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

Abstract

To provide a technique capable of selectively processing a desired surface among inner surfaces of a recess formed in a substrate.SOLUTION: (a) providing a substrate having a first end and a second end, the first end defining at least a portion of an inner surface of a recess, the second end being different from the first end; and (b) exposing the substrate to a treatment solution comprising a liquid reactive with the first end and an additive that reduces the surface tension of the liquid, thereby selectively removing the first end relative to the second end.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a program, and a substrate processing apparatus. [Background technology]

[0002] BACKGROUND ART As one step in the manufacturing process of a semiconductor device, a substrate having recesses formed on its surface may be subjected to a predetermined treatment (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2023-123717 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that enables selective processing of a desired surface among the inner surfaces of a recess formed in a substrate. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a) a first surface having a first termination and constituting at least a portion of an inner surface of the recess; a second surface having a second termination different from the first termination; providing a substrate comprising: (b) selectively removing the first termination relative to the second termination by exposing the substrate to a treatment liquid comprising a liquid reactive with the first termination and an additive that reduces the surface tension of the liquid; The present invention provides a technique having the following. [Effects of the Invention]

[0006] According to the present disclosure, it is possible to selectively process a desired surface among the inner surfaces of a recess formed in a substrate. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram of a substrate processing apparatus 100 that is preferably used in one embodiment of the present disclosure. [Figure 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a film forming apparatus 500 provided in the substrate processing apparatus 100 suitably used in one embodiment of the present disclosure, and is a vertical cross-sectional view of the processing furnace 202 portion. [Figure 3] FIG. 3 is a schematic configuration diagram of a vertical processing furnace of a film forming apparatus 500 provided in the substrate processing apparatus 100 suitably used in one embodiment of the present disclosure, and is a cross-sectional view of the processing furnace 202 taken along line AA in FIG. [Figure 4] FIG. 4 is a schematic diagram of a cleaning apparatus 600 provided in the substrate processing apparatus 100 suitably used in one embodiment of the present disclosure. [Figure 5] FIG. 5 is a schematic configuration diagram of the controller 121 of the substrate processing apparatus 100 suitably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. [Figure 6] Fig. 6(a) is a schematic cross-sectional view showing the surface portion of a wafer 200 having recesses on the surface, first underlayers arranged on the inner surfaces of the recesses, and second underlayers arranged on the upper surfaces of the recesses. Fig. 6(b) is a schematic cross-sectional view showing the surface portion of a wafer 200 having recesses on the surface, and first underlayers and second underlayers arranged alternately on the inner surfaces of the recesses. [Figure 7]FIG. 7(a) is a partial enlarged cross-sectional view showing a surface portion of a wafer 200 according to an embodiment of the present disclosure, having a recess on its surface. FIG. 7(b) is a partial enlarged cross-sectional view showing a surface portion of a wafer 200 according to an embodiment of the present disclosure after step a1 has been performed from the state of FIG. 7(a). FIG. 7(c) is a partial enlarged cross-sectional view showing a surface portion of a wafer 200 according to an embodiment of the present disclosure after step a3 has been performed from the state of FIG. 7(b). FIG. 7(d) is a partial enlarged cross-sectional view showing a surface portion of a wafer 200 according to an embodiment of the present disclosure after step a2 has been performed from the state of FIG. 7(c). FIG. 7(e) is a partial enlarged cross-sectional view showing a surface portion of a wafer 200 according to an embodiment of the present disclosure after step B has been performed from the state of FIG. 7(d). FIG. 7(f) is a partial enlarged cross-sectional view showing a surface portion of a wafer 200 according to an embodiment of the present disclosure after step C has been performed from the state of FIG. 7(e). DETAILED DESCRIPTION OF THE INVENTION

[0008] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described with reference to the drawings. Note that all drawings used in the following description are schematic, and the dimensional relationships, ratios, etc. of elements shown in the drawings do not necessarily match those of reality. Furthermore, the dimensional relationships, ratios, etc. of elements between multiple drawings do not necessarily match.

[0009] (1) Configuration of the Substrate Processing Apparatus 100 As shown in FIG. 1, the substrate processing apparatus 100 mainly includes a film forming apparatus 500, a cleaning apparatus 600, and a transfer chamber 700.

[0010] The film forming apparatus 500 is an apparatus that performs a film forming process on the wafer 200 in the substrate processing process described below. The cleaning apparatus 600 is an apparatus that performs a cleaning process on the wafer 200 in the substrate processing process described below. The transfer chamber 700 is an area where the wafer 200 is transferred between the film forming apparatus 500 and the cleaning apparatus 600.

[0011] (i) Configuration of the film forming apparatus 500 2, the process furnace 202 has a heater 207 as a temperature control unit (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gases with heat.

[0012] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 has a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a serving as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to accommodate wafers 200 as substrates. In this processing chamber 201, processing of a wafer 200 is performed.

[0013] Nozzles 249a and 249b serving as a first supply unit and a second supply unit are provided in the processing chamber 201, respectively, so as to penetrate the sidewall of the manifold 209. The nozzles 249a and 249b are also referred to as a first nozzle and a second nozzle, respectively. The nozzles 249a and 249b are made of a heat-resistant material such as quartz or SiC. The nozzles 249a and 249b are each configured as a shared nozzle used to supply multiple types of gases.

[0014] Gas supply pipes 232a and 232b serving as first and second pipes are connected to the nozzles 249a and 249b, respectively. The gas supply pipes 232a and 232b are configured as shared pipes used to supply multiple types of gases. Mass flow controllers (MFCs) 241a and 241b, which are flow rate controllers (flow rate control units), and valves 243a and 243b, which are on-off valves, are respectively provided on the gas supply pipes 232a and 232b, in this order from the upstream side of the gas flow. Gas supply pipes 232c and 232d are respectively connected to the gas supply pipe 232a downstream of the valve 243a. MFCs 241c and 241d and valves 243c and 243d are respectively provided on the gas supply pipes 232c and 232d, in this order from the upstream side of the gas flow. A gas supply pipe 232e is connected to the gas supply pipe 232b downstream of the valve 243b. The gas supply pipe 232e is provided with an MFC 241e and a valve 243e in this order from the upstream side of the gas flow.

[0015] As shown in FIG. 3 , the nozzles 249a and 249b are provided in the space between the inner wall of the reaction tube 203 and the wafers 200, extending from the bottom to the top of the inner wall of the reaction tube 203 and rising upward in the arrangement direction of the wafers 200. That is, the nozzles 249a and 249b are provided in regions horizontally surrounding the wafer arrangement region on the sides of the wafer arrangement region where the wafers 200 are arranged, extending along the wafer arrangement region. Gas supply holes 250a and 250b for supplying gas are provided on the side surfaces of the nozzles 249a and 249b, respectively. The gas supply holes 250a and 250b each open toward the center of the wafer 200 in a plan view, allowing gas to be supplied toward the wafer 200. A plurality of gas supply holes 250a and 250b are provided from the bottom to the top of the reaction tube 203.

[0016] From the gas supply pipe 232a, a raw material serving as a film forming agent is supplied into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0017] An oxidizing agent serving as a film forming agent is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0018] The first and second modifying agents are supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249a.

