Plasma processing apparatus and substrate processing apparatus

Abstract

To suppress an abnormality in the shape of a semiconductor pattern.SOLUTION: A substrate processing method realized by a substrate processing apparatus includes step a) and step b). Step a) is a step of partially etching an object to be processed to form a recessed portion. Step b) is a step of forming a film having a different thickness along a depth direction of the recessed portion on a side wall of the recessed portion. Step b) includes step b-1) and step b-2). Step b-1) is a step of supplying a first reactant and adsorbing the first reactant onto the side wall of the recessed portion. Step b-2) is a step of supplying a second reactant and causing the first reactant and the second reactant to react with each other to form a film.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The following disclosure: Plasma processing equipment and a substrate processing apparatus. [Background technology]

[0002] As semiconductor device integration progresses not only horizontally but also vertically, the aspect ratio of the patterns formed during semiconductor device manufacturing is also increasing. For example, in the manufacturing of 3D NAND, channel holes are formed in a direction that penetrates multiple metal wiring layers. When forming 64-layer memory cells, the aspect ratio of the channel hole can be as high as 45.

[0003] Various methods have been proposed for forming high-aspect ratio patterns with high precision. For example, a method has been proposed in which etching and film deposition are repeatedly performed in an opening formed in a dielectric material of a substrate to suppress lateral etching (Patent Document 1). Another method has been proposed in which etching and film deposition are combined to form a protective film to prevent lateral etching of the dielectric layer (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] US Patent Application Publication No. 2016 / 0343580 [Patent Document 2] US Patent Application Publication No. 2018 / 0174858 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure provides a technique capable of suppressing shape abnormalities in semiconductor patterns. [Means for solving the problem]

[0006] A substrate processing method realized by a substrate processing apparatus according to one embodiment of the present disclosure includes steps a) and b). Step a) is a step of partially etching an object to be processed to form a recess. Step b) is a step of forming a film on the sidewall of the recess, the film having a thickness that varies along the depth direction of the recess. Step b) includes steps b-1) and b-2). Step b-1) is a step of supplying a first reactant and causing the first reactant to be adsorbed on the sidewall of the recess. Step b-2) is a step of supplying a second reactant and causing the first reactant to react with the second reactant to form a film. [Effects of the Invention]

[0007] According to the present disclosure, shape abnormalities in semiconductor patterns can be suppressed. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a flowchart showing an example of the flow of a substrate processing method according to an embodiment. [Figure 2] FIG. 2 is a diagram for explaining an example of a pattern formed by a substrate processing method according to an embodiment. [Figure 3] FIG. 3 is a diagram for explaining suppression of shape abnormalities in a semiconductor pattern by a substrate processing method according to an embodiment. [Figure 4] FIG. 4 is a diagram for explaining a first example of a substrate processing method according to an embodiment. [Figure 5] FIG. 5 is a diagram for explaining a second example of a substrate processing method according to an embodiment. [Figure 6] FIG. 6 is a diagram for explaining control of the coverage of the protective film formed by the substrate processing method according to an embodiment. [Figure 7] FIG. 7 is a diagram for explaining the thickness of the protective film formed by the substrate processing method according to one embodiment. [Figure 8] FIG. 8 is a diagram for explaining the relationship between the thickness of the protective film formed by the substrate processing method according to one embodiment and the pressure inside the processing chamber. [Figure 9] FIG. 9 is a diagram for explaining an improvement in etching rate when a substrate processing method according to an embodiment is used. [Figure 10] FIG. 10 is a flowchart showing an example of the flow of the substrate processing method according to the second embodiment. [Figure 11] FIG. 11 is a diagram showing an example of a pattern formed by the substrate processing method according to the second embodiment. [Figure 12] FIG. 12 is a first diagram for explaining prevention of opening blockage by the substrate processing method according to the second embodiment. [Figure 13] FIG. 13 is a second diagram for explaining prevention of opening blockage by the substrate processing method according to the second embodiment. [Figure 14] FIG. 14 is a diagram for explaining a substrate processing method according to the third embodiment. [Figure 15] FIG. 15 is a flowchart showing an example of the flow of the substrate processing method according to the third embodiment. [Figure 16] FIG. 16 is a flowchart showing an example of the flow of the substrate processing method according to the first modification. [Figure 17] FIG. 17 is a diagram for explaining an example of an object to be processed by the substrate processing method according to the first modification. [Figure 18] FIG. 18 is a flowchart showing an example of the flow of the substrate processing method according to the fourth embodiment. [Figure 19] FIG. 19 is a view showing an example of an object to be processed by the substrate processing method according to the fourth embodiment. [Figure 20] FIG. 20 is a view showing another example of an object to be processed by the substrate processing method according to the fourth embodiment. [Figure 21] FIG. 21 is a diagram for explaining the relationship between the temperature of the object to be processed and the amount of film formation. [Figure 22] FIG. 22 is a diagram for explaining an example of an object to be processed by the substrate processing method according to the third modification. [Figure 23]FIG. 23 is a diagram illustrating an example of a substrate processing apparatus according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0009] The disclosed embodiments will be described in detail below with reference to the drawings. Note that the present embodiments are not limiting. Furthermore, the embodiments can be appropriately combined as long as the processing contents are not contradictory. Note that the same or equivalent parts in each drawing are designated by the same reference numerals.

[0010] It is known that shape defects occur when etching patterns with high aspect ratios. For example, when forming an opening in the vertical direction, a shape defect in which the inner periphery bulges horizontally can occur. This type of shape defect is called bowing. To prevent this, a method of forming a protective film on the sidewall of the opening has been proposed. In forming fine patterns, it is also desirable to prevent the opening from being blocked by the protective film and a decrease in the etching rate due to film formation on the bottom of the opening.

[0011] In the following description, "pattern" refers to a general shape formed on a substrate. A pattern refers to the entirety of multiple shapes formed on a substrate, such as holes, trenches, and lines and spaces. A "recess" refers to a portion of a pattern formed on a substrate that is recessed in the thickness direction of the substrate. A recess has a "sidewall" that is the inner surface of the recessed shape, a "bottom" that is the bottom portion of the recessed shape, and an "apex" that is the substrate surface near the sidewall and continuous with the sidewall. The space surrounded by the apex is called an "opening." The term "opening" is also used to refer to the entire space surrounded by the bottom and sidewall of a recess, or any position in the space.

[0012] (Example of flow of substrate processing method according to one embodiment) FIG. 1 is a flowchart showing an example of the flow of a substrate processing method according to one embodiment. First, a substrate to be processed is provided (step S100). For example, a substrate having a high aspect ratio pattern formed thereon is placed in a processing chamber. Alternatively, for example, a substrate without a pattern formed thereon is placed in the processing chamber, and the substrate is partially etched to form a pattern (step (a)). Next, a first gas (hereinafter also referred to as a precursor or a first reactant) is introduced into the processing chamber (step S101, the first step or step (b-1)). Next, the processing chamber is purged to discharge components of the first gas that are excessively adsorbed on the surface of the substrate to be processed (step S102). Next, a second gas (hereinafter also referred to as a reactant gas or a second reactant) is introduced into the processing chamber (step S103, the second step or step (b-2)). Then, the processing chamber is purged to discharge components of the second gas that are excessively adsorbed on the surface of the substrate to be processed (step S104). Step S100 and steps S101 to S104 may be performed in the same processing chamber (in-situ) or in different processing chambers (ex-situ). Next, it is determined whether the protective film formed on the object to be processed in steps S101 to S104 has reached a predetermined thickness (step S105). The determination of whether the protective film has reached a predetermined thickness may be made based on the number of times steps S101 to S104 are performed. Alternatively, it may be made based on the measured thickness of the protective film. The measured value may include a parameter indicating the state of the protective film, such as the thickness distribution. The protective film may be measured by any method, and may be measured by an optical method, for example. In the case of in-situ film thickness measurement, the film thickness is measured using a measuring device installed in advance in the processing chamber. On the other hand, in the case of ex-situ film thickness measurement, the film thickness may be measured using a measuring device installed outside the processing chamber. As a result, if it is determined that the predetermined thickness has not been reached (No in step S105), the process returns to step S101 and repeats steps up to step S104. In this case, in steps S101 to S104, the processing conditions may be adjusted based on the measured values. On the other hand, if it is determined that the predetermined film thickness has been reached (step S105, Yes), the object to be processed is etched (step S106). At this time, the etching conditions may be adjusted based on the measured values ​​measured in step S105.Then, it is determined whether the post-etching pattern has a predetermined shape (step S107). The determination of whether the post-etching pattern has a predetermined shape may be made based on the execution time of step S106. Alternatively, it may be made based on the measurement value of the etching pattern shape. The pattern shape measurement method is not particularly limited, and may be measured, for example, by an optical method. In the case of in-situ measurement, the pattern shape is measured using a measurement device installed in advance in the processing chamber. On the other hand, in the case of ex-situ measurement, the pattern shape may be measured using a measurement device installed outside the processing chamber. As a result, if it is determined that the pattern has not achieved the predetermined shape (step S107, No), the process returns to step S101 and repeats the process from the first step. On the other hand, if it is determined that the pattern has achieved the predetermined shape (step S107, Yes), the process ends. This is an example of the process flow of the substrate processing method according to the embodiment.

[0013] 1, the processing conditions in the first and second processes are set so that the coverage of the protective film of at least one of the first and second gases changes along the depth direction of the pattern. The coverage is the area ratio of the protective film formed to a certain thickness per unit area. In other words, the thickness of the protective film formed through the first and second processes is set so that it changes along the depth direction of the pattern. Note that the purging in steps S102 and S104 may be omitted.

[0014] The determination in step S105 is made, for example, based on whether steps S101 to S104 have been performed a predetermined number of times. The determination in step S107 is made, for example, based on whether step S106 has been performed a predetermined number of times on the same object to be processed. The etching performed in step S106 may be performed multiple times.

[0015] Steps S101 and S103 may be performed using plasma or without plasma. Each step may be performed in the same processing chamber while maintaining a reduced pressure atmosphere, or may be performed in different processing chambers. When performed in different processing chambers, each step may be performed while maintaining a reduced pressure atmosphere, or may be performed via a normal pressure atmosphere.

[0016] 2 is a diagram for explaining an example of a pattern formed by the substrate processing method according to an embodiment, The substrate processing method according to an embodiment will be further described with reference to FIG.

[0017] The object S to be processed shown in FIG. 2 includes a substrate 101 on which a film 102 to be etched and a mask 120 are stacked. First, the object S is placed in a processing chamber. Next, in step S101, a first gas is introduced into the processing chamber. The first gas is adsorbed to the top 200T, sidewall 200S, and bottom 200B surrounding the opening 200 of the object S to form the layer shown in FIG. 2A. After purging the processing chamber, a second gas is introduced into the processing chamber in step S103 (FIG. 2B). The processing conditions in steps S101 and S103 are set so that the reaction between the components of the second gas and the components of the first gas adsorbed on the object S is not completed across the entire surface of the object. After a processing time based on the set processing conditions has elapsed, the processing chamber is purged. The second gas reacts with the top 200T and the upper part of the sidewall 200S to form a protective film 300 (FIG. 2C). Thereafter, steps S101 to S104 are repeated to form a protective film 301 having a desired thickness (FIG. 2(D)). Then, in step S106, the etching target film 102 is etched. By previously forming the protective film 301 in a portion where shape abnormalities may occur due to etching, the occurrence of shape abnormalities after etching is prevented.

[0018] (Suppression of abnormal shape) FIG. 3 is a diagram illustrating suppression of shape abnormalities in a semiconductor pattern by a substrate processing method according to an embodiment. The object S shown in FIG. 3A is similar to the object S shown in FIG. 2D, and has a protective film 301 formed on the top 200T and sidewall 200S. During etching, bowing often occurs at the position where the mask switches to the film to be etched. For example, bowing often occurs at the position indicated by R1 in FIG. 3A. However, in the example of FIG. 3, the protective film 301 is formed so that it becomes thinner at the position R1 in the depth direction of the pattern. Therefore, after etching, the object S is etched such that the protective film 301 is significantly removed at R1, resulting in uniform opening dimensions in the depth direction, as shown in FIG. 3B. Repeated etching further removes the protective film 301, and the opening dimensions become substantially uniform from the top to the bottom of the opening 200, as shown in FIG. 3C, resulting in a shape such as that shown in FIG. 3D. If bowing of the protective film 301 occurs due to etching (corresponding to No in step S107), the first and second steps are executed again to re-form the protective film 301. In this way, according to the substrate processing method of one embodiment, shape abnormalities in the semiconductor pattern can be suppressed.

