Substrate processing method

Abstract

A substrate processing method capable of forming a film having improved step coverage and / or improved and / or more uniform properties on a surface of a gap structure having a high aspect ratio is provided. An exemplary substrate processing method includes providing a gap structure; supplying a gas including a source gas onto the interstitial structure; generating an active substance from the source gas; generating neutral molecules by neutralizing the active material and moving the neutral molecules in a direction toward a lower surface of a recess extending between the first step portion and the second step portion; and exciting the neutral molecules to move in a direction toward the lower surface.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. continuation-in-part application No. 18 / 205,716, filed on June 5, 2023, entitled “SUBSTRATE PROCESSING METHOD,” the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] One or more embodiments are directed to methods of processing a substrate including a recessed region, and more particularly, to methods of depositing a material within the recessed region. Background Art

[0004] As the integration of semiconductor devices increases, the aspect ratio (A / R) of the gap structure also generally increases. As the depth of the gap structure increases compared to the width of the gap structure entrance, the technical difficulty of filling the gap structure (also referred to herein as the recessed region) without seams or gaps becomes increasingly difficult.

[0005] Atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) has the advantage of being able to deposit a film with uniform thickness on the wall and bottom surfaces of the gap structure. However, since source gas and reactant gas are sequentially supplied and purged with a time difference, the substrate processing speed is slow.

[0006] On the other hand, in chemical vapor deposition (CVD) or plasma enhanced chemical vapor deposition (PECVD), source gas and reactant gas are supplied simultaneously, and therefore, the film formation rate and substrate processing speed are greater than those of ALD, but there is a limitation in maintaining a uniform film thickness over the gap structure. When the gap is filled by using CVD, the film formation rate of the upper portion of the gap structure is high, generating what is generally called a protrusion, so that the entrance of the gap is closed before the inside of the gap is filled.

[0007] In particular, as the miniaturization of semiconductor devices accelerates, the aspect ratio of the gap structure and the surface area inside the gap are increasing. Therefore, in order to fill the gap structure by conventional ALD, the supply time and purge time of the source gas and the reactant gas increase, and the substrate processing speed decreases. Conventional CVD also has a large difference in the film formation rate between the upper and lower regions of the gap structure, and the entrance of the gap is first closed, so that the gap or seam remains inside the gap. In addition, in the case of an atomic layer deposition process or a chemical vapor deposition process using plasma, it is difficult for the active material to reach the bottom surface of the gap, and the characteristics of the films deposited on the upper and lower regions of the gap are different, so that cracks may occur during subsequent heat treatment.

[0008] Additionally, for the PEALD process, the ion density at the bottom of the high aspect ratio gap can be relatively low. The relatively low ion density can result in relatively poor material being deposited near the bottom of the gap. The resulting uneven film quality in the vertical direction within the gap can lead to crack formation in the material deposited within the gap.

[0009] Therefore, there is a need for improved methods of depositing materials within gaps, particularly high aspect ratio gaps (eg, having an aspect ratio greater than 10). Summary of the invention

[0010] One or more embodiments include atomic layer deposition and chemical vapor deposition in a gap fill process. In more detail, one or more embodiments include methods capable of increasing film formation rates while depositing uniform thin films with improved step coverage on surfaces of gap structures having high aspect ratios (HAR) (e.g., aspect ratios greater than 10).

[0011] One or more embodiments include forming a film having uniform properties on upper and lower regions of a gap structure having a relatively high aspect ratio.

[0012] One or more embodiments include suppressing the occurrence of voids inside a gap by maintaining a width of a gap entrance greater than a width inside the gap during filling of a gap structure having a higher aspect ratio.

[0013] According to one or more embodiments, a substrate processing method includes: providing a gap structure having a first step and a second step; supplying a gas including a source gas to the gap structure; generating an active substance from the source gas; neutralizing the active substance and generating neutral molecules, and moving the neutral molecules in a direction toward a lower surface of a recess extending between the first step and the second step; and exciting the neutral molecules moving in a direction toward the lower surface.

[0014] According to an example of the substrate processing method, during excitation of neutral molecules, layer formation in a first region adjacent to a lower surface of the recessed portion between the first step and the second step may be promoted.

[0015] According to another example of the substrate processing method, during generation of active species from a source gas, layer formation in a second region adjacent to edges of the first step and the second step may be promoted.

[0016] According to another example of the substrate processing method, by exciting neutral molecules and generating active species from a source gas, step coverage of layers formed on the first region and the second region may be increased.

[0017] According to another example of the substrate processing method, during the neutralization of the active species, an edge potential formed at the edges of the first step and the second step may be reduced.

[0018] According to another example of the substrate processing method, when the neutral molecules move in the direction toward the lower surface, the remaining active species may move in the direction toward the lower surface without being affected by the edge potential.

[0019] According to another example of the substrate processing method, the substrate processing method may further include applying plasma in a pulsed manner.

[0020] According to another example of the substrate processing method, during the application of plasma, at least one of a first frequency RF power of 13 MHz or higher and a second frequency RF power of 1 MHz or lower may be applied.

[0021] According to another example of the substrate processing method, applying plasma in the operation of generating active species may include an on period during which generation of active species from a source gas may be performed and an off period during which neutralization of the active species may be performed.

[0022] According to another example of the substrate processing method, excitation of neutral molecules moving in a direction toward the lower surface may be performed during the on period.

[0023] According to another example of the substrate processing method, during supplying of a gas including a source gas, a reactant gas or a reactive purge gas may be supplied together with the source gas.

[0024] According to another example of the substrate processing method, the substrate processing method may further include post-processing.

[0025] According to another example of the substrate processing method, during the post-processing, supply of the source gas may be stopped.

[0026] According to another example of a substrate processing method, during post-processing, the layer may be densified.

[0027] According to another example of a substrate processing method, during post-processing, protruding portions of a layer may be removed.

[0028] According to another example of the substrate processing method, RF power during the post-processing may be greater than RF power during the generation of active species from the source gas.

[0029] According to another example of the substrate processing method, an RF frequency during the post-processing may be lower than an RF frequency during the generation of active species from the source gas.

[0030] According to another example of the substrate processing method, the RF frequency during the post-processing may further include an RF frequency supplied during the generation of active species from the source gas.

[0031] According to one or more embodiments, a substrate processing method includes: providing a gap structure having a first step and a second step; and supplying a gas including a source gas on the gap structure, wherein plasma is applied in a pulsed manner during the supplying of the gas including the source gas so that dissociated molecules of the source gas can diffuse between the first step and the second step in a direction toward a lower surface of the gap structure.

[0032] According to one or more embodiments, a substrate processing method includes: supplying a gas including a source gas onto a first step and a second step; generating active species from the source gas; and reducing ion trajectory distortion of the active species by reducing an edge potential at edges of the first step and the second step.

