second elements is less likely to contain components from the hindering group 13. Furthermore, in the subsequent step b1, the physical or chemical adsorption of the second gas can be further promoted.

[0092] In this specification, "gas exposure" refers to the value obtained by integrating the partial pressure of the gas over time. When the partial pressure of the gas is considered constant, it can be calculated as the product of the partial pressure of the gas and the gas supply time.

[0093] Here, it is preferable that the supply time of the desorbed gas in this step is longer than the supply time of the promoting gas in step a2. Furthermore, it is preferable that the processing pressure in this step is higher than the processing pressure in step a2. Furthermore, it is preferable that the supply flow rate of the desorbed gas in this step is greater than the supply flow rate of the promoting gas in step a2. Furthermore, it is preferable that the supply flow rate of the inactive gas in this step is less than the supply flow rate of the inactive gas in step a2. Furthermore, it is preferable that the partial pressure of the desorbed gas in this step is higher than the partial pressure of the promoting gas in step a2. Furthermore, it is preferable that the mole fraction of the desorbed gas in this step is greater than the mole fraction of the promoting gas in step a2. By implementing one or more of these measures, the exposure amount of the desorbed gas to the wafer 200 in step a4 can be greater than the exposure amount of the promoting gas to the wafer 200 in step a2.

[0094] After the surface of wafer 200 is saturated with the removal gas to form the fourth layer 17, valve 243f is closed to stop the supply of removal gas to the processing chamber 201. Then, vacuum exhaust and purging of the processing chamber 201 are performed in the same manner as in step b1.

[0095] [Number of times stipulated for implementation] By performing the second cycle of steps a1 to a4 in sequence n times (n is an integer of 1 or 2 or more), the fourth layer 17 of the desired film thickness can be formed on the surface of the wafer 200 as a layer containing the first element.

[0096] For example, when the removal gas is set to an oxidizing gas, an oxide layer containing the first element can be formed on the wafer 200. For example, when using an Al-containing gas as the first gas and an oxidizing gas as the removal gas, an oxide layer (AlO layer) containing aluminum can be formed on the wafer 200.

[0097] [Number of times stipulated for implementation] Then, steps b and a are performed a predetermined number of times (p times, where p is an integer of 1 or 2 or higher), wherein step b is the first cycle of performing steps b1 and b2 sequentially performed m times, and step a is the second cycle of performing steps a1 to a4 sequentially performed n times. Thus, on the surface of wafer 200, at least a portion of the second gas is physically or chemically adsorbed onto the fourth layer 17 to form a fifth layer 18, and a layer 19 containing the first element and the second element (see...). Figure 3 (G) Figure 3 (H) in the middle.

[0098] Therefore, while suppressing the increase in the concentration of the first element in the layer 19 containing the first and second elements, the difference in the adsorption amount of the first element atoms 15 between the regions where the first gas is easily supplied and the regions where the first gas is not easily supplied can be reduced. Thus, a homogeneous film containing the second element and uniformly supplemented with trace amounts of the first element can be formed on the wafer 200.

[0099] For example, when using an Al-containing gas as the first gas, an oxidizing gas as the removal gas, an Hf-containing gas as the second gas, and an oxidizing gas as the reaction gas, a hafnium oxide layer (HfO layer) with a trace amount of Al added (doped) can be formed on the wafer 200.

[0100] (Post-purge and atmospheric pressure recovery) After the film formation process is completed, the treatment chamber 201 is purged (post-purging) using the same procedure as in step b1. Then, the atmosphere in the treatment chamber 201 is replaced with an inactive gas (inactive gas replacement), and the pressure in the treatment chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration).

[0101] (Crystal boat unloading and wafer removal) The sealing cover 219 is lowered by the crystal boat lift 115, opening the lower end of the manifold 209, and the crystal boat 217 is moved outside the reaction tube 203 (crystal boat unloading). Then, the gate 219s is moved, sealing the lower end opening of the manifold 209 with an O-ring 220c (gate closing). After the processed wafer 200 is moved outside the reaction tube 203, it is removed from the crystal boat 217 (wafer removal).

[0102] <Other aspects of the invention> Next, use Figure 4 (A) ~ Figure 4In section (C), a case is described in which grooves, slots, holes, and other recesses that are three-dimensional structures are formed on the surface of the wafer 200, and a layer 19 containing the first element and the second element is formed in the recesses, that is, a layer 19 containing the second element with a trace amount of the first element added.

[0103] As described above, when a layer 19 containing a second element and a trace amount of a first element is formed in the recess of the wafer 200, the first gas is easily supplied to the opening side but not easily supplied to the deep side. Therefore, the concentration of the first element on the opening side of the recess becomes higher, and the concentration of the first element on the deep side of the recess becomes lower.

[0104] Through step a1 described above, the barrier group 13 is adsorbed into the recess of the wafer 200. At this time, the opening side of the recess is easily supplied with barrier gas, thus the barrier group 13 is easily formed, while the deep side of the recess is not easily supplied with barrier gas, thus the barrier group 13 is not easily formed. That is, compared with the deep side of the recess, the barrier group 13 is preferentially adsorbed on the opening side of the recess.