[0019] (ALD control to change film thickness in the depth direction of the pattern) As described above, the substrate processing method according to the embodiment forms a protective film on the inner circumferential surface of the opening, the coverage (film thickness) of which decreases in the depth direction. Methods for forming the protective film include chemical vapor deposition and atomic layer deposition (ALD). The substrate processing method according to the embodiment forms a protective film with a different film thickness in the depth direction of the opening, while varying the coverage in the depth direction of the opening by utilizing the self-regulating properties of the film formed by ALD.

[0020] Before describing the substrate processing method according to the embodiment, we will first explain so-called ALD. ALD typically involves four processing steps. First, a first gas (also called a precursor) is introduced into a processing chamber containing a workpiece, such as a substrate. The first material contained in the first gas adsorbs onto the surface of the workpiece. After the surface is covered with the first material, the processing chamber is evacuated. Next, a second gas (also called a reactive gas) containing a second material that reacts with the first material is introduced into the processing chamber. The second material reacts with the first material on the workpiece to form a film. Film formation is completed when the reaction with the first material on the surface is complete. ALD forms a film by self-limiting adsorption and reaction of a specific material with a substance already present on the workpiece surface. For this reason, ALD typically achieves conformal film formation by providing sufficient processing time.

[0021] In contrast, in the substrate processing method according to this embodiment, processing conditions are set so that the self-limiting adsorption or reaction on the surface of the processing target is not completed. There are at least the following two processing modes. (1) The precursor is adsorbed onto the entire surface of the workpiece, and then the reactive gas introduced is controlled so that it does not reach the entire surface of the workpiece. (2) The precursor is adsorbed only to a portion of the surface of the workpiece, and the reactive gas introduced thereafter forms a film only on the surface portion where the precursor is adsorbed. A substrate processing method according to one embodiment uses the technique (1) or (2) to suppress the formation of a protective film on the lower sidewalls and bottom of an opening in a semiconductor pattern, for example.

[0022] 4 is a diagram illustrating a first example of a substrate processing method according to an embodiment. The object to be processed shown in FIG. 4 includes an etching target film EL1 and a mask MA formed on a substrate (not shown). A recess having an opening OP is formed in the stack of the etching target film EL1 and the mask MA.

[0023] First, precursor P is introduced into the processing chamber containing the workpiece (FIG. 4A). By allowing sufficient processing time for the precursor P to adsorb, the precursor P adsorbs to the entire surface of the workpiece (FIG. 4B). Once the precursor P has adsorbed, the processing chamber is purged. Next, reactive gas R is introduced into the processing chamber (FIG. 4C). The introduced reactive gas R reacts with the precursor P on the workpiece to gradually form a protective film PF, starting from above the mask MA. Before the protective film PF reaches below the etching target film EL1, the reactive gas R is purged. This process allows the ALD technique to be used, but the protective film PF is formed only on the mask MA and the upper portion of the etching target film EL1, rather than on the entire sidewall of the recess (FIG. 4D). In FIG. 4D, the protective film PF is formed on the upper and top sidewalls of the recess, but not on the lower and bottom sidewalls.

[0024] 5 is a diagram for explaining a second example of a substrate processing method according to an embodiment of the present invention, in which the object to be processed shown in FIG.

[0025] In the example of FIG. 5, precursor P is adsorbed only to the upper part of the workpiece (FIG. 5(A)). After purging the precursor P, reactive gas R is introduced into the processing chamber (FIG. 5(B)). At this time, reactive gas R reacts and forms a film only at the position where precursor P is adsorbed, so a protective film PF is formed only on the upper part of the workpiece (FIG. 5(C)).

[0026] (Processing conditions for selective adsorption and reaction) As described above, in the substrate processing method according to one embodiment, the adsorption of the precursor in the second example or the reaction of the reactive gas in the first example occurs in a predetermined portion of the pattern. For example, to form a protective film only above the openings of the pattern, the processing conditions are adjusted so that the adsorption of the precursor or the reaction of the reactive gas occurs only above the openings of the pattern.

[0027] The process parameters that are adjusted to realize the above-described substrate processing method include, for example, the temperature of the stage on which the object to be processed is placed, the pressure in the process chamber, the flow rate and introduction time of the precursor to be introduced, the flow rate and introduction time of the reactive gas to be introduced, the process time, etc. In addition, in the case of a process that uses plasma, the film formation position can also be adjusted by adjusting the value of the radio frequency (RF) power applied to generate the plasma.

[0028] 6 is a diagram for explaining control of the coverage of a protective film formed by a substrate processing method according to one embodiment. In FIG. 6, the horizontal axis represents processing time, and the vertical axis represents coverage. The solid line represents the coverage at the top of the recess of the pattern, the dashed-dotted line represents the coverage at the middle of the sidewall in the recess, and the dashed line represents the coverage at the bottom of the recess. Note that FIG. 6 shows a rough tendency and does not represent exact numerical values.

[0029] As shown in Figure 6, when a film is formed in a recess in a pattern, the film formation (adsorption or reaction) rate differs at the top, center of the sidewall, and bottom of the recess. Film formation progresses gradually from the top, where the precursor or reactant gas first enters, toward the bottom. First, as shown by the solid line in Figure 6, the coverage gradually increases at the top, and film formation is completed first among the sections (time T1, 100% coverage). Next, as shown by the dashed line, film formation progresses slightly slower at the center of the sidewall than at the top, and film formation is completed at a time (T2) slightly later than the time when film formation at the top is completed. Next, film formation progresses at the bottom, as shown by the dashed line, and film formation is completed latest among the sections at time T3.

[0030] Therefore, when the process of adsorbing the precursor or reacting the reactive gas is completed after timing T1 and before timing T3, the process can be completed in a state where the precursor is adsorbed or a protective film is formed on the top of the recess, but the adsorption or formation of the protective film is not completed at the center of the sidewall or the bottom.

[0031] In Figure 6, the coverage is plotted against the horizontal axis of the processing time as a processing parameter. Alternatively, the coverage can be adjusted by keeping the processing time constant and changing the temperature of the mounting table, the pressure in the processing chamber, the gas flow rate (dilution) of the precursor or reactive gas, or the absolute value of the radio frequency (RF) power applied for plasma generation. For example, lowering the temperature of the mounting table can slow the film formation below the pattern. Lowering the pressure in the processing chamber can also slow the film formation below the pattern. Lowering the flow rate of the precursor contained in the introduced gas can also slow the progress of adsorption below the pattern. Lowering the flow rate of the introduced reactive gas can also slow the film formation below the pattern. When using plasma, lowering the absolute value of the radio frequency power applied for plasma generation can also slow the film formation below the pattern.

[0032] For example, the temperature of the mounting table, the pressure in the processing chamber, the dilution of the introduced gas (precursor), and the absolute value of the high-frequency power are each set to a value lower than the value at which adsorption of the precursor to the entire surface of the workpiece is completed when other processing conditions are the same.Also, for example, the temperature of the mounting table, the pressure in the processing chamber, and the absolute value of the high-frequency power are each set to a value lower than the value at which reaction of the reactive gas on the entire surface of the workpiece is completed when other processing conditions are the same.Also, for example, the dilution of the introduced gas (reactive gas) is set to a value higher than the value at which reaction of the reactive gas on the entire surface of the workpiece is completed when other processing conditions are the same.

[0033] In the substrate processing method according to one embodiment, the processing conditions are adjusted in this way to end the processing in a state where the adsorption of the precursor is unsaturated as shown in Example 2 or the reaction of the reactant gas is unsaturated as shown in Example 1. Therefore, the substrate processing method according to one embodiment can form a protective film only above the pattern.

[0034] (Thickness of protective film formed by substrate processing method according to one embodiment) FIG. 7 is a diagram illustrating the thickness of a protective film formed by a substrate processing method according to an embodiment. As described above, in one embodiment, processing conditions are adjusted so that the protective film is formed above a pattern. The inventors processed a processing object using a substrate processing method according to an embodiment and investigated the thickness of the protective film formed. FIG. 7A is a schematic diagram of a processing object used in the experiment. The processing object includes an etching target film EL1, a mask MA formed on the etching target film EL1, and a recess having an opening OP formed in the mask MA and the etching target film EL1. FIG. 7A shows a state in which a protective film PF is formed on the entire inner surface of the recess. CD is the lateral dimension at an arbitrary position in the space surrounded by the sidewall of the recess (hereinafter also referred to as the opening dimension).

[0035] FIG. 7B plots the opening dimensions of the workpiece in its initial state, the opening dimensions after processing in Example 1, and the opening dimensions after processing in Reference Example 1, all plotted against the depth within the etching target film EL1. The initial state is the state before the protective film PF is formed. Example 1 is a case where a protective film is formed on the workpiece using a substrate processing method according to one embodiment. Specifically, the processing time for the reaction of the reactive gas is shortened (see timing T2 in FIG. 6). Reference Example 1 is a case where a protective film is formed on the workpiece using conventional ALD. Conventional ALD refers to ALD that is performed with sufficient time for the precursor and reactive gas to complete adsorption and reaction on the entire surface of the workpiece, thereby achieving conformal film formation.

[0036] As shown in FIG. 7B, in the initial state, the opening dimension is approximately 40 nanometers (nm) at a depth of approximately 0.0 micrometers (μm), and approximately 30 nm at a depth of approximately 1.4 μm. The opening dimension decreases with increasing depth. In contrast, after conventional ALD, a protective film is formed with a substantially constant thickness regardless of depth. At a depth of approximately 0.0 μm, the opening dimension is approximately 25 nm, and at a depth of approximately 1.4 μm, the opening dimension is approximately 18 nm. Although there is some variation depending on the depth, a protective film with a thickness of approximately 12 to 15 nm is formed. In contrast, after processing using the substrate processing method according to one embodiment (Example 1), the opening dimension is 30 nm at a depth of approximately 0.0 μm, approximately 34 nm at a depth of approximately 0.4 μm, and approximately 30 nm at a depth of approximately 1.3 μm. In other words, the thickness of the protective film formed generally gradually decreases from the top to the bottom of the recess. In this manner, the protective film formed by the substrate processing method according to one embodiment has a thickness that gradually changes from the top to the bottom of the recess. In other words, the substrate processing method according to one embodiment uses an ALD technique to form a protective film that is not conformal but, so to speak, subconformal.

[0037] FIG. 8 illustrates the relationship between the depth distribution of the protective film formed by a substrate processing method according to one embodiment and the pressure in the processing chamber. Because the total deposition amount of the deposited film varies significantly depending on the pressure when all other processing conditions are constant, the total deposition amount calculated by integrating the thickness of the deposited film up to a depth of 1.5 μm is normalized to 1, and the ratio of the deposition amount from a depth of 0 μm to a predetermined depth is plotted to show the difference between conditions. Reference Example 1 in FIG. 8 illustrates a case in which a protective film was formed on a substrate using conventional ALD. Conventional ALD achieves conformal film formation, so the film thickness is constant in the depth direction. Therefore, the graph in FIG. 8 depicts a linear curve. The graph also illustrates the film thickness distribution when the pressure in the processing chamber during the reaction of the reactive gas is changed to 200 millitorr (mT), 20 mT, and 10 mT, among the processing conditions of Example 1 in FIG. 7B. As shown in FIG. 8, the total deposition amount of the deposited film is greater at shallower depths than Reference Example 1 at all pressure values. This indicates that a subconformal protective film is formed. It can be seen that the total deposition amount of the deposited film is particularly large at shallower depths when the pressure is 10 mT. In other words, in order to vary the protective film thickness depending on the depth and to increase the film thickness near the top, it is advantageous to set the pressure in the processing chamber low.

[0038] The inventors also investigated the change in protective film thickness depending on the dilution level of oxygen gas during the reaction of the reactive gas under the processing conditions of Example 1 in Figure 7(B), using oxygen gas (O2) as the reactive gas and a substrate with a pattern having an aspect ratio of approximately 10 as the workpiece. The dilution level of oxygen gas refers to the ratio of the dilution gas to the total flow rate of oxygen gas and dilution gas. The dilution level of oxygen gas may also be expressed as the partial pressure of the dilution gas. Note that the dilution gas refers to a gas consisting of non-reactive substances, such as rare gases, that do not contribute to the reaction. O2 was used as the reactive gas and argon gas as the dilution gas, and these were mixed in a predetermined ratio. As a result, the protective film thickness varied depending on the depth of the recess, and the film thickness variation increased with the dilution level of O2. This is thought to be because O radicals are easily distributed at the bottom of the recess, and increasing the dilution level suppresses the amount of O radicals supplied to the bottom.