[0033] According to an additional embodiment of the present disclosure, a substrate processing method includes providing a substrate having a gap structure thereon into a reaction chamber of a reactor, and forming a first layer using a first cycle process, and forming a second layer using a second cycle process. The first cycle process may include supplying a first source gas into the reaction chamber, activating the first source gas, supplying a reactant into the reaction chamber, activating the reactant, and optionally repeating the steps of supplying the first source gas, activating the first source gas, and activating the reactant (which may be continuously supplied in the first and / or second process). The second cycle process may include supplying a second source gas into the reaction chamber, supplying a reactant into the reaction chamber, activating the reactant, and repeating the steps of supplying a second source gas and activating the reactant. According to a further example, the method may include the step of adjusting the reaction chamber.

[0034] Additional aspects will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the embodiments presented in the disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The above and other aspects, features and advantages of certain embodiments of the present disclosure will become more apparent from the following description in conjunction with the accompanying drawings, in which:

[0036] Figure 1 is a flow chart of a substrate processing method according to an embodiment;

[0037] Figures 2 to 5 is Figure 1 A cross-sectional view of a substrate processed in each step of the substrate processing method shown;

[0038] Figure 6 is a flow chart of a substrate processing method according to an embodiment;

[0039] Figure 7 is a flow chart of a substrate processing method according to an embodiment;

[0040] Figure 8is a flow chart of a substrate processing method according to an embodiment;

[0041] Fig. 9 is a flow chart of a substrate processing method according to an embodiment of the inventive concept;

[0042] Fig.10 is a view showing a gap filling method according to an embodiment;

[0043] Fig.11 It is shown Fig.10 A view of a first step (t1) showing the definition of the duty cycle;

[0044] 12(a) and 12(b) are views showing various types of RF pulses according to an embodiment;

[0045] Fig.13 is a view showing that a potential difference is formed in a reaction space when RF power is applied;

[0046] Fig.14 yes Fig.13 an enlarged view of a portion of a substrate;

[0047] Fig.15 are views showing step coverage when a SiO2 film is deposited on a gap structure by a continuous method (continuous wave pulsed CVD followed by plasma treatment) and by a pulsed method (pulsed wave pulsed CVD followed by plasma treatment), respectively, in a case where a gap filling process is performed by supplying RF power;

[0048] 16( a ) and 16( b ) are views showing a modified embodiment according to the present disclosure;

[0049] Fig.17 is a view showing an embodiment in which a substrate processing method according to an embodiment of the inventive concept is applied to a TSV process; and

[0050] Fig.18 Another exemplary method according to an embodiment of the present disclosure is shown. DETAILED DESCRIPTION

[0051] Reference will now be made in detail to embodiments, examples of which are shown in the accompanying drawings, wherein the same reference numerals represent the same elements throughout. In this regard, the present embodiment may have different forms and should not be construed as being limited to the description set forth herein. Therefore, the embodiments are described below only by reference to the accompanying drawings to explain various aspects of this specification. As used herein, the term "and / or" includes any and all combinations of one or more related listed items. When preceding a list of elements, expressions such as "at least one of..." modify the entire list of elements, without modifying the individual elements of the list.

[0052] In this regard, the embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Rather, these embodiments are provided to make this disclosure thorough and complete, and to fully convey the scope of the disclosure to those of ordinary skill in the art.

[0053] The terms used herein are used to describe specific embodiments and are not intended to limit the present disclosure. As used herein, the singular forms "a", "an", and "the" are also intended to include the plural forms, unless the context clearly indicates otherwise. It should also be understood that the terms "comprises", "includes", and variations thereof used herein specify the presence of stated features, integers, steps, processes, components, parts, and / or combinations thereof, but do not exclude the presence or addition of one or more other features, integers, steps, processes, components, parts, and / or combinations thereof.

[0054] It should be understood that although the terms first, second, etc. can be used here to describe various components, parts, regions, layers and / or parts, these components, parts, regions, layers and / or parts should not be limited by these terms. These terms do not represent any order, quantity or importance, but are only used to distinguish one component, region, layer and / or part from another component, region, layer and / or part. Therefore, without departing from the teachings of the embodiments, the first component, component, region, layer or part discussed below may be referred to as the second component, component, region, layer or part.

[0055] Embodiments of the present disclosure will be described below with reference to the accompanying drawings, in which exemplary embodiments of the present disclosure are schematically shown. In the accompanying drawings, variations from the shapes shown can be expected due to, for example, manufacturing techniques and / or tolerances. Therefore, embodiments of the present disclosure should not be interpreted as limited to the specific shapes of the regions shown herein, but may include deviations in shapes caused by, for example, the manufacturing process.

[0056] Figure 1 is a flow chart of a substrate processing method according to an embodiment. Figures 2 to 5 is Figure 1 A cross-sectional view of a substrate processed in each step of the substrate processing method is shown.

[0057] Reference Figure 1 and Figure 2 First, in operation S100, a gap structure 200 having a first protrusion P1 and a second protrusion P2 is provided. Each of the first step P1 and the second step P2 may have an edge portion E between an upper surface and a side surface. In addition, the edge portion E of the first step P1 and the second step P2 may have a certain curvature.

[0058] The gap structure 200 is a non-planar structure and may include an upper surface 202, a lower surface 204, and a side surface 206 connecting the upper surface 202 and the lower surface 204. The gap structure 200 can be used to form an active area, or can be used to form a gate pattern or a metal pattern. For example, when the gap structure 200 is used in a through silicon via (TSV) process, the gap structure 200 can be a structure stacking at least two silicon substrates. In addition, a metal line for electrical connection of the silicon substrate can be formed in a recess formed by the first step P1 and the second step P2. In some cases, the gap structure 200 can be a through hole, a recess, or a trench, where P1 and P2 show opposite sides of the gap structure.

[0059] The gap structure 200 may include a high aspect ratio gap, ie, a recess. The recess may be formed between the first step P1 and the second step P2. For example, the recess may have a depth of 1 to 100 micrometers and a width of 0.01 to 1 micrometer.

[0060] In another example, the gap structure 200 may be formed on a substrate, which may be, for example, a semiconductor substrate or a display substrate. The substrate may include, for example, any one of silicon, silicon on insulator, silicon on sapphire, germanium, silicon germanium, and gallium arsenide.

[0061] Refer again Figure 1 and Figure 2 , operation S110 of supplying a gas including a source gas S onto the gap structure 200 is performed. The source gas S may include a precursor for layer formation. For example, when a silicon oxide layer and / or a silicon nitride layer is to be formed on the gap structure, the source gas S may include a silicon precursor. Figure 2 A state in which a gas including a source gas S is supplied so that molecules of the source gas S are located on and / or within the gap structure 200 is shown.

[0062] In addition to the source gas, the gas including the source gas S may include at least one of a purge gas and a reactant gas. In other words, during operation S110 of supplying the gas including the source gas, the purge gas and / or the reactant gas may be supplied together with the source gas. In another embodiment, the purge gas and / or the reactant gas may be supplied after operation S110 of supplying the gas including the source gas.