[0019] Inert gas is supplied from the gas supply pipes 232d and 232e through the MFCs 241d and 241ef, the valves 243d and 243e, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0020] A raw material supply system is mainly composed of the gas supply pipe 232a, MFC 241a, and valve 243a. An oxidizing agent supply system is mainly composed of the gas supply pipe 232b, MFC 241b, and valve 243b. A modifying agent (first and second modifying agents) supply system is mainly composed of the gas supply pipe 232c, MFC 241c, and valve 243c. An inert gas supply system is mainly composed of the gas supply pipes 232d and 232e, MFCs 241d and 241e, and valves 243d and 243e. The raw material supply system and oxidizing agent supply system are also collectively referred to as a film-forming agent supply system. Nozzles connected to the gas supply pipes constituting the various supply systems described above may also be included in the supply systems.

[0021] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a to 243e, the MFCs 241a to 241e, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232e, and is configured such that the supply operation of various substances (various gases) into the gas supply pipes 232a to 232e, that is, the opening and closing operation of the valves 243a to 243e and the flow rate adjustment operation by the MFCs 241a to 241e, are controlled by a controller 121, which will be described later.

[0022] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the bottom of the sidewall of the reaction tube 203. As shown in FIG. 3, the exhaust port 231a is provided at a position facing the nozzles 249a and 249b (gas supply holes 250a and 250b) across the wafer 200 in a plan view. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 serving as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (pressure detection unit) that detects the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure adjustment unit). The APC valve 244 can evacuate and stop the evacuation inside the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. A vacuum pump 246 may be included in the exhaust system.

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating a boat 217 (described later). A rotation shaft 255 of the rotation mechanism 267 penetrates the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 serving as an elevating mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that raises and lowers the seal cap 219 to load and unload (transfer) the wafers 200 into and out of the process chamber 201.

[0024] A shutter 219s serving as a furnace port cover is provided below the manifold 209, and is capable of airtightly closing the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is carried out of the processing chamber 201. An O-ring 220c serving as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the shutter 219s. The opening and closing operation (lifting and lowering operation, rotation operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0025] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals, in multiple stages. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported in multiple stages.

[0026] A temperature sensor 263 serving as a temperature detector is installed inside the reaction tube 203. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 can be adjusted to a desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] (ii) Configuration of the cleaning device 600 As shown in FIG. 4, the cleaning apparatus 600 includes a processing bath 610. The processing bath 610 can accommodate one or more wafers 200. A processing liquid supply pipe 640 is connected to a processing liquid tank (not shown) via a liquid mass flow controller (LMFC) 650, and is configured to supply the processing liquid into the processing bath 610. The processing bath 610 stores a processing liquid for exposure, and the wafers 200 are immersed in the processing liquid. The processing liquid supply pipe 640 and the LMFC 650 configure a processing liquid supply system that supplies the processing liquid to the wafers 200. The processing liquid supply system may further include the processing bath 610. The cleaning apparatus 600 includes a temperature sensor 620 that detects the temperature of the processing liquid and a heater 630 that adjusts the temperature of the processing liquid. The temperature sensor 620 is installed along the inner wall of the processing bath 610. The heater 630 is disposed near the processing bath 610 and is configured to maintain the processing liquid in the processing bath 610 at an appropriate temperature based on the temperature sensor 620 .

[0028] (iii) Configuration of the transfer chamber 700 1, the transfer chamber 700 is configured between the film forming apparatus 500 and the cleaning apparatus 600. A transfer mechanism 750 for transferring the wafer 200 is provided inside the transfer chamber 700. The transfer mechanism 750 places the wafer 200 on a substrate placement portion provided on an arm, and transfers the wafer 200 between the film forming apparatus 500 and the cleaning apparatus 600.

[0029] (iv) Control Unit As shown in FIG. 5, the controller 121, which is a control unit (control means) for the film forming apparatus 500, the cleaning apparatus 600, and the transfer chamber 700, 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 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. An external storage device 123 can also be connected to the controller 121. The substrate processing apparatus 100 may be configured to include one or more control units. That is, the control for performing the processing sequence described below may be performed using one or more control units. Furthermore, the multiple control units may be configured as a control system connected to each other via a wired or wireless communication network, and the control for carrying out the processing sequence described below may be performed by the entire control system. When the term "control unit" is used in this specification, it may include one control unit, multiple control units, or a control system configured by multiple control units.

[0030] The storage device 121c includes, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. Control programs for controlling the operation of the substrate processing apparatus 100 and process recipes describing procedures and conditions for substrate processing (described later) are readably recorded and stored in the storage device 121c. The process recipe is a combination of procedures for substrate processing (described later) that are executed by the controller 121 in the substrate processing apparatus 100 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipes, control programs, etc. are collectively referred to simply as programs (program products). The process recipes are also simply referred to as recipes. In this specification, the term "program" may refer to a recipe alone, a control program alone, or both. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0031] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241e, valves 243a to 243e, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensors 263 and 620, heaters 207 and 630, transfer mechanism 750, and the like.

[0032] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241e, the opening and closing operation of the valves 243a to 243e, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heaters 207, 630 based on the temperature sensors 263, 620, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, the operation of the transfer mechanism 750, and the like.

[0033] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, or a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both. Note that the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0034] (2) Substrate processing process This section describes a method for processing a substrate using the substrate processing apparatus 100 described above as one step in a semiconductor device manufacturing process. Specifically, this describes an example of a processing sequence for forming a film on the first surface of a wafer 200, which has a first surface and a second surface. In this embodiment, steps A, B, and C, which will be described later, are performed in this order. In step A, a wafer 200 is prepared, which includes a first surface having a first end and constituting at least a portion of the inner surface of a recess, and a second surface having a second end different from the first end (preparation step). In step B, the wafer 200 is exposed to a processing liquid containing a liquid that reacts with the first end and an additive that reduces the surface tension of the liquid, thereby selectively removing the first end relative to the second end (removal step). In step C, a film-forming agent is supplied to the wafer 200, thereby selectively forming a film on the first surface (film formation step). Step A is performed in the film formation apparatus 500, step B in the cleaning apparatus 600, and step C in the film formation apparatus 500. In the following description, the operation of each component of the substrate processing apparatus 100 is controlled by a controller 121 .

[0035] In this specification, the meanings of "selectively remove" and "selectively process" are not limited to cases where removal or processing is performed on only one side and no removal or processing is performed on the other side. This meaning also includes cases where the amount, speed, probability, etc. of removal or processing on one side is relatively greater than the amount, speed, probability, etc. of removal or processing on the other side. In other words, this meaning includes cases where removal or processing is performed preferentially on one side over the other side. Similarly, the meanings of "selectively form" and "selectively adsorb" are not limited to cases where formation or adsorption is performed on only one side and no formation or adsorption is performed on the other side. This meaning also includes cases where the amount, speed, probability, etc. of formation or adsorption on one side is relatively greater than the amount, speed, probability, etc. of formation or adsorption on the other side. In other words, this meaning includes cases where formation or adsorption is performed preferentially on one side over the other side.

[0036] In this embodiment, an example is described in which a wafer 200 is used in which a recess such as a trench, groove, or hole having a three-dimensional structure is formed on its surface. The inner surface of the recess formed in the wafer 200 has a first underlayer and a second underlayer, with the surface of the region where the first underlayer is formed constituting the first surface, and the surface of the region where the second underlayer is formed constituting the second surface (see FIGS. 6(a) and 6(b)). At least one region of the second surface on the inner surface of the recess is provided closer to the opening than the first surface. In the following, as an example, a case is described in which the first underlayer is a silicon oxide film (SiO film) and the second underlayer is a silicon nitride film (SiN film). Furthermore, the recess in this embodiment has a shape in which the width of at least one of the opening and the interior (particularly the width at the minimum width) is 100 μm or less, and the ratio of the width of the opening to the length in the depth direction of the recess (depth / width, i.e., aspect ratio) is 1 or more. In the following, a case where the width of the opening and the inside of the recess are both 100 μm or less and the aspect ratio is 1 or more will be particularly described.