[0039] Thus, one embodiment of the substrate processing method employs ALD techniques to adjust processing conditions to form a self-limiting film with varying coverage and film thickness along the depth direction of the pattern.

[0040] (Improved etching rate) 9 is a diagram for explaining an improvement in etching rate by a substrate processing method according to an embodiment, and shows an experimental result in which a mask (MA) made of a silicon oxynitride film is stacked on an amorphous carbon layer, which is an etching target film (EL1), and the amorphous carbon layer is etched using a pattern formed on the mask.

[0041] 9 (initial state) shows the state of the object to be processed at the start of processing. In the initial state, the opening dimension is slightly larger near the top of the etching target film EL1, and tapers in the depth direction.

[0042] The second diagram from the left in FIG. 9 (Reference Example 1) shows the results of direct etching of an initial workpiece. In Reference Example 1, the opening dimensions are significantly enlarged below the mask, resulting in bowing (shown as "A1" in FIG. 9). The second diagram from the right in FIG. 9 (Reference Example 2) shows the results of etching after forming a protective film by conventional ALD. Compared to Reference Example 1, bowing is suppressed immediately below the mask and within the film to be etched (shown as "A2" in FIG. 9), but the depth of the recess formed by etching is significantly reduced. The rightmost diagram in FIG. 9 (Example 1) shows the results of etching after forming a protective film using a substrate processing method according to one embodiment. Compared to Reference Example 2, the degree of bowing suppression is roughly the same (shown as "A3" in FIG. 9), but the depth of the recess formed by etching is significantly increased.

[0043] When a protective film is formed by conventional ALD, the protective film is formed not only on the sidewalls of the recesses but also on the bottom of the recesses. As a result, the protective film acts as an etch stop layer, reducing the etching rate. In contrast, in the substrate processing method according to the embodiment, film formation on the bottom of the recesses is suppressed and a protective film is formed on the sidewalls of the recesses. As a result, the protective film formed on the bottom of the recesses does not act as an etch stop layer, and a reduction in the etching rate can be suppressed.

[0044] Furthermore, according to one embodiment of the substrate processing method, since film formation on the sidewalls near the bottom of the recess is suppressed, dimensional control of the bottom of the recess can be achieved. For example, when a recess whose diameter decreases from the top to the bottom is formed, the protective film can be used to suppress dimensional variation of the sidewalls while increasing the dimension of the bottom.

[0045] Furthermore, the substrate processing method according to the embodiment uses the ALD technique to form a film, which allows for precise control of the film thickness, thereby preventing the opening at the top of the recess from being blocked.

[0046] (Film type of the object to be treated) In the embodiment, the type of the etching target film 102 is not particularly limited. The etching target film 102 may be, for example, a silicon-containing film, a carbon-containing film, an organic film, a metal film, etc. The silicon-containing film may be a silicon dielectric film, examples of which include a silicon oxide film, a silicon nitride film, a silicon oxynitride film, and a silicon carbide film.

[0047] The protective films 300, 301 formed by the substrate processing method according to the above embodiment may be made of the same material as the etching target film 102. For example, the protective films 300, 301 may be silicon-containing films, carbon-containing films, organic films, metal films, etc. Examples of carbon-containing films include amorphous carbon layers (ACLs) and spin-on carbon films. Examples of silicon-containing dielectric films include silicon dioxide (SiO), silicon nitride (SiN), silicon oxynitride (SiON), or a combination thereof. Examples of metal films include titanium (Ti) films and tungsten (W) films. By using the same material for the protective films 300, 301 and the etching target film 102, subsequent processing can be more easily controlled. For example, the etching rates of the protective films 300, 301 and the etching target film 102 can be made uniform during etching. This allows for easy control of the dimensions of the bottom portion 200B during etching after the protective films 300, 301 are formed. For example, if the protective films 300, 301 are made of a different material than the etching target film 102, the protective films 300, 301 may remain unremoved in a subsequent etching step, potentially resulting in excessive etching of the bottom portion 200B of the etching target film 102. In contrast, if the protective films 300, 301 and the etching target film 102 are made of the same material, it is easy to control the amount removed by etching. Furthermore, when the protective films 300, 301 are removed in a subsequent process, they can be removed together with the etching target film 102 without requiring a separate removal step for the protective films 300, 301.

[0048] The etching target film 102 may be a laminated film in which multiple layers are stacked. For example, the etching target film 102 may be an ONON (silicon oxide film / silicon nitride film) film or an OPOP (silicon oxide film / polysilicon film) film.

[0049] When forming silicon oxide films as the protective films 300 and 301, precursors such as aminosilanes, SiCl4, and SiF4 can be used, and reactive gases such as O2 can be used. When forming silicon nitride films as the protective films 300 and 301, precursors such as aminosilanes, SiCl 4, Dichlorosilane (DCS), hexachlorodisilane (HCDS), etc. can be used, and nitrogen-containing gases such as N2 and NH3 can be used as the reactive gas. Furthermore, molecular layer deposition (MLD) can be used as a method for forming organic films as the protective films 300 and 301. Furthermore, when forming titanium films or titanium oxide films as the protective films 300 and 301, precursors such as TDMAT (tetrakis(dimethylamino)titanium) and titanium tetrachloride (TiCl4) can be used, and reactive gases can be reducing or oxidizing gases. Furthermore, when forming tungsten films, precursors such as WF6 can be used, and reactive gases can be reducing gases.

[0050] The precursor can be selected to control the depth of the protective films 300, 301 to be formed. For example, among aminosilane-based gases, when selecting a precursor for forming the protective films 300, 301 only above the pattern, it is preferable to use an aminosilane gas having two or three amino groups (divalent aminosilane or trivalent aminosilane) rather than an aminosilane gas having one amino group (monovalent aminosilane). Furthermore, it is preferable to use a monovalent aminosilane gas to form the protective films 300, 301 at a deep position in the pattern. Furthermore, by combining the precursor with process parameters such as the process time, the temperature of the mounting table, and the pressure in the process chamber, the controllability of the unsaturated state can be improved.

[0051] In addition, plasma may be generated when supplying the precursor and reactive gas. For example, the plasma can dissociate the precursor and reactive gas to generate more adsorbent precursor radicals and more reactive reactive gas radicals, thereby promoting precursor adsorption and reactive gas reaction. However, if the precursor and reactive gas react sufficiently spontaneously on their own, plasma generation is not necessarily required.

[0052] The substrate processing method according to the above embodiment can be applied to the manufacture of semiconductor devices having high aspect ratio patterns, not limited to 3D NAND, DRAM, etc. For example, it can be applied to the processing of high aspect ratio organic films used in multilayer resist masks, etc. Here, a high aspect ratio means that the ratio of the depth to the width of the recess is at least 5, or 10 or more.

[0053] (Second embodiment - Control using inhibitors) FIG. 10 is a flowchart showing an example of the flow of a substrate processing method according to a second embodiment. FIG. 11 is a diagram showing an example of a pattern formed by a substrate processing method according to a second embodiment. The workpiece shown in FIG. 11A is the same as the workpiece shown in FIG. 2A. In the first embodiment, subconformal film formation is achieved by adjusting the adsorption position and reaction position for at least one of the first gas and the second gas. In the second embodiment, a factor that inhibits precursor adsorption (hereinafter also referred to as an inhibitor) is further formed in advance on a part of the surface of the workpiece to control the precursor adsorption position. For example, a factor that forms a hydrophobic group that inhibits precursor adsorption is formed on the upper part of the workpiece by CVD.

[0054] First, a workpiece is provided (step S200). For example, a substrate on which a high aspect ratio pattern is formed is placed in the processing chamber, as in the first embodiment. Alternatively, for example, a substrate without a pattern is placed in the processing chamber, and the substrate is partially etched to form a pattern. Next, a gas containing an inhibitor that inhibits adsorption of the first gas is introduced into the processing chamber (step S201). The gas containing the inhibitor is, for example, a gas containing carbon. The gas containing carbon is, for example, a fluorocarbon gas, a fluorohydrocarbon gas, or a hydrocarbon gas. In FIG. 11A, when plasma CVD is performed using a fluorocarbon gas, a fluorohydrocarbon film is formed as the inhibitor layer IN. In FIG. 11A, when plasma CVD is performed using a fluorohydrocarbon gas, a fluorohydrocarbon film is formed as the inhibitor layer IN. In FIG. 11A, when plasma CVD is performed using a hydrocarbon gas, a hydrocarbon film is formed as the inhibitor layer IN. The fluorocarbon film, the fluorohydrocarbon film, and the hydrocarbon film are hydrophobic films. Here, the processing conditions of the plasma CVD are adjusted to form the inhibitor layer IN as shown in Fig. 11(B). In the example of Fig. 11(B), the inhibitor layer IN is formed on the top portion 200T and the bottom portion 200B.

[0055] Next, as shown in FIG. 11C, a first gas (precursor P, first reactant) is introduced into the processing chamber (step S202, first process). The precursor P does not adsorb to the portion where the inhibitor layer IN is formed. Therefore, the precursor P is selectively adsorbed to the sidewall 200S (see FIG. 11D). After purging the processing chamber (step S203), a second gas (reactant gas R, second reactant) is introduced into the processing chamber (step S204, second process, FIG. 11E). The reactant gas R reacts with atoms of the precursor P only at the positions where the precursor P adsorbed, forming a protective film 302. Therefore, as shown in FIG. 11E, the protective film 302 is formed only on the sidewall 200S. The processing chamber is then purged (step S205). Steps S206 to S208 are the same as steps S105 to S107 in FIG.

[0056] In the second embodiment, for example, an aminosilane-based gas, a silicon-containing gas, a titanium-containing gas, a hafnium-containing gas, a tantalum-containing gas, a zirconium-containing gas, an organic substance-containing gas, or the like can be used as the precursor P. The precursor P is adsorbed only in the region where the inhibitor layer IN is not formed, thereby forming a precursor layer. Note that plasma may or may not be generated when the precursor P is adsorbed.

[0057] After the introduction of the precursor P, a purging step is performed using an inert gas such as argon or nitrogen gas before the introduction of the reaction gas R to reduce or remove the precursor P remaining in the processing chamber, mainly in the gas phase. Alternatively, the purging step may be performed by evacuating the processing chamber. Excess precursor P is removed by purging, resulting in a precursor layer that is approximately a monolayer.

[0058] The reactive gas R may be an oxygen-containing gas, a nitrogen-containing gas, a hydrogen-containing gas, or the like. The reactive gas R may contain, for example, any of O2 gas, CO2 gas, NO gas, SO2 gas, N2 gas, H2 gas, and NH3 gas. The reactive gas R modifies the precursor layer to form the protective film 302, and at the same time, removes the surface of the inhibitor layer IN, thereby reducing or eliminating the thickness of the inhibitor layer IN.

[0059] The purging step after forming the protective film 302 is performed using an inert gas such as argon or nitrogen gas to reduce or eliminate the reaction gas R remaining in the processing chamber. Alternatively, the purging step may be performed by evacuating the processing chamber.

[0060] In this way, when the protective film 302 is formed using an inhibitor, the formation position and film thickness of the protective film 302 can be further adjusted. Furthermore, the formation position of the protective film 302 can be controlled in the same manner as in the first embodiment. Therefore, according to the second embodiment, the formation of the protective film 302 on the top portion can be prevented by the inhibitor, and the formation of the protective film 302 on the lower sidewall can be prevented by adjusting the processing conditions. Therefore, according to the second embodiment, in addition to the effects obtained from the first embodiment, it is possible to more effectively prevent the opening from being blocked during the formation of the protective film.

[0061] 12 and 13 are diagrams illustrating the prevention of opening blockage by the substrate processing method according to the second embodiment. (A) and (B) of FIG. 12 show CD sizes of patterns on a processing object in the initial state and after film formation, corresponding to the depth direction from the interface between the mask and the film to be etched. Note that the difference between the CD size in the initial state and the CD size after film formation, divided by 2, indicates the amount of film formed on the sidewall (one side) of the pattern. In (A) of FIG. 12, the dashed line indicates the initial state of the processing object. The dashed line indicates the result of film formation by conventional ALD on a processing object in the initial state (Reference Example 1). The solid line indicates the result of film formation by conventional ALD on a processing object in the initial state after forming an inhibitor layer by plasma CVD on the processing object in the initial state (Reference Example 2). In (B) of FIG. 12, the dashed line indicates the initial state of the processing object. The dashed line indicates the result of film formation by the substrate processing method according to the first embodiment on a processing object in the initial state (Example 1). The solid line shows the result of film formation on an object to be processed in an initial state using the substrate processing method according to the second embodiment (Example 2).