[0063] In some embodiments, the gas including the source gas S may include a reactive purge gas. When not activated by plasma, the reactive purge gas may purge the reactor without reacting with the source gas S. On the other hand, when activated by plasma, the reactive purge gas may be excited / activated and chemically react with the source gas S to form a layer or film.

[0064] Reference Figure 1 and Figure 3, an operation S120 of generating active material A from source gas is performed. For example, source gas S( Figure 2 The decomposition of the (in) can be initiated by applying energy such as heat or plasma. For example, when using plasma as energy, RF power can be provided. In some embodiments, the RF power can have a frequency of, for example, 10 MHz, 13 MHz or higher. In an optional embodiment, two types of frequency power can be applied to the plasma application. For example, a first frequency power of 13 MHz or higher and a second frequency power of 1 MHz or lower can be applied.

[0065] Plasma application can be performed by a substrate processing device including a gas supply unit and a substrate support unit. The gas supply unit can be used as an electrode in a plasma process, such as a capacitively coupled plasma (CCP) method. In the CCP method, the substrate support unit can also be used as an electrode, so that capacitive coupling can be achieved by the gas supply unit used as a first electrode and the substrate support unit used as a second electrode.

[0066] During operation S120, as the source gas molecules are dissociated into negative ion electrons (not shown) and positive ion active species A, a source gas S ( Figure 2 For example, when operation S120 is performed without a separate reactant gas or reactive purge gas, a first layer L1 based on source gas molecules may be formed on upper and side surfaces of the first and second steps P1 and P2 and a lower surface 204 connecting the first and second steps P1 and P2.

[0067] In some embodiments, a reactant gas (or reactive purge gas) may be supplied during operation S110, in which case, during operation S120, source gas molecules may react with the reactant gas or reactive purge gas. Figure 2 A layer for gaseous reaction between the reactant gas and the reactant gas may be formed on the gap structure.

[0068] In some embodiments, during operation S120 of generating active species from a gas including a source gas, formation of a first layer L1 in an upper region adjacent to edges of the first step P1 and the second step P2 may be promoted. The formation of the first layer L1 in the upper region may be facilitated by edge potentials (at Figure 3 '-' in the figure) to promote. Figure 3 , a state in which the formation of the first layer L1 in the upper region is promoted, and the first layer L1 may include a protruding portion O.

[0069] In more detail, since charges are accumulated more in the sharp edge portion E than in the flat portion, the electric field applied between the gas supply unit and the substrate support unit of the substrate processing apparatus may be concentrated to the edge portion E of the gap structure. As a result, the active species A of the cations also move toward the edge portion E, thereby facilitating the formation of the first layer L1 in the upper region adjacent to the edge portion E, and the protrusion O may be formed.

[0070] The first layer L1 on which the protrusion O is formed may have a non-uniform thickness on the surface of the recess. For example, the thickness of the first layer L1 formed in the upper region of the recess may be greater than the thickness of the first layer L1 formed in the lower region of the recess. For example, when the average thickness of the first layer L1 in the upper 10% of the recess formed after the operation S120 of generating the active material is x1, and when the average thickness of the first layer L1 in the lower 10% of the recess is x2, the ratio of the two may be greater than 1, such as x1 / x2, which may be defined as a first thickness ratio.

[0071] Afterwards, refer to Figure 1 and Figure 4 , an operation S130 of neutralizing the active substance to generate neutral molecules N is performed. During the neutralization of the active substance, the electric field that has been applied between the gas supply unit and the substrate support unit of the substrate processing equipment may be removed. For example, by eliminating the plasma application in the substrate processing equipment, the electric field of the substrate may be removed and the active substance A ( Figure 3 of).

[0072] Neutral molecules N generated by neutralizing the active substance may move in a direction toward the lower surface of the concave portion extending between the first step P1 and the second step P2 of the gap structure ( Figure 4 with active substance A ( Figure 3 Compared to the upper and lower surfaces, the neutral molecules N can move relatively freely toward the lower surface.

[0073] In more detail, the active material A as a cation may be affected by the external electric field, while the neutral molecule N may not be affected by the external electric field. Even if the edge potential remains in the edge portion E of the first step P1 and / or the second step P2 of the gap structure, the neutral molecule N may move to the lower region of the recess without being affected by such edge potential.

[0074] In addition, in some optional embodiments, the edge potential formed at the edges of the first step P1 and the second step P2 can be reduced during the neutralization of the active substance A. For example, by turning off the plasma, the electric field that has been applied between the gas supply unit and the substrate support unit can be removed, and the edge potential can be reduced accordingly. In this case, the active substance A of the remaining cations can be unaffected by the edge potential.

[0075] For example, although according to some embodiments, Figure 4 Only neutral molecules N (and their movement into the lower region of the concave portion) are shown in FIG, but in addition to the neutral molecules N, active substances A may remain on, near, or within the gap structure. In this case, due to the reduced edge potential described above, the remaining active substances A may move to the lower region of the concave portion without being affected by the external electric field, thereby achieving an increase in mobility.

[0076] In some embodiments, the movement of the neutral molecules N and the movement of the remaining active material A may be performed simultaneously. In this case, when the neutral molecules N move in a direction toward the lower surface of the recess, the remaining active material A may move in a direction toward the lower surface without being affected by the edge potential.

[0077] Afterwards, refer to Figure 1 and Figure 5 , an operation S140 of exciting the neutral molecules N that have moved in the direction toward the lower surface is performed. To this end, for example, by turning on plasma, an electric field that has been applied between the gas supply unit and the substrate support unit may be generated. The neutral molecules N may be excited by the electric field and separated again into electrons (not shown) and active species A'.

[0078] Since the neutral molecules N are excited after moving in the direction toward the lower surface, the active material A' can be generated in the lower region of the concave portion. Therefore, during the excitation of the neutral molecules N, the second layer L2 can be formed in the lower region of the lower surface of the concave portion between the first step P1 and the second step P2.

[0079] As described above, during the operation S120 of generating the active material A from the gas including the source gas S, the formation of the first layer L1 in the upper region of the recess may be promoted, and during the operation S140 of exciting the neutral molecules N with the active material A', the formation of the second layer L2 in the lower region of the recess may be promoted. Therefore, by alternately performing these operations (i.e., through the above-mentioned operation S120 of generating the active material and the operation S140 of exciting the neutral molecules), the step coverage of the second layer L2 formed on the first layer L1 on the upper region and the lower region of the recess may be improved. That is, the second layer L2 may be uniformly formed on the first layer L1.

[0080] Figure 5A layer with improved step coverage is shown in FIG, and the second layer L2 formed during operation S140 of exciting the neutral molecules N can have a uniform thickness. For example, the average thickness of the second layer L2 at the top 10% of the recess and the average thickness of the second layer L2 at the bottom 10% of the recess can both be x3. In this case, the average thickness of the entire layer in the top 10% of the recess will be x1+x3, and the average thickness of the entire layer at the bottom 10% of the recess will be x2+x3. The ratio of x1+x3 and x2+x3 can be greater than 1, which can be defined as a second thickness ratio. In addition, by repeating the process of generating active substances, forming neutral molecules, and exciting neutral molecules, more improved step coverage can be achieved compared to the conventional method of applying only the operation of generating active substances.