[0037] As described above, step A in this embodiment includes: (a) a first surface having a first termination and constituting at least a portion of an inner surface of the recess; a second surface having a second termination different from the first termination; This is a step of preparing a wafer 200 including the above (see FIG. 7(d)).

[0038] In this embodiment, in step A, (a-1) Step a1 of forming a first termination on a first surface by supplying a first modifying agent to the wafer 200; (a-3) Step a3 of selectively forming a third termination on the second surface relative to the first surface; (a-2) Step a2 of supplying a second modifier to the wafer 200 to react the third termination with the second modifier to form a second termination on the second surface; A case where the above steps are performed in this order will be described (see FIGS. 7(b) to (d)).

[0039] In this embodiment, in step a3, (a-3a) Step a3a of supplying raw material to the wafer 200; (a-3b) Step a3b of supplying an oxidizing agent to the wafer 200; This section explains a case where an intermediate layer having a surface as a second surface on which a third termination is formed is formed by performing a cycle including the above a predetermined number of times (n1 times, where n1 is an integer of 1 or greater) (see Figure 7(c)).

[0040] As described above, step B in this embodiment includes: (b) selectively removing the first termination relative to the second termination by exposing the wafer 200 to a processing liquid containing a liquid that reacts with the first termination and an additive that reduces the surface tension of the liquid (see FIG. 7(e)).

[0041] As described above, step C in this embodiment includes: (c) A step of selectively forming a film on the first surface by supplying a film forming agent to the wafer 200 after step B has been performed (see FIG. 7(f)).

[0042] In this embodiment, in step C, Step c1 of supplying raw material to the wafer 200; Step c2 of supplying an oxidizing agent to the wafer 200; A case will be described in which a film is formed on the first surface by repeating a cycle including the above a predetermined number of times (n2 times, where n2 is an integer of 1 or 2 or more).

[0043] In this specification, the above-described processing sequence may be expressed as follows for convenience: Similar notations will be used in the following explanations of modified examples and other aspects.

[0044] First modifier → (raw material → purge → oxidizer → purge) × n1 → Second modifier → exposure to treatment liquid → (raw material → purge → oxidizer → purge) × n2

[0045] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0046] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. Liquid substances include mist substances. That is, each of the film-forming agent (raw material, oxidizing agent), the first modifier, and the second modifier may contain a gaseous substance, a liquid substance such as a mist substance, or both.

[0047] The term "layer" as used herein includes at least one of a continuous layer and a discontinuous layer. For example, the first to sixth layers and the intermediate layer may include a continuous layer, a discontinuous layer, or both.

[0048] In this specification, when we talk about the film-forming agent (raw material, oxidizing agent), the first modifier, and the second modifier respectively adsorbing to or reacting with the surface of the wafer 200, it may include not only the manner in which they adsorb to or react with the wafer surface without decomposing, but also the manner in which they decompose or the intermediates generated by the detachment of their ligands adsorb to or react with the surface of the wafer 200.

[0049] (Wafer charge and boat load) When a plurality of wafers 200 are loaded into the boat 217 by the transfer mechanism 750 (wafer charge), the shutter 219s is moved by the shutter opening / closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in Fig. 2, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0050] An SiO film as a first underlayer and an SiN film as a second underlayer are exposed on the surface of the wafer 200 loaded into the boat 217. In the wafer 200, the first surface has OH terminations, which are adsorption sites, over the entire area, while most areas of the second surface do not have OH terminations (see FIG. 7(a)).

[0051] (pressure and temperature regulation) After the boat loading is completed, the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so that the interior of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside 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 wafers 200 in the processing chamber 201 are heated by the heater 207 so that the desired processing temperature is reached. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the desired temperature distribution is achieved inside the processing chamber 201. The rotation mechanism 267 starts to rotate the wafers 200. The heater 630 is controlled based on temperature information detected by the temperature sensor 620 so that the processing liquid in the processing bath 610 is at a desired temperature. The evacuation inside the processing chamber 201, the heating and rotation of the wafers 200, and the temperature adjustment of the processing liquid are all continued at least until the processing of the wafers 200 is completed.

[0052] Thereafter, the following steps A, B, and C are executed in sequence. In step A, the following steps a1, a3, and a2 are executed in sequence.

[0053] [Step A: Preparation Process] (Step a1) In this step, the first modifying agent is supplied to the wafer 200 in the processing chamber 201.

[0054] Specifically, the valve 243c is opened to allow the first modifying agent to flow into the gas supply pipe 232c. The flow rate of the first modifying agent is adjusted by the MFC 241c, and the first modifying agent is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the first modifying agent is supplied to the wafer 200 (first modifying agent supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a and 249b, respectively.

[0055] In this step, the processing conditions for supplying the first modifier are as follows: Treatment temperature: 25 to 500°C, preferably 50 to 300°C Treatment pressure: 1 to 13,300 Pa, preferably 50 to 1,330 Pa First modifier supply flow rate: 0.01 to 3 slm, preferably 0.5 to 1 slm First modifier supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0056] In this specification, when a numerical range such as "25 to 500°C" is expressed, both the lower and upper limits are included in the range. For example, "25 to 500°C" means "25°C or higher and 500°C or lower." The same applies to other numerical ranges. In this specification, the process temperature refers to the temperature of the wafer 200 or the temperature inside the process chamber 201, and the process pressure refers to the pressure inside the process chamber 201, in other words, the pressure in the space in which the wafer 200 is present. The process time refers to the time the process continues. In addition, when the supply flow rate includes 0 slm, 0 slm means that the substance is not supplied. These terms also apply to the following explanations.

[0057] By supplying the first modifier to the wafer 200 under the above-described processing conditions, at least a portion of the molecular structure of the molecules constituting the first modifier is selectively (preferentially) adsorbed to the first surface, thereby selectively forming a first layer (first adsorption-suppressing layer) on the first surface. Specifically, while suppressing adsorption of at least a portion of the molecular structure of the molecules constituting the first modifier to the second surface, the OH terminations formed on the first surface are reacted with the first modifier, thereby selectively adsorbing at least a portion of the molecular structure of the molecules constituting the first modifier to the first surface. This makes it possible to terminate the first surface with at least a portion of the molecular structure of the molecules constituting the first modifier. Examples of at least a portion of the molecular structure of the molecules constituting the first modifier include a residue (e.g., Si—H) containing a bond between an atom (e.g., Si) that reacts with an OH termination and a hydrogen group (e.g., H group) and a residue (e.g., Si—OR) in which an atom that reacts with an OH termination is bonded to an alkoxy group. When the first surface is terminated with these residues, an H-terminus or an alkoxy group is formed as the first terminus (see FIG. 7(b)). The first terminus formed on the first surface acts as an inhibitor that inhibits the adsorption of the raw material, the second modifier, and the film-forming agent onto the first surface in steps a3, a2, and C described below.