[0105] Next, through step a2 described above, the promoting group 14 is adsorbed into the recess of the wafer 200. At this time, the opening side of the recess is easily supplied with promoting gas, but the adsorption of the promoting group 14 is hindered by the blocking group 13 formed on the opening side. The deeper side of the recess is not easily supplied with promoting gas, but it is supplied until the reaction is saturated, thus not easily hindering the adsorption of the promoting group 14 (see...). Figure 4 (A)). That is, the promoting group 14 is not easily adsorbed on the opening side of the recess, but is easily adsorbed on the deep side of the recess. In other words, regarding the promoting group 14, compared with the opening side of the recess, the promoting group 14 is preferentially adsorbed on the deep side of the recess.

[0106] Next, following step a3 above, at least a portion of the first gas is physically or chemically adsorbed into the recess of the wafer 200, forming a third layer 16. At this time, on the opening side of the recess, the physical or chemical adsorption of the first gas is hindered by the hindering groups 13 formed on the opening side; on the deep side of the recess, the physical or chemical adsorption of the first gas is promoted by the promoting groups 14 formed on the deep side (see...). Figure 4 (B) in the middle.

[0107] Next, by performing step a4 above, at least a portion of the hindering group 13 within the recess is removed, thus modifying the third layer 16. Then, by performing step a (the step of performing steps a1 to a4 a predetermined number of times) and step b (the step of performing steps b1 and b2 a predetermined number of times) a predetermined number of times, a layer 19 containing a second element and uniformly supplemented with trace amounts of the first element is formed within the recess of the wafer 200. Figure 4(C) in the middle.

[0108] In this method, the same effect as described above can be obtained. That is, since the concentration of the first element at the opening side of the recess, where gas is easily supplied, can be reduced, a layer 19 containing the second element, in which a trace amount of the first element is uniformly added (doped), can be formed on the surface of the wafer 200. In this method, the concentration difference of the first element in the layer containing the first and second elements can also be reduced between the opening side and the deep side of the recess. That is, a homogeneous film can be formed on the wafer 200.

[0109] The foregoing has specifically described the methods of the present invention. However, the present invention is not limited to the methods described above, and various modifications can be made without departing from its spirit.

[0110] The process for each process is preferably prepared separately according to the processing content, and recorded and stored in the storage device 121c via an electrical communication line, an external storage device 123. Furthermore, when starting each process, the CPU 121a preferably selects an appropriate process from the multiple processes recorded and stored in the storage device 121c according to the processing content. This allows for the reproducible formation of films of various types, compositions, qualities, and thicknesses using a single substrate processing device. Additionally, it reduces the operator's workload, enabling rapid initiation of each process while minimizing operational errors.

[0111] The aforementioned process is not limited to the case of new fabrication; for example, it can also be prepared by modifying an existing process already installed in the substrate processing apparatus. In the case of process modification, the modified process can also be installed in the substrate processing apparatus via an electrical communication line and a recording medium containing the process. Alternatively, the existing process already installed in the substrate processing apparatus can be directly modified by operating the input / output device 122 of the existing substrate processing apparatus.

[0112] In the above-described method, an example of forming a layer using a batch substrate processing apparatus that processes multiple substrates at a time has been described. The present invention is not limited to the above-described method; for example, it can also be appropriately applied to the case of forming a layer using a single-sheet substrate processing apparatus that processes one or more substrates at a time. Furthermore, in the above-described method, an example of forming a layer using a substrate processing apparatus with a hot-wall type processing furnace has been described. The present invention is not limited to the above-described method; it can also be appropriately applied to the case of forming a layer using a substrate processing apparatus with a cold-wall type processing furnace. Furthermore, in the above-described method, an example of activating gas by heat has been described. However, the present invention is not limited to this. For example, it can also be appropriately applied to the case of activating gas by plasma generated inside or outside the processing chamber 201, or by activating gas by irradiating it with electromagnetic waves using a lamp or the like.

[0113] When using these substrate processing devices, each process can be performed with the same processing steps and conditions as described above, and the same effect as described above can be obtained.

[0114] In the above description, the process sequence of forming a layer containing a second element and a first element with trace amounts of a first element added (doped) on wafer 200 was described as an example. However, the present invention is not limited to this. For example, even when using a gas containing the same element as the first element as the second element as the second gas, the same effect as described above can be obtained. In this case, since the first element adsorbed on wafer 200 can be homogenized, a layer (or film) of uniform thickness can be formed on the surface of wafer 200, that is, a homogeneous film can be formed.

[0115] The above methods can be used in combination as appropriate. In this case, the processing steps and conditions can be set to be the same as those in the methods described above.

Claims

1. A substrate processing method comprising: (a) performing the steps described below (a1), (a2), and (a3) ​​to form a layer comprising a first element on a substrate, (a1) The step of supplying a barrier gas to the substrate and forming barrier groups on the substrate, wherein, The barrier group prevents the adsorption of the first gas containing atoms of the first element onto the substrate; (a2) A step of supplying a promoting gas to the substrate and forming a promoting group on the substrate, which is later than the start of (a1), wherein the promoting group promotes the adsorption of the first gas onto the substrate; (a3) is the process of supplying the first gas to the substrate after (a2).