[0081] In some embodiments, the substrate processing method may include applying plasma in a pulsed manner, and the operation S120 of generating active species and the operation S140 of exciting neutral molecules may be performed by applying plasma. During the application of plasma, at least one of a first frequency RF power (i.e., high frequency RF power) of 13 MHz or more and a second frequency RF power (i.e., low frequency RF power) of 1 MHz or less may be applied.

[0082] In more detail, the above-mentioned operation S120 of generating active substances and the operation S140 of exciting neutral molecules can be implemented by applying plasma, and the operation S130 of generating neutral molecules can be performed by stopping the application of plasma. In one example, applying plasma in the operation S120 of generating active substances may include an on period and an off period, and the operation S120 of generating active substances from the source gas and / or the operation S140 of exciting neutral molecules may be implemented during the on period, and the operation S130 of generating neutral molecules (i.e., neutralization of active substance A) may be performed during the off period. In particular, as the on / off period of the plasma pulse becomes shorter, the generation of active substances, the generation of neutral molecules, and the excitation of neutral molecules are performed almost simultaneously, which has the technical benefit of forming a more uniform film almost simultaneously in the upper and lower regions of the recessed structure. Therefore, as Figures 3 to 5 As shown, there is a technical benefit of suppressing the formation of a thicker film in the upper region of the recess structure and achieving more improved step coverage.

[0083] In some embodiments, the opening portion of the operation S120 for generating active substances may be defined as a first time period, the closing portion of the operation S130 for generating neutral molecules may be defined as a second time period, and the opening portion of the operation S140 for exciting neutral molecules may be defined as a third time period. In this case, in one example, the second time period may be greater than the first time period, thereby allowing more neutral molecules to be generated and move into the recess of the gap structure. In another example, the first time period may be less than the third time period, thereby minimizing the protruding portion of the layer formed during the first time period.

[0084] As described above, according to an embodiment of the technical concept of the present disclosure, a film having a uniform thickness can be formed by supplying plasma power in the form of pulses so that the source gas S diffuses to the lower region of the gap structure. In addition, according to an optional embodiment, the film formation rate can be increased by dissociating the source gas and the reactant gas together through plasma application.

[0085] Although not shown in the figure, according to some embodiments, the substrate processing method may further include post-processing of the formed layer. The post-processing may be a subsequent processing operation on the formed layer, and the supply of the source gas S may be interrupted during the post-processing. In some embodiments, during the post-processing, the layer may be densified, or the protruding portion O'( Figure 5 ) can be removed.

[0086] According to an embodiment, in a process of forming a layer by stacking a layer on a surface of a gap structure, a layer is formed in a deposition operation in which a source gas, a reactant gas, and a high-frequency RF power are simultaneously supplied, and then the layer is densified in a plasma post-processing operation. In the plasma post-processing operation, by supplying a low-frequency RF power, uniform densification can be performed from an upper region to a lower region of the gap. Thus, in a deposition process for a gap structure having a high aspect ratio (e.g., greater than 10), the uniformity of film formation rate, step coverage, and film properties (e.g., etching properties) can be simultaneously improved.

[0087] Figure 6 is a flow chart illustrating a substrate processing method according to an additional exemplary embodiment. Figure 6 The substrate processing method of the illustrated embodiment may be a modification of the substrate processing method according to the above-described embodiment. Hereinafter, a repeated description of the embodiment will not be given here.

[0088] Reference Figure 6 ,and Figure 1As in the embodiment of the present invention, in operation S100, a gap structure is prepared, and in operation S110, a source gas (and a reactant gas) are supplied to the gap structure. Thereafter, in operation S120, an active substance is generated from the source gas so that layer formation is concentrated in the upper region of the concave portion, and after neutralizing the active substance to generate neutral molecules in operation S130, in operation S140, the neutral molecules are excited so that layer formation is concentrated in the lower region of the concave portion.

[0089] In some embodiments, the operation S130 of generating neutral molecules and the operation S140 of exciting neutral molecules may be repeated multiple times as a layer formation cycle. After the cycle is repeated a certain number of times, the layer formation cycle is terminated and the operation S160 of post-processing is performed, but if not, after the operation S150 of determining whether the cycle is terminated, the number of cycles is increased, and then the operations S130 and S140 may be repeated. In some embodiments, the source gas may be continuously supplied during the operation S140 of exciting neutral molecules, and thus, the active material may continue to be supplied while the layer formation cycle is repeated.

[0090] After the layer formation cycle of S130 to S140 is terminated, the post-processing operation S160 is performed. As described above, since the post-processing operation S160 is an operation for subsequent processing of the formed layer, the supply of the source gas may be interrupted during the post-processing operation S160. In addition, plasma may be applied during the post-processing operation S160. The conditions (i.e., parameters) of the plasma applied during the post-processing operation S160 may be adjusted according to the purpose of the post-processing.

[0091] For example, during operation S160 of the post-processing, plasma may be applied to densify the previously formed layer. In this case, the RF power during operation S160 of the post-processing may be set to be greater than the RF power during operation S120 of generating active species from the source gas (i.e., RF power sufficient to dissociate source gas molecules). Thus, an ion bombardment effect of high RF power may be achieved, and as a result, smooth densification of the layer may be achieved.

[0092] In some embodiments, the RF frequency during operation S160 of the post-processing may be lower than the RF frequency during operation S120 of generating the active species from the source gas. For example, low-frequency RF power (e.g., RF power of 1 MHz or less) may be applied during operation S160 of the post-processing. Such low-frequency power plasma may increase the moving distance of the active species, and the active species may move to the lower region of the recess, thereby achieving densification of the layer in the lower region.

[0093] In another embodiment, a high frequency RF power (e.g., 13 MHz or higher RF power) may be applied during the operation S160 of the post-processing, by which the amount of ions generated and the ion density may be increased, so that a large amount of ions and active substances may be supplied to the recess between the first step and the second step. The frequency of the RF power applied in the operation S160 of the post-processing may match the frequency of the RF power used in the above-mentioned layer formation cycle. In another embodiment, the frequency of the RF power supplied during the operation S160 of the post-processing may further include the plasma frequency of the RF power supplied during the operation S120 of generating active substances from the source gas. For example, the frequency of the RF power supplied for generating active substances from the source gas may be a high frequency, and the frequency of the RF power supplied for the post-processing may be a mixture of high and low frequencies. That is, the RF frequency used for the post-processing may further include the RF frequency used for generating active substances from the source gas in the layer formation cycle.

[0094] Figure 7 is a flow chart illustrating a substrate processing method according to an additional exemplary embodiment. Figure 7 The substrate processing method of the illustrated embodiment may be a modification of the substrate processing method according to the above-described embodiment. Hereinafter, a repeated description of the embodiment will not be given here.