[0058] Examples of the first modifier include tris(dimethylamino)silane (Si[N(CH3)2]3H), bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tertiarybutylamino)silane (SiH2[NH(C4H9)]2), (diisopropylamino)silane (SiH3[N(C3H7)2]), (diisobutylamino)silane (SiH3[N(C4H9)2]), (diisopentylamino)silane (SiH3[N(C5H 11 )2]), a substance in which hydrogen (H) and an amino group are bonded to Si, i.e., an aminosilane, can be used. In particular, it is preferable to use a substance in which three H and one amino group are bonded to Si, i.e., a monoaminosilane, such as (diisobutylamino)silane or (diisopropylamino)silane. By using a monoaminosilane as the first modifier, it is possible to form H terminations more uniformly and sufficiently on the first surface in this step.

[0059] Furthermore, as the first modifier, for example, a substance in which an alkoxy group and an amino group are bonded to Si, such as (dimethylamino)trimethoxysilane (Si(OCH3)3[N(CH3)2]), (dimethylamino)triethoxysilane (Si(OC2H5)3[N(CH3)2]), (dimethylamino)triprotoxysilane (Si(OC3H7)3[N(CH3)2]), or (dimethylamino)tributoxysilane (Si(OC4H9)3[N(CH3)2]), can be used. In particular, it is preferable to use a substance in which three alkoxy groups and one amino group are bonded to Si. By using such a substance as the first modifier, alkoxy group termination can be formed more uniformly and sufficiently on the first surface in this step.

[0060] As the first modifier, one or more of these can be used.

[0061] As the inert gas, nitrogen (N2) gas or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. One or more of these can be used as the inert gas. This also applies to each step described below.

[0062] After selectively forming a first termination on the first surface of the wafer 200 (the first surface constituting the inner surface of the recess), the valve 243c is closed to stop the supply of the first modifying agent into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201. At this time, the valves 243d and 243e are opened to supply an inert gas into the processing chamber 201 through the nozzles 249a and 249b. The inert gas supplied from the nozzles 249a and 249b acts as a purge gas, thereby purging the space in which the wafer 200 exists, i.e., the processing chamber 201.

[0063] The processing conditions for purging in step a1 are as follows: Treatment temperature: 25 to 500°C, preferably 50 to 300°C Treatment pressure: 1 to 1330 Pa, preferably 1 to 400 Pa Treatment time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0.5 to 10 slm, preferably 1 to 5 slm Inert gas supply time: 1 to 120 seconds is exemplified.

[0064] (Step a3) After step a1 is completed, raw material and oxidizing agent are supplied to the wafer 200. This selectively forms an oxide layer (intermediate layer) on the second surface. Specifically, in this step, the following steps a3a and a3b are sequentially performed.

[0065] [Step a3a] After step a1 is completed, a raw material is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the first termination has been selectively formed on the first surface that constitutes the inner surface of the recess.

[0066] Specifically, the valve 243a is opened to allow the raw material to flow into the gas supply pipe 232a. The raw material has a flow rate adjusted by the MFC 241a, is supplied into the processing chamber 201 through the nozzle 249a, and is exhausted from the exhaust port 231a. At this time, the raw material is supplied to the wafer 200 (raw material supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a and 249b, respectively.

[0067] The processing conditions for supplying the raw material in this step are as follows: Treatment temperature: room temperature to 600°C, preferably 50 to 400°C Treatment pressure: 1 to 101325 Pa, preferably 1 to 1300 Pa Raw material supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Raw material supply time: 1 second to 240 minutes, preferably 30 seconds to 120 minutes Other processing conditions may be the same as the processing conditions when the first modifying agent is supplied in step a1.

[0068] By supplying the raw material to the wafer 200 under the above-described processing conditions, at least a part of the molecular structure of the molecules constituting the raw material is selectively (preferentially) adsorbed to the second surface on which the first termination is not formed, and a second layer can be selectively formed on the second surface. At this time, the adsorption suppression effect of the first termination formed on the first surface suppresses the adsorption of at least a part of the molecular structure of the molecules constituting the raw material to the first surface.

[0069] The raw material may be, for example, a Si-containing material containing silicon (Si) as the main element constituting the intermediate layer formed in step a3. The Si-containing material may be, for example, a material containing halogen and Si, i.e., a halosilane. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. The halosilane may be, for example, a material containing Cl and Si, i.e., a chlorosilane.

[0070] As a raw material, for example, chlorosilanes such as monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), and octachlorotrisilane (Si3Cl8) can be used.

[0071] In addition to chlorosilanes, other raw materials that can be used include fluorosilanes such as tetrafluorosilane (SiF4) and difluorosilane (SiH2F2), bromosilanes such as tetrabromosilane (SiBr4) and dibromosilane (SiH2Br2), and iodosilanes such as tetraiodosilane (SiI4) and diiodosilane (SiH2I2).

[0072] In addition to these, a substance containing an amino group and Si, i.e., aminosilane, can also be used as a raw material. An amino group is a monovalent functional group formed by removing H from ammonia, a primary amine, or a secondary amine, and can be represented as -NH2, -NHR, or -NR2. R represents an alkyl group, and the two Rs in -NR2 may be the same or different.

[0073] As raw materials, for example, aminosilanes such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4), tris(dimethylamino)silane, bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tertiarybutylamino)silane (SiH2[NH(C4H9)]2), and (diisopropylamino)silane (SiH3[N(C3H7)2]) can also be used.

[0074] As the raw material, one or more of these can be used.

[0075] After selectively forming the second layer on the second surface of the wafer 200 (the second surface constituting the inner surface of the recess), the valve 243a is closed to stop the supply of raw materials into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing procedure and conditions as those for purging in step a1.

[0076] [Step a3b] After step a3a is completed, an oxidizing agent is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the second layer has been selectively formed on the second surface that constitutes the inner surface of the recess.

[0077] Specifically, the valve 243b is opened to allow an oxidizing agent to flow into the gas supply pipe 232b. The flow rate of the oxidizing agent is adjusted by the MFC 241b, and the oxidizing agent is supplied into the processing chamber 201 through the nozzle 249b and exhausted from the exhaust port 231a. At this time, the oxidizing agent is supplied to the wafer 200 (oxidizing agent supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a and 249b, respectively.

[0078] The processing conditions for supplying the oxidizing agent in this step are as follows: Treatment temperature: room temperature to 600°C, preferably 50 to 400°C Treatment pressure: 1 to 101325 Pa, preferably 1 to 1300 Pa Oxidant supply flow rate: 0.001 to 20 slm, preferably 0.001 to 10 slm Oxidizing agent supply time: 1 second to 240 minutes, preferably 30 seconds to 120 minutes Other processing conditions may be the same as the processing conditions when the first modifying agent is supplied in step a1.

[0079] By supplying an oxidizing agent to the wafer 200 under the above-described processing conditions, at least a portion of the second layer formed on the second surface in step a3a can be oxidized, thereby forming a third layer on the second surface, in which the second layer is oxidized and OH group (hydroxyl group) terminations (OH terminations) are formed on the surface.

[0080] As the oxidizing agent, for example, an oxygen (O)-containing substance can be used. As the O-containing substance, for example, oxygen (O), ozone (O), nitrous oxide (NO), nitric oxide (NO), nitrogen dioxide (NO), carbon monoxide (CO), carbon dioxide (CO), etc. can be used. As the oxidizing agent, one or more of these can be used.