[0062] As shown in FIG. 12A, when a film is formed using conventional ALD, the use of an inhibitor layer suppresses the formation of a protective film down to a depth of approximately 0.6 μm below the mask. However, at depths deeper than approximately 0.6 μm, a nearly conformal protective film is formed. On the other hand, as shown in FIG. 12B, when a film is formed using the substrate processing method according to the second embodiment, the use of an inhibitor layer reduces the thickness of the protective film down to a depth of approximately 0.6 μm below the mask by approximately half, and at depths deeper than approximately 0.6 μm, the formation of the protective film is suppressed as if an inhibitor layer were not used. In this way, the use of an inhibitor layer allows for even finer control of the thickness of the protective film above the pattern. Furthermore, the thickness difference of the protective film in the depth direction of the pattern can be maintained.

[0063] Furthermore, FIG. 13 schematically illustrates the state of the openings at the top of the masks in the initial state shown in FIG. 12 and in each of Reference Example 1, Reference Example 2, Example 1, and Example 2. In the initial state, the opening size near the top of the mask is approximately 45 nanometers (nm). In contrast, when a film is formed by conventional ALD (Reference Example 1), the opening size decreases to approximately 30 nm. On the other hand, when a film is formed by conventional ALD after forming an inhibitor layer (Reference Example 2), the opening size remains at approximately 42 nm. In contrast, when a film is formed by the substrate processing method according to the first embodiment (Example 1), the opening size is approximately 21 nm. On the other hand, when a film is formed by the substrate processing method according to the second embodiment after forming an inhibitor layer (Example 2), the opening size remains at approximately 40 nm. Thus, the effect of preventing the opening from being blocked by using an inhibitor layer to suppress film formation near the top of the mask as in the second embodiment was confirmed.

[0064] Furthermore, in the second embodiment, the protective film can be formed at any position by adjusting the position where the inhibitor layer is formed. Therefore, the protective film can be formed at a desired position while adjusting the thickness of the protective film according to expected pattern shape abnormalities, such as bowing and necking. Furthermore, by making the inhibitor layer formation position aspect-dependent, the film formation position on the sidewall can be adjusted. Furthermore, by changing the composition of the inhibitor layer, it is possible to inhibit either the adsorption of ALD precursors or the adsorption of reactant gases. For example, forming an inhibitor layer containing carbon can inhibit oxidation, while forming an inhibitor layer containing CF can inhibit precursor adsorption.

[0065] (Third embodiment) In the first and second embodiments, a film is formed by varying the coverage rate in the height direction of a high aspect ratio pattern. However, the embodiments disclosed herein are applicable not only to high aspect ratio patterns but also to low aspect ratio patterns, for example, patterns with an aspect ratio of less than 5. Therefore, as the third embodiment, an embodiment applicable to low aspect ratio patterns will be described. In the following description, "low aspect ratio" refers to an aspect ratio of less than 5.

[0066] 14 is a diagram illustrating a substrate processing method according to a third embodiment. The object to be processed in FIG. 14 includes a substrate 101 and an etching target film 102 and a mask 120, which are stacked on the substrate 101, similar to the object to be processed S shown in FIG.

[0067] First, a processing object is prepared in which a pattern having an aspect ratio of less than 5 is formed in the etching target film 102 (FIG. 14(A)). At this time, the aspect ratio calculated from the upper surface of the mask 120 may be less than 5, and the aspect ratio calculated from the upper surface of the etching target film 102 may be about 1 to 2.

[0068] Next, a process is performed to narrow the width of the opening 200 formed in the object to be processed, i.e., the width of the top portion 200T. For example, a preliminary film 303 is formed on the upper portion of the sidewall 200S by chemical vapor deposition (CVD) or physical vapor deposition (PVD). The preliminary film 303 is formed using process conditions that cause it to be formed mainly on the upper portion of the sidewall 200S, but not on the lower portion of the sidewall 200S or the bottom portion 200B (FIG. 14(B)).

[0069] Next, similarly to the first embodiment, a protective film 304 is formed by ALD under conditions in which the process is terminated when the adsorption of the precursor or the reaction of the reactant gas is not saturated, i.e., when the process is not completed down to the bottom surface. At this time, the protective film 304 is formed on the sidewall 200S, but not on the bottom 200B (FIG. 14C).

[0070] Next, the etching target film 102 is etched (FIG. 14(D)). When the depth dimension of the recess reaches a preset dimension or when the etching processing time reaches a preset processing time, the etching is terminated. The timing at which the etching is terminated can be set arbitrarily.

[0071] Next, the preliminary film 303 and the protective film 304 remaining on the top portion 200T and the upper portion of the sidewall 200S are removed (FIG. 14(E)).

[0072] As described above, according to the substrate processing method of the third embodiment, etching is performed after covering with the protective film 300 the position where shape abnormalities such as bowing may occur, i.e., the portion of the etching target film 102 directly below the mask 120, and therefore shape abnormalities such as bowing can be suppressed.

[0073] Furthermore, the substrate processing method according to the third embodiment allows for the formation of a subconformal ALD film for a pattern with a small aspect ratio, e.g., less than 5. In the first and second embodiments, when forming a protective film for a high-aspect-ratio pattern, the amount of film deposition is controlled to gradually decrease from the top to the bottom of the sidewall. However, when the aspect ratio of the pattern formed on the workpiece is small, the precursor and reaction gases reach the bottom of the recess in a short time. For this reason, it is difficult to form a subconformal ALD film for a low-aspect-ratio pattern. On the other hand, when using CVD or PVD for a low-aspect-ratio pattern, precise control of the film thickness is difficult.

[0074] Therefore, in the third embodiment, when the aspect ratio of a pattern formed on a processing target is small, a process for reducing the opening dimensions of the pattern is performed in advance (FIG. 14B). By performing such a process, the aspect ratio of the pattern is increased and the amount of precursor and reactant gas entering the opening is reduced. Therefore, according to the third embodiment, a subconformal ALD film can be formed even for a pattern with a low aspect ratio, achieving fine film thickness control.

[0075] FIG. 15 is a flowchart showing an example of the flow of a substrate processing method according to the third embodiment. First, a mask 120 is formed on an etching target film 102, and a processing target is provided, with a pattern for etching formed on the mask 120 (step S1501). Alternatively, an unpatterned processing target may be introduced into a chamber and partially etched to form a pattern on the mask. Next, the etching target film 102 is etched (step S1502). It is determined whether the depth of the recess formed in the etching target film 102 after etching reaches a predetermined value (step S1503). If it is determined that the depth does not reach the predetermined value (step S1503, NO), the process returns to step S1502 and repeats the etching. On the other hand, if it is determined that the depth reaches the predetermined value (step S1503, YES), it is determined whether the aspect ratio of the recess is equal to or greater than a predetermined value (e.g., 10) (step S1504). If it is determined that the aspect ratio is less than the predetermined value (step S1504, NO), a preliminary film 303 is formed to narrow the width of the opening 200 (step S1505). Then, the process returns to step S1504. On the other hand, if it is determined that the aspect ratio is equal to or greater than the predetermined value (step S1504, YES), the protective film 304 is formed (step S1506). The process for forming the protective film 304 is similar to the process for forming the protective film in the first embodiment. For example, the protective film 304 can be formed by performing steps S101 to S105 in FIG. 1. After the protective film 304 is formed, etching is further performed (step S1507). Then, it is determined whether the object has a predetermined shape (step S1508). For example, it is determined whether the depth of the recess formed in the etching target film 102 by etching has reached a predetermined depth. If it is determined that the object has not achieved the predetermined shape (step S1508, NO), the process returns to step S1504 and repeats. On the other hand, if it is determined that the object has achieved the predetermined shape (step S1508, YES), the process ends. This concludes the substrate processing method according to the third embodiment.

[0076] In this way, in the third embodiment, even for a pattern with a low aspect ratio, a protective film can be formed by subconformal ALD with a high aspect ratio by performing a process to narrow the opening in advance.

[0077] In the third embodiment, a "low aspect ratio" is defined as an aspect ratio of less than 5, and the process according to the third embodiment is applied to a pattern with a low aspect ratio. However, even for a pattern with an aspect ratio of 5 or more, if the aspect ratio is less than 10, it may be difficult to achieve subconformal film formation. Therefore, the method of the third embodiment may be applied to a pattern with an aspect ratio of 5 to 10.

[0078] It is preferable that the preliminary film 303 be formed of a material that can be removed in subsequent processing. For example, the preliminary film 303 is formed of SiO2, SiN, SiC, or the like. When forming the preliminary film 303 of SiO2, aminosilane-based gases, SiCl4, SiF4, or the like can be used as precursors. When forming the preliminary film 303 of SiN, aminosilane-based gases, SiCl4, DCS, HCDS, or the like can be used as precursors. Furthermore, the preliminary film 303 may be, for example, an organic film such as a carbon-containing film, or a metal film containing titanium (Ti) or tungsten (W), or the like.

[0079] (Variation 1 - Changing the processing conditions according to the mask thickness) So far, the first to third embodiments have been described. Each embodiment can be further modified. FIG. 16 is a flowchart showing an example of the flow of a substrate processing method according to Modification 1. FIG. 17 is a diagram for explaining an example of a process target object processed by the substrate processing method according to Modification 1. Modification 1 addresses a reduction in the film thickness of a mask during processing of a process target object based on the techniques of the first and second embodiments.

[0080] The object to be processed S1 shown in FIG. 17A has the same shape as the object to be processed S shown in FIG. 2. In the substrate processing method according to the first modification, the processes from providing the object to be processed S1 (step S100) to etching (step S106) are the same as those in the first embodiment. By the processes from step S100 to step S106, for example, the object to be processed S1 shown in FIG. 17B is formed. The object to be processed S1 has an etching target film 102A and a mask 120A formed on a substrate 101A. A recess having an opening 200A is formed in the etching target film 102A and the mask 120A. A protective film 130A is formed on the top and above the sidewall of the recess. The protective film 130A is formed up to just below the mask 120A, where shape abnormalities due to etching are likely to occur. Furthermore, the inner wall of the protective film 130A is removed by etching. 17B, ​​when steps S101 to S106 are repeatedly performed, the top of the mask 120A is gradually removed, and the distance from the top of the mask 120A to the upper surface of the etching target film 102A changes (FIG. 17C). In this case, if the protective film 130A is formed without changing the processing conditions of the first and second steps, the position where the protective film 130A is formed will be lower than directly below the mask 120A, where shape abnormalities occur.

[0081] Therefore, in Modification 1, after etching (Step S106) and Step S107, it is determined whether the film thickness of the mask 120A is a predetermined value (Step S108). The determination of whether the film thickness of the mask 120A is a predetermined value may be made based on the film thickness of the mask 120A before processing the object S1 and the number of times Steps S101 to S106 are performed. Alternatively, the determination of whether the film thickness of the mask 120A is a predetermined value may be made based on a measured film thickness. The film thickness measurement method is not particularly limited, and for example, the film thickness may be measured by an optical method. If it is determined that the film thickness of the mask 120A is a predetermined value (Step S108, Yes), the processing conditions for the first or second step are reset (Step S109). For example, if the processing conditions for the first step are set so that the coverage rate varies along the depth direction of the pattern, the processing conditions are changed so that the first gas is adsorbed only to a portion higher in the pattern. For example, the processing time for the next first step is made shorter than the processing time for the immediately preceding first step. Furthermore, for example, if the processing conditions are set so that the coverage in the second step varies along the depth direction of the pattern, the processing conditions are changed so that the second gas reacts only with the upper portion of the pattern. For example, the temperature of the processing chamber is lowered. On the other hand, if it is determined that the film thickness of the mask 120A is not the predetermined value (step S108, No), the processing conditions are not changed and the process returns to step S101.

[0082] In this way, by adjusting the processing conditions according to the film thickness of the mask 120A, the protective film 130A can be selectively formed in locations where shape abnormalities are likely to occur. For example, in the object to be processed shown in FIG. 17C, the film thickness of the mask 120A is about half that at the start of processing, and the distance from the top to the etching target film 102A is shortened. In this case, the processing conditions are changed to shorten the depth direction distance over which the protective film 130A is formed. As a result, as shown in FIG. 17D, the protective film 130A can be continuously formed in locations directly below the mask 120A where shape abnormalities are likely to occur.

[0083] Furthermore, even if bowing occurs in the etching target film 102A, the pattern shape can be corrected by updating the processing conditions and executing steps S101 to S104.