[0095] Reference Figure 7 ,and Figure 1 As in the embodiment of the present invention, in operation S100, a gap structure is prepared, and in operation S110, a gas including a source gas is supplied to the gap structure. Thereafter, in operation S200, a film forming process is performed by applying plasma in a pulsed manner to dissociate the source gas. The source gas dissociated by the plasma may react with a reactant gas supplied at the same time or a reactant gas supplied subsequently, and as a result, a layer may be formed on the gap structure. Operation S110 of supplying a gas including a source gas and operation S200 of dissociating the source gas may be repeated as a layer formation cycle. In other words, during operation S210 of determining whether film formation is terminated, it is determined whether the layer formation cycle is equal to a predetermined number of times, and if not, operations S110 and S200 may be repeatedly performed by increasing the number of cycles.

[0096] In some embodiments, the pulsed plasma applied to dissociate the source gas can be configured to generate neutral ions from the active species. In addition, in some other embodiments, the pulsed plasma applied to dissociate the source gas can be configured to reduce the edge potential of the step edge. In another embodiment, the pulsed plasma used to dissociate the source gas can be configured to generate neutral ions from the active species and reduce the edge potential of the step edge.

[0097] Figure 8is a flow chart showing a substrate processing method according to yet another exemplary embodiment. Figure 8 The substrate processing method of the illustrated embodiment may be a modification of the substrate processing method according to the above-described embodiment. Hereinafter, a repeated description of the embodiment will not be given here.

[0098] refer to Figure 8 ,and Figure 1 As in the embodiment of the present invention, in operation S100, a gap structure is provided. Thereafter, in operation S310, a gas is supplied to the gap structure. The gas may be a gas including a source gas. Thereafter, in operation S320, an active substance is generated from the gas. The generation of such an active substance may be achieved by a variety of known methods. For example, the energy applied to generate the active substance may include electrical energy, thermal energy, or light energy.

[0099] Thereafter, an operation S330 of reducing the edge potential of the step edge of the gap structure is performed. By reducing the edge potential, the ion trajectory distortion of the active material can be reduced. As a result, smooth migration of the active material into the lower region of the recess can be achieved. As an example of a method of reducing the edge potential of the step edge, a reverse potential (i.e., a positive potential) may be applied to the negatively charged substrate support unit for a specific period of time.

[0100] Fig. 9 is a flow chart showing a substrate processing method according to yet another exemplary embodiment. Fig. 9 The substrate processing method of the illustrated embodiment may be a modification of the substrate processing method according to the above-described embodiment. Hereinafter, a repeated description of the embodiment will not be given here.

[0101] Reference Fig. 9 , first, in operation S100, a gap structure is prepared, and then a source gas (and a reactant gas or a reactive purge gas) is supplied, and in operation S410, an active substance is generated by plasma application or the like. Thereafter, an operation S420 of neutralizing the active substance is performed, and a sub-cycle including the above-mentioned operations S410 to S420 is repeated a predetermined number of times to form a layer. After operation S430 of determining whether the sub-cycle is terminated, in operation S440, residual gas is purged, and in operation S450, a reactant gas or a reactive purge gas is supplied. When a reactive purge gas is supplied as described above, the gas supplied during the purge operation S440 and the reactant gas supply operation S450 may be the same as each other.

[0102] During operation S450 of supplying the reactant gas, active species may be generated by plasma application, etc. Thereafter, in operation S460, the residual gas is purged, and it is determined whether the film formation is terminated. When the film formation is not terminated, the sub-cycle including S410 to S420 may be performed again, and operation S440 of purging and operation S450 of supplying the reactant gas may be performed.

[0103] Fig.10 is a view illustrating a gap filling method according to an embodiment.

[0104] Reference Fig.10 , the first step (t1) is a chemical vapor deposition step in which a source gas, a reactant gas, and RF power are supplied together, and then a plasma post-treatment step (t3) is performed as a third step (t3). In the deposition step (t1), RF power is supplied in a pulsed manner (e.g., a pulse wave). Each step will be described in detail below.

[0105] First step (t1): In the first step (t1), a source gas (e.g., a precursor), a reactant gas, and RF power are supplied together to the reaction space of the reactor. The RF power dissociates the source gas and the reactant gas to induce a gas phase reaction between the two gas molecules, thereby promoting film formation on the substrate. However, the RF power supplied in this step is supplied with an intensity sufficient to induce the dissociation of the source gas molecules, so that in addition to the gas phase reaction between the source gas and the reactant gas in the reaction space, a surface reaction between the source gas molecules and the substrate also proceeds simultaneously. Therefore, it is a technical benefit to improve the uniformity of the thin film deposited on the substrate while improving the film formation rate of the thin film deposited on the substrate.

[0106] In the first step, RF power is supplied in the form of pulses, in particular. In general, in the gap filling process using plasma, the active material or ions supplied to the inner region of the gap react with the sidewalls of the upper region of the gap where electrons are gathered before reaching the sidewalls or bottom of the lower region of the gap. Therefore, the film deposition rate in the lower region of the gap is less than the film deposition rate in the upper region. However, in the RF off period of the pulse region (t1), since the active material or ions are neutralized, they may reach the lower region of the gap. In other words, by improving the ion mobility on the surface of the gap structure, uniform film deposition from the upper region of the gap structure to the lower region is possible, and there is a technical benefit of improving the step coverage on the surface of the gap structure. The RF power supplied in the first step can be provided as a high frequency RF power (HRF), a low frequency RF power (LRF) or a combination thereof. That is, high frequency RF power and low frequency RF power can be supplied together with source gas. The frequency of the high frequency RF power can be 13MHz or higher. For example, the frequency can be 13.56MHz, 27.12MHz or 60MHz. The frequency of the low frequency RF power may be 1 MHz or 500 kHz or lower. For example, the frequency may be 430 kHz or 320 kHz.

[0107] In the first step, the intensity of the applied RF power becomes different according to the duty cycle (the ratio of the RF-on period to the pulse period including RF-on and RF-off). For example, the intensity of the applied RF power when the duty cycle is large may be smaller than the intensity of the applied RF power when the duty cycle is small. However, the intensity of the total applied RF power may be the same. For example, when the duty cycle is large, the applied RF power may be small, and when the duty cycle is small, the applied RF power may be large. Fig.11 The definition of duty cycle is shown.

[0108] Fig.11 It is shown Fig.10 The first step (t1) of FIG. 1 shows the definition of the duty cycle. The duty cycle is expressed as the ratio of the RF on time (a) to the unit period of the RF pulse (a+b). That is, Fig.11 In , the duty cycle is defined as a / (a+b) or a / c.

[0109] 12(a) and 12(b) illustrate various types of RF pulses according to an embodiment.

[0110] The duty ratios of Figure 12(a) and Figure 12(b) differ by 1 / 3 and 2 / 3, respectively. However, the intensity of the applied RF unit power is the same (RF on time x RF power).