[0081] Furthermore, for example, an O- and H-containing substance can be used as the oxidizing agent. For example, water vapor (H2O), hydrogen peroxide (H2O2), H2 + O2, H2 + O3, etc. can be used as the O- and H-containing gas. That is, an O-containing substance + H-containing substance can also be used as the O- and H-containing substance. In this case, a deuterium (D)-containing substance can also be used instead of the H-containing substance. Deuterium (D2) can also be used as the D-containing substance. One or more of these can be used as the oxidizing agent.

[0082] In this specification, a combined description such as "H2+O2" means a mixture of H2 and O2. When supplying a mixture, the two substances may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two substances may be supplied separately from different supply pipes into the processing chamber 201 and mixed (postmixed) in the processing chamber 201.

[0083] After the second layer selectively formed on the second surface of the wafer 200 (the second surface constituting the inner surface of the recess) is changed into the third layer, the valve 243b is closed to stop the supply of the oxidizing agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) using the same processing procedure and processing conditions as those for purging in step a1.

[0084] [Perform the specified number of times] By performing the above-described steps a3a and a3b asynchronously, i.e., in this order, n1 times (n1 is an integer of 1 or greater), a cycle can be performed. An intermediate layer can be selectively formed on the second surface of the wafer 200. For example, when using the above-described raw materials and oxidizing agents, an intermediate layer, such as a SiO layer, can be selectively formed on the second surface. In this manner, an OH termination as a third termination can be selectively formed on the second surface relative to the first surface (see FIG. 7(c)). In this manner, an intermediate layer having a surface with an OH termination formed as the second surface can be formed (see FIG. 7(c)). The third termination, such as an OH termination, formed on the second surface acts as an adsorption site for the second modifier supplied in step a2, which will be described later. That is, the intermediate layer having the third termination acts as an adsorption-promoting layer for the second modifier. It is preferable to repeat the above-described cycle multiple times. That is, it is preferable to set the thickness of the third layer formed per cycle thinner than the desired film thickness, and to repeat the above-described cycle multiple times until the thickness of the intermediate layer formed by stacking the third layer reaches the desired film thickness.

[0085] (Step a2) After step a3 is completed, a second modifying agent is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the third termination has been selectively formed on the second surface that constitutes the inner surface of the recess.

[0086] Specifically, the valve 243c is opened to allow the second modifying agent to flow into the gas supply pipe 232c. The flow rate of the second modifying agent is adjusted by the MFC 241c, and the second modifying agent is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the second modifying agent is supplied to the wafer 200 (second modifying agent supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a and 249b, respectively.

[0087] In this step, the processing conditions for supplying the second modifier are as follows: Treatment temperature: room temperature (25°C) to 500°C, preferably room temperature to 250°C Treatment pressure: 5 to 2000 Pa, preferably 10 to 1000 Pa Second modifier supply flow rate: 1 to 3 slm, preferably 1 to 0.5 slm Second modifier supply time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes Other processing conditions may be the same as the processing conditions when the first modifying agent is supplied in step a1.

[0088] By supplying the second modifier to the wafer 200 under the above-described processing conditions, at least a portion of the molecular structure of the molecules constituting the second modifier is selectively adsorbed onto the second surface, thereby selectively forming a fourth layer (second adsorption-suppressing layer) on the second surface. Specifically, while suppressing adsorption of at least a portion of the molecular structure of the molecules constituting the second modifier onto the first surface, the third terminus formed on the second surface is reacted with the second modifier, thereby selectively adsorbing at least a portion of the molecular structure of the molecules constituting the second modifier onto the second surface. This makes it possible to terminate the second surface with at least a portion of the molecular structure of the molecules constituting the second modifier. Examples of at least a portion of the molecular structure of the molecules constituting the second modifier include residues containing a bond between an atom (e.g., Si) that reacts with the third terminus and an alkyl group (e.g., a methyl group (Me group), an ethyl group (Et group), or a tert-butyl group (tert-Bu group)). More specifically, examples of such residues include trimethylsilyl (Si-Me), triethylsilyl (Si-Et), and tert-butyldimethylsilyl (Si-(CH)C(CH)). In this case, the Si constituting these silyl groups contained in the second modifier bonds with the O of the OH termination (OH group) on the second surface, forming an alkyl group termination as a second termination on the second surface (see FIG. 7(d)). The second termination, such as the alkyl group termination, formed on the second surface acts as an inhibitor that inhibits adsorption of the film-forming agent to the second surface in Step C, which will be described later.

[0089] The first termination formed on the first surface and the second termination formed on the second surface both impart hydrophobicity to the surfaces on which they are formed. Furthermore, since the second termination, such as an H termination, is more hydrophobic than the first termination, the second surface on which the second termination is formed is more hydrophobic than the first surface on which the first termination is formed. Note that "highly hydrophobic" here can also be expressed as "highly water-repellent" or "lowly hydrophilic."

[0090] The first terminal end reacts with the processing liquid to which the wafer 200 is exposed in step C, which will be described later, and is thereby removed from the first surface. On the other hand, the second terminal end is less likely to react with the processing liquid and is less likely to be removed from the second surface than the first terminal end. In other words, the first terminal end reacts more easily with the processing liquid and is more likely to be selectively removed than the second terminal end.

[0091] 6(a), the second surface is located closer to the opening than the first surface on the inner surface of the recess. As a result, after step a2 is completed, the second surface on which the second end is formed is located closer to the opening than the first surface on which the first end is formed on the inner surface of the recess.

[0092] Examples of the second modifier include alkylaminosilanes, which are compounds in which an amino group and an alkyl group are bonded to silicon, such as (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3), (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3), (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3), (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3), and (diisopropylamino)trimethylsilane ((C3H7)2NSi(CH3)3). It is particularly preferable to use trialkylaminosilanes, such as (dimethylamino)trimethylsilane and (diethylamino)triethylsilane, which are compounds in which three alkyl groups and one amino group are bonded to silicon. One or more of these compounds can be used as the second modifier.

[0093] After selectively forming the second termination on the second surface of the wafer 200 (the second surface constituting the inner surface of the recess), the valve 243c is closed to stop the supply of the second modifying agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing procedure and processing conditions as those for purging in step a1.

[0094] (After purging and atmospheric pressure recovery) After step a2 is completed, an inert gas serving as a purge gas is supplied into the processing chamber 201 from each of the nozzles 249a and 249b and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

[0095] (Boat unloading and wafer discharge) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the wafers 200, supported by the boat 217, are unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After the boat unloading, the shutter 219s is moved, and the opening at the lower end of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being unloaded to the outside of the reaction tube 203, the wafers 200 are removed from the boat 217 by the transfer mechanism 750 (wafer discharge).

[0096] The wafer 200 removed by the transfer mechanism 750 has a first end on its first surface and a second end on its second surface (see FIG. 7(d)).

[0097] The wafer 200 is taken out of the boat 217 by the transfer mechanism 750 and placed on a table (not shown) provided in the cleaning device 600 via the transfer chamber 700 .

[0098] [Step B: Removal process] In this step, the wafer 200 is exposed to the processing liquid supplied through the supply pipe 640 and stored in the processing bath 610 .

[0099] Specifically, a moving mechanism (not shown) installed in the cleaning apparatus 600 immerses the wafer 200 placed on a mounting table in the cleaning apparatus 600 in the processing liquid stored in the processing tank 610 (i.e., supplies the processing liquid to the wafer 200).