[0084] In this way, if the aspect ratio of the recess having the opening 200A increases due to etching (step S106) after the first and second steps, the processing conditions may be changed. For example, the processing conditions of at least one of the first step (step b-1) and the second step (step b-2) may be changed depending on the increase in aspect ratio. For example, the transport amount of radicals generated in the second step may be increased. That is, as the number of etching steps (step S106) increases, the processing conditions may be changed so that the position where the protective film 130A is formed is above the etching target film 102A. Note that the processing conditions may be different each time the first and second steps are repeated, or may be different after the first and second steps are repeated several times. The processing conditions may also be changed appropriately depending on factors other than the mask film thickness.

[0085] (Fourth embodiment) In the first embodiment, it was explained that when a recess whose diameter decreases from the top to the bottom is formed, the protective film can be used to suppress dimensional variations in the sidewall while increasing the dimension of the bottom (see paragraph 0044). As a fourth embodiment, the dimensional control of the recess will be further described. The substrate processing method according to the fourth embodiment can improve the degree of freedom in controlling the shape of the pattern to be formed.

[0086] Fig. 18 is a flowchart showing an example of the flow of the substrate processing method according to the fourth embodiment. Fig. 19 and Fig. 20 are views showing examples of objects to be processed by the substrate processing method according to the fourth embodiment.

[0087] First, a processing target S2 (see FIG. 19(A)) is provided (step S1800). The processing target S2 includes a substrate 101B, an etching target film 102B formed on the substrate 101B, and a mask 120B (see FIG. 19(A)). The mask 120B has an opening 200A'. The opening 200A' has a bottom 201 and a sidewall 202. The bottom 201 of the opening 200A' reaches the etching target film 102B. In step S1800, the etching target film 102B is partially etched through the mask 120B.

[0088] Next, as in the first embodiment, a protective film 130A (see FIG. 17) is formed by a first process (step S1801), purging (step S1802), a second process (step S1803), and purging (step S1804). When the protective film 130A reaches a predetermined thickness (step S1805, Yes), the object to be processed S2 is etched (step S1806). On the other hand, when it is determined that the protective film 130A does not reach the predetermined thickness (step S1805, No), the process returns to step S1801 and is repeated. The processes of steps S1801 to S1806 are the same as the processes of steps S101 to S106 in FIG. 16, and the purging of steps S1802 and S1804 may be omitted. In addition, in this embodiment, when etching the workpiece S2 in step S1806, if the bowing described in the first embodiment does not occur or the impact of the bowing is small, it is possible to omit the processing of steps S1801 to S1804.

[0089] Next, it is determined whether the depth of the opening 200A' formed in the object S2 to be processed has reached a predetermined value (step S1807). For example, it is determined whether the depth of the opening 200A' has reached the upper surface of the substrate 101B. If it is determined that the depth of the opening 200A' has not reached the upper surface of the substrate 101B (step S1807, No), the process returns to step S1805 and is repeated. On the other hand, if it is determined that the depth of the opening 200A' has reached the upper surface of the substrate 101B (step S1807, Yes), it is determined whether the opening dimension of the bottom 201 is equal to or greater than a predetermined value (step S1808). The opening dimension of the bottom 201 is the lateral dimension of the bottom 201. Hereinafter, the lateral dimension of the bottom 201 will also be referred to as the bottom CD (Critical Dimension). The "predetermined value" in steps S1807 and S1808 is set in advance based on the device design, etc.

[0090] Here, it is assumed that the ideal shape of opening 200A' is one in which sidewalls 202 extend vertically from the top to the bottom 201. It is also assumed that the "predetermined value" in step S1808 is set to the bottom CD of the ideal shape. It is also assumed that opening 200A' is formed with the tapered shape shown in FIG. 19(B). In this case, it is determined in step S1808 that the bottom CD is less than the predetermined value (No in step S1808). If it is determined that the bottom CD is less than the predetermined value, protective film 130B is formed (step S1809, see FIG. 19(C)). Protective film 130B is formed on top 203 and sidewalls 202 of opening 200A'. In the example of FIG. 19(C), protective film 130B is formed so that its thickness gradually decreases from the upper side to the lower side of sidewall 202. The protective film 130B may be formed by subconformal ALD, as with the protective film 130A (see FIG. 17), or by plasma enhanced chemical vapor deposition (PECVD). When PECVD is used, the process gas may be, for example, SiCl, O, or a rare gas. The rare gas may be, for example, Ar, He, or Kr. The chamber pressure may be 10 mTorr to 1 Torr, and the radio frequency (RF) power may be 50 W or more.

[0091] Next, the object to be processed S2 on which the protective film 103B is formed is etched (trimmed) (step S1810). At this time, the portion of the sidewall 202 covered with the protective film 130B is not etched, and the width of the uncovered lower portion or the lower portion where the protective film 130B is thinner than the upper portion is increased by etching compared to the upper portion (see FIG. 19(D)). After the etching in step S18010, the process returns to step S1808.

[0092] If it is determined in step S1808 that the bottom CD is equal to or greater than the predetermined value (Yes in step S1808), the process ends. For example, if the predetermined value in step S1808 is set to be substantially equal to the top dimension of the opening, the shape of the object S2 to be processed at the end of the process will be, for example, the shape shown in FIG. 19(D).

[0093] The etching in step S1806 and the etching in step S1810 are performed under different processing conditions. The processing conditions for the etching in step S1806 are set so as to mainly dig opening 200A' in the depth direction. On the other hand, the processing conditions for the etching in step S1810 are set so as to enlarge bottom 201 of opening 200A' in the lateral direction. For example, the processing conditions for step S1806 are set so as to achieve anisotropic etching, and the processing conditions for step S1810 are set so as to achieve isotropic etching. The processing in step S1810 may be performed using, instead of etching, for example, COR (Chemical Oxide Removal), a method of Modification 3 described below.

[0094] For example, if the etching target film 102B is a silicon oxide (SiO2) film, a fluorocarbon (CF)-based etching gas can be used in the etching of step S1806. For example, C4F6, C4F8, etc. can be used. Alternatively, a mixture of a CF-based gas with argon (Ar) gas and oxygen (O2) gas can be used. Furthermore, a hydrofluorocarbon (CHF)-based etching gas such as CH3F, CH2F2, or CHF3 can be added. On the other hand, a fluorine-containing gas can be used as the etching gas in step S1810. For example, NF3 can be used.

[0095] Furthermore, for example, if the etching target film 102B is an organic film, an oxygen-containing gas can be used in the etching of step S1806. For example, O, CO, CO, etc. can be used as the etching gas. In this case, an oxygen-containing gas can also be used as the etching gas in step S1810.

[0096] As for processing conditions other than the processing gas, it is preferable that the chamber pressure during the processing of step S1806 is about 10 to 30 mTorr, and that during the processing of step S1810 it is 100 mTorr or more. Also, the radio frequency (RF) voltage for bias generation applied during plasma generation is set to be higher during the processing of step S1806 than during the processing of step S1810.

[0097] When the method of Modification 3 is used in step S1810, a mixed gas of a fluorine-containing gas and NH3, or a mixed gas of N2 and H2 can be used. As the fluorine-containing gas, NF3, SF6, or CF-based gas can be used.

[0098] In this manner, in the substrate processing method according to the fourth embodiment, after forming an opening of a desired depth, a film of varying thickness is formed along the depth direction of the opening, and the processing object is then etched. This allows the dimensions of the lower portion of the opening that is not covered by the film to be expanded laterally, thereby adjusting the dimensions of the opening. Therefore, according to the fourth embodiment, abnormalities in the shape of the pattern in the film to be etched can be further suppressed.

[0099] Furthermore, the substrate processing method according to the fourth embodiment may be performed not only after the bottom 201 of the opening 200A' reaches the upper surface of the substrate 101B, but also during etching of the etching target film 102B. Figure 20 shows an example in which the substrate processing method according to the fourth embodiment is applied during etching of the etching target film 102B.

[0100] The object S2 shown in FIG. 20A is the same as the object S2 shown in FIG. 19A. The shape shown in FIG. 20B is obtained during the process of digging the opening 200A′ from the state shown in FIG. 19A to the state shown in FIG. 19B. For example, in step S1807 of FIG. 18, the “predetermined value” is set to a depth that does not reach the substrate 101B. Then, step S1808 is executed when the bottom 201 of the opening 200A′ is located within the etching target film 102B. Furthermore, for example, based on the execution times of steps S1800 and S1806, step S1808 is executed when the bottom 201 of the opening 200A′ is located within the etching target film 102B. Then, from the state shown in FIG. 20B, the formation of a protective film in step S1809 (see FIG. 20C) and the etching in step S1810 (see FIG. 20D) are executed. By changing the determination process in this way, it is possible to start the process for enlarging the bottom CD from the state shown in Fig. 20(B), which makes it possible to adjust the shape of opening 200A' while suppressing damage to substrate 101B.

[0101] In this way, in the substrate processing method according to the fourth embodiment, the protective film 130B may be formed when the bottom 201 of the opening 200A' is located within the etching target film 102B. Therefore, according to the fourth embodiment, it is possible to suppress a decrease in the bottom CD and also suppress the occurrence of bowing.

[0102] (Bottom CD determination) The method of determination in step S1808 is not limited. For example, the bottom CD may be determined by inspecting the shape of the object S2 to be processed by optical means or the like. Alternatively, the bottom CD may be determined based on the number of times or the time taken for steps S1801 to S1804 and step S1806 to be performed. Alternatively, if step S1810 is performed, the bottom CD may be determined based on the time taken for step S1810 to be performed. The "predetermined value" in step S1808 is set in advance based on a design value.

[0103] (Determining whether or not a protective film needs to be formed) Furthermore, whether or not to form a protective film (step S1809) may be determined before step S1809. The method of determination is not particularly limited. For example, whether or not to form the protective film 130B may be determined depending on the thickness and / or position of the protective film 130B remaining on the sidewall 202. Furthermore, for example, whether or not to form the protective film 130B may be determined depending on the number of times or the time for which steps S1801 to S1804 and step S1806 are performed. Furthermore, if the protective film (130A in FIG. 17) formed in steps S1801 to S1804 remains, whether or not to perform step S1809 may be determined depending on the thickness and / or position of the protective film.

[0104] Note that the determination of whether to form the protective film in step S1808 may be performed collectively. For example, the process may end when the number of executions of steps S1801 to S1804 and step S1806 reaches the value V1. Also, when the number of executions of steps S1801 to S1804 and step S1806 is less than the value V2 (V2 < V1), the protective film 130B may be formed. Further, when the number of executions of steps S1801 to S1804 and step S1806 is less than the value V3 (V3 < V2), etching (S1810) may be performed without forming the protective film 130B.

[0105] (Film type) The film types of the etching target film 102B, the mask 120B, and the protective film 130B are not particularly limited. For example, the substrate 101B may be a silicon wafer. The etching target film 102B may be a dielectric film, for example, a silicon-containing dielectric film. The etching target film 102B may be formed by laminating a plurality of types of films. For example, the etching target film 102B may be a layer in which a silicon oxide film and a silicon nitride film are sequentially laminated. The etching target film 102B may be a layer in which a silicon oxide film and a polysilicon film are sequentially laminated. The mask 120B may be a carbon-containing film. The carbon-containing film may be formed of an amorphous carbon layer (ACL) or a spin-on carbon film (SOC). Alternatively, the mask 120B may be formed of a metal film. Also, although not shown in FIGS. 19 and 20, there may be a silicon oxynitride film (SiON) or a backside antireflection coating (BARC) having an opening pattern similar to that of the mask 120B formed on the mask 120B. The protective film 130B may be a silicon-containing film. Also, the film types of the mask 120B and the etching target film 102B may be the same.

[0106] In the substrate processing method according to the embodiment, when the etching target film 102B is a silicon-containing dielectric film, the mask 120B may be a carbon-containing film such as ACL or SOC. Also, when the etching target film 102B is a polysilicon film, the mask 120B may be a silicon oxide film formed using TEOS (tetraethoxysilane) or the like.

[0107] In the substrate processing method according to the fourth embodiment, plasma may or may not be used in forming the protective film in step S1809 and in etching in step S1810.

[0108] Furthermore, the substrate processing method according to the fourth embodiment can be applied to patterns with various aspect ratios, including not only high aspect ratio patterns but also low aspect ratio patterns. For example, the substrate processing method according to the fourth embodiment can be suitably applied to patterns with aspect ratios of 10 to 20.