[0111] In addition, when RF power is provided in the form of pulses, the ion energy is reduced, so there is a technical benefit of preventing damage to the underlying film. For example, in one embodiment, when RF power is supplied in a pulsed mode, sublayer loss (e.g., carbon loss) can be reduced by up to 75% compared to when RF power is supplied in a continuous mode.

[0112] Second step (t2): Fig.10 The second step (t2) is a purging step in which the reaction by-products produced in the first step (t1) are removed from the reaction space.

[0113] The third step (t3): Fig.10 The third step (t3) is a plasma post-treatment step. In this step, the film is densified while applying RF power to the reactant gas or the purge gas without supplying the source gas. The intensity of the RF power applied to the densified film in the third step (t3) may be greater than the intensity of the RF power applied in the first step (t1). As described above, the film deposited on the surface of the gap structure in the first step (t1) is formed by providing a weak RF power sufficient to dissociate the source gas molecules, so the film is not dense. Therefore, in the third step, high RF power is applied to densify the film by the ion bombardment effect. In particular, by supplying low-frequency RF power, the moving distance of the active material increases, thereby improving the uniformity of the film properties from the upper region of the gap to the lower region. For example, there is a technical benefit of improving the uniformity of the density of the formed film. Therefore, there is a technical benefit of preventing cracks from being generated due to uneven thermal expansion inside the film filling the gap during the subsequent annealing process.

[0114] In this step, low frequency RF power (LRF) can be supplied, but in another embodiment, high frequency RF power (HRF) can be supplied. Alternatively, in another embodiment, low frequency RF power (LRF) and high frequency RF power (HRF) can be supplied together with source gas. Therefore, there is a technical benefit of increasing the number of ions and ion density generated, supplying more ions and active substances to the lower region of the gap, and further improving the uniformity of the film density from the upper region to the lower region of the gap. In another embodiment, by supplying an RF power greater than the RF power supplied in the deposition step (t1), there is a technical benefit of increasing the amount of ions and active substances generated and increasing the film density. The frequency of the high frequency RF power can be 13 MHz or higher. For example, the frequency can be 13.56 MHz, 27.12 MHz, or 60 MHz. The frequency of the low frequency RF power can be 1 MHz or lower. For example, the frequency can be 430 kHz or 320 kHz.

[0115] In addition, the ion bombardment of the plasma applied in this step may induce a sputtering effect on the film formed in the upper region of the gap. Therefore, there is a technical advantage of preventing the formation of voids inside the gap by destroying the film of the protruding structure formed in the upper region of the gap by the sputtering effect to keep the width of the gap entrance greater than the width inside the gap. In other words, there is a technical benefit in that the uniformity of the characteristics of the thin film deposited on the inner wall of the gap from the upper region to the lower region of the gap is improved by supplying low-frequency RF power, and the characteristics (such as density) of the thin film are improved by increasing the amount of ion active substances by supplying high-frequency RF power together or increasing the intensity of the supplied RF power.

[0116] Fourth step (t4): Fig.10 The fourth step (t4) is a purge step in which the reaction by-products produced in the third step (t3) are removed from the reaction space.

[0117] Fig.10 The deposition steps (t1) and (t2) and the plasma post-treatment steps (t3) and (t4) are repeated at least once and multiple times (m and n cycles), respectively, and the deposition steps and the plasma post-treatment steps are repeated multiple times to constitute a super cycle (x cycles).

[0118] Fig.13 2 is a schematic diagram showing that when RF power is applied to the showerhead electrode 1, a potential difference is formed in a reaction space between the showerhead electrode 1 and the substrate 2 located on the heating block 3. For example, the showerhead electrode 1 may be positively charged and the opposite substrate may be negatively charged, so that a potential difference may be formed therebetween.

[0119] Fig.14 yes Fig.13 An enlarged view of a portion of substrate 2. Fig.14 In the present invention, the substrate includes a pattern structure. Cations (e.g., dissociated source gas) and electrons are mixed in the plasma, so the ion trajectory of the cations may be distorted by the electrons in the gap structure (ion trajectory distortion). However, when Fig.10 When the RF power is interrupted in the RF-off state during the deposition step, the plasma remains in the reactor (i.e., after the glow), but the ion energy of the residual plasma becomes lower due to the interruption of the RF power. Therefore, the electrons are neutralized and gathered on the top of the pattern structure. Therefore, the ions (e.g., dissociated source gas molecules) are less affected by the electrons and diffuse deeper into the gap, reducing the ion trajectory distortion.

[0120] Therefore, in Fig.10In an embodiment, by supplying RF power in pulses rather than continuously, more ion active species, such as more source gas, can be supplied to the lower region of the gap. In an embodiment, when the duty cycle is lower as shown in FIG. 12( a), this technical benefit becomes more apparent because the ions are less affected by the electrons and the diffusion time is extended. Of course, in this case, the intensity of the RF power used to increase the dissociation rate of the source gas may need to be increased accordingly.

[0121] Fig.15 2 is a view showing step coverage when a SiO2 film is deposited on a gap structure by a continuous method (continuous wave mode CVD followed by plasma treatment) and by a pulse method (pulsed wave mode CVD followed by plasma treatment) according to an embodiment, respectively, in the case where a gap filling process is performed by supplying RF power.

[0122] exist Fig.15 In the TEM photograph of , when RF power is supplied in a pulsed manner, it can be seen that the thickness of the film deposited on the lower area of ​​the gap when RF power is supplied in a pulsed manner is greater than the thickness of the film when RF power is supplied in a continuous wave manner, and the step coverage is improved by about 40% from the upper area to the lower area of ​​the gap. Fig.15 It is shown that in addition to the gap filling process, the present disclosure can also be used as an insulating film between a metal film and a silicon substrate in a hole in a TSV (through silicon via) process.

[0123] 16( a ) and 16 ( b ) are views showing a modified embodiment according to the present disclosure.

[0124] Figures 16(a) and 16(b) show multiple embodiments of plasma post-treatment. For example, as shown in Figure 16(a), after increasing the ion density by supplying high-frequency RF power (HRF), low-frequency RF power (LRF) can be supplied to uniformly densify the membrane until the lower region of the gap structure, so that the mean free path (MFP) of the ion active species can be increased. Alternatively, as shown in Figure 16(b), by supplying high-frequency RF power and low-frequency RF power together, and then supplying low-frequency RF power, the membrane is uniformly densified to the lower region of the gap structure while maintaining the MFP of the ion active species. In another embodiment, the RF power intensity in each step of the two-step plasma post-treatment of Figures 16(a) and 16(b) can be different.

[0125] Table 1 shows the experimental conditions according to the embodiment.