[0100] The treatment conditions for exposure to the treatment solution in this step are as follows: Exposure temperature: 0 to 100°C, preferably 15 to 50°C Exposure time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes is exemplified.

[0101] In this specification, the exposure temperature refers to the temperature of the wafer 200 in the processing liquid or the temperature of the processing liquid, and the exposure time refers to the time the exposure continues.

[0102] By exposing wafer 200 to the processing solution under the above-described processing conditions, the first termination formed on the first surface can be selectively removed (desorbed or destroyed) relative to the second termination formed on the second surface. Specifically, the first termination formed on the first surface can be removed while leaving the second termination formed on the second surface (see FIG. 7(e)). More specifically, in step C described below, the first termination that inhibits adsorption of the film-forming agent on the first surface can be removed while leaving the second termination that inhibits adsorption of the film-forming agent on the second surface.

[0103] The treatment liquid is a liquid containing a liquid that reacts with the first terminal and an additive that reduces the surface tension of the liquid. The additive that reduces the surface tension of the liquid that reacts with the first terminal has a surface tension lower than that of the liquid that reacts with the first terminal, or has the effect of reducing the surface tension of the liquid that reacts with the first terminal by being mixed with the liquid that reacts with the first terminal. By containing the liquid that reacts with the first terminal and the additive, the treatment liquid becomes a liquid with a surface tension lower than that of the liquid that reacts with the first terminal.

[0104] The liquid that reacts with the first terminus can be, for example, a liquid compound containing an OH terminus in the molecule, such as HO or HO. In particular, when the first terminus contains an H terminus, a liquid compound such as these can be suitably used as the liquid that reacts with the first terminus. One or more of these can be used as the liquid that reacts with the first terminus. Furthermore, by using a liquid compound containing an OH terminus in the molecule as the liquid that reacts with the first terminus, the reacted H terminus can be replaced with an OH terminus.

[0105] Furthermore, for example, a liquid containing H2O can be used as the liquid that reacts with the first termination, and a liquid further containing H2O2 (which can also be called hydrogen peroxide solution) can be used as the treatment liquid. By using a liquid further containing H2O2 as the treatment liquid, the effect of removing the first termination formed on the first surface can be further enhanced.

[0106] The additive may be, for example, a compound having the structural formula R-COH, such as alkyl ethers such as polyoxyethylene alkyl ether, polyhydric alcohol ethers such as alkyl glycoside, or fatty acid esters such as sorbitan fatty acid ester. Here, R may be at least one of carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and fluorine (F), or at least one of C, H, and O.

[0107] In addition, additives include, for example, C m H (2m+2) Alkanes (especially paraffinic hydrocarbons) represented by m H 2m Compounds containing alkenes (particularly olefinic hydrocarbons) represented by the following formula (wherein one or more H atoms have been substituted with OH) (that is, they can also be called alcohols) can be used.

[0108] In addition, additives include, for example, C m H (2m+2) Alkanes (especially paraffinic hydrocarbons) represented by m H 2mand a compound in which one or more H atoms of an aromatic hydrocarbon are substituted with OH (i.e., it can be called a phenol).

[0109] In addition, additives include, for example, CR m (OH) (4-m) (However, R=C n H (2n+2) Or C n H 2n ) can be used.

[0110] The additive may contain one or more compounds selected from the group consisting of methanol, ethanol, propanol, butanol, and ethylene glycol. Even when ethanol with an alcohol concentration of approximately 100% is used as the additive, HO may be contained in the ethanol as an impurity. HO as an impurity may act as a liquid that reacts with the first terminus in the processing liquid.

[0111] In addition to the additives mentioned above, any surfactant that can reduce the surface tension of the liquid that reacts with the first terminal end can be used.

[0112] The concentration of the additive in the treatment liquid, or the ratio of the liquid reactive with the first terminus to the additive, is desirably adjusted based on at least one of the following: (i) the hydrophobicity of at least one of the first terminus and the second terminus; (ii) the width of at least one of the opening and the interior of the recess (particularly the width at the minimum width); and (iii) the aspect ratio of the recess. Specifically, for example, the concentration of the additive can be adjusted to be higher as the hydrophobicity of at least one of the first terminus and the second terminus increases. Furthermore, the concentration of the additive can be adjusted to be higher as the width of at least one of the opening and the interior of the recess decreases. Furthermore, the concentration of the additive can be adjusted to be higher as the aspect ratio of the recess increases. In particular, when the second surface on which the second terminus is formed is closer to the opening than the first surface on which the first terminus is formed, the concentration of the additive is desirably adjusted based on the size of the second terminus to be a concentration that allows the treatment liquid to penetrate into the portion where the second terminus is formed.

[0113] For example, when water is used as the liquid that reacts with the first terminus and ethanol is used as the additive, the concentration of the additive in the treatment liquid is exemplified as 0.1 to 99.9%, preferably 10 to 90%, and the additive concentration is exemplified as a concentration that makes the contact angle θ of the treatment liquid with the surface terminated with the first terminus or the second terminus 10 to 100°, preferably 10 to 90°.

[0114] After selectively removing the first end on the first surface of the wafer 200 (the first surface that constitutes the inner surface of the recess), the moving mechanism lifts the wafer 200 from the processing tank 610 and places it on a mounting table in the cleaning device 600. The transfer mechanism 750 carries the wafer 200 placed on the mounting table out of the cleaning device 600 and loads it into the boat 217 via the transfer chamber 700.

[0115] (Wafer charge and boat load) Thereafter, the wafers 200 are loaded into the boat 217 and carried into the processing chamber 201 in the same manner as in the wafer charging and boat loading procedures described above.

[0116] (pressure and temperature regulation) Thereafter, the pressure and temperature inside the processing chamber 201 are adjusted in the same manner as in the pressure adjustment and temperature adjustment described above.

[0117] [Step C: Film formation process] In this step, a film forming agent is supplied to the wafer 200. As a result, a film is selectively formed on the first surface. Specifically, in this step, the following steps c1 and c2 are executed in order.

[0118] [Step c1] After step B is completed, raw materials are supplied to the wafer 200 that has been loaded from the cleaning device 600 into the processing chamber 201 in the film forming device 500, i.e., the wafer 200 after the first termination on the first surface that forms the inner surface of the recess has been selectively removed. In this step, raw materials can be supplied to the wafer 200 using the same processing procedure and processing conditions as those for supplying raw materials in step a3a.

[0119] By supplying the source material to the wafer 200 under the above-described processing conditions, at least a portion of the molecular structure of the molecules constituting the source material is selectively adsorbed onto the first surface from which the first terminations have been removed, thereby selectively forming a fifth layer on the first surface. At this time, the adsorption-suppressing effect of the second terminations formed on the second surface suppresses adsorption of at least a portion of the molecular structure of the molecules constituting the source material onto the second surface. The first surface from which the H terminations have been removed is preferably a surface on which OH terminations have been formed in step B, replacing the H terminations.

[0120] Furthermore, the raw material supplied to the wafer 200 in this step can be a gas containing one or more of the gases given as examples of the raw material supplied to the wafer 200 in step a3a. The raw material used in this step may be the same as or different from the raw material used in step a3a.

[0121] After the fifth layer is selectively formed on the first surface of the wafer 200 (the first surface constituting the inner surface of the recess), the valve 243a is closed to stop the supply of raw materials into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing procedures and conditions as those for purging in step a1.