[0109] (Variation 2 - Adjusting film thickness within the wafer surface) In the first embodiment, the coverage and thickness of the protective film are adjusted by adjusting the processing conditions. The processing conditions in the first and second steps can be adjusted from the following two perspectives. (1) By controlling the amount of precursor and reactive gas introduced, the film formation position in the depth direction of the pattern can be controlled. (2) Controlling the thickness of the protective film to be formed

[0110] In the first and second embodiments, the film formation position is controlled mainly from the viewpoint of (1). In the second modification, the processing conditions are further adjusted from the viewpoint of (2). FIG. 21 is a diagram for explaining the relationship between the temperature of the object to be processed and the amount of film formation. The wafer processed in the substrate processing apparatus is, for example, a disk-shaped wafer with a diameter of approximately 300 mm. It is known that when a film formation process is performed on a wafer, the amount of film formation varies depending on the wafer temperature. (A) of FIG. 21 shows the relationship between the wafer temperature and the amount of film formation. As shown in (A), the amount of film formation increases as the wafer temperature increases, and decreases as the wafer temperature decreases.

[0111] In Modification 2, the wafer mounting table (electrostatic chuck) is divided into multiple concentric zones, and the temperature of each zone can be controlled independently. This allows the thickness of the protective film formed at any position to be controlled to a desired thickness. For example, it is known that during processing such as etching, shape abnormalities (e.g., bowing) are small in the center of the wafer and large in the edge of the wafer. In such a case, the temperature of the center, where shape abnormalities tend to be small, is controlled to be lower than that of the edge, where shape abnormalities tend to be large. By controlling in this manner, the thickness of the protective film formed can be adjusted according to the radial position of the wafer, improving the in-plane uniformity of the dimensions of the formed openings.

[0112] In addition, by providing multiple zones divided into radial and circumferential directions for film thickness control and independently controlling the temperature in each zone as shown in Figure 21(B), temperature control can be used to improve in-plane uniformity as well. For example, it is possible to realize processes such as forming openings of different shapes by changing the thickness of the protective film formed at each position on the wafer.

[0113] (Variation 3 - Removal of oxide film) When manufacturing a semiconductor device, a native oxide film may form on the wafer W. This native oxide film may need to be removed, which may result in the removal or damage of other surrounding films. Therefore, it is preferable to remove the native oxide film without damaging the surrounding films. The substrate processing method according to this embodiment allows the amount of film formation to be varied in the depth direction of the pattern. Therefore, a protective film is not formed on the oxide film formed on the bottom of the recess, but is formed on other portions, thereby suppressing damage during the removal of the native oxide film.

[0114] FIG. 22 is a diagram illustrating an example of a process target object processed by the substrate processing method according to Modification 3. FIG. 22A is a diagram illustrating an example of a process target object on which an oxide film is formed. The process target object (e.g., a semiconductor wafer W) has an SiO2 film 140 formed on an underlying silicon (Si) layer 101C. A pattern is formed on the SiO2 film 140. In FIG. 22, a recess reaching the Si layer 101C is formed as the pattern in the SiO2 film 140. The upper surface of the SiO2 film 140 and the sidewall of the recess are covered with a SiN film 150. Furthermore, the wafer W has a native oxide film 160 (SiO2) formed on the Si layer 101C at the bottom of the recess. The Si layer 101C is shown with a different pattern because the portion of the native oxide film 160 that will become the bottom of the recess has been converted to silicon germanium or the like.

[0115] In the substrate processing method according to the third modification, a protective film 300C is formed on the sidewalls of the recess, the thickness of which decreases in the depth direction, using steps S101 to S104 of the first embodiment. In the substrate processing method according to the first embodiment, a film is not formed on the bottom of the recess, but on the sidewalls and top. This allows the protective film 300C shown in FIG. 22B to be formed. Then, after the protective film 300C is formed, etching is performed. Because the sidewalls are covered with the protective film 300C, damage to the SiN film 150 below the protective film 300C can be suppressed, and the native oxide film 160 on the bottom and the protective film 300C on the sidewalls can be removed. As a result, the object to be processed shown in FIG. 22C is obtained.

[0116] In this way, when the protective film 300C is formed using subconformal ALD, it is possible to form a film on the sidewalls and top of the recess but not on the bottom, so that the native oxide film 160 can be removed without reducing the etching rate at the bottom. Furthermore, by forming the protective film 300C on the sidewalls of the recess, damage to the SiO2 film 140 and the SiN film 150 can be suppressed.

[0117] In the above embodiment, an example has been described in which a protective film is used to suppress the occurrence of shape abnormalities in a semiconductor pattern. However, the present invention is not limited to this example, and if a shape abnormality occurs in a mask during pattern formation, the substrate processing method according to the embodiment can be used to correct the shape abnormality.

[0118] (Conditioning in the chamber) In the above embodiment, for example, the film formation in steps S101 to S104 in FIG. 1 and the etching in step S106 may be performed in a single chamber. In this case, by-products generated by the etching may adhere to the chamber interior and affect the conditions during film formation. In contrast, if only the film formation process of the same film is performed in a single chamber, a film of the same type as the film formed on the workpiece may be incidentally formed on the inner walls of the chamber and on the surfaces of other components. Therefore, the state of the film formed by film formation may differ when only the film formation process is performed in a single chamber compared to when both film formation and etching are performed in a single chamber.

[0119] Therefore, after performing the etching of this embodiment (for example, step S106 in FIG. 1), conditioning of the surfaces exposed to the plasma space in the chamber may be performed. Conditioning can include (1) cleaning the inside of the chamber and (2) coating the inside of the chamber.

[0120] The inside of the chamber is cleaned, for example, by generating plasma from a predetermined cleaning gas in the chamber and then discharging it. Examples of cleaning gases that can be used include oxygen-containing gases such as O2 and CO2, and hydrogen-containing gases such as H2 and NH3. The cleaning method is not particularly limited. The inside of the chamber is cleaned under conditions that remove carbon and fluorine adhering to the outermost surface (the inner surface of the chamber), for example.

[0121] Coating inside the chamber is performed by converting a specific coating gas into plasma inside the chamber and then discharging it. A silicon oxide film (SiO2) or the like can be formed by CVD or ALD using a silicon-containing gas such as SiCl4 or an aminosilane-based gas and an oxygen-containing gas such as O2 as the coating gas. The coating method is not particularly limited. The material to be coated is also not particularly limited. Coating is performed, for example, after plasma processing using fluorine (CF, etc.). The coating covers by-products exposed on the outermost surface of the chamber, preventing them from being exposed to the plasma processing space.

[0122] The cleaning and coating for conditioning are performed under conditions that treat the entire inner wall of the chamber, not just the area around the stage on which the workpiece is placed. Furthermore, the cleaning and coating for conditioning may be performed after each plasma processing run, or after a predetermined number of plasma processing runs. This prevents the inner surface, to which by-products have adhered, from being exposed to the plasma processing space. This prevents fluctuations in the conditions and state within the chamber between processes, stabilizing the state of the film formed.

[0123] (Other variations) In the above embodiment, the first and second steps constitute one cycle, and the cycle may be repeated any number of times. Furthermore, in the above embodiment, a film formed by ALD was described as an example of a film having self-regulating properties. However, the present invention is not limited to this, and a self-assembled monolayer (SAM), for example, may also be used as the protective film.

[0124] (An example of a substrate processing apparatus according to an embodiment) FIG. 23 is a diagram showing an example of a substrate processing apparatus according to an embodiment that is used to perform a substrate processing method according to an embodiment. FIG. 23 schematically shows a cross-sectional structure of a substrate processing apparatus 10 that can be used in various embodiments of the substrate processing method according to an embodiment. As shown in FIG. 23, the substrate processing apparatus 10 is a plasma etching apparatus equipped with parallel plate electrodes and includes a processing vessel 12. The processing vessel 12 has a substantially cylindrical shape and defines a processing space Sp. The processing vessel 12 is made of, for example, aluminum, and its inner wall surface is anodized. The processing vessel 12 is protectively grounded.

[0125] A substantially cylindrical support member 14 is provided on the bottom of the processing vessel 12. The support member 14 is made of, for example, an insulating material. The insulating material that forms the support member 14 may contain oxygen, such as quartz. The support member 14 extends vertically from the bottom of the processing vessel 12 within the processing vessel 12. A mounting table PD is provided within the processing vessel 12. The mounting table PD is supported by the support member 14.

[0126] The mounting table PD holds the wafer W on its upper surface. The main surface FW of the wafer W is located opposite the back surface of the wafer W that contacts the upper surface of the mounting table PD and faces the upper electrode 30. The mounting table PD has a lower electrode LE and an electrostatic chuck ESC. The lower electrode LE includes a first plate 18a and a second plate 18b. The first plate 18a and the second plate 18b are made of a metal such as aluminum and have a substantially disk shape. The second plate 18b is provided on the first plate 18a and is electrically connected to the first plate 18a.

[0127] An electrostatic chuck ESC is provided on the second plate 18b. The electrostatic chuck ESC has a structure in which an electrode, which is a conductive film, is disposed between a pair of insulating layers or a pair of insulating sheets. A DC power supply 22 is electrically connected to the electrode of the electrostatic chuck ESC via a switch 23. When the wafer W is placed on the mounting table PD, the wafer W comes into contact with the electrostatic chuck ESC. The back surface of the wafer W (the surface opposite to the main surface FW) comes into contact with the electrostatic chuck ESC. The electrostatic chuck ESC attracts the wafer W by electrostatic force such as Coulomb force generated by a DC voltage from the DC power supply 22. This allows the electrostatic chuck ESC to hold the wafer W.

[0128] An edge ring ER is disposed on the peripheral portion of the second plate 18b so as to surround the edge of the wafer W and the electrostatic chuck ESC. The edge ring ER is provided to improve etching uniformity. The edge ring ER is made of a material appropriately selected depending on the material of the film to be etched, and may be made of, for example, silicon or quartz.

[0129] A coolant flow path 24 is provided inside the second plate 18b. The coolant flow path 24 constitutes a temperature control mechanism. A coolant is supplied to the coolant flow path 24 from a chiller unit (not shown) provided outside the processing chamber 12 via a pipe 26a. The coolant supplied to the coolant flow path 24 is returned to the chiller unit via a pipe 26b. In this manner, the coolant is supplied to the coolant flow path 24 so as to circulate. By controlling the temperature of this coolant, the temperature of the wafer W supported by the electrostatic chuck ESC can be controlled.

[0130] The substrate processing apparatus 10 is provided with a gas supply line 28. The gas supply line 28 supplies a heat transfer gas, for example, He gas, from a heat transfer gas supply mechanism to between the upper surface of the electrostatic chuck ESC and the back surface of the wafer W.

[0131] The substrate processing apparatus 10 is provided with a temperature adjustment unit HT that adjusts the temperature of the wafer W. The temperature adjustment unit HT is built into the electrostatic chuck ESC. A heater power supply HP is connected to the temperature adjustment unit HT. When power is supplied from the heater power supply HP to the temperature adjustment unit HT, the temperature of the electrostatic chuck ESC is adjusted, and the temperature of the wafer W placed on the electrostatic chuck ESC is adjusted. The temperature adjustment unit HT may also be embedded in the second plate 18b.

[0132] The substrate processing apparatus 10 includes an upper electrode 30. The upper electrode 30 is disposed above the mounting table PD and faces the mounting table PD. The lower electrode LE and the upper electrode 30 are disposed substantially parallel to each other and form parallel plate electrodes. A processing space Sp for processing the wafer W is provided between the upper electrode 30 and the lower electrode LE.

[0133] The upper electrode 30 is supported on the upper part of the processing chamber 12 via an insulating shielding member 32. The insulating shielding member 32 is made of an insulating material, and may contain oxygen, such as quartz. The upper electrode 30 may include an electrode plate 34 and an electrode support 36. The electrode plate 34 faces the processing space Sp and has a plurality of gas discharge holes 34a. In one embodiment, the electrode plate 34 contains silicon (hereinafter, may be referred to as silicon). In another embodiment, the electrode plate 34 may contain silicon oxide.

[0134] The electrode support 36 detachably supports the electrode plate 34 and may be made of a conductive material such as aluminum. The electrode support 36 may have a water-cooled structure. A gas diffusion chamber 36a is provided inside the electrode support 36. A plurality of gas flow holes 36b that communicate with the gas discharge holes 34a extend downward from the gas diffusion chamber 36a.

[0135] The substrate processing apparatus 10 includes a first high-frequency power supply 62 and a second high-frequency power supply 64. The first high-frequency power supply 62 generates a first high-frequency power for plasma generation at a frequency of 27 to 100 MHz, for example, 60 MHz. The first high-frequency power supply 62 is pulse-driven and can be controlled at a frequency of 0.1 to 50 kHz with a duty cycle of 5 to 100%. The first high-frequency power supply 62 is connected to the lower electrode LE via a matching device 66. The matching device 66 is a circuit for matching the output impedance of the first high-frequency power supply 62 with the input impedance of the load (lower electrode LE side). The first high-frequency power supply 62 may also be connected to the upper electrode 30 via the matching device 66.