2. The substrate processing method according to claim 1, further comprising: (b) a step of forming a layer comprising the second element on the substrate by performing a predetermined number of cycles comprising (b1) and (b2) below, (b1) A step of supplying the substrate with a second gas containing atoms of the second element, wherein, The second element is an element that is different from the first element; (b2) The process of supplying the reactant gas to the substrate, In the substrate processing method, by performing (a) and (b), a layer comprising the first element and the second element is formed on the substrate.

3. The substrate processing method according to claim 1 or 2, wherein, (a) also includes: (a4) is a step that, after the start of (a3), supplies a removal gas to the substrate to remove at least a portion of the barrier groups on the substrate.

4. The substrate processing method according to claim 3, wherein, The exposure of the substrate to the removal gas in (a4) is greater than the exposure of the substrate to the promoting gas in (a2).

5. The substrate processing method according to claim 3 or 4, wherein, As the removal gas, a gas that is more likely to remove the hindering groups from the substrate compared to the promoting gas is used.

6. The substrate processing method according to any one of claims 3 to 5, wherein, Specifically, a first oxidizing gas is used as the removal gas, and a second oxidizing gas, different from the first oxidizing gas, is used as the reaction gas.

7. The substrate processing method according to any one of claims 3 to 5, wherein, Specifically, nitriding gas is used as the removal gas, and oxidizing gas is used as the reaction gas.

8. The substrate processing method according to any one of claims 3 to 5, wherein, Specifically, a first nitriding gas is used as the removal gas, and a second nitriding gas, different from the first nitriding gas, is used as the reaction gas.

9. The substrate processing method according to any one of claims 3 to 8, wherein, (a4) is carried out until the reaction between the removed gas and the surface of the substrate is saturated.

10. The substrate processing method according to any one of claims 1 to 9, wherein, (a2) is carried out until the reaction between the promoting gas and the surface of the substrate is saturated.

11. The substrate processing method according to any one of claims 1 to 10, wherein, The hindering gas does not contain atoms of the first element.

12. The substrate processing method according to any one of claims 1 to 11, wherein, The barrier groups are formed by adsorbing at least a portion of the molecular structure of the barrier gas onto the substrate. The promoting group is formed by at least a portion of the molecular structure of the promoting gas being adsorbed onto regions of the substrate where the hindering group has not formed.

13. The substrate processing method according to any one of claims 1 to 12, wherein, The gas used as both the promoting gas and the hindering gas is configured such that the molecular size of the promoting gas is smaller than that of the hindering gas.

14. The substrate processing method according to any one of claims 1 to 13, wherein, The hindering gas is a gas containing functional groups of organic systems.

15. The substrate processing method according to any one of claims 1 to 14, wherein, The promoting gas is a gas containing two or more OH bonds in its molecular structure, or a gas containing two or more NH bonds in its molecular structure.

16. The substrate processing method according to any one of claims 1 to 15, wherein, A recess is formed on the surface of the substrate.

17. A method for manufacturing a semiconductor device, comprising: (a) a step of forming a layer comprising a first element on a substrate by performing the steps described in (a1), (a2), and (a3) ​​below. (a1) The step of supplying a barrier gas to the substrate and forming barrier groups on the substrate, wherein, The barrier group prevents the adsorption of the first gas containing atoms of the first element onto the substrate; (a2) A step of supplying a promoting gas to the substrate and forming a promoting group on the substrate, which is later than the start of (a1), wherein the promoting group promotes the adsorption of the first gas onto the substrate; (a3) is the process of supplying the first gas to the substrate after (a2).

18. A substrate processing apparatus, comprising: A gas supply system for supplying a barrier gas, a promoting gas, and a first gas containing atoms of the first element to a substrate; and The control unit is configured to control the gas supply system in a manner described in (a), whereby (a) is a process of forming a layer containing the first element on the substrate by performing (a1), (a2), and (a3) ​​as described below. (a1) A process of supplying the barrier gas to the substrate and forming barrier groups on the substrate, the barrier groups preventing the adsorption of the first gas onto the substrate; (a2) A process in which the promoting gas is supplied to the substrate later than (a1) to form promoting groups on the substrate, wherein, The promoting group promotes the adsorption of the first gas onto the substrate; (a3) The process of supplying the first gas to the substrate is performed after (a2).

19. A process product which, by means of a computer, causes a substrate processing apparatus to perform (a) the steps of (a1), (a2), and (a3) ​​described below to form a layer containing the first element on a substrate. (a1) The step of supplying a barrier gas to the substrate and forming barrier groups on the substrate, wherein, The barrier group prevents the adsorption of the first gas containing atoms of the first element onto the substrate; (a2) A step of supplying a promoting gas to the substrate and forming a promoting group on the substrate, which is later than the start of (a1), wherein the promoting group promotes the adsorption of the first gas onto the substrate; (a3) The step of supplying the first gas to the substrate after the start of (a2).

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