[0122] [Step c2] After step c1 is completed, an oxidizing agent is supplied to the wafer 200 in the processing chamber 201, i.e., the wafer 200 after the fifth layer has been selectively formed on the first surface that constitutes the inner surface of the recess. In this step, the oxidizing agent can be supplied to the wafer 200 by the same processing procedure and processing conditions as those for supplying the oxidizing agent in step a3b.

[0123] By supplying an oxidizing agent to the wafer 200 under the above-described processing conditions, at least a portion of the fifth layer formed on the first surface in step c1 can be oxidized, thereby forming a sixth layer on the first surface, in which the fifth layer is oxidized and OH termination is formed on the surface.

[0124] In addition, the oxidizing agent supplied to the wafer 200 in this step can be a gas containing one or more of the gases given as examples of the oxidizing agent supplied to the wafer 200 in step a3b. The oxidizing agent used in this step may be the same as or different from that used in step a3b.

[0125] After the fifth layer formed on the first surface of the wafer 200 (the first surface constituting the inner surface of the recess) is changed to a sixth layer, the valve 243b is closed to stop the supply of the oxidizing agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) using the same processing procedure and processing conditions as those for purging in step a1.

[0126] [Perform the specified number of times] By performing the above-described steps c1 and c2 in this order asynchronously, i.e., non-synchronized, n2 times (n2 is an integer of 1 or greater), a film can be selectively formed on the first surface of wafer 200 (see FIG. 7(f)). The above-described cycle is preferably repeated multiple times. That is, it is preferable to make the thickness of the sixth layer formed per cycle thinner than the desired film thickness, and to repeat the above-described cycle multiple times until the film formed by stacking the sixth layer reaches the desired film thickness.

[0127] (After purging and atmospheric pressure recovery) After step C is completed, the inside of the processing chamber 201 is purged and the pressure inside the processing chamber 201 is returned to normal pressure by the same procedure as the after-purging and atmospheric pressure return described above.

[0128] (Boat unloading and wafer discharge) Thereafter, the wafers 200 are carried out of the reaction tube 203 and taken out of the boat 217 in the same manner as in the boat unloading and wafer discharging procedures described above.

[0129] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0130] (a) In step B, a wafer 200 including a first surface having a first termination and constituting at least a portion of the inner surface of the recess, and a second surface having a second termination different from the first termination, is exposed to a processing liquid containing a liquid reactive with the first termination and an additive that reduces the surface tension of the liquid. By exposing the wafer 200 to the processing liquid containing a liquid reactive with the first termination and an additive that reduces the surface tension of the liquid, the first termination formed on the inner surface of the recess can be selectively removed relative to the second termination, allowing for selective processing on the first surface. Specifically, by exposing the wafer 200 to a processing liquid containing a liquid reactive with the first termination and an additive with a lower surface tension than the first termination, the processing liquid can be distributed more thoroughly inside the recess than by exposing the wafer 200 only to a liquid reactive with the first termination that does not contain an additive, thereby selectively removing the first termination formed on the inner surface of the recess. Selectively removing the first termination formed on the first surface allows for selective processing, such as a film formation process, on the first surface.

[0131] (b) In step B, the treatment liquid can be spread throughout the recess by using a liquid that reacts with the first terminus and an additive that has a lower surface tension than the liquid. This allows the first terminus to be selectively removed even when a second surface on which a second terminus having a higher hydrophobicity than the first terminus is formed is located closer to the opening of the recess than the first surface on which the first terminus is formed.

[0132] (c) When a first termination is formed on the inner surface of a recess having a width of 100 μm or less at the opening or the interior, it may be difficult to spread the processing liquid inside the recess even when the wafer 200 is exposed to a liquid (e.g., water) that does not contain an additive and reacts with the first termination. This problem is particularly pronounced when a hydrophobic termination is formed on the surface of the opening or the interior and / or when the aspect ratio of the recess is 1 or greater. In step B, by using a processing liquid that contains a liquid that reacts with the first termination and an additive with a lower surface tension than the liquid, the processing liquid can be spread inside the recess even when a first termination is formed on the inner surface of the recess having a width of 100 μm or less at the opening or the interior. In particular, the processing liquid can be spread inside the recess even when a first termination is formed on the inner surface of the recess having a width of 100 μm or less at the opening.

[0133] The above-mentioned problem becomes more pronounced under at least one of the following conditions (i) and (ii). Therefore, under such conditions, it is more desirable to use this embodiment in order to spread the treatment liquid throughout the recesses. (i) The width of at least one of the opening and the interior must be 50 μm or less. In more severe cases, the width must be 10 μm or less. (ii) The aspect ratio of the recess is 2 or more. In cases where the problem is more significant, the aspect ratio is 10 or more.

[0134] (d) In step C, a film forming agent is supplied to the wafer 200 after step B has been performed, thereby allowing a film to be selectively formed on the first surface.

[0135] (e) The second termination inhibits the adsorption of the film-forming agent to the second surface, thereby enabling selective formation of a film on the first surface in step C.

[0136] (f) In step B, the first termination that inhibits the adsorption of the film-forming agent to the first surface is removed, so that in step C, a film can be selectively formed on the first surface.

[0137] (g) In step B, by using a liquid compound containing OH terminations in its molecules as the liquid that reacts with the first terminations, for example, H terminations as the first terminations formed on the first surface can be efficiently removed, which allows a film to be formed more selectively on the first surface in step C.

[0138] (h) The second surface on which the second termination is formed is more hydrophobic than the first surface on which the first termination is formed, which allows for more selective removal of the first termination relative to the second termination in step B. This allows for more selective formation of a film on the first surface in step C.

[0139] (i) The concentration of the additive contained in the treatment liquid can be adjusted depending on the degree of hydrophobicity of the second end. If the hydrophobicity of the second end is high and the treatment liquid cannot penetrate into the recess, it is desirable to adjust the concentration of the additive to a concentration that allows the treatment liquid to penetrate into the recess. Furthermore, the concentration of the additive contained in the treatment liquid can be adjusted depending on the width of the minimum width portion of the recess. If the minimum width of the recess is small and the treatment liquid cannot penetrate into the minimum width portion, it is desirable to adjust the concentration of the additive to a concentration that allows the treatment liquid to penetrate into that portion. However, the higher the concentration of the additive, the lower the concentration of the liquid that reacts with the first end. Therefore, it is desirable to set the concentration of the additive to a value that is equal to or not significantly exceeding the minimum value of the additive concentration that allows the treatment liquid to penetrate into the minimum width portion of the recess.

[0140] <Other Aspects of the Present Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0141] For example, in the above-described embodiment, the predetermined element contained in the raw material is Si. However, the present disclosure is not limited to this embodiment. For example, the predetermined element may be a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W), or germanium (Ge). In these cases, a metal oxide film such as a titanium oxide film (TiO film), a zirconium oxide film (ZrO film), a hafnium oxide film (HfO film), a tantalum oxide film (TaO film), a niobium oxide film (NbO film), an aluminum oxide film (AlO film), a molybdenum oxide film (MoO film), a tungsten oxide film (WO film), or a germanium oxide film (GeO film) is formed. This embodiment also provides the same effects as the above-described embodiment.