[0136] The second high frequency power supply 64 is a power supply that generates second high frequency power, i.e., high frequency bias power, for attracting ions into the wafer W. The second high frequency power supply 64 generates high frequency bias power at a frequency within a range of 400 kHz to 40.68 MHz, for example, a frequency of 13.56 MHz. The second high frequency power supply 64 is pulse-type and can be controlled at a frequency of 0.1 to 50 kHz with a duty cycle of 5 to 100%. The second high frequency power supply 64 is connected to the lower electrode LE via a matching box 68. The matching box 68 is a circuit for matching the output impedance of the second high frequency power supply 64 with the input impedance of the load side (lower electrode LE side).

[0137] The substrate processing apparatus 10 further includes a power supply 70. The power supply 70 is connected to the upper electrode 30. The power supply 70 applies a voltage to the upper electrode 30 to attract positive ions present in the processing space Sp to the electrode plate 34. In one example, the power supply 70 is a DC power supply that generates a negative DC voltage. When such a voltage is applied from the power supply 70 to the upper electrode 30, the positive ions present in the processing space Sp collide with the electrode plate 34. This can cause secondary electrons and / or silicon to be emitted from the electrode plate 34.

[0138] An exhaust plate 48 is provided on the bottom side of the processing vessel 12, between the support 14 and the sidewall of the processing vessel 12. The exhaust plate 48 can be made, for example, of aluminum coated with ceramics such as Y2O3. An exhaust port 12e is provided below the exhaust plate 48 and in the processing vessel 12. An exhaust unit 50 is connected to the exhaust port 12e via an exhaust pipe 52. The exhaust unit 50 has a vacuum pump such as a turbomolecular pump and can reduce the pressure inside the processing vessel 12 to a desired vacuum level. A loading / unloading port 12g for the wafer W is provided in the sidewall of the processing vessel 12, and the loading / unloading port 12g can be opened and closed by a gate valve 54.

[0139] The gas source group 40 has a plurality of gas sources. The plurality of gas sources may include various gas sources such as an aminosilane-based gas source containing organic compounds, a fluorocarbon-based gas source (CxFy gas (x and y are integers from 1 to 10)), a gas source containing oxygen atoms (oxygen gas, etc.), and an inert gas source. Any gas such as nitrogen gas, Ar gas, or He gas may be used as the inert gas.

[0140] The valve group 42 includes a plurality of valves, and the flow rate controller group 44 includes a plurality of flow rate controllers such as mass flow controllers. Each of the plurality of gas sources in the gas source group 40 is connected to the gas supply pipe 38 and the gas supply pipe 82 via a corresponding valve in the valve group 42 and a corresponding flow rate controller in the flow rate controller group 44. Therefore, the substrate processing apparatus 10 can supply gases from one or more selected gas sources from the plurality of gas sources in the gas source group 40 into the processing chamber 12 at individually adjusted flow rates.

[0141] The processing chamber 12 is provided with a gas inlet 36c. The gas inlet 36c is provided above the wafer W placed on the mounting table PD inside the processing chamber 12. The gas inlet 36c is connected to one end of a gas supply pipe 38. The other end of the gas supply pipe 38 is connected to a valve group 42. The gas inlet 36c is provided in the electrode support 36. The gas supplied from the gas inlet 36c to the processing space Sp via the gas diffusion chamber 36a is supplied to a spatial region above the wafer W between the wafer W and the upper electrode 30.

[0142] The processing chamber 12 is provided with a gas inlet 52a. The gas inlet 52a is provided in the processing chamber 12 on the side of the wafer W placed on the mounting table PD. The gas inlet 52a is connected to one end of a gas supply pipe 82. The other end of the gas supply pipe 82 is connected to the valve group 42. The gas inlet 52a is provided in the sidewall of the processing chamber 12. The gas supplied from the gas inlet 52a to the processing space Sp is supplied to a spatial region above the wafer W between the wafer W and the upper electrode 30.

[0143] In the substrate processing apparatus 10, a deposit shield 46 is detachably provided along the inner wall of the processing vessel 12. The deposit shield 46 is also provided on the outer periphery of the support part 14. The deposit shield 46 prevents etching by-products (deposits) from adhering to the processing vessel 12, and may be formed by coating an aluminum material with a ceramic such as Y2O3. In addition to Y2O3, the deposit shield may also be formed from a material containing oxygen, such as quartz.

[0144] The control unit Cnt is a computer including a processor, a storage unit, an input device, a display device, etc., and controls each unit of the substrate processing apparatus 10 shown in FIG.

[0145] The control unit Cnt operates in accordance with a computer program (a program based on an input recipe) for controlling each part of the substrate processing apparatus 10 in each step of a substrate processing method according to an embodiment, and sends control signals. Each part of the substrate processing apparatus 10 is controlled by a control signal from the control unit Cnt. Specifically, in the substrate processing apparatus 10 shown in FIG. 23 , the control unit Cnt can use control signals to control the selection and flow rate of gas supplied from the gas source group 40, the exhaust of the exhaust device 50, the power supply from the first high-frequency power supply 62 and the second high-frequency power supply 64, the voltage application from the power supply 70, the power supply from the heater power supply HP, the coolant flow rate and coolant temperature from the chiller unit, and the like. Note that each step of the substrate processing method disclosed herein can be performed by operating each part of the substrate processing apparatus 10 under the control of the control unit Cnt. A computer program for executing the substrate processing method according to an embodiment and various data used in executing the method are readably stored in a memory unit of the control unit Cnt.

[0146] (Effects of the embodiment) The substrate processing method according to the embodiment includes steps a) and b). In step a), the workpiece is partially etched to form a recess. In step b), a film having a thickness that varies along the depth direction of the recess is formed on the sidewall of the recess. Step b) includes steps b-1) and b-2). In step b-1), a first reactant is supplied and adsorbed onto the sidewall of the recess. In step b-2), a second reactant is supplied and the first reactant and the second reactant are reacted to form a film. Therefore, according to the embodiment, the thickness of a film formed on a high aspect ratio pattern can be varied along the depth direction. Therefore, according to the embodiment, a protective film can be formed in advance with a thickness that varies along the depth direction in a pattern position where shape abnormalities are likely to occur. Therefore, according to the embodiment, shape abnormalities in a semiconductor pattern can be suppressed. Furthermore, according to the embodiment, a self-controlling film, such as an ALD film, is formed, so the thickness of the protective film to be formed can be precisely controlled. Therefore, according to the embodiment, clogging of openings in a pattern can be suppressed. Furthermore, according to the embodiment, by suppressing the formation of a protective film on the bottom of the pattern, it is possible to prevent etch stop and improve the etching rate. Furthermore, according to the embodiment, by adjusting the processing conditions of steps b-1) and b-2), it is possible to significantly change the coverage of the protective film along the depth direction of the pattern.

[0147] In addition, in the embodiment, in step b), step b-1) does not allow the first reactant to be adsorbed on the entire surface of the recess, and / or step b-2) does not allow the first reactant and the second reactant to react on the entire surface of the recess. That is, the substrate processing method according to the embodiment may be terminated before the first reactant is completely adsorbed on the entire surface in the depth direction of the pattern. Therefore, by adjusting the processing conditions in step b-1), the position where the protective film is formed can be adjusted. In addition, in the embodiment, step b-2) may be terminated before the reaction of the second reactant on the entire surface in the depth direction of the pattern is completely completed. Therefore, by adjusting the processing conditions in step b-2), the position where the protective layer is formed can be adjusted. For example, by not forming the protective layer at the bottom, a decrease in the etching rate can be suppressed.

[0148] Furthermore, the substrate processing method according to the embodiment may further include, after step b), step c) of etching the bottom of the recess to form a recess with a high aspect ratio. Therefore, according to the embodiment, the pattern after the formation of the protective layer can be further processed to achieve a desired shape.

[0149] In addition, in the substrate processing method according to the embodiment, step b) may be further performed after step c), so that, according to the embodiment, even if the protective film is lost due to etching, the protective film can be formed again to form a desired pattern.

[0150] In the substrate processing method according to the embodiment, the workpiece may include a substrate, a film to be etched formed on the substrate, and a mask formed on the film to be etched. The substrate processing method may further include a step d) of forming a preliminary film on the mask to reduce the opening dimensions of the recess. Therefore, the substrate processing method according to the embodiment may reduce the opening dimensions of the top of the recess by, for example, forming a preliminary film on the pattern formed on the workpiece by chemical vapor deposition or physical vapor deposition. Therefore, the substrate processing method according to the embodiment increases the aspect ratio of the recess. Therefore, according to the embodiment, film formation using subconformal ALD can be achieved even for recesses with low aspect ratios.

[0151] In the substrate processing method according to the embodiment, step d) may be performed before step b), so that sub-conformal ALD can be performed after correcting the aspect ratio of the recess.

[0152] In the substrate processing method according to the embodiment, step d) may be performed when the aspect ratio of the recess is less than 10. In the substrate processing method according to the embodiment, step d) may be performed when the ratio of the depth dimension from the upper surface of the mask to the bottom of the recess to the top opening dimension of the recess is less than 15. In the substrate processing method according to the embodiment, steps a) and b) may be repeatedly performed when the aspect ratio of the recess is 10 or more, or when the ratio of the depth dimension from the upper surface of the mask to the bottom of the recess to the top opening dimension of the recess is 15 or more. Therefore, according to the embodiment, when the aspect ratio of the recess becomes low, subconformal ALD can be interrupted and a process to increase the aspect ratio can be performed. Furthermore, while the aspect ratio of the recess is high, subconformal ALD can be effectively performed. In this way, according to the embodiment, the aspect ratio of the recess can be adjusted to a value suitable for film formation control, and then film formation can be performed.

[0153] In the substrate processing method according to the embodiment, after step a) or step c), the processing conditions of at least one of steps b-1) and b-2) may be changed depending on the aspect ratio of the recessed portion. Therefore, according to the embodiment, a protective film suitable for the state of the pattern after etching can be formed, and pattern processing can be continued.

[0154] Furthermore, in the substrate processing method according to the embodiment, in step b) which is repeatedly performed n times (n is a natural number of 2 or more), processing conditions may be changed between the nth processing and the (n-1)th processing. This may change the position and / or thickness of the film formed in the repeatedly performed b). Therefore, according to the embodiment, the shape and / or position of the film to be formed can be adjusted more finely.

[0155] Furthermore, in the substrate processing method according to the embodiment, in step b) which is repeatedly performed n' times (n' is a natural number of 2 or more), the first reactant and the second reactant used in the n'th process and the (n'-1)th process may be changed. This may change the position and / or thickness of the film formed in the repeatedly performed step b). Therefore, according to the embodiment, the shape and / or position of the film to be formed can be adjusted more finely.

[0156] Furthermore, a substrate processing method according to an embodiment may include steps a), b), and e). In step a), a processing object placed on a mounting table in a processing chamber is etched to form a recess. In step b), a film having a thickness that varies along the depth direction of the recess is formed on the sidewall of the recess. In step e), the processing object is etched while suppressing variations in the opening dimension of the upper part of the recess by the film formed in step b), and the opening dimension of the lower part of the recess that is not covered by the film formed in step b) is expanded in the lateral direction.

[0157] In the substrate processing method according to the embodiment, step e) may widen the opening dimension of the lower part of the recess not covered with the film in the vertical direction in addition to the horizontal direction. Also, when step b) is followed by a step of etching the bottom of the recess to form a recess with a high aspect ratio, step c) may etch the bottom of the recess by anisotropic etching, and step e) may widen the opening dimension of the lower part of the recess by isotropic etching in the horizontal direction.

[0158] In the substrate processing method according to the embodiment, in step b), each of a plurality of independently temperature-controllable zones provided on the mounting table on which the workpiece is placed may be controlled to a different temperature depending on the in-plane position of each of the plurality of zones. This allows the thickness of the film to be changed depending on the temperatures of the plurality of zones. Therefore, according to the embodiment, the film formation state can be adjusted by controlling the temperature of the mounting table.

[0159] In addition, in the substrate processing method according to the embodiment, steps a), b), and c) may be repeated at least n" (n" is a natural number equal to or greater than 2). Then, in step b-2) of the (n"-1)th iteration, each of a plurality of independently temperature-controllable zones provided on a mounting table on which the object to be processed is placed may be controlled to a first temperature distribution. This may result in the formation of a first film having a first film thickness distribution in the depth direction. Furthermore, in step b-2) of the n"th iteration, each of the plurality of zones may be controlled to a second temperature distribution. This may result in the formation of a second film having a second film thickness distribution in the depth direction. Therefore, according to the embodiment, the film formation state can be adjusted by controlling the temperature of the mounting table.