[0126]

[0127] In Table 1, in the deposition step, high frequency RF power is applied in a pulsed manner with a duty cycle between 0.2 and 0.8. In the plasma post-treatment step, high frequency RF power and low frequency RF power are applied. In the example according to Table 1, a SiO2 film is deposited on the gap structure, and at least one of an aminosilane-based, iodosilane-based, and halide-based source is used as a Si source. For example, the silicon source may include at least one of the following: TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu) 2; BITS, SiH2(NHSiMe3)2; DIPAS, SiH3N(iPr)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; 3DMAS, SiH(N(Me)2)3; BEMAS, SiH2[N(Et)(Me)]2; AHEAD, Si2(NHEt)6; TEAS, Si(NHEt)4; Si3H8; DCS, SiH2Cl2; SiHI3; SiH2I2; and trimer-trimethylsilylamine, or a derivative thereof or a mixture thereof. The oxygen reactant gas may include at least one of: O2, O3, CO2, H2O, NO2, N2O or a mixture thereof. In another embodiment, Si may be deposited x N y or SiCN film. In this case, the nitrogen reactant gas may be at least one of: N2, N2H2 (diimide) and NH3, NH4 or a mixture thereof.

[0128] Although the above detailed description has been described for the gap filling process, the present disclosure can also be applied to the TSV process. The TSV process is a technology for increasing the integration of semiconductor devices by combining two silicon substrates, and the present disclosure can be applied to the liner process of depositing an insulating film on the inner wall of a through hole penetrating two silicon substrates. Fig.17 An embodiment of a TSV process is shown.

[0129] exist Fig.17In the present invention, a metal film 3 is filled in a through hole 5 penetrating two substrates 1 and 2 bonded to each other, and an insulating film 4 is formed as a liner layer between the metal film 3 and the inner wall of the through hole 5. The insulating film 4 prevents the metal film from diffusing into the substrate, and therefore needs to have a uniform thickness and uniform characteristics along the inner wall of the through hole 5 having a high aspect ratio (HAR). Therefore, the present disclosure has a technical benefit of being effectively applied to the deposition of a liner insulating film in a TSV process.

[0130] In some cases, it may be desirable to fill a gap structure, such as gap structure 200 ( Figure 2 ), while mitigating void and / or seam formation of deposited material within the gap structure and / or while providing relatively uniform material properties within the gap.

[0131] As described above, an exemplary method according to another embodiment of the present disclosure may start by providing a substrate having a gap structure (e.g., with an aspect ratio greater than 10) thereon into a reaction chamber of a reactor. Thereafter, the method may be performed, for example, according to Fig.18 The timing shown is carried out.

[0132] Fig.18 A sequence 1800 of a substrate processing method according to an example of the present disclosure is shown. The sequence 1800 includes a step 1802 of forming a first layer, a step 1804 of forming a second layer, and an optional chamber conditioning step 1806. The substrate temperature during steps 1802-1806 may be between about 200°C and about 600°C.

[0133] Step 1802 of forming the first layer may be combined with the above Fig.10 The gap filling methods described are the same or similar. In the illustrated example, step 1802 includes supplying a first source gas into the reaction chamber, activating the first source gas, supplying a reactant into the reaction chamber, and activating the reactant.

[0134] In more detail, step 1802 includes M deposition cycles and N treatment cycles. Each M deposition cycle includes t0-t2, and each N treatment cycle includes t3 and t4. The ratio of the M cycle to the N cycle can be in the range of about 1:1 to about 1:10.

[0135] In the example shown, at t0, reactants and purge gas are provided to the reaction chamber. The reactants may be or include, for example, an oxygen reactant gas and / or a nitrogen reactant gas as described above.

[0136] During t0, the pressure in the reaction chamber and / or the flow of the purge gas and the reactant gas may be allowed to stabilize. For example, during t0 and / or step 1802, the pressure in the reaction chamber may be between about 1 Torr and about 3 Torr. In addition, as shown, the flow of the reactant and / or the purge gas may continue through one or more of steps 1802-1806. The duration of t0 may be between about 0.01 seconds and about 2 seconds.

[0137] During t1, a first gas source (eg, a precursor as described herein) is provided (eg, pulsed) to the reaction chamber, plasma power is provided, and reactant and / or purge gas may continue to be provided. The duration of t1 may be between about 0.01 seconds and about 2 seconds.

[0138] As described above, an exemplary precursor may include silicon. For example, the first gas source may be or include one or more of an aminosilane, an iodosilane, or a halide-based silicon source. As specific examples, the first gas source may be or include TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(N HtBu)2; BITS, SiH2(NHSiMe3)2; DIPAS, SiH3N(iPr)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; 3DMAS, SiH(N(Me)2)3; BEMAS, SiH2[N(Et)(Me)]2; AHEAD, Si2(NHEt)6; TEAS, Si(NHEt)4; Si3H8; DCS, SiH2Cl2; SiHI3; SiH2I2, derivatives thereof or mixtures thereof or any combination thereof.

[0139] The first source gas and reactant are activated by the first layer plasma power to form activated species from the first source gas and reactant. During t1, PECVD or PECVD-like deposition occurs.

[0140] In the example shown, the first layer plasma power is pulsed—for example, as described above in conjunction with Figure 10-12. The frequency of the first layer plasma power can be as described above. For example, the frequency can be or include the high frequency as described above. The first layer plasma power can be between about 100 W and about 1000 W. The duty cycle of the pulsed first layer plasma power can be between about 10% and about 70% or between about 15% and about 35%.

[0141] During t2, the flow of the first source gas and the first layer plasma power have been stopped, and the reaction chamber is allowed to be purged—for example, by continuing to flow the reactants and / or the purge gas. The duration of t2 may be between about 0.01 seconds and about 2 seconds.

[0142] Before the method proceeds to N cycle / t3, t0-T2 (M cycle) can be repeated one or more times. For example, before proceeding to the next step, M cycle can be repeated between about 1 and about 50 times.

[0143] During t3, the first layer deposited during one or more M cycles is processed. In the illustrated example, the reactants and purge gas are activated during t3. The processing step (N cycle) can be as described above and can include providing a processing plasma power. The processing plasma power frequency can be as described above. For example, the processing plasma power can include a mixture of high frequency and low frequency as described above. The plasma power during t4 can be between about 100W and about 1000W. The duration of t3 can be between about 0.01 and about 2 seconds.

[0144] During t4, the flow of the first source gas and the process plasma power has ceased, and the reaction chamber is allowed to be purged—for example, by continuing to flow the reactants and / or the purge gas. The duration of t4 may be between about 0.01 seconds and about 2 seconds.

[0145] T3 and T4 (N cycles) can be repeated one or more times before the method proceeds to another M cycle or forms a second layer (O cycle). For example, the N cycle can be repeated between about 1 and about 50 times before proceeding to the next step.

[0146] During step 1804 of forming the second layer, a PEALD or PEALD-like process may be used to form the second layer. In the example shown, step 1804 includes supplying a second source gas into the reaction chamber, supplying a reactant into the reaction chamber, activating the reactant, and may include repeating the steps of supplying the second source gas and activating the reactant. According to an example of the present disclosure, the pressure in the reaction chamber during step 1804 is higher than the pressure in the reaction chamber during step 1802. For example, during step 1804, the pressure in the reaction chamber may be between about 3 Torr and about 7 Torr.