[0142] For example, in the above embodiment, the first surface (first base) is an SiO film and the second surface (second base) is an SiN film. However, the present disclosure is not limited to such an embodiment. For example, the first surface and the second surface may be a film containing a semiconductor element such as a silicon oxycarbonitride film (SiOCN film), SiOC film, silicon oxynitride film (SiON film), SiCN film, silicon carbide film (SiC film), silicon borocarbonitride film (SiBCN film), silicon boronitride film (SiBN film), silicon borocarbide film (SiBC film), silicon film (Si film), germanium film (Ge film), silicon germanium film (SiGe film), a film containing a metal element such as a titanium nitride film (TiN film), tantalum nitride film (TaN film), tungsten film (W film), molybdenum film (Mo film), ruthenium film (Ru film), cobalt film (Co film), nickel film (Ni film), copper film (Cu film), an amorphous carbon film (aC film), or single crystal Si (Si wafer), etc. Any base on which the first termination can be formed can be used as the first base (first surface). Any substrate on which the second termination can be formed can be used as the second substrate (second surface). In this embodiment, the same effects as those in the above embodiment can be obtained.

[0143] For example, the above-described embodiment has been described with reference to an example in which an oxide film is formed on the first surface in step C. However, the present disclosure is not limited to such an embodiment. The film selectively formed on the first surface may be any film that can be formed on the first surface after step B, and may be, for example, a nitride film or a film of a simple substance such as Si or a metal element. This embodiment also provides the same effects as the above-described embodiment.

[0144] For example, in the above-described embodiment, the first termination formed on the first surface and the second termination formed on the second surface are both terminations that impart hydrophobicity to the formed surfaces. However, the present disclosure is not limited to such an embodiment. For example, at least one of the first termination and the second termination may be a termination that imparts hydrophobicity to the formed surface. This embodiment also provides the same effects as the above-described embodiment.

[0145] For example, in the above embodiment, a case where a film-forming agent is supplied to wafer 200 after step B has been performed has been described as an example. However, the present disclosure is not limited to such an embodiment. For example, an etching agent may be supplied to wafer 200 after step B has been performed. In this embodiment, the same effect as in the above embodiment can be obtained, that is, a selective etching process can be performed on the first surface.

[0146] It is preferable that the recipes used for each process are individually prepared according to the process content and recorded and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process content from the multiple recipes recorded and stored in the storage device 121c. This makes it possible to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses using a single substrate processing apparatus 100. It also reduces the burden on the operator, prevents operational errors, and enables each process to be started quickly.

[0147] The above-mentioned recipes do not necessarily have to be newly created, but may be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus 100. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus 100 via an electric communication line or a recording medium on which the modified recipe has been recorded. Alternatively, an existing recipe that has already been installed in the substrate processing apparatus 100 may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus 100.

[0148] In the above-described embodiment, an example of forming a film using a batch-type substrate processing apparatus 100 that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described embodiment, and can be suitably applied, for example, to a case where a film is formed using a single-wafer-type substrate processing apparatus 100 that processes one or several substrates at a time. Furthermore, in the above-described embodiment, an example of forming a film using a substrate processing apparatus 100 having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-described embodiment, and can be suitably applied to a case where a film is formed using a substrate processing apparatus 100 having a cold-wall type processing furnace.

[0149] When using these substrate processing apparatuses 100, the processes can be performed under the same processing procedures and conditions as those in the above-described embodiments and modifications, and the same effects as those in the above-described embodiments and modifications can be obtained.

[0150] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications, for example. [Explanation of symbols]

[0151] 200 wafers (substrates)

Claims

1. (a) a first surface having a first termination and constituting at least a portion of an inner surface of the recess; a second surface having a second termination different from the first termination; providing a substrate comprising: (b) selectively removing the first termination relative to the second termination by exposing the substrate to a treatment liquid comprising a liquid reactive with the first termination and an additive that reduces the surface tension of the liquid; A substrate processing method comprising:

2. (c) forming a film on the first surface by supplying a film-forming agent to the substrate after (b), The substrate processing method according to claim 1 .

3. the second termination inhibits adsorption of the film-forming agent to the second surface. The substrate processing method according to claim 2 .

4. the first termination inhibits adsorption of the film-forming agent to the first surface; 4. The substrate processing method according to claim 2 or 3.

5. The liquid is a liquid of a compound containing an OH terminal in the molecule. The substrate processing method according to claim 1 .

6. The first terminus is an H terminus or an alkoxy group terminus. The substrate processing method according to claim 1 .

7. the second terminus is an alkyl group terminus; The substrate processing method according to claim 1 .

8. At least one of the first end and the second end is an end that imparts hydrophobicity to the formed surface. The substrate processing method according to claim 1 .

9. the second surface on which the second termination is formed is more hydrophobic than the first surface on which the first termination is formed; The substrate processing method according to claim 1 .

10. an inner surface of the recess including the first surface and the second surface; The substrate processing method according to claim 1 .

11. The liquid that reacts with the first terminal is H ２ O or H ２ O ２ is a liquid comprising The substrate processing method according to claim 1 .

12. The liquid that reacts with the first terminal is H ２ The treatment liquid is a liquid containing O, ２ O ２ Further comprising The substrate processing method according to claim 1 .

13. the additive is a compound having the structural formula R—COH, R is at least one of C, H, O, N, and F; The substrate processing method according to claim 1 .

14. (a) is (a-1) forming the first termination on the first surface by supplying a first modifier to the substrate; (a-2) forming the second termination on the second surface by supplying a second modifier to the substrate; Further comprising: The substrate processing method according to claim 1 .

15. (a) is (a-3) after (a-1) and before (a-2), further comprising the step of forming a third termination on the second surface selectively with respect to the first surface; In (a-2), the second terminal end is formed on the second surface by reacting the third terminal end with the second modifier. The substrate processing method according to claim 14.

16. In (a-3), (a-3a) supplying a raw material to the substrate; (a-3b) supplying an oxidizing agent to the substrate; a predetermined number of cycles, thereby forming an intermediate layer having a surface as the second surface on which the third termination is formed. The substrate processing method according to claim 15.

17. (a) a first surface having a first termination and constituting at least a portion of an inner surface of the recess; a second surface having a second termination different from the first termination; providing a substrate comprising: (b) selectively removing the first termination relative to the second termination by exposing the substrate to a treatment liquid comprising a liquid reactive with the first termination and an additive that reduces the surface tension of the liquid; A method for manufacturing a semiconductor device having the above structure.

18. (a) a first surface having a first termination and constituting at least a portion of an inner surface of the recess; a second surface having a second termination different from the first termination; providing a substrate comprising: (b) selectively removing the first termination relative to the second termination by exposing the substrate to a treatment liquid comprising a liquid reactive with the first termination and an additive that reduces the surface tension of the liquid; A program that causes a computer to execute the above in a substrate processing apparatus.

19. a processing liquid supply system for supplying a processing liquid to the substrate; a control unit configured to be capable of controlling the processing liquid supply system to perform a process of selectively removing the first end relative to the second end by exposing the substrate, which includes a first surface having a first end and constituting at least a part of an inner surface of a recess, and a second surface having a second end different from the first end, to the processing liquid containing a liquid that reacts with the first end and an additive that reduces the surface tension of the liquid; and A substrate processing apparatus having:

20. a first modifying agent supply system that supplies a first modifying agent to the substrate; a second modifying agent supply system that supplies a second modifying agent to the substrate; and 20. The substrate processing apparatus of claim 19, wherein the control unit is configured to be capable of controlling the first modifier supply system and the second modifier supply system to perform a process of forming the first termination on the first surface by supplying the first modifier to the substrate, and a process of forming the second termination on the second surface by supplying the second modifier to the substrate.

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