[0160] In the substrate processing method according to the embodiment, the pressure of the processing chamber in step b-1) may be set to a value lower than the pressure that completes adsorption of the first reactant to the entire surface in the depth direction of the recess, under the same processing conditions. The processing time in step b-1) may be set to a time shorter than the processing time that completes adsorption of the first reactant to the entire surface in the depth direction of the recess, under the same processing conditions. The dilution of the first reactant in step b-1) may be set to a value higher than the dilution that completes adsorption of the first reactant to the entire surface in the depth direction of the recess, under the same processing conditions. The temperature of the workpiece mounting table in step b-1) may be set to a temperature lower than the temperature that completes adsorption of the first reactant to the entire surface in the depth direction of the recess, under the same processing conditions. When plasma is generated in step b-1), the absolute value of the radio frequency (RF) power applied for plasma generation may be set to a value smaller than the absolute value that completes the reaction of the second reactant to the entire surface in the depth direction of the recess, under the same processing conditions. In this way, by adjusting the processing conditions in step b-1), the coverage rate along the depth direction of the recesses can be changed, thereby realizing adsorption of the components contained in the first reactant onto the processing target.

[0161] In the substrate processing method according to the embodiment, the pressure of the processing chamber in step b-2) may be set to a value lower than the pressure that completes the reaction of the second reactant on the entire surface in the depth direction of the recess, under the same processing conditions. The processing time in step b-2) may be set to a time shorter than the processing time that completes the reaction of the second reactant on the entire surface in the depth direction of the recess, under the same processing conditions. The dilution of the second reactant in step b-2) may be set to a value higher than the dilution that completes the reaction of the second reactant on the entire surface in the depth direction of the recess, under the same processing conditions. The temperature of the workpiece mounting table in step b-2) may be set to a temperature lower than the temperature that completes the reaction of the second reactant on the entire surface in the depth direction of the recess, under the same processing conditions. When plasma is generated in step b-2), the absolute value of the radio frequency (RF) power applied for plasma generation may be set to a value smaller than the absolute value that completes the reaction of the second reactant on the entire surface in the depth direction of the recess, under the same processing conditions. In this way, by adjusting the processing conditions in step b-2), the coverage rate along the depth direction of the recesses can be changed, and the reaction of the components contained in the second reactant on the surface of the object to be processed can be achieved.

[0162] Furthermore, the substrate processing method according to the above embodiment may further include, before step b-1), step f) of forming an inhibitor that inhibits adsorption of the first reactant on the sidewall of the recess, so that the protective film can be formed at any position according to the embodiment.

[0163] Furthermore, the substrate processing method according to the above embodiment may further include, after step a), step g) of applying a coating to cover by-products adhering to the inner wall of the processing chamber. Therefore, according to the embodiment, fluctuations in the conditions and state within the processing chamber can be prevented. Therefore, according to the embodiment, the state of the formed film can be stabilized.

[0164] In the substrate processing method according to the above embodiment, step b) may further include steps b-3), b-4), and b-5). In step b-3), a parameter indicating the state of the formed film is measured. In step b-4), it is determined whether the film is in a preset state based on the measured value. In step b-5), if the film is not in the preset state, the processing conditions are adjusted based on the measured value, and steps b-1) and b-2) are repeated.

[0165] Furthermore, the substrate processing apparatus according to the above embodiment includes one or more processing chambers, at least one of which is configured to perform etching and at least one of which is configured to form a film, and a control unit. The processing chamber includes a gas supply unit that supplies a processing gas into the processing chamber. The control unit controls each unit to perform a substrate processing method. The substrate processing method includes steps a) and b). Step a) partially etches the object to form a recess. Step b) forms a film on the sidewall of the recess, the film having a thickness that varies along the depth direction of the recess. Step b) also includes steps b-1) and b-2). Step b-1) supplies a first reactant into the processing chamber configured to form a film, causing the first reactant to adsorb on the sidewall of the recess. Step b-2) supplies a second reactant into the processing chamber configured to form a film, and reacts the first reactant with the second reactant to form a film. Therefore, according to the embodiment, the film thickness of the film formed on a high aspect ratio pattern can be varied along the depth direction. Therefore, according to the embodiment, a protective film can be formed with a thickness that is varied in advance in the depth direction at a position of a pattern where shape abnormalities are likely to occur. Therefore, according to the embodiment, shape abnormalities of a semiconductor pattern can be suppressed. Furthermore, according to the embodiment, a film having self-controlling properties, such as an ALD film, is formed, so the film thickness of the protective film to be formed can be precisely controlled. Therefore, according to the embodiment, blocking of openings in the pattern can be suppressed. Furthermore, according to the embodiment, by suppressing the formation of a protective film at the bottom of the pattern, etch stop can be prevented and the etching rate can be improved. Furthermore, according to the embodiment, the coverage rate of the protective film along the depth direction of the pattern can be significantly changed by adjusting the processing conditions of steps b-1) and b-2).

[0166] Furthermore, in the substrate processing apparatus according to the above embodiment, the processing chamber configured for etching may be the same processing chamber as the processing chamber configured for forming the film, and steps a) and b) may be performed in the same processing chamber.

[0167] In the substrate processing apparatus according to the above embodiment, the processing chamber configured for etching may be a processing chamber different from the processing chamber configured for forming the film, and the control unit may cause each unit to execute a substrate processing method further including the step of: h) transferring the substrate between the processing chamber configured for etching and the processing chamber configured for forming the film.

[0168] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive, and the above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims. [Explanation of symbols]

[0169] 10. Substrate processing equipment 12 Processing container 14 Support part 22 DC power supply 24 refrigerant flow path 28 Gas supply line 30 Upper electrode 32 Insulating shielding material 101, 101A, 101B board 102, 102A, 102B Etching target film 120, 120A, 120B Masks 130A,130B Protective film 140 SiO2 film 150 SiN film 160 Native oxide film 200,200A,200A' opening 300,301,302,304 Protective film 303 Spare Film ESC electrostatic chuck ER Edge Ring HT temperature control section HP Heater Power Supply LE bottom electrode PD mounting stand Sp processing space W wafer

Claims

1. a processing chamber; a mounting table within the processing chamber; a gas supply unit that supplies a processing gas to the processing chamber; a first high frequency power supply for generating a first high frequency power for generating plasma; a second RF power supply for generating RF bias power; a control unit configured to control the gas supply unit, the first high frequency power supply, and the second high frequency power supply; Equipped with The control unit controls the gas supply unit, the first high frequency power supply, and the second high frequency power supply to perform a process including etching, and the process includes: (a) preparing a processing object having a tapered opening formed therein on the mounting table; (b) forming a film having a thickness that varies along a depth direction of the opening on a sidewall of the opening; (c) enlarging the opening size of a lower portion of the opening; (d) repeating steps (b) and (c); Including, The step (c) includes etching the bottom of the opening.

2. a processing chamber; a mounting table within the processing chamber; a gas supply unit that supplies a processing gas to the processing chamber; a first high frequency power supply for generating a first high frequency power for generating plasma; a second RF power supply for generating RF bias power; a control unit configured to control the gas supply unit, the first high frequency power supply, and the second high frequency power supply; Equipped with The control unit controls the gas supply unit, the first high frequency power supply, and the second high frequency power supply to perform a process including etching, and the process includes: (a) preparing a processing object having a tapered opening formed therein on the mounting table; (b) forming a film having a thickness that varies along a depth direction of the opening on a sidewall of the opening; (c) enlarging the opening size of a lower portion of the opening; (d) after (c), etching the bottom of the opening; A plasma processing apparatus comprising:

3. a processing chamber; a mounting table within the processing chamber; a gas supply unit that supplies a processing gas to the processing chamber; a first high frequency power supply for generating a first high frequency power for generating plasma; a second RF power supply for generating RF bias power; a control unit configured to control the gas supply unit, the first high frequency power supply, and the second high frequency power supply; Equipped with The control unit controls the gas supply unit, the first high frequency power supply, and the second high frequency power supply to perform a process including etching, and the process includes: (a) preparing a processing object having a tapered opening formed therein on the mounting table; (b) forming a film having a thickness that varies along a depth direction of the opening on a sidewall of the opening; (c) enlarging the opening size of a lower portion of the opening; Including, The (b) is (b-1) supplying a first reactant and allowing the first reactant to be adsorbed on the sidewall of the opening; (b-2) supplying a second reactant and reacting the first reactant with the second reactant to form a film; A plasma processing apparatus comprising:

4. (b-1) does not allow the first reactant to be adsorbed on the entire surface of the opening, and / or 4. The plasma processing apparatus according to claim 3, wherein the step (b-2) prevents the first reactant from reacting with the second reactant over the entire surface of the opening.

5. The plasma processing apparatus of claim 3, further comprising, before (b-1), a step of forming an inhibitor that inhibits adsorption of the first reactant on the sidewall of the opening.

6. A plasma processing apparatus described in any one of claims 3 to 5, wherein after (c), the processing conditions of at least one of (b-1) and (b-2) are changed depending on the aspect ratio of the opening.

7. a processing chamber; a mounting table within the processing chamber; a gas supply unit that supplies a processing gas to the processing chamber; a first high frequency power supply for generating a first high frequency power for generating plasma; a second RF power supply for generating RF bias power; a control unit configured to control the gas supply unit, the first high frequency power supply, and the second high frequency power supply; Equipped with The control unit controls the gas supply unit, the first high frequency power supply, and the second high frequency power supply to perform a process including etching, and the process includes: (a) preparing a processing object having a tapered opening formed therein on the mounting table; (b) forming a film having a thickness that varies along a depth direction of the opening on a sidewall of the opening; (c) enlarging the opening size of a lower portion of the opening; (e) forming a pre-film on top of the mask to reduce the opening size of the opening, the pre-film being performed after (a) and before (b); Including, The plasma processing apparatus, wherein the object to be processed includes a substrate, an etching target film formed on the substrate, and the mask formed on the etching target film.

8. The plasma processing apparatus according to claim 1 , wherein the step (c) enlarges the size of the lower opening by using the film while suppressing a change in the size of the upper opening of the opening.

9. a first chamber configured to etch; a second chamber configured to form a membrane; A control unit; Equipped with The control unit (a) placing a workpiece having a tapered opening formed therein in the first chamber; (b) forming a film having a thickness that varies along a depth direction of the opening on a sidewall of the opening; (c) transferring the object to be processed from the first chamber to the second chamber; (d) placing the object to be treated on which the film is formed in the second chamber; (e) enlarging the opening size of a lower portion of the opening; A substrate processing apparatus that performs a process including the steps of:

10. The substrate processing apparatus according to claim 9 , wherein the step (e) enlarges the size of the lower opening by the film while suppressing a change in the size of the upper opening of the opening.

11. The substrate processing apparatus according to claim 9 , wherein the step (e) includes etching a bottom of the opening.

12. The control unit (f) performing a process further including a step of transferring the object to be processed from the second chamber to the first chamber; The substrate processing apparatus according to claim 11 , wherein the steps (b) to (f) are repeated.

13. The control unit The substrate processing apparatus according to claim 9 , further comprising: (g) performing a process including, after (e), etching the bottom of the opening.

14. The control unit, in (b), (b-1) supplying a first reactant and allowing the first reactant to be adsorbed on the sidewall of the opening; (b-2) supplying a second reactant and reacting the first reactant with the second reactant to form a film; The substrate processing apparatus according to claim 9 , wherein the substrate processing apparatus performs a process including the steps of:

15. (b-1) does not allow the first reactant to be adsorbed on the entire surface of the opening, and / or 15. The substrate processing apparatus according to claim 14, wherein (b-2) prevents the first reactant from reacting with the second reactant over the entire surface of the opening.

16. 15. The substrate processing apparatus according to claim 14, wherein the control unit executes a process further including, before (b-1), forming an inhibitor that inhibits adsorption of the first reactant on a sidewall of the opening.

17. The substrate processing apparatus according to any one of claims 14 to 16, wherein the control unit, after (e), executes a process of changing the processing conditions of at least one of (b-1) and (b-2) depending on the aspect ratio of the opening.

18. the workpiece includes a substrate, an etching target film formed on the substrate, and a mask formed on the etching target film; The control unit 18. The substrate processing apparatus of claim 9, further comprising: (h) performing a process that is performed after (a) and before (b), and further includes a step of forming a preliminary film on top of the mask to reduce an opening size of the opening.

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