[0147] Step 1804 may start from t5 and include supplying (e.g., pulsing) a second source gas into the reaction chamber, e.g., while reactants and purge gases continue to be supplied to the reaction chamber. The second source gas may be, for example, any precursor mentioned above in conjunction with the first source gas. In some cases, the first source gas and the second source gas may be the same. As shown, plasma power is not provided during t5. The duration of t5 may be between about 0.01 seconds and about 2 seconds. Although not shown separately, sequence 1800 may include purging the reaction chamber after the step of supplying the second source gas and before t6.

[0148] During t6, a second layer plasma power is supplied during the second layer deposition step 1804 to form an activated species from the reactant. According to an example of the present disclosure, the second layer plasma during t6 is formed after the flow of the second source gas is stopped. The duration of t6 may be between about 0.01 seconds and about 2 seconds.

[0149] The frequency of the second layer plasma power can be as described above. For example, the power can include high frequency and low frequency, as described above. The second layer plasma power can be between about 100 W and about 1000 W. According to an example of the present disclosure, in contrast to t1, the plasma power during t6 is not pulsed. According to another example, the first layer plasma power is equal to or lower than the second layer plasma power.

[0150] During t7, the reaction chamber is purged. For example, reactants and purge gases may continue to flow during t7. The duration of t7 may be between about 0.01 seconds and about 2 seconds.

[0151] Step 1804 may be repeated multiple times before proceeding to step 1806 or 1802. According to an example of the present disclosure, a cycle ratio of the first step 1802 to the second step 1804 is 1:10 or less.

[0152] During step 1806, chamber conditioning is performed by forming an activated species from the inert gas. During step 1802 and / or step 1804, the activated species from the inert gas can be used to harden the film formed on the inner wall of the reaction chamber. Step 1806 can be performed while the substrate is in the reaction chamber or after the substrate is removed from the reaction chamber. In addition, step 1806 can be repeated before the next step is performed, such as removing the substrate from the reaction chamber.

[0153] As shown, step 1806 may include t8 and t9. During t8, an inert gas (e.g., a purge gas) is provided to the reaction chamber, and a regulated plasma power is applied within the reaction chamber. The regulated plasma power may include a high frequency and / or a low frequency as described above. The plasma power during t8 may be between about 100 W and about 1000 W. The duration of t8 may be between about 10 seconds and about 300 seconds.

[0154] During t9, the reaction chamber may be purged. For example, the purge gas may continue to flow during step t9.

[0155] During step 1806, the pressure within the reaction chamber may be between about 1 Torr and about 3 Torr. The pressure within the reaction chamber during step 1806 may be less than the pressure within the reaction chamber during step 1804.

[0156] It should be understood that the embodiments described herein should be considered to be merely illustrative and not for limiting purposes. The description of features or aspects in each embodiment should generally be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made without departing from the spirit and scope of the present disclosure as defined by the appended claims.

Claims

1. A substrate processing method, comprising: providing a substrate having a gap structure thereon into a reaction chamber of a reactor; Forming the first layer includes the following steps: supplying a first source gas into the reaction chamber; activating a first source gas; supplying reactants into the reaction chamber; activating reactants during deposition of the first layer; and optionally repeating the steps of supplying a first source gas, activating the first source gas, and activating the reactant; and Forming the second layer comprises the following steps: supplying a second source gas into the reaction chamber; supplying reactants into the reaction chamber; activating the reactants during deposition of the second layer; and The steps of supplying the second source gas and activating the reactant are repeated.

2. The substrate processing method according to claim 1, further comprising at least one of the following: During the formation of the first layer, purging the reaction chamber after the step of activating the first source gas; During formation of the first layer, purging the reaction chamber after the step of activating the reactants; During the forming of the second layer, purging the reaction chamber after the step of supplying the second source gas; and During the formation of the second layer, the reaction chamber is purged after the step of activating the reactants.

3. The substrate processing method according to claim 2, wherein: During the steps of forming the first layer and forming the second layer, the purge gas is continuously supplied into the reaction chamber.

4. The substrate processing method according to claim 3, wherein: During the steps of forming the first layer and forming the second layer, reactants are continuously supplied into the reaction chamber.

5. The substrate processing method according to claim 1, wherein: Activating the first source gas includes applying a first layer of plasma power to the reactor in pulses.

6. The substrate processing method according to claim 5, wherein: The first layer plasma power is applied at a duty cycle between about 10% and about 70%.

7. The substrate processing method according to claim 1, wherein: Activating the reactants during deposition of the second layer includes applying a second layer of plasma power to the reactor.

8. The substrate processing method according to claim 5, wherein: The first layer plasma power is between about 100W and about 1000W.

9. The substrate processing method according to claim 8, wherein: The first layer plasma power is equal to or lower than the second layer plasma power.

10. The substrate processing method according to claim 8, wherein: The first layer plasma power has a frequency of 10 MHz or higher.

11. The substrate processing method according to claim 9, wherein: The second layer plasma power includes dual frequencies including a high frequency of 10 MHz or higher and a low frequency of 500 kHz or lower.

12. The substrate processing method according to claim 1, wherein: The cycle ratio of the step of forming the first layer to the step of forming the second layer is 1:10 or less.

13. The method according to claim 1, wherein The first source gas and the second source gas contain silicon.

14. The substrate processing method according to claim 13, wherein: The first source gas and the second source gas include one or more of aminosilane, iodosilane, or a halide-based silicon source.

15. The substrate processing method according to claim 14, wherein: The first source gas and the second source gas are at least one of the following: TSA, (SiH3)3N; DSO, (SiH3)2; DSMA, (SiH3)2NMe; DSEA, (SiH3)2NEt; DSIPA, (SiH3)2N(iPr); DSTBA, (SiH3)2N(tBu); DEAS, SiH3NEt2; DTBAS, SiH3N(tBu)2; BDEAS, SiH2(NEt2)2; BDMAS, SiH2(NMe2)2; BTBAS, SiH2(NHtBu)2; BITS, SiH2(NHSiMe3)2; DIPAS, SiH3N(iPr)2; TEOS, Si(OEt)4; SiCl4; HCD, Si2Cl6; 3DMAS, SiH(N(Me)2)3; BEMAS, SiH2[N(Et)(Me)]2; AHEAD, Si2(NHEt)6; TEAS, Si(NHEt)4; Si3H8; DCS, SiH2Cl2; SiHI3; SiH2I2, derivatives thereof or mixtures thereof.

16. The substrate processing method according to claim 1, wherein: The reactants include oxygen reactant gas.

17. The substrate processing method according to claim 1, wherein: The reactant includes nitrogen reactant gas.

18. The substrate processing method according to claim 1, wherein: The pressure in the reaction chamber during the step of forming the second layer is higher than the pressure in the reaction chamber during the step of forming the first layer.

19. The substrate processing method according to claim 1, further comprising a chamber conditioning step.

20. The substrate processing method according to claim 19, wherein: The chamber conditioning is performed by forming an activated species from an inert gas to harden a film formed on a wall within the reaction chamber